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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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期刊内热点文章
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
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Development of electron and hole selective contact materials for perovskite solar cells
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(8): 111084
doi: 10.1016/j.cclet.2025.111084
摘要:
Lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries have attracted attention as a unique subset of lithium-sulfur batteries owing to their effectiveness in mitigating the shuttle effect caused by the dissolution of polysulfides. However, traditional SPAN electrodes typically exhibit an active material loading capacity of < 40 wt% and demonstrate suboptimal reaction kinetics, which limits their actual performance. In this study, a composite film (CoS2/FeS2@SeSPAN/CNTs) was developed, which is poised to serve as the cathode in commercial Li-SPAN batteries. The film was fabricated by forming a PAN framework through casting, subsequently growing Fe-ZIF-67 on it via hydrothermal processing, and converting it into CoS2/FeS2 heterostructure and SeSPAN through heat treatment. The porous structure of this material provided numerous sites for active material storage. This effect led to an active material loading capacity of 61 wt%. Experimental results and density functional theory simulations indicated that, owing to the shielding effect of the cathode solid electrolyte interface, the additionally stored active material exhibited an extended all-solid-state reaction mechanism. Furthermore, the internal electric field generated by the CoS2/FeS2 heterostructure effectively enhanced the adsorption and catalytic conversion of solid polysulfides, thereby improving lithium-ion migration efficiency. As a result, the active material stored in dual-mode exhibited high utilization rates. At a current density of 1 C, the capacity retention of the CoS2/FeS2@SeSPAN/CNTs cathode was 97.9% after 800 cycles. This result demonstrated that the design and development of the CoS2/FeS2@SeSPAN/CNTs composite film significantly enhanced the electrochemical performance of Li-SPAN batteries while paving the way for the commercial exploration of other heterostructural materials in energy storage systems.
Lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries have attracted attention as a unique subset of lithium-sulfur batteries owing to their effectiveness in mitigating the shuttle effect caused by the dissolution of polysulfides. However, traditional SPAN electrodes typically exhibit an active material loading capacity of < 40 wt% and demonstrate suboptimal reaction kinetics, which limits their actual performance. In this study, a composite film (CoS2/FeS2@SeSPAN/CNTs) was developed, which is poised to serve as the cathode in commercial Li-SPAN batteries. The film was fabricated by forming a PAN framework through casting, subsequently growing Fe-ZIF-67 on it via hydrothermal processing, and converting it into CoS2/FeS2 heterostructure and SeSPAN through heat treatment. The porous structure of this material provided numerous sites for active material storage. This effect led to an active material loading capacity of 61 wt%. Experimental results and density functional theory simulations indicated that, owing to the shielding effect of the cathode solid electrolyte interface, the additionally stored active material exhibited an extended all-solid-state reaction mechanism. Furthermore, the internal electric field generated by the CoS2/FeS2 heterostructure effectively enhanced the adsorption and catalytic conversion of solid polysulfides, thereby improving lithium-ion migration efficiency. As a result, the active material stored in dual-mode exhibited high utilization rates. At a current density of 1 C, the capacity retention of the CoS2/FeS2@SeSPAN/CNTs cathode was 97.9% after 800 cycles. This result demonstrated that the design and development of the CoS2/FeS2@SeSPAN/CNTs composite film significantly enhanced the electrochemical performance of Li-SPAN batteries while paving the way for the commercial exploration of other heterostructural materials in energy storage systems.
2026, 37(8): 111173
doi: 10.1016/j.cclet.2025.111173
摘要:
O3-layered oxides are considered promising for various applications due to their high capacity. However, these O3-type materials are prone to undergo an irreversible O3-P3 phase transition, which adversely impacts their structural stability. Elemental doping has been identified as an effective strategy to mitigate this issue. However, substituting Cu at the redox center reduces the capacity of the pristine material. The unique introduction of the Sb element reduces the lattice oxygen ratio, leading to a significant increase in initial capacity. Thus, the Cu/Sb co-doped material NaNi0.37Mn0.49Cu0.13Sb0.01O2 (NNMCS) with unique O3-dominated phase transition process, was successfully prepared using the high temperature solid-phase method. Cu/Sb doping increases Mn4+ concentration through the charge compensation mechanism at transition metal sites, mitigating the negative structural effects of the dual simplicial state eg orbitals in the high-spin Mn3+ state. Doping with Cu/Sb increases the electron cloud density at the transition metal sites, enhancing the electron shielding effect and ultimately causing the distance between the transition metal sites to expand. The increased distance between the transition metal sites indirectly promotes flexibility during transition metal migration, resulting in electrode materials with a smaller rate of lattice parameter change during cycling and ultimately enhancing phase transition reversibility. As a result, NNMCS demonstrates a high initial specific capacity of 188 mAh/g and 78% capacity retention after 200 cycles at 1 C within a 2.0–4.3 V window. This work provides valuable insights into the coupling mechanism between capacity and structural stability in layered oxides for sodium-ion batteries.
O3-layered oxides are considered promising for various applications due to their high capacity. However, these O3-type materials are prone to undergo an irreversible O3-P3 phase transition, which adversely impacts their structural stability. Elemental doping has been identified as an effective strategy to mitigate this issue. However, substituting Cu at the redox center reduces the capacity of the pristine material. The unique introduction of the Sb element reduces the lattice oxygen ratio, leading to a significant increase in initial capacity. Thus, the Cu/Sb co-doped material NaNi0.37Mn0.49Cu0.13Sb0.01O2 (NNMCS) with unique O3-dominated phase transition process, was successfully prepared using the high temperature solid-phase method. Cu/Sb doping increases Mn4+ concentration through the charge compensation mechanism at transition metal sites, mitigating the negative structural effects of the dual simplicial state eg orbitals in the high-spin Mn3+ state. Doping with Cu/Sb increases the electron cloud density at the transition metal sites, enhancing the electron shielding effect and ultimately causing the distance between the transition metal sites to expand. The increased distance between the transition metal sites indirectly promotes flexibility during transition metal migration, resulting in electrode materials with a smaller rate of lattice parameter change during cycling and ultimately enhancing phase transition reversibility. As a result, NNMCS demonstrates a high initial specific capacity of 188 mAh/g and 78% capacity retention after 200 cycles at 1 C within a 2.0–4.3 V window. This work provides valuable insights into the coupling mechanism between capacity and structural stability in layered oxides for sodium-ion batteries.
2026, 37(8): 111179
doi: 10.1016/j.cclet.2025.111179
摘要:
The under-barrier Raman relaxation process has long presented a formidable challenge in advancing the performance of single-molecule magnets (SMMs). Exploring the nuanced differences in Raman relaxation processes between two structurally analogous systems remains relatively uncharted territory. Herein, two Dy(Ⅲ)-based single-ion magnets (SIMs) with pentagonal bipyramidal geometry were reported, and their Raman relaxation behaviors were regulated by precisely adjusting the protonation level of the bis-hydrazone moiety. Intriguingly, under the optimal magnetic field, the degree of protonation shows no impact on the Raman exponent n but causes a distinct variation in the Raman relaxation coefficient C. The effects of deprotonation on the molecular geometry and charge distribution were elucidated through ab initio and electrostatic potential (ESP) calculations. Deprotonation results in an asymmetric charge distribution within the equatorial plane, causing the coefficient C to increase substantially by 3.5 times, aligning closely with the theoretical calculation value of approximately 2.8 times. This study provides concise and effective molecular archetypes for investigating the Raman relaxation process.
The under-barrier Raman relaxation process has long presented a formidable challenge in advancing the performance of single-molecule magnets (SMMs). Exploring the nuanced differences in Raman relaxation processes between two structurally analogous systems remains relatively uncharted territory. Herein, two Dy(Ⅲ)-based single-ion magnets (SIMs) with pentagonal bipyramidal geometry were reported, and their Raman relaxation behaviors were regulated by precisely adjusting the protonation level of the bis-hydrazone moiety. Intriguingly, under the optimal magnetic field, the degree of protonation shows no impact on the Raman exponent n but causes a distinct variation in the Raman relaxation coefficient C. The effects of deprotonation on the molecular geometry and charge distribution were elucidated through ab initio and electrostatic potential (ESP) calculations. Deprotonation results in an asymmetric charge distribution within the equatorial plane, causing the coefficient C to increase substantially by 3.5 times, aligning closely with the theoretical calculation value of approximately 2.8 times. This study provides concise and effective molecular archetypes for investigating the Raman relaxation process.
2026, 37(8): 111180
doi: 10.1016/j.cclet.2025.111180
摘要:
Decorating semiconductor metal oxides (SMOs) with noble metals particles has been proved to be effective method to enhance their gas-sensing performance. However, the issue of noble metal particles aggregation might affect the sensitivity and stability of the material. Herein, a strategy is proposed for the construction of noble metals particles decorated SMOs featuring optimized gas sensing performance through the derivation of metal-organic frameworks (MOFs). By utilizing Sn/Zn-ZIF-8 framework as precursor to encapsulate Pt nanoparticles (NPs) followed by calcination, a core-shell structure of SnO2-ZnO encapsulated with Pt NPs (Pt@SnO2-ZnO) was successfully constructed. The Sn/Zn-ZIF-8 framework structure prevents the aggregation of Pt NPs, which facilitates the adsorption and dissociation of oxygen and methanol molecules. Thereby the Pt@SnO2-ZnO based gas sensor exhibited significantly enhanced response (73.6) towards 10 ppm methanol at 320 ℃ and exceptionally low theoretical detection limit (0.18 ppb), providing an effective approach for the modification of SMOs-based gas-sensing materials.
Decorating semiconductor metal oxides (SMOs) with noble metals particles has been proved to be effective method to enhance their gas-sensing performance. However, the issue of noble metal particles aggregation might affect the sensitivity and stability of the material. Herein, a strategy is proposed for the construction of noble metals particles decorated SMOs featuring optimized gas sensing performance through the derivation of metal-organic frameworks (MOFs). By utilizing Sn/Zn-ZIF-8 framework as precursor to encapsulate Pt nanoparticles (NPs) followed by calcination, a core-shell structure of SnO2-ZnO encapsulated with Pt NPs (Pt@SnO2-ZnO) was successfully constructed. The Sn/Zn-ZIF-8 framework structure prevents the aggregation of Pt NPs, which facilitates the adsorption and dissociation of oxygen and methanol molecules. Thereby the Pt@SnO2-ZnO based gas sensor exhibited significantly enhanced response (73.6) towards 10 ppm methanol at 320 ℃ and exceptionally low theoretical detection limit (0.18 ppb), providing an effective approach for the modification of SMOs-based gas-sensing materials.
2026, 37(8): 111181
doi: 10.1016/j.cclet.2025.111181
摘要:
The development of electrode materials with a rapid diffusion kinetics and low polarization is crucial for improving energy storage in magnesium ion batteries (MIBs). Herein, the magnesium tungstate with thermal stability and good chemical stability is proposed as the electrode material in MIBs for the first time. According to the simulated results of density functional theory (DFT) calculations, the high exposed (001) plane of MgWO4 can be achieved as the preferred orientation for Mg2+ fast insertion/extraction. The MgWO4 microflowers with exposed (001) plane architecting by uniform nanosheets were successfully synthesized through a high-efficient microwave radiation strategy. The synthesis mechanism of MgWO4 microflowers was explored as "self-assembly-dissolution-recrystallization-Ostwald ripening" through the evolutions of the morphology and microstructure under continuous reaction timespan. As a MIB electrode material, the MgWO4 microflowers exhibit a good reversible specific capacity (54.6 mAh/g) and cycling stability (70.9% capacity retention after 100 cycles). In conclusion, the MgWO4 material with exposed (001) facet and layered pore structure effectively overcomes the slow diffusion kinetics in MIBs, presenting a new avenue for the design and synthesis of novel reversible electrode materials of MIBs.
The development of electrode materials with a rapid diffusion kinetics and low polarization is crucial for improving energy storage in magnesium ion batteries (MIBs). Herein, the magnesium tungstate with thermal stability and good chemical stability is proposed as the electrode material in MIBs for the first time. According to the simulated results of density functional theory (DFT) calculations, the high exposed (001) plane of MgWO4 can be achieved as the preferred orientation for Mg2+ fast insertion/extraction. The MgWO4 microflowers with exposed (001) plane architecting by uniform nanosheets were successfully synthesized through a high-efficient microwave radiation strategy. The synthesis mechanism of MgWO4 microflowers was explored as "self-assembly-dissolution-recrystallization-Ostwald ripening" through the evolutions of the morphology and microstructure under continuous reaction timespan. As a MIB electrode material, the MgWO4 microflowers exhibit a good reversible specific capacity (54.6 mAh/g) and cycling stability (70.9% capacity retention after 100 cycles). In conclusion, the MgWO4 material with exposed (001) facet and layered pore structure effectively overcomes the slow diffusion kinetics in MIBs, presenting a new avenue for the design and synthesis of novel reversible electrode materials of MIBs.
2026, 37(8): 111189
doi: 10.1016/j.cclet.2025.111189
摘要:
Zeolite-like metal–organic frameworks (ZMOFs) are a unique branch of MOFs, compared to MOFs, the design and synthesis of ZMOFs is challenging due to the peculiar T-O-T angle. Herein, the first ZMOF with unique two-fold interpenetrated SOD topology, [(CH3)2NH2][Zn(2,5-ABTC)0.5(TAZ)]·DMF ·H2O (JLU-MOF119, 2,5-H4ABTC = 2,2′,5,5′-azobenzene tetracarboxylic, TAZ = 1H-tetraazol, DMF = N,N-dimethylformamide), was successfully constructed by utilizing a novel 4 + 4 + 2 strategy. In such a structure, the 4-connected 2,5-H4ABTC ligand serves as the 4-membered ring (4MR) of the structural building units, and the TAZ linker coordinates with the Zn2+ center to form a 6-membered ring (6MR), which assembles with the tetrahedral building units (TBU) to construct the SOD topology. Notably, the stretched and distorted 4MR, which gives rise to two distinct 6MR and a twisted framework, finally leads to the formation of a unique 2-fold interpenetrated SOD framework. The pore structure of JLU-MOF119 is featured by the ultra-microporous pore and the polar surface of the SOD cages caused by uncoordinated N and O sites coming from 2,5-H4ABTC and TAZ ligands, resulting in one-step C2H4 purification from C2H2/CO2/C2H4 mixtures. The dynamic breakthrough and recycling experiments confirm that the C2H4 purity is high up to 99.2%. The successful construction of JLU-MOF119 in this work breaks the theory of forbidden interpenetration in ZMOFs, which will provide more possibilities for structural design and the construction of more complicated structures.
Zeolite-like metal–organic frameworks (ZMOFs) are a unique branch of MOFs, compared to MOFs, the design and synthesis of ZMOFs is challenging due to the peculiar T-O-T angle. Herein, the first ZMOF with unique two-fold interpenetrated SOD topology, [(CH3)2NH2][Zn(2,5-ABTC)0.5(TAZ)]·DMF ·H2O (JLU-MOF119, 2,5-H4ABTC = 2,2′,5,5′-azobenzene tetracarboxylic, TAZ = 1H-tetraazol, DMF = N,N-dimethylformamide), was successfully constructed by utilizing a novel 4 + 4 + 2 strategy. In such a structure, the 4-connected 2,5-H4ABTC ligand serves as the 4-membered ring (4MR) of the structural building units, and the TAZ linker coordinates with the Zn2+ center to form a 6-membered ring (6MR), which assembles with the tetrahedral building units (TBU) to construct the SOD topology. Notably, the stretched and distorted 4MR, which gives rise to two distinct 6MR and a twisted framework, finally leads to the formation of a unique 2-fold interpenetrated SOD framework. The pore structure of JLU-MOF119 is featured by the ultra-microporous pore and the polar surface of the SOD cages caused by uncoordinated N and O sites coming from 2,5-H4ABTC and TAZ ligands, resulting in one-step C2H4 purification from C2H2/CO2/C2H4 mixtures. The dynamic breakthrough and recycling experiments confirm that the C2H4 purity is high up to 99.2%. The successful construction of JLU-MOF119 in this work breaks the theory of forbidden interpenetration in ZMOFs, which will provide more possibilities for structural design and the construction of more complicated structures.
2026, 37(8): 111191
doi: 10.1016/j.cclet.2025.111191
摘要:
The CO2 electroreduction is a valuable technology towards carbon neutrality but facing great challenge in fabricating efficient and stable electrode. Here we propose the construction of self-supported nanoarray electrode of ultrathin carbon-coated Bi nanospheres through a self-assembly and Joule heating method for high-efficiency electrocatalytic CO2 reduction. The electrode combines the advantages of facilitating electron transfer, accelerating the subsequent electro-proton coupling step in CO2 reduction process and protecting Bi nanoparticles from aggregation or electrochemical corrosion. The highest Faraday efficiency for formic acid in a solid-state electrolyte cell reaches 95.46% with a partial current density of 119.10 mA/cm2 and remains above 90% for 110 h. This route for assembling self-supported nanoarray electrode is rapid, facile, and can be employed in the large-scale fabrication of industrial electrodes in the future.
The CO2 electroreduction is a valuable technology towards carbon neutrality but facing great challenge in fabricating efficient and stable electrode. Here we propose the construction of self-supported nanoarray electrode of ultrathin carbon-coated Bi nanospheres through a self-assembly and Joule heating method for high-efficiency electrocatalytic CO2 reduction. The electrode combines the advantages of facilitating electron transfer, accelerating the subsequent electro-proton coupling step in CO2 reduction process and protecting Bi nanoparticles from aggregation or electrochemical corrosion. The highest Faraday efficiency for formic acid in a solid-state electrolyte cell reaches 95.46% with a partial current density of 119.10 mA/cm2 and remains above 90% for 110 h. This route for assembling self-supported nanoarray electrode is rapid, facile, and can be employed in the large-scale fabrication of industrial electrodes in the future.
2026, 37(8): 111192
doi: 10.1016/j.cclet.2025.111192
摘要:
Electrochemical ozone production (EOP) has emerged as an eco-friendly, cost-effective alternative to the current industrial corona discharge approach; however, the low Faradaic efficiency (FE) of electrochemical ozone production (EOP) and anode instability at high current density of the conventional plate electrode hinders its actual application. Herein, we introduce a strategy to enhance the EOP performance of β-PbO2 by constructing a three-dimensional (3D) porous architecture. This approach elevates the EOP FE of the 3D-porous β-PbO2@Ti mesh anode (14.73%) to over twice that of the conventional β-PbO2@Ti mesh (6.11%) at a current density of 100 mA/cm2. Furthermore, it demonstrates a robust service life and consistent O3 production capability, sustaining stable output over extended periods (70 h, 20 h) at higher current densities (100, 250 mA/cm2). This strategy of external structural anode modification exerts a beneficial effect on the internal oxygen environment within β-PbO2, increasing the availability of adsorption sites for oxygen intermediates and thus providing favorable conditions for efficient O3 generation. This work shows the potential of 3D porous anode for practical industrial deployment of EOP.
Electrochemical ozone production (EOP) has emerged as an eco-friendly, cost-effective alternative to the current industrial corona discharge approach; however, the low Faradaic efficiency (FE) of electrochemical ozone production (EOP) and anode instability at high current density of the conventional plate electrode hinders its actual application. Herein, we introduce a strategy to enhance the EOP performance of β-PbO2 by constructing a three-dimensional (3D) porous architecture. This approach elevates the EOP FE of the 3D-porous β-PbO2@Ti mesh anode (14.73%) to over twice that of the conventional β-PbO2@Ti mesh (6.11%) at a current density of 100 mA/cm2. Furthermore, it demonstrates a robust service life and consistent O3 production capability, sustaining stable output over extended periods (70 h, 20 h) at higher current densities (100, 250 mA/cm2). This strategy of external structural anode modification exerts a beneficial effect on the internal oxygen environment within β-PbO2, increasing the availability of adsorption sites for oxygen intermediates and thus providing favorable conditions for efficient O3 generation. This work shows the potential of 3D porous anode for practical industrial deployment of EOP.
2026, 37(8): 111212
doi: 10.1016/j.cclet.2025.111212
摘要:
Transition metal oxides are regarded as promising alternatives to graphite anode material due to their high theoretical capacities. However, their low conductivity, large volume change and fragile structure during battery operation hamper large-scale applications. Herein, we synthesize F-doping and oxygen defect CoO composite (F/O-CoO) through a facile hydrothermal and following annealing process. Benefiting from the synergy of F-doping and oxygen defect, the F/O-CoO anode material delivers a high reversible capacity of 1112 mAh/g at 0.5 C and capacity retention of 609 mAh/g (79.1%) at 2 C after 400 cycles, as well as a rate capacity of 449 mAh/g at 5 C. This superior capacity enhancement is attributed to the enrichment of oxygen defect and necessary substitution of lattice oxygen atom by F, which play an important role in improving electrical conductivity and thus reducing polarization. DFT calculation provides a further explanation that F doping can reduce the Li+ adsorption energy and the bandgap energy of F/O-CoO material, as well as increase Li+ storage sites and Li+/e- conductivity.
Transition metal oxides are regarded as promising alternatives to graphite anode material due to their high theoretical capacities. However, their low conductivity, large volume change and fragile structure during battery operation hamper large-scale applications. Herein, we synthesize F-doping and oxygen defect CoO composite (F/O-CoO) through a facile hydrothermal and following annealing process. Benefiting from the synergy of F-doping and oxygen defect, the F/O-CoO anode material delivers a high reversible capacity of 1112 mAh/g at 0.5 C and capacity retention of 609 mAh/g (79.1%) at 2 C after 400 cycles, as well as a rate capacity of 449 mAh/g at 5 C. This superior capacity enhancement is attributed to the enrichment of oxygen defect and necessary substitution of lattice oxygen atom by F, which play an important role in improving electrical conductivity and thus reducing polarization. DFT calculation provides a further explanation that F doping can reduce the Li+ adsorption energy and the bandgap energy of F/O-CoO material, as well as increase Li+ storage sites and Li+/e- conductivity.
2026, 37(8): 111227
doi: 10.1016/j.cclet.2025.111227
摘要:
Although the distinctive physicochemical properties of Pt-based intermetallic nanomaterials are well-recognized, the critical influence of Pt skin-induced lattice strain effects on their enzyme-mimicking catalytic performance remains unexplored. This knowledge gap primarily stems from the technical challenges in achieving atomic-level precision and structural uniformity when engineering active sites within Pt-based intermetallic systems. Herein, we demonstrate exceptional peroxidase-like catalytic activity (25.545 U/mg) and remarkable specificity through strain-engineered L10 PtCo@Pt core-shell architectures. Experimental and theoretical analyses reveal that significantly reduces H2O2 adsorption energy (-1.49 eV) and the energy barrier of rate-determining step (0.128 eV). This strain-driven electronic modulation enables a 17.4-fold enhancement in peroxidase-like activity compared to conventional Pt nanoparticles, establishing a quantitative correlation between interfacial lattice compression (3.5% strain) and catalytic efficiency. Three key advances emerge from this work: (1) Identification of lattice strain as a dominant descriptor for nanozyme specificity in H2O2 activation, (2) development of a universal synthesis framework (<1 min) for ordered intermetallic core-shell systems, and (3) demonstration of strain engineering as a generalizable strategy exceeding noble metal-dependent activity enhancement. The developed methodology not only resolves long-standing challenges in scalable nanozyme production but also opens new avenues for designing biocatalysts through atomic-level strain manipulation.
Although the distinctive physicochemical properties of Pt-based intermetallic nanomaterials are well-recognized, the critical influence of Pt skin-induced lattice strain effects on their enzyme-mimicking catalytic performance remains unexplored. This knowledge gap primarily stems from the technical challenges in achieving atomic-level precision and structural uniformity when engineering active sites within Pt-based intermetallic systems. Herein, we demonstrate exceptional peroxidase-like catalytic activity (25.545 U/mg) and remarkable specificity through strain-engineered L10 PtCo@Pt core-shell architectures. Experimental and theoretical analyses reveal that significantly reduces H2O2 adsorption energy (-1.49 eV) and the energy barrier of rate-determining step (0.128 eV). This strain-driven electronic modulation enables a 17.4-fold enhancement in peroxidase-like activity compared to conventional Pt nanoparticles, establishing a quantitative correlation between interfacial lattice compression (3.5% strain) and catalytic efficiency. Three key advances emerge from this work: (1) Identification of lattice strain as a dominant descriptor for nanozyme specificity in H2O2 activation, (2) development of a universal synthesis framework (<1 min) for ordered intermetallic core-shell systems, and (3) demonstration of strain engineering as a generalizable strategy exceeding noble metal-dependent activity enhancement. The developed methodology not only resolves long-standing challenges in scalable nanozyme production but also opens new avenues for designing biocatalysts through atomic-level strain manipulation.
2026, 37(8): 111228
doi: 10.1016/j.cclet.2025.111228
摘要:
The nickel-rich layered cathode materials (LiNixCoyMn1-x-yO2) in lithium-ion batteries suffer from labile surface reactivity, leading to the formation of residual lithium impurities and the induction of interfacial side reactions, ultimately degrading battery performance. Here, a controlled reaction between residual lithium and the glassy material H3BO3 on the surface of commercial LiNi0.82Co0.12Mn0.06O2 cathode materials converts into a protective fast ionic conductor layer. It was observed that sintering temperatures distinctly influenced the composition and structure of interface coating, subsequently affecting electrochemical properties of cathode. Notably, upon treatment at a relatively low temperature of 300 ℃, the surface of sample was enveloped in an amorphous LiBO2 layer, which effectively alleviates interfacial side reactions, stabilizes the crystal structure and enhances lithium-ion transport kinetics. Furthermore, during cycling, the amorphous LiBO2 coating facilitates the formation of a stable cathode electrolyte interphase layer enriched with LiF. Consequently, the material exhibits exceptional electrochemical performance, balancing high capacity and excellent cycling stability. This interfacial engineering strategy, compatible with industrial-scale processing, provides a viable pathway to enhance the durability of nickel-rich cathodes for high-energy-density batteries.
The nickel-rich layered cathode materials (LiNixCoyMn1-x-yO2) in lithium-ion batteries suffer from labile surface reactivity, leading to the formation of residual lithium impurities and the induction of interfacial side reactions, ultimately degrading battery performance. Here, a controlled reaction between residual lithium and the glassy material H3BO3 on the surface of commercial LiNi0.82Co0.12Mn0.06O2 cathode materials converts into a protective fast ionic conductor layer. It was observed that sintering temperatures distinctly influenced the composition and structure of interface coating, subsequently affecting electrochemical properties of cathode. Notably, upon treatment at a relatively low temperature of 300 ℃, the surface of sample was enveloped in an amorphous LiBO2 layer, which effectively alleviates interfacial side reactions, stabilizes the crystal structure and enhances lithium-ion transport kinetics. Furthermore, during cycling, the amorphous LiBO2 coating facilitates the formation of a stable cathode electrolyte interphase layer enriched with LiF. Consequently, the material exhibits exceptional electrochemical performance, balancing high capacity and excellent cycling stability. This interfacial engineering strategy, compatible with industrial-scale processing, provides a viable pathway to enhance the durability of nickel-rich cathodes for high-energy-density batteries.
2026, 37(8): 111230
doi: 10.1016/j.cclet.2025.111230
摘要:
We report herein the synthesis, structure and catalysis of a cobalt-kernelled icosahedral gold nanocluster CoAu12, providing an opportunity for the in-depth understanding of rarely reported Co-doped gold nanoclusters. CoAu12 possesses a symmetric and contracted metal kernel compared to the 4d and 5d metal-kernelled MAu12 nanoclusters (M = Pd, Pt, Rh, Ir, Au), thus exhibiting highly structural stability. Meanwhile, CoAu12 demonstrates efficient energy and electron transfer activity toward oxygen, thus endowing this nanocluster with exceptional catalytic activity in converting oxygen to singlet oxygen as well as superoxide. Structural features such as the unpaired electron of CoAu12 have been verified as contributing to its catalytic activity. Efficient organic transformations involving singlet oxygen and superoxide were developed based on the structurally stable and catalytically active CoAu12 nanocluster.
We report herein the synthesis, structure and catalysis of a cobalt-kernelled icosahedral gold nanocluster CoAu12, providing an opportunity for the in-depth understanding of rarely reported Co-doped gold nanoclusters. CoAu12 possesses a symmetric and contracted metal kernel compared to the 4d and 5d metal-kernelled MAu12 nanoclusters (M = Pd, Pt, Rh, Ir, Au), thus exhibiting highly structural stability. Meanwhile, CoAu12 demonstrates efficient energy and electron transfer activity toward oxygen, thus endowing this nanocluster with exceptional catalytic activity in converting oxygen to singlet oxygen as well as superoxide. Structural features such as the unpaired electron of CoAu12 have been verified as contributing to its catalytic activity. Efficient organic transformations involving singlet oxygen and superoxide were developed based on the structurally stable and catalytically active CoAu12 nanocluster.
2026, 37(8): 111263
doi: 10.1016/j.cclet.2025.111263
摘要:
The low-temperature performance of lithium iron phosphate (LiFePO4) batteries remains a significant challenge. Electrolyte engineering has emerged as an effective strategy to address this issue efficiently. Herein, ethyl pentafluoropropionate (pFEP) is introduced into the carbonate-based electrolyte as a functional additive that enables LiLFP cells to cycle at −20 ℃ or even −40 ℃. Molecular dynamics (MD) simulations and spectroscopic characterization demonstrate that adding only 3% pFEP could effectively modify the electrolyte solvation structure, significantly increasing the content of contact ion pairs (CIPs) and aggregates (AGGs). This structural modification promotes the formation of a uniform LiF-rich interphase, which is crucial for improved battery performance. As a result, LiLFP cell with active cathode loading of 8.5 mg/cm2 delivers 117.2 mAh/g and cycling stability over 130 cycles at −20 ℃. This work provides a cost-effective strategy for enhancing the low-temperature performance of LFP batteries.
The low-temperature performance of lithium iron phosphate (LiFePO4) batteries remains a significant challenge. Electrolyte engineering has emerged as an effective strategy to address this issue efficiently. Herein, ethyl pentafluoropropionate (pFEP) is introduced into the carbonate-based electrolyte as a functional additive that enables LiLFP cells to cycle at −20 ℃ or even −40 ℃. Molecular dynamics (MD) simulations and spectroscopic characterization demonstrate that adding only 3% pFEP could effectively modify the electrolyte solvation structure, significantly increasing the content of contact ion pairs (CIPs) and aggregates (AGGs). This structural modification promotes the formation of a uniform LiF-rich interphase, which is crucial for improved battery performance. As a result, LiLFP cell with active cathode loading of 8.5 mg/cm2 delivers 117.2 mAh/g and cycling stability over 130 cycles at −20 ℃. This work provides a cost-effective strategy for enhancing the low-temperature performance of LFP batteries.
2026, 37(8): 111264
doi: 10.1016/j.cclet.2025.111264
摘要:
Self-trapped exciton (STE) emissions based on Sb3+ ion materials have recently received widespread attention, due to the excellent photoluminescence (PL) properties and stereochemical activity of Sb3+ ions. Pressure can precisely regulate the electronic structure and configuration of chromophores, becoming an effective approach to enhance the STE emissions. Recently, STE emission enhancements in Sb3+-based materials under pressure mainly focus on metal halides, however, studies on inorganic oxides are very limited. Herein, the high-pressure STE behavior of SbTaO4 was investigated up to 13.2 GPa. The STE emission exhibits a bi-peak feature, and the strongest emission occurs at 3.8 GPa, in which two peaks are enhanced by ~20 and ~3 times and the STE emission displays a bright green color. The mechanism is explained using a variety of methods, including steady-state PL spectroscopy, kinetic spectroscopy, Raman spectroscopy, cryogenic PL spectroscopy and theoretical calculations. It shows that the strong electron-phonon coupling of SbTaO4 is weakened, which suppresses non-radiative transitions. Also, the distortion of the [SbO4] unit inhibits the transition between two STE states. The synergistic effect of these factors leads to a strong enhancement of the STE emission in SbTaO4 under pressure. The STE emission enhancement of SbTaO4 highlights the potential of inorganic oxides for future high-pressure STE exploration and provides the promising material in photonic devices under extreme conditions.
Self-trapped exciton (STE) emissions based on Sb3+ ion materials have recently received widespread attention, due to the excellent photoluminescence (PL) properties and stereochemical activity of Sb3+ ions. Pressure can precisely regulate the electronic structure and configuration of chromophores, becoming an effective approach to enhance the STE emissions. Recently, STE emission enhancements in Sb3+-based materials under pressure mainly focus on metal halides, however, studies on inorganic oxides are very limited. Herein, the high-pressure STE behavior of SbTaO4 was investigated up to 13.2 GPa. The STE emission exhibits a bi-peak feature, and the strongest emission occurs at 3.8 GPa, in which two peaks are enhanced by ~20 and ~3 times and the STE emission displays a bright green color. The mechanism is explained using a variety of methods, including steady-state PL spectroscopy, kinetic spectroscopy, Raman spectroscopy, cryogenic PL spectroscopy and theoretical calculations. It shows that the strong electron-phonon coupling of SbTaO4 is weakened, which suppresses non-radiative transitions. Also, the distortion of the [SbO4] unit inhibits the transition between two STE states. The synergistic effect of these factors leads to a strong enhancement of the STE emission in SbTaO4 under pressure. The STE emission enhancement of SbTaO4 highlights the potential of inorganic oxides for future high-pressure STE exploration and provides the promising material in photonic devices under extreme conditions.
2026, 37(8): 111266
doi: 10.1016/j.cclet.2025.111266
摘要:
In this study, we employed sodium hydroxide and 2,6-pyridinedimethanol as modulators to tailor the structure of metal-organic crystals via “coordination modulation strategy”. Based on this strategy, two copper-based crystalline materials were synthesized via hydrothermal synthesis and structurally characterized. Single-crystal X-ray diffraction analysis elucidates that [Cu2(μ2–OH)(μ3–OH)(H2dcppa)(H2O)]·H2O (dcppa = 3-(3′,5′-dicarboxyphenoxy)phthalic acid, CP-1) exist a kind of [Cu4(μ2–OH)2(μ3–OH)2(H2O)2]4+ cluster. Each [Cu4(μ2–OH)2(μ3–OH)2(H2O)2]4+ is interconnected in-plane with H2dcppa ligands, forming a four-directional extended coordination network that ultimately generates a periodically arranged layered architecture. In [Cu4(Hdcppa)2(H2dcppa)(H2O)3] (MOF-1), there are two types of binuclear copper building blocks, [Cu2(H2O)]4+ and [Cu2(H2O)2]4+, respectively. The adjacent [Cu2(H2O)]4+ units are interconnected via Hdcppa ligands, forming a 1D metal-organic chain. These 1D chains are connected by [Cu2(H2O)2]4+ to establish a 2D layer, which is further extended by H2dcppa ligands to a 3D framework. The successful implementation of this synthetic route further validates the feasibility and effectiveness of combining hydrothermal methods with coordination modulation strategies for the targeted construction of functionalized metal-organic crystals. The proton conductivities (σ) of CP-1 and MOF-1 were measured under conditions of 85 ℃ and 98% relative humidity (RH), resulting in values of 2.14 × 10−3 and 2.55 × 10–2 S/cm, respectively. This study presents a novel approach to fabricating MOFs as proton conductors through coordination modulation strategy.
In this study, we employed sodium hydroxide and 2,6-pyridinedimethanol as modulators to tailor the structure of metal-organic crystals via “coordination modulation strategy”. Based on this strategy, two copper-based crystalline materials were synthesized via hydrothermal synthesis and structurally characterized. Single-crystal X-ray diffraction analysis elucidates that [Cu2(μ2–OH)(μ3–OH)(H2dcppa)(H2O)]·H2O (dcppa = 3-(3′,5′-dicarboxyphenoxy)phthalic acid, CP-1) exist a kind of [Cu4(μ2–OH)2(μ3–OH)2(H2O)2]4+ cluster. Each [Cu4(μ2–OH)2(μ3–OH)2(H2O)2]4+ is interconnected in-plane with H2dcppa ligands, forming a four-directional extended coordination network that ultimately generates a periodically arranged layered architecture. In [Cu4(Hdcppa)2(H2dcppa)(H2O)3] (MOF-1), there are two types of binuclear copper building blocks, [Cu2(H2O)]4+ and [Cu2(H2O)2]4+, respectively. The adjacent [Cu2(H2O)]4+ units are interconnected via Hdcppa ligands, forming a 1D metal-organic chain. These 1D chains are connected by [Cu2(H2O)2]4+ to establish a 2D layer, which is further extended by H2dcppa ligands to a 3D framework. The successful implementation of this synthetic route further validates the feasibility and effectiveness of combining hydrothermal methods with coordination modulation strategies for the targeted construction of functionalized metal-organic crystals. The proton conductivities (σ) of CP-1 and MOF-1 were measured under conditions of 85 ℃ and 98% relative humidity (RH), resulting in values of 2.14 × 10−3 and 2.55 × 10–2 S/cm, respectively. This study presents a novel approach to fabricating MOFs as proton conductors through coordination modulation strategy.
2026, 37(8): 111268
doi: 10.1016/j.cclet.2025.111268
摘要:
The bulk anomalous photovoltaic effect (BAPV) in non-centrosymmetric materials can produce photovoltage exceeding the bandgap, distinguishing them from traditional semiconductors and offering substantial potential in photovoltaics. Chiral hybrid perovskites, characterized by asymmetric structure and structural tunability, present promise to generate BAPV with desired optoelectronic properties. Herein, we introduced chiral (S)- and (R)-α-methylbenzylamine (S/R-α-MBA) cations to construct a pair of lead-free chiral-polar perovskites, denoted as (S-α-MBA)4Bi2I10 and (R-α-MBA)4Bi2I10 (1S and 1R). Remarkably, 1S and 1R exhibited the distinctive BAPV effect with an impressive photovoltage of 15 V, highlighting the potential for prominent photovoltaic performance. Furthermore, self-powered broadband photoresponse is realized via photo-induced pyroelectricity based on inherent spontaneous polarization in 1S and 1R. The fabricated photodetectors demonstrated enhanced photocurrent response compared to those relying on the photovoltaic effect alone. This innovation eliminates the confinement of photodetection by material semiconductor properties, thereby effectively broadening their application scope.
The bulk anomalous photovoltaic effect (BAPV) in non-centrosymmetric materials can produce photovoltage exceeding the bandgap, distinguishing them from traditional semiconductors and offering substantial potential in photovoltaics. Chiral hybrid perovskites, characterized by asymmetric structure and structural tunability, present promise to generate BAPV with desired optoelectronic properties. Herein, we introduced chiral (S)- and (R)-α-methylbenzylamine (S/R-α-MBA) cations to construct a pair of lead-free chiral-polar perovskites, denoted as (S-α-MBA)4Bi2I10 and (R-α-MBA)4Bi2I10 (1S and 1R). Remarkably, 1S and 1R exhibited the distinctive BAPV effect with an impressive photovoltage of 15 V, highlighting the potential for prominent photovoltaic performance. Furthermore, self-powered broadband photoresponse is realized via photo-induced pyroelectricity based on inherent spontaneous polarization in 1S and 1R. The fabricated photodetectors demonstrated enhanced photocurrent response compared to those relying on the photovoltaic effect alone. This innovation eliminates the confinement of photodetection by material semiconductor properties, thereby effectively broadening their application scope.
2026, 37(8): 111280
doi: 10.1016/j.cclet.2025.111280
摘要:
The Sierpiński triangle (ST) is a widely-known deterministic fractal structure that has attracted considerable attention recently. The fabrication of nitrogen-doped defect-free STs is appealing yet challenging. This is due to factors such as the increase in active sites, the random generation of nucleation centers, and the experimental growth conditions. In this contribution, we utilize a combination of density functional theory (DFT), Monte Carlo simulation (MC) and scanning tunneling microscopy (STM) to investigate the formation of nitrogen-doped STs. These STs are formed with nitrogen-rich, conformationally flexible 2,2′:6′,2′′-terpyridine-6,6′′-dicarbonitrile (TDBT) molecules and Fe atoms on Au(111). The replacement of benzenes with three pyridine side groups facilitates the formation of the nitrogen-doped STs with a relatively high order because of the energetic preference of molecular configurations. The introduction of the rigid 4,4″-dicyano-1,1′:3′,1″-terphenyl (C3PC) molecules markedly induces the structural transformation of the STs from ordered to high-entropy. Moreover, the nitrogen-doped STs with an order of up to 4 can be directly visualized by low-temperature STM.
The Sierpiński triangle (ST) is a widely-known deterministic fractal structure that has attracted considerable attention recently. The fabrication of nitrogen-doped defect-free STs is appealing yet challenging. This is due to factors such as the increase in active sites, the random generation of nucleation centers, and the experimental growth conditions. In this contribution, we utilize a combination of density functional theory (DFT), Monte Carlo simulation (MC) and scanning tunneling microscopy (STM) to investigate the formation of nitrogen-doped STs. These STs are formed with nitrogen-rich, conformationally flexible 2,2′:6′,2′′-terpyridine-6,6′′-dicarbonitrile (TDBT) molecules and Fe atoms on Au(111). The replacement of benzenes with three pyridine side groups facilitates the formation of the nitrogen-doped STs with a relatively high order because of the energetic preference of molecular configurations. The introduction of the rigid 4,4″-dicyano-1,1′:3′,1″-terphenyl (C3PC) molecules markedly induces the structural transformation of the STs from ordered to high-entropy. Moreover, the nitrogen-doped STs with an order of up to 4 can be directly visualized by low-temperature STM.
2026, 37(8): 111310
doi: 10.1016/j.cclet.2025.111310
摘要:
Lithium metal anodes are a compelling option for high-energy-density rechargeable batteries. However, they face challenges such as uncontrolled dendrite growth and unstable interphase, particularly at elevated areal capacities. In this study, we introduce a multi-functional skeleton design that promotes uniform nucleation and growth of Li metal, enhancing interfacial stability. Our innovation features a skeleton-alloy-fluorinated hybrid framework, incorporating abundantly N-doped lithiophilic sites and MgF2 particles within a carbon fiber matrix. The lithophilic carbon fiber provides numerous Li nucleation sites, mitigating Li deposition inhomogeneity and suppressing dendrite formation. The LiMg alloy phase formed by MgF2 further promotes homogeneous Li growth. Additionally, the resulting LiF can passivate and protect Li metal at the electrode-electrolyte interface, enhancing the cycling stability of Li anode. Employing this co-engineering strategy, the as-designed composite Li anode lasts over 1000 h in symmetric cells. Li-S full cells deliver 3.9 mAh/cm2 after 200 cycles at a high sulfur loading of 11.0 mg/cm2. This multi-functional approach provides insights for advancing lithium metal battery applications.
Lithium metal anodes are a compelling option for high-energy-density rechargeable batteries. However, they face challenges such as uncontrolled dendrite growth and unstable interphase, particularly at elevated areal capacities. In this study, we introduce a multi-functional skeleton design that promotes uniform nucleation and growth of Li metal, enhancing interfacial stability. Our innovation features a skeleton-alloy-fluorinated hybrid framework, incorporating abundantly N-doped lithiophilic sites and MgF2 particles within a carbon fiber matrix. The lithophilic carbon fiber provides numerous Li nucleation sites, mitigating Li deposition inhomogeneity and suppressing dendrite formation. The LiMg alloy phase formed by MgF2 further promotes homogeneous Li growth. Additionally, the resulting LiF can passivate and protect Li metal at the electrode-electrolyte interface, enhancing the cycling stability of Li anode. Employing this co-engineering strategy, the as-designed composite Li anode lasts over 1000 h in symmetric cells. Li-S full cells deliver 3.9 mAh/cm2 after 200 cycles at a high sulfur loading of 11.0 mg/cm2. This multi-functional approach provides insights for advancing lithium metal battery applications.
2026, 37(8): 111311
doi: 10.1016/j.cclet.2025.111311
摘要:
We report a facile low-temperature synthesis of Fe-doped NiSe2 nanoparticles as an efficient pre-catalyst, which undergoes complete electrochemical reconstruction into amorphous γ-FexNi1-xOOH nanosheets (< 2 nm thickness) during activation process of cyclic voltammetry. The reconstituted catalyst achieves record-low overpotentials of 163 mV at 20 mA/cm2 and 230 mV at 300 mA/cm2, with a Tafel slope of 33.8 mV/dec and a turnover frequency (TOF) of 0.1 s-1 at overpotential of 210 mV. Remarkably, it shows outstanding operational stability with negligible activity decay after 300 h chronopotentiometry at 100 mA/cm2. Through multimodal ex situ/in situ characterizations, we conclusively identify the in situ-formed amorphous γ-FexNi1-xOOH nanosheets as the active phase, where Fe doping optimizes the electronic structure of Ni sites while the ultrathin morphology maximizes exposed active centers. This work establishes a universal precatalyst engineering strategy through controlled structural evolution of metastable precursors, applicable to diverse energy conversion systems.
We report a facile low-temperature synthesis of Fe-doped NiSe2 nanoparticles as an efficient pre-catalyst, which undergoes complete electrochemical reconstruction into amorphous γ-FexNi1-xOOH nanosheets (< 2 nm thickness) during activation process of cyclic voltammetry. The reconstituted catalyst achieves record-low overpotentials of 163 mV at 20 mA/cm2 and 230 mV at 300 mA/cm2, with a Tafel slope of 33.8 mV/dec and a turnover frequency (TOF) of 0.1 s-1 at overpotential of 210 mV. Remarkably, it shows outstanding operational stability with negligible activity decay after 300 h chronopotentiometry at 100 mA/cm2. Through multimodal ex situ/in situ characterizations, we conclusively identify the in situ-formed amorphous γ-FexNi1-xOOH nanosheets as the active phase, where Fe doping optimizes the electronic structure of Ni sites while the ultrathin morphology maximizes exposed active centers. This work establishes a universal precatalyst engineering strategy through controlled structural evolution of metastable precursors, applicable to diverse energy conversion systems.
2026, 37(8): 111312
doi: 10.1016/j.cclet.2025.111312
摘要:
Transition metal phosphides (TMPs) are a promising class of functional nanomaterials with significant potential for energy-related applications. However, a universal synthesis method that is both efficient and scalable remains a challenge. This study introduces an ultrafast carbothermal shock (UCS) technique as efficient method for synthesizing various TMPs, including Rh2P, Ir2P, Pd5P2, RuP and PtP2, in just 15 s under ambient air conditions. Notably, the as synthesized Rh2P exhibits remarkable hydrogen evolution reaction (HER) performance with low overpotentials of 13 and 70 mV to reach current densities of 10 and 100 mA/cm2, respectively, coupled with excellent operational stability for over 20 h. This technique not only provides a universal platform for producing various metal phosphides, but also holds significant promise for advancing their applications in energy conversion and storage devices, catalysis, and biosensors.
Transition metal phosphides (TMPs) are a promising class of functional nanomaterials with significant potential for energy-related applications. However, a universal synthesis method that is both efficient and scalable remains a challenge. This study introduces an ultrafast carbothermal shock (UCS) technique as efficient method for synthesizing various TMPs, including Rh2P, Ir2P, Pd5P2, RuP and PtP2, in just 15 s under ambient air conditions. Notably, the as synthesized Rh2P exhibits remarkable hydrogen evolution reaction (HER) performance with low overpotentials of 13 and 70 mV to reach current densities of 10 and 100 mA/cm2, respectively, coupled with excellent operational stability for over 20 h. This technique not only provides a universal platform for producing various metal phosphides, but also holds significant promise for advancing their applications in energy conversion and storage devices, catalysis, and biosensors.
2026, 37(8): 111326
doi: 10.1016/j.cclet.2025.111326
摘要:
The emergence of aqueous K/Zn dual-ion batteries has opened a promising new frontier in energy storage by leveraging the high energy density of zinc-ion batteries (ZIBs) and the voltage enhancement provided by cation intercalation mechanisms. However, the lifespan of these batteries has been significantly limited by dendrite growth and side reactions at the zinc negative electrode. To address this challenge, we successfully fabricated an organic framework, Zn-MOF-74, in-situ on the surface of the zinc negative electrode. The large-pore, one-dimensional channel structure of Zn-MOF-74 effectively enhances electrolyte permeability, reduces steric hindrance, and promotes efficient battery operation. Moreover, the open metal sites in Zn-MOF-74 effectively suppress side reactions, further improving battery performance. Notably, the average CE remained remarkably high at 99.43% after 1000 cycles. Furthermore, the Zn-MOF-74@Zn//ZnHCF configuration demonstrated exceptional cycling stability, retaining 88% of its initial capacity even after 1000 cycles at a current density of 1 A/g.
The emergence of aqueous K/Zn dual-ion batteries has opened a promising new frontier in energy storage by leveraging the high energy density of zinc-ion batteries (ZIBs) and the voltage enhancement provided by cation intercalation mechanisms. However, the lifespan of these batteries has been significantly limited by dendrite growth and side reactions at the zinc negative electrode. To address this challenge, we successfully fabricated an organic framework, Zn-MOF-74, in-situ on the surface of the zinc negative electrode. The large-pore, one-dimensional channel structure of Zn-MOF-74 effectively enhances electrolyte permeability, reduces steric hindrance, and promotes efficient battery operation. Moreover, the open metal sites in Zn-MOF-74 effectively suppress side reactions, further improving battery performance. Notably, the average CE remained remarkably high at 99.43% after 1000 cycles. Furthermore, the Zn-MOF-74@Zn//ZnHCF configuration demonstrated exceptional cycling stability, retaining 88% of its initial capacity even after 1000 cycles at a current density of 1 A/g.
2026, 37(8): 111327
doi: 10.1016/j.cclet.2025.111327
摘要:
Porous single crystal (PSC) materials have a large specific surface area, higher structural stability, and more active sites by combining porosity and structural coherence, which provide a clear advantage in the field of catalysis. Platinum-based catalysts are precious metal catalysts commonly used in the dehydrogenation of low-carbon alkanes, with excellent dehydrogenation activity and good catalytic activity for the anaerobic dehydrogenation of ethane. By lattice reconstruction strategy we grow PSC MgO from the parent MgF2 single crystal and load Pt nanoparticles on its surface for growing PSC Pt/MgO. Oxygen vacancies are introduced by constructing active sites on a clear surface structure, which improve catalytic activity and durability. The PSC Pt/MgO catalyst for the direct dehydrogenation of ethane achieves an ethane conversion rate of approximately 28% and ethylene selectivity of over 97%, with good stability over 100 h. The present work offers significant value for the growth and application of porous single crystal oxides loaded with metal nanoparticles.
Porous single crystal (PSC) materials have a large specific surface area, higher structural stability, and more active sites by combining porosity and structural coherence, which provide a clear advantage in the field of catalysis. Platinum-based catalysts are precious metal catalysts commonly used in the dehydrogenation of low-carbon alkanes, with excellent dehydrogenation activity and good catalytic activity for the anaerobic dehydrogenation of ethane. By lattice reconstruction strategy we grow PSC MgO from the parent MgF2 single crystal and load Pt nanoparticles on its surface for growing PSC Pt/MgO. Oxygen vacancies are introduced by constructing active sites on a clear surface structure, which improve catalytic activity and durability. The PSC Pt/MgO catalyst for the direct dehydrogenation of ethane achieves an ethane conversion rate of approximately 28% and ethylene selectivity of over 97%, with good stability over 100 h. The present work offers significant value for the growth and application of porous single crystal oxides loaded with metal nanoparticles.
2026, 37(8): 111328
doi: 10.1016/j.cclet.2025.111328
摘要:
Metal-organic framework (MOF) derived metal oxides and their composites have shown remarkable potential in enhancing the sensitivity and lowering the detection limits of gas sensors, emerging as promising candidates for volatile organic compound (VOC) detection. Here, the Pt-sensitized In2O3 hollow microtubes were synthesized from MIL-68 via hydrothermal and sacrificial template methods, demonstrating exceptional trace detection capability (0.01–1 ppm) to p-xylene. The 2% Pt NPs-In2O3 showed the highest response of 68.7 at 50 ppb, with a theoretical detection limit as low as 0.027 ppb. The role of Pt was elucidated through comprehensive characterization, revealing that highly dispersed Pt nanoparticles form a well-defined interface with In2O3, enhancing gas adsorption, electron transfer, and reaction kinetics, thereby significantly boosting sensor performance. By integrating in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), this study provides fundamental insights into gas-solid interfacial sensing mechanisms, elucidating how Pt modulation enhances gas sensor performance at the molecular level. Additionally, the aging mechanisms of 2% Pt NPs-In2O3 sensors were explored through in situ characterization, revealing the evolution of surface morphology and gas adsorption capacity before and after aging under different conditions: 200 ℃/0% RH, 200 ℃/50% RH, and 250 ℃/0% RH for 20 days. These findings offer valuable guidance for improving the long-term stability and reliability of Pt-modified In2O3 gas sensors.
Metal-organic framework (MOF) derived metal oxides and their composites have shown remarkable potential in enhancing the sensitivity and lowering the detection limits of gas sensors, emerging as promising candidates for volatile organic compound (VOC) detection. Here, the Pt-sensitized In2O3 hollow microtubes were synthesized from MIL-68 via hydrothermal and sacrificial template methods, demonstrating exceptional trace detection capability (0.01–1 ppm) to p-xylene. The 2% Pt NPs-In2O3 showed the highest response of 68.7 at 50 ppb, with a theoretical detection limit as low as 0.027 ppb. The role of Pt was elucidated through comprehensive characterization, revealing that highly dispersed Pt nanoparticles form a well-defined interface with In2O3, enhancing gas adsorption, electron transfer, and reaction kinetics, thereby significantly boosting sensor performance. By integrating in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), this study provides fundamental insights into gas-solid interfacial sensing mechanisms, elucidating how Pt modulation enhances gas sensor performance at the molecular level. Additionally, the aging mechanisms of 2% Pt NPs-In2O3 sensors were explored through in situ characterization, revealing the evolution of surface morphology and gas adsorption capacity before and after aging under different conditions: 200 ℃/0% RH, 200 ℃/50% RH, and 250 ℃/0% RH for 20 days. These findings offer valuable guidance for improving the long-term stability and reliability of Pt-modified In2O3 gas sensors.
2026, 37(8): 111329
doi: 10.1016/j.cclet.2025.111329
摘要:
Graphite, the most widely used anode material in lithium-ion batteries, faces significant limitations due to sluggish lithium-ion diffusion across the conventional organic solid electrolyte interphase (SEI) during cycling. In this work, we propose the incorporation of SO3Li-grafted graphene as an ion-conducting agent (ICA) to enhance lithium-ion transport kinetics within graphite anodes. The –SO3Li functional groups regulate the Li+ solvation structure through anion-solvent dipole interactions, promoting the formation of a lithium fluoride (LiF)-rich SEI that ensures uniform lithium-ion flux and significantly extends battery cycle life. This SO3Li-grafted ICA also mitigates mechanical strain within the graphite anode during repeated cycling, improving structural integrity over long-term operation, evidenced by fiber optic sensing technology. As a result, a 3 Ah GrLiFePO4 pouch cell incorporating this functionalized ion-conducting agent achieves excellent cycling performance, retaining 86.4% of its capacity after 1200 cycles at 1 C. These findings demonstrate the effectiveness of functionalized ICAs in addressing the intrinsic limitations of graphite, providing a promising strategy for developing long-life lithium-ion batteries for practical energy storage applications.
Graphite, the most widely used anode material in lithium-ion batteries, faces significant limitations due to sluggish lithium-ion diffusion across the conventional organic solid electrolyte interphase (SEI) during cycling. In this work, we propose the incorporation of SO3Li-grafted graphene as an ion-conducting agent (ICA) to enhance lithium-ion transport kinetics within graphite anodes. The –SO3Li functional groups regulate the Li+ solvation structure through anion-solvent dipole interactions, promoting the formation of a lithium fluoride (LiF)-rich SEI that ensures uniform lithium-ion flux and significantly extends battery cycle life. This SO3Li-grafted ICA also mitigates mechanical strain within the graphite anode during repeated cycling, improving structural integrity over long-term operation, evidenced by fiber optic sensing technology. As a result, a 3 Ah GrLiFePO4 pouch cell incorporating this functionalized ion-conducting agent achieves excellent cycling performance, retaining 86.4% of its capacity after 1200 cycles at 1 C. These findings demonstrate the effectiveness of functionalized ICAs in addressing the intrinsic limitations of graphite, providing a promising strategy for developing long-life lithium-ion batteries for practical energy storage applications.
2026, 37(8): 111349
doi: 10.1016/j.cclet.2025.111349
摘要:
Lithium−oxygen (Li−O2) batteries exhibit a superior energy density compared with any other battery currently available on the market. However, the practical application has been impeded by the insulated, insoluble discharge product (Li2O2). The limitations caused by Li2O2 are hardly to be addressed through the conventional catalyst design, which relies on the electronic structure and interfacial charge transfer characteristics. Herein, a magnetic/thermal coupling assisted Li−O2 batteries based on the thermoelectric material of MoS2 and magnetism single atom cobalt (SA−Co/MoS2) was constructed for the first time, by combing the magnetic heating and the thermoelectric catalytic effect. The spin polarization of the single atom Co may be promoted and a magnetic heating effect is generated by an external magnetic field, speeding up the oxygen evolution process (OER) and oxygen reduction reaction (ORR), as well as promoting the parallel spin arrangement of oxygen atoms. Because of its special SA−Co/MoS2 cathode, the Li−O2 battery with magnetic/thermal coupling assistance offers an ultra-low charging platform of 3.33 V and an ultra-high discharge platform of 2.90 V. The proposed novel method of sustaining the magnetic and thermal fields provides a crucial guidance for adjusting the excessive overpotential in metal−air battery systems.
Lithium−oxygen (Li−O2) batteries exhibit a superior energy density compared with any other battery currently available on the market. However, the practical application has been impeded by the insulated, insoluble discharge product (Li2O2). The limitations caused by Li2O2 are hardly to be addressed through the conventional catalyst design, which relies on the electronic structure and interfacial charge transfer characteristics. Herein, a magnetic/thermal coupling assisted Li−O2 batteries based on the thermoelectric material of MoS2 and magnetism single atom cobalt (SA−Co/MoS2) was constructed for the first time, by combing the magnetic heating and the thermoelectric catalytic effect. The spin polarization of the single atom Co may be promoted and a magnetic heating effect is generated by an external magnetic field, speeding up the oxygen evolution process (OER) and oxygen reduction reaction (ORR), as well as promoting the parallel spin arrangement of oxygen atoms. Because of its special SA−Co/MoS2 cathode, the Li−O2 battery with magnetic/thermal coupling assistance offers an ultra-low charging platform of 3.33 V and an ultra-high discharge platform of 2.90 V. The proposed novel method of sustaining the magnetic and thermal fields provides a crucial guidance for adjusting the excessive overpotential in metal−air battery systems.
2026, 37(8): 111411
doi: 10.1016/j.cclet.2025.111411
摘要:
A composite solid-state electrolyte with a triplex ionic transport architecture (TITA) was developed by integrating nanoscale fillers, short-chain crosslinkers and polymer matrix via solution casting and in situ photopolymerization. This structure creates efficient ion-conduction pathways, reduces ion aggregation, and enhances mechanical stability. As a result, the electrolyte achieves a high ionic conductivity of 7.36 × 10−4 S/cm and demonstrates excellent cycling performance when paired with an NCM622 cathode, showing great promise for solid-state lithium battery applications.
A composite solid-state electrolyte with a triplex ionic transport architecture (TITA) was developed by integrating nanoscale fillers, short-chain crosslinkers and polymer matrix via solution casting and in situ photopolymerization. This structure creates efficient ion-conduction pathways, reduces ion aggregation, and enhances mechanical stability. As a result, the electrolyte achieves a high ionic conductivity of 7.36 × 10−4 S/cm and demonstrates excellent cycling performance when paired with an NCM622 cathode, showing great promise for solid-state lithium battery applications.
2026, 37(8): 111479
doi: 10.1016/j.cclet.2025.111479
摘要:
The key to electrolytic water includes two half-reaction processes: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Transition metal phosphides (TMPs) are a class of prospective bifunctional electrocatalysts, but their performances are still far from the commercial catalysts. In this work, we design several kinds of Ni2P@CoP hetero-structured catalysts by the modification of Ru atom. The 0.1Ru-Ni2P@CoP catalyst presents the overpotentials of 82.7 (HER) and 245.3 mV (OER) at 10 mA/cm2 in 1 mol/L KOH solution. Moreover, it effectively promotes water splitting under alkaline conditions (ƞ10 = 1.21 V) and seawater conditions (ƞ10 = 1.13 V). The surface self-reconfiguration also makes it remain stable under prolonged cycling in both electrolytes. Density functional theory (DFT) calculations further indicate that doping engineering and heterostructures cause electronic modulation and electron transfer thereby increasing the intrinsic activity of the catalyst.
The key to electrolytic water includes two half-reaction processes: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Transition metal phosphides (TMPs) are a class of prospective bifunctional electrocatalysts, but their performances are still far from the commercial catalysts. In this work, we design several kinds of Ni2P@CoP hetero-structured catalysts by the modification of Ru atom. The 0.1Ru-Ni2P@CoP catalyst presents the overpotentials of 82.7 (HER) and 245.3 mV (OER) at 10 mA/cm2 in 1 mol/L KOH solution. Moreover, it effectively promotes water splitting under alkaline conditions (ƞ10 = 1.21 V) and seawater conditions (ƞ10 = 1.13 V). The surface self-reconfiguration also makes it remain stable under prolonged cycling in both electrolytes. Density functional theory (DFT) calculations further indicate that doping engineering and heterostructures cause electronic modulation and electron transfer thereby increasing the intrinsic activity of the catalyst.
2026, 37(8): 111514
doi: 10.1016/j.cclet.2025.111514
摘要:
To mitigate the slow conversion kinetics and "shuttle effect" of polysulfides, a flexible, self-supporting Ni-nitrilotriacetic acid coordination polymer nanowires/few layer Ti3C2Tx MXene (Ni-NTA/f-Ti3C2Tx) interlayers with three-dimensional network is elaborately devised and fabricated. In this framework, the M–O–M (M = metal ion) linkages on polymer nanowires present superior catalytic activity towards the conversion of lithium polysulfides (LiPSs). Meanwhile, physical blocking and chemical trapping of LiPSs are also achieved, owing to the hierarchical porous structure and polar surface of hybrid interlayer. As a result, the lithium sulfur batteries assembled with Ni-NTA/f-Ti3C2Tx exhibit a high specific capacity of 899.5 mAh/g at 1 C and 529.6 mAh/g can be kept after 500 cycles with a decay rate of 0.08% per cycle, confirming the efficient alleviation of shuttle effect.
To mitigate the slow conversion kinetics and "shuttle effect" of polysulfides, a flexible, self-supporting Ni-nitrilotriacetic acid coordination polymer nanowires/few layer Ti3C2Tx MXene (Ni-NTA/f-Ti3C2Tx) interlayers with three-dimensional network is elaborately devised and fabricated. In this framework, the M–O–M (M = metal ion) linkages on polymer nanowires present superior catalytic activity towards the conversion of lithium polysulfides (LiPSs). Meanwhile, physical blocking and chemical trapping of LiPSs are also achieved, owing to the hierarchical porous structure and polar surface of hybrid interlayer. As a result, the lithium sulfur batteries assembled with Ni-NTA/f-Ti3C2Tx exhibit a high specific capacity of 899.5 mAh/g at 1 C and 529.6 mAh/g can be kept after 500 cycles with a decay rate of 0.08% per cycle, confirming the efficient alleviation of shuttle effect.
2026, 37(8): 111751
doi: 10.1016/j.cclet.2025.111751
摘要:
Coinfection with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and influenza virus exacerbates pulmonary inflammation and tissue damage, significantly increasing the risks of respiratory failure, acute respiratory distress syndrome (ARDS), and secondary bacterial infections. Currently, there are no approved therapeutic agents specifically targeting these two viruses' coinfection. Human dihydroorotate dehydrogenase (DHODH), a key enzyme catalyzing the fourth step in the de novo pyrimidine biosynthesis pathway through the oxidation of dihydroorotate to orotate, serves as the rate-limiting enzyme in pyrimidine biosynthesis. This critical metabolic checkpoint has emerged as a promising broad-spectrum antiviral target. In this study, we designed and synthesized a series of DHODH-targeting proteolysis-targeting chimeras (PROTACs), among which PROTACs 17 and 19 connected via flexible alkyl linkers were identified as the most potent molecules. Mechanistic investigations revealed that 17 and 19 induced DHODH degradation through the proteasome- and cereblon (CRBN)-dependent pathways. Remarkably, 17 and 19 exhibited significant antiviral activities against both influenza virus and SARS-CoV-2 in vitro. These findings collectively present a novel and effective strategy for the treatment of coinfection caused by SARS-CoV-2 and influenza virus.
Coinfection with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and influenza virus exacerbates pulmonary inflammation and tissue damage, significantly increasing the risks of respiratory failure, acute respiratory distress syndrome (ARDS), and secondary bacterial infections. Currently, there are no approved therapeutic agents specifically targeting these two viruses' coinfection. Human dihydroorotate dehydrogenase (DHODH), a key enzyme catalyzing the fourth step in the de novo pyrimidine biosynthesis pathway through the oxidation of dihydroorotate to orotate, serves as the rate-limiting enzyme in pyrimidine biosynthesis. This critical metabolic checkpoint has emerged as a promising broad-spectrum antiviral target. In this study, we designed and synthesized a series of DHODH-targeting proteolysis-targeting chimeras (PROTACs), among which PROTACs 17 and 19 connected via flexible alkyl linkers were identified as the most potent molecules. Mechanistic investigations revealed that 17 and 19 induced DHODH degradation through the proteasome- and cereblon (CRBN)-dependent pathways. Remarkably, 17 and 19 exhibited significant antiviral activities against both influenza virus and SARS-CoV-2 in vitro. These findings collectively present a novel and effective strategy for the treatment of coinfection caused by SARS-CoV-2 and influenza virus.
2026, 37(8): 111757
doi: 10.1016/j.cclet.2025.111757
摘要:
Genetically encoded fluorescence (FL) sensors play vital roles in monitoring cell metabolism dynamics, gene transcription, DNA repair, apoptosis, and nutrient sensing. In genetically encoded FL sensors study, microscope acquires multimodal images that contain bright-field (BF) and FL images. BF and FL images can provide different information on cell phenotypes and gray level. Here, we developed an artificial intelligence (AI)-driven system “AI-cell metabolism dynamic analyzer (AI-CMDA)” for high-throughput automatically cell division metabolism dynamics processing by fusing multimodal information. The system consists of a deep learning model based on multimodal images dedicated to division nodes extraction and an adaptive correlation filter tracker for associating cell sequences. The division extraction method enables fast filtering of dividing cells without manual selection, and the adaptive correlation filter can achieve robust, accurate tracking during cell transforms with time. We apply the system with 3 genetically encoded FL sensors for nicotinamide adenine dinucleotides (NAD+/NADH) ratio, reduced nicotinamide adenine dinucleotide phosphate (NADPH) and H2O2, respectively, to monitor the redox metabolism within cell division sequences. The results show that this system can reduce the processing time to seconds compared with several hours’ manual labeling and can achieve accuracy and fastness.
Genetically encoded fluorescence (FL) sensors play vital roles in monitoring cell metabolism dynamics, gene transcription, DNA repair, apoptosis, and nutrient sensing. In genetically encoded FL sensors study, microscope acquires multimodal images that contain bright-field (BF) and FL images. BF and FL images can provide different information on cell phenotypes and gray level. Here, we developed an artificial intelligence (AI)-driven system “AI-cell metabolism dynamic analyzer (AI-CMDA)” for high-throughput automatically cell division metabolism dynamics processing by fusing multimodal information. The system consists of a deep learning model based on multimodal images dedicated to division nodes extraction and an adaptive correlation filter tracker for associating cell sequences. The division extraction method enables fast filtering of dividing cells without manual selection, and the adaptive correlation filter can achieve robust, accurate tracking during cell transforms with time. We apply the system with 3 genetically encoded FL sensors for nicotinamide adenine dinucleotides (NAD+/NADH) ratio, reduced nicotinamide adenine dinucleotide phosphate (NADPH) and H2O2, respectively, to monitor the redox metabolism within cell division sequences. The results show that this system can reduce the processing time to seconds compared with several hours’ manual labeling and can achieve accuracy and fastness.
2026, 37(8): 111758
doi: 10.1016/j.cclet.2025.111758
摘要:
Adenomyosis remains a poorly understood condition characterized by the limited efficacy of current pharmacotherapy. Traditional treatments using dydrogesterone (DG) for adenomyosis often yield suboptimal outcomes due to poor targeting and susceptibility to immune rejection. Therefore, there is an urgent need to identify an effective approach to enhancing the therapeutic efficacy of DG. Given the enrichment of macrophages in the uterus associated with adenomyosis, this study sought to develop a supramolecular cell-based macrophage membrane-encapsulated DG nanoparticle (MM-DG-NP) delivery system for targeted drug delivery and effective treatment of adenomyosis. The MM-DG-NP system leverages a multifaceted therapeutic mechanism by evading phagocytic clearance and enhancing targeted drug delivery efficacy. The supramolecular cell framework, constructed through dynamic non-covalent interactions, provides structural stability and biofunctional adaptability to the MM-DG-NP system, enabling precise homing to uterine macrophage-rich pathological sites. The MM-DG-NP system demonstrated therapeutic efficacy superior to that of traditional DG therapy in murine models, characterized by a pronounced reduction in endometrial invasion depth within the myometrium; effective inhibition of epithelial–mesenchymal transition (EMT) progression in the glandular epithelium; significant attenuation of local inflammatory cytokine release in the uterus, including interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), and interferon-gamma (IFN-γ); and notable alleviation of pain responses. These results highlight the critical role of supramolecular cell engineering in enhancing the biocompatibility and targeting precision of nanomedicines. MM-DG-NPs thus represent a promising strategy for overcoming current pharmacotherapeutic limitations in adenomyosis, warranting further investigation to explore their potential clinical translation.
Adenomyosis remains a poorly understood condition characterized by the limited efficacy of current pharmacotherapy. Traditional treatments using dydrogesterone (DG) for adenomyosis often yield suboptimal outcomes due to poor targeting and susceptibility to immune rejection. Therefore, there is an urgent need to identify an effective approach to enhancing the therapeutic efficacy of DG. Given the enrichment of macrophages in the uterus associated with adenomyosis, this study sought to develop a supramolecular cell-based macrophage membrane-encapsulated DG nanoparticle (MM-DG-NP) delivery system for targeted drug delivery and effective treatment of adenomyosis. The MM-DG-NP system leverages a multifaceted therapeutic mechanism by evading phagocytic clearance and enhancing targeted drug delivery efficacy. The supramolecular cell framework, constructed through dynamic non-covalent interactions, provides structural stability and biofunctional adaptability to the MM-DG-NP system, enabling precise homing to uterine macrophage-rich pathological sites. The MM-DG-NP system demonstrated therapeutic efficacy superior to that of traditional DG therapy in murine models, characterized by a pronounced reduction in endometrial invasion depth within the myometrium; effective inhibition of epithelial–mesenchymal transition (EMT) progression in the glandular epithelium; significant attenuation of local inflammatory cytokine release in the uterus, including interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), and interferon-gamma (IFN-γ); and notable alleviation of pain responses. These results highlight the critical role of supramolecular cell engineering in enhancing the biocompatibility and targeting precision of nanomedicines. MM-DG-NPs thus represent a promising strategy for overcoming current pharmacotherapeutic limitations in adenomyosis, warranting further investigation to explore their potential clinical translation.
2026, 37(8): 111760
doi: 10.1016/j.cclet.2025.111760
摘要:
Deubiquitinases (DUBs) that remove conjugated ubiquitin from substrates are critical regulators of protein homeostasis and cellular signaling. Understanding the spatial distribution of DUBs in subcellular compartments is essential for uncovering their roles in stress responses and disease pathogenesis. Herein, we developed an Escherichia coli (E. coli)-based biosynthetic strategy for the expedient generation of biotin-labeled ubiquitin probe (Biotin-Ub-PA) through co-expression of Avi-Ub and BirA in E. coli, thus bypassing tedious chemical synthesis. Combined with affinity purification and proteomics, we utilized the biosynthetic probe to covalently capture active DUBs in subcellular compartments and revealed the distribution of DUBs in the cytoplasm and nucleus. As a proof of concept, hydrogen peroxide-induced activity changes of DUBs in the cytoplasm and nucleus were analyzed by the same probe. The results suggest that some DUBs, such as ubiquitin-specific protease 36 (USP36) and USP16, may undergo subcellular translocation and activity alterations under oxidative stress. Our study presents a reliable workflow for the spatial distribution analysis of DUBs under different stimuli or disease conditions.
Deubiquitinases (DUBs) that remove conjugated ubiquitin from substrates are critical regulators of protein homeostasis and cellular signaling. Understanding the spatial distribution of DUBs in subcellular compartments is essential for uncovering their roles in stress responses and disease pathogenesis. Herein, we developed an Escherichia coli (E. coli)-based biosynthetic strategy for the expedient generation of biotin-labeled ubiquitin probe (Biotin-Ub-PA) through co-expression of Avi-Ub and BirA in E. coli, thus bypassing tedious chemical synthesis. Combined with affinity purification and proteomics, we utilized the biosynthetic probe to covalently capture active DUBs in subcellular compartments and revealed the distribution of DUBs in the cytoplasm and nucleus. As a proof of concept, hydrogen peroxide-induced activity changes of DUBs in the cytoplasm and nucleus were analyzed by the same probe. The results suggest that some DUBs, such as ubiquitin-specific protease 36 (USP36) and USP16, may undergo subcellular translocation and activity alterations under oxidative stress. Our study presents a reliable workflow for the spatial distribution analysis of DUBs under different stimuli or disease conditions.
2026, 37(8): 111771
doi: 10.1016/j.cclet.2025.111771
摘要:
Triggering mitochondria-targeted ferroptosis is the effective way to bypass apoptotic resistance of sonodynamic therapy (SDT), but it suffers from discounted therapeutic efficacy due to the anti-ferroptosis mechanism via mitochondrial dihydroorotate dehydrogenase (DHODH). Herein, iron porphyrin-based nanometal organic frameworks (PCN-600) were synthesized by hydrothermal method for loading the ferroptosis inducer sulfasalazine (SAS) and DHODH inhibitor brequinar (BQR), and finally surface-modified with short chains of mitochondria-targeting triphenylphosphine (TPP) and long chains contained tumor-targeting groups of biotin that can be cleaved by intratumoral glutathione (GSH) to re-expose TPP. The nanosystem could be successfully delivered into the mitochondria of cancer cells which was an important location of cell apoptosis and ferroptosis, released SAS/BQR, and produced amounts of ROS under ultrasound activation to induce ferroptosis and overcome ferroptosis resistance for dual-synergism with apoptosis to enhance the anti-tumor efficacy of SDT both in vitro and in vivo. The GSH-activated mitochondria-targeting nanosystem for devasting mitochondrial anti-ferroptosis provides a novel method for ferroptosis-based enhancement of anti-tumor efficacy of SDT.
Triggering mitochondria-targeted ferroptosis is the effective way to bypass apoptotic resistance of sonodynamic therapy (SDT), but it suffers from discounted therapeutic efficacy due to the anti-ferroptosis mechanism via mitochondrial dihydroorotate dehydrogenase (DHODH). Herein, iron porphyrin-based nanometal organic frameworks (PCN-600) were synthesized by hydrothermal method for loading the ferroptosis inducer sulfasalazine (SAS) and DHODH inhibitor brequinar (BQR), and finally surface-modified with short chains of mitochondria-targeting triphenylphosphine (TPP) and long chains contained tumor-targeting groups of biotin that can be cleaved by intratumoral glutathione (GSH) to re-expose TPP. The nanosystem could be successfully delivered into the mitochondria of cancer cells which was an important location of cell apoptosis and ferroptosis, released SAS/BQR, and produced amounts of ROS under ultrasound activation to induce ferroptosis and overcome ferroptosis resistance for dual-synergism with apoptosis to enhance the anti-tumor efficacy of SDT both in vitro and in vivo. The GSH-activated mitochondria-targeting nanosystem for devasting mitochondrial anti-ferroptosis provides a novel method for ferroptosis-based enhancement of anti-tumor efficacy of SDT.
2026, 37(8): 111772
doi: 10.1016/j.cclet.2025.111772
摘要:
The clinical application of photodynamic therapy (PDT) is usually limited by the low penetration depth of light and the hypoxic condition of tumor microenvironment. Therefore, it is urgent to develop a drug system that can activate photosensitizers (PSs) in deeply seated tumors and spontaneously generate O2 to enhance the efficacy of PDT. Herein, we design a liquid polyethylene glycol (PEG) 200 (PEG200)-based drug depot containing calcium peroxide (CaO2) nanoparticles, bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl]oxalate (CPPO, a high-energy compound), and chlorin e6 (Ce6, a PS) for achieving O2/H2O2 self-supplied chemiexcited (light irradiation-free) PDT and immunotherapy. By injecting the drug depot into the tumor, CaO2 can react with water to produce H2O2, which can activate CPPO to generate chemical energy, further stimulating Ce6 to produce 1O2. Meanwhile, CaO2 can also generate O2 to enhance PDT. Besides, CaO2 can neutralize the acidic tumor microenvironment by the formation of Ca(OH)2, cause calcium overload in tumor cells, and lead to tumor calcification. Further experiments show that CaO2, CPPO, and Ce6 can cause mitochondrial damage, trigger immunogenic cell death, and significantly improve the therapeutic effect of programmed death-1 (PD-1) monoclonal antibody. This work highlights the application potential of the rational combination of CaO2, CPPO, and Ce6 for realizing light irradiation-free PDT and immunotherapy.
The clinical application of photodynamic therapy (PDT) is usually limited by the low penetration depth of light and the hypoxic condition of tumor microenvironment. Therefore, it is urgent to develop a drug system that can activate photosensitizers (PSs) in deeply seated tumors and spontaneously generate O2 to enhance the efficacy of PDT. Herein, we design a liquid polyethylene glycol (PEG) 200 (PEG200)-based drug depot containing calcium peroxide (CaO2) nanoparticles, bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl]oxalate (CPPO, a high-energy compound), and chlorin e6 (Ce6, a PS) for achieving O2/H2O2 self-supplied chemiexcited (light irradiation-free) PDT and immunotherapy. By injecting the drug depot into the tumor, CaO2 can react with water to produce H2O2, which can activate CPPO to generate chemical energy, further stimulating Ce6 to produce 1O2. Meanwhile, CaO2 can also generate O2 to enhance PDT. Besides, CaO2 can neutralize the acidic tumor microenvironment by the formation of Ca(OH)2, cause calcium overload in tumor cells, and lead to tumor calcification. Further experiments show that CaO2, CPPO, and Ce6 can cause mitochondrial damage, trigger immunogenic cell death, and significantly improve the therapeutic effect of programmed death-1 (PD-1) monoclonal antibody. This work highlights the application potential of the rational combination of CaO2, CPPO, and Ce6 for realizing light irradiation-free PDT and immunotherapy.
2026, 37(8): 111773
doi: 10.1016/j.cclet.2025.111773
摘要:
Accumulating evidence highlights the therapeutic potential of soluble epoxide hydrolase (sEH) inhibitors with anti-inflammatory and neuroprotective properties for Alzheimer’s disease (AD). In this work, an ent–atisane diterpenoid J12 was identified as a hit compound against sEH with moderate inhibitory activity from five distinct series of compounds (J1–J44) isolated from Excoecaria agallocha L. After rational structural modification, a novel sEH inhibitor HXY14 with improved sEH inhibitory activity (half maximal inhibitory concentration (IC50) = 1.6 µmol/L, 10-fold compared to J12) was obtained. The cellular thermal shift assay (CETSA) demonstrated direct binding of HXY14 to sEH. In an Aβ-induced neuroinflammation cell model, treatment with HXY14 increased epoxyeicosatrienoic acids (EETs) levels, leading to reduced neuroinflammation and concomitant neuroprotection. HXY14 could ameliorate memory impairment and exhibited cognitive improvement in Aβ1–42-induced AD model and exhibited preferable safety in vivo. Treatment with HXY14 significantly decreased the expression levels of inflammatory factors and attenuated microglia activation, thereby inhibiting neuroinflammation. Furthermore, HXY14 could promote neuroprotection and alleviate synaptic dysfunction in AD model mice. This study expands the discovery of novel naturally derived sEH inhibitors and provides evidence for the utility of sEH inhibitors for AD therapy.
Accumulating evidence highlights the therapeutic potential of soluble epoxide hydrolase (sEH) inhibitors with anti-inflammatory and neuroprotective properties for Alzheimer’s disease (AD). In this work, an ent–atisane diterpenoid J12 was identified as a hit compound against sEH with moderate inhibitory activity from five distinct series of compounds (J1–J44) isolated from Excoecaria agallocha L. After rational structural modification, a novel sEH inhibitor HXY14 with improved sEH inhibitory activity (half maximal inhibitory concentration (IC50) = 1.6 µmol/L, 10-fold compared to J12) was obtained. The cellular thermal shift assay (CETSA) demonstrated direct binding of HXY14 to sEH. In an Aβ-induced neuroinflammation cell model, treatment with HXY14 increased epoxyeicosatrienoic acids (EETs) levels, leading to reduced neuroinflammation and concomitant neuroprotection. HXY14 could ameliorate memory impairment and exhibited cognitive improvement in Aβ1–42-induced AD model and exhibited preferable safety in vivo. Treatment with HXY14 significantly decreased the expression levels of inflammatory factors and attenuated microglia activation, thereby inhibiting neuroinflammation. Furthermore, HXY14 could promote neuroprotection and alleviate synaptic dysfunction in AD model mice. This study expands the discovery of novel naturally derived sEH inhibitors and provides evidence for the utility of sEH inhibitors for AD therapy.
2026, 37(8): 111780
doi: 10.1016/j.cclet.2025.111780
摘要:
Two novel anthrone–macrolide hybrids, neonectones A and B (1 and 2), one new 10-membered macrolide neonectone C (3), and one new oxaphenalenone derivative, (±)-neonectone D (4), together with five known compounds (5–9) were isolated from the crude extract of the ascomycete fungus Neonectria sp. Compounds 1 and 2 represent the first example of anthrone–ten-membered lactone heterodimers, possessing an unprecedented 5-(10-oxo-9,10-dihydroanthracen-9-yl)oxecane-2,7-dione skeleton. Their structures and absolute configurations were established by a combination of extensive spectroscopic analysis, 13C nuclear magnetic resonance spectroscopy (NMR) chemical shifts calculations with DP4+ probability analysis and electronic circular dichroism (ECD) calculations. Bioactivity evaluation revealed that compounds 1, 2 and 9 exhibited anti-methicillin-resistant Staphylococcus aureus (MRSA) activity. Compound 9 exhibited anti-MRSA activity through disrupting membrane integrity, suppressing energy and nucleotide metabolism, modulating membrane transport and transcription/translation regulatory factors, as well as inhibiting quorum sensing and biofilm formation.
Two novel anthrone–macrolide hybrids, neonectones A and B (1 and 2), one new 10-membered macrolide neonectone C (3), and one new oxaphenalenone derivative, (±)-neonectone D (4), together with five known compounds (5–9) were isolated from the crude extract of the ascomycete fungus Neonectria sp. Compounds 1 and 2 represent the first example of anthrone–ten-membered lactone heterodimers, possessing an unprecedented 5-(10-oxo-9,10-dihydroanthracen-9-yl)oxecane-2,7-dione skeleton. Their structures and absolute configurations were established by a combination of extensive spectroscopic analysis, 13C nuclear magnetic resonance spectroscopy (NMR) chemical shifts calculations with DP4+ probability analysis and electronic circular dichroism (ECD) calculations. Bioactivity evaluation revealed that compounds 1, 2 and 9 exhibited anti-methicillin-resistant Staphylococcus aureus (MRSA) activity. Compound 9 exhibited anti-MRSA activity through disrupting membrane integrity, suppressing energy and nucleotide metabolism, modulating membrane transport and transcription/translation regulatory factors, as well as inhibiting quorum sensing and biofilm formation.
2026, 37(8): 111786
doi: 10.1016/j.cclet.2025.111786
摘要:
Inhibiting the contraction of cardiac myosin is an important strategy for treating hypertrophic cardiomyopathy (HCM). However, currently only MYK-461 has been approved for market, and its safety and pharmacokinetic (PK) properties still have deficiencies. Herein, we reported the discovery of a novel and potent cardiac myosin inhibitor Z5–11 through rational structural optimization of MYK-461. Compared with MYK-461, Z5–11 exhibited stronger inhibitory activity against myosin ATPase and could significantly inhibit myocardial cell contraction, as well as alleviate Ang Ⅱ-induced cardiac hypertrophy. The cytotoxicity assessment on rat myocardial cells showed that Z5–11 exhibited better safety than MYK-461. The PK study revealed that Z5–11 had reasonable half-life time (t1/2 = 2.74 h), and excellent oral bioavailability (F = 105.2%). More importantly, Z5–11 can effectively ameliorate transverse aortic constriction (TAC)-induced cardiac dysfunction and cardiac hypertrophy and remodeling in mice. These findings suggest that Z5–11 can be developed as a promising drug candidate for treating HCM.
Inhibiting the contraction of cardiac myosin is an important strategy for treating hypertrophic cardiomyopathy (HCM). However, currently only MYK-461 has been approved for market, and its safety and pharmacokinetic (PK) properties still have deficiencies. Herein, we reported the discovery of a novel and potent cardiac myosin inhibitor Z5–11 through rational structural optimization of MYK-461. Compared with MYK-461, Z5–11 exhibited stronger inhibitory activity against myosin ATPase and could significantly inhibit myocardial cell contraction, as well as alleviate Ang Ⅱ-induced cardiac hypertrophy. The cytotoxicity assessment on rat myocardial cells showed that Z5–11 exhibited better safety than MYK-461. The PK study revealed that Z5–11 had reasonable half-life time (t1/2 = 2.74 h), and excellent oral bioavailability (F = 105.2%). More importantly, Z5–11 can effectively ameliorate transverse aortic constriction (TAC)-induced cardiac dysfunction and cardiac hypertrophy and remodeling in mice. These findings suggest that Z5–11 can be developed as a promising drug candidate for treating HCM.
2026, 37(8): 111794
doi: 10.1016/j.cclet.2025.111794
摘要:
Methamphetamine (METH) addiction represents a severe global public health crisis with currently limited therapeutic options, highlighting an urgent need for innovative approaches. Emerging evidence indicates that neuroinflammation, particularly microglial activation and subsequent cytokine release, significantly contributes to the neuropathology associated with METH use. Cannabidiol (CBD), a phytocannabinoid with promising anti-inflammatory and neuroprotective properties, has demonstrated therapeutic potential in mitigating METH-related neuroimmune responses. However, its clinical translation is severely restricted due to low bioavailability, rapid hepatic metabolism, and limited blood-brain barrier (BBB) penetration. To address these challenges, we developed a novel therapeutic platform utilizing exosomes derived from hypoxia-preconditioned human umbilical vein endothelial cells. These exosomes were loaded with CBD and surface-functionalized with the transcriptional activator protein (TAT) peptide, generating HP-Exo-CBD-TAT, to enhance brain targeting. Intranasal administration of HP-Exo-CBD-TAT significantly improved BBB penetration and brain accumulation compared to unmodified CBD-loaded exosomes (HP-Exo-CBD). In mouse models of METH addiction, treatment with HP-Exo-CBD-TAT markedly attenuated behavioral sensitization and conditioned place preference (CPP), two key indicators of addiction-like behaviors. The observed therapeutic effects correlated strongly with reductions in microglial activation and pro-inflammatory cytokine expression (interleukin-1β (IL-1β), IL-6, tumor necrosis factor-α (TNF-α)) in critical addiction-associated brain regions, such as the medial prefrontal cortex and ventral tegmental area. Importantly, even the carrier alone (HP-Exo-TAT) exhibited intrinsic immunomodulatory effects, underscoring the dual therapeutic action of this delivery system. Our findings highlight HP-Exo-CBD-TAT as a highly efficient, biocompatible, and non-invasive strategy that effectively targets neuroinflammation and addictive behaviors. This intranasal exosomal platform demonstrates significant translational promise for the clinical management of METH addiction.
Methamphetamine (METH) addiction represents a severe global public health crisis with currently limited therapeutic options, highlighting an urgent need for innovative approaches. Emerging evidence indicates that neuroinflammation, particularly microglial activation and subsequent cytokine release, significantly contributes to the neuropathology associated with METH use. Cannabidiol (CBD), a phytocannabinoid with promising anti-inflammatory and neuroprotective properties, has demonstrated therapeutic potential in mitigating METH-related neuroimmune responses. However, its clinical translation is severely restricted due to low bioavailability, rapid hepatic metabolism, and limited blood-brain barrier (BBB) penetration. To address these challenges, we developed a novel therapeutic platform utilizing exosomes derived from hypoxia-preconditioned human umbilical vein endothelial cells. These exosomes were loaded with CBD and surface-functionalized with the transcriptional activator protein (TAT) peptide, generating HP-Exo-CBD-TAT, to enhance brain targeting. Intranasal administration of HP-Exo-CBD-TAT significantly improved BBB penetration and brain accumulation compared to unmodified CBD-loaded exosomes (HP-Exo-CBD). In mouse models of METH addiction, treatment with HP-Exo-CBD-TAT markedly attenuated behavioral sensitization and conditioned place preference (CPP), two key indicators of addiction-like behaviors. The observed therapeutic effects correlated strongly with reductions in microglial activation and pro-inflammatory cytokine expression (interleukin-1β (IL-1β), IL-6, tumor necrosis factor-α (TNF-α)) in critical addiction-associated brain regions, such as the medial prefrontal cortex and ventral tegmental area. Importantly, even the carrier alone (HP-Exo-TAT) exhibited intrinsic immunomodulatory effects, underscoring the dual therapeutic action of this delivery system. Our findings highlight HP-Exo-CBD-TAT as a highly efficient, biocompatible, and non-invasive strategy that effectively targets neuroinflammation and addictive behaviors. This intranasal exosomal platform demonstrates significant translational promise for the clinical management of METH addiction.
2026, 37(8): 111799
doi: 10.1016/j.cclet.2025.111799
摘要:
Prostate cancer poses a severe threat to the health of middle-aged and elderly males. In recent years, the development and clinical utilization of prostate-specific membrane antigen (PSMA)-targeted agents have significantly expanded diagnostic options for this malignancy. However, tumor heterogeneity substantially compromises the efficacy of radionuclide therapy, necessitating the exploration of multi-target strategies as potential solutions. This study presents a novel heterodimeric construct engineered for prostate cancer management, labeled with both diagnostic and therapeutic radionuclides to enable concurrent application in positron emission computed tomography (PET) imaging and radionuclide therapy. Our investigation primarily evaluates the therapeutic efficacy of ultra-low-dose (3.7 MBq) radionuclide therapy combined with anti-programmed cell death protein-1 (PD-1) antibody immunotherapy. In the RM-1 prostate cancer model with elevated PSMA expression, we have validated that the combination of ultra-low-dose radionuclide treatment and anti-PD-1 antibody immunotherapy yields superior therapeutic outcomes. Notably, compared to the immunotherapy-only group, the combination regimen elicited a significant increase in dendritic cells (DCs) and natural killer (NK) cells populations, with enhancements ranging from 32% to 103%. This ultra-low-dose radioimmunotherapy strategy offers a valuable theoretical framework for clinical translation, holding promise for further enhancing therapeutic efficacy in prostate cancer treatment.
Prostate cancer poses a severe threat to the health of middle-aged and elderly males. In recent years, the development and clinical utilization of prostate-specific membrane antigen (PSMA)-targeted agents have significantly expanded diagnostic options for this malignancy. However, tumor heterogeneity substantially compromises the efficacy of radionuclide therapy, necessitating the exploration of multi-target strategies as potential solutions. This study presents a novel heterodimeric construct engineered for prostate cancer management, labeled with both diagnostic and therapeutic radionuclides to enable concurrent application in positron emission computed tomography (PET) imaging and radionuclide therapy. Our investigation primarily evaluates the therapeutic efficacy of ultra-low-dose (3.7 MBq) radionuclide therapy combined with anti-programmed cell death protein-1 (PD-1) antibody immunotherapy. In the RM-1 prostate cancer model with elevated PSMA expression, we have validated that the combination of ultra-low-dose radionuclide treatment and anti-PD-1 antibody immunotherapy yields superior therapeutic outcomes. Notably, compared to the immunotherapy-only group, the combination regimen elicited a significant increase in dendritic cells (DCs) and natural killer (NK) cells populations, with enhancements ranging from 32% to 103%. This ultra-low-dose radioimmunotherapy strategy offers a valuable theoretical framework for clinical translation, holding promise for further enhancing therapeutic efficacy in prostate cancer treatment.
2026, 37(8): 111800
doi: 10.1016/j.cclet.2025.111800
摘要:
Hydrogen sulfide (H2S), a gaseous signaling molecule with diverse biological functions, exhibits abnormal concentrations that are closely associated with arthritic pathogenesis and serve as a characteristic indicator of protein-rich food spoilage. To address the need for reliable H2S detection, this study developed a novel fluorescent probe, BHP-PC, by rationally integrating methylene blue and benzothiazole fluorophores. The probe demonstrates remarkable spectral separation (215 nm) and high selectivity, enabling simultaneous monitoring of fluorescence signals in both blue (detection limit: 12.5 nmol/L) and red (detection limit: 22.6 nmol/L) channels for highly sensitive H2S quantification. BHP-PC exhibits excellent dual-color imaging capabilities in both cellular and zebrafish models. The distinct colorimetric response facilitated the successful development of test strips for practical H2S detection in spoiled proteinaceous samples. Furthermore, the probe’s application in a λ-carrageenan-induced murine arthritis model enabled real-time H2S visualization, demonstrating its potential as an analytical tool for arthritis diagnosis and therapeutic monitoring.
Hydrogen sulfide (H2S), a gaseous signaling molecule with diverse biological functions, exhibits abnormal concentrations that are closely associated with arthritic pathogenesis and serve as a characteristic indicator of protein-rich food spoilage. To address the need for reliable H2S detection, this study developed a novel fluorescent probe, BHP-PC, by rationally integrating methylene blue and benzothiazole fluorophores. The probe demonstrates remarkable spectral separation (215 nm) and high selectivity, enabling simultaneous monitoring of fluorescence signals in both blue (detection limit: 12.5 nmol/L) and red (detection limit: 22.6 nmol/L) channels for highly sensitive H2S quantification. BHP-PC exhibits excellent dual-color imaging capabilities in both cellular and zebrafish models. The distinct colorimetric response facilitated the successful development of test strips for practical H2S detection in spoiled proteinaceous samples. Furthermore, the probe’s application in a λ-carrageenan-induced murine arthritis model enabled real-time H2S visualization, demonstrating its potential as an analytical tool for arthritis diagnosis and therapeutic monitoring.
2026, 37(8): 111812
doi: 10.1016/j.cclet.2025.111812
摘要:
Ovarian cancer (OC) manifests the second deadliest gynecologic malignancy and shows severe conventional therapies-resistance, underscoring the urgent need for new therapeutic interventions. Disulfidptosis, caused in solute carrier family 7 member 11 (SLC7A11)-overexpressing (SLC7A11high) cancer cells under glucose deficiency, has emerged as an appealing alternative approach. Herein we identified the significantly high expression of SLC7A11 in OC, and demonstrated that disulfidptosis induced by 6-aminonicotinamide (6-AN) effectively kill SLC7A11high OC cells. Hence, to enhance the therapeutic effect of 6-AN, we engineered a novel nanodrug, FA-L@AI, utilizing folic acid (FA)-modified liposome, and also illustrated the detailed therapeutic mechanism. Upon exposed to FA-L@AI, SLC7A11high OC cells endured internal nicotinamide adenine dinucleotide phosphate (NADPH) pools deleting, which leads to cystine accumulations. The elevated cystine levels resulted in disulfide bonds formation in actin cytoskeletal protein, ultimately triggering disulfidptosis. FA-L@AI nanoparticles exhibited an impactful suppression of tumor cells growth through 6-AN-induced disulfidptosis both in vitro and in vivo. Consistently, mRNA transcriptomic analysis further elucidated the underlying mechanism of disulfidptosis. Altogether, our work displays a unique strategy mediating disulfidptosis for OC specific therapy.
Ovarian cancer (OC) manifests the second deadliest gynecologic malignancy and shows severe conventional therapies-resistance, underscoring the urgent need for new therapeutic interventions. Disulfidptosis, caused in solute carrier family 7 member 11 (SLC7A11)-overexpressing (SLC7A11high) cancer cells under glucose deficiency, has emerged as an appealing alternative approach. Herein we identified the significantly high expression of SLC7A11 in OC, and demonstrated that disulfidptosis induced by 6-aminonicotinamide (6-AN) effectively kill SLC7A11high OC cells. Hence, to enhance the therapeutic effect of 6-AN, we engineered a novel nanodrug, FA-L@AI, utilizing folic acid (FA)-modified liposome, and also illustrated the detailed therapeutic mechanism. Upon exposed to FA-L@AI, SLC7A11high OC cells endured internal nicotinamide adenine dinucleotide phosphate (NADPH) pools deleting, which leads to cystine accumulations. The elevated cystine levels resulted in disulfide bonds formation in actin cytoskeletal protein, ultimately triggering disulfidptosis. FA-L@AI nanoparticles exhibited an impactful suppression of tumor cells growth through 6-AN-induced disulfidptosis both in vitro and in vivo. Consistently, mRNA transcriptomic analysis further elucidated the underlying mechanism of disulfidptosis. Altogether, our work displays a unique strategy mediating disulfidptosis for OC specific therapy.
2026, 37(8): 111818
doi: 10.1016/j.cclet.2025.111818
摘要:
Calcitonin (CT), a 32-amino acid polypeptide drug, is crucial in regulating calcium homeostasis and inhibiting osteoclast activity. CT is primarily administered via injections and nasal sprays. However, injections usually suffer from poor patient compliance, while nasal sprays may cause side effects such as epistaxis, rhinitis, and nasal mucosal ulcers, coupled with low bioavailability. Deep eutectic solvents (DESs), formed by hydrogen-bond donors and acceptors, have shown potential in overcoming intestinal permeability barriers and facilitating the oral delivery of peptide drugs. Herein, we developed an intestinal drug delivery system for CT using DESs, which is expected to facilitate the subsequent development of oral preparations. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge), followed by the investigation of the interaction between CT and Ch-Ge-based DESs (CAGE). Intestinal transport studies revealed that CAGE significantly promoted the jejunal absorption of CT-CAGE 1:2 (Ch and Ge in a 1:2 ratio), exhibiting the most pronounced pro-permeability effect. In vivo pharmacokinetic and pharmacodynamic results indicated that, compared with the aqueous CT solution, the CT-CAGE formulation increased bioavailability to 3.53%, with a significant hypocalcemic effect. In vitro studies further demonstrated that CAGE increased the transmembrane transport and membrane permeability of CT. The pro-permeability mechanism of CAGE may be related to the opening of tight junctions between intestinal cells and the improvement of paracellular transport efficiency. This DES-based drug delivery system offers a novel and promising approach for the oral delivery design of CT, addressing the limitations of administration routes.
Calcitonin (CT), a 32-amino acid polypeptide drug, is crucial in regulating calcium homeostasis and inhibiting osteoclast activity. CT is primarily administered via injections and nasal sprays. However, injections usually suffer from poor patient compliance, while nasal sprays may cause side effects such as epistaxis, rhinitis, and nasal mucosal ulcers, coupled with low bioavailability. Deep eutectic solvents (DESs), formed by hydrogen-bond donors and acceptors, have shown potential in overcoming intestinal permeability barriers and facilitating the oral delivery of peptide drugs. Herein, we developed an intestinal drug delivery system for CT using DESs, which is expected to facilitate the subsequent development of oral preparations. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge), followed by the investigation of the interaction between CT and Ch-Ge-based DESs (CAGE). Intestinal transport studies revealed that CAGE significantly promoted the jejunal absorption of CT-CAGE 1:2 (Ch and Ge in a 1:2 ratio), exhibiting the most pronounced pro-permeability effect. In vivo pharmacokinetic and pharmacodynamic results indicated that, compared with the aqueous CT solution, the CT-CAGE formulation increased bioavailability to 3.53%, with a significant hypocalcemic effect. In vitro studies further demonstrated that CAGE increased the transmembrane transport and membrane permeability of CT. The pro-permeability mechanism of CAGE may be related to the opening of tight junctions between intestinal cells and the improvement of paracellular transport efficiency. This DES-based drug delivery system offers a novel and promising approach for the oral delivery design of CT, addressing the limitations of administration routes.
2026, 37(8): 111835
doi: 10.1016/j.cclet.2025.111835
摘要:
Colorectal cancer (CRC) is one of the most prevalent malignancies worldwide, frequently presenting with metastatic progression to the liver. A hallmark of CRC is redox dysregulation, characterized by elevated levels of γ-glutamyl transferase (GGT) and hypochlorite (ClO−). However, bioluminescent probes capable of simultaneously detecting GGT and ClO− for sensitive in vivo CRC diagnosis and ex vivo fecal analysis remain lacking. Herein, we report a novel dual-locked bioluminescent probe, GClO-luc, designed for the simultaneous detection of GGT and ClO− in CRC and stool testing. GClO-luc remains silent until sequentially activated by GGT and ClO−, generating a turn-on bioluminescence response in both aqueous solution and fLuc-transfected CT26 cells. Notably, this probe enabled real-time visualization of small tumors in both CRC and colorectal cancer liver metastasis (CRLM) mouse models, achieving high signal-to-background ratios of 65:1 and 41:1, respectively. Moreover, GClO-luc was successfully applied to fecal analysis, showing significantly higher bioluminescence intensity in the feces from CRC and CRLM mice. These findings demonstrate that GClO-luc represents a powerful dual-responsive diagnostic tool for cancer diagnosis and stool examinations.
Colorectal cancer (CRC) is one of the most prevalent malignancies worldwide, frequently presenting with metastatic progression to the liver. A hallmark of CRC is redox dysregulation, characterized by elevated levels of γ-glutamyl transferase (GGT) and hypochlorite (ClO−). However, bioluminescent probes capable of simultaneously detecting GGT and ClO− for sensitive in vivo CRC diagnosis and ex vivo fecal analysis remain lacking. Herein, we report a novel dual-locked bioluminescent probe, GClO-luc, designed for the simultaneous detection of GGT and ClO− in CRC and stool testing. GClO-luc remains silent until sequentially activated by GGT and ClO−, generating a turn-on bioluminescence response in both aqueous solution and fLuc-transfected CT26 cells. Notably, this probe enabled real-time visualization of small tumors in both CRC and colorectal cancer liver metastasis (CRLM) mouse models, achieving high signal-to-background ratios of 65:1 and 41:1, respectively. Moreover, GClO-luc was successfully applied to fecal analysis, showing significantly higher bioluminescence intensity in the feces from CRC and CRLM mice. These findings demonstrate that GClO-luc represents a powerful dual-responsive diagnostic tool for cancer diagnosis and stool examinations.
2026, 37(8): 111836
doi: 10.1016/j.cclet.2025.111836
摘要:
Inflammatory bowel disease (IBD) exhibits pathological heterogeneity driven by multifactorial origins and patient variability, posing therapeutic challenges due to divergent immune microenvironment dynamics. Notably, neutrophils and macrophages showed prominent heterogeneity in IBD patients and underwent different reprogramming during the acute and chronic inflammatory phases. To address this pathological complexity, an orally administered TH@PVP-gel system integrating tanshinone IIA (Tan) and hemin (Hem) was engineered to address the heterogeneity of IBD pathology with the aim of achieving multi-targeted modulation of IBD. TH@PVP-gel specifically promoted neutrophil apoptosis and facilitated macrophage M2 polarization in the inflamed environment of the colon, targeting inflammatory heterogeneity and remodeling the inflammatory environment. In addition, the TH@PVP-gel efficiently scavenged reactive oxygen species (ROS), inhibited the death of colonic epithelial cells, and restored the intestinal barrier. Ultimately, the TH@PVP-gel demonstrated excellent therapeutic efficacy in both acute and chronic colitis, providing a potential strategy for the broad-spectrum treatment of IBD.
Inflammatory bowel disease (IBD) exhibits pathological heterogeneity driven by multifactorial origins and patient variability, posing therapeutic challenges due to divergent immune microenvironment dynamics. Notably, neutrophils and macrophages showed prominent heterogeneity in IBD patients and underwent different reprogramming during the acute and chronic inflammatory phases. To address this pathological complexity, an orally administered TH@PVP-gel system integrating tanshinone IIA (Tan) and hemin (Hem) was engineered to address the heterogeneity of IBD pathology with the aim of achieving multi-targeted modulation of IBD. TH@PVP-gel specifically promoted neutrophil apoptosis and facilitated macrophage M2 polarization in the inflamed environment of the colon, targeting inflammatory heterogeneity and remodeling the inflammatory environment. In addition, the TH@PVP-gel efficiently scavenged reactive oxygen species (ROS), inhibited the death of colonic epithelial cells, and restored the intestinal barrier. Ultimately, the TH@PVP-gel demonstrated excellent therapeutic efficacy in both acute and chronic colitis, providing a potential strategy for the broad-spectrum treatment of IBD.
2026, 37(8): 111837
doi: 10.1016/j.cclet.2025.111837
摘要:
The combination of sonodynamic therapy (SDT) and immunotherapy exhibits potent anticancer efficacy. However, most sonosensitizers produce reactive oxygen species (ROS) with low efficiency under ultrasound (US). Chemotherapy-induced immunogenic cell death (ICD) is also plagued by toxic side effects, suboptimal efficacy, and immune escape. Herein, we developed a cancer therapy platform based on a sonosensitizer, iron porphyrin (Fe(Ⅲ) meso-tetra(4-carboxyphenyl)porphine chloride, FeTCPPCl), which self-assembles into a hydrogen-bonded organic framework (PHOF-1). This platform enables precise activation and spatiotemporal controlled release of prodrugs, thereby inducing ICD efficiently and safely. Specifically, PHOF-1 bioorthogonally activates the doxorubicin prodrug (pro-DOX) in situ, synergizing with sonodynamic immunotherapy. This strategy, which combines SDT with in situ prodrug activation, minimizes drug side effects and maximizes therapeutic effects. Additionally, this system activates the metformin (Glucophage) prodrug (pro-MET), with ATP depletion leading to upregulated adenosine monophosphate activated protein kinase (AMPK) expression, increased programmed death-ligand 1 (PD-L1) degradation, and reversal of tumor immunosuppression. Remarkably, SDT combined with bioorthogonal in situ immune activation represents a novel approach to enhance cancer immunotherapy. This synergy effectively converts "cold" tumors into "hot" tumors by promoting ICD and reducing PD-L1 expression, thereby improving immunotherapy efficacy. The integration of SDT and bioorthogonal chemistry offers a controllable therapeutic strategy with reduced immune-related adverse effects, providing a promising avenue for safer and more effective cancer immunotherapy through the induction of adaptive antitumor immunity.
The combination of sonodynamic therapy (SDT) and immunotherapy exhibits potent anticancer efficacy. However, most sonosensitizers produce reactive oxygen species (ROS) with low efficiency under ultrasound (US). Chemotherapy-induced immunogenic cell death (ICD) is also plagued by toxic side effects, suboptimal efficacy, and immune escape. Herein, we developed a cancer therapy platform based on a sonosensitizer, iron porphyrin (Fe(Ⅲ) meso-tetra(4-carboxyphenyl)porphine chloride, FeTCPPCl), which self-assembles into a hydrogen-bonded organic framework (PHOF-1). This platform enables precise activation and spatiotemporal controlled release of prodrugs, thereby inducing ICD efficiently and safely. Specifically, PHOF-1 bioorthogonally activates the doxorubicin prodrug (pro-DOX) in situ, synergizing with sonodynamic immunotherapy. This strategy, which combines SDT with in situ prodrug activation, minimizes drug side effects and maximizes therapeutic effects. Additionally, this system activates the metformin (Glucophage) prodrug (pro-MET), with ATP depletion leading to upregulated adenosine monophosphate activated protein kinase (AMPK) expression, increased programmed death-ligand 1 (PD-L1) degradation, and reversal of tumor immunosuppression. Remarkably, SDT combined with bioorthogonal in situ immune activation represents a novel approach to enhance cancer immunotherapy. This synergy effectively converts "cold" tumors into "hot" tumors by promoting ICD and reducing PD-L1 expression, thereby improving immunotherapy efficacy. The integration of SDT and bioorthogonal chemistry offers a controllable therapeutic strategy with reduced immune-related adverse effects, providing a promising avenue for safer and more effective cancer immunotherapy through the induction of adaptive antitumor immunity.
2026, 37(8): 111841
doi: 10.1016/j.cclet.2025.111841
摘要:
Rapid hemostasis is a paramount issue in tissue wound repair treatment. Currently, hydrophilic hemostatic materials are favored for their absorption concentration capabilities in achieving swift hemostasis. However, the subsequent adherence of these materials to the wound presents another challenge, impacting the overall therapeutic outcome. Here, we reported a flexible electrospinning membrane (75D-P) composed of polyacrylonitrile (PAN) and diatom biosilica (DB), which integrated the submicron-sized pores of fiber membranes with the hierarchical porous structure of DB. It exhibited weak interfacial hydrophobicity, enabling rapid plasma protein adsorption capacity and accelerating blood coagulation at the material interface. The clotting time of kaolin commercial hemostatic agent-QuikClot® (QC) was 200 s, and that of 75D-P was 100 s, with the minimum tissue adhesion (0.06 N). Importantly, in the rabbit injury models, the dosage of the 75D-P was far below that of the QC group, yet it maintained comparable clotting time (about 400 s) and blood loss (4 g). We have integrated DB and PAN in electrospinning membrane could achieve a distinct water repellenting separation effect on blood components, promoting efficient interfacial blood coagulation. These offer insights into facilitating the blood clots formation at interfacial, thereby mitigating excessive material blood absorption and tissue adhesion.
Rapid hemostasis is a paramount issue in tissue wound repair treatment. Currently, hydrophilic hemostatic materials are favored for their absorption concentration capabilities in achieving swift hemostasis. However, the subsequent adherence of these materials to the wound presents another challenge, impacting the overall therapeutic outcome. Here, we reported a flexible electrospinning membrane (75D-P) composed of polyacrylonitrile (PAN) and diatom biosilica (DB), which integrated the submicron-sized pores of fiber membranes with the hierarchical porous structure of DB. It exhibited weak interfacial hydrophobicity, enabling rapid plasma protein adsorption capacity and accelerating blood coagulation at the material interface. The clotting time of kaolin commercial hemostatic agent-QuikClot® (QC) was 200 s, and that of 75D-P was 100 s, with the minimum tissue adhesion (0.06 N). Importantly, in the rabbit injury models, the dosage of the 75D-P was far below that of the QC group, yet it maintained comparable clotting time (about 400 s) and blood loss (4 g). We have integrated DB and PAN in electrospinning membrane could achieve a distinct water repellenting separation effect on blood components, promoting efficient interfacial blood coagulation. These offer insights into facilitating the blood clots formation at interfacial, thereby mitigating excessive material blood absorption and tissue adhesion.
2026, 37(8): 111852
doi: 10.1016/j.cclet.2025.111852
摘要:
Synergistic strategy of cationic antibacterial and nanoparticle mediated photothermal conversion provides new opportunities to address bacterial infections. However, the conventional post-modification and lack of precise structural regulation, leads to the complexity of operation and unsatisfying synergistic effect on antibacterial performance. To address these challenges, herein, a novel "selective extraction and domain-restricted growth" approach has been proposed to successfully synthesize quaternized mesoporous silica nanosphere (QMSN) encapsulating gold nanorods (GNRs) inside the pore channel (GNRs@QMSN) for the treatment of bacterial infected diabetic wound. The strategy exhibits extensive convenience, enabling the ultra-uniform microporous core-mesoporous shell structure with positive charges. Most importantly, GNRs@QMSN demonstrated an excellent photothermal conversion efficiency up to 63.73%, due to the unique pore-domain-limited effect. Under the synergistic effect of positive charge surface for enhanced bacteria adhesion, intrinsic antibacterial quaternization and GNRs-mediated photothermal conversion, GNRs@QMSN exhibited excellent antibacterial and antibiofilm performance in vitro. The feasibility of GNRs@QMSN was further validated in a mouse diabetic wound infection model. This novel QMSN encapsulating GNRs is expected to be a promising paradigm for bacterial infected wound healing.
Synergistic strategy of cationic antibacterial and nanoparticle mediated photothermal conversion provides new opportunities to address bacterial infections. However, the conventional post-modification and lack of precise structural regulation, leads to the complexity of operation and unsatisfying synergistic effect on antibacterial performance. To address these challenges, herein, a novel "selective extraction and domain-restricted growth" approach has been proposed to successfully synthesize quaternized mesoporous silica nanosphere (QMSN) encapsulating gold nanorods (GNRs) inside the pore channel (GNRs@QMSN) for the treatment of bacterial infected diabetic wound. The strategy exhibits extensive convenience, enabling the ultra-uniform microporous core-mesoporous shell structure with positive charges. Most importantly, GNRs@QMSN demonstrated an excellent photothermal conversion efficiency up to 63.73%, due to the unique pore-domain-limited effect. Under the synergistic effect of positive charge surface for enhanced bacteria adhesion, intrinsic antibacterial quaternization and GNRs-mediated photothermal conversion, GNRs@QMSN exhibited excellent antibacterial and antibiofilm performance in vitro. The feasibility of GNRs@QMSN was further validated in a mouse diabetic wound infection model. This novel QMSN encapsulating GNRs is expected to be a promising paradigm for bacterial infected wound healing.
2026, 37(8): 111868
doi: 10.1016/j.cclet.2025.111868
摘要:
Aqueous Zn//MnO2 batteries with Mn2+/MnO2 conversion reactions are highly promising due to their high redox potential and low cost. Typically, the conversion of Mn2+/MnO2 occurs at a strong acidic environment to ensure sufficient proton participation in the reaction, which will lead to Zn anode corrosion and electrolyte decomposition. Here, an acid-free mild electrolyte with Al2(SO4)3 as the additive to trigger Mn2+/MnO2 conversion through the hydrolysis of Al3+. This approach not only provides protons to enhance the two-electron transfer reaction but also utilizes the electrostatic shielding effect of Al3+ effectively inhibiting the formation of Zn dendrites and protecting the Zn anode. As a result, the assembled aqueous Zn//MnO2 battery exhibits high discharge voltage (1.6 V), long cycling stability (1900 cycles without decay) and excellent rate performance. Meanwhile, the anode-friendly electrolyte facilitates stable Zn plating/stripping and high Coulombic efficiency. This work proposes an effective strategy for enabling the two-electron process of MnO2 in mild aqueous Zn batteries.
Aqueous Zn//MnO2 batteries with Mn2+/MnO2 conversion reactions are highly promising due to their high redox potential and low cost. Typically, the conversion of Mn2+/MnO2 occurs at a strong acidic environment to ensure sufficient proton participation in the reaction, which will lead to Zn anode corrosion and electrolyte decomposition. Here, an acid-free mild electrolyte with Al2(SO4)3 as the additive to trigger Mn2+/MnO2 conversion through the hydrolysis of Al3+. This approach not only provides protons to enhance the two-electron transfer reaction but also utilizes the electrostatic shielding effect of Al3+ effectively inhibiting the formation of Zn dendrites and protecting the Zn anode. As a result, the assembled aqueous Zn//MnO2 battery exhibits high discharge voltage (1.6 V), long cycling stability (1900 cycles without decay) and excellent rate performance. Meanwhile, the anode-friendly electrolyte facilitates stable Zn plating/stripping and high Coulombic efficiency. This work proposes an effective strategy for enabling the two-electron process of MnO2 in mild aqueous Zn batteries.
2026, 37(8): 111877
doi: 10.1016/j.cclet.2025.111877
摘要:
Vitiligo is a chronic autoimmune disorder characterized by progressive melanocyte loss. Conventional narrowband ultraviolet B (NB-UVB) phototherapy for vitiligo faces limitations due to reactive oxygen species (ROS)-induced phototoxicity and insufficient melanocyte regeneration in chronic applications. In this study, we propose a differential dual-release bilayer microneedle loaded with two natural plant-derived polyphenols nanoparticles, which integrates rapid antioxidant defense and sustained melanogenic reprogramming for precision vitiligo phototherapy. The upper layer, composed of hyaluronic acid (HA), encapsulates curcumin-fructose self-assembled nanomicelles (CF NMs) for rapid ROS scavenging (68.50% within 15 min), to prevent photodamage and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB)-mediated inflammation. The lower gelatin methacryloyl (GelMA) hydrogel layer sustains the release of psoralen-loaded melanin-mimetic mesoporous polydopamine nanoparticles (PMPN), which persistently inhibits the Janus kinase-signal transducer and activator of transcription (JAK-STAT) signaling pathway and reduces autophagy-induced apoptosis, while enhancing tyrosinase activity (0.47-fold increase) to promote melanogenesis. In monobenzone-induced vitiligo mice, the CF/HA-PMPN/GelMA-MNs combined with NB-UVB demonstrated superior outcomes with 80.55% repigmentation at day 14 (vs. 25.90% in NB-UVB alone). This "rapid defense-sustained regeneration" paradigm provides a clinically translatable strategy to enhance efficacy and safety in vitiligo phototherapy.
Vitiligo is a chronic autoimmune disorder characterized by progressive melanocyte loss. Conventional narrowband ultraviolet B (NB-UVB) phototherapy for vitiligo faces limitations due to reactive oxygen species (ROS)-induced phototoxicity and insufficient melanocyte regeneration in chronic applications. In this study, we propose a differential dual-release bilayer microneedle loaded with two natural plant-derived polyphenols nanoparticles, which integrates rapid antioxidant defense and sustained melanogenic reprogramming for precision vitiligo phototherapy. The upper layer, composed of hyaluronic acid (HA), encapsulates curcumin-fructose self-assembled nanomicelles (CF NMs) for rapid ROS scavenging (68.50% within 15 min), to prevent photodamage and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB)-mediated inflammation. The lower gelatin methacryloyl (GelMA) hydrogel layer sustains the release of psoralen-loaded melanin-mimetic mesoporous polydopamine nanoparticles (PMPN), which persistently inhibits the Janus kinase-signal transducer and activator of transcription (JAK-STAT) signaling pathway and reduces autophagy-induced apoptosis, while enhancing tyrosinase activity (0.47-fold increase) to promote melanogenesis. In monobenzone-induced vitiligo mice, the CF/HA-PMPN/GelMA-MNs combined with NB-UVB demonstrated superior outcomes with 80.55% repigmentation at day 14 (vs. 25.90% in NB-UVB alone). This "rapid defense-sustained regeneration" paradigm provides a clinically translatable strategy to enhance efficacy and safety in vitiligo phototherapy.
2026, 37(8): 111878
doi: 10.1016/j.cclet.2025.111878
摘要:
Current immunotherapy for melanoma remains limited by low immunogenicity, immune-related toxicity, and an immunosuppressive tumor microenvironment (TME), necessitating more effective strategies to enhance treatment outcomes. Enhancing immunogenic cell death (ICD) induction with immune remodelling offers a promising approach to boost antitumor immunity. Here, we develop a transdermal microneedle (MN) system co-delivering garlic-derived nanovesicles (Ve) and immunomodulatory garlic polysaccharides (GP) to synergistically activate a self-reinforcing cell death pathway and reprogram the immunosuppressive TME. The dissolving MN platform enables efficient intratumoral delivery of Ve-fused thermosensitive liposomes (TSVL@PTX/ICG), loaded with paclitaxel (PTX) and the photosensitizer indocyanine green (ICG). Upon near-infrared (NIR) irradiation, ICG-mediated photothermal heating triggers rapid drug release, inducing pyroptosis via gasdermin E (GSDME) cleavage while amplifying photodynamic therapy (PDT)-driven mitochondrial damage. This dual cell death mechanism elicits robust ICD, releasing tumor antigens and damage-associated molecular patterns (DAMPs) to enhance dendritic cell activation and cytotoxic T-cell infiltration. Concurrently, GP reprograms tumor-associated macrophages (TAMs) from immunosuppressive M2 to pro-inflammatory M1 phenotypes, reshaping the TME into an immunostimulatory niche. This multi-modal approach, combining pyroptosis-driven ICD, PDT, and immune remodelling achieves potent antitumor immunity and melanoma suppression, highlighting the potential of plant-derived therapeutics in cancer immunotherapy.
Current immunotherapy for melanoma remains limited by low immunogenicity, immune-related toxicity, and an immunosuppressive tumor microenvironment (TME), necessitating more effective strategies to enhance treatment outcomes. Enhancing immunogenic cell death (ICD) induction with immune remodelling offers a promising approach to boost antitumor immunity. Here, we develop a transdermal microneedle (MN) system co-delivering garlic-derived nanovesicles (Ve) and immunomodulatory garlic polysaccharides (GP) to synergistically activate a self-reinforcing cell death pathway and reprogram the immunosuppressive TME. The dissolving MN platform enables efficient intratumoral delivery of Ve-fused thermosensitive liposomes (TSVL@PTX/ICG), loaded with paclitaxel (PTX) and the photosensitizer indocyanine green (ICG). Upon near-infrared (NIR) irradiation, ICG-mediated photothermal heating triggers rapid drug release, inducing pyroptosis via gasdermin E (GSDME) cleavage while amplifying photodynamic therapy (PDT)-driven mitochondrial damage. This dual cell death mechanism elicits robust ICD, releasing tumor antigens and damage-associated molecular patterns (DAMPs) to enhance dendritic cell activation and cytotoxic T-cell infiltration. Concurrently, GP reprograms tumor-associated macrophages (TAMs) from immunosuppressive M2 to pro-inflammatory M1 phenotypes, reshaping the TME into an immunostimulatory niche. This multi-modal approach, combining pyroptosis-driven ICD, PDT, and immune remodelling achieves potent antitumor immunity and melanoma suppression, highlighting the potential of plant-derived therapeutics in cancer immunotherapy.
2026, 37(8): 111883
doi: 10.1016/j.cclet.2025.111883
摘要:
Lithium-sulfur (Li-S) batteries are considered as one of the most promising next-generation energy storage systems owing to their high theoretical capacity and energy density. However, conventional polyolefin-based separators suffer from randomly distributed pores with broad size distributions, which are ineffective in suppressing the polysulfide shuttle effect. Moreover, they lack functional groups for catalyzing polysulfides conversion and promoting uniform lithium-ion deposition. Herein, we synthesized a hybrid material (denoted as DAAQ-TFP/MXene) via in situ growth of redox-active covalent organic frameworks (DAAQ-TFP) on amine-functionalized MXene nanosheets. The resulting DAAQ-TFP/MXene hybrid features a porous architecture and dual binding/catalytic sites, enabling efficient polysulfides adsorption and catalytic conversion, enhanced lithium-ion transport, and uniform lithium deposition. Consequently, the DAAQ-TFP/MXene-coated PP separator exhibits a high lithium-ion transference number (0.53). The LiLi symmetric cell incorporating this separator operates stably for 3800 h at 5 mA/cm2 and 1 mAh/cm2. Furthermore, Li-S full cells using DAAQ-TFP/MXene@PP separator delivers a high specific capacity (1224 mAh/g at 0.1 C), excellent rate performance (631 mAh/g at 5 C), and long-term cycling stability (71.3% capacity retention after 300 cycles at 1 C). This study provides a promising strategy for designing MXene-COF hybrid materials as functional coatings to improve the performance of Li-S batteries.
Lithium-sulfur (Li-S) batteries are considered as one of the most promising next-generation energy storage systems owing to their high theoretical capacity and energy density. However, conventional polyolefin-based separators suffer from randomly distributed pores with broad size distributions, which are ineffective in suppressing the polysulfide shuttle effect. Moreover, they lack functional groups for catalyzing polysulfides conversion and promoting uniform lithium-ion deposition. Herein, we synthesized a hybrid material (denoted as DAAQ-TFP/MXene) via in situ growth of redox-active covalent organic frameworks (DAAQ-TFP) on amine-functionalized MXene nanosheets. The resulting DAAQ-TFP/MXene hybrid features a porous architecture and dual binding/catalytic sites, enabling efficient polysulfides adsorption and catalytic conversion, enhanced lithium-ion transport, and uniform lithium deposition. Consequently, the DAAQ-TFP/MXene-coated PP separator exhibits a high lithium-ion transference number (0.53). The LiLi symmetric cell incorporating this separator operates stably for 3800 h at 5 mA/cm2 and 1 mAh/cm2. Furthermore, Li-S full cells using DAAQ-TFP/MXene@PP separator delivers a high specific capacity (1224 mAh/g at 0.1 C), excellent rate performance (631 mAh/g at 5 C), and long-term cycling stability (71.3% capacity retention after 300 cycles at 1 C). This study provides a promising strategy for designing MXene-COF hybrid materials as functional coatings to improve the performance of Li-S batteries.
2026, 37(8): 111908
doi: 10.1016/j.cclet.2025.111908
摘要:
The rational design of high-performance electrocatalysts for hydrogen evolution reaction (HER) through real-time tracking of dynamic active site evolution is both challenging and essential for the progress of sustainable energy technologies. Herein, NixCo1-xMoO4 solid solution nanotubes have been synthesized via electrospinning followed by calcination for electrocatalytic HER in a 1.0 mol/L KOH electrolyte. Optimized Ni0.25Co0.75MoO4 (denoted as NCMO-1) demonstrates high specific surface area, enhances charge transfer kinetics, and improves HER activity, achieving a low overpotential of 123 mV at 10 mA/cm2. Based on the inherent structural stability, the surface reconstruction relies on the reaction potential and the pH electrolyte via integrated approach, which involves hydroxide ion can etch the Mo species into the electrolyte accompanied by collapse and transformation from MO6 polyhedrons to amorphous cobalt-nickel hydroxides (M(OH)x (M = Co and Ni) with the electron transfer from Co to Ni sites via the oxygen-bridged cobalt-nickel bond (Co-O-Ni). Meanwhile, the dissolution of Mo enhances the hydroxylation at Co/Ni sites by revealing additional defect sites, while the formation of Co(OH)x and Ni(OH)x alters the local electronic environment. Due to the amorphous nature and structural complexity of the reconstructed sites, theoretical calculations indicate that the interaction between Co and Ni sites in NCMO-1 enhances charge transfer, strengthens adsorption, and accelerates the conversion of hydrogen and the key intermediate (*H···OH). This study provides fundamental insights into surface reconstruction behavior through the strategic integration of multi-scale in-situ characterization techniques and offers guidance for the rational design of advanced HER electrocatalysts.
The rational design of high-performance electrocatalysts for hydrogen evolution reaction (HER) through real-time tracking of dynamic active site evolution is both challenging and essential for the progress of sustainable energy technologies. Herein, NixCo1-xMoO4 solid solution nanotubes have been synthesized via electrospinning followed by calcination for electrocatalytic HER in a 1.0 mol/L KOH electrolyte. Optimized Ni0.25Co0.75MoO4 (denoted as NCMO-1) demonstrates high specific surface area, enhances charge transfer kinetics, and improves HER activity, achieving a low overpotential of 123 mV at 10 mA/cm2. Based on the inherent structural stability, the surface reconstruction relies on the reaction potential and the pH electrolyte via integrated approach, which involves hydroxide ion can etch the Mo species into the electrolyte accompanied by collapse and transformation from MO6 polyhedrons to amorphous cobalt-nickel hydroxides (M(OH)x (M = Co and Ni) with the electron transfer from Co to Ni sites via the oxygen-bridged cobalt-nickel bond (Co-O-Ni). Meanwhile, the dissolution of Mo enhances the hydroxylation at Co/Ni sites by revealing additional defect sites, while the formation of Co(OH)x and Ni(OH)x alters the local electronic environment. Due to the amorphous nature and structural complexity of the reconstructed sites, theoretical calculations indicate that the interaction between Co and Ni sites in NCMO-1 enhances charge transfer, strengthens adsorption, and accelerates the conversion of hydrogen and the key intermediate (*H···OH). This study provides fundamental insights into surface reconstruction behavior through the strategic integration of multi-scale in-situ characterization techniques and offers guidance for the rational design of advanced HER electrocatalysts.
2026, 37(8): 112001
doi: 10.1016/j.cclet.2025.112001
摘要:
Aptamers as synthetic oligonucleotide, exhibit exceptional target specificity and are increasingly employed in the development of high-performance aptamer-based sensors (aptasensors). Dye-displacement-based aptasensors have emerged as a label-free strategy, wherein between the aptamer and its cognate target displaces a pre-associated dye, eliciting an optical response. Despite this, conventional aptasensors rely on a single output signal, which constrains both sensitivity and detection robustness. Herein, we present a dual-mode aptasensor (DMApt) platform with fluorescence and colorimetric signal outputs derived from a systematic screening of a cyanine dye library, with CyFluor-8 identified as an optimal reporter. Notably, the DMApt features an ultrafast response time (5 s), making it highly suited for rapid, on-site detection applications. This approach leverages the superior binding affinity of native aptamers, avoiding the need for modification and ensuring high sensitivity. Mechanistically, signal generation arises from the concerted contributions of disaggregation-induced emission (DIE) and the attenuation of twisted intramolecular charge-transfer (TICT) through its application to a range of small-molecule and ionic targets, as well as its compatibility with aptamers exhibiting diverse secondary structures. This work establishes a modular, label-free framework for high-sensitivity small-molecule sensing, offering rapid response and excellent practicality for on-site biochemical, environmental, and diagnostic monitoring.
Aptamers as synthetic oligonucleotide, exhibit exceptional target specificity and are increasingly employed in the development of high-performance aptamer-based sensors (aptasensors). Dye-displacement-based aptasensors have emerged as a label-free strategy, wherein between the aptamer and its cognate target displaces a pre-associated dye, eliciting an optical response. Despite this, conventional aptasensors rely on a single output signal, which constrains both sensitivity and detection robustness. Herein, we present a dual-mode aptasensor (DMApt) platform with fluorescence and colorimetric signal outputs derived from a systematic screening of a cyanine dye library, with CyFluor-8 identified as an optimal reporter. Notably, the DMApt features an ultrafast response time (5 s), making it highly suited for rapid, on-site detection applications. This approach leverages the superior binding affinity of native aptamers, avoiding the need for modification and ensuring high sensitivity. Mechanistically, signal generation arises from the concerted contributions of disaggregation-induced emission (DIE) and the attenuation of twisted intramolecular charge-transfer (TICT) through its application to a range of small-molecule and ionic targets, as well as its compatibility with aptamers exhibiting diverse secondary structures. This work establishes a modular, label-free framework for high-sensitivity small-molecule sensing, offering rapid response and excellent practicality for on-site biochemical, environmental, and diagnostic monitoring.
2026, 37(8): 112016
doi: 10.1016/j.cclet.2025.112016
摘要:
Mimicking natural energy conversion processes, the pursuit of metal-free porous organic polymers (POPs) as heterogeneous catalysts for photocatalytic oxidation is a major driving force in materials science, seeking to achieve high-performance artificial photochemical systems. In this work, we report the bottom-up synthesis of a hydrazone-linked pillararene POP in its keto form. The inherent pillararene cavities provide a unique nanoconfinement environment, enabling effective substrate recognition and electron enrichment, thereby facilitating sensitive photo-response and efficient photoenergy-to-chemical energy conversion for photocatalytic oxidation coupling of primary amines (up to 99% conversion). Crucially, the framework’s tautomeric state is precisely modulated via an irreversible keto-to-enol conversion using sodium borohydride reduction. This controlled tautomerism permanently tunes the nanoconfinement microenvironment, amplifying the polymer’s electron-rich character and optimizing pore electrostatic properties. Leveraging this tunable nanoconfinement, the resulting enol form framework achieves highly efficient adsorption of cationic pollutants (up to 95% removal for Rhodamine B). This work establishes tautomerism as a chemical tool to engineer nanoconfinement in macrocycle-based POPs, expanding the toolbox for advanced porous materials with tailored functionalities for diverse applications like photocatalysis and adsorption.
Mimicking natural energy conversion processes, the pursuit of metal-free porous organic polymers (POPs) as heterogeneous catalysts for photocatalytic oxidation is a major driving force in materials science, seeking to achieve high-performance artificial photochemical systems. In this work, we report the bottom-up synthesis of a hydrazone-linked pillararene POP in its keto form. The inherent pillararene cavities provide a unique nanoconfinement environment, enabling effective substrate recognition and electron enrichment, thereby facilitating sensitive photo-response and efficient photoenergy-to-chemical energy conversion for photocatalytic oxidation coupling of primary amines (up to 99% conversion). Crucially, the framework’s tautomeric state is precisely modulated via an irreversible keto-to-enol conversion using sodium borohydride reduction. This controlled tautomerism permanently tunes the nanoconfinement microenvironment, amplifying the polymer’s electron-rich character and optimizing pore electrostatic properties. Leveraging this tunable nanoconfinement, the resulting enol form framework achieves highly efficient adsorption of cationic pollutants (up to 95% removal for Rhodamine B). This work establishes tautomerism as a chemical tool to engineer nanoconfinement in macrocycle-based POPs, expanding the toolbox for advanced porous materials with tailored functionalities for diverse applications like photocatalysis and adsorption.
2026, 37(8): 112017
doi: 10.1016/j.cclet.2025.112017
摘要:
A significant challenge in organic synthesis has been the direct transformation of azaarenes into synthetically important aromatic aldehydes via formal nitrogen extrusion and carbon insertion. In this study, we present an efficient approach to reshape easily accessible azaarene-based onium salts, such as isoquinoliniums, pyridiniums, and pyrimidiniums, into functionalized multi-substituted aromatic aldehydes. This strategy relies on the strategic use of an inverse-electron-demand [4 + 2] cycloaddition-inspired cascade process with a wide tolerance of allenes, alkynes or alkenes as dienophiles. DFT calculations were conducted to gain insight into the reaction mechanism, revealing the significant catalytic roles of Na2CO3 and H2O for aldehyde formation and deamination. The operational simplicity enables widespread application of this strategy which has successfully been expanded towards the direct transformation of fused pyridinium and isoquinolinium salts as well as naturally occurring pharmaceuticals berberine sulfate and palmatine chloride into structurally novel atropisomeric N/P compounds. The resultant N/P compounds have demonstrated their potential application as ligands.
A significant challenge in organic synthesis has been the direct transformation of azaarenes into synthetically important aromatic aldehydes via formal nitrogen extrusion and carbon insertion. In this study, we present an efficient approach to reshape easily accessible azaarene-based onium salts, such as isoquinoliniums, pyridiniums, and pyrimidiniums, into functionalized multi-substituted aromatic aldehydes. This strategy relies on the strategic use of an inverse-electron-demand [4 + 2] cycloaddition-inspired cascade process with a wide tolerance of allenes, alkynes or alkenes as dienophiles. DFT calculations were conducted to gain insight into the reaction mechanism, revealing the significant catalytic roles of Na2CO3 and H2O for aldehyde formation and deamination. The operational simplicity enables widespread application of this strategy which has successfully been expanded towards the direct transformation of fused pyridinium and isoquinolinium salts as well as naturally occurring pharmaceuticals berberine sulfate and palmatine chloride into structurally novel atropisomeric N/P compounds. The resultant N/P compounds have demonstrated their potential application as ligands.
2026, 37(8): 112033
doi: 10.1016/j.cclet.2025.112033
摘要:
Reductive amination between glycolaldehyde derivatives and lysine residues is a widely used strategy for constructing neoglycoproteins in biomedical applications. Here, α- and β-glycolaldehyde glycosides of five biologically relevant monosaccharides (Glc, Gal, Man, GlcNAc, GalNAc) were synthesized and conjugated to protein at a fixed sugar-to-protein ratio. Continuous kinetic monitoring revealed that anomeric configuration markedly influences both reaction rates and final sugar loading: α-Man > β-Man; β-Gal/GalNAc > their α-counterparts; Glc and GlcNAc showed no significant anomeric preferences. NMR analysis identified cyclic intermediates that reduce the effective concentration of reactive aldehyde, while DFT calculations provided complementary insight into anomer-specific electrophilic character. These findings offer a mechanistic rationale for selecting anomeric configuration in glycoconjugate design.
Reductive amination between glycolaldehyde derivatives and lysine residues is a widely used strategy for constructing neoglycoproteins in biomedical applications. Here, α- and β-glycolaldehyde glycosides of five biologically relevant monosaccharides (Glc, Gal, Man, GlcNAc, GalNAc) were synthesized and conjugated to protein at a fixed sugar-to-protein ratio. Continuous kinetic monitoring revealed that anomeric configuration markedly influences both reaction rates and final sugar loading: α-Man > β-Man; β-Gal/GalNAc > their α-counterparts; Glc and GlcNAc showed no significant anomeric preferences. NMR analysis identified cyclic intermediates that reduce the effective concentration of reactive aldehyde, while DFT calculations provided complementary insight into anomer-specific electrophilic character. These findings offer a mechanistic rationale for selecting anomeric configuration in glycoconjugate design.
2026, 37(8): 112034
doi: 10.1016/j.cclet.2025.112034
摘要:
Precise control over the dimensionality and morphology of supramolecular assemblies remains a key challenge in hybrid material design. Here we report a directional assembly strategy that exploits synergistic portal-specific hydrogen bonding and ion–dipole interactions between cucurbit[5]uril (CB[5]) and an Anderson-type polyoxometalate (POM) functionalized with terminal protonated amines. This tailored interaction drives the formation of elongated two-dimensional hybrid sheets with spatial confinement and anisotropic growth. The resulting CB[5]-NH2POM hybrids exhibit high thermal stability and surface-accessible CB[5] units, enabling hierarchical integration with gold nanorods (AuNRs). These AuNRs@CB[5]-NH2POM hybrids demonstrate efficient photothermal conversion (37.8%) and enable near-quantitative catalytic conversion (>99%) in NIR-triggered sulfide oxidation. Comparative controls confirm the critical role of CB[5]-mediated portal interactions in both structural definition and functional performance. This study highlights a transferable supramolecular design principle for dimensional control and modular interface engineering, offering a promising platform for developing adaptive hybrid materials in photothermal catalysis and related applications.
Precise control over the dimensionality and morphology of supramolecular assemblies remains a key challenge in hybrid material design. Here we report a directional assembly strategy that exploits synergistic portal-specific hydrogen bonding and ion–dipole interactions between cucurbit[5]uril (CB[5]) and an Anderson-type polyoxometalate (POM) functionalized with terminal protonated amines. This tailored interaction drives the formation of elongated two-dimensional hybrid sheets with spatial confinement and anisotropic growth. The resulting CB[5]-NH2POM hybrids exhibit high thermal stability and surface-accessible CB[5] units, enabling hierarchical integration with gold nanorods (AuNRs). These AuNRs@CB[5]-NH2POM hybrids demonstrate efficient photothermal conversion (37.8%) and enable near-quantitative catalytic conversion (>99%) in NIR-triggered sulfide oxidation. Comparative controls confirm the critical role of CB[5]-mediated portal interactions in both structural definition and functional performance. This study highlights a transferable supramolecular design principle for dimensional control and modular interface engineering, offering a promising platform for developing adaptive hybrid materials in photothermal catalysis and related applications.
2026, 37(8): 112035
doi: 10.1016/j.cclet.2025.112035
摘要:
Site-selective deuterated reduction of quinoline to deuterium-labelled 1,2,3,4-tetrahydroquinoline scaffold can offer a powerful strategy for drug development, mechanistic studies, and synthesis of isotopically labeled standards. Existing deuterated reduction methods predominantly produce fully deuterated piperidines, lacking control over regioselectivity and deuterium stoichiometry. Herein, we report a Ni-catalyzed sequential deuteration protocol that enables regio- and multiplicity-controlled synthesis of mono-, di-, and tri-deuterated tetrahydroquinolines with simple deuterating reagents. Nucleophilic and electrophilic deuterating sources were combined to achieve site-selective reductive deuteration at 2-, 3- and 4-positions of quinolines. The method features broad functional group compatibility and delivers D-labeled tetrahydroquinolines in high yields with excellent positional deuterium incorporation. The protocol was further extended to the double-deuteration of different classes of olefins, quinoxalines and acridines, thus providing a unified platform for efficient synthesis of selectively D-labeled N-containing heterocycles and alkenes derivatives.
Site-selective deuterated reduction of quinoline to deuterium-labelled 1,2,3,4-tetrahydroquinoline scaffold can offer a powerful strategy for drug development, mechanistic studies, and synthesis of isotopically labeled standards. Existing deuterated reduction methods predominantly produce fully deuterated piperidines, lacking control over regioselectivity and deuterium stoichiometry. Herein, we report a Ni-catalyzed sequential deuteration protocol that enables regio- and multiplicity-controlled synthesis of mono-, di-, and tri-deuterated tetrahydroquinolines with simple deuterating reagents. Nucleophilic and electrophilic deuterating sources were combined to achieve site-selective reductive deuteration at 2-, 3- and 4-positions of quinolines. The method features broad functional group compatibility and delivers D-labeled tetrahydroquinolines in high yields with excellent positional deuterium incorporation. The protocol was further extended to the double-deuteration of different classes of olefins, quinoxalines and acridines, thus providing a unified platform for efficient synthesis of selectively D-labeled N-containing heterocycles and alkenes derivatives.
Metal-free carbon quantum dots as photocatalyst for phosphonation of undirected heteroaryl compounds
2026, 37(8): 112050
doi: 10.1016/j.cclet.2025.112050
摘要:
Nitrogen-doped carbon dots (N-CDs) were synthesized via a hydrothermal method, utilizing citric acid and urea as precursor materials. Through a systematic characterization and evaluation process, the N-CDs variant with the highest amino group density was identified as an outstanding metal-free photocatalyst. Under ambient conditions, this photocatalyst exhibited remarkable catalytic performance in promoting visible-light-driven cross-dehydrogenative coupling (CDC) reactions between heteroaryl substrates and a wide range of H-phosphine oxide derivatives. This methodology presents several noteworthy advantages, such as operational stability and recyclability of the photocatalyst system, compatibility with various functional groups, mild reaction parameters, scalability for practical applications, and eco-friendly implementation using a mixed solvent system composed of 2-methyl tetrahydrofuran (2-Me THF) and water as the solvent medium. The developed protocol demonstrates enhanced process sustainability through its combination of environmental benignity and technical practicality.
Nitrogen-doped carbon dots (N-CDs) were synthesized via a hydrothermal method, utilizing citric acid and urea as precursor materials. Through a systematic characterization and evaluation process, the N-CDs variant with the highest amino group density was identified as an outstanding metal-free photocatalyst. Under ambient conditions, this photocatalyst exhibited remarkable catalytic performance in promoting visible-light-driven cross-dehydrogenative coupling (CDC) reactions between heteroaryl substrates and a wide range of H-phosphine oxide derivatives. This methodology presents several noteworthy advantages, such as operational stability and recyclability of the photocatalyst system, compatibility with various functional groups, mild reaction parameters, scalability for practical applications, and eco-friendly implementation using a mixed solvent system composed of 2-methyl tetrahydrofuran (2-Me THF) and water as the solvent medium. The developed protocol demonstrates enhanced process sustainability through its combination of environmental benignity and technical practicality.
2026, 37(8): 112104
doi: 10.1016/j.cclet.2025.112104
摘要:
The development of recyclable materials has been the key to designing sustainable materials. Dynamic supramolecular polymers, taking advantages of the reversibility of noncovalent and dynamic covalent bonds, offer many opportunities for constructing responsive and recyclable material. Here, we report dynamic supramolecular network polymers based on the cooperation between hydrogen bond and the pillar[5]arene-based host–guest interaction. The backbones of the polymer network are constructed by poly(disulfides) and the side chains are cross-linked by hydrogen bond and the pillar[5]arene-based host–guest interaction. The introduction of host-guest interaction renders the resulting network with enhanced mechanical performances. The dynamic performance of poly(disulfides) backbones and the noncovalent side chain endow the polymer materials with depolymerization ability into monomer in a closed-loop manner. We foresee this dynamic supramolecular polymer system will show widespread potential toward developing sustainable materials.
The development of recyclable materials has been the key to designing sustainable materials. Dynamic supramolecular polymers, taking advantages of the reversibility of noncovalent and dynamic covalent bonds, offer many opportunities for constructing responsive and recyclable material. Here, we report dynamic supramolecular network polymers based on the cooperation between hydrogen bond and the pillar[5]arene-based host–guest interaction. The backbones of the polymer network are constructed by poly(disulfides) and the side chains are cross-linked by hydrogen bond and the pillar[5]arene-based host–guest interaction. The introduction of host-guest interaction renders the resulting network with enhanced mechanical performances. The dynamic performance of poly(disulfides) backbones and the noncovalent side chain endow the polymer materials with depolymerization ability into monomer in a closed-loop manner. We foresee this dynamic supramolecular polymer system will show widespread potential toward developing sustainable materials.
2026, 37(8): 112105
doi: 10.1016/j.cclet.2025.112105
摘要:
Lactic acid plays a crucial role in tumor growth, maintenance, and metastasis. Given its significant impact on tumorigenesis, modulating lactic acid levels within the tumor microenvironment (TME) presents new opportunities for cancer therapy. Herein we developed a supramolecularly engineered bacterial reactor using a strong host-guest interaction between cucurbit[7]uril (CB[7])-modified attenuated Salmonella typhimurium VNP20009 (VNP) and adamantane (ADA)-functionalized lactate oxidase (LOX)-loaded liposomes. The VNP-mediated tumor colonization of these reactors facilitated LOX-driven lactic acid depletion in the hypoxic TME, simultaneously producing hydrogen peroxide (H2O2). The presence of H2O2 triggered the expression of catalase in VNP, which, in turn, catalyzed the conversion of H2O2 to oxygen (O2). This cyclic cascade reactor thus provided a continuous and stable oxygen source, promoting sustained lactic acid consumption for metabolic treatment, ultimately leading to tumor growth suppression and an enhanced anticancer effect.
Lactic acid plays a crucial role in tumor growth, maintenance, and metastasis. Given its significant impact on tumorigenesis, modulating lactic acid levels within the tumor microenvironment (TME) presents new opportunities for cancer therapy. Herein we developed a supramolecularly engineered bacterial reactor using a strong host-guest interaction between cucurbit[7]uril (CB[7])-modified attenuated Salmonella typhimurium VNP20009 (VNP) and adamantane (ADA)-functionalized lactate oxidase (LOX)-loaded liposomes. The VNP-mediated tumor colonization of these reactors facilitated LOX-driven lactic acid depletion in the hypoxic TME, simultaneously producing hydrogen peroxide (H2O2). The presence of H2O2 triggered the expression of catalase in VNP, which, in turn, catalyzed the conversion of H2O2 to oxygen (O2). This cyclic cascade reactor thus provided a continuous and stable oxygen source, promoting sustained lactic acid consumption for metabolic treatment, ultimately leading to tumor growth suppression and an enhanced anticancer effect.
2026, 37(8): 112106
doi: 10.1016/j.cclet.2025.112106
摘要:
The interfacial electronic interaction between the support and catalyst has been demonstrated to play a significant role in regulating the d-band structure of metal centers. Still, it requires dedicated control over the interaction in a reasonable manner. Herein, we developed a heterostructured support by covalently linking carbon nitride quantum dots (CNQDs) on TiO2, to anchor electroactive CoP clusters (TiO2–CNQD/CoP) for hydrogen evolution reaction (HER). The interfacial electronic interaction between the heterostructured support (TiO2–CNQD) and CoP can be controlled by varying the size of CNQDs, owing to the number of conjugated N-heterocycles in CNQDs induces tunable π-electron delocalization. As a result, a volcano-shaped correlation between the shift of the Co d-band center (Δd) and the HER performance was established, suggesting that TiO2–CNQD/CoP-C2 with a moderate size of CNQD is the optimal HER catalyst. This study highlights the critical role of interfacial interaction in supported catalysts, providing a predictive descriptor focusing on the support design of advanced HER catalysts.
The interfacial electronic interaction between the support and catalyst has been demonstrated to play a significant role in regulating the d-band structure of metal centers. Still, it requires dedicated control over the interaction in a reasonable manner. Herein, we developed a heterostructured support by covalently linking carbon nitride quantum dots (CNQDs) on TiO2, to anchor electroactive CoP clusters (TiO2–CNQD/CoP) for hydrogen evolution reaction (HER). The interfacial electronic interaction between the heterostructured support (TiO2–CNQD) and CoP can be controlled by varying the size of CNQDs, owing to the number of conjugated N-heterocycles in CNQDs induces tunable π-electron delocalization. As a result, a volcano-shaped correlation between the shift of the Co d-band center (Δd) and the HER performance was established, suggesting that TiO2–CNQD/CoP-C2 with a moderate size of CNQD is the optimal HER catalyst. This study highlights the critical role of interfacial interaction in supported catalysts, providing a predictive descriptor focusing on the support design of advanced HER catalysts.
2026, 37(8): 112107
doi: 10.1016/j.cclet.2025.112107
摘要:
Bifunctional molecules incorporating both germyl and boryl groups represent a significant class of compounds that have attracted considerable attention in organic synthesis due to their unique reactivity and versatility in diverse chemical trans-formations. Here, we present a highly efficient, one-step synthesis of such molecules through the catalytic C–H borylation of parent organogermanes, utilizing germanium as a directing atom. The process employs an iridium catalyst in conjunction with a ligand and acetate base, facilitating the formation of a germylametallacycle intermediate within the catalytic cycle. This methodology demonstrates broad substrate scope, successfully accommodating three distinct classes of organogermanes: benzylhydrogermanes, biaryl-type hydrogermanes, and triarylhydrogermanes, encompassing both sp2 and sp3 C–H activation. The versatile reactivity of the products, derived from both boron and germanium chemistry, highlights their potential utility in various applications.
Bifunctional molecules incorporating both germyl and boryl groups represent a significant class of compounds that have attracted considerable attention in organic synthesis due to their unique reactivity and versatility in diverse chemical trans-formations. Here, we present a highly efficient, one-step synthesis of such molecules through the catalytic C–H borylation of parent organogermanes, utilizing germanium as a directing atom. The process employs an iridium catalyst in conjunction with a ligand and acetate base, facilitating the formation of a germylametallacycle intermediate within the catalytic cycle. This methodology demonstrates broad substrate scope, successfully accommodating three distinct classes of organogermanes: benzylhydrogermanes, biaryl-type hydrogermanes, and triarylhydrogermanes, encompassing both sp2 and sp3 C–H activation. The versatile reactivity of the products, derived from both boron and germanium chemistry, highlights their potential utility in various applications.
2026, 37(8): 112154
doi: 10.1016/j.cclet.2025.112154
摘要:
Metal-catalyzed alkylarylation of two carbon−carbon (C-C) bonds across vicinal C(sp2) sites in olefins can provide access to diverse combinatorial chemical space. Pre-activated arenes are often used as aryl sources, but the direct utilization of Csp2−H bond instead of pre-activated arenes remains underdeveloped. Herein, ruthenium-catalyzed alkylarylation of alkenes via para-selective C-H functionalization of unprotected aniline has been reported. It bears good functional group tolerance and enables late functionalization of complex natural products. Evaluation of cone angle and minimum percent buried volume help to determine the optimal ligand. The mechanism studies reveal the dissociation of p-cymene during the catalytic cycle which triggers the redox processes for radical generation.
Metal-catalyzed alkylarylation of two carbon−carbon (C-C) bonds across vicinal C(sp2) sites in olefins can provide access to diverse combinatorial chemical space. Pre-activated arenes are often used as aryl sources, but the direct utilization of Csp2−H bond instead of pre-activated arenes remains underdeveloped. Herein, ruthenium-catalyzed alkylarylation of alkenes via para-selective C-H functionalization of unprotected aniline has been reported. It bears good functional group tolerance and enables late functionalization of complex natural products. Evaluation of cone angle and minimum percent buried volume help to determine the optimal ligand. The mechanism studies reveal the dissociation of p-cymene during the catalytic cycle which triggers the redox processes for radical generation.
2026, 37(8): 112156
doi: 10.1016/j.cclet.2025.112156
摘要:
The radical-mediated 1,2-difunctionalization of alkenes or alkynes has emerged as an efficient strategy for augmenting molecular diversity and complexity. Nevertheless, developing remote 1,4-difunctionalization reactions through radical cascade additions involving two intermolecular unsaturated bonds confronts complex chemo-, regio-, and stereoselectivity challenges. Here, we report a photocatalytic strategy that enables the first radical 1,4-difunctionalization across simple alkenes and arylacetylenes, leveraging the distinct reactivity between alkyl phosphites and different carbon radicals, by employing 1 mol% fac-Ir(ppy)3 as the photocatalyst and quinuclidine as the base. Mechanistic studies reveal that the photoexcited Ir(Ⅲ)* synergistically governs two processes: (1) Single-electron transfer (SET) activation of Rf-X to generate fluoroalkyl radicals, and (2) triplet energy transfer (TEnT)-mediated stereo-control of the constructed alkenyl phosphonates to achieve high Z/E selectivity. This method enables the efficient synthesis of various δ-fluoroalkyl-substituted alkenyl phosphonates with high Z/E selectivity under mild conditions. Furthermore, some products exhibit a synergistic inhibitory effect on porcine epidemic diarrhea virus (PEDV), effectively blocking viral adsorption and replication while preventing PEDV-induced cell apoptosis in vitro.
The radical-mediated 1,2-difunctionalization of alkenes or alkynes has emerged as an efficient strategy for augmenting molecular diversity and complexity. Nevertheless, developing remote 1,4-difunctionalization reactions through radical cascade additions involving two intermolecular unsaturated bonds confronts complex chemo-, regio-, and stereoselectivity challenges. Here, we report a photocatalytic strategy that enables the first radical 1,4-difunctionalization across simple alkenes and arylacetylenes, leveraging the distinct reactivity between alkyl phosphites and different carbon radicals, by employing 1 mol% fac-Ir(ppy)3 as the photocatalyst and quinuclidine as the base. Mechanistic studies reveal that the photoexcited Ir(Ⅲ)* synergistically governs two processes: (1) Single-electron transfer (SET) activation of Rf-X to generate fluoroalkyl radicals, and (2) triplet energy transfer (TEnT)-mediated stereo-control of the constructed alkenyl phosphonates to achieve high Z/E selectivity. This method enables the efficient synthesis of various δ-fluoroalkyl-substituted alkenyl phosphonates with high Z/E selectivity under mild conditions. Furthermore, some products exhibit a synergistic inhibitory effect on porcine epidemic diarrhea virus (PEDV), effectively blocking viral adsorption and replication while preventing PEDV-induced cell apoptosis in vitro.
2026, 37(8): 112162
doi: 10.1016/j.cclet.2025.112162
摘要:
Here an enantioselective total synthesis of bioactive 3-deoxy-epothilone B is reported. Key features of this synthesis include Nelson’s alkaloid-catalyzed asymmetric ketene-aldehyde [2 + 2] cycloaddition to expeditiously construct the froward cis/trans configuration of C6−C8 position in a stereospecific manner and the subsequent allylic transposition nucleophilic addition to forge the C2−C4 unit. Other key steps involve an iridium-catalyzed asymmetric hydrogenation (AH) to introduce the C15 stereogenic center and a rhodium-catalyzed linear selective hydroformylation to install the C1 unit with our catalytic systems. In addition, the highly electrophilic enantioenriched β-lactone is regarded as a potential synthon for modular syntheses of a series of C1−C4 modified epothilones. Further biological activity evaluation indicated significant cytotoxicity of 3-deoxy-epothilone B against a panel of human tumor cell lines.
Here an enantioselective total synthesis of bioactive 3-deoxy-epothilone B is reported. Key features of this synthesis include Nelson’s alkaloid-catalyzed asymmetric ketene-aldehyde [2 + 2] cycloaddition to expeditiously construct the froward cis/trans configuration of C6−C8 position in a stereospecific manner and the subsequent allylic transposition nucleophilic addition to forge the C2−C4 unit. Other key steps involve an iridium-catalyzed asymmetric hydrogenation (AH) to introduce the C15 stereogenic center and a rhodium-catalyzed linear selective hydroformylation to install the C1 unit with our catalytic systems. In addition, the highly electrophilic enantioenriched β-lactone is regarded as a potential synthon for modular syntheses of a series of C1−C4 modified epothilones. Further biological activity evaluation indicated significant cytotoxicity of 3-deoxy-epothilone B against a panel of human tumor cell lines.
2026, 37(8): 112188
doi: 10.1016/j.cclet.2025.112188
摘要:
Transition-metal-catalyzed substitution of propargylic electrophiles with secondary phosphine oxides (SPOs) has emerged as a powerful strategy to phosphorus-containing frameworks. However, precise regiocontrol remains elusive due to competing pathways in allenyl-metal intermediates and SPO tautomerism. Herein, we report a dynamic coordination strategy that leverages the tunable binding modes of SPOs to achieve regiodivergent dienylation of propargylic esters, thereby accessing a diverse range of 1,3-dienyl phosphines. Through fine-tuning of ligands and the strategic use of Brønsted or Lewis acid-assisted catalytic systems, we demonstrate switchable C2- versus C3-selective dienylation, governed by dynamic control over the coordination modes and reactivities of SPOs. Mechanistic studies reveal that the dynamic inner- or outer-sphere coordination dictates the regiochemical outcome, which proceeds via relay catalysis or bimetallic cooperative catalysis pathways, thus offering a rationale for the observed regiodivergence. This method provides a robust and modular platform for synthesizing multisubstituted 1,3-dienyl phosphines with broad substrate scope and excellent regio- and stereoselectivity, underscoring the potential of coordination-controlled reactivity in complex bond-forming processes.
Transition-metal-catalyzed substitution of propargylic electrophiles with secondary phosphine oxides (SPOs) has emerged as a powerful strategy to phosphorus-containing frameworks. However, precise regiocontrol remains elusive due to competing pathways in allenyl-metal intermediates and SPO tautomerism. Herein, we report a dynamic coordination strategy that leverages the tunable binding modes of SPOs to achieve regiodivergent dienylation of propargylic esters, thereby accessing a diverse range of 1,3-dienyl phosphines. Through fine-tuning of ligands and the strategic use of Brønsted or Lewis acid-assisted catalytic systems, we demonstrate switchable C2- versus C3-selective dienylation, governed by dynamic control over the coordination modes and reactivities of SPOs. Mechanistic studies reveal that the dynamic inner- or outer-sphere coordination dictates the regiochemical outcome, which proceeds via relay catalysis or bimetallic cooperative catalysis pathways, thus offering a rationale for the observed regiodivergence. This method provides a robust and modular platform for synthesizing multisubstituted 1,3-dienyl phosphines with broad substrate scope and excellent regio- and stereoselectivity, underscoring the potential of coordination-controlled reactivity in complex bond-forming processes.
2026, 37(8): 112246
doi: 10.1016/j.cclet.2025.112246
摘要:
Aging of Pt in diesel oxidation catalyst (DOC) leads to diminished catalytic activity, presenting a considerable challenge for catalyst regeneration and enhancement. This work investigates on the regeneration of Pt/Al2O3-SiO2 (Pt/AS) catalysts in DOC utilizing the synergistic effect of the indirect non-thermal plasma (INTP) and direct non-thermal plasma (DNTP) to optimize catalytic performance for efficient and stable conversion of gaseous pollutants. The distinctive properties of DNTP-INTP promote the removal of surface particulate matter (PM) and increase the availability of adsorbed oxygen (Oads) on the catalyst surface. Moreover, DNTP effectively reduces the particle size of sintered catalysts by applying a high-energy electric field. This process facilitates the conversion of PtOx to metallic Pt0. Additionally, agglomerated Pt structures can be reverted into regular hexahedral nanoparticles through the synergistic process. The regenerated catalyst demonstrates exceptional catalytic performance and stability, which can rival the performance of newly prepared catalysts. Notably, compared to the aged catalyst, the low-temperature performance improves significantly, with a reduction of 90 ℃ in the temperature at the onset of catalytic activity. These results highlight the considerable potential of plasma-assisted synergistic catalysts regeneration for revitalizing aged DOC within the context of advancing clean energy technologies.
Aging of Pt in diesel oxidation catalyst (DOC) leads to diminished catalytic activity, presenting a considerable challenge for catalyst regeneration and enhancement. This work investigates on the regeneration of Pt/Al2O3-SiO2 (Pt/AS) catalysts in DOC utilizing the synergistic effect of the indirect non-thermal plasma (INTP) and direct non-thermal plasma (DNTP) to optimize catalytic performance for efficient and stable conversion of gaseous pollutants. The distinctive properties of DNTP-INTP promote the removal of surface particulate matter (PM) and increase the availability of adsorbed oxygen (Oads) on the catalyst surface. Moreover, DNTP effectively reduces the particle size of sintered catalysts by applying a high-energy electric field. This process facilitates the conversion of PtOx to metallic Pt0. Additionally, agglomerated Pt structures can be reverted into regular hexahedral nanoparticles through the synergistic process. The regenerated catalyst demonstrates exceptional catalytic performance and stability, which can rival the performance of newly prepared catalysts. Notably, compared to the aged catalyst, the low-temperature performance improves significantly, with a reduction of 90 ℃ in the temperature at the onset of catalytic activity. These results highlight the considerable potential of plasma-assisted synergistic catalysts regeneration for revitalizing aged DOC within the context of advancing clean energy technologies.
2026, 37(8): 112283
doi: 10.1016/j.cclet.2025.112283
摘要:
Solar-driven hydrogen peroxide (H2O2) production presents a sustainable alternative to energy-intensive industrial methods, yet its efficiency using covalent organic frameworks (COFs) suffer from energy loss caused by strong exciton interactions. Herein, we designed COFs with donor-π-acceptor (D-π-A) architectures, using 2,5-dimethoxy-1,4-benzenedicarboxaldehyde as the D unit and optimizing the N-containing π-bridge units. The resulting TAPT–OCH3 COF, incorporating 4,4′,4′'-(1,3,5-triazine-2,4,6-triyl)trianiline as the A unit, demonstrated the extended electron pathways and the reduced exciton recombination, markedly boosting photocatalytic performance. Experimental results revealed that TAPT–OCH3 achieved a solar-to-chemical efficiency of 0.23% and a quantum yield of 2.21% at 420 nm, outperforming most reported COFs and metal-free catalysts. In situ characterization and theoretical calculations revealed that the TAPT–OCH3 enhances charge separation to drive H2O2 production via a 2e- oxygen reduction pathway, while its tailored electronic structure simultaneously improves the 1e- water oxidation process. Crucially, TAPT–OCH3 maintained high efficacy across diverse water sources and continuous-flow reactors under natural sunlight, enabling scalable H2O2 synthesis for water purification. Life cycle assessment confirmed the application stability of this material, underscoring its potential for sustainable environmental remediation. This work establishes a design paradigm for optimizing exciton dynamics in COF, highlighting the critical role of structural design for artificial H2O2 photosynthesis.
Solar-driven hydrogen peroxide (H2O2) production presents a sustainable alternative to energy-intensive industrial methods, yet its efficiency using covalent organic frameworks (COFs) suffer from energy loss caused by strong exciton interactions. Herein, we designed COFs with donor-π-acceptor (D-π-A) architectures, using 2,5-dimethoxy-1,4-benzenedicarboxaldehyde as the D unit and optimizing the N-containing π-bridge units. The resulting TAPT–OCH3 COF, incorporating 4,4′,4′'-(1,3,5-triazine-2,4,6-triyl)trianiline as the A unit, demonstrated the extended electron pathways and the reduced exciton recombination, markedly boosting photocatalytic performance. Experimental results revealed that TAPT–OCH3 achieved a solar-to-chemical efficiency of 0.23% and a quantum yield of 2.21% at 420 nm, outperforming most reported COFs and metal-free catalysts. In situ characterization and theoretical calculations revealed that the TAPT–OCH3 enhances charge separation to drive H2O2 production via a 2e- oxygen reduction pathway, while its tailored electronic structure simultaneously improves the 1e- water oxidation process. Crucially, TAPT–OCH3 maintained high efficacy across diverse water sources and continuous-flow reactors under natural sunlight, enabling scalable H2O2 synthesis for water purification. Life cycle assessment confirmed the application stability of this material, underscoring its potential for sustainable environmental remediation. This work establishes a design paradigm for optimizing exciton dynamics in COF, highlighting the critical role of structural design for artificial H2O2 photosynthesis.
2026, 37(8): 112284
doi: 10.1016/j.cclet.2025.112284
摘要:
Achieving biomimetic leaves with high reflectance and polarization spectral similarity to vegetation is highly desirable. However, the polarization, often masked by the complex compositions of coatings, has long been overlooked. Herein, the reflectance and polarization spectral properties are simultaneously realized via electrostatic adsorption between hypoxanthine (HX) and sodium copper chlorophyllin (SCC). The SCC-doped HX coating exhibits high reflectance spectral similarity to vegetation, with a correlation coefficient of 0.9440 and a spectral angle cosine of 0.9685. Additionally, the degree of linear polarization is reduced by 39.3%. This study provides a reference for obtaining high-performance pigments for biomimetic leaves.
Achieving biomimetic leaves with high reflectance and polarization spectral similarity to vegetation is highly desirable. However, the polarization, often masked by the complex compositions of coatings, has long been overlooked. Herein, the reflectance and polarization spectral properties are simultaneously realized via electrostatic adsorption between hypoxanthine (HX) and sodium copper chlorophyllin (SCC). The SCC-doped HX coating exhibits high reflectance spectral similarity to vegetation, with a correlation coefficient of 0.9440 and a spectral angle cosine of 0.9685. Additionally, the degree of linear polarization is reduced by 39.3%. This study provides a reference for obtaining high-performance pigments for biomimetic leaves.
2026, 37(8): 112285
doi: 10.1016/j.cclet.2025.112285
摘要:
Overcoming the penetration barrier of nanomedicines remains a paramount challenge in antitumor therapy. Apoptotic bodies (ApoBDs), which are naturally generated from apoptotic cells, can mediate a potent neighboring effect by transferring drug to neighboring tumor cells via macropinocytosis. To amplify this process, we developed a tumor microenvironment-responsive nanoplatform (named as AD-NVs@CPP) to selectively enhance chemokine (C-X-C motif) receptor 4 (CXCR4) receptor-stimulated macropinocytosis. This platform was constructed by co-encapsulating doxorubicin (DOX) and the hypoxia-activated prodrug AQ4N into homologous tumor cell membrane-derived nanovesicles (AD-NVs), followed by biomineralization of a calcium phosphate (CaP) shell that incorporated a CXCR4-targeting peptide (RFFE-SHAPAKPVSLSYR). The resultant AD-NVs@CPP exhibited a core-shell structure with a hydrodynamic diameter of ~180 nm and achieved a high peptide encapsulation efficiency of 81.6% ± 8.2%. The CaP shell demonstrated excellent pH-responsive dissolution, releasing ~50% of the peptide within 24 h at pH 6.5 (vs. negligible release at pH 7.4), which consequently promoted cellular uptake and enhanced cytotoxicity under acidic conditions in vitro. Additionally, AD-NVs@CPP-induced ApoBDs served as efficient drug reservoirs, delivering drugs to adjacent cells with an IC50 value of 0.98 µg/mL (in terms of protein concentration). In vivo, AD-NVs@CPP significantly prolonged the blood circulation time (increasing the half-life of DOX compared to the free drug solution) and improved tumor accumulation. Crucially, it enabled programmed drug penetration: AQ4N was selectively delivered into deep hypoxic tumor regions, mediating comprehensive tumor growth inhibition while maintaining a favorable safety profile. This work provides a robust strategy for achieving deep tumor penetration through the synergistic enhancement of macropinocytosis and the ApoBD-mediated neighboring effect.
Overcoming the penetration barrier of nanomedicines remains a paramount challenge in antitumor therapy. Apoptotic bodies (ApoBDs), which are naturally generated from apoptotic cells, can mediate a potent neighboring effect by transferring drug to neighboring tumor cells via macropinocytosis. To amplify this process, we developed a tumor microenvironment-responsive nanoplatform (named as AD-NVs@CPP) to selectively enhance chemokine (C-X-C motif) receptor 4 (CXCR4) receptor-stimulated macropinocytosis. This platform was constructed by co-encapsulating doxorubicin (DOX) and the hypoxia-activated prodrug AQ4N into homologous tumor cell membrane-derived nanovesicles (AD-NVs), followed by biomineralization of a calcium phosphate (CaP) shell that incorporated a CXCR4-targeting peptide (RFFE-SHAPAKPVSLSYR). The resultant AD-NVs@CPP exhibited a core-shell structure with a hydrodynamic diameter of ~180 nm and achieved a high peptide encapsulation efficiency of 81.6% ± 8.2%. The CaP shell demonstrated excellent pH-responsive dissolution, releasing ~50% of the peptide within 24 h at pH 6.5 (vs. negligible release at pH 7.4), which consequently promoted cellular uptake and enhanced cytotoxicity under acidic conditions in vitro. Additionally, AD-NVs@CPP-induced ApoBDs served as efficient drug reservoirs, delivering drugs to adjacent cells with an IC50 value of 0.98 µg/mL (in terms of protein concentration). In vivo, AD-NVs@CPP significantly prolonged the blood circulation time (increasing the half-life of DOX compared to the free drug solution) and improved tumor accumulation. Crucially, it enabled programmed drug penetration: AQ4N was selectively delivered into deep hypoxic tumor regions, mediating comprehensive tumor growth inhibition while maintaining a favorable safety profile. This work provides a robust strategy for achieving deep tumor penetration through the synergistic enhancement of macropinocytosis and the ApoBD-mediated neighboring effect.
2026, 37(8): 112286
doi: 10.1016/j.cclet.2025.112286
摘要:
In this study, a simple N2 plasma strategy was employed to modify the surface of Co3O4, significantly enhancing its efficiency in activating peroxymonosulfate (PMS) for the degradation of tetracycline hydrochloride (TC). Co3O4 treated with plasma for 30 min (Co3O4–30) achieved a TC degradation efficiency of 93.2% within 30 min (k = 0.078 min−1), which was significantly higher than that of the pristine Co3O4 (k = 0.023 min−1). Studies demonstrated that plasma treatment induced the generation of oxygen vacancies (Ov) on the surface of Co3O4, which serve as key active sites during the catalytic process and facilitate the adsorption of PMS to generate singlet oxygen (1O2). As the dominant reactive oxygen species, the steady-state concentration of 1O2 was positively correlated with the TC degradation rate. Additionally, dominated by the non-radical pathway, the PMS/Co3O4–30 system exhibited high selectivity toward electron-rich pollutants as well as strong anti-interference capability against anions and complex water matrices. This study demonstrates that plasma technology serves as a viable approach for defect engineering in catalysts, enabling the selective generation of 1O2 from PMS.
In this study, a simple N2 plasma strategy was employed to modify the surface of Co3O4, significantly enhancing its efficiency in activating peroxymonosulfate (PMS) for the degradation of tetracycline hydrochloride (TC). Co3O4 treated with plasma for 30 min (Co3O4–30) achieved a TC degradation efficiency of 93.2% within 30 min (k = 0.078 min−1), which was significantly higher than that of the pristine Co3O4 (k = 0.023 min−1). Studies demonstrated that plasma treatment induced the generation of oxygen vacancies (Ov) on the surface of Co3O4, which serve as key active sites during the catalytic process and facilitate the adsorption of PMS to generate singlet oxygen (1O2). As the dominant reactive oxygen species, the steady-state concentration of 1O2 was positively correlated with the TC degradation rate. Additionally, dominated by the non-radical pathway, the PMS/Co3O4–30 system exhibited high selectivity toward electron-rich pollutants as well as strong anti-interference capability against anions and complex water matrices. This study demonstrates that plasma technology serves as a viable approach for defect engineering in catalysts, enabling the selective generation of 1O2 from PMS.
2026, 37(8): 112298
doi: 10.1016/j.cclet.2025.112298
摘要:
Selenium (Se) speciation analysis is typically performed using complex and costly hyphenated analytical systems. In this study, we developed a novel strategy for Se speciation using gas chromatography combined with a 3D-printed point discharge micro atomic emission detector (GC-PD-μAED), coupled with chemical vapor generation (CVG) and headspace-solid phase microextraction (HS-SPME), for the simultaneous determination of selenite (Se(Ⅳ)), dimethylselenide (DMSe) and dimethyldiselenide (DMDSe) in aqueous matrices. The method involves derivatization of Se(Ⅳ) to volatile diethylselenide (DEtSe) using NaBEt4, followed by HS-SPME preconcentration of all three Se species prior to GC separation and PD-μAED detection at the Se emission line of 196.03 nm. The optimized method achieved limits of detection (LODs) of 2.34, 0.28 and 0.13 μg/L (as Se) for DMSe, DMDSe and Se(Ⅳ), respectively, with precision (RSD) ranging from 4.6% to 4.9%. The accuracy and practicability of the developed method were demonstrated through speciation analysis of Se in seven water samples with excellent recoveries (90.4%−107.9%). Moreover, this novel approach offers simplified instrumentation, significantly lower costs, and minimal use of consumables while maintaining robust analytical performance comparable to conventional methods, making it particularly valuable for resource-limited settings.
Selenium (Se) speciation analysis is typically performed using complex and costly hyphenated analytical systems. In this study, we developed a novel strategy for Se speciation using gas chromatography combined with a 3D-printed point discharge micro atomic emission detector (GC-PD-μAED), coupled with chemical vapor generation (CVG) and headspace-solid phase microextraction (HS-SPME), for the simultaneous determination of selenite (Se(Ⅳ)), dimethylselenide (DMSe) and dimethyldiselenide (DMDSe) in aqueous matrices. The method involves derivatization of Se(Ⅳ) to volatile diethylselenide (DEtSe) using NaBEt4, followed by HS-SPME preconcentration of all three Se species prior to GC separation and PD-μAED detection at the Se emission line of 196.03 nm. The optimized method achieved limits of detection (LODs) of 2.34, 0.28 and 0.13 μg/L (as Se) for DMSe, DMDSe and Se(Ⅳ), respectively, with precision (RSD) ranging from 4.6% to 4.9%. The accuracy and practicability of the developed method were demonstrated through speciation analysis of Se in seven water samples with excellent recoveries (90.4%−107.9%). Moreover, this novel approach offers simplified instrumentation, significantly lower costs, and minimal use of consumables while maintaining robust analytical performance comparable to conventional methods, making it particularly valuable for resource-limited settings.
2026, 37(8): 112299
doi: 10.1016/j.cclet.2025.112299
摘要:
Widespread arsenic contamination in aquatic environments poses a major threat to human health and ecosystems, underscoring the urgent need for effective and selective remediation strategies. However, conventional technologies often suffer from reduced efficiency due to strong competition from coexisting anions such as phosphate, limiting their real-world applicability. In this study, we present a pH-regulated strategy for selective arsenate removal using ferric oxide (α-Fe2O3), a low-cost, non-toxic, and naturally abundant material. By integrating batch adsorption experiments, in-situ ATR-FTIR spectroscopy, two-dimensional correlation spectroscopy, and density functional theory simulations, we demonstrate that acidic conditions significantly enhance arsenate selectivity by promoting protonation-induced surface complexation. Protonation strengthens hydrogen bonding and facilitates a transition from monodentate to bidentate coordination, improving arsenate binding. We further identify the Fe-Fe interatomic distance as a key structural parameter governing complexation geometry and selectivity: Shorter distances (< 3.27 Å) enable dual coordination, while longer distances (~5.10 Å) restrict it. These mechanistic insights highlight the pivotal role of surface structure and protonation in dictating competitive adsorption outcomes. Overall, these findings provide a mechanistic framework for understanding and optimizing arsenate selectivity in multi-anion systems. By leveraging naturally occurring ferric oxide and simple pH adjustment, this work offers a scalable and practical approach to arsenic remediation in phosphate-rich waters.
Widespread arsenic contamination in aquatic environments poses a major threat to human health and ecosystems, underscoring the urgent need for effective and selective remediation strategies. However, conventional technologies often suffer from reduced efficiency due to strong competition from coexisting anions such as phosphate, limiting their real-world applicability. In this study, we present a pH-regulated strategy for selective arsenate removal using ferric oxide (α-Fe2O3), a low-cost, non-toxic, and naturally abundant material. By integrating batch adsorption experiments, in-situ ATR-FTIR spectroscopy, two-dimensional correlation spectroscopy, and density functional theory simulations, we demonstrate that acidic conditions significantly enhance arsenate selectivity by promoting protonation-induced surface complexation. Protonation strengthens hydrogen bonding and facilitates a transition from monodentate to bidentate coordination, improving arsenate binding. We further identify the Fe-Fe interatomic distance as a key structural parameter governing complexation geometry and selectivity: Shorter distances (< 3.27 Å) enable dual coordination, while longer distances (~5.10 Å) restrict it. These mechanistic insights highlight the pivotal role of surface structure and protonation in dictating competitive adsorption outcomes. Overall, these findings provide a mechanistic framework for understanding and optimizing arsenate selectivity in multi-anion systems. By leveraging naturally occurring ferric oxide and simple pH adjustment, this work offers a scalable and practical approach to arsenic remediation in phosphate-rich waters.
2026, 37(8): 112310
doi: 10.1016/j.cclet.2025.112310
摘要:
Metal-organic frameworks (MOFs) hold promise as electrochemiluminescence (ECL) emitters but are limited by high operating potentials and low efficiencies, leading to substantial electrochemical interference and reduced sensitivity. Here, we report a defect-rich Fe(Ⅲ)-based MOF (De-Fe(Ⅲ)-MOF) that exhibits highly efficient ECL triggered at an ultralow potential (-0.3 V vs. Ag/AgCl). Prepared using electron-deficient 3,4,9,10-perylenetetracarboxylic acid (PTCA) as ligands and H3PO4 as the acid modulator, De-Fe(Ⅲ)-MOF features abundant open-metal catalytic sites, which achieves an exceptional cathodic ECL efficiency of 553.06%, even using classical Ru(bpy)3Cl2/S2O82− system triggered at -1.2 V as a standard. This outstanding performance is attributed to three key factors: (1) The abundant Fe(Ⅲ) active sites that efficiently catalyze S2O82− to produce SO4•- radicals at ultralow potentials; (2) the electron-deficient PTCA ligand that enables simultaneous reduction at similarly low potentials; and (3) the unified porous frame that facilitates efficient electron transfer through an ultrashort pathway, enhancing ECL efficiency. These features collectively minimize electrochemical side reactions and significantly enhance the sensitivity of the sensing platform. To demonstrate its practical application, we constructed an ECL sensor for carboxylesterase activity, achieving a limit of detection of 6.6 × 10–7 U/L with minimal interference.
Metal-organic frameworks (MOFs) hold promise as electrochemiluminescence (ECL) emitters but are limited by high operating potentials and low efficiencies, leading to substantial electrochemical interference and reduced sensitivity. Here, we report a defect-rich Fe(Ⅲ)-based MOF (De-Fe(Ⅲ)-MOF) that exhibits highly efficient ECL triggered at an ultralow potential (-0.3 V vs. Ag/AgCl). Prepared using electron-deficient 3,4,9,10-perylenetetracarboxylic acid (PTCA) as ligands and H3PO4 as the acid modulator, De-Fe(Ⅲ)-MOF features abundant open-metal catalytic sites, which achieves an exceptional cathodic ECL efficiency of 553.06%, even using classical Ru(bpy)3Cl2/S2O82− system triggered at -1.2 V as a standard. This outstanding performance is attributed to three key factors: (1) The abundant Fe(Ⅲ) active sites that efficiently catalyze S2O82− to produce SO4•- radicals at ultralow potentials; (2) the electron-deficient PTCA ligand that enables simultaneous reduction at similarly low potentials; and (3) the unified porous frame that facilitates efficient electron transfer through an ultrashort pathway, enhancing ECL efficiency. These features collectively minimize electrochemical side reactions and significantly enhance the sensitivity of the sensing platform. To demonstrate its practical application, we constructed an ECL sensor for carboxylesterase activity, achieving a limit of detection of 6.6 × 10–7 U/L with minimal interference.
2026, 37(8): 112321
doi: 10.1016/j.cclet.2025.112321
摘要:
High-salinity wastewater, especially reverse osmosis (RO) concentrate, is difficult to treat due to severe microbial inhibition and the presence of refractory organics. Herein, a salinity-tolerant bacterium (Chryseobacterium sp.) was isolated and applied in combination with ionizing irradiation to develop an efficient coupled process for RO concentrate treatment. The strain metabolically degraded phenol, p-cresol, indole, and benzoic acid, and transcriptomic analysis revealed that salt tolerance was associated with the synthesis of specific salt-tolerant proteins and enzymes (i.e., branched-chain amino acid). Although elevated chloride and sulfate concentrations reduced the phenol removal rate, complete degradation was achieved. The coupled process achieved up to 78.3% COD removal and completely inactivated Chryseobacterium sp. in the effluent, ensuring biosafety. This study provides a promising strategy integrating halotolerant biodegradation and advanced oxidation for efficient treatment of high-salinity wastewater.
High-salinity wastewater, especially reverse osmosis (RO) concentrate, is difficult to treat due to severe microbial inhibition and the presence of refractory organics. Herein, a salinity-tolerant bacterium (Chryseobacterium sp.) was isolated and applied in combination with ionizing irradiation to develop an efficient coupled process for RO concentrate treatment. The strain metabolically degraded phenol, p-cresol, indole, and benzoic acid, and transcriptomic analysis revealed that salt tolerance was associated with the synthesis of specific salt-tolerant proteins and enzymes (i.e., branched-chain amino acid). Although elevated chloride and sulfate concentrations reduced the phenol removal rate, complete degradation was achieved. The coupled process achieved up to 78.3% COD removal and completely inactivated Chryseobacterium sp. in the effluent, ensuring biosafety. This study provides a promising strategy integrating halotolerant biodegradation and advanced oxidation for efficient treatment of high-salinity wastewater.
2026, 37(8): 112322
doi: 10.1016/j.cclet.2025.112322
摘要:
Linear mRNA-encoded bispecific T cell engagers (BiTEs) have shown promising efficacy in cancer treatment; however, their clinical translation remains constrained by poor stability and transient protein expression. To overcome these limitations, we engineered a circular RNA (cRNA) encoding PD-L1×CD3 BiTEs using permuted intron-exon splicing and CVB3-IRES elements, and encapsulated it into novel ionizable lipid nanoparticles (D1LNPs) synthesized via a streamlined one-step reaction. This platform, termed D1LNP@cRNABiTEs, achieved robust and sustained in vivo expression of the BiTEs, significantly outperforming conventional linear mRNA formulations. In murine models of colorectal cancer, monotherapy with D1LNP@cRNABiTEs potently inhibited tumor growth, enhanced CD8+ T-cell infiltration into the tumor microenvironment, and elevated levels of proinflammatory cytokines. Furthermore, ELISpot analysis confirmed the enhancement of systemic antigen-specific T cell responses. The D1LNPs delivery system also demonstrated excellent stability and favorable safety profile. In conclusion, our study provides compelling evidence for the D1LNPs@cRNA platform as a potent and scalable strategy for cancer immunotherapy, effectively addressing key challenges of RNA stability and delivery.
Linear mRNA-encoded bispecific T cell engagers (BiTEs) have shown promising efficacy in cancer treatment; however, their clinical translation remains constrained by poor stability and transient protein expression. To overcome these limitations, we engineered a circular RNA (cRNA) encoding PD-L1×CD3 BiTEs using permuted intron-exon splicing and CVB3-IRES elements, and encapsulated it into novel ionizable lipid nanoparticles (D1LNPs) synthesized via a streamlined one-step reaction. This platform, termed D1LNP@cRNABiTEs, achieved robust and sustained in vivo expression of the BiTEs, significantly outperforming conventional linear mRNA formulations. In murine models of colorectal cancer, monotherapy with D1LNP@cRNABiTEs potently inhibited tumor growth, enhanced CD8+ T-cell infiltration into the tumor microenvironment, and elevated levels of proinflammatory cytokines. Furthermore, ELISpot analysis confirmed the enhancement of systemic antigen-specific T cell responses. The D1LNPs delivery system also demonstrated excellent stability and favorable safety profile. In conclusion, our study provides compelling evidence for the D1LNPs@cRNA platform as a potent and scalable strategy for cancer immunotherapy, effectively addressing key challenges of RNA stability and delivery.
2026, 37(8): 112327
doi: 10.1016/j.cclet.2025.112327
摘要:
Colorectal cancer (CRC) is a common malignant tumor of the digestive tract and has become a serious threat to human health worldwide. As an important part of systems biology, metabolomics is an effective tool to study the pathogenesis of diseases and search for potential biomarkers. Particularly, liquid chromatography-high resolution mass spectrometry (LC-HRMS)-based untargeted metabolomics plays crucial roles in the discovery of CRC biomarkers. However, previous studies still have some limitations, such as small sample cohorts, lack of standardized procedures and independent validation. In this study, LC-HRMS based non-targeted metabolomics analysis was performed to acquire metabolic profiling of 156 urine samples from healthy controls (HC, n = 43), colorectal adenoma patients (CRA, n = 51) and CRC patients (n = 62) to reveal metabolite disturbance, and then differential metabolites were verified in another sample set including 200 urine samples. Compared with CRA patients and HC, the levels of some lipids and lipid-like molecules, organic acids and derivatives, and organic oxygen compounds were increased, whereas the levels of most amino acids and derivatives, benzenoids, lipids and lipid-like molecules, nucleosides, nucleotides, and analogues, organic acids and derivatives, organoheterocyclic compounds as well as phenylpropanoids and polyketides were significantly decreased in CRC patients. Moreover, a potential biomarkers panel consisting of 4 metabolites was defined and validated for CRC diagnosis, and high area under the curve (0.963 for distinguishing CRC from non-CRC subjects) as well as good specificity and sensitivity were obtained. Although further extensive validation with larger sample sizes in different populations is needed before it can be recommended for clinical use, clinical diagnosis of CRC in the future may benefit from the biomarkers panel developed in this study.
Colorectal cancer (CRC) is a common malignant tumor of the digestive tract and has become a serious threat to human health worldwide. As an important part of systems biology, metabolomics is an effective tool to study the pathogenesis of diseases and search for potential biomarkers. Particularly, liquid chromatography-high resolution mass spectrometry (LC-HRMS)-based untargeted metabolomics plays crucial roles in the discovery of CRC biomarkers. However, previous studies still have some limitations, such as small sample cohorts, lack of standardized procedures and independent validation. In this study, LC-HRMS based non-targeted metabolomics analysis was performed to acquire metabolic profiling of 156 urine samples from healthy controls (HC, n = 43), colorectal adenoma patients (CRA, n = 51) and CRC patients (n = 62) to reveal metabolite disturbance, and then differential metabolites were verified in another sample set including 200 urine samples. Compared with CRA patients and HC, the levels of some lipids and lipid-like molecules, organic acids and derivatives, and organic oxygen compounds were increased, whereas the levels of most amino acids and derivatives, benzenoids, lipids and lipid-like molecules, nucleosides, nucleotides, and analogues, organic acids and derivatives, organoheterocyclic compounds as well as phenylpropanoids and polyketides were significantly decreased in CRC patients. Moreover, a potential biomarkers panel consisting of 4 metabolites was defined and validated for CRC diagnosis, and high area under the curve (0.963 for distinguishing CRC from non-CRC subjects) as well as good specificity and sensitivity were obtained. Although further extensive validation with larger sample sizes in different populations is needed before it can be recommended for clinical use, clinical diagnosis of CRC in the future may benefit from the biomarkers panel developed in this study.
2026, 37(8): 112335
doi: 10.1016/j.cclet.2025.112335
摘要:
The matrix deposition method is one of the critical factors influencing the performance of matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI), as it determines matrix crystal sizes and coating uniformity, thereby impacting ionization efficiency and spatial resolution. Currently, automated sprayers are widely utilized for matrix deposition due to their convenience, speed, and robust reproducibility. However, existing automated spraying techniques typically produce micrometer-sized crystal particles, limiting high-resolution imaging quality and sensitivity. To overcome this, we introduce cluster airflow assisted matrix coating (CAAMC), which employs multiple cluster airflows to achieve a more uniform dispersion and atomization of the matrix droplets, resulting in nano-sized crystal particles—an advance beyond traditional deposition methods. This method represented the first successful automatic spray method for nano-matrix crystallization, surpassing regular-one channel pneumatic spraying and sublimation in producing smaller, more homogeneous crystals. Application to rat brain tissues and single cells demonstrates that CAAMC significantly enhances small molecule and lipid detection efficiency and imaging quality (lateral resolution of 5 μm), exceeding the performance of regular-one channel pneumatic spraying and sublimation. Overall, CAAMC significantly broadens the potential of automated matrix spraying techniques in high-resolution MALDI-MSI.
The matrix deposition method is one of the critical factors influencing the performance of matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI), as it determines matrix crystal sizes and coating uniformity, thereby impacting ionization efficiency and spatial resolution. Currently, automated sprayers are widely utilized for matrix deposition due to their convenience, speed, and robust reproducibility. However, existing automated spraying techniques typically produce micrometer-sized crystal particles, limiting high-resolution imaging quality and sensitivity. To overcome this, we introduce cluster airflow assisted matrix coating (CAAMC), which employs multiple cluster airflows to achieve a more uniform dispersion and atomization of the matrix droplets, resulting in nano-sized crystal particles—an advance beyond traditional deposition methods. This method represented the first successful automatic spray method for nano-matrix crystallization, surpassing regular-one channel pneumatic spraying and sublimation in producing smaller, more homogeneous crystals. Application to rat brain tissues and single cells demonstrates that CAAMC significantly enhances small molecule and lipid detection efficiency and imaging quality (lateral resolution of 5 μm), exceeding the performance of regular-one channel pneumatic spraying and sublimation. Overall, CAAMC significantly broadens the potential of automated matrix spraying techniques in high-resolution MALDI-MSI.
2026, 37(8): 112343
doi: 10.1016/j.cclet.2025.112343
摘要:
Oxalic acid (OA) promotes the production of reactive oxygen species (ROS) and the degradation of pollutants, while it also enhances the reduction of trivalent iron (Fe(Ⅲ)) in homogeneous Fenton systems. However, due to the coexistence of Fe(Ⅱ) and OA-Fe(Ⅲ)/hydroperoxide complex, the generation pathways of ROS and degradation mechanisms of pollutants have not been clarified. In this work, bisphenol A (BPA) was selected and its degradation mechanisms in the OA/Fe(Ⅲ)/sodium percarbonate (SPC) system were investigated. Results showed that 99% of BPA degradation in OA/Fe(Ⅲ)/SPC system, which was higher than that of single Fe(Ⅲ) and SPC system (degradation ratio < 10%). OA promoted the formation of carbonate radicals (CO3•-) and hydroxyl radicals (•OH). There was no remarkable relationship between the degradation ratio of BPA and the change of Fe(Ⅱ) concentration, suggesting that the reduction properties of OA was not the direct cause of BPA degradation. By further analysis, the chelation of Fe(Ⅲ) and OA resulted in an enormous potential difference between Fe(Ⅱ) and Fe(Ⅲ)-OA complex, which was more favorable for accepting electrons from Fe(Ⅱ) intermediate, and forming more reactive ferrous complexes; moreover, iron oxalate (Fe2(C2O4)3) enhanced BPA degradation in the Fe(Ⅱ)/SPC system, which also evidenced the above findings. Under neutral conditions (pH 7.0), peroxy intermediate (OA-Fe(Ⅲ)-OOH) complex also contributed to CO3•-/•OH production and enhanced BPA degradation. These findings highlight the important role of OA in degradation of pollutants, which provides valuable insights for designing sustainable Fenton-based advanced oxidation processes.
Oxalic acid (OA) promotes the production of reactive oxygen species (ROS) and the degradation of pollutants, while it also enhances the reduction of trivalent iron (Fe(Ⅲ)) in homogeneous Fenton systems. However, due to the coexistence of Fe(Ⅱ) and OA-Fe(Ⅲ)/hydroperoxide complex, the generation pathways of ROS and degradation mechanisms of pollutants have not been clarified. In this work, bisphenol A (BPA) was selected and its degradation mechanisms in the OA/Fe(Ⅲ)/sodium percarbonate (SPC) system were investigated. Results showed that 99% of BPA degradation in OA/Fe(Ⅲ)/SPC system, which was higher than that of single Fe(Ⅲ) and SPC system (degradation ratio < 10%). OA promoted the formation of carbonate radicals (CO3•-) and hydroxyl radicals (•OH). There was no remarkable relationship between the degradation ratio of BPA and the change of Fe(Ⅱ) concentration, suggesting that the reduction properties of OA was not the direct cause of BPA degradation. By further analysis, the chelation of Fe(Ⅲ) and OA resulted in an enormous potential difference between Fe(Ⅱ) and Fe(Ⅲ)-OA complex, which was more favorable for accepting electrons from Fe(Ⅱ) intermediate, and forming more reactive ferrous complexes; moreover, iron oxalate (Fe2(C2O4)3) enhanced BPA degradation in the Fe(Ⅱ)/SPC system, which also evidenced the above findings. Under neutral conditions (pH 7.0), peroxy intermediate (OA-Fe(Ⅲ)-OOH) complex also contributed to CO3•-/•OH production and enhanced BPA degradation. These findings highlight the important role of OA in degradation of pollutants, which provides valuable insights for designing sustainable Fenton-based advanced oxidation processes.
2026, 37(8): 112353
doi: 10.1016/j.cclet.2025.112353
摘要:
Heavy metals complexed with organic reagents in wastewater jeopardize environmental safety, resist conventional removal methods, but are also valuable metallic resources. Herein, a novel fissured-phosphorylated zero-valent iron (P-ZVIbm&ln) was synthesized via mechanochemical phosphorylation and liquid-nitrogen-quenching, and applied to benzohydroxamic acid-complexed Cu(Ⅱ) (Cu(Ⅱ)-BHA) degradation and synchronous copper recovery. During mechanochemical phosphorylation, a ferrous phosphate shell with abundant surface ferrous (≡Fe2+) was constructed on ZVI, which facilitated the activation of molecular oxygen into reactive oxygen species (ROS) for Cu(Ⅱ)-BHA degradation. Moreover, the subsequent liquid-nitrogen-quenching created surface cracks for more Fe0 cores exposure, which triggered the comproportionation reaction (Fe0 + 2Fe3+ → 3Fe2+), thereby strengthening Fe2+ regeneration and sustainable molecular oxygen activation for efficient oxidative decomplexation and metal recovery. In the P-ZVIbm&ln/Cu(Ⅱ)-BHA decontamination process, nearly 100% of Cu was recovered and BHA was degraded, while P-ZVIbm&ln showed excellent cyclic reaction performance. Through diverse experiments and density functional theory (DFT) calculations, researchers shed light on the mechanism. Meanwhile, the P-ZVIbm&ln could effectively treat other metal-BHA complexes (e.g., Cr(Ⅲ), Mn(Ⅱ), Ni(Ⅱ), Ag(Ⅰ), Cd(Ⅱ), and Pb(Ⅱ)) and actual mine wastewater containing Cu(Ⅱ) complexes with satisfactory metal recovery, showing promising application prospects in treatment of heavy-metal complex wastewater and sustainable development.
Heavy metals complexed with organic reagents in wastewater jeopardize environmental safety, resist conventional removal methods, but are also valuable metallic resources. Herein, a novel fissured-phosphorylated zero-valent iron (P-ZVIbm&ln) was synthesized via mechanochemical phosphorylation and liquid-nitrogen-quenching, and applied to benzohydroxamic acid-complexed Cu(Ⅱ) (Cu(Ⅱ)-BHA) degradation and synchronous copper recovery. During mechanochemical phosphorylation, a ferrous phosphate shell with abundant surface ferrous (≡Fe2+) was constructed on ZVI, which facilitated the activation of molecular oxygen into reactive oxygen species (ROS) for Cu(Ⅱ)-BHA degradation. Moreover, the subsequent liquid-nitrogen-quenching created surface cracks for more Fe0 cores exposure, which triggered the comproportionation reaction (Fe0 + 2Fe3+ → 3Fe2+), thereby strengthening Fe2+ regeneration and sustainable molecular oxygen activation for efficient oxidative decomplexation and metal recovery. In the P-ZVIbm&ln/Cu(Ⅱ)-BHA decontamination process, nearly 100% of Cu was recovered and BHA was degraded, while P-ZVIbm&ln showed excellent cyclic reaction performance. Through diverse experiments and density functional theory (DFT) calculations, researchers shed light on the mechanism. Meanwhile, the P-ZVIbm&ln could effectively treat other metal-BHA complexes (e.g., Cr(Ⅲ), Mn(Ⅱ), Ni(Ⅱ), Ag(Ⅰ), Cd(Ⅱ), and Pb(Ⅱ)) and actual mine wastewater containing Cu(Ⅱ) complexes with satisfactory metal recovery, showing promising application prospects in treatment of heavy-metal complex wastewater and sustainable development.
2026, 37(8): 112363
doi: 10.1016/j.cclet.2026.112363
摘要:
The development of highly sensitive electrocatalysts for the electrochemical detection of ortho-nitrophenol (ONP) is critical for environmental monitoring due to its high toxicity in water environment. Herein, a novel electronic configuration engineering on CoSeO3/AlO(OH) heterostructure with precisely modulated d-band centers is successfully designed. Crucially, a negative shift in the d-band center enhances the catalysis and adsorption ability of the heterostructure. Benefiting from the electron transfer behavior from AlO(OH) to CoSeO3, the electrocatalyst exhibits exceptional ONP sensing performance, achieving an ultrahigh sensitivity of 0.499 μA L μmol-1 and a record-low detection limit of 5.353 nmol/L. Furthermore, the experimental characterizations and density functional theory (DFT) calculations reveal that the heterostructure-induced d-band center downshifting optimizes the adsorption strength of ONP, further accelerating the electrochemical redox kinetics. The CoSeO3/AlO(OH) also demonstrates good stability, anti-interference capabilities, and successful application in detecting ONP in real water samples. This study offers a promising strategy for designing advanced electrochemical sensors through heterointerface-based electronic structure engineering.
The development of highly sensitive electrocatalysts for the electrochemical detection of ortho-nitrophenol (ONP) is critical for environmental monitoring due to its high toxicity in water environment. Herein, a novel electronic configuration engineering on CoSeO3/AlO(OH) heterostructure with precisely modulated d-band centers is successfully designed. Crucially, a negative shift in the d-band center enhances the catalysis and adsorption ability of the heterostructure. Benefiting from the electron transfer behavior from AlO(OH) to CoSeO3, the electrocatalyst exhibits exceptional ONP sensing performance, achieving an ultrahigh sensitivity of 0.499 μA L μmol-1 and a record-low detection limit of 5.353 nmol/L. Furthermore, the experimental characterizations and density functional theory (DFT) calculations reveal that the heterostructure-induced d-band center downshifting optimizes the adsorption strength of ONP, further accelerating the electrochemical redox kinetics. The CoSeO3/AlO(OH) also demonstrates good stability, anti-interference capabilities, and successful application in detecting ONP in real water samples. This study offers a promising strategy for designing advanced electrochemical sensors through heterointerface-based electronic structure engineering.
2026, 37(8): 112416
doi: 10.1016/j.cclet.2026.112416
摘要:
The iron-based pyrophosphate Na2FeP2O7 (NFPO) exhibits remarkable advantages including economic viability, exceptional structural stability, and outstanding safety characteristics. Nevertheless, the widespread implementation is fundamentally constrained by its poor inherent electronic conductivity and inadequate Na+ transport kinetics. This work employs a Cu doping strategy to achieve systematic electrochemical optimization through inducing local lattice distortions. The optimized Na2Fe0.97Cu0.03P2O7@C (0.03Cu-NFPO@C) composite delivers an impressive specific capacity of 91.32 mAh/g at 0.05 C and exhibits remarkable rate capability of 39.07 mAh/g at 50 C, whereas pristine NFPO@C merely provides 24.12 mAh/g. Furthermore, 0.03Cu-NFPO@C demonstrates extraordinary cycling stability, retaining 86.40% capacity after 12, 000 cycles at 40 C. Structural characterization through in-situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) confirms that Cu doping effectively stabilizes the crystal framework, modifies Fe coordination environments and shortens Fe-O bond lengths. Theory calculations demonstrate that Cu doping reduces the band gap and lowers Na+ diffusion barriers, thereby optimizing intrinsic electronic conductivity and ion transport kinetics. This study introduces an innovative methodology for designing polyanionic cathodes, accelerating the commercialization of sodium-ion batteries for grid-scale energy storage.
The iron-based pyrophosphate Na2FeP2O7 (NFPO) exhibits remarkable advantages including economic viability, exceptional structural stability, and outstanding safety characteristics. Nevertheless, the widespread implementation is fundamentally constrained by its poor inherent electronic conductivity and inadequate Na+ transport kinetics. This work employs a Cu doping strategy to achieve systematic electrochemical optimization through inducing local lattice distortions. The optimized Na2Fe0.97Cu0.03P2O7@C (0.03Cu-NFPO@C) composite delivers an impressive specific capacity of 91.32 mAh/g at 0.05 C and exhibits remarkable rate capability of 39.07 mAh/g at 50 C, whereas pristine NFPO@C merely provides 24.12 mAh/g. Furthermore, 0.03Cu-NFPO@C demonstrates extraordinary cycling stability, retaining 86.40% capacity after 12, 000 cycles at 40 C. Structural characterization through in-situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) confirms that Cu doping effectively stabilizes the crystal framework, modifies Fe coordination environments and shortens Fe-O bond lengths. Theory calculations demonstrate that Cu doping reduces the band gap and lowers Na+ diffusion barriers, thereby optimizing intrinsic electronic conductivity and ion transport kinetics. This study introduces an innovative methodology for designing polyanionic cathodes, accelerating the commercialization of sodium-ion batteries for grid-scale energy storage.
2026, 37(8): 112429
doi: 10.1016/j.cclet.2026.112429
摘要:
We present the synthesis and host-guest complexation of endo-functionalized shape-persistent hexa(ethynylpyridine) macrocycles (Py6MCs). The challenging macrocyclization of linear hexapyridine precursors was achieved by using catalytic amount of PdCl2(PPh3)2 and stoichiometric CuI in the Sonogashira reaction, or with K2CO3 as an additive under copper-free conditions. Single-crystal X-ray diffraction revealed that Py6MCs with different side chains all feature a near-planar framework, with notable flexibility to adopt chair-like or boat-like conformations. The polar and electron-rich cavities of Py6MCs render them attractive hosts for cationic guests. 1H NMR and fluorescence titrations showed that Py6MC1 and Py6MC2 formed 1:1 complexes with N-methyl pyridinium and quaternary ammonium cations, and high affinity (up to 3.1 × 105 L/mol) was achieved for cations of distinct shapes and sizes. Density functional theory (DFT) calculations showed that Py6MC readily deforms to complement the structures of different guests, demonstrating a high level of adaptivity.
We present the synthesis and host-guest complexation of endo-functionalized shape-persistent hexa(ethynylpyridine) macrocycles (Py6MCs). The challenging macrocyclization of linear hexapyridine precursors was achieved by using catalytic amount of PdCl2(PPh3)2 and stoichiometric CuI in the Sonogashira reaction, or with K2CO3 as an additive under copper-free conditions. Single-crystal X-ray diffraction revealed that Py6MCs with different side chains all feature a near-planar framework, with notable flexibility to adopt chair-like or boat-like conformations. The polar and electron-rich cavities of Py6MCs render them attractive hosts for cationic guests. 1H NMR and fluorescence titrations showed that Py6MC1 and Py6MC2 formed 1:1 complexes with N-methyl pyridinium and quaternary ammonium cations, and high affinity (up to 3.1 × 105 L/mol) was achieved for cations of distinct shapes and sizes. Density functional theory (DFT) calculations showed that Py6MC readily deforms to complement the structures of different guests, demonstrating a high level of adaptivity.
2026, 37(8): 112448
doi: 10.1016/j.cclet.2026.112448
摘要:
In this work, a series of novel non-nucleoside reverse transcriptase inhibitors featuring pyridine-difluoro/dimethylaniline fragment and 4-aminepiperidine moiety were synthesized based on structure-based design strategy. Among these, the dimethyl-substituted analogue 20m, characterized by a larger dihedral angle, emerged as the most potent inhibitor against wild-type (WT) human immunodeficiency virus-1 (HIV-1) as well as multiple resistant strains. Compound 20m exhibited remarkable antiviral activity with median effect concentration (EC50) values of 0.003 µmol/L (WT), 0.011 µmol/L (L100I), 0.001 µmol/L (K103N), 0.006 µmol/L (Y181C), 0.108 µmol/L (Y188L), 0.008 µmol/L (E138K), 0.196 µmol/L (F227L + V106A), and 0.032 µmol/L (Y181C + K103N), consistently outperforming efavirenz (EFV). Notably, 20m also demonstrated dramatically enhanced aqueous solubility, reaching >3954.5 µg/mL in phosphate buffer at pH 4.5 and >7380.6 µg/mL at pH 2.0, far exceeding that of etravirine (ETR). Collectively, these findings lay a robust foundation for the future optimization and development of next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs).
In this work, a series of novel non-nucleoside reverse transcriptase inhibitors featuring pyridine-difluoro/dimethylaniline fragment and 4-aminepiperidine moiety were synthesized based on structure-based design strategy. Among these, the dimethyl-substituted analogue 20m, characterized by a larger dihedral angle, emerged as the most potent inhibitor against wild-type (WT) human immunodeficiency virus-1 (HIV-1) as well as multiple resistant strains. Compound 20m exhibited remarkable antiviral activity with median effect concentration (EC50) values of 0.003 µmol/L (WT), 0.011 µmol/L (L100I), 0.001 µmol/L (K103N), 0.006 µmol/L (Y181C), 0.108 µmol/L (Y188L), 0.008 µmol/L (E138K), 0.196 µmol/L (F227L + V106A), and 0.032 µmol/L (Y181C + K103N), consistently outperforming efavirenz (EFV). Notably, 20m also demonstrated dramatically enhanced aqueous solubility, reaching >3954.5 µg/mL in phosphate buffer at pH 4.5 and >7380.6 µg/mL at pH 2.0, far exceeding that of etravirine (ETR). Collectively, these findings lay a robust foundation for the future optimization and development of next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs).
2026, 37(8): 112568
doi: 10.1016/j.cclet.2026.112568
摘要:
White-light organic molecules (WLOMs) exhibit distinct advantages over multi-component systems, such as good reproducibility and high long-term stability. However, the complex synthesis method and the unsatisfactory CIE coordinates hinder their further application. To meet this challenge, a series of novel white-light-emitting single-molecule compounds (BTP-Phs) based on the benzothiazolopyridinone skeleton were rationally designed and synthesized by modulating the donor-acceptor (D-A) structure of the molecules. The study of the structure-spectra relationship indicated that the strong electron-donating ability of the aromatic substituents and the synergistic effect of the extended π-conjugated system enhanced the intramolecular charge transfer (ICT), which reduces the energy gap of the molecules and favors the long-wavelength emission of BTP-Phs. Notably, ideal white light emission (0.31, 0.34) was achieved through the aldehyde-gemdiol equilibrium in mixed solvents. The emission color could be finely tuned by solvent composition, excitation wavelength and concentration. In addition, a fluorescent ink was developed based on BTP-CHO-OPh as a functional material, which could realize information storage and encryption through QR codes or ASCII binary encoding. This study not only provides valuable design strategies for constructing WLOMs based on aldehyde-geminal diol equilibrium, but also highlights their potential in the field of secure information technology.
White-light organic molecules (WLOMs) exhibit distinct advantages over multi-component systems, such as good reproducibility and high long-term stability. However, the complex synthesis method and the unsatisfactory CIE coordinates hinder their further application. To meet this challenge, a series of novel white-light-emitting single-molecule compounds (BTP-Phs) based on the benzothiazolopyridinone skeleton were rationally designed and synthesized by modulating the donor-acceptor (D-A) structure of the molecules. The study of the structure-spectra relationship indicated that the strong electron-donating ability of the aromatic substituents and the synergistic effect of the extended π-conjugated system enhanced the intramolecular charge transfer (ICT), which reduces the energy gap of the molecules and favors the long-wavelength emission of BTP-Phs. Notably, ideal white light emission (0.31, 0.34) was achieved through the aldehyde-gemdiol equilibrium in mixed solvents. The emission color could be finely tuned by solvent composition, excitation wavelength and concentration. In addition, a fluorescent ink was developed based on BTP-CHO-OPh as a functional material, which could realize information storage and encryption through QR codes or ASCII binary encoding. This study not only provides valuable design strategies for constructing WLOMs based on aldehyde-geminal diol equilibrium, but also highlights their potential in the field of secure information technology.
2026, 37(8): 112623
doi: 10.1016/j.cclet.2026.112623
摘要:
Equilateral triangular lattices (TLs) with antiferromagnetic interactions are ideal templates for inducing magnetic frustration, offering a platform to explore exotic quantum spin states that are crucial for advancing quantum science and technology. However, few examples meet these structural criteria, and even fewer realize these fascinating physical properties. We report four novel equilateral TL magnets realized through a crystal-symmetry-protected molecular-brick strategy. By deliberately selecting a high-symmetry nonmagnetic structural template and incorporating magnetic molecular building blocks, magnetic ions are geometrically constrained by three-fold rotational symmetry within the a-b plane, enforcing an ideal equilateral TL and turning on magnetism in a nonmagnetic structural template. Magnetic susceptibility and specific heat measurements reveal a long-range magnetic ordering in BaCoBe2(BO3)2F2 around 180 mK, while BaNiBe2(BO3)2F2 remains disordered at 140 mK. Furthermore, crystal orbital Hamilton population analysis shows that different molecular bricks exhibit distinct bonding characteristics, resulting in diverse magnetic properties. Our results demonstrate that the molecular-brick chemical strategy offers valuable insights into the investigation of geometrically frustrated magnets.
Equilateral triangular lattices (TLs) with antiferromagnetic interactions are ideal templates for inducing magnetic frustration, offering a platform to explore exotic quantum spin states that are crucial for advancing quantum science and technology. However, few examples meet these structural criteria, and even fewer realize these fascinating physical properties. We report four novel equilateral TL magnets realized through a crystal-symmetry-protected molecular-brick strategy. By deliberately selecting a high-symmetry nonmagnetic structural template and incorporating magnetic molecular building blocks, magnetic ions are geometrically constrained by three-fold rotational symmetry within the a-b plane, enforcing an ideal equilateral TL and turning on magnetism in a nonmagnetic structural template. Magnetic susceptibility and specific heat measurements reveal a long-range magnetic ordering in BaCoBe2(BO3)2F2 around 180 mK, while BaNiBe2(BO3)2F2 remains disordered at 140 mK. Furthermore, crystal orbital Hamilton population analysis shows that different molecular bricks exhibit distinct bonding characteristics, resulting in diverse magnetic properties. Our results demonstrate that the molecular-brick chemical strategy offers valuable insights into the investigation of geometrically frustrated magnets.
2026, 37(8): 112817
doi: 10.1016/j.cclet.2026.112817
摘要:
Covalent organic frameworks (COFs) are burgeoning for visible-light photoredox catalysis owing to their modular building blocks and convertible covalent linkages. Herein, the polycondensation of 1,3,6,8-tetra(4-formylphenyl)pyrene (Py) and 4,4′-biphenyldiamine (BD) affords an imine-linked COF, PyBD-COF. Consequently, the conversion of imine into thiazole yields a thiazole-linked COF, PyBTZ-COF. Both pyrene COFs possess well-defined crystallinity and porosity. Compared to PyBD-COF, PyBTZ-COF exhibits superior chemical stability and better electronic structure, attributable to its stable and photoactive thiazole linkages. Both PyBD-COF and PyBTZ-COF drive highly selective sulfoxidation by blue-light photoredox catalysis. Notably, 3 mol% TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) as electron transfer mediator enhances the conversions to approximately twofold for both PyBD-COF and PyBTZ-COF compared to TEMPO-free conditions. Due to its better electronic structure, PyBTZ-COF outperforms PyBD-COF for selective aerobic sulfoxidation, irrespective of addition of 3 mol% TEMPO. PyBTZ-COF photoredox catalysis with TEMPO exhibits excellent stability and broad applicability for selective sulfoxidation. The conversion of the linkage of COFs offers a way forward for enhancing performance in photoredox catalysis.
Covalent organic frameworks (COFs) are burgeoning for visible-light photoredox catalysis owing to their modular building blocks and convertible covalent linkages. Herein, the polycondensation of 1,3,6,8-tetra(4-formylphenyl)pyrene (Py) and 4,4′-biphenyldiamine (BD) affords an imine-linked COF, PyBD-COF. Consequently, the conversion of imine into thiazole yields a thiazole-linked COF, PyBTZ-COF. Both pyrene COFs possess well-defined crystallinity and porosity. Compared to PyBD-COF, PyBTZ-COF exhibits superior chemical stability and better electronic structure, attributable to its stable and photoactive thiazole linkages. Both PyBD-COF and PyBTZ-COF drive highly selective sulfoxidation by blue-light photoredox catalysis. Notably, 3 mol% TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) as electron transfer mediator enhances the conversions to approximately twofold for both PyBD-COF and PyBTZ-COF compared to TEMPO-free conditions. Due to its better electronic structure, PyBTZ-COF outperforms PyBD-COF for selective aerobic sulfoxidation, irrespective of addition of 3 mol% TEMPO. PyBTZ-COF photoredox catalysis with TEMPO exhibits excellent stability and broad applicability for selective sulfoxidation. The conversion of the linkage of COFs offers a way forward for enhancing performance in photoredox catalysis.
2026, 37(8): 111211
doi: 10.1016/j.cclet.2025.111211
摘要:
Bone abnormalities induced due to inflammation, trauma, or diabetes have emerged as a serious issue during treatment and post-treatment. Currently, the prevalent treatments for bone abnormalities are surgery and antibiotics. However, they are progressively struggling to meet clinical needs. Metal-organic frameworks (MOFs) are acquiring attention among many bone repair and bone regeneration materials due to their excellent role in this area of research. MOFs -based nanomaterials are characterized by long-term stability, large specific surface area, and can be easily modifiable. Furthermore, their porous structure and increased mechanical capabilities are similar to alternative tissues, making them useful for bone repair and regeneration. This review article outlines the application of MOFs in bone repair and bone regeneration therapy. First, the mechanics of bone repair and regeneration are discussed, followed by a summary of the most frequent synthetic methods of MOFs for treating bone defects. Secondly, the strategies of different types of MOFs in bone repair and bone regeneration therapies are reviewed. Eventually, the challenges and future of MOFs in bone repairs and bone regeneration therapies are described, introducing a novel approach to treating bone abnormalities.
Bone abnormalities induced due to inflammation, trauma, or diabetes have emerged as a serious issue during treatment and post-treatment. Currently, the prevalent treatments for bone abnormalities are surgery and antibiotics. However, they are progressively struggling to meet clinical needs. Metal-organic frameworks (MOFs) are acquiring attention among many bone repair and bone regeneration materials due to their excellent role in this area of research. MOFs -based nanomaterials are characterized by long-term stability, large specific surface area, and can be easily modifiable. Furthermore, their porous structure and increased mechanical capabilities are similar to alternative tissues, making them useful for bone repair and regeneration. This review article outlines the application of MOFs in bone repair and bone regeneration therapy. First, the mechanics of bone repair and regeneration are discussed, followed by a summary of the most frequent synthetic methods of MOFs for treating bone defects. Secondly, the strategies of different types of MOFs in bone repair and bone regeneration therapies are reviewed. Eventually, the challenges and future of MOFs in bone repairs and bone regeneration therapies are described, introducing a novel approach to treating bone abnormalities.
2026, 37(8): 111229
doi: 10.1016/j.cclet.2025.111229
摘要:
The diverse structure and hierarchical bonding found within Zintl phases play a crucial role in decoupling the electrical and thermal transport properties, thus conferring them with the desired "phonon-glass, electron-crystal" characteristics necessary for high thermoelectric performance. In the last twenty years, a multitude of promising Zintl thermoelectrics have been explored and investigated, with significant systems such as the 1–2–2 phase, 3–1–3 phase, 5–2–6 phase, 9–4–9 phase, 10–1–9 phase, and 14–1–11 phase standing out. More recently, the emergence of 1–1–1 type Zintl phase compounds as potential thermoelectric candidates have sparked considerable interest. In particular, the low lattice thermal conductivity in these compounds offers great possibilities to achieve high thermoelectric figure of merit zT. This review provides a summary of the crystal structures and thermoelectric performance of typical 1–1–1 type Zintl compounds ABSb (A stands for alkali, alkali-earth, or divalent rare-earth metals, B stands for IA, IB or IIB metals). The focus is placed on elucidating the interesting mechanisms of low lattice thermal conductivity in real-space (r-space) and reciprocal-space (k-space), such as huge fluctuation in bonding strengths, larger atomic displacement parameters, rattling-like behavior of atomic vibration, intrinsic vacancy structure, soft optical phonons, phonon softening strategy, avoided crossing effect. This comprehensive review enhances the understanding of structure-property relationships and offers guidance for further improving the thermoelectric performance of 1–1–1 type Zintl compounds.
The diverse structure and hierarchical bonding found within Zintl phases play a crucial role in decoupling the electrical and thermal transport properties, thus conferring them with the desired "phonon-glass, electron-crystal" characteristics necessary for high thermoelectric performance. In the last twenty years, a multitude of promising Zintl thermoelectrics have been explored and investigated, with significant systems such as the 1–2–2 phase, 3–1–3 phase, 5–2–6 phase, 9–4–9 phase, 10–1–9 phase, and 14–1–11 phase standing out. More recently, the emergence of 1–1–1 type Zintl phase compounds as potential thermoelectric candidates have sparked considerable interest. In particular, the low lattice thermal conductivity in these compounds offers great possibilities to achieve high thermoelectric figure of merit zT. This review provides a summary of the crystal structures and thermoelectric performance of typical 1–1–1 type Zintl compounds ABSb (A stands for alkali, alkali-earth, or divalent rare-earth metals, B stands for IA, IB or IIB metals). The focus is placed on elucidating the interesting mechanisms of low lattice thermal conductivity in real-space (r-space) and reciprocal-space (k-space), such as huge fluctuation in bonding strengths, larger atomic displacement parameters, rattling-like behavior of atomic vibration, intrinsic vacancy structure, soft optical phonons, phonon softening strategy, avoided crossing effect. This comprehensive review enhances the understanding of structure-property relationships and offers guidance for further improving the thermoelectric performance of 1–1–1 type Zintl compounds.
2026, 37(8): 111309
doi: 10.1016/j.cclet.2025.111309
摘要:
Sodium-based batteries (SBBs) are considered as promising next-generation energy storage devices owing to the low cost and natural abundance of raw materials. As the blood of SSBs, electrolytes are required to exhibit specific properties, including broad electrochemical stability windows, high thermal stability, prior ionic conductivity, and so on. Therefore, a diverse array of materials and compositions were developed to form novel electrolytes, thereby satisfying the practical requirements of SSBs. In this review, we comprehensively summarize the latest advances and the corresponding electrochemical properties of different electrolytes for SBBs. First, this review describes the desirable characteristics of electrolytes in detail. Subsequently, the latest progress in the design and regulation of electrolytes is systematically analyzed from four key aspects: organic liquid electrolytes, aqueous electrolytes, solid-state electrolytes, and quasi-solid-state electrolytes. Finally, this review delivers an exhaustive illustration on the challenges and research prospects concerning the further development of electrolytes in SBBs.
Sodium-based batteries (SBBs) are considered as promising next-generation energy storage devices owing to the low cost and natural abundance of raw materials. As the blood of SSBs, electrolytes are required to exhibit specific properties, including broad electrochemical stability windows, high thermal stability, prior ionic conductivity, and so on. Therefore, a diverse array of materials and compositions were developed to form novel electrolytes, thereby satisfying the practical requirements of SSBs. In this review, we comprehensively summarize the latest advances and the corresponding electrochemical properties of different electrolytes for SBBs. First, this review describes the desirable characteristics of electrolytes in detail. Subsequently, the latest progress in the design and regulation of electrolytes is systematically analyzed from four key aspects: organic liquid electrolytes, aqueous electrolytes, solid-state electrolytes, and quasi-solid-state electrolytes. Finally, this review delivers an exhaustive illustration on the challenges and research prospects concerning the further development of electrolytes in SBBs.
2026, 37(8): 111759
doi: 10.1016/j.cclet.2025.111759
摘要:
As the most common primary intracranial brain tumor, glioma is confronted with critical therapeutic dilemmas characterized by dismal prognosis and restricted treatment modalities. The current standard treatment for glioma includes maximally safe resection combined with radiotherapy and temozolomide (TMZ) chemotherapy. However, the presence of the blood-brain barrier (BBB) significantly impedes drug penetration into the brain, further exacerbating the therapeutic challenges in glioma treatment. Consequently, developing effective strategies to deliver drugs across the BBB remains pivotal for glioma therapy. Hence, this comprehensive review examines innovative drug delivery strategies designed to overcome BBB through two principal approaches: in-situ drug depots and advanced systemic delivery systems. The first section analyzes the fundamental biological and anatomical barriers impeding effective glioma management. Then, we critically evaluate emerging in-situ delivery modalities, including biodegradable wafer implants, intratumoral injectable depots, and convection-enhanced delivery (CED) systems. The last section explores advanced systemic drug delivery systems (DDS) and summarizes cutting-edge strategies using functionalized nanoparticles (NPs), biomimetic delivery vectors, and stimulus-responsive DDS for efficient and safe systemic drug delivery. Challenges and future developments related to the application of drug-delivery strategies for glioma treatment are also discussed. In summary, this review not only maps the current landscape of drug delivery strategies but also illuminates transformative research trajectories that can pave the way for precision medicine in glioma treatment.
As the most common primary intracranial brain tumor, glioma is confronted with critical therapeutic dilemmas characterized by dismal prognosis and restricted treatment modalities. The current standard treatment for glioma includes maximally safe resection combined with radiotherapy and temozolomide (TMZ) chemotherapy. However, the presence of the blood-brain barrier (BBB) significantly impedes drug penetration into the brain, further exacerbating the therapeutic challenges in glioma treatment. Consequently, developing effective strategies to deliver drugs across the BBB remains pivotal for glioma therapy. Hence, this comprehensive review examines innovative drug delivery strategies designed to overcome BBB through two principal approaches: in-situ drug depots and advanced systemic delivery systems. The first section analyzes the fundamental biological and anatomical barriers impeding effective glioma management. Then, we critically evaluate emerging in-situ delivery modalities, including biodegradable wafer implants, intratumoral injectable depots, and convection-enhanced delivery (CED) systems. The last section explores advanced systemic drug delivery systems (DDS) and summarizes cutting-edge strategies using functionalized nanoparticles (NPs), biomimetic delivery vectors, and stimulus-responsive DDS for efficient and safe systemic drug delivery. Challenges and future developments related to the application of drug-delivery strategies for glioma treatment are also discussed. In summary, this review not only maps the current landscape of drug delivery strategies but also illuminates transformative research trajectories that can pave the way for precision medicine in glioma treatment.
2026, 37(8): 111797
doi: 10.1016/j.cclet.2025.111797
摘要:
Breast cancer is the most prevalent cancer in women worldwide and a major contributor to cancer-related death. It has been established for decades that natural bioactive compounds are a crucial source for developing novel anticancer drugs. However, their poor targeting, limited solubility and bioavailability, and instability hinder the effectiveness of treatment. With advancements in nanotechnology, nanomedicine delivery systems have emerged as viable approaches to enhance drug bioavailability and therapeutic effectiveness, with natural polymer-based drug carriers gaining significant attention for breast cancer treatment. Chitosan's distinct physicochemical characteristics, biocompatibility, and low immunogenicity make it a popular choice for carrier materials in nanomedicine delivery systems. Their desired qualities include the extent of chemical modification, controlled drug release, surface flexibility, non-toxicity, enhanced stability, cellular uptake, anticancer drug solubility, modulation of release kinetics, and biodistribution. This review aims to illustrate current concerns regarding breast cancer treatment, highlighting the untapped potential of natural bioactive compounds while promoting the latest developments of using chitosan-based nanocarriers to deliver natural bioactive compounds. Finally, this review spotlights the limitations of existing research and the futuristic prospects in this emerging field.
Breast cancer is the most prevalent cancer in women worldwide and a major contributor to cancer-related death. It has been established for decades that natural bioactive compounds are a crucial source for developing novel anticancer drugs. However, their poor targeting, limited solubility and bioavailability, and instability hinder the effectiveness of treatment. With advancements in nanotechnology, nanomedicine delivery systems have emerged as viable approaches to enhance drug bioavailability and therapeutic effectiveness, with natural polymer-based drug carriers gaining significant attention for breast cancer treatment. Chitosan's distinct physicochemical characteristics, biocompatibility, and low immunogenicity make it a popular choice for carrier materials in nanomedicine delivery systems. Their desired qualities include the extent of chemical modification, controlled drug release, surface flexibility, non-toxicity, enhanced stability, cellular uptake, anticancer drug solubility, modulation of release kinetics, and biodistribution. This review aims to illustrate current concerns regarding breast cancer treatment, highlighting the untapped potential of natural bioactive compounds while promoting the latest developments of using chitosan-based nanocarriers to deliver natural bioactive compounds. Finally, this review spotlights the limitations of existing research and the futuristic prospects in this emerging field.
2026, 37(8): 111801
doi: 10.1016/j.cclet.2025.111801
摘要:
Hydrogen evolution reaction (HER) is the critical process of hydrogen production through water electrolysis. However, the dependence on precious metal catalysts limits its large-scale application. Transition metal phosphides (TMPs) are promising alternatives due to their metal-like conductivity, adjustable electronic structure and low cost. Yet they still show some shortcomings such as insufficient intrinsic activity and poor surface stability. This review first systematically summarizes the HER reaction mechanism and its implications for TMPs catalyst design. Subsequently, it details the characteristics, limitations, and performance optimization strategies for monometallic TMPs. Furthermore, it discusses advances in polymetallic TMPs and composite structures for overcoming the activity limitations of monometallic TMPs. Finally, we propose key obstacles limiting TMPs in HER and their research directions and development prospects in the future.
Hydrogen evolution reaction (HER) is the critical process of hydrogen production through water electrolysis. However, the dependence on precious metal catalysts limits its large-scale application. Transition metal phosphides (TMPs) are promising alternatives due to their metal-like conductivity, adjustable electronic structure and low cost. Yet they still show some shortcomings such as insufficient intrinsic activity and poor surface stability. This review first systematically summarizes the HER reaction mechanism and its implications for TMPs catalyst design. Subsequently, it details the characteristics, limitations, and performance optimization strategies for monometallic TMPs. Furthermore, it discusses advances in polymetallic TMPs and composite structures for overcoming the activity limitations of monometallic TMPs. Finally, we propose key obstacles limiting TMPs in HER and their research directions and development prospects in the future.
2026, 37(8): 111817
doi: 10.1016/j.cclet.2025.111817
摘要:
Metal-based nanomedicine, which involves nanoparticles (NPs) composed of metals such as gold, silver, iron, and platinum, has emerged as a promising approach in drug delivery, cancer therapy, imaging, and diagnostics. This review systematically examines a variety of metal-containing NPs (MNPs), including elemental metal NPs, metal oxides, metal-organic frameworks, nanozymes, and up-conversion NPs, highlighting their unique physicochemical properties and biomedical applications. The biological functions of MNPs, particularly in drug delivery, imaging, and therapeutic contexts, are critically discussed. Key engineering strategies aimed at optimizing targeted delivery, drug loading, responsive release, and biocompatibility are explored, with a focus on enhancing clinical outcomes. Recent advances underscore the potential of MNPs in innovative applications such as liquid biopsy, tumor imaging, chemotherapy, immunotherapy, physical therapy, and nanozyme-mediated treatments. Despite promising developments, clinical translation remains hindered by challenges such as toxicity, scalability, and regulatory hurdles. This review concludes with an outlook on future directions for MNPs, emphasizing their potential to revolutionize disease diagnosis and treatment through innovative biomaterial design and engineering.
Metal-based nanomedicine, which involves nanoparticles (NPs) composed of metals such as gold, silver, iron, and platinum, has emerged as a promising approach in drug delivery, cancer therapy, imaging, and diagnostics. This review systematically examines a variety of metal-containing NPs (MNPs), including elemental metal NPs, metal oxides, metal-organic frameworks, nanozymes, and up-conversion NPs, highlighting their unique physicochemical properties and biomedical applications. The biological functions of MNPs, particularly in drug delivery, imaging, and therapeutic contexts, are critically discussed. Key engineering strategies aimed at optimizing targeted delivery, drug loading, responsive release, and biocompatibility are explored, with a focus on enhancing clinical outcomes. Recent advances underscore the potential of MNPs in innovative applications such as liquid biopsy, tumor imaging, chemotherapy, immunotherapy, physical therapy, and nanozyme-mediated treatments. Despite promising developments, clinical translation remains hindered by challenges such as toxicity, scalability, and regulatory hurdles. This review concludes with an outlook on future directions for MNPs, emphasizing their potential to revolutionize disease diagnosis and treatment through innovative biomaterial design and engineering.
2026, 37(8): 111846
doi: 10.1016/j.cclet.2025.111846
摘要:
Chronic cutaneous wounds such as diabetic foot and pressure ulcers are increasing worldwide and remain difficult to manage. Conventional approaches are hindered by prolonged healing and antibiotic resistance, highlighting the need for advanced biomaterial strategies. Thus, the production of advanced biomaterials for efficient wound healing has become of special urgency. Mesoporous silica (MS), with its specific features of exceptional biocompatibility, easily tunable pore architectures, and multifunctional surface functionalization, has emerged as a promising choice in such applications. The review systematically overviews the most recent advances in the wound healing application of MS, with its participation in drug delivery, controlled inflammation, modulation of immune response, tissue regeneration, and angiogenesis. Synthesis methods, surface functionalization techniques, and incorporation of advanced technology such as stimulus responsive systems and multifunctional composites are also extensively reviewed. Furthermore, this review critically examines the key barriers to the clinical translation of MS, including long-term biosafety, immune compatibility, and scalable manufacturing. Overcoming these challenges is crucial for harnessing its full potential in next-generation wound healing. By integrating MS with precision medicine and emerging biomedical technologies, this review highlights its transformative role in advancing personalized wound care and regenerative medicine.
Chronic cutaneous wounds such as diabetic foot and pressure ulcers are increasing worldwide and remain difficult to manage. Conventional approaches are hindered by prolonged healing and antibiotic resistance, highlighting the need for advanced biomaterial strategies. Thus, the production of advanced biomaterials for efficient wound healing has become of special urgency. Mesoporous silica (MS), with its specific features of exceptional biocompatibility, easily tunable pore architectures, and multifunctional surface functionalization, has emerged as a promising choice in such applications. The review systematically overviews the most recent advances in the wound healing application of MS, with its participation in drug delivery, controlled inflammation, modulation of immune response, tissue regeneration, and angiogenesis. Synthesis methods, surface functionalization techniques, and incorporation of advanced technology such as stimulus responsive systems and multifunctional composites are also extensively reviewed. Furthermore, this review critically examines the key barriers to the clinical translation of MS, including long-term biosafety, immune compatibility, and scalable manufacturing. Overcoming these challenges is crucial for harnessing its full potential in next-generation wound healing. By integrating MS with precision medicine and emerging biomedical technologies, this review highlights its transformative role in advancing personalized wound care and regenerative medicine.
2026, 37(8): 111887
doi: 10.1016/j.cclet.2025.111887
摘要:
Respiratory diseases constitute a major global health burden, impacting both public health and socioeconomic conditions. Pulmonary mRNA delivery systems are now emerging as a promising therapeutic strategy to treat respiratory diseases, overcoming challenges of conventional mRNA formulations such as low pulmonary bioavailability and adverse side effects. Notably, lipid and polymer nanoparticles integrated into compatible inhaler devices represent the predominant pulmonary mRNA delivery systems. Despite the promising aspects, pulmonary mRNA delivery systems in respiratory diseases treatments face four key challenges, viz. complex airway tract structure, mucociliary clearance system, immune system, and the "last hurdle" intracellular delivery barrier. All these challenges are critical to the treatment effectiveness and safety. Recent progress made on inhalable mRNA delivery methods based on various vectors is highlighted for addressing the above challenges, boosting prospective development of mRNA-based therapies for the treatment of respiratory diseases. This review examines current challenges, strategies, and advances in inhalable mRNA formulations for respiratory diseases and explores prospects for pulmonary mRNA delivery systems, which hold great promise as a next-generation therapeutic platform.
Respiratory diseases constitute a major global health burden, impacting both public health and socioeconomic conditions. Pulmonary mRNA delivery systems are now emerging as a promising therapeutic strategy to treat respiratory diseases, overcoming challenges of conventional mRNA formulations such as low pulmonary bioavailability and adverse side effects. Notably, lipid and polymer nanoparticles integrated into compatible inhaler devices represent the predominant pulmonary mRNA delivery systems. Despite the promising aspects, pulmonary mRNA delivery systems in respiratory diseases treatments face four key challenges, viz. complex airway tract structure, mucociliary clearance system, immune system, and the "last hurdle" intracellular delivery barrier. All these challenges are critical to the treatment effectiveness and safety. Recent progress made on inhalable mRNA delivery methods based on various vectors is highlighted for addressing the above challenges, boosting prospective development of mRNA-based therapies for the treatment of respiratory diseases. This review examines current challenges, strategies, and advances in inhalable mRNA formulations for respiratory diseases and explores prospects for pulmonary mRNA delivery systems, which hold great promise as a next-generation therapeutic platform.
2026, 37(8): 111910
doi: 10.1016/j.cclet.2025.111910
摘要:
Sub-nanometer high-entropy materials (HEMs) have opened new pathways in electrocatalysis and biomedicine, leveraging their tunable composition, ultrahigh specific surface area, abundant active sites, and multi-element synergy. In electrocatalysis, their highly disordered multi-element structures significantly enhance the intrinsic activity and stability for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CO2RR), while their unique "cocktail effect" enables precise electronic structure modulation. For biomedical applications, their ultrasmall size facilitates cellular uptake and tissue penetration. Simultaneously, their multi-element composition endows them with multifunctionality, including photothermal/photodynamic/catalytic/magnetic therapy, multimodal imaging, and drug delivery, while also optimizing biocompatibility and reducing toxicity. However, challenges remain in the precise synthesis and mechanistic understanding of sub-nanometer HEMs, hindering their development for next-generation high-performance electrocatalysts and intelligent theranostic platforms. In this review, we comprehensively explore the composition-structure design principles of HEMs, with a focus on the multifunctional properties achieved by small sizes, particularly in the sub-nano range, and their applications in electrocatalysis and biomedicine. Additionally, this paper prospectively discusses emerging strategies that may drive the future development of HEMs, with particular emphasis on the application potential of sub-nanometer HEMs.
Sub-nanometer high-entropy materials (HEMs) have opened new pathways in electrocatalysis and biomedicine, leveraging their tunable composition, ultrahigh specific surface area, abundant active sites, and multi-element synergy. In electrocatalysis, their highly disordered multi-element structures significantly enhance the intrinsic activity and stability for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CO2RR), while their unique "cocktail effect" enables precise electronic structure modulation. For biomedical applications, their ultrasmall size facilitates cellular uptake and tissue penetration. Simultaneously, their multi-element composition endows them with multifunctionality, including photothermal/photodynamic/catalytic/magnetic therapy, multimodal imaging, and drug delivery, while also optimizing biocompatibility and reducing toxicity. However, challenges remain in the precise synthesis and mechanistic understanding of sub-nanometer HEMs, hindering their development for next-generation high-performance electrocatalysts and intelligent theranostic platforms. In this review, we comprehensively explore the composition-structure design principles of HEMs, with a focus on the multifunctional properties achieved by small sizes, particularly in the sub-nano range, and their applications in electrocatalysis and biomedicine. Additionally, this paper prospectively discusses emerging strategies that may drive the future development of HEMs, with particular emphasis on the application potential of sub-nanometer HEMs.
2026, 37(8): 111951
doi: 10.1016/j.cclet.2025.111951
摘要:
Due to the abundant potassium resources, potassium ion batteries (PIBs) are gradually becoming a promising choice for large-scale energy storage. Among the many anode materials that have been investigated, antimony anode has attracted much attention due to its high theoretical specific capacity, low reaction potential and high electrical conductivity. However, these antimony anodes undergo significant volume changes (≈407%) during the potassium alloying reaction, which negatively affect their cycle stability and rate performance. In this paper, the research progress of antimony anodes in recent years is reviewed. Modification strategies to improve the performance of antimony anodes, including architectural design, alloying with other metals, composite system construction and electrolyte optimization, are discussed in depth. In addition, the possible future development directions for antimony anodes in PIBs with a view to accelerating their practical application are proposed. It is hoped that this review will help researchers design high-performance antimony anode materials more efficiently.
Due to the abundant potassium resources, potassium ion batteries (PIBs) are gradually becoming a promising choice for large-scale energy storage. Among the many anode materials that have been investigated, antimony anode has attracted much attention due to its high theoretical specific capacity, low reaction potential and high electrical conductivity. However, these antimony anodes undergo significant volume changes (≈407%) during the potassium alloying reaction, which negatively affect their cycle stability and rate performance. In this paper, the research progress of antimony anodes in recent years is reviewed. Modification strategies to improve the performance of antimony anodes, including architectural design, alloying with other metals, composite system construction and electrolyte optimization, are discussed in depth. In addition, the possible future development directions for antimony anodes in PIBs with a view to accelerating their practical application are proposed. It is hoped that this review will help researchers design high-performance antimony anode materials more efficiently.
2026, 37(8): 111973
doi: 10.1016/j.cclet.2025.111973
摘要:
Lithium batteries have an exceptional energy density, efficiency, and long service lives, but their anodes show poor interfacial stability. This review summarizes recent advances in the use of atomic layer deposition (ALD) for interfacial modification of lithium battery anodes. It focuses on challenges, including the poor rate performance of intercalation-type anodes, the volume expansion and low initial Coulombic efficiency (ICE) of alloy-type anodes, and dendrite growth and solid-electrolyte interphase (SEI) instability in lithium-metal anodes. Based on this, the multifunctional roles of ALD-derived nanoscale passivation layers in regulating interfacial reactions, suppressing parasitic processes, and enhancing structural integrity are discussed. By evaluating the ability of ALD to improve the cycling lifespan, rate capability, and capacity retention, its application potential for fabricating high-energy-density storage systems is analyzed. This work provides theoretical principles and engineering pathways for the rational design of advanced anode materials.
Lithium batteries have an exceptional energy density, efficiency, and long service lives, but their anodes show poor interfacial stability. This review summarizes recent advances in the use of atomic layer deposition (ALD) for interfacial modification of lithium battery anodes. It focuses on challenges, including the poor rate performance of intercalation-type anodes, the volume expansion and low initial Coulombic efficiency (ICE) of alloy-type anodes, and dendrite growth and solid-electrolyte interphase (SEI) instability in lithium-metal anodes. Based on this, the multifunctional roles of ALD-derived nanoscale passivation layers in regulating interfacial reactions, suppressing parasitic processes, and enhancing structural integrity are discussed. By evaluating the ability of ALD to improve the cycling lifespan, rate capability, and capacity retention, its application potential for fabricating high-energy-density storage systems is analyzed. This work provides theoretical principles and engineering pathways for the rational design of advanced anode materials.
2026, 37(8): 112325
doi: 10.1016/j.cclet.2025.112325
摘要:
Ammonia (NH3) is a pivotal industrial chemical extensively utilized in agricultural production, energy storage systems, and chemical manufacturing processes. However, the conventional NH3 synthesis method, the Haber-Bosch process, is not only highly energy-intensive but also produces substantial greenhouse gas emissions. On the other hand, a sustainable alternative is offered by the ambient electrocatalytic nitrate (NO3−) reduction reaction (NO3RR) to NH3, which utilizes renewable electricity. This process not only converts NO3− pollutants into valuable NH3 but also addresses environmental concerns by effectively utilizing NO3− waste. In this review, we focus on the electrocatalytic synthesis of NH3 via NO3RR, systematically outlining the background of NO3RR, the fundamental reaction pathways, and the methods for detecting products and intermediates. We also highlight the advantages of copper (Cu)-based catalysts in this reaction. We explore various strategies to enhance Cu catalysis, including nanoparticle synthesis, facet engineering, alloying, oxidation state tuning, and single-atom dispersion. Additionally, we provide an overview of how electrolyte composition and characteristics affect NO3− reduction efficiency and clarify the processes that underlie these effects. We delve into NO3RR's challenges and the likelihood of NH3 synthesis in the future. The goal of this work is to shed light on how to achieve environmental sustainability and create more effective NH3 synthesis strategies.
Ammonia (NH3) is a pivotal industrial chemical extensively utilized in agricultural production, energy storage systems, and chemical manufacturing processes. However, the conventional NH3 synthesis method, the Haber-Bosch process, is not only highly energy-intensive but also produces substantial greenhouse gas emissions. On the other hand, a sustainable alternative is offered by the ambient electrocatalytic nitrate (NO3−) reduction reaction (NO3RR) to NH3, which utilizes renewable electricity. This process not only converts NO3− pollutants into valuable NH3 but also addresses environmental concerns by effectively utilizing NO3− waste. In this review, we focus on the electrocatalytic synthesis of NH3 via NO3RR, systematically outlining the background of NO3RR, the fundamental reaction pathways, and the methods for detecting products and intermediates. We also highlight the advantages of copper (Cu)-based catalysts in this reaction. We explore various strategies to enhance Cu catalysis, including nanoparticle synthesis, facet engineering, alloying, oxidation state tuning, and single-atom dispersion. Additionally, we provide an overview of how electrolyte composition and characteristics affect NO3− reduction efficiency and clarify the processes that underlie these effects. We delve into NO3RR's challenges and the likelihood of NH3 synthesis in the future. The goal of this work is to shed light on how to achieve environmental sustainability and create more effective NH3 synthesis strategies.
2026, 37(8): 112326
doi: 10.1016/j.cclet.2025.112326
摘要:
Metal-organic frameworks (MOFs) nanomachines (MNMs) merge high surface area, porosity, and the tunability of MOFs with mobility and intelligence of smart nanomachines. This review provides comprehensive overview of synthesis and post synthetic modifications for MOF tailored for water purification. Further MOF transformation into nanorobots has been elucidated, relating MNM shapes to their functionality. Propulsion modes: Both chemical and physical are also critically evaluated, and research gaps have been explored. For the environmental applications of MNMs, mechanisms of working, ability to remove metal ions, organic pollutants and dyes, sensing and disinfection have been explored. Future potential for the use of MNMs under harsh water conditions has also been discussed. Finally, the review identifies toxicological concerns related to long-term MNMs, research gaps and future challenges, giving a road map for future research, suggesting use of computational chemistry (artificial intelligence (AI) and machine learning (ML)) for effective purposes. By bringing synthesis, PSM, transformation, structural engineering at one place and relating them with propulsion mechanisms as well as with environmental applications of MNMs, this review will act as foundational reference for researchers working to fabricate MNMs for sustainable water treatment.
Metal-organic frameworks (MOFs) nanomachines (MNMs) merge high surface area, porosity, and the tunability of MOFs with mobility and intelligence of smart nanomachines. This review provides comprehensive overview of synthesis and post synthetic modifications for MOF tailored for water purification. Further MOF transformation into nanorobots has been elucidated, relating MNM shapes to their functionality. Propulsion modes: Both chemical and physical are also critically evaluated, and research gaps have been explored. For the environmental applications of MNMs, mechanisms of working, ability to remove metal ions, organic pollutants and dyes, sensing and disinfection have been explored. Future potential for the use of MNMs under harsh water conditions has also been discussed. Finally, the review identifies toxicological concerns related to long-term MNMs, research gaps and future challenges, giving a road map for future research, suggesting use of computational chemistry (artificial intelligence (AI) and machine learning (ML)) for effective purposes. By bringing synthesis, PSM, transformation, structural engineering at one place and relating them with propulsion mechanisms as well as with environmental applications of MNMs, this review will act as foundational reference for researchers working to fabricate MNMs for sustainable water treatment.
2026, 37(8): 112337
doi: 10.1016/j.cclet.2025.112337
摘要:
Membrane separation technology offers significant advantages in water treatment but faces challenges such as membrane fouling and limited separation capabilities, which often fail to meet the urgent demands of water purification. Integrating versatile piezoelectric materials into conventional membranes is expected to overcome the limitations of existing techniques. This review analyzes recent advancements in piezoelectric membranes for efficient water purification, beginning with the historical evolution and foundational principles of the piezoelectric effect and piezocatalysis. It then presents an overview of conventional and emerging piezoelectric materials used in advanced membrane fabrication. The typical strategies for producing high-performance piezoelectric membranes are outlined, including solution blending, electrospinning, dry pressing, and sintering. The energy sources, applications, and mechanisms of piezoelectric membranes in water purification are examined, covering catalytic degradation, fouling mitigation, and antibacterial effects. Finally, this review assesses the main challenges facing piezoelectric membrane separation technology and considers future development pathways.
Membrane separation technology offers significant advantages in water treatment but faces challenges such as membrane fouling and limited separation capabilities, which often fail to meet the urgent demands of water purification. Integrating versatile piezoelectric materials into conventional membranes is expected to overcome the limitations of existing techniques. This review analyzes recent advancements in piezoelectric membranes for efficient water purification, beginning with the historical evolution and foundational principles of the piezoelectric effect and piezocatalysis. It then presents an overview of conventional and emerging piezoelectric materials used in advanced membrane fabrication. The typical strategies for producing high-performance piezoelectric membranes are outlined, including solution blending, electrospinning, dry pressing, and sintering. The energy sources, applications, and mechanisms of piezoelectric membranes in water purification are examined, covering catalytic degradation, fouling mitigation, and antibacterial effects. Finally, this review assesses the main challenges facing piezoelectric membrane separation technology and considers future development pathways.
2026, 37(8): 112352
doi: 10.1016/j.cclet.2025.112352
摘要:
Sulfur is a key element in global biogeochemical cycles, participating in the energy exchange among the terrestrial, marine, and atmospheric systems. In the early days, the natural sulfur cycle maintained an input-output balance. However, the rapid expansion of industrial activities has disrupted this equilibrium by altering sulfur species conversion pathways and flux distributions. This has led us to have to explore new sulfur balance states to reduce the impact on the ecological environment. So far, researchers have conducted a series of studies on the modern sulfur cycle, but these findings have not yet been systematically organized. This review systematically examines the sulfur cycle from integrated natural and anthropogenic perspectives. Among them, the natural sulfur cycle encompasses the terrestrial, marine and atmospheric systems of the Earth, focusing on sulfur species, transformation and circulation flux. Furthermore, the investigation of the industrial metabolic process of sulfur has revealed that human activities have disrupted the balance of the Earth’s sulfur cycle, leading to resource depletion and environmental degradation. To mitigate these effects, advancing intra-industrial sulfur recycling strategies is critical for reducing primary resource consumption and waste emissions. This review provided a foundational framework for achieving sustainable sulfur utilization and restoring global sulfur balance.
Sulfur is a key element in global biogeochemical cycles, participating in the energy exchange among the terrestrial, marine, and atmospheric systems. In the early days, the natural sulfur cycle maintained an input-output balance. However, the rapid expansion of industrial activities has disrupted this equilibrium by altering sulfur species conversion pathways and flux distributions. This has led us to have to explore new sulfur balance states to reduce the impact on the ecological environment. So far, researchers have conducted a series of studies on the modern sulfur cycle, but these findings have not yet been systematically organized. This review systematically examines the sulfur cycle from integrated natural and anthropogenic perspectives. Among them, the natural sulfur cycle encompasses the terrestrial, marine and atmospheric systems of the Earth, focusing on sulfur species, transformation and circulation flux. Furthermore, the investigation of the industrial metabolic process of sulfur has revealed that human activities have disrupted the balance of the Earth’s sulfur cycle, leading to resource depletion and environmental degradation. To mitigate these effects, advancing intra-industrial sulfur recycling strategies is critical for reducing primary resource consumption and waste emissions. This review provided a foundational framework for achieving sustainable sulfur utilization and restoring global sulfur balance.
2026, 37(8): 112357
doi: 10.1016/j.cclet.2025.112357
摘要:
The properties of biomass-derived multifunctional materials have garnered increasing attention in the fields of environmental remediation, energy storage, and heterogeneous catalysis due to their abundant content of N and C, which can effectively modulate electronic structure and facilitate the anchoring of active centers. In this review, we summarized the progress of our team over the past decade on a variety of multifunctional materials with diverse morphologies, electronic structures, and geometric sites, developed through novel synthetic strategies that employ biomass and its derivatives as carbon sources. Those multifunctional materials exhibited excellent catalytic performance for the adsorption and degradation of pollutants in wastewater, absorption of electromagnetic waves (EMW), and photocatalytic reactions. Moreover, the underlying mechanisms of adsorption, degradation, and activation during the reaction process as well as the relationship between activity and structure are also discussed. This review offers comprehensive insights for fabricating biomass-derived materials, with a specific emphasis on their physicochemical properties characterized by controlled morphology, tunable electronic properties, and precise localization of active species, as well as the aspect of the intricate relationship between activity-structure and catalytic mechanisms, providing reference for future advancements in various catalysis fields involving biomass-derived materials.
The properties of biomass-derived multifunctional materials have garnered increasing attention in the fields of environmental remediation, energy storage, and heterogeneous catalysis due to their abundant content of N and C, which can effectively modulate electronic structure and facilitate the anchoring of active centers. In this review, we summarized the progress of our team over the past decade on a variety of multifunctional materials with diverse morphologies, electronic structures, and geometric sites, developed through novel synthetic strategies that employ biomass and its derivatives as carbon sources. Those multifunctional materials exhibited excellent catalytic performance for the adsorption and degradation of pollutants in wastewater, absorption of electromagnetic waves (EMW), and photocatalytic reactions. Moreover, the underlying mechanisms of adsorption, degradation, and activation during the reaction process as well as the relationship between activity and structure are also discussed. This review offers comprehensive insights for fabricating biomass-derived materials, with a specific emphasis on their physicochemical properties characterized by controlled morphology, tunable electronic properties, and precise localization of active species, as well as the aspect of the intricate relationship between activity-structure and catalytic mechanisms, providing reference for future advancements in various catalysis fields involving biomass-derived materials.
2026, 37(8): 112405
doi: 10.1016/j.cclet.2026.112405
摘要:
Indole-containing polyheterocycles belong to an extremely important class of organic compounds, and the related skeletons are found in many natural products and bioactive molecules. They play an important role in synthetic and medicinal chemistry, agrochemicals, and advanced materials. Moreover, they also serve as versatile building blocks and tools for constructing more complex molecules. Thus, development of efficient methods for assembly of indole-containing polyheterocycles has attracted considerable attention in recent years. The aim of this review is to summarize recent developments in the synthesis of indole-fused or spired polycyclic compounds via cyclization of indole-tethered alkenes. Indole-tethered alkenes with alkenyl species linked to different position of indole moiety is presented.
Indole-containing polyheterocycles belong to an extremely important class of organic compounds, and the related skeletons are found in many natural products and bioactive molecules. They play an important role in synthetic and medicinal chemistry, agrochemicals, and advanced materials. Moreover, they also serve as versatile building blocks and tools for constructing more complex molecules. Thus, development of efficient methods for assembly of indole-containing polyheterocycles has attracted considerable attention in recent years. The aim of this review is to summarize recent developments in the synthesis of indole-fused or spired polycyclic compounds via cyclization of indole-tethered alkenes. Indole-tethered alkenes with alkenyl species linked to different position of indole moiety is presented.
2026, 37(8): 112484
doi: 10.1016/j.cclet.2026.112484
摘要:
Triketones are fundamental building blocks in discovering many bioactive compounds due to their unique structural features. With three carbonyl groups and the ability to tautomerize into enol forms, triketones can form hydrogen bond donors and acceptors when binding to receptors and serve as metal chelation function groups. This structural diversity enables triketone compounds to be widely applied in herbicides, fungicides, insecticides, anticancer treatments, and tyrosine metabolism disorders, particularly applications as HPPD (4-hydroxyphenylpyruvate dioxygenase) inhibitors, where their herbicidal activity stems from the disruption of plant photosynthesis processes to effectively control weed growth. Moreover, in materials applications, their excellent reactivity allows for the post-polymerization modification of triketone-modified polymers. To facilitate the discovery of triketone pesticides and drugs, in this review, we summarize the current research progress of triketone compounds, highlighting their potential mechanisms of action and environmental fate.
Triketones are fundamental building blocks in discovering many bioactive compounds due to their unique structural features. With three carbonyl groups and the ability to tautomerize into enol forms, triketones can form hydrogen bond donors and acceptors when binding to receptors and serve as metal chelation function groups. This structural diversity enables triketone compounds to be widely applied in herbicides, fungicides, insecticides, anticancer treatments, and tyrosine metabolism disorders, particularly applications as HPPD (4-hydroxyphenylpyruvate dioxygenase) inhibitors, where their herbicidal activity stems from the disruption of plant photosynthesis processes to effectively control weed growth. Moreover, in materials applications, their excellent reactivity allows for the post-polymerization modification of triketone-modified polymers. To facilitate the discovery of triketone pesticides and drugs, in this review, we summarize the current research progress of triketone compounds, highlighting their potential mechanisms of action and environmental fate.
2026, 37(8): 112643
doi: 10.1016/j.cclet.2026.112643
摘要:
Transarterial chemoembolization (TACE) remains the standard of care for patients with unresectable hepatocellular carcinoma (HCC). However, clinical outcomes are frequently compromised by off-target toxicity, incomplete tumour necrosis, and the induction of a post-procedural immunosuppressive microenvironment. The integration of nanotechnology represents a paradigm shift designed to circumvent these biological and technical barriers. For instance, magnesium-enhanced TACE has demonstrated an objective response rate of ~93.3%, substantially surpassing that of conventional TACE therapies. This review evaluates nanotechnology's impact on TACE through four domains: Smart nanocarriers for stimuli-responsive delivery; theranostic platforms for real-time imaging; immune remodeling to boost immunotherapy; and next-generation embolic materials such as biodegradable polymers and liquid metals. Finally, we address the preclinical-to-clinical translation gap and outline a roadmap for personalized, high-precision interventional oncology.
Transarterial chemoembolization (TACE) remains the standard of care for patients with unresectable hepatocellular carcinoma (HCC). However, clinical outcomes are frequently compromised by off-target toxicity, incomplete tumour necrosis, and the induction of a post-procedural immunosuppressive microenvironment. The integration of nanotechnology represents a paradigm shift designed to circumvent these biological and technical barriers. For instance, magnesium-enhanced TACE has demonstrated an objective response rate of ~93.3%, substantially surpassing that of conventional TACE therapies. This review evaluates nanotechnology's impact on TACE through four domains: Smart nanocarriers for stimuli-responsive delivery; theranostic platforms for real-time imaging; immune remodeling to boost immunotherapy; and next-generation embolic materials such as biodegradable polymers and liquid metals. Finally, we address the preclinical-to-clinical translation gap and outline a roadmap for personalized, high-precision interventional oncology.
2026, 37(8): 112699
doi: 10.1016/j.cclet.2026.112699
摘要:
The global spread of antibiotic resistance (AR) poses a critical public health threat, urgently requiring effective strategies to control antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) in water. Ultraviolet-based advanced oxidation processes (UVC/AOPs) offer a promising solution. By leveraging synergy between UVC light and oxidants (e.g., H2O2, PMS, O3, PAA, Cl2) to generate reactive radicals, they efficiently inactivate ARB, degrade ARGs, and suppress horizontal gene transfer (HGT). This review synthesizes recent advances, emphasizing: (1) Combined mechanisms of direct UVC damage and radical-mediated oxidation; (2) critical efficacy factors like radical kinetics and water matrix effects (DOM, salinity); and (3) key challenges including mechanistic gaps, particulate shielding of ARGs, and variable microbial susceptibility. To address these, we propose a machine learning-augmented approach integrating quantum chemical calculations and real-time spectroscopy to build predictive "radical-biotarget" models for intelligent optimization. While UVC/AOPs show broad efficacy and environmental promise, future research must prioritize elucidating fundamental mechanisms, optimizing parameters for diverse waters, and developing intelligent control systems to enhance specificity and resilience. Through such innovations, UVC/AOPs can become a core technology for precise AR risk management in water systems, providing a sustainable barrier against resistance spread.
The global spread of antibiotic resistance (AR) poses a critical public health threat, urgently requiring effective strategies to control antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) in water. Ultraviolet-based advanced oxidation processes (UVC/AOPs) offer a promising solution. By leveraging synergy between UVC light and oxidants (e.g., H2O2, PMS, O3, PAA, Cl2) to generate reactive radicals, they efficiently inactivate ARB, degrade ARGs, and suppress horizontal gene transfer (HGT). This review synthesizes recent advances, emphasizing: (1) Combined mechanisms of direct UVC damage and radical-mediated oxidation; (2) critical efficacy factors like radical kinetics and water matrix effects (DOM, salinity); and (3) key challenges including mechanistic gaps, particulate shielding of ARGs, and variable microbial susceptibility. To address these, we propose a machine learning-augmented approach integrating quantum chemical calculations and real-time spectroscopy to build predictive "radical-biotarget" models for intelligent optimization. While UVC/AOPs show broad efficacy and environmental promise, future research must prioritize elucidating fundamental mechanisms, optimizing parameters for diverse waters, and developing intelligent control systems to enhance specificity and resilience. Through such innovations, UVC/AOPs can become a core technology for precise AR risk management in water systems, providing a sustainable barrier against resistance spread.
2026, 37(8): 112721
doi: 10.1016/j.cclet.2026.112721
摘要:
The application of MXene-based single-atom catalysts (SACs) in Fenton-like processes has emerged as a rapidly advancing research frontier in recent years. Early studies have demonstrated their superior activity in activating peroxymonosulfate or hydrogen peroxide for pollutant degradation compared to conventional nanoparticle catalysts, while recent efforts have shifted toward precise structural engineering and mechanistic understanding of reaction pathways. However, the transition from laboratory-scale synthesis to industrial implementation remains challenging, due to difficulties in developing green and scalable fabrication methods, long-term instability in complex water matrices, leaching of metal active centers, and the lack of cost-effective integration into continuous-flow systems such as fixed-bed reactors. To date, comprehensive reviews addressing their engineering applications remain limited. This review systematically summarizes advances in synthetic strategies and characterization techniques for achieving atomic dispersion, elucidates the structure–activity relationships and synergistic radical/non-radical mechanisms, and evaluates reactor design and scale-up potential. Particular emphasis is placed on operational adaptability and economic feasibility under real-world conditions. Future perspectives include the rational design of novel MXene supports, machine learning-assisted catalyst optimization, hybrid process integration, and the development of sustainability assessment frameworks, aiming to bridge the gap between fundamental discoveries and practical water purification technologies.
The application of MXene-based single-atom catalysts (SACs) in Fenton-like processes has emerged as a rapidly advancing research frontier in recent years. Early studies have demonstrated their superior activity in activating peroxymonosulfate or hydrogen peroxide for pollutant degradation compared to conventional nanoparticle catalysts, while recent efforts have shifted toward precise structural engineering and mechanistic understanding of reaction pathways. However, the transition from laboratory-scale synthesis to industrial implementation remains challenging, due to difficulties in developing green and scalable fabrication methods, long-term instability in complex water matrices, leaching of metal active centers, and the lack of cost-effective integration into continuous-flow systems such as fixed-bed reactors. To date, comprehensive reviews addressing their engineering applications remain limited. This review systematically summarizes advances in synthetic strategies and characterization techniques for achieving atomic dispersion, elucidates the structure–activity relationships and synergistic radical/non-radical mechanisms, and evaluates reactor design and scale-up potential. Particular emphasis is placed on operational adaptability and economic feasibility under real-world conditions. Future perspectives include the rational design of novel MXene supports, machine learning-assisted catalyst optimization, hybrid process integration, and the development of sustainability assessment frameworks, aiming to bridge the gap between fundamental discoveries and practical water purification technologies.
2026, 37(8): 112527
doi: 10.1016/j.cclet.2026.112527
摘要:
2026, 37(8): 112642
doi: 10.1016/j.cclet.2026.112642
摘要:
2026, 37(5): 110827
doi: 10.1016/j.cclet.2025.110827
摘要:
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
2026, 37(5): 110829
doi: 10.1016/j.cclet.2025.110829
摘要:
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
2026, 37(5): 110851
doi: 10.1016/j.cclet.2025.110851
摘要:
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
2026, 37(5): 110852
doi: 10.1016/j.cclet.2025.110852
摘要:
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
2026, 37(5): 110858
doi: 10.1016/j.cclet.2025.110858
摘要:
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
2026, 37(5): 110859
doi: 10.1016/j.cclet.2025.110859
摘要:
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
2026, 37(5): 110862
doi: 10.1016/j.cclet.2025.110862
摘要:
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
2026, 37(5): 110863
doi: 10.1016/j.cclet.2025.110863
摘要:
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
2026, 37(5): 110864
doi: 10.1016/j.cclet.2025.110864
摘要:
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
2026, 37(5): 110889
doi: 10.1016/j.cclet.2025.110889
摘要:
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
2026, 37(5): 110891
doi: 10.1016/j.cclet.2025.110891
摘要:
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
2026, 37(5): 110892
doi: 10.1016/j.cclet.2025.110892
摘要:
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
2026, 37(5): 110893
doi: 10.1016/j.cclet.2025.110893
摘要:
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
2026, 37(5): 110952
doi: 10.1016/j.cclet.2025.110952
摘要:
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
2026, 37(5): 110953
doi: 10.1016/j.cclet.2025.110953
摘要:
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
2026, 37(5): 110954
doi: 10.1016/j.cclet.2025.110954
摘要:
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
2026, 37(5): 110974
doi: 10.1016/j.cclet.2025.110974
摘要:
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
2026, 37(5): 111158
doi: 10.1016/j.cclet.2025.111158
摘要:
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
2026, 37(5): 111236
doi: 10.1016/j.cclet.2025.111236
摘要:
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
2026, 37(5): 111248
doi: 10.1016/j.cclet.2025.111248
摘要:
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
2026, 37(5): 111257
doi: 10.1016/j.cclet.2025.111257
摘要:
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
2026, 37(5): 111274
doi: 10.1016/j.cclet.2025.111274
摘要:
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
2026, 37(5): 111282
doi: 10.1016/j.cclet.2025.111282
摘要:
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
2026, 37(5): 111284
doi: 10.1016/j.cclet.2025.111284
摘要:
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
PROTAC degraders of FSP1 act as potent GPX4 sensitizers to induce ferroptosis for hepatoma treatment
2026, 37(5): 111285
doi: 10.1016/j.cclet.2025.111285
摘要:
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
2026, 37(5): 111291
doi: 10.1016/j.cclet.2025.111291
摘要:
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
2026, 37(5): 111292
doi: 10.1016/j.cclet.2025.111292
摘要:
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
2026, 37(5): 111318
doi: 10.1016/j.cclet.2025.111318
摘要:
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
2026, 37(5): 111324
doi: 10.1016/j.cclet.2025.111324
摘要:
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
2026, 37(5): 111334
doi: 10.1016/j.cclet.2025.111334
摘要:
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
2026, 37(5): 111336
doi: 10.1016/j.cclet.2025.111336
摘要:
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
2026, 37(5): 111337
doi: 10.1016/j.cclet.2025.111337
摘要:
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
2026, 37(5): 111338
doi: 10.1016/j.cclet.2025.111338
摘要:
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
2026, 37(5): 111343
doi: 10.1016/j.cclet.2025.111343
摘要:
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
2026, 37(5): 111347
doi: 10.1016/j.cclet.2025.111347
摘要:
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
2026, 37(5): 111350
doi: 10.1016/j.cclet.2025.111350
摘要:
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
2026, 37(5): 111356
doi: 10.1016/j.cclet.2025.111356
摘要:
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
2026, 37(5): 111381
doi: 10.1016/j.cclet.2025.111381
摘要:
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
2026, 37(5): 111399
doi: 10.1016/j.cclet.2025.111399
摘要:
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
2026, 37(5): 111401
doi: 10.1016/j.cclet.2025.111401
摘要:
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
2026, 37(5): 111403
doi: 10.1016/j.cclet.2025.111403
摘要:
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
2026, 37(5): 111405
doi: 10.1016/j.cclet.2025.111405
摘要:
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
2026, 37(5): 111407
doi: 10.1016/j.cclet.2025.111407
摘要:
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
2026, 37(5): 111419
doi: 10.1016/j.cclet.2025.111419
摘要:
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
2026, 37(5): 111426
doi: 10.1016/j.cclet.2025.111426
摘要:
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
2026, 37(5): 111429
doi: 10.1016/j.cclet.2025.111429
摘要:
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
2026, 37(5): 111430
doi: 10.1016/j.cclet.2025.111430
摘要:
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
2026, 37(5): 111442
doi: 10.1016/j.cclet.2025.111442
摘要:
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
2026, 37(5): 111443
doi: 10.1016/j.cclet.2025.111443
摘要:
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
2026, 37(5): 111454
doi: 10.1016/j.cclet.2025.111454
摘要:
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
2026, 37(5): 111461
doi: 10.1016/j.cclet.2025.111461
摘要:
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
2026, 37(5): 111484
doi: 10.1016/j.cclet.2025.111484
摘要:
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
2026, 37(5): 111499
doi: 10.1016/j.cclet.2025.111499
摘要:
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
2026, 37(5): 111501
doi: 10.1016/j.cclet.2025.111501
摘要:
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
2026, 37(5): 111544
doi: 10.1016/j.cclet.2025.111544
摘要:
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
2026, 37(5): 111555
doi: 10.1016/j.cclet.2025.111555
摘要:
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
2026, 37(5): 111614
doi: 10.1016/j.cclet.2025.111614
摘要:
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
2026, 37(5): 111615
doi: 10.1016/j.cclet.2025.111615
摘要:
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
2026, 37(5): 111616
doi: 10.1016/j.cclet.2025.111616
摘要:
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
2026, 37(5): 111617
doi: 10.1016/j.cclet.2025.111617
摘要:
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
2026, 37(5): 111649
doi: 10.1016/j.cclet.2025.111649
摘要:
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
2026, 37(5): 111706
doi: 10.1016/j.cclet.2025.111706
摘要:
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
2026, 37(5): 111717
doi: 10.1016/j.cclet.2025.111717
摘要:
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
2026, 37(5): 111720
doi: 10.1016/j.cclet.2025.111720
摘要:
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
2026, 37(5): 111789
doi: 10.1016/j.cclet.2025.111789
摘要:
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
2026, 37(5): 111790
doi: 10.1016/j.cclet.2025.111790
摘要:
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
2026, 37(5): 111791
doi: 10.1016/j.cclet.2025.111791
摘要:
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
2026, 37(5): 111811
doi: 10.1016/j.cclet.2025.111811
摘要:
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
2026, 37(5): 111825
doi: 10.1016/j.cclet.2025.111825
摘要:
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
2026, 37(5): 111838
doi: 10.1016/j.cclet.2025.111838
摘要:
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
2026, 37(5): 111839
doi: 10.1016/j.cclet.2025.111839
摘要:
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
2026, 37(5): 111840
doi: 10.1016/j.cclet.2025.111840
摘要:
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
2026, 37(5): 111844
doi: 10.1016/j.cclet.2025.111844
摘要:
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
2026, 37(5): 111851
doi: 10.1016/j.cclet.2025.111851
摘要:
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
2026, 37(5): 111853
doi: 10.1016/j.cclet.2025.111853
摘要:
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
2026, 37(5): 111857
doi: 10.1016/j.cclet.2025.111857
摘要:
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
2026, 37(5): 111858
doi: 10.1016/j.cclet.2025.111858
摘要:
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
2026, 37(5): 111860
doi: 10.1016/j.cclet.2025.111860
摘要:
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
2026, 37(5): 111862
doi: 10.1016/j.cclet.2025.111862
摘要:
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
2026, 37(5): 111864
doi: 10.1016/j.cclet.2025.111864
摘要:
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
2026, 37(5): 111874
doi: 10.1016/j.cclet.2025.111874
摘要:
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
2026, 37(5): 111903
doi: 10.1016/j.cclet.2025.111903
摘要:
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
2026, 37(5): 111914
doi: 10.1016/j.cclet.2025.111914
摘要:
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
2026, 37(5): 111923
doi: 10.1016/j.cclet.2025.111923
摘要:
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
2026, 37(5): 111927
doi: 10.1016/j.cclet.2025.111927
摘要:
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
2026, 37(5): 111931
doi: 10.1016/j.cclet.2025.111931
摘要:
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
2026, 37(5): 111935
doi: 10.1016/j.cclet.2025.111935
摘要:
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
2026, 37(5): 111975
doi: 10.1016/j.cclet.2025.111975
摘要:
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
2026, 37(5): 112064
doi: 10.1016/j.cclet.2025.112064
摘要:
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
2026, 37(5): 112202
doi: 10.1016/j.cclet.2025.112202
摘要:
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
2026, 37(5): 112348
doi: 10.1016/j.cclet.2025.112348
摘要:
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
2026, 37(5): 112373
doi: 10.1016/j.cclet.2026.112373
摘要:
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
2026, 37(5): 112417
doi: 10.1016/j.cclet.2026.112417
摘要:
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
2026, 37(5): 110860
doi: 10.1016/j.cclet.2025.110860
摘要:
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
2026, 37(5): 110973
doi: 10.1016/j.cclet.2025.110973
摘要:
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
2026, 37(5): 111262
doi: 10.1016/j.cclet.2025.111262
摘要:
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
2026, 37(5): 111319
doi: 10.1016/j.cclet.2025.111319
摘要:
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
2026, 37(5): 111390
doi: 10.1016/j.cclet.2025.111390
摘要:
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
2026, 37(5): 111392
doi: 10.1016/j.cclet.2025.111392
摘要:
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
2026, 37(5): 111396
doi: 10.1016/j.cclet.2025.111396
摘要:
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
2026, 37(5): 111707
doi: 10.1016/j.cclet.2025.111707
摘要:
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
2026, 37(5): 111843
doi: 10.1016/j.cclet.2025.111843
摘要:
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
2026, 37(5): 111861
doi: 10.1016/j.cclet.2025.111861
摘要:
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
2026, 37(5): 111902
doi: 10.1016/j.cclet.2025.111902
摘要:
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
2026, 37(5): 111904
doi: 10.1016/j.cclet.2025.111904
摘要:
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
2026, 37(5): 111915
doi: 10.1016/j.cclet.2025.111915
摘要:
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
2026, 37(5): 111929
doi: 10.1016/j.cclet.2025.111929
摘要:
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
2026, 37(5): 111960
doi: 10.1016/j.cclet.2025.111960
摘要:
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
2026, 37(5): 112142
doi: 10.1016/j.cclet.2025.112142
摘要:
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
2026, 37(5): 112235
doi: 10.1016/j.cclet.2025.112235
摘要:
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
2026, 37(5): 111876
doi: 10.1016/j.cclet.2025.111876
摘要:
2026, 37(5): 112260
doi: 10.1016/j.cclet.2025.112260
摘要:
