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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: 9.4
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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
2025, 36(9): 110303
doi: 10.1016/j.cclet.2024.110303
摘要:
An Fe-doped bimetallic ZnFe–MOF precursor was prepared using a microchannel reactor, and carbonization was conducted to synthesize a bimetallic catalyst (ZnFe–NC). The fundamental reason for the efficient activity of the catalyst was determined through an in-depth analysis of its structural composition and close correlation with the oxygen reduction reaction (ORR). The ZnFe–NC catalyst maintains a stable truncated rhombohedral morphology and a rich microporous structure, exhibiting excellent ORR activity and long-term stability. The experimental results show that compared with the reversible hydrogen electrode, it has a high half-wave potential of 0.902 V (E1/2), retains 94% of activity after 35,000 s of stability testing, and exhibits significant methanol tolerance in alkaline media. Density functional theory calculations confirm the synergistic effect between the Zn and Fe sites. Furthermore, the results indicate that the interaction between ZnFe–N6 coordination structures reduces the reaction energy barrier, thus enhancing intermediate adsorption during the ORR.
An Fe-doped bimetallic ZnFe–MOF precursor was prepared using a microchannel reactor, and carbonization was conducted to synthesize a bimetallic catalyst (ZnFe–NC). The fundamental reason for the efficient activity of the catalyst was determined through an in-depth analysis of its structural composition and close correlation with the oxygen reduction reaction (ORR). The ZnFe–NC catalyst maintains a stable truncated rhombohedral morphology and a rich microporous structure, exhibiting excellent ORR activity and long-term stability. The experimental results show that compared with the reversible hydrogen electrode, it has a high half-wave potential of 0.902 V (E1/2), retains 94% of activity after 35,000 s of stability testing, and exhibits significant methanol tolerance in alkaline media. Density functional theory calculations confirm the synergistic effect between the Zn and Fe sites. Furthermore, the results indicate that the interaction between ZnFe–N6 coordination structures reduces the reaction energy barrier, thus enhancing intermediate adsorption during the ORR.
2025, 36(9): 110304
doi: 10.1016/j.cclet.2024.110304
摘要:
Due to the ionic feature of the lanthanide ions, to straightly bridge two lanthanide (Ln) ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization (QTM) for single-molecule magnets (SMMs), a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent. Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ) complexes - {[LnLA(4-NH2py)5]2(µ-Cl)}[BPh4]3 (For LA- = 1-AdO-, 1Ln; for LA- = tBuO-, 2Ln; Ln = Dy, Gd). More uniquely, the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ) ions with local C5v symmetry. The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K (τ2K = 2706.89 and 1437.05 s for 1Dy and 2Dy) compared to the diluted ones with the approaching magnetic property of the C5v motifs (τ2K = 0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y). Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic, it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
Due to the ionic feature of the lanthanide ions, to straightly bridge two lanthanide (Ln) ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization (QTM) for single-molecule magnets (SMMs), a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent. Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ) complexes - {[LnLA(4-NH2py)5]2(µ-Cl)}[BPh4]3 (For LA- = 1-AdO-, 1Ln; for LA- = tBuO-, 2Ln; Ln = Dy, Gd). More uniquely, the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ) ions with local C5v symmetry. The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K (τ2K = 2706.89 and 1437.05 s for 1Dy and 2Dy) compared to the diluted ones with the approaching magnetic property of the C5v motifs (τ2K = 0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y). Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic, it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
2025, 36(9): 110305
doi: 10.1016/j.cclet.2024.110305
摘要:
Lithium-ion capacitors (LICs) hold promise as next-generation energy storage devices due to the synergy of the advantageous features of lithium-ion batteries (LIBs) and supercapacitors (SCs). Recently, the use of nanostructured conjugated carboxylate organic anode materials in LICs has attracted tremendous attention due to their high capacity, excellent capacitive behavior, design flexibility, and environmental friendliness. Nevertheless, no studies have reported the use of non-conjugated organic compounds in LICs. In this study, we report for the first time that non-conjugated adipamide (ADIPAM) nanocrystals fabricated using a dissolution-recrystallization self-assembly technique serve as an excellent anode material for LICs. The unique ADIPAM nanocrystals–PVDF–Super P conductive integrated network architecture accelerates Li+ ion and electron diffusion and enhances lithium storage capability. Consequently, ADIPAM electrodes exhibit a high capacity of 705.8 mAh/g, exceptional cycling stability (308 mAh/g after 2100 cycles at 5 A/g), and remarkable rate capability. Furthermore, a LIC full cell comprising the ADIPAM anode with a porous activated carbon cathode demonstrates a wide working window (4.5 V), high energy density (238.3 Wh/kg), and superb power density (22,500 W/kg). We believe this work may introduce a new approach to the design of non-conjugated organic materials for LICs.
Lithium-ion capacitors (LICs) hold promise as next-generation energy storage devices due to the synergy of the advantageous features of lithium-ion batteries (LIBs) and supercapacitors (SCs). Recently, the use of nanostructured conjugated carboxylate organic anode materials in LICs has attracted tremendous attention due to their high capacity, excellent capacitive behavior, design flexibility, and environmental friendliness. Nevertheless, no studies have reported the use of non-conjugated organic compounds in LICs. In this study, we report for the first time that non-conjugated adipamide (ADIPAM) nanocrystals fabricated using a dissolution-recrystallization self-assembly technique serve as an excellent anode material for LICs. The unique ADIPAM nanocrystals–PVDF–Super P conductive integrated network architecture accelerates Li+ ion and electron diffusion and enhances lithium storage capability. Consequently, ADIPAM electrodes exhibit a high capacity of 705.8 mAh/g, exceptional cycling stability (308 mAh/g after 2100 cycles at 5 A/g), and remarkable rate capability. Furthermore, a LIC full cell comprising the ADIPAM anode with a porous activated carbon cathode demonstrates a wide working window (4.5 V), high energy density (238.3 Wh/kg), and superb power density (22,500 W/kg). We believe this work may introduce a new approach to the design of non-conjugated organic materials for LICs.
2025, 36(9): 110307
doi: 10.1016/j.cclet.2024.110307
摘要:
Nickel-rich layered oxide cathode materials such as LiNi0.8Co0.1Mn0.1O2 (NCM811) undergo deleterious side reactions when coupled with sulfide solid-state electrolytes (SSEs). To address this issue, we propose a dual-functional Ti3(PO4)4 coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs. The electrochemically stabilized Ti3(PO4)4 coating prevents direct contact between the SSEs and NCM811, thereby inhibiting interfacial side reactions. In addition, the internal structure of NCM811 can be stabilized by Ti doping, which inhibits the oxygen release behavior of NCM811 at high charge state, preventing further electrochemical oxidation of the SSEs. The modified NCM811@TiP cathode exhibits excellent long cycle stability, with 74.4% capacity retention after 100 cycles at a cut-off voltage of 4.2 V. This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
Nickel-rich layered oxide cathode materials such as LiNi0.8Co0.1Mn0.1O2 (NCM811) undergo deleterious side reactions when coupled with sulfide solid-state electrolytes (SSEs). To address this issue, we propose a dual-functional Ti3(PO4)4 coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs. The electrochemically stabilized Ti3(PO4)4 coating prevents direct contact between the SSEs and NCM811, thereby inhibiting interfacial side reactions. In addition, the internal structure of NCM811 can be stabilized by Ti doping, which inhibits the oxygen release behavior of NCM811 at high charge state, preventing further electrochemical oxidation of the SSEs. The modified NCM811@TiP cathode exhibits excellent long cycle stability, with 74.4% capacity retention after 100 cycles at a cut-off voltage of 4.2 V. This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
2025, 36(9): 110326
doi: 10.1016/j.cclet.2024.110326
摘要:
Non-covalent interactions-driven host-guest assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties. We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip AgⅠ or CuⅠ cations for circularly polarized phosphorescence (CPP), driven by the integration of two-fold coordination and heterometallophilic interactions. The AuⅠ-based hosts and metal ions-guests formed sandwich structures in 1:1 ratio with high binding affinity. The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals, which were attributed to the newly formed ligand to metal-metal charge transfer process. Remarkably, the host-guest supramolecular adducts showed turn-on phosphorescence and CPP, which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime. Overall, our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-guest complexes.
Non-covalent interactions-driven host-guest assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties. We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip AgⅠ or CuⅠ cations for circularly polarized phosphorescence (CPP), driven by the integration of two-fold coordination and heterometallophilic interactions. The AuⅠ-based hosts and metal ions-guests formed sandwich structures in 1:1 ratio with high binding affinity. The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals, which were attributed to the newly formed ligand to metal-metal charge transfer process. Remarkably, the host-guest supramolecular adducts showed turn-on phosphorescence and CPP, which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime. Overall, our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-guest complexes.
2025, 36(9): 110327
doi: 10.1016/j.cclet.2024.110327
摘要:
Here, we present a regulation strategy involving heteroatom doping and structural construction to adjust zincophilic sites and electric field distribution, achieving a robust and dendrite-free Zn host anode. Theoretical calculations and experimental results confirm that sulfur atoms can provide moderate zincophilicity, while graphene-like nanosheets can even the electric field distribution, imparting the sulfur-doped graphene-like network (S-GP) with a longer lifespan (exceeding 500 h) and acceptable coulombic efficiency. Importantly, the S-GP host is used as the substrate for flexible Zn-ion batteries, exhibiting impressive electrochemical performance and great mechanical flexibility, indicating a broad application prospect in portable and wearable electronic devices.
Here, we present a regulation strategy involving heteroatom doping and structural construction to adjust zincophilic sites and electric field distribution, achieving a robust and dendrite-free Zn host anode. Theoretical calculations and experimental results confirm that sulfur atoms can provide moderate zincophilicity, while graphene-like nanosheets can even the electric field distribution, imparting the sulfur-doped graphene-like network (S-GP) with a longer lifespan (exceeding 500 h) and acceptable coulombic efficiency. Importantly, the S-GP host is used as the substrate for flexible Zn-ion batteries, exhibiting impressive electrochemical performance and great mechanical flexibility, indicating a broad application prospect in portable and wearable electronic devices.
2025, 36(9): 110328
doi: 10.1016/j.cclet.2024.110328
摘要:
The NASICON-structured Na3MnTi(PO4)3 (NMTP) cathode has attracted widespread attention due to its prominent thermal stability, stable 3D structure and rapid sodium ion transport channel. However, the poor cycling stability, limited electronic conductivity and phase transition represent significant obstacles to for its commercialization. Herein, an innovative mixed-conducting interphase, comprising amorphous carbon and Ti3C2-MXene, was developed for NMTP. NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption, and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte. Furthermore, DFT calculations demonstrate that MXene enhances both electron and ion transport processes. Therefore, the mixed-conducting interphase, forming an interconnected network on the NMTP surface, serves as an artificial cathode electrolyte interface, significantly enhancing the dynamic processes and cycle stability of the NMTP cathode. The NMTP/C@Ti3C2 exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis. An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C, corresponding to an extremely high energy density of 466.6 Wh/kg. This study presents an effective approach for developing high-energy SIB cathodes.
The NASICON-structured Na3MnTi(PO4)3 (NMTP) cathode has attracted widespread attention due to its prominent thermal stability, stable 3D structure and rapid sodium ion transport channel. However, the poor cycling stability, limited electronic conductivity and phase transition represent significant obstacles to for its commercialization. Herein, an innovative mixed-conducting interphase, comprising amorphous carbon and Ti3C2-MXene, was developed for NMTP. NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption, and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte. Furthermore, DFT calculations demonstrate that MXene enhances both electron and ion transport processes. Therefore, the mixed-conducting interphase, forming an interconnected network on the NMTP surface, serves as an artificial cathode electrolyte interface, significantly enhancing the dynamic processes and cycle stability of the NMTP cathode. The NMTP/C@Ti3C2 exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis. An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C, corresponding to an extremely high energy density of 466.6 Wh/kg. This study presents an effective approach for developing high-energy SIB cathodes.
2025, 36(9): 110329
doi: 10.1016/j.cclet.2024.110329
摘要:
The synthesis of Ta-substituted polyoxometalates has always been an attractive but challenging goal. Three novel tantalum-containing 12-tungsto-2-phosphates were successfully prepared using the water bath method. The monomer, K11Li[P2W12(TaO2)6O56]·19H2O (1), is composed of {P2W12} and 6 {Ta(O2)} building blocks, similar to [P2W12(NbO2)6O56]12−. Monomer 1 polymerized to form two cis-trans dimers, K13Li6H-cis-[P2W12Ta4(TaO2)2O59]2·61H2O (2) and KNa3Li4H12-trans-[P2W12Ta4(TaO2)2O59]2·37H2O (3). Compounds 1–3 can serve as a structural motif to manufacture additional fascinating molecular clusters, promoting the advancement of POM chemistry. In contrast to [P2W12(NbO2)6O56]12−, compound 1 exhibits exceptional stability, evidenced by ESI-MS, IR, and NMR spectroscopy. In addition, 2 and 3 exhibit high proton conductivity and superior water adsorption properties.
The synthesis of Ta-substituted polyoxometalates has always been an attractive but challenging goal. Three novel tantalum-containing 12-tungsto-2-phosphates were successfully prepared using the water bath method. The monomer, K11Li[P2W12(TaO2)6O56]·19H2O (1), is composed of {P2W12} and 6 {Ta(O2)} building blocks, similar to [P2W12(NbO2)6O56]12−. Monomer 1 polymerized to form two cis-trans dimers, K13Li6H-cis-[P2W12Ta4(TaO2)2O59]2·61H2O (2) and KNa3Li4H12-trans-[P2W12Ta4(TaO2)2O59]2·37H2O (3). Compounds 1–3 can serve as a structural motif to manufacture additional fascinating molecular clusters, promoting the advancement of POM chemistry. In contrast to [P2W12(NbO2)6O56]12−, compound 1 exhibits exceptional stability, evidenced by ESI-MS, IR, and NMR spectroscopy. In addition, 2 and 3 exhibit high proton conductivity and superior water adsorption properties.
2025, 36(9): 110330
doi: 10.1016/j.cclet.2024.110330
摘要:
Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks (COFs) because of the different electronic and porous structures. However, very rare attention has been paid on the dimensionality and function correlations of COF materials. In the present work, one new two-dimensional phthalocyanine COF, namely 2D-NiPc-COF, and one new three-dimensional phthalocyanine COF, namely 3D-NiPc-COF, were fabricated according to the imide reaction between tetraanhydrides of 2, 3, 9, 10, 16, 17, 23, 24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2, 2-bipyridine]-5, 5-diamine and tetrakis(4-aminophenyl) methane, respectively. The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis, computational simulation, and high resolution transmission electron microscopy measurement. Notably, 3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%, almost two times higher than the in-plane stacking 2D-NiPc-COF measured by electrochemical measurement, in turn resulting in its superior electrocatalytic performance with high CO2-to-CO Faradaic efficiency over 90% in a wide potential window, a large partial CO current density of −13.97 mA/cm2 at −0.9 V (vs. reversible hydrogen electrode) to 2D-NiPc-COF. Moreover, 3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s-1 at −0.8 V during 8 h lasting measurement. The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.
Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks (COFs) because of the different electronic and porous structures. However, very rare attention has been paid on the dimensionality and function correlations of COF materials. In the present work, one new two-dimensional phthalocyanine COF, namely 2D-NiPc-COF, and one new three-dimensional phthalocyanine COF, namely 3D-NiPc-COF, were fabricated according to the imide reaction between tetraanhydrides of 2, 3, 9, 10, 16, 17, 23, 24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2, 2-bipyridine]-5, 5-diamine and tetrakis(4-aminophenyl) methane, respectively. The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis, computational simulation, and high resolution transmission electron microscopy measurement. Notably, 3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%, almost two times higher than the in-plane stacking 2D-NiPc-COF measured by electrochemical measurement, in turn resulting in its superior electrocatalytic performance with high CO2-to-CO Faradaic efficiency over 90% in a wide potential window, a large partial CO current density of −13.97 mA/cm2 at −0.9 V (vs. reversible hydrogen electrode) to 2D-NiPc-COF. Moreover, 3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s-1 at −0.8 V during 8 h lasting measurement. The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.
2025, 36(9): 110345
doi: 10.1016/j.cclet.2024.110345
摘要:
Conventional polycrystalline LiMn2O4 (PC-LMO) suffers from poor Li+ diffusion rates and structural instability, negatively affecting its electrochemical performance. Here, we design a single-crystal LMO cathode material using BaO flux (SC-LMOB) to address these issues. The BaO flux enables the fabrication of brick-like single-crystal particles, enhancing Li+ diffusion by shortening the diffusion path and increasing the unit cell volume. This process also reduces the specific surface area and stabilizes the crystal structure, effectively mitigating Mn dissolution and polarization. As a result, SC-LMOB exhibits ultra-high rate performance and superior structural stability, retaining 88.8% of its capacity at a 20 C discharge rate and achieving capacity retentions of 85.3% and 86.0% after 500 and 300 cycles at 1 C at room and elevated temperatures, respectively. This structural design offers a low-cost, scalable approach for fabricating single-crystal cathode materials with excellent performance.
Conventional polycrystalline LiMn2O4 (PC-LMO) suffers from poor Li+ diffusion rates and structural instability, negatively affecting its electrochemical performance. Here, we design a single-crystal LMO cathode material using BaO flux (SC-LMOB) to address these issues. The BaO flux enables the fabrication of brick-like single-crystal particles, enhancing Li+ diffusion by shortening the diffusion path and increasing the unit cell volume. This process also reduces the specific surface area and stabilizes the crystal structure, effectively mitigating Mn dissolution and polarization. As a result, SC-LMOB exhibits ultra-high rate performance and superior structural stability, retaining 88.8% of its capacity at a 20 C discharge rate and achieving capacity retentions of 85.3% and 86.0% after 500 and 300 cycles at 1 C at room and elevated temperatures, respectively. This structural design offers a low-cost, scalable approach for fabricating single-crystal cathode materials with excellent performance.
2025, 36(9): 110346
doi: 10.1016/j.cclet.2024.110346
摘要:
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost, environmentally friendly and high safety. Nevertheless, the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance. Cation-disordered rocksalt (DRX) Li2FeTiO4 shows promising properties as symmetric electrodes, based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window. Unfortunately, this cation-disordered structure would not provide a cross-path for the rapid migration of Li+, ultimately resulting in inferior electrochemical dynamics and cycle stability. Herein, Li2FeTiO4 nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants. Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic (e.g., stable Fe2+/Fe3+, Ti3+/Ti4+ and moderated Fe3+/Fe4+) and anionic redox, and maintain the DRX structure well during the cycling process. The half cells with nano-sized Li2FeTiO4 as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g, respectively. Besides, the Li2FeTiO4//Li2FeTiO4 symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles. This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost, environmentally friendly and high safety. Nevertheless, the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance. Cation-disordered rocksalt (DRX) Li2FeTiO4 shows promising properties as symmetric electrodes, based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window. Unfortunately, this cation-disordered structure would not provide a cross-path for the rapid migration of Li+, ultimately resulting in inferior electrochemical dynamics and cycle stability. Herein, Li2FeTiO4 nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants. Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic (e.g., stable Fe2+/Fe3+, Ti3+/Ti4+ and moderated Fe3+/Fe4+) and anionic redox, and maintain the DRX structure well during the cycling process. The half cells with nano-sized Li2FeTiO4 as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g, respectively. Besides, the Li2FeTiO4//Li2FeTiO4 symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles. This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
2025, 36(9): 110371
doi: 10.1016/j.cclet.2024.110371
摘要:
In recent years, metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides. However, they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics. Herein, yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom (N, P, S)-doped carbon framework (Co9S8/CoP@NPSC) were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes. The synergistic effect of Co9S8 and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability. In addition, the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na+/K+ transport. The electrochemical results demonstrated that Co9S8/CoP@NPSC exhibited the pleasant reversible capacity (360.47 mAh/g at 1 A/g) after 300 cycles and an unpredictable cycling stability (103.22 mAh/g after 1000 cycles) in the SIBs application. The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure. This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.
In recent years, metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides. However, they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics. Herein, yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom (N, P, S)-doped carbon framework (Co9S8/CoP@NPSC) were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes. The synergistic effect of Co9S8 and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability. In addition, the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na+/K+ transport. The electrochemical results demonstrated that Co9S8/CoP@NPSC exhibited the pleasant reversible capacity (360.47 mAh/g at 1 A/g) after 300 cycles and an unpredictable cycling stability (103.22 mAh/g after 1000 cycles) in the SIBs application. The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure. This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.
2025, 36(9): 110547
doi: 10.1016/j.cclet.2024.110547
摘要:
The photocatalytic reduction of CO2 presents a promising avenue for carbon fuel conversion. However, the efficiency of charge utilization remains a critical barrier to industrial applications. In this study, we introduce a tandem design of Bi2WO6-BiOCl with an atomically matched interface, achieving highly efficient photoreduction of CO2 to CO. By incorporating WO42− ions and tuning coordination environment, the (110) facet of BiOCl was in-situ grown on the (200) facet of Bi2WO6. Compared to single phases and ball-milling samples, Bi2WO6-BiOCl exhibits a remarkable CO yield of 68.03 µmol g−1 h−1 with a selectivity of 98%. Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport. Density functional theory (DFT) calculations and in-situ Fourier transform infrared (FTIR) spectroscopy provide insights into the intrinsic active sites and reaction mechanisms. The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.
The photocatalytic reduction of CO2 presents a promising avenue for carbon fuel conversion. However, the efficiency of charge utilization remains a critical barrier to industrial applications. In this study, we introduce a tandem design of Bi2WO6-BiOCl with an atomically matched interface, achieving highly efficient photoreduction of CO2 to CO. By incorporating WO42− ions and tuning coordination environment, the (110) facet of BiOCl was in-situ grown on the (200) facet of Bi2WO6. Compared to single phases and ball-milling samples, Bi2WO6-BiOCl exhibits a remarkable CO yield of 68.03 µmol g−1 h−1 with a selectivity of 98%. Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport. Density functional theory (DFT) calculations and in-situ Fourier transform infrared (FTIR) spectroscopy provide insights into the intrinsic active sites and reaction mechanisms. The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.
2025, 36(9): 110653
doi: 10.1016/j.cclet.2024.110653
摘要:
Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor (CMOS) image sensors. Herein, a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups (NO2, CN, Br) as diazo components were designed and synthesized. The presence of intermolecular hydrogen bonding between the hydrogen atom on the NH group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring. Additionally, the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure. As a result, these azo dyes (P-2, P-3, P-4, P-5) exhibit not only excellent light stability but also ultra-highly thermal stability (Td > 260 ℃). Therein, the synthesized dyes P-2 and P-3 with great bright yellow color (~400 nm), proper solubility (~6.00 g/100 g) were selected to make for color films. And their dye-based color films displayed ultra-highly thermal and light stability (color difference ΔE < 3). Notably, the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance (>90%) in the 550–780 nm wavelength range and the solvent resistance of the dye-based color films. This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.
Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor (CMOS) image sensors. Herein, a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups (NO2, CN, Br) as diazo components were designed and synthesized. The presence of intermolecular hydrogen bonding between the hydrogen atom on the NH group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring. Additionally, the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure. As a result, these azo dyes (P-2, P-3, P-4, P-5) exhibit not only excellent light stability but also ultra-highly thermal stability (Td > 260 ℃). Therein, the synthesized dyes P-2 and P-3 with great bright yellow color (~400 nm), proper solubility (~6.00 g/100 g) were selected to make for color films. And their dye-based color films displayed ultra-highly thermal and light stability (color difference ΔE < 3). Notably, the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance (>90%) in the 550–780 nm wavelength range and the solvent resistance of the dye-based color films. This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.
2025, 36(9): 110658
doi: 10.1016/j.cclet.2024.110658
摘要:
Rheumatoid arthritis (RA) is a refractory autoimmune disease with limited treatment options. Plant-derived exosomes-like nanovesicles (PDENs) have emerged as a novel nanomedical approach, with the inherent bioactive compounds from their source plants. The roots of Morinda officinalis How. (MO), a Chinese herb, exhibit notable anti-inflammatory activities and hold promising therapeutic value. We engineered a joint-targeting delivery system (termed MOE@EM) by masking MO-derived exosomes-like nanovesicles (MOE) with erythrocyte membrane (EM). This biomimetic strategy, using EM camouflage, is intended to improve the in vivo fate of MOE. We investigated the antioxidative and anti-inflammatory activities, immunogenicity, drug accumulation in the joint, and therapeutic efficacy to ascertain its suitability for RA therapy. UV irradiation significantly increased the activities of catalase and peroxidase of MOE, and enhanced the anti-inflammatory effects via the Wnt/β-catenin pathway. Furthermore, MOE@EM markedly attenuated dendritic cell activation. MOE@EM exhibited joint-specific delivery, with substantial reduction in paw swelling, and favorable modulation of immune microenvironment.
Rheumatoid arthritis (RA) is a refractory autoimmune disease with limited treatment options. Plant-derived exosomes-like nanovesicles (PDENs) have emerged as a novel nanomedical approach, with the inherent bioactive compounds from their source plants. The roots of Morinda officinalis How. (MO), a Chinese herb, exhibit notable anti-inflammatory activities and hold promising therapeutic value. We engineered a joint-targeting delivery system (termed MOE@EM) by masking MO-derived exosomes-like nanovesicles (MOE) with erythrocyte membrane (EM). This biomimetic strategy, using EM camouflage, is intended to improve the in vivo fate of MOE. We investigated the antioxidative and anti-inflammatory activities, immunogenicity, drug accumulation in the joint, and therapeutic efficacy to ascertain its suitability for RA therapy. UV irradiation significantly increased the activities of catalase and peroxidase of MOE, and enhanced the anti-inflammatory effects via the Wnt/β-catenin pathway. Furthermore, MOE@EM markedly attenuated dendritic cell activation. MOE@EM exhibited joint-specific delivery, with substantial reduction in paw swelling, and favorable modulation of immune microenvironment.
2025, 36(9): 110659
doi: 10.1016/j.cclet.2024.110659
摘要:
In this work, atomic Co catalysts are anchored on a three-dimensional (3D) interconnected g-C3N4 (SACo-CN) through Co-N coordination, which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate (PMS). The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples. The 3D interconnected structure, combined with the synergistic interplay between Co-N coordination and visible light irradiation, results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation. This leads to a degradation rate of 98.8% for oxytetracycline (OTC) within 30 min under visible light. The research proposes three potential mineralization pathways with eight intermediates, leading to a significant decrease in the toxicity of the intermediates. This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
In this work, atomic Co catalysts are anchored on a three-dimensional (3D) interconnected g-C3N4 (SACo-CN) through Co-N coordination, which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate (PMS). The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples. The 3D interconnected structure, combined with the synergistic interplay between Co-N coordination and visible light irradiation, results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation. This leads to a degradation rate of 98.8% for oxytetracycline (OTC) within 30 min under visible light. The research proposes three potential mineralization pathways with eight intermediates, leading to a significant decrease in the toxicity of the intermediates. This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
2025, 36(9): 110661
doi: 10.1016/j.cclet.2024.110661
摘要:
The healing of diabetic wounds poses a significant healthcare burden due to persistent inflammation, M1 macrophage aggregation, and high glucose levels in the microenvironment. Previous studies have demonstrated that immunomodulatory hydrogel dressings can facilitate diabetic wound healing. However, current immunomodulatory hydrogels require costly and complex treatments such as cell therapy and cytokines. Herein, a hierarchical hydrogel dressing with continuous biochemical gradient based on glycyrrhizic acid (GA) was constructed to modulate immunomodulatory processes in diabetic wounds. The hydrogels present many desirable features, such as tunable mechanical properties, broad antibacterial ability, outstanding conductive, transparent, and self-adhesive properties. The resultant hydrogel can promote diabetic wound healing by preventing bacterial infection, promoting macrophage polarization, improving the inflammatory microenvironment, and inducing angiogenesis and neurogenesis. Furthermore, electrical stimulation (ES) can further promote the healing of chronic diabetic wounds, providing valuable guidance for relevant clinical practice.
The healing of diabetic wounds poses a significant healthcare burden due to persistent inflammation, M1 macrophage aggregation, and high glucose levels in the microenvironment. Previous studies have demonstrated that immunomodulatory hydrogel dressings can facilitate diabetic wound healing. However, current immunomodulatory hydrogels require costly and complex treatments such as cell therapy and cytokines. Herein, a hierarchical hydrogel dressing with continuous biochemical gradient based on glycyrrhizic acid (GA) was constructed to modulate immunomodulatory processes in diabetic wounds. The hydrogels present many desirable features, such as tunable mechanical properties, broad antibacterial ability, outstanding conductive, transparent, and self-adhesive properties. The resultant hydrogel can promote diabetic wound healing by preventing bacterial infection, promoting macrophage polarization, improving the inflammatory microenvironment, and inducing angiogenesis and neurogenesis. Furthermore, electrical stimulation (ES) can further promote the healing of chronic diabetic wounds, providing valuable guidance for relevant clinical practice.
2025, 36(9): 110671
doi: 10.1016/j.cclet.2024.110671
摘要:
Worsened air pollution has been linked to elevated rates of cardiovascular disease (CVD) morbidity and mortality. Atherosclerosis, a shared pathophysiological foundation for various CVD manifestations, plays a crucial role. Although foam cell formation is hypothesized to be a contributing factor, the precise mechanisms by which air pollution accelerates the advancement of atherosclerotic plaques remain unidentified. In this study, an atherosclerosis-susceptible apolipoprotein E-deficient (ApoE−/−) mouse model was employed to examine the influence of real-world environmental PM2.5 exposure on atherosclerosis. Metabolomic analysis was performed to identify potential biomarkers that may play a role in atherogenesis following PM2.5 exposure. Our findings revealed that mice fed a high-cholesterol diet (HCD) exhibited susceptibility to PM2.5 exposure, as evidenced by increased inflammation, enhanced fibrosis, and enlarged foam cell formation in the aorta. The interactive effects between PM2.5 exposure and HCD disrupted the secretion of certain chemokines. The metabolomic data provided additional insights into how PM2.5 exposure alters prostaglandin levels, contributing to the progression of atherosclerotic lesions. These findings enhance our understanding of the pivotal role of arachidonic acid metabolism in the etiology of PM2.5-induced cardiovascular risks and elucidate the mechanisms by which PM2.5 exposure leads to vascular damage in populations with high cholesterol intake.
Worsened air pollution has been linked to elevated rates of cardiovascular disease (CVD) morbidity and mortality. Atherosclerosis, a shared pathophysiological foundation for various CVD manifestations, plays a crucial role. Although foam cell formation is hypothesized to be a contributing factor, the precise mechanisms by which air pollution accelerates the advancement of atherosclerotic plaques remain unidentified. In this study, an atherosclerosis-susceptible apolipoprotein E-deficient (ApoE−/−) mouse model was employed to examine the influence of real-world environmental PM2.5 exposure on atherosclerosis. Metabolomic analysis was performed to identify potential biomarkers that may play a role in atherogenesis following PM2.5 exposure. Our findings revealed that mice fed a high-cholesterol diet (HCD) exhibited susceptibility to PM2.5 exposure, as evidenced by increased inflammation, enhanced fibrosis, and enlarged foam cell formation in the aorta. The interactive effects between PM2.5 exposure and HCD disrupted the secretion of certain chemokines. The metabolomic data provided additional insights into how PM2.5 exposure alters prostaglandin levels, contributing to the progression of atherosclerotic lesions. These findings enhance our understanding of the pivotal role of arachidonic acid metabolism in the etiology of PM2.5-induced cardiovascular risks and elucidate the mechanisms by which PM2.5 exposure leads to vascular damage in populations with high cholesterol intake.
2025, 36(9): 110673
doi: 10.1016/j.cclet.2024.110673
摘要:
In this study, we present a self-driven photoelectrocatalytic (SD-PEC) system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power. The system utilizes a titanium dioxide nanorod array (TNR) photoelectrode coupled with a silicon solar cell to optimize electron transport, while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes (CCNT/CF), which efficiently reduce UO22+. The results demonstrate significant removal efficiency of uranium (complete removal in 25 min at a rate constant of ~0.248 min-1), as well as substantial degradation of organic impurities. Furthermore, the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions, including simulated seawater and real uranium tailings wastewater. These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater. The significance of this research extends to global environmental challenges, offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.
In this study, we present a self-driven photoelectrocatalytic (SD-PEC) system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power. The system utilizes a titanium dioxide nanorod array (TNR) photoelectrode coupled with a silicon solar cell to optimize electron transport, while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes (CCNT/CF), which efficiently reduce UO22+. The results demonstrate significant removal efficiency of uranium (complete removal in 25 min at a rate constant of ~0.248 min-1), as well as substantial degradation of organic impurities. Furthermore, the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions, including simulated seawater and real uranium tailings wastewater. These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater. The significance of this research extends to global environmental challenges, offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.
2025, 36(9): 110674
doi: 10.1016/j.cclet.2024.110674
摘要:
Periodontitis is a chronic inflammatory disease caused by oral pathogens, and the osteogenic potential of human periodontal ligament stem cells (hPDLSCs) is severely impaired under the inflammatory environment. Current clinical periodontitis treatment strategies such as surgical interventions and antibiotic delivery still suffer from poor antibacterial efficacy, difficulty in ameliorating excessive inflammatory responses and slow periodontal tissue regeneration. Here, we have innovatively developed a non-surgical treatment strategy based on a functional composite hydrogel. A composite hydrogel system (Pt@ZIF-8/ALN-ac/Gel) containing bioactive zeolite imidazolate framework-8 (ZIF-8) integrated with platinum nanoparticles (Pt@ZIF-8) and alendronate acrylamide (ALN-ac) was constructed on the basis of gelatin methacryloyl (GelMA) to achieve enhanced antibacterial effect and reactive oxygen species (ROS) scavenging ability while promoting the osteogenic potential of hPDLSCs. We confirmed that Pt@ZIF-8/ALN-ac/Gel was able to continuously release Zn2+ and exerted an obvious antibacterial effect against Porphyromonas gingivalis. In vitro experiments proved that Pt@ZIF-8/ALN-ac/Gel had good biocompatibility, while efficiently featuring excellent reactive oxygen species (ROS) scavenging capacity, increasing alkaline phosphatase activity, and promoting extracellular matrix mineralization by hPDLSCs. In vivo, Pt@ZIF-8/ALN-ac/Gel significantly inhibited the alveolar bone deterioration and reduced osteoclast activation and inflammation, thereby promoting the regeneration of damaged tissues. These findings demonstrated superior therapeutic efficacy in the reported clinical periodontitis treatment, exhibiting great potential for application.
Periodontitis is a chronic inflammatory disease caused by oral pathogens, and the osteogenic potential of human periodontal ligament stem cells (hPDLSCs) is severely impaired under the inflammatory environment. Current clinical periodontitis treatment strategies such as surgical interventions and antibiotic delivery still suffer from poor antibacterial efficacy, difficulty in ameliorating excessive inflammatory responses and slow periodontal tissue regeneration. Here, we have innovatively developed a non-surgical treatment strategy based on a functional composite hydrogel. A composite hydrogel system (Pt@ZIF-8/ALN-ac/Gel) containing bioactive zeolite imidazolate framework-8 (ZIF-8) integrated with platinum nanoparticles (Pt@ZIF-8) and alendronate acrylamide (ALN-ac) was constructed on the basis of gelatin methacryloyl (GelMA) to achieve enhanced antibacterial effect and reactive oxygen species (ROS) scavenging ability while promoting the osteogenic potential of hPDLSCs. We confirmed that Pt@ZIF-8/ALN-ac/Gel was able to continuously release Zn2+ and exerted an obvious antibacterial effect against Porphyromonas gingivalis. In vitro experiments proved that Pt@ZIF-8/ALN-ac/Gel had good biocompatibility, while efficiently featuring excellent reactive oxygen species (ROS) scavenging capacity, increasing alkaline phosphatase activity, and promoting extracellular matrix mineralization by hPDLSCs. In vivo, Pt@ZIF-8/ALN-ac/Gel significantly inhibited the alveolar bone deterioration and reduced osteoclast activation and inflammation, thereby promoting the regeneration of damaged tissues. These findings demonstrated superior therapeutic efficacy in the reported clinical periodontitis treatment, exhibiting great potential for application.
2025, 36(9): 110687
doi: 10.1016/j.cclet.2024.110687
摘要:
Two racemic pairs of new stilbenoid dimers, (±)-heterosmilaxones A (1) and B (2), with unique 6/6/6and 6/5/7 tricyclic core systems, respectively, were isolated from the rhizomes of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic analyses, quantum chemical calculations and X-ray diffraction crystallography. Compound (+)-1, initially reported as syagrusin Awith a 1,4,4a,9a-tetrahydrofluoren-9-one skeleton, is now revised to a new structure characteristic witha benzo bicyclo[3.3.1] nonene scaffold. And compound 2 bears an unprecedented carbon skeleton withfour continuous chiral centers in the central benzo bicyclo[4.2.1]nonene motif. Biogenetically, both 1 and 2 were proposed to derive from 3,3',4,5,5'-pentahydroxy stilbene and could be generated through keyinverse-electron-demand [4 + 2] and [5 + 2] cycloadditions, respectively. Interestingly, both (±)-1 and(±)-2 showed significant inhibition against α-glucosidase. (±)-1 and its pure enantiomers could modulate protein tyrosine phosphatase-1B (PTP1B) enzyme activities and increased glucose consumption inHepG2 cells in a dose-dependent manner.
Two racemic pairs of new stilbenoid dimers, (±)-heterosmilaxones A (1) and B (2), with unique 6/6/6and 6/5/7 tricyclic core systems, respectively, were isolated from the rhizomes of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic analyses, quantum chemical calculations and X-ray diffraction crystallography. Compound (+)-1, initially reported as syagrusin Awith a 1,4,4a,9a-tetrahydrofluoren-9-one skeleton, is now revised to a new structure characteristic witha benzo bicyclo[3.3.1] nonene scaffold. And compound 2 bears an unprecedented carbon skeleton withfour continuous chiral centers in the central benzo bicyclo[4.2.1]nonene motif. Biogenetically, both 1 and 2 were proposed to derive from 3,3',4,5,5'-pentahydroxy stilbene and could be generated through keyinverse-electron-demand [4 + 2] and [5 + 2] cycloadditions, respectively. Interestingly, both (±)-1 and(±)-2 showed significant inhibition against α-glucosidase. (±)-1 and its pure enantiomers could modulate protein tyrosine phosphatase-1B (PTP1B) enzyme activities and increased glucose consumption inHepG2 cells in a dose-dependent manner.
2025, 36(9): 110703
doi: 10.1016/j.cclet.2024.110703
摘要:
The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes, therefore greatly restricting its convenient and broad application. In this study, a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase (ALP) detection was established, only employing Prussian blue (PB) nanozymes and a commercially available chromogen of o-phenylenediamine (OPD). PB nanozymes with remarkable peroxidase-like (POD-like) activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine (OPDox) with an intense yellow fluorescence at 573 nm emission peak. Target ALP can facilitate ascorbic acid 2-phosphate (AAP) dephosphorylation to generate phosphate and ascorbic acid (AA). Significantly, both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dual-path based inhibition on the PB nanozymes POD-like activity. On the other hand, the generated dehydroascorbic acid (DHAA) from AA oxidation would exclusively react with OPD chromogen to yield 3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one (DFQ) with a strong blue fluorescent signal at 434 nm, which further providing a significant enhancement on the sensing selectivity of ALP detection. As a result, an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition. A robust linear relationship between the fluorescence ratio of F434/F573 and ALP activity ranging from 0.25 U/L to 6 U/L was obtained, with a low detection limit of 0.112 U/L. This proposed method demonstrates high sensitivity, excellent selectivity, cost-effectiveness, and operational simplicity, yet enabling an effective detection of ALP levels in human serum.
The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes, therefore greatly restricting its convenient and broad application. In this study, a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase (ALP) detection was established, only employing Prussian blue (PB) nanozymes and a commercially available chromogen of o-phenylenediamine (OPD). PB nanozymes with remarkable peroxidase-like (POD-like) activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine (OPDox) with an intense yellow fluorescence at 573 nm emission peak. Target ALP can facilitate ascorbic acid 2-phosphate (AAP) dephosphorylation to generate phosphate and ascorbic acid (AA). Significantly, both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dual-path based inhibition on the PB nanozymes POD-like activity. On the other hand, the generated dehydroascorbic acid (DHAA) from AA oxidation would exclusively react with OPD chromogen to yield 3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one (DFQ) with a strong blue fluorescent signal at 434 nm, which further providing a significant enhancement on the sensing selectivity of ALP detection. As a result, an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition. A robust linear relationship between the fluorescence ratio of F434/F573 and ALP activity ranging from 0.25 U/L to 6 U/L was obtained, with a low detection limit of 0.112 U/L. This proposed method demonstrates high sensitivity, excellent selectivity, cost-effectiveness, and operational simplicity, yet enabling an effective detection of ALP levels in human serum.
2025, 36(9): 110704
doi: 10.1016/j.cclet.2024.110704
摘要:
Nanomaterials that can sequentially respond to internal and external stimuli, functioning as a sequential gate, have great potential for targeting different aspects of antitumor immunity. Herein, we construct a mannose-modified, pH and reactive oxygen species (ROS) sequential-responsive, transformable dual-immunofunction nanoprodrug (MpRTNP). This nanoprodrug encapsulates a transforming growth factor-β (TGF-β) receptor inhibitor SD-208 (MpRTNP@SD), to simultaneously alleviate the immunosuppressive effects of TGF-β and tumor-associated macrophages (TAMs). In the weakly acidic tumor microenvironment (TME), the vesicle-micelle morphology transformation occurs owing to the protonation of PC7A, which is accompanied by SD-208 release to inhibit cancer-associated fibroblasts and regulatory T cells. The transformed micelles then target TAMs via mannose receptor-mediated endocytosis. Upon laser irradiation, the thioketal linker is cleaved, releasing conjugated chlorin e6 and generating ROS, which facilitates TAM polarization. The PC7A+ segment activates the stimulator of the interferon gene in TAMs with elevated phosphorylation of TANK binding kinase 1 and interferon regulatory factor 3, and type Ⅰ interferon secretion. MpRTNP@SD displays superior abscopal effects and robust antitumor immunity, as evidenced by increased CD8+/CD4+ T cell infiltration and reduced regulatory T cell (Treg) ratios. Mouse survival time is prolonged after combination with the CD47 antibody. This study provides a novel strategy for potent antitumor immunotherapy through pH and ROS sequential-gated spatiotemporal regulation of the TME.
Nanomaterials that can sequentially respond to internal and external stimuli, functioning as a sequential gate, have great potential for targeting different aspects of antitumor immunity. Herein, we construct a mannose-modified, pH and reactive oxygen species (ROS) sequential-responsive, transformable dual-immunofunction nanoprodrug (MpRTNP). This nanoprodrug encapsulates a transforming growth factor-β (TGF-β) receptor inhibitor SD-208 (MpRTNP@SD), to simultaneously alleviate the immunosuppressive effects of TGF-β and tumor-associated macrophages (TAMs). In the weakly acidic tumor microenvironment (TME), the vesicle-micelle morphology transformation occurs owing to the protonation of PC7A, which is accompanied by SD-208 release to inhibit cancer-associated fibroblasts and regulatory T cells. The transformed micelles then target TAMs via mannose receptor-mediated endocytosis. Upon laser irradiation, the thioketal linker is cleaved, releasing conjugated chlorin e6 and generating ROS, which facilitates TAM polarization. The PC7A+ segment activates the stimulator of the interferon gene in TAMs with elevated phosphorylation of TANK binding kinase 1 and interferon regulatory factor 3, and type Ⅰ interferon secretion. MpRTNP@SD displays superior abscopal effects and robust antitumor immunity, as evidenced by increased CD8+/CD4+ T cell infiltration and reduced regulatory T cell (Treg) ratios. Mouse survival time is prolonged after combination with the CD47 antibody. This study provides a novel strategy for potent antitumor immunotherapy through pH and ROS sequential-gated spatiotemporal regulation of the TME.
2025, 36(9): 110708
doi: 10.1016/j.cclet.2024.110708
摘要:
The investigation of reaction kinetics is the key to understanding the nature of reaction processes. However, monitoring fast photochemical reactions by mass spectrometry remains challenging. Herein, we developed an optical focusing inductive electrospray (OF-iESI) mass spectrometry platform for real-time and in-situ photoreaction monitoring. Coaxial irradiation from back of nanoelectrospray emitter with a taper section was utilized, so the emitter could act as optical lens to help achieving much larger optical power density at emitter tip compared to other sections, which allowed for in-situ reaction monitoring of photoreactions. Through theoretical calculations, the highest optical power density region volume was ca. 45 nL. We also integrated a controller for the laser source (450 nm), enabling the modulation of pulse duration (>1 ms). This facilitates the study of photochemical reaction kinetics. The in-situ capability of this device was proved by capturing the short-lived photogenerated intermediates during the dehydrogenation of tetrahydroquinoline. This device was further used to investigate the kinetics of triplet energy transfer based Paternò–Büchi reaction. The reaction order has hitherto remained undetermined while the result of OF-iESI suggested it followed pseudo-second-order reaction kinetics. The short-lived donor-acceptor collision complex intermediate was also successfully identified by tandem mass spectrometry.
The investigation of reaction kinetics is the key to understanding the nature of reaction processes. However, monitoring fast photochemical reactions by mass spectrometry remains challenging. Herein, we developed an optical focusing inductive electrospray (OF-iESI) mass spectrometry platform for real-time and in-situ photoreaction monitoring. Coaxial irradiation from back of nanoelectrospray emitter with a taper section was utilized, so the emitter could act as optical lens to help achieving much larger optical power density at emitter tip compared to other sections, which allowed for in-situ reaction monitoring of photoreactions. Through theoretical calculations, the highest optical power density region volume was ca. 45 nL. We also integrated a controller for the laser source (450 nm), enabling the modulation of pulse duration (>1 ms). This facilitates the study of photochemical reaction kinetics. The in-situ capability of this device was proved by capturing the short-lived photogenerated intermediates during the dehydrogenation of tetrahydroquinoline. This device was further used to investigate the kinetics of triplet energy transfer based Paternò–Büchi reaction. The reaction order has hitherto remained undetermined while the result of OF-iESI suggested it followed pseudo-second-order reaction kinetics. The short-lived donor-acceptor collision complex intermediate was also successfully identified by tandem mass spectrometry.
2025, 36(9): 110712
doi: 10.1016/j.cclet.2024.110712
摘要:
Active sulfur dissolution and shuttle effect of lithium polysulfides (LiPSs) are the main obstacles hindering the practical application of lithium-sulfur batteries (LSBs), which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte. The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur. Herein, conductive composite nanofabrics (CCN) with multifunctional groups are employed as the interlayer of sulfur-loading cathode, in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance, and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs. As demonstrated by the experimental data and material characterizations, the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs, but also strengthens the interface stability of both Li anode and sulfur-loading cathode. Interestingly, the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g. This work will provide new ideas for the elaborate design of functional interlayers/separators for LSBs and lithium metal batteries.
Active sulfur dissolution and shuttle effect of lithium polysulfides (LiPSs) are the main obstacles hindering the practical application of lithium-sulfur batteries (LSBs), which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte. The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur. Herein, conductive composite nanofabrics (CCN) with multifunctional groups are employed as the interlayer of sulfur-loading cathode, in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance, and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs. As demonstrated by the experimental data and material characterizations, the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs, but also strengthens the interface stability of both Li anode and sulfur-loading cathode. Interestingly, the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g. This work will provide new ideas for the elaborate design of functional interlayers/separators for LSBs and lithium metal batteries.
2025, 36(9): 110713
doi: 10.1016/j.cclet.2024.110713
摘要:
Rheumatoid arthritis (RA) is a chronic inflammatory disease with multi-system damage and autoimmune features. The main clinical manifestations of RA include joint pain, swelling, and stiffness, and RA may lead to joint deformity and dysfunction in severe cases. The pathologic development of RA involves complex interactions of multiple biomarkers, and detecting a single biomarker may produce false-positive results due to other confounding factors. Therefore, fluorescent probes that can detect multiple biomarkers simultaneously are crucial for precise RA diagnosis. Peroxynitrite (ONOO−) and viscosity are inflammation-related factors in cells. In this study, we developed a dual responsive near-infrared fluorescent probe, YLS, for ONOO− and viscosity. The probe features dual-channel turn-on fluorescence responses at 625 and 760 nm upon the presence of ONOO− and viscosity, respectively. Supported by YLS, we found that during RA pathology, lymphocyte infiltration not only increases the concentration of proteins in the joint fluid resulting in elevated viscosity; at the same time, the overproduction of ONOO− exacerbates oxidative stress and inflammatory responses. This multiparameter assay is expected to improve the diagnostic accuracy of the early stages of RA, thus providing a scientific basis for early intervention and personalized treatment.
Rheumatoid arthritis (RA) is a chronic inflammatory disease with multi-system damage and autoimmune features. The main clinical manifestations of RA include joint pain, swelling, and stiffness, and RA may lead to joint deformity and dysfunction in severe cases. The pathologic development of RA involves complex interactions of multiple biomarkers, and detecting a single biomarker may produce false-positive results due to other confounding factors. Therefore, fluorescent probes that can detect multiple biomarkers simultaneously are crucial for precise RA diagnosis. Peroxynitrite (ONOO−) and viscosity are inflammation-related factors in cells. In this study, we developed a dual responsive near-infrared fluorescent probe, YLS, for ONOO− and viscosity. The probe features dual-channel turn-on fluorescence responses at 625 and 760 nm upon the presence of ONOO− and viscosity, respectively. Supported by YLS, we found that during RA pathology, lymphocyte infiltration not only increases the concentration of proteins in the joint fluid resulting in elevated viscosity; at the same time, the overproduction of ONOO− exacerbates oxidative stress and inflammatory responses. This multiparameter assay is expected to improve the diagnostic accuracy of the early stages of RA, thus providing a scientific basis for early intervention and personalized treatment.
2025, 36(9): 110715
doi: 10.1016/j.cclet.2024.110715
摘要:
Although aggregation-induced emission (AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging, the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood. Herein, we elucidate the mechanisms governing the tetraphenylethene (TPE)’s function (rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7. Our study shows that modulating the frontier orbital energy difference (ΔE (DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3, act as a rotor in Cy5 uniquely devoid of aggregation activation, or neither in Cy7. In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity. We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.
Although aggregation-induced emission (AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging, the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood. Herein, we elucidate the mechanisms governing the tetraphenylethene (TPE)’s function (rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7. Our study shows that modulating the frontier orbital energy difference (ΔE (DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3, act as a rotor in Cy5 uniquely devoid of aggregation activation, or neither in Cy7. In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity. We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.
2025, 36(9): 110716
doi: 10.1016/j.cclet.2024.110716
摘要:
The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. The solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.
The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. The solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.
2025, 36(9): 110717
doi: 10.1016/j.cclet.2024.110717
摘要:
Majority of photodynamic therapy (PDT) or photothermal therapy (PTT) is achieved by the integration of photosensitizers or photothermal agents into nanocarriers, which may bring risks due to uncertain leakage with serious nonspecific damage to normal tissues. Thus, we report an imine-linked nanoscale covalent organic framework (COF) with intrinsic photo-response ability, showing a high singlet oxygen generation ability by 660 nm irradiation, followed by the surface fabrication of polydopamine (PDA) that displays an excellent photothermal conversion performance under 808 nm irradiation. Furthermore, therapeutic agents with the modulation capacity of subcellular organelle such as mitochondria, shows more precision and effectiveness in cancer therapy. Herein, the obtained COF@PDA nanoplatform not only provides an excellent PDT/PTT-in-one therapeutic effect on inhibition of MCF-7 cancer cells, but also gives a prominent photo-induced mitochondrial regulation performance for enhanced treatment.
Majority of photodynamic therapy (PDT) or photothermal therapy (PTT) is achieved by the integration of photosensitizers or photothermal agents into nanocarriers, which may bring risks due to uncertain leakage with serious nonspecific damage to normal tissues. Thus, we report an imine-linked nanoscale covalent organic framework (COF) with intrinsic photo-response ability, showing a high singlet oxygen generation ability by 660 nm irradiation, followed by the surface fabrication of polydopamine (PDA) that displays an excellent photothermal conversion performance under 808 nm irradiation. Furthermore, therapeutic agents with the modulation capacity of subcellular organelle such as mitochondria, shows more precision and effectiveness in cancer therapy. Herein, the obtained COF@PDA nanoplatform not only provides an excellent PDT/PTT-in-one therapeutic effect on inhibition of MCF-7 cancer cells, but also gives a prominent photo-induced mitochondrial regulation performance for enhanced treatment.
2025, 36(9): 110718
doi: 10.1016/j.cclet.2024.110718
摘要:
Drug resistance poses a significant challenge to effective long-term treatment across various medical fields. This study proposed a feasible strategy to enhance lysosomal alkalinization by transporting mitochondria-targeting quaternary ammonium salts into lysosomes, creating a deprotonated environment. This environment allows drugs to bypass protonation issues in lysosomes, thereby reversing drug resistance and improving therapeutic efficacy. As a proof of concept, a quaternary ammonium salt-based pH indicator was developed, berberrubine (BRB), enhancing the action of the anticancer drug hydroxycamptothecin (HCPT) in resistant cells. BRB-induced alkalinization increased lysosomal pH and deactivated lysosomal activity, enabling HCPT to bypass protonation constraints. This enhancement markedly improved the anticancer efficacy of HCPT in resistant cells, providing an innovative approach to address drug resistance and advancing therapeutic technologies.
Drug resistance poses a significant challenge to effective long-term treatment across various medical fields. This study proposed a feasible strategy to enhance lysosomal alkalinization by transporting mitochondria-targeting quaternary ammonium salts into lysosomes, creating a deprotonated environment. This environment allows drugs to bypass protonation issues in lysosomes, thereby reversing drug resistance and improving therapeutic efficacy. As a proof of concept, a quaternary ammonium salt-based pH indicator was developed, berberrubine (BRB), enhancing the action of the anticancer drug hydroxycamptothecin (HCPT) in resistant cells. BRB-induced alkalinization increased lysosomal pH and deactivated lysosomal activity, enabling HCPT to bypass protonation constraints. This enhancement markedly improved the anticancer efficacy of HCPT in resistant cells, providing an innovative approach to address drug resistance and advancing therapeutic technologies.
2025, 36(9): 110720
doi: 10.1016/j.cclet.2024.110720
摘要:
For chromatographic separation, the reasonable modulation of stationary phases is the key factor to achieve high separation performance. We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution. MIL-125, MIL-125-NH2, MIL-143-BTB, and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands. MIL-125-NH2 and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts, MIL-125 and MIL-143-BTB, respectively. The investigation of the separation mechanism indicated that thermodynamic interaction, rather than kinetic diffusion, was responsible for the separation improvement. MIL-125-NH2 and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB, respectively, resulting in enhanced separation performance. This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.
For chromatographic separation, the reasonable modulation of stationary phases is the key factor to achieve high separation performance. We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution. MIL-125, MIL-125-NH2, MIL-143-BTB, and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands. MIL-125-NH2 and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts, MIL-125 and MIL-143-BTB, respectively. The investigation of the separation mechanism indicated that thermodynamic interaction, rather than kinetic diffusion, was responsible for the separation improvement. MIL-125-NH2 and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB, respectively, resulting in enhanced separation performance. This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.
2025, 36(9): 110721
doi: 10.1016/j.cclet.2024.110721
摘要:
DNA repair enzymes are important in the repair of DNA lesions for maintaining the genome stability, and their abnormal expression induced various human cancers. Simultaneous detection of these DNA enzymes could provide convincing evidence based on the comparison of the activity of multiple enzymes than on that of single enzyme. Although fluorescence approach has been applied for the simultaneous detection both of DNA repair enzymes, the spectral overlap and multiwavelength excitation severely restrict the number of available fluorophores. Thus, it is difficult to simultaneously detect three enzymes in a single analysis by fluorescence detection. Herein, we developed a method for the simultaneous determination of three DNA repair enzymes including human flap DNA endonuclease 1 (FEN1), human alkyladenine DNA glycosylase (hAAG) and uracil DNA glycosylase (UDG) based on the combination of template-free amplification system with capillary electrophoresis-laser induced fluorescence (CE-LIF) detection. The amplification system was adopted to transfer and amplify the enzymatic products into different length DNA fragments which could be separated effectively by CE-LIF without the complicated modification of the capillary inner wall or labeling different tails on signal probes for separation. The method demonstrated a detection limit of 0.07 U/mL (0.08-160 U/mL) for FEN1, 2.40 U/mL (2.5-250 U/mL) for hAAG and 2.1 × 10−4 U/mL (0.0004-2.5 U/mL) for UDG, the relative standard deviations (RSDs) of peak time and peak area for different analytes were as follows: 2.50%-4.37% and 3.24%-7.18% (inter-day); 1.37%-2.71% and 1.43%-3.02% (intra-day), 4.28%-6.08% and 4.16%-7.57% (column to column), respectively. And it can identify the inhibitor-like drugs, evaluate enzymatic kinetics and achieve the detection of three enzymes in cell extracts, providing a simple and powerful platform for simultaneous detection of more DNA repair enzymes.
DNA repair enzymes are important in the repair of DNA lesions for maintaining the genome stability, and their abnormal expression induced various human cancers. Simultaneous detection of these DNA enzymes could provide convincing evidence based on the comparison of the activity of multiple enzymes than on that of single enzyme. Although fluorescence approach has been applied for the simultaneous detection both of DNA repair enzymes, the spectral overlap and multiwavelength excitation severely restrict the number of available fluorophores. Thus, it is difficult to simultaneously detect three enzymes in a single analysis by fluorescence detection. Herein, we developed a method for the simultaneous determination of three DNA repair enzymes including human flap DNA endonuclease 1 (FEN1), human alkyladenine DNA glycosylase (hAAG) and uracil DNA glycosylase (UDG) based on the combination of template-free amplification system with capillary electrophoresis-laser induced fluorescence (CE-LIF) detection. The amplification system was adopted to transfer and amplify the enzymatic products into different length DNA fragments which could be separated effectively by CE-LIF without the complicated modification of the capillary inner wall or labeling different tails on signal probes for separation. The method demonstrated a detection limit of 0.07 U/mL (0.08-160 U/mL) for FEN1, 2.40 U/mL (2.5-250 U/mL) for hAAG and 2.1 × 10−4 U/mL (0.0004-2.5 U/mL) for UDG, the relative standard deviations (RSDs) of peak time and peak area for different analytes were as follows: 2.50%-4.37% and 3.24%-7.18% (inter-day); 1.37%-2.71% and 1.43%-3.02% (intra-day), 4.28%-6.08% and 4.16%-7.57% (column to column), respectively. And it can identify the inhibitor-like drugs, evaluate enzymatic kinetics and achieve the detection of three enzymes in cell extracts, providing a simple and powerful platform for simultaneous detection of more DNA repair enzymes.
2025, 36(9): 110723
doi: 10.1016/j.cclet.2024.110723
摘要:
The androgenetic alopecia (AGA) is the most prevalent clinical manifestation of hair loss, believed to be associated with excessive dihydrotestosterone (DHT) caused by type Ⅱ 5α-reductase (5αR2). The utilization of oral finasteride (FNS), which selectively inhibits 5αR2, is frequently constrained by its adverse effects. Topical FNS formulations can mitigate adverse effects but often exhibit limited dermal permeability. Nanocarriers show great potential in augmenting the cutaneous permeation of loaded FNS due to their inherent properties of selective accumulation within the hair follicles (HFs). In this study, hollow mesoporous silica nanoparticles (HMSN) with varying sizes were utilized as the nanocarriers for FNS, following mixing with the Carbopol hydrogel (F@H/Gel) for direct topical application. Specifically, the influence of size on the targeted delivery of FNS to HFs, and its enhanced therapeutic efficacy for the AGA mice model was evaluated. Results showed that the HMSN, with a diameter of approximately 300 nm, exhibited significant enhancement in FNS retention within skin and HFs, as well as remarkably accelerated hair regrowth on an AGA mouse model. In conclusion, this FNS topical formulation has proved to be a viable approach in offering a secure and efficient treatment modality for AGA.
The androgenetic alopecia (AGA) is the most prevalent clinical manifestation of hair loss, believed to be associated with excessive dihydrotestosterone (DHT) caused by type Ⅱ 5α-reductase (5αR2). The utilization of oral finasteride (FNS), which selectively inhibits 5αR2, is frequently constrained by its adverse effects. Topical FNS formulations can mitigate adverse effects but often exhibit limited dermal permeability. Nanocarriers show great potential in augmenting the cutaneous permeation of loaded FNS due to their inherent properties of selective accumulation within the hair follicles (HFs). In this study, hollow mesoporous silica nanoparticles (HMSN) with varying sizes were utilized as the nanocarriers for FNS, following mixing with the Carbopol hydrogel (F@H/Gel) for direct topical application. Specifically, the influence of size on the targeted delivery of FNS to HFs, and its enhanced therapeutic efficacy for the AGA mice model was evaluated. Results showed that the HMSN, with a diameter of approximately 300 nm, exhibited significant enhancement in FNS retention within skin and HFs, as well as remarkably accelerated hair regrowth on an AGA mouse model. In conclusion, this FNS topical formulation has proved to be a viable approach in offering a secure and efficient treatment modality for AGA.
2025, 36(9): 110735
doi: 10.1016/j.cclet.2024.110735
摘要:
In this work, we synthesize two luminescent Pt(Ⅱ) complexes using different π-conjugated bidentate ligands. Both complexes are assembled into three-dimensional (3D) networks through non-classical intermolecular interactions in the crystal state. Unexpectedly, substituting pyridine with the more extensively π-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands. This alteration disrupts the π-π interactions between molecules, resulting in distinct optical properties upon exposure to external stimuli. By integrating these complexes into polymers, we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes. These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials, achieved through the employment of simple chromophores.
In this work, we synthesize two luminescent Pt(Ⅱ) complexes using different π-conjugated bidentate ligands. Both complexes are assembled into three-dimensional (3D) networks through non-classical intermolecular interactions in the crystal state. Unexpectedly, substituting pyridine with the more extensively π-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands. This alteration disrupts the π-π interactions between molecules, resulting in distinct optical properties upon exposure to external stimuli. By integrating these complexes into polymers, we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes. These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials, achieved through the employment of simple chromophores.
2025, 36(9): 110737
doi: 10.1016/j.cclet.2024.110737
摘要:
Structure-based virtual screening utilizing the approved drugs is an intriguing and laudable approach to excavate novel alternatives for different indications based on the vast amount of reported experimental data. Virus superfamily 1 helicase could resolve hydrogen bonds between base pairs and participate in nucleic acid replication and has emerged as a potential target for managing virus infection. Nonetheless, current drug exploitation targeting viral helicases is still in infancy. This work establishes an intelligent multi-computational screening programme to screen potential inhibitors targeting tobacco mosaic virus (TMV) helicase using Food and Drug Administration (FDA)-approved commercially available molecule library. The ranked top 6 hits were further validated by root mean square deviations/fluctuations (RMSD/F), molecular mechanics Poisson Boltzmann surface area (MM-PBSA), density functional theory (DFT) calculations, and bioactivity evaluation. Encouragingly, lumacaftor (ΔEtotal = −29.0 kcal/mol, Kd = 0.22 µmol/L, half maximal inhibitory concentration (IC50) = 162.5 µmol/L) displayed superior binding strength and enzyme inhibition against TMV helicase compared to ningnanmycin (Kd = 9.35 µmol/L, IC50 > 200 µmol/L). Therefore, lumacaftor may be able to inhibit TMV replication by binding to helicase and interfering with its biofunctionability. Besides, the lumacaftor-helicase binding mode changes from H-bonding/electrostatic interactions to hydrophobic interactions in trajectory analysis. Overall, current findings suggest this state-of-the-art stratagem is fruitful and has the potential to be engaged in rapid mining of other target inhibitors for disease treatment.
Structure-based virtual screening utilizing the approved drugs is an intriguing and laudable approach to excavate novel alternatives for different indications based on the vast amount of reported experimental data. Virus superfamily 1 helicase could resolve hydrogen bonds between base pairs and participate in nucleic acid replication and has emerged as a potential target for managing virus infection. Nonetheless, current drug exploitation targeting viral helicases is still in infancy. This work establishes an intelligent multi-computational screening programme to screen potential inhibitors targeting tobacco mosaic virus (TMV) helicase using Food and Drug Administration (FDA)-approved commercially available molecule library. The ranked top 6 hits were further validated by root mean square deviations/fluctuations (RMSD/F), molecular mechanics Poisson Boltzmann surface area (MM-PBSA), density functional theory (DFT) calculations, and bioactivity evaluation. Encouragingly, lumacaftor (ΔEtotal = −29.0 kcal/mol, Kd = 0.22 µmol/L, half maximal inhibitory concentration (IC50) = 162.5 µmol/L) displayed superior binding strength and enzyme inhibition against TMV helicase compared to ningnanmycin (Kd = 9.35 µmol/L, IC50 > 200 µmol/L). Therefore, lumacaftor may be able to inhibit TMV replication by binding to helicase and interfering with its biofunctionability. Besides, the lumacaftor-helicase binding mode changes from H-bonding/electrostatic interactions to hydrophobic interactions in trajectory analysis. Overall, current findings suggest this state-of-the-art stratagem is fruitful and has the potential to be engaged in rapid mining of other target inhibitors for disease treatment.
2025, 36(9): 110740
doi: 10.1016/j.cclet.2024.110740
摘要:
The induction of antitumor immunity by tumor antigens released from cancer cells following regional photothermal therapy (PTT) alone may not be adequate for achieving complete tumor elimination. Combination therapy with immune adjuvants enhances antitumor immune responses, but faces challenges such as targeting deficiencies, systemic toxicity, and uncontrolled release behavior. Herein, we introduce a novel dual-functional hybrid membrane nanoparticle (HM-NP) incorporating gold nanorods (GNRs) and a thermally responsive polymer shell. HM-NP demonstrates exceptional homotypic targeting efficacy beneath the tumor cell membrane (TM), leading to substantial tumor accumulation. Upon in situ near-infrared (NIR) stimulation, GNRs within HM-NP generate heat, triggering the burst release of HM by facilitating the contraction and disintegration of the thermally responsive polymer shell. HM-NP exhibits excellent photothermal conversion efficiency under NIR irradiation, enabling effective destruction of primary tumors, release of tumor-associated antigens, and stimulation of potent anti- cancer immune. Simultaneously, the immune responses are strengthened by TM and Escherichia coli membrane (EM) through promoting the maturation of antigen presenting cells (APCs) and activating cytotoxic T lymphocytes (CTLs). Moreover, the use of polymer shells enables efficient cancer therapy with minimal host clearance and adverse effects. This photothermally triggered immunotherapy holds promise for precise and personalized treatment of tumors.
The induction of antitumor immunity by tumor antigens released from cancer cells following regional photothermal therapy (PTT) alone may not be adequate for achieving complete tumor elimination. Combination therapy with immune adjuvants enhances antitumor immune responses, but faces challenges such as targeting deficiencies, systemic toxicity, and uncontrolled release behavior. Herein, we introduce a novel dual-functional hybrid membrane nanoparticle (HM-NP) incorporating gold nanorods (GNRs) and a thermally responsive polymer shell. HM-NP demonstrates exceptional homotypic targeting efficacy beneath the tumor cell membrane (TM), leading to substantial tumor accumulation. Upon in situ near-infrared (NIR) stimulation, GNRs within HM-NP generate heat, triggering the burst release of HM by facilitating the contraction and disintegration of the thermally responsive polymer shell. HM-NP exhibits excellent photothermal conversion efficiency under NIR irradiation, enabling effective destruction of primary tumors, release of tumor-associated antigens, and stimulation of potent anti- cancer immune. Simultaneously, the immune responses are strengthened by TM and Escherichia coli membrane (EM) through promoting the maturation of antigen presenting cells (APCs) and activating cytotoxic T lymphocytes (CTLs). Moreover, the use of polymer shells enables efficient cancer therapy with minimal host clearance and adverse effects. This photothermally triggered immunotherapy holds promise for precise and personalized treatment of tumors.
2025, 36(9): 110742
doi: 10.1016/j.cclet.2024.110742
摘要:
Current research in the direction of electrocatalytic reduction of CO2 (ECO2R) focuses on the preparation of catalysts with excellent performance, but little has been reported on the effect of electrolyte type on the selectivity of ECO2R gas products. In this work, the ECO2R performance of unmodified Cu foam (CF) was systematically investigated in four electrolytes (KCl, NaCl, KHCO3, and NaHCO3) at different concentrations (0.1, 0.5 and 1.0 mol/L), using CF as the working electrode. The results showed that CF exhibited high selectivity for C2H4 in KCl solution, while high selectivity for CH4 in low concentration NaCl and NaHCO3 solutions containing Na+. In addition, serious hydrogen evolution reactions (HERs) were observed in both KHCO3 and NaHCO3 solutions at higher concentrations, which were attributed to the lower local pH of the two buffer solutions. It was also shown that solution resistance of the cathode electrolyte during ECO2R process decreased consistently due to the trans-membrane diffusion of K+ and Na+, especially at the low concentration of electrolyte of 0.1 mol/L. It was detrimental to keep the reduction process stabilized for a long period of time. Furthermore, the non-buffered solutions KCl and NaCl also maintained a neutral pH (≈ 6.7) after a period of ECO2R, resulting in a stable ECO2R. The results of this work will provide significant insights into the design of reaction systems of ECO2R in the future.
Current research in the direction of electrocatalytic reduction of CO2 (ECO2R) focuses on the preparation of catalysts with excellent performance, but little has been reported on the effect of electrolyte type on the selectivity of ECO2R gas products. In this work, the ECO2R performance of unmodified Cu foam (CF) was systematically investigated in four electrolytes (KCl, NaCl, KHCO3, and NaHCO3) at different concentrations (0.1, 0.5 and 1.0 mol/L), using CF as the working electrode. The results showed that CF exhibited high selectivity for C2H4 in KCl solution, while high selectivity for CH4 in low concentration NaCl and NaHCO3 solutions containing Na+. In addition, serious hydrogen evolution reactions (HERs) were observed in both KHCO3 and NaHCO3 solutions at higher concentrations, which were attributed to the lower local pH of the two buffer solutions. It was also shown that solution resistance of the cathode electrolyte during ECO2R process decreased consistently due to the trans-membrane diffusion of K+ and Na+, especially at the low concentration of electrolyte of 0.1 mol/L. It was detrimental to keep the reduction process stabilized for a long period of time. Furthermore, the non-buffered solutions KCl and NaCl also maintained a neutral pH (≈ 6.7) after a period of ECO2R, resulting in a stable ECO2R. The results of this work will provide significant insights into the design of reaction systems of ECO2R in the future.
2025, 36(9): 110768
doi: 10.1016/j.cclet.2024.110768
摘要:
The objective of this study was to predict, screen, synthesize, and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid (PA). To improve the efficiency and success rate of experimental screening, two virtual tools based on hydrogen bond propensity (HBP) and modified molecular electrostatic potential (MEP) maps were used. The prediction accuracy of HBP and MEP is 58.82% and 94.11%, respectively, presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals. Among the 12 successfully obtained cocrystals, 4 single crystals of PA with luteolin (LUT), genistein (GEN), taxifolin (TAX), dihydromyricetin (DHM) were obtained for the first time. Charged-assisted OH···O and NH···O hydrogen bonds appear as main hydrogen bonding synthons, and PA adopts a zwitterionic form after cocrystallization. GEN-PA, TAX-PA, and DHM-PA showed higher DPPH• radical-scavenging capacities; LUT-PA and DHM-PA showed higher ABTS+ radical-scavenging capacities; GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl2 than corresponding pure flavonoids.
The objective of this study was to predict, screen, synthesize, and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid (PA). To improve the efficiency and success rate of experimental screening, two virtual tools based on hydrogen bond propensity (HBP) and modified molecular electrostatic potential (MEP) maps were used. The prediction accuracy of HBP and MEP is 58.82% and 94.11%, respectively, presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals. Among the 12 successfully obtained cocrystals, 4 single crystals of PA with luteolin (LUT), genistein (GEN), taxifolin (TAX), dihydromyricetin (DHM) were obtained for the first time. Charged-assisted OH···O and NH···O hydrogen bonds appear as main hydrogen bonding synthons, and PA adopts a zwitterionic form after cocrystallization. GEN-PA, TAX-PA, and DHM-PA showed higher DPPH• radical-scavenging capacities; LUT-PA and DHM-PA showed higher ABTS+ radical-scavenging capacities; GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl2 than corresponding pure flavonoids.
2025, 36(9): 110783
doi: 10.1016/j.cclet.2024.110783
摘要:
Chondroitin sulfate (CS) B and T are rare subtypes of CS, which are scare in nature. There are also limited synthetic methods to prepare them. Here we report an ingenious semisynthetic approach to prepare a library of disaccharides, tetrasaccharides and hexasaccharides of CS-B and CS-T based on the acid or enzymatic degradation of natural CS polysaccharide in 9 or 10 steps. Our approach is the shortest synthetic route toward size-defined CS-B and CS-T oligosaccharides reported to date. In addition, a regioselective protection method of hydroxyls is highlighted, which has achieved the regioselective protection of 4 hydroxyl groups among 7 equatorial hydroxyl groups. By preparing size-defined rare CS oligosaccharides from commercially available natural CS polysaccharides, this strategy has the potential to meet the need of rare natural oligosaccharides.
Chondroitin sulfate (CS) B and T are rare subtypes of CS, which are scare in nature. There are also limited synthetic methods to prepare them. Here we report an ingenious semisynthetic approach to prepare a library of disaccharides, tetrasaccharides and hexasaccharides of CS-B and CS-T based on the acid or enzymatic degradation of natural CS polysaccharide in 9 or 10 steps. Our approach is the shortest synthetic route toward size-defined CS-B and CS-T oligosaccharides reported to date. In addition, a regioselective protection method of hydroxyls is highlighted, which has achieved the regioselective protection of 4 hydroxyl groups among 7 equatorial hydroxyl groups. By preparing size-defined rare CS oligosaccharides from commercially available natural CS polysaccharides, this strategy has the potential to meet the need of rare natural oligosaccharides.
2025, 36(9): 110785
doi: 10.1016/j.cclet.2024.110785
摘要:
Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials. Traditional structures like α-helices and β-sheets rely on such interactions for stability, limiting control over exposed interacting moieties. Here, we reported a novel, frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions. This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes. By introducing mutations at specific sites, we controlled packing orientations, offering new options for tunable self-assembly. Our scaffold provides a versatile platform for designing advanced peptide materials, with applications in nanotechnology and biomaterials.
Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials. Traditional structures like α-helices and β-sheets rely on such interactions for stability, limiting control over exposed interacting moieties. Here, we reported a novel, frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions. This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes. By introducing mutations at specific sites, we controlled packing orientations, offering new options for tunable self-assembly. Our scaffold provides a versatile platform for designing advanced peptide materials, with applications in nanotechnology and biomaterials.
2025, 36(9): 110786
doi: 10.1016/j.cclet.2024.110786
摘要:
Advances in controllable growth of ultrathin two-dimensional molecular crystals (2DMCs) or even monolayer molecular crystals (MMCs) propelled their application in high-performance, high-sensitivity, low-contact-resistance optoelectronic devices. However, the rational molecular design strategies for materials prone to grow into ultrathin 2DMC or MMC have rarely been addressed. Here, systematically tailoring the π-conjugation and alkyl chain types of asymmetric anthracene derivatives, 2DMCs and even MMCs were obtained under the synergetic regulation of inter- and intralayer interactions. High-quality MMCs were obtained for SAP-C6 by traditional physical vapor transport technique (PVT), and corresponding organic field-effect transistors (OFETs) exhibited high mobility of 3.22 cm2 V-1 s-1. In addition, band-like charge transport with low activation energy was achieved by SAP-C6 MMC-OFETs. Furthermore, the SAP-C6 MMC-based device exhibits excellent thermal stability, retaining ~70% of its initial performance at 140 ℃ in air, which is the first report on the thermal stability of MMC devices. This research highlights the potential of alkyl-substituted asymmetric molecules as a design strategy to achieve ultrathin 2DMC or MMC growth, and improve the mobility and thermal stability in OFETs.
Advances in controllable growth of ultrathin two-dimensional molecular crystals (2DMCs) or even monolayer molecular crystals (MMCs) propelled their application in high-performance, high-sensitivity, low-contact-resistance optoelectronic devices. However, the rational molecular design strategies for materials prone to grow into ultrathin 2DMC or MMC have rarely been addressed. Here, systematically tailoring the π-conjugation and alkyl chain types of asymmetric anthracene derivatives, 2DMCs and even MMCs were obtained under the synergetic regulation of inter- and intralayer interactions. High-quality MMCs were obtained for SAP-C6 by traditional physical vapor transport technique (PVT), and corresponding organic field-effect transistors (OFETs) exhibited high mobility of 3.22 cm2 V-1 s-1. In addition, band-like charge transport with low activation energy was achieved by SAP-C6 MMC-OFETs. Furthermore, the SAP-C6 MMC-based device exhibits excellent thermal stability, retaining ~70% of its initial performance at 140 ℃ in air, which is the first report on the thermal stability of MMC devices. This research highlights the potential of alkyl-substituted asymmetric molecules as a design strategy to achieve ultrathin 2DMC or MMC growth, and improve the mobility and thermal stability in OFETs.
2025, 36(9): 110797
doi: 10.1016/j.cclet.2024.110797
摘要:
The gut pathogen Enterocloster bolteae (E. bolteae) has been associated with autism spectrum disorder (ASD). The development of an E. bolteae vaccine to prevent gastrointestinal diseases, might be beneficial for understanding and treating ASD. Capsular polysaccharide (CPS) is a major virulence factor for E. bolteae. Based on an antigenicity evaluation of oligosaccharides associated with E. bolteae CPS and a structural revision of this carbohydrate antigen, two series of glycans including the d-Manp-d-Rhap type oligosaccharides 13–18 and the d-Ribp-d-Rhap type disaccharides 19–23 related to E. bolteae WAL-16351 CPS were prepared. The hydrogen-bond mediated glycosylation and conformational locking strategy facilitated the constructions of two 1,2-cis-β-glycosidic linkages. Glycan microarray analysis revealed that oligosaccharides 4, 5, and 19 are recognized by antibodies in the anti-E. bolteae sera. The sera IgG antibodies induced by glycoconjugate 19-CRM197 recognize the CPS and bacteria specifically, whereas the IgG antibodies induced respectively by glycoconjugates 4-CRM197 and 5-CRM197 showed almost no binding to the CPS and bacteria. These results indicated that disaccharide 19 is a potential candidate for the development of E. bolteae vaccines.
The gut pathogen Enterocloster bolteae (E. bolteae) has been associated with autism spectrum disorder (ASD). The development of an E. bolteae vaccine to prevent gastrointestinal diseases, might be beneficial for understanding and treating ASD. Capsular polysaccharide (CPS) is a major virulence factor for E. bolteae. Based on an antigenicity evaluation of oligosaccharides associated with E. bolteae CPS and a structural revision of this carbohydrate antigen, two series of glycans including the d-Manp-d-Rhap type oligosaccharides 13–18 and the d-Ribp-d-Rhap type disaccharides 19–23 related to E. bolteae WAL-16351 CPS were prepared. The hydrogen-bond mediated glycosylation and conformational locking strategy facilitated the constructions of two 1,2-cis-β-glycosidic linkages. Glycan microarray analysis revealed that oligosaccharides 4, 5, and 19 are recognized by antibodies in the anti-E. bolteae sera. The sera IgG antibodies induced by glycoconjugate 19-CRM197 recognize the CPS and bacteria specifically, whereas the IgG antibodies induced respectively by glycoconjugates 4-CRM197 and 5-CRM197 showed almost no binding to the CPS and bacteria. These results indicated that disaccharide 19 is a potential candidate for the development of E. bolteae vaccines.
2025, 36(9): 110807
doi: 10.1016/j.cclet.2024.110807
摘要:
Pyridine (Py) and 3-methylpyridine (3-MP) are crucial intermediates in chemical industrial processes. Here, we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril (Q[6]). The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases, with separation purities close to 100%. The selectivity is attributed to the varying stability of the host–guest complexes after the absorption of Py or 3-MP, as revealed by the single-crystal structure analysis. ITC experimental results and DFT calculations indicate that, compared to 3-MP, Q[6] has a higher binding strength and lower binding energy with Py. In addition, pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion, enabling Q[6] reuse via reversible guest loading. This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.
Pyridine (Py) and 3-methylpyridine (3-MP) are crucial intermediates in chemical industrial processes. Here, we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril (Q[6]). The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases, with separation purities close to 100%. The selectivity is attributed to the varying stability of the host–guest complexes after the absorption of Py or 3-MP, as revealed by the single-crystal structure analysis. ITC experimental results and DFT calculations indicate that, compared to 3-MP, Q[6] has a higher binding strength and lower binding energy with Py. In addition, pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion, enabling Q[6] reuse via reversible guest loading. This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.
2025, 36(9): 110808
doi: 10.1016/j.cclet.2024.110808
摘要:
Sulfur dioxide (SO2), being one of the therapeutic gaseous molecules, has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety. Nevertheless, the in situ-triggered and efficient transportation of SO2 to tumors are the main obstacles that restrict its clinical application. To overcome this impediment, we functionalized pillar[5]arene with 2, 4-dinitrobenzene sulfonic acid (DNSB) and then self-assembled it with tetraphenyl-PEG (TPE-PEG) in aqueous media to form fluorescent nanoparticles (PSTPE NPs). Meanwhile, the target guest (NH2-PEG-FA) was encapsulated within the spacious cavity of pillar[5]arene via host-guest interaction. The resulting nanoparticles possess distinctive characteristics: (Ⅰ) dual GSH recognition motifs for enhanced SO2 release kinetics; (Ⅱ) incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells; and (Ⅲ) surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility, biocompatibility, and fluorescence properties in aqueous environments. Collectively, this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO2 gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.
Sulfur dioxide (SO2), being one of the therapeutic gaseous molecules, has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety. Nevertheless, the in situ-triggered and efficient transportation of SO2 to tumors are the main obstacles that restrict its clinical application. To overcome this impediment, we functionalized pillar[5]arene with 2, 4-dinitrobenzene sulfonic acid (DNSB) and then self-assembled it with tetraphenyl-PEG (TPE-PEG) in aqueous media to form fluorescent nanoparticles (PSTPE NPs). Meanwhile, the target guest (NH2-PEG-FA) was encapsulated within the spacious cavity of pillar[5]arene via host-guest interaction. The resulting nanoparticles possess distinctive characteristics: (Ⅰ) dual GSH recognition motifs for enhanced SO2 release kinetics; (Ⅱ) incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells; and (Ⅲ) surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility, biocompatibility, and fluorescence properties in aqueous environments. Collectively, this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO2 gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.
2025, 36(9): 110809
doi: 10.1016/j.cclet.2024.110809
摘要:
Mechanistic studies of the cleavage and transformation of unactivated Csp3–H bonds are a significant field of chemistry. Overcoming the inherent low acidity of C–H bonds to activate the inert substrates is challenge under mild conditions. And their complex multi-step transformations may also hinder mechanistic understanding. Herein, we perform theoretical calculations and experimental studies to explore the Csp3–H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA. A synergistic "main and auxiliary" model was revealed involving dual lithium metal by LDA dimers, and the aryl dilithium species as an intermediate base can facilitate Csp3–H activation. This model not only aids in understanding the acidity of unactivated Csp3–H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions, but also predicts unusual kinetic isotope effects (KIE) for newly designed 2-(methylthio)naphthalene that are experimentally validated. This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated Csp3–H bonds and the development of new functionalities for alkali metal reagents.
Mechanistic studies of the cleavage and transformation of unactivated Csp3–H bonds are a significant field of chemistry. Overcoming the inherent low acidity of C–H bonds to activate the inert substrates is challenge under mild conditions. And their complex multi-step transformations may also hinder mechanistic understanding. Herein, we perform theoretical calculations and experimental studies to explore the Csp3–H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA. A synergistic "main and auxiliary" model was revealed involving dual lithium metal by LDA dimers, and the aryl dilithium species as an intermediate base can facilitate Csp3–H activation. This model not only aids in understanding the acidity of unactivated Csp3–H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions, but also predicts unusual kinetic isotope effects (KIE) for newly designed 2-(methylthio)naphthalene that are experimentally validated. This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated Csp3–H bonds and the development of new functionalities for alkali metal reagents.
2025, 36(9): 110810
doi: 10.1016/j.cclet.2024.110810
摘要:
Herein, a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution (SNAr) using TMSCN as a cheap cyanide source under mild conditions has been presented. This transformation utilizes commercially available reagents, cheap electrodes, and simple equipment. Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope, excellent functional group tolerance, and selective C−O bond cleavage. Furthermore, late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy. Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation, and undergoing the followed SNAr process.
Herein, a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution (SNAr) using TMSCN as a cheap cyanide source under mild conditions has been presented. This transformation utilizes commercially available reagents, cheap electrodes, and simple equipment. Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope, excellent functional group tolerance, and selective C−O bond cleavage. Furthermore, late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy. Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation, and undergoing the followed SNAr process.
2025, 36(9): 110820
doi: 10.1016/j.cclet.2025.110820
摘要:
Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects. Achieving a single enantiomer of a chiral anticancer drug is arduous, but it can significantly improve its pharmacokinetics for tumor therapy. Here, the chiral nanocatchers, known as d-biotin-P5⊃MCC NCs, were designed and prepared based on host-guest self-assembly between d-biotin anchored pillar[5]arene (d-biotin-P5) and myristoyl chloride choline (MCC). d-Biotin-P5⊃MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of (R,R)-OXA enantiomers into tumor cells. Furthermore, the use of d-biotin-P5⊃MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA, with the drug being efficiently released to MCF-7 breast cancer cells. This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA, while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells. This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.
Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects. Achieving a single enantiomer of a chiral anticancer drug is arduous, but it can significantly improve its pharmacokinetics for tumor therapy. Here, the chiral nanocatchers, known as d-biotin-P5⊃MCC NCs, were designed and prepared based on host-guest self-assembly between d-biotin anchored pillar[5]arene (d-biotin-P5) and myristoyl chloride choline (MCC). d-Biotin-P5⊃MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of (R,R)-OXA enantiomers into tumor cells. Furthermore, the use of d-biotin-P5⊃MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA, with the drug being efficiently released to MCF-7 breast cancer cells. This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA, while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells. This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.
2025, 36(9): 110821
doi: 10.1016/j.cclet.2025.110821
摘要:
This investigation focuses on the utilization of cucurbit[6]uril (Q[6]) as the host compound for the development of long-lasting afterglow materials. By strategically manipulating the outer surface interactions of Q[6], classical aggregation-caused quenching (ACQ) compounds such as fluorescein sodium (FluNa) and calcein sodium (CalNa) were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light. This transformation was facilitated through a host-guest doping method combined with coordination with metal ions. Even at a reduced doping concentration of 5 × 10–5 wt%, the materials exhibit remarkable afterglow properties, lasting up to 2 s, with a phosphorescence lifetime of up to 150 ms. Moreover, by adjusting the concentration of the guest compound, the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green. These findings suggest that the developed afterglow materials hold significant potential for multi-level anti-counterfeiting and information encryption applications when exposed to ultraviolet light. The supramolecular assembly strategy, which relies on the outer surface interactions of cucurbit[n]uril, offers a simpler and more efficient approach to crafting multi-color luminescent materials. Additionally, this method opens avenues for enhancing the application potential of aggregation-caused quenching (ACQ) compounds in various technological domains.
This investigation focuses on the utilization of cucurbit[6]uril (Q[6]) as the host compound for the development of long-lasting afterglow materials. By strategically manipulating the outer surface interactions of Q[6], classical aggregation-caused quenching (ACQ) compounds such as fluorescein sodium (FluNa) and calcein sodium (CalNa) were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light. This transformation was facilitated through a host-guest doping method combined with coordination with metal ions. Even at a reduced doping concentration of 5 × 10–5 wt%, the materials exhibit remarkable afterglow properties, lasting up to 2 s, with a phosphorescence lifetime of up to 150 ms. Moreover, by adjusting the concentration of the guest compound, the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green. These findings suggest that the developed afterglow materials hold significant potential for multi-level anti-counterfeiting and information encryption applications when exposed to ultraviolet light. The supramolecular assembly strategy, which relies on the outer surface interactions of cucurbit[n]uril, offers a simpler and more efficient approach to crafting multi-color luminescent materials. Additionally, this method opens avenues for enhancing the application potential of aggregation-caused quenching (ACQ) compounds in various technological domains.
2025, 36(9): 110822
doi: 10.1016/j.cclet.2025.110822
摘要:
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.
2025, 36(9): 110831
doi: 10.1016/j.cclet.2025.110831
摘要:
The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates. Cucurbit[7]uril (CB[7]) possesses high binding affinities for a variety of molecular guests. However, its moderate water solubility limits broader application. Here we report the synthesis of three CB[7] derivatives M1-M3 by modifying an average of 4.2, 5.5, and 5.9 sulfonatopropoxy groups onto their "equator" carbons. Compared to CB[7], their water-solubility increased by at least 26.6-, 23.6-, and 19.2-fold, respectively, while the maximum tolerated doses (MTD) of M1 and M2 improved by 2.5- and 2.3-fold. Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs. In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%, but also substantially reduces its side effect of gastric ulcer.
The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates. Cucurbit[7]uril (CB[7]) possesses high binding affinities for a variety of molecular guests. However, its moderate water solubility limits broader application. Here we report the synthesis of three CB[7] derivatives M1-M3 by modifying an average of 4.2, 5.5, and 5.9 sulfonatopropoxy groups onto their "equator" carbons. Compared to CB[7], their water-solubility increased by at least 26.6-, 23.6-, and 19.2-fold, respectively, while the maximum tolerated doses (MTD) of M1 and M2 improved by 2.5- and 2.3-fold. Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs. In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%, but also substantially reduces its side effect of gastric ulcer.
2025, 36(9): 110842
doi: 10.1016/j.cclet.2025.110842
摘要:
A novel [3]rotaxane, featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites, a secondary dialkylammonium (AM) unit and a 4,4′-bipyridinium (BP) unit, has been synthesized. This multi-stimuli-responsive [3]rotaxane exhibits unique molecular motion, with the macrocycles shuttling along the axle in response to acid-base reactions, temperature changes, solvent variations, and light irradiation. The molecular shuttle and reversibility were investigated by 1H NMR, 2D NOESY, HRESI-MS, and UV-vis spectroscopy. This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness, highlighting its potential for multi-state control over the motion of interlocked rings on an axle. The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
A novel [3]rotaxane, featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites, a secondary dialkylammonium (AM) unit and a 4,4′-bipyridinium (BP) unit, has been synthesized. This multi-stimuli-responsive [3]rotaxane exhibits unique molecular motion, with the macrocycles shuttling along the axle in response to acid-base reactions, temperature changes, solvent variations, and light irradiation. The molecular shuttle and reversibility were investigated by 1H NMR, 2D NOESY, HRESI-MS, and UV-vis spectroscopy. This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness, highlighting its potential for multi-state control over the motion of interlocked rings on an axle. The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
2025, 36(9): 110843
doi: 10.1016/j.cclet.2025.110843
摘要:
The amide moiety plays an important role as a powerful bioactive backbone, and as the synthetic chemistry community moves toward more sp3-rich scaffolds, alkyl halides have become the feedstock of choice for obtaining carbonylation products. With the development of photoredox catalysis, several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis. Considering the demands for green sustainable chemical synthesis, here we report a metal-free, exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide. Through a combination of EDA and XAT strategies, the reaction occurs efficiently under only light irradiation at room temperature.
The amide moiety plays an important role as a powerful bioactive backbone, and as the synthetic chemistry community moves toward more sp3-rich scaffolds, alkyl halides have become the feedstock of choice for obtaining carbonylation products. With the development of photoredox catalysis, several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis. Considering the demands for green sustainable chemical synthesis, here we report a metal-free, exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide. Through a combination of EDA and XAT strategies, the reaction occurs efficiently under only light irradiation at room temperature.
2025, 36(9): 110861
doi: 10.1016/j.cclet.2025.110861
摘要:
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development. Compared with the kinetically sluggish oxygen evolution reaction (OER), the thermodynamically advantageous sulfion oxidation reaction (SOR) enables the S2- pollutants recovery while reducing the energy input of water electrolysis. Here, a nanoporous NiMo alloy ligament (np-NiMo) with AlNi3/Al5Mo heterostructure was prepared for hydrogen evolution reaction (HER, -0.134 V versus reversible hydrogen electrode (vs. RHE) at 50 mA/cm2), which needs an Al89Ni10Mo1 as a precursor and dealloying operation. Further, the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS2 (np-NiMo-S) for OER (1.544 V vs. RHE at 50 mA/cm2) and SOR (0.364 V vs. RHE at 50 mA/cm2), while still maintaining the nanostructuring advantages. Moreover, for a two-electrode electrolyzer system with np-NiMo cathode (1 M KOH + seawater) coupling np-NiMo-S anode (1 mol/L KOH + seawater + 1 mol/L Na2S), a remarkably ultra-low cell potential of 0.532 V is acquired at 50 mA/cm2, which is about 1.015 V below that of normal alkaline seawater splitting. The theory calculations confirmed that the AlNi3/Al5Mo heterostructure within np-NiMo promotes H2O dissociation for excellent HER, while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from *S4 to *S8. This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development. Compared with the kinetically sluggish oxygen evolution reaction (OER), the thermodynamically advantageous sulfion oxidation reaction (SOR) enables the S2- pollutants recovery while reducing the energy input of water electrolysis. Here, a nanoporous NiMo alloy ligament (np-NiMo) with AlNi3/Al5Mo heterostructure was prepared for hydrogen evolution reaction (HER, -0.134 V versus reversible hydrogen electrode (vs. RHE) at 50 mA/cm2), which needs an Al89Ni10Mo1 as a precursor and dealloying operation. Further, the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS2 (np-NiMo-S) for OER (1.544 V vs. RHE at 50 mA/cm2) and SOR (0.364 V vs. RHE at 50 mA/cm2), while still maintaining the nanostructuring advantages. Moreover, for a two-electrode electrolyzer system with np-NiMo cathode (1 M KOH + seawater) coupling np-NiMo-S anode (1 mol/L KOH + seawater + 1 mol/L Na2S), a remarkably ultra-low cell potential of 0.532 V is acquired at 50 mA/cm2, which is about 1.015 V below that of normal alkaline seawater splitting. The theory calculations confirmed that the AlNi3/Al5Mo heterostructure within np-NiMo promotes H2O dissociation for excellent HER, while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from *S4 to *S8. This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
2025, 36(9): 110870
doi: 10.1016/j.cclet.2025.110870
摘要:
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis. However, examples of asymmetric Meinwald rearrangements are quite scarce, and these reactions have so far been limited to the use of chiral Brønsted acids as catalysts. Here, we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction, allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Thus, this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement, but also constitutes the first example of asymmetric formal monocarbon insertion into C–O bond of ester. Moreover, theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis. However, examples of asymmetric Meinwald rearrangements are quite scarce, and these reactions have so far been limited to the use of chiral Brønsted acids as catalysts. Here, we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction, allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Thus, this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement, but also constitutes the first example of asymmetric formal monocarbon insertion into C–O bond of ester. Moreover, theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
2025, 36(9): 110896
doi: 10.1016/j.cclet.2025.110896
摘要:
Many azo compounds and their intermediates are toxic and have been linked to various health issues, representing a growing global problem. Molecular engineering for selective encapsulation of azobenzene compounds is critical, given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries. However, the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins, pillar[n]arenes and cucurbit[n]urils, demonstrating a moderate affinity. This report describes that a novel 3,3′-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism, surpassing the extensively reported supramolecular systems. 1D & 2D NMR experiments, UV–vis spectrum, X-ray crystallography and computational modeling were carried out to understand the host-guest complexation. It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary, ternary and seawater systems. Furthermore, upon UV/white light irradiation, the reversible conversion between (E)-4,4′-azobisbenzoate and (Z)-4,4′-azobisbenzoate triggers the dissociation/recomplexation of the host-guest complex within 3 min. This reversible photo-switchable (E)-disodium 4,4′-azobisbenzoate-BPy-Box4+ supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.
Many azo compounds and their intermediates are toxic and have been linked to various health issues, representing a growing global problem. Molecular engineering for selective encapsulation of azobenzene compounds is critical, given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries. However, the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins, pillar[n]arenes and cucurbit[n]urils, demonstrating a moderate affinity. This report describes that a novel 3,3′-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism, surpassing the extensively reported supramolecular systems. 1D & 2D NMR experiments, UV–vis spectrum, X-ray crystallography and computational modeling were carried out to understand the host-guest complexation. It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary, ternary and seawater systems. Furthermore, upon UV/white light irradiation, the reversible conversion between (E)-4,4′-azobisbenzoate and (Z)-4,4′-azobisbenzoate triggers the dissociation/recomplexation of the host-guest complex within 3 min. This reversible photo-switchable (E)-disodium 4,4′-azobisbenzoate-BPy-Box4+ supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.
2025, 36(9): 110937
doi: 10.1016/j.cclet.2025.110937
摘要:
Microporous organic networks (MONs) are attractive adsorbents for use in sample pretreatment owning to their unique structure and properties. However, methods for constructing functional MONs are still limited because the lack of monomers via direct synthesis and their complex procedures via post-modification. To address this issue, a facile one-pot in situ doping strategy was proposed herein for synthesis a novel phenylboronic acid-functionalized magnetic cyclodextrin-based microporous organic network ([PBA]3/4−MCD-MON-0.04). [PBA]3/4−MCD-MON-0.04 was used for the selective and efficient extraction of sulfonylurea herbicides (SUHs) from complex food and environmental water samples via the synergistic hydrogen bonding, host-guest, hydrophobic and π-π interactions and the specific B-N coordination. [PBA]3/4−MCD-MON-0.04 had a large surface area, high saturation magnetism, good reusability, and remarkable stability. A rapid, sensitive, and selective method was proposed for monitoring SUHs from diverse matrices. This study provides a new strategy for synthesizing novel and multifunctional magnetic CD-MONs-based adsorbents and reveals the considerable potential of CD-MONs in sample pretreatment.
Microporous organic networks (MONs) are attractive adsorbents for use in sample pretreatment owning to their unique structure and properties. However, methods for constructing functional MONs are still limited because the lack of monomers via direct synthesis and their complex procedures via post-modification. To address this issue, a facile one-pot in situ doping strategy was proposed herein for synthesis a novel phenylboronic acid-functionalized magnetic cyclodextrin-based microporous organic network ([PBA]3/4−MCD-MON-0.04). [PBA]3/4−MCD-MON-0.04 was used for the selective and efficient extraction of sulfonylurea herbicides (SUHs) from complex food and environmental water samples via the synergistic hydrogen bonding, host-guest, hydrophobic and π-π interactions and the specific B-N coordination. [PBA]3/4−MCD-MON-0.04 had a large surface area, high saturation magnetism, good reusability, and remarkable stability. A rapid, sensitive, and selective method was proposed for monitoring SUHs from diverse matrices. This study provides a new strategy for synthesizing novel and multifunctional magnetic CD-MONs-based adsorbents and reveals the considerable potential of CD-MONs in sample pretreatment.
2025, 36(9): 110955
doi: 10.1016/j.cclet.2025.110955
摘要:
In this study, different types of small molecular carbon sources such as melamine, dicyandiamine, pyrocatechol, and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbon-based composites (Fe-N/C), which were used to activate peroxymonosulfate (PMS). The relationship between different small molecular carbon sources and the electronic structure was investigated. The characteristics of metal-carrier interaction in the Fe-N/C were clarified. As a result, there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources, which was related to the types of active sites. Density functional theory (DFT) and experiments results showed that the catalyst rich in CO-C and FeNx exhibited better catalytic activity, which may be attributed to the higher adsorption energy for PMS. The main active species for catalytic degradation of ofloxacin were identified as sulfate radical (SO4•-) and hydroxyl radical (•OH) by electron paramagnetic resonance (EPR) spectra. The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface, thereby regulating the generation and migration of radicals.
In this study, different types of small molecular carbon sources such as melamine, dicyandiamine, pyrocatechol, and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbon-based composites (Fe-N/C), which were used to activate peroxymonosulfate (PMS). The relationship between different small molecular carbon sources and the electronic structure was investigated. The characteristics of metal-carrier interaction in the Fe-N/C were clarified. As a result, there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources, which was related to the types of active sites. Density functional theory (DFT) and experiments results showed that the catalyst rich in CO-C and FeNx exhibited better catalytic activity, which may be attributed to the higher adsorption energy for PMS. The main active species for catalytic degradation of ofloxacin were identified as sulfate radical (SO4•-) and hydroxyl radical (•OH) by electron paramagnetic resonance (EPR) spectra. The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface, thereby regulating the generation and migration of radicals.
Metallic cobalt mediated molybdenum nitride for efficient glycerol upgrading with water electrolysis
2025, 36(9): 111010
doi: 10.1016/j.cclet.2025.111010
摘要:
Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen. However, developing efficient electrocatalyst towards this technology remains challenging. Herein, a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam (Co@Mo2N/NF) for the glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER). Remarkably, the obtained Co@Mo2N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm2 for HER and high Faradaic efficiency of formate of 95.03% at 1.35 Ⅴ vs. RHE for GOR, respectively. The systematic in-situ experiments reveal that the Co@Mo2N heterostructure promotes the cleavage of CC bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product. Moreover, the density functional theory (DFT) calculations confirm the strong interaction at Co@Mo2N interface, which contributes to the optimized water dissociation and the transformation of H* to H2. Benefiting from those advantages, the built HERGOR electrolyzer delivers a low voltage of 1.61 Ⅴ at 50 mA/cm2, high Faradaic efficiency, and robust stability over 120 h for sustained and stable electrolysis.
Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen. However, developing efficient electrocatalyst towards this technology remains challenging. Herein, a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam (Co@Mo2N/NF) for the glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER). Remarkably, the obtained Co@Mo2N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm2 for HER and high Faradaic efficiency of formate of 95.03% at 1.35 Ⅴ vs. RHE for GOR, respectively. The systematic in-situ experiments reveal that the Co@Mo2N heterostructure promotes the cleavage of CC bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product. Moreover, the density functional theory (DFT) calculations confirm the strong interaction at Co@Mo2N interface, which contributes to the optimized water dissociation and the transformation of H* to H2. Benefiting from those advantages, the built HERGOR electrolyzer delivers a low voltage of 1.61 Ⅴ at 50 mA/cm2, high Faradaic efficiency, and robust stability over 120 h for sustained and stable electrolysis.
2025, 36(9): 111030
doi: 10.1016/j.cclet.2025.111030
摘要:
Tumor heterogeneity and diversity significantly undermine the effectiveness of monotherapy. Collaborative therapy emerges as a promising approach to mitigate tumor recurrence resulting from monotherapy. Combining chemodynamic therapy (CDT) with photothermal therapy (PTT) offers a compelling solution for eradicating residual tumor cells post-PTT. In this study, we harness the Fenton-like response facilitated by glucose oxidase (GOD) and the mild hyperthermia induced by polyethyleneimine (PEI) functionalized nitrogen-containing graphene oxide to enhance tumor therapy through a metal-free bionic nanozyme. GOD catalyzes a substantial amount of hydrogen peroxide, and, with the carrier's involvement, triggers a Fenton-like reaction, yielding a wealth of hydroxyl radicals. These hydroxyl radicals effectively target tumor cells following photothermal action, bolstering CDT and culminating in a bidirectional amplification treatment that effectively prevents tumor recurrence and metastasis. This research amalgamates the physical and chemical attributes of nanomaterials with the unique characteristics of the tumor microenvironment, presenting a compelling and efficacious alternative for tumor treatment.
Tumor heterogeneity and diversity significantly undermine the effectiveness of monotherapy. Collaborative therapy emerges as a promising approach to mitigate tumor recurrence resulting from monotherapy. Combining chemodynamic therapy (CDT) with photothermal therapy (PTT) offers a compelling solution for eradicating residual tumor cells post-PTT. In this study, we harness the Fenton-like response facilitated by glucose oxidase (GOD) and the mild hyperthermia induced by polyethyleneimine (PEI) functionalized nitrogen-containing graphene oxide to enhance tumor therapy through a metal-free bionic nanozyme. GOD catalyzes a substantial amount of hydrogen peroxide, and, with the carrier's involvement, triggers a Fenton-like reaction, yielding a wealth of hydroxyl radicals. These hydroxyl radicals effectively target tumor cells following photothermal action, bolstering CDT and culminating in a bidirectional amplification treatment that effectively prevents tumor recurrence and metastasis. This research amalgamates the physical and chemical attributes of nanomaterials with the unique characteristics of the tumor microenvironment, presenting a compelling and efficacious alternative for tumor treatment.
2025, 36(9): 111152
doi: 10.1016/j.cclet.2025.111152
摘要:
Amorphous bimetallic borides, as a new generation of catalytic nanomaterials with modifiable electronic properties, are of great importance in the design of high-efficiency catalysts for NaBH4 hydrolysis. This study synthesizes an amorphous Co3B-Mo2B5 catalyst using a self-sacrificial template strategy and NaBH4 reduction for both NaBH4 hydrolysis and the reduction of 4-nitrophenol. The catalyst delivers an impressive hydrogen generation rate of 7690.5 mL min−1 g−1 at 25 ℃, coupled with a rapid reaction rate of 0.701 min−1 in the reduction of 4-nitrophenol. The enhanced catalytic performance is attributed to the unique amorphous structure and the electron rearrangement between Co3B and Mo2B5. Experimental and theoretical analyses suggest electron transfer from Co3B to the Mo2B5, with the electron-deficient Co3B site favoring BH4− adsorption, while the electron-rich Mo2B5 site favoring H2O adsorption. Furthermore, Co3B-Mo2B5 demonstrated potential for energy applications, delivering a power output of 0.3 V in a hydrogen-air fuel cell.
Amorphous bimetallic borides, as a new generation of catalytic nanomaterials with modifiable electronic properties, are of great importance in the design of high-efficiency catalysts for NaBH4 hydrolysis. This study synthesizes an amorphous Co3B-Mo2B5 catalyst using a self-sacrificial template strategy and NaBH4 reduction for both NaBH4 hydrolysis and the reduction of 4-nitrophenol. The catalyst delivers an impressive hydrogen generation rate of 7690.5 mL min−1 g−1 at 25 ℃, coupled with a rapid reaction rate of 0.701 min−1 in the reduction of 4-nitrophenol. The enhanced catalytic performance is attributed to the unique amorphous structure and the electron rearrangement between Co3B and Mo2B5. Experimental and theoretical analyses suggest electron transfer from Co3B to the Mo2B5, with the electron-deficient Co3B site favoring BH4− adsorption, while the electron-rich Mo2B5 site favoring H2O adsorption. Furthermore, Co3B-Mo2B5 demonstrated potential for energy applications, delivering a power output of 0.3 V in a hydrogen-air fuel cell.
2025, 36(9): 111194
doi: 10.1016/j.cclet.2025.111194
摘要:
Organic afterglow materials hold significant potential for applications in information storage, anti-counterfeiting, and biological imaging. However, studies on afterglow materials capable of ultra-wide range excitation and emission simultaneously are limited. To enhance the practicality of strong emission single-component organic afterglow systems, overcoming the constraints of crystalline or other rigid environments is essential. We have developed solid-state dual-persistent thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions spanning yellow to red under visible light excitation, utilizing a single-molecule terminal group regulation strategy. The RTP lifetime extends from 4.19 ms to 399.70 ms. These afterglow materials exhibit an ultra-wide absorption range from 200 nm to 800 nm, rendering them capable of being excited by both sunlight simulator and near-infrared radiation. The upconversion phosphorescence lifetime under 808 nm excitation reaches 13.72 µs. The double persistent emission of these compounds is temperature-sensitive. Moreover, following grinding or heat treatment, accompanied by extensive afterglow color conversion due to planarization of excited state conformations and additional efficient kRISC generation. In addition, the amorphous state post melt annealing facilitates the afterglow transition from yellow to green. Crucially, these compounds also maintain stable ultra-long afterglow emission in aqueous and acid-base environments. Overall, we have successfully developed a series of single-component intelligent luminescent materials that demonstrate significant benefits, including dual TADF and RTP emissions, adjustable afterglow lifetimes, a broad range of excitation and emission wavelengths, multi-modal luminescence not restricted to crystalline states, and robust afterglow performance in challenging environments, setting the stage for the practical deployment of afterglow materials in engineering applications, the upconversion afterglow emission also holds promising potential for applications in the field of biological imaging.
Organic afterglow materials hold significant potential for applications in information storage, anti-counterfeiting, and biological imaging. However, studies on afterglow materials capable of ultra-wide range excitation and emission simultaneously are limited. To enhance the practicality of strong emission single-component organic afterglow systems, overcoming the constraints of crystalline or other rigid environments is essential. We have developed solid-state dual-persistent thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions spanning yellow to red under visible light excitation, utilizing a single-molecule terminal group regulation strategy. The RTP lifetime extends from 4.19 ms to 399.70 ms. These afterglow materials exhibit an ultra-wide absorption range from 200 nm to 800 nm, rendering them capable of being excited by both sunlight simulator and near-infrared radiation. The upconversion phosphorescence lifetime under 808 nm excitation reaches 13.72 µs. The double persistent emission of these compounds is temperature-sensitive. Moreover, following grinding or heat treatment, accompanied by extensive afterglow color conversion due to planarization of excited state conformations and additional efficient kRISC generation. In addition, the amorphous state post melt annealing facilitates the afterglow transition from yellow to green. Crucially, these compounds also maintain stable ultra-long afterglow emission in aqueous and acid-base environments. Overall, we have successfully developed a series of single-component intelligent luminescent materials that demonstrate significant benefits, including dual TADF and RTP emissions, adjustable afterglow lifetimes, a broad range of excitation and emission wavelengths, multi-modal luminescence not restricted to crystalline states, and robust afterglow performance in challenging environments, setting the stage for the practical deployment of afterglow materials in engineering applications, the upconversion afterglow emission also holds promising potential for applications in the field of biological imaging.
2025, 36(9): 111205
doi: 10.1016/j.cclet.2025.111205
摘要:
Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthesizing polymer-inorganic composite crystals, where guest nanoparticles are distributed within the crystal matrix. However, systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge. In this study, we employ a one-step, soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert‑butyl methacrylate) (PtBMA/PEI) nanoparticles. These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction. This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals. Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content. This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.
Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthesizing polymer-inorganic composite crystals, where guest nanoparticles are distributed within the crystal matrix. However, systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge. In this study, we employ a one-step, soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert‑butyl methacrylate) (PtBMA/PEI) nanoparticles. These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction. This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals. Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content. This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.
2025, 36(9): 111223
doi: 10.1016/j.cclet.2025.111223
摘要:
Hydrogen-bonded framework (HOF) offers an attractive platform to encapsulate enzymes and stabilize their conformation, due to the advantages of mild synthesis conditions, tailorable pore structure, and backbone biocompatibility. However, the efficiency of this HOF approach relies on the interfacial interactions between enzyme guest and the ligand precursors, limiting its adaptability to enzymes with varying surface chemistry property. In this study, we report a site-specific surface modification strategy to positively tailor the enzyme surface charge, facilitating the biomimetic encapsulation of enzymes within HOF in situ. Both experimental results and computational simulation reveal that site-specific amination of enzyme surface's acidic residues contributes to the interfacial accumulation of carboxylic ligand precursors in aqueous solutions via synergistic electrostatic and hydrogen bonding interactions. This substantially facilitates the in situ growth of porous HOF surrounding the aminated enzyme biotemplates, with up to 100% enzyme loading efficiency. The resultant hydrogen-bonded biohybrid framework (HBF) retains high biocatalytic functions while exhibiting exceptional stability under harsh conditions. By leveraging the marked catalytic activity of GOx-NH2@HBF-1 and a H2O2-sensitive QD, a highly sensitive glucose fluorescence sensor is fabricated with a wide linear range (5–2000 µmol/L) and a low quantification limit of 5 µmol/L. This work presents a simple yet effective enzyme surface engineering approach for integrating enzyme into HOF, opening new avenues for the construction of multifunctional HOF biocomposites.
Hydrogen-bonded framework (HOF) offers an attractive platform to encapsulate enzymes and stabilize their conformation, due to the advantages of mild synthesis conditions, tailorable pore structure, and backbone biocompatibility. However, the efficiency of this HOF approach relies on the interfacial interactions between enzyme guest and the ligand precursors, limiting its adaptability to enzymes with varying surface chemistry property. In this study, we report a site-specific surface modification strategy to positively tailor the enzyme surface charge, facilitating the biomimetic encapsulation of enzymes within HOF in situ. Both experimental results and computational simulation reveal that site-specific amination of enzyme surface's acidic residues contributes to the interfacial accumulation of carboxylic ligand precursors in aqueous solutions via synergistic electrostatic and hydrogen bonding interactions. This substantially facilitates the in situ growth of porous HOF surrounding the aminated enzyme biotemplates, with up to 100% enzyme loading efficiency. The resultant hydrogen-bonded biohybrid framework (HBF) retains high biocatalytic functions while exhibiting exceptional stability under harsh conditions. By leveraging the marked catalytic activity of GOx-NH2@HBF-1 and a H2O2-sensitive QD, a highly sensitive glucose fluorescence sensor is fabricated with a wide linear range (5–2000 µmol/L) and a low quantification limit of 5 µmol/L. This work presents a simple yet effective enzyme surface engineering approach for integrating enzyme into HOF, opening new avenues for the construction of multifunctional HOF biocomposites.
2025, 36(9): 111234
doi: 10.1016/j.cclet.2025.111234
摘要:
Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers, dauroxonanols A (1) and B (2), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton, were isolated from Rhododendron dauricum. The nuclear magnetic resonance (NMR) spectra of 1 and 2 showed very broad resonances, and 13C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis, chiral separation, and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring. Dauroxonanols A (1) and B (2) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose, an antidiabetic drug targeting α-glucosidase in clinic.
Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers, dauroxonanols A (1) and B (2), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton, were isolated from Rhododendron dauricum. The nuclear magnetic resonance (NMR) spectra of 1 and 2 showed very broad resonances, and 13C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis, chiral separation, and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring. Dauroxonanols A (1) and B (2) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose, an antidiabetic drug targeting α-glucosidase in clinic.
2025, 36(9): 111271
doi: 10.1016/j.cclet.2025.111271
摘要:
The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties. The electrosynthesis of 2,5-furanodicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) oxidation is one of the most promising means for the production of bioplastic monomers. In this work, we constructed a novel P-doped Ni3S2 and Ni heterojunction on nickel foam (P-Ni3S2/Ni/NF) using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA (HMFOR) and the cathodic hydrogen evolution reaction (HER). On one hand, the synergistic promotion of P doping and the heterojunction of Ni3S2 and Ni accelerated electron transfer, and on the other hand, the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites. The prepared P-Ni3S2/Ni/NF exhibited remarkable performance with high HMF conversion (99.2%), FDCA yield (98.1%), and Faraday efficiency (98.8%), and excellent stability with good product selectivity for 7 consecutive cycles, which stands at a higher level than majority of previously published electrocatalysts. Furthermore, P-Ni3S2/Ni/NF also shows a significant response in HER. By using HMFOR and HER as the anodic reaction and cathodic reaction, respectively, the biomass upgrading and hydrogen production can be carried out simultaneously. The synthesized P-Ni3S2/Ni/NF only need a voltage of 1.31 V to achieve a current density of 10 mA/cm2 in a two-electrode system of HMFOR and HER, which is much lower than that of 1.48 V in OER and HER process, thus potentially reducing the cost of this process.
The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties. The electrosynthesis of 2,5-furanodicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) oxidation is one of the most promising means for the production of bioplastic monomers. In this work, we constructed a novel P-doped Ni3S2 and Ni heterojunction on nickel foam (P-Ni3S2/Ni/NF) using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA (HMFOR) and the cathodic hydrogen evolution reaction (HER). On one hand, the synergistic promotion of P doping and the heterojunction of Ni3S2 and Ni accelerated electron transfer, and on the other hand, the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites. The prepared P-Ni3S2/Ni/NF exhibited remarkable performance with high HMF conversion (99.2%), FDCA yield (98.1%), and Faraday efficiency (98.8%), and excellent stability with good product selectivity for 7 consecutive cycles, which stands at a higher level than majority of previously published electrocatalysts. Furthermore, P-Ni3S2/Ni/NF also shows a significant response in HER. By using HMFOR and HER as the anodic reaction and cathodic reaction, respectively, the biomass upgrading and hydrogen production can be carried out simultaneously. The synthesized P-Ni3S2/Ni/NF only need a voltage of 1.31 V to achieve a current density of 10 mA/cm2 in a two-electrode system of HMFOR and HER, which is much lower than that of 1.48 V in OER and HER process, thus potentially reducing the cost of this process.
2025, 36(9): 111272
doi: 10.1016/j.cclet.2025.111272
摘要:
Photocatalytic hydrogen peroxide (H2O2) production (PHP) offers significant advantages to traditional production methods, including solar energy utilization, mild reaction conditions, environmental friendliness, pollution-free processes, sustainability, and high selectivity. However, despite its potential as a green and sustainable technology, photocatalytic H2O2 production (PHP) is constrained by limited visible light absorption by photocatalysts and the rapid recombination of photogenerated charge carriers, which reduce yield and efficiency. In this study, we synthesized an organic amine constrained Zn0.5Cd0.5S-DETA/g-C3N4 (ZCS-D/CN) S-scheme heterojunction via a hydrothermal method to enhance PHP. Anchoring ZCS-D on the surface of CN and forming an S-scheme heterojunction effectively prevented ZCS-D agglomeration, modulated the band structure of CN, and enhanced the migration and redox capabilities of photogenerated charge carriers. The optimized heterojunction (ZCS-D/CN) achieved a H2O2 yield of 5124 µmol g-1 h-1 in pure H2O, significantly outperforming pure CN (24 µmol g-1 h-1) and ZCS-D (4012 µmol g-1 h-1). These results demonstrate that ZCS-D/CN S-scheme heterojunction holds substantial potential for photocatalytic applications, particularly in the efficient production of H2O2.
Photocatalytic hydrogen peroxide (H2O2) production (PHP) offers significant advantages to traditional production methods, including solar energy utilization, mild reaction conditions, environmental friendliness, pollution-free processes, sustainability, and high selectivity. However, despite its potential as a green and sustainable technology, photocatalytic H2O2 production (PHP) is constrained by limited visible light absorption by photocatalysts and the rapid recombination of photogenerated charge carriers, which reduce yield and efficiency. In this study, we synthesized an organic amine constrained Zn0.5Cd0.5S-DETA/g-C3N4 (ZCS-D/CN) S-scheme heterojunction via a hydrothermal method to enhance PHP. Anchoring ZCS-D on the surface of CN and forming an S-scheme heterojunction effectively prevented ZCS-D agglomeration, modulated the band structure of CN, and enhanced the migration and redox capabilities of photogenerated charge carriers. The optimized heterojunction (ZCS-D/CN) achieved a H2O2 yield of 5124 µmol g-1 h-1 in pure H2O, significantly outperforming pure CN (24 µmol g-1 h-1) and ZCS-D (4012 µmol g-1 h-1). These results demonstrate that ZCS-D/CN S-scheme heterojunction holds substantial potential for photocatalytic applications, particularly in the efficient production of H2O2.
2025, 36(9): 111295
doi: 10.1016/j.cclet.2025.111295
摘要:
The electrocatalytic nitrogen reduction reaction (NRR) is challenging but crucial for the sustainable development of both industry and agriculture. To enhance NRR performance, it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity. However, the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity. Herein, we propose a dual-site catalyst, RuNi, to optimize the binding strength, which leads to superior electrocatalytic performance, achieving a high NH3 yield rate of 5.07 µg h-1 cm-2 at -0.2 V vs. RHE and a Faradaic efficiency (FE) of 26.2% at -0.1 V vs. RHE in 0.1 mol/L Na2SO4. Owing to the synergistic interaction between Ru and Ni, a remarkable performance is realized over the RuNi catalyst. In-situ characterization evidenced that hydrogen radicals (H*) on the Ni site of the RuNi catalyst participate in the dissociation of N2 adsorbed on the Ru site, and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates. This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
The electrocatalytic nitrogen reduction reaction (NRR) is challenging but crucial for the sustainable development of both industry and agriculture. To enhance NRR performance, it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity. However, the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity. Herein, we propose a dual-site catalyst, RuNi, to optimize the binding strength, which leads to superior electrocatalytic performance, achieving a high NH3 yield rate of 5.07 µg h-1 cm-2 at -0.2 V vs. RHE and a Faradaic efficiency (FE) of 26.2% at -0.1 V vs. RHE in 0.1 mol/L Na2SO4. Owing to the synergistic interaction between Ru and Ni, a remarkable performance is realized over the RuNi catalyst. In-situ characterization evidenced that hydrogen radicals (H*) on the Ni site of the RuNi catalyst participate in the dissociation of N2 adsorbed on the Ru site, and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates. This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
2025, 36(9): 111400
doi: 10.1016/j.cclet.2025.111400
摘要:
Wound dressings with tissue adhesion, good mechanical, antioxidant and anti-inflammatory performance are urgently needed. In this work, we present a multifunctional selenium nanoparticles (SeNPs)/citric acid/gelatin/hydroxysuccinimide-grafted polyacrylic acid nanocomposite hydrogel adhesive (SCA) specifically designed for wound healing applications. The SCA was prepared via a one-pot processing, where SeNPs synthesized via chemical reduction were incorporated. These SeNPs not only endowed SCA with robust wet adhesion ability, excellent stretchability, and skin-matched elasticity modulus by serving as a physical crosslinker to modulate swelling equilibrium and molecular slippage, but also enhanced the biocompatibility and free radical scavenging capacity of SCA. Furthermore, in vivo evaluation of full-thickness cutaneous defects of rats revealed that SCA effectively reduced inflammation, promoted wound closure, and increased collagen deposition. All these results demonstrated that the developed SCA offers a promising therapeutic strategy for wound healing applications.
Wound dressings with tissue adhesion, good mechanical, antioxidant and anti-inflammatory performance are urgently needed. In this work, we present a multifunctional selenium nanoparticles (SeNPs)/citric acid/gelatin/hydroxysuccinimide-grafted polyacrylic acid nanocomposite hydrogel adhesive (SCA) specifically designed for wound healing applications. The SCA was prepared via a one-pot processing, where SeNPs synthesized via chemical reduction were incorporated. These SeNPs not only endowed SCA with robust wet adhesion ability, excellent stretchability, and skin-matched elasticity modulus by serving as a physical crosslinker to modulate swelling equilibrium and molecular slippage, but also enhanced the biocompatibility and free radical scavenging capacity of SCA. Furthermore, in vivo evaluation of full-thickness cutaneous defects of rats revealed that SCA effectively reduced inflammation, promoted wound closure, and increased collagen deposition. All these results demonstrated that the developed SCA offers a promising therapeutic strategy for wound healing applications.
2025, 36(9): 110325
doi: 10.1016/j.cclet.2024.110325
摘要:
Flexible and stretchable energy storage devices are highly desirable for wearable electronics, particularly in the emerging fields of smart clothes, medical instruments, and stretchable skin. Lithium metal batteries (LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices. However, the current LMBs are usually too rigid and bulky to meet the requirements of these devices. The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs. Among various electrolytes, gel polymer electrolytes (GPEs) perform excellent flexibility, safety, and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes, fulfilling the next generation deformable LMBs. This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field. Additionally, the multifunctional GPEs with self-healing, flame retardant, and temperature tolerance abilities are summarized. Finally, the perspectives and opportunities for flexible and stretchable GPEs are discussed.
Flexible and stretchable energy storage devices are highly desirable for wearable electronics, particularly in the emerging fields of smart clothes, medical instruments, and stretchable skin. Lithium metal batteries (LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices. However, the current LMBs are usually too rigid and bulky to meet the requirements of these devices. The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs. Among various electrolytes, gel polymer electrolytes (GPEs) perform excellent flexibility, safety, and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes, fulfilling the next generation deformable LMBs. This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field. Additionally, the multifunctional GPEs with self-healing, flame retardant, and temperature tolerance abilities are summarized. Finally, the perspectives and opportunities for flexible and stretchable GPEs are discussed.
2025, 36(9): 110370
doi: 10.1016/j.cclet.2024.110370
摘要:
As an emergent energy carrier, ammonia benefits from a well-established industrial infrastructure for its transportation and production, positioning it as a promising candidate toward a carbon-free energy landscape. Within this context, the electrocatalytic ammonia oxidation reaction (AOR) is pivotal. Platinum (Pt), recognized as the most efficient AOR catalyst, has undergone extensive development over the years, yielding notable advancements across various domains, ranging from elucidating the reaction mechanism to exploring innovative materials. This review begins by elucidating the mechanism of ammonia oxidation, summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods. Subsequently, it outlines the research progress surrounding different Pt-based catalysts, followed by a discussion on standard protocols for electrochemical ammonia oxidation testing, which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts. Moreover, the review addresses current challenges in ammonia oxidation and outlines potential future directions, providing a comprehensive outlook on the field.
As an emergent energy carrier, ammonia benefits from a well-established industrial infrastructure for its transportation and production, positioning it as a promising candidate toward a carbon-free energy landscape. Within this context, the electrocatalytic ammonia oxidation reaction (AOR) is pivotal. Platinum (Pt), recognized as the most efficient AOR catalyst, has undergone extensive development over the years, yielding notable advancements across various domains, ranging from elucidating the reaction mechanism to exploring innovative materials. This review begins by elucidating the mechanism of ammonia oxidation, summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods. Subsequently, it outlines the research progress surrounding different Pt-based catalysts, followed by a discussion on standard protocols for electrochemical ammonia oxidation testing, which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts. Moreover, the review addresses current challenges in ammonia oxidation and outlines potential future directions, providing a comprehensive outlook on the field.
2025, 36(9): 110652
doi: 10.1016/j.cclet.2024.110652
摘要:
Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures. To mimic this ability, chemists are designing framework structures that resemble real enzymes. The use of metal-organic frameworks (MOFs) to mimic natural enzymes has advanced recently; this paper reviews these developments. This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs. By identifying and attaching to substrates, MOFs can accelerate changes in a manner akin to that of real enzymes. The role of MOFs in simulating catalytic processes, enzyme activity, and potential uses in brain chemistry are also investigated in this work. It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain. The report finishes with a discussion of future research areas and potential applications, providing useful insights for researchers in the subject.
Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures. To mimic this ability, chemists are designing framework structures that resemble real enzymes. The use of metal-organic frameworks (MOFs) to mimic natural enzymes has advanced recently; this paper reviews these developments. This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs. By identifying and attaching to substrates, MOFs can accelerate changes in a manner akin to that of real enzymes. The role of MOFs in simulating catalytic processes, enzyme activity, and potential uses in brain chemistry are also investigated in this work. It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain. The report finishes with a discussion of future research areas and potential applications, providing useful insights for researchers in the subject.
2025, 36(9): 110664
doi: 10.1016/j.cclet.2024.110664
摘要:
Low-valent sulfur oxy-acid salts (LVSOs) represent a category of oxygen-containing salts characterized by their potent reducing capabilities. Notably, sulfite, dithionite, and thiosulfate are prevalent reducing agents that are readily available, cost-effective, and exhibit minimal ecological toxicity. These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants, which makes them widely used in advanced oxidation processes (AOPs) and advanced reduction processes (ARPs). This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs, alongside an examination of the fundamental principles governing the generation of active species within these processes. LVSOs fulfill three primary functions in AOPs: Serving as sources of reactive oxygen species (ROS), auxiliary agents, and activators. Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs, in conjunction with metal ions, metal oxides, ultraviolet light (UV), and ozone, produce potent oxidizing agents in both homogeneous and heterogeneous systems. Regarding ARPs, this review delineates the mechanisms by which LVSOs generate strong reducing agents, including hydrated electrons, hydrogen radicals, and sulfite radicals, under UV irradiation, while also exploring the interactions between these reductants and pollutants. The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
Low-valent sulfur oxy-acid salts (LVSOs) represent a category of oxygen-containing salts characterized by their potent reducing capabilities. Notably, sulfite, dithionite, and thiosulfate are prevalent reducing agents that are readily available, cost-effective, and exhibit minimal ecological toxicity. These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants, which makes them widely used in advanced oxidation processes (AOPs) and advanced reduction processes (ARPs). This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs, alongside an examination of the fundamental principles governing the generation of active species within these processes. LVSOs fulfill three primary functions in AOPs: Serving as sources of reactive oxygen species (ROS), auxiliary agents, and activators. Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs, in conjunction with metal ions, metal oxides, ultraviolet light (UV), and ozone, produce potent oxidizing agents in both homogeneous and heterogeneous systems. Regarding ARPs, this review delineates the mechanisms by which LVSOs generate strong reducing agents, including hydrated electrons, hydrogen radicals, and sulfite radicals, under UV irradiation, while also exploring the interactions between these reductants and pollutants. The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
2025, 36(9): 110677
doi: 10.1016/j.cclet.2024.110677
摘要:
Stochastic optical reconstruction microscopy (STORM), as a typical technique of single-molecule localization microscopy (SMLM), has overcome the diffraction limit by randomly switching fluorophores between fluorescent and dark states, allowing for the precise localization of isolated emission patterns and the super-resolution reconstruction from millions of localized positions of single fluorophores. A critical factor influencing localization precision is the photo-switching behavior of fluorophores, which is affected by the imaging buffer. The imaging buffer typically comprises oxygen scavengers, photo-switching reagents, and refractive index regulators. Oxygen scavengers help prevent photobleaching, photo-switching reagents assist in facilitating the conversion of fluorophores, and refractive index regulators are used to adjust the refractive index of the solution. The synergistic interaction of these components promotes stable blinking of fluorophores, reduces irreversible photobleaching, and thereby ensures high-quality super-resolution imaging. This review provides a comprehensive overview of the essential compositions and functionalities of imaging buffers used in STORM, serving as a valuable resource for researchers seeking to select appropriate imaging buffers for their experiments.
Stochastic optical reconstruction microscopy (STORM), as a typical technique of single-molecule localization microscopy (SMLM), has overcome the diffraction limit by randomly switching fluorophores between fluorescent and dark states, allowing for the precise localization of isolated emission patterns and the super-resolution reconstruction from millions of localized positions of single fluorophores. A critical factor influencing localization precision is the photo-switching behavior of fluorophores, which is affected by the imaging buffer. The imaging buffer typically comprises oxygen scavengers, photo-switching reagents, and refractive index regulators. Oxygen scavengers help prevent photobleaching, photo-switching reagents assist in facilitating the conversion of fluorophores, and refractive index regulators are used to adjust the refractive index of the solution. The synergistic interaction of these components promotes stable blinking of fluorophores, reduces irreversible photobleaching, and thereby ensures high-quality super-resolution imaging. This review provides a comprehensive overview of the essential compositions and functionalities of imaging buffers used in STORM, serving as a valuable resource for researchers seeking to select appropriate imaging buffers for their experiments.
2025, 36(9): 110685
doi: 10.1016/j.cclet.2024.110685
摘要:
Thanks to its abundant reserves, relatively high energy density, and low reduction potential, potassium ion batteries (PIBs) have a high potential for large-scale energy storage applications. Due to the large radius of potassium ions, most conventional anode materials undergo severe volume expansion, making it difficult to achieve stable and reversible energy storage. Therefore, developing high-performance anode materials is one of the critical factors in developing PIBs. In this sense, antimony (Sb)-based anode materials with high theoretical capacity and safe reaction potentials have a broad potential for application in PIBs. However, overcoming the rapid capacity decay induced by the large radius of potassium ions is still an issue that needs to be focused on. This paper reviews the latest research on different types of Sb-based anode materials and provides an in-depth analysis of their optimization strategies. We focus on material selection, structural design, and storage mechanisms to develop a detailed description of the material. In addition, the current challenges still faced by Sb-based anode materials are summarized, and some further optimization strategies have been added. We hope to provide some insights for researchers developing Sb-based anode materials for next-generation advanced PIBs.
Thanks to its abundant reserves, relatively high energy density, and low reduction potential, potassium ion batteries (PIBs) have a high potential for large-scale energy storage applications. Due to the large radius of potassium ions, most conventional anode materials undergo severe volume expansion, making it difficult to achieve stable and reversible energy storage. Therefore, developing high-performance anode materials is one of the critical factors in developing PIBs. In this sense, antimony (Sb)-based anode materials with high theoretical capacity and safe reaction potentials have a broad potential for application in PIBs. However, overcoming the rapid capacity decay induced by the large radius of potassium ions is still an issue that needs to be focused on. This paper reviews the latest research on different types of Sb-based anode materials and provides an in-depth analysis of their optimization strategies. We focus on material selection, structural design, and storage mechanisms to develop a detailed description of the material. In addition, the current challenges still faced by Sb-based anode materials are summarized, and some further optimization strategies have been added. We hope to provide some insights for researchers developing Sb-based anode materials for next-generation advanced PIBs.
2025, 36(9): 110686
doi: 10.1016/j.cclet.2024.110686
摘要:
The technology of three dimensional (3D) printing, also known as additive manufacturing, is a cutting-edge type of fabrication method that utilizes a computer-aided design platform and employs layer-by-layer stacking to construct objects with exceptional flexibility. Due to its capacity to produce a substantial quantity of products within a short period of time, 3D printing has emerged as one of the most significant manufacturing technology. Over the past two decades, remarkable advancements have been made in the application of 3D printing technology in the realm of bone tissue engineering. This review presents an innovative and systematic discussion on the potential application of 3D printing technology in bone tissue engineering, particularly in the treatment of infected bone defects. It comprehensively evaluates the materials utilized in 3D printing, highlights the interplay between cells and bone regeneration, and addresses and resolves challenges associated with current 3D printing technology. These challenges include material selection, fabrication of intricate 3D structures, integration of different cell types, streamlining design processes and material selection procedures, enhancing the clinical translational potential of 3D printing technology, and ultimately exploring future applications of four dimensional (4D) printing technology. The 3D printing technology has demonstrated significant potential in the synthesis of bone substitutes, offering consistent mechanical properties and ease of use. It has found extensive applications in personalized implant customization, prosthetic limb manufacturing, surgical tool production, tissue engineering, biological modeling, and cell diagnostics. Simultaneously, 3D bioprinting provides an effective solution to address the issue of organ donor shortage. However, challenges still exist in material selection, management of structural complexity, integration of different cell types, and construction of functionally mature tissues. With advancements in multi-material printing techniques as well as bioprinting and 4D printing technologies emerging on the horizon; 3D printing holds immense prospects for revolutionizing the means by which infectious bone defects are repaired.
The technology of three dimensional (3D) printing, also known as additive manufacturing, is a cutting-edge type of fabrication method that utilizes a computer-aided design platform and employs layer-by-layer stacking to construct objects with exceptional flexibility. Due to its capacity to produce a substantial quantity of products within a short period of time, 3D printing has emerged as one of the most significant manufacturing technology. Over the past two decades, remarkable advancements have been made in the application of 3D printing technology in the realm of bone tissue engineering. This review presents an innovative and systematic discussion on the potential application of 3D printing technology in bone tissue engineering, particularly in the treatment of infected bone defects. It comprehensively evaluates the materials utilized in 3D printing, highlights the interplay between cells and bone regeneration, and addresses and resolves challenges associated with current 3D printing technology. These challenges include material selection, fabrication of intricate 3D structures, integration of different cell types, streamlining design processes and material selection procedures, enhancing the clinical translational potential of 3D printing technology, and ultimately exploring future applications of four dimensional (4D) printing technology. The 3D printing technology has demonstrated significant potential in the synthesis of bone substitutes, offering consistent mechanical properties and ease of use. It has found extensive applications in personalized implant customization, prosthetic limb manufacturing, surgical tool production, tissue engineering, biological modeling, and cell diagnostics. Simultaneously, 3D bioprinting provides an effective solution to address the issue of organ donor shortage. However, challenges still exist in material selection, management of structural complexity, integration of different cell types, and construction of functionally mature tissues. With advancements in multi-material printing techniques as well as bioprinting and 4D printing technologies emerging on the horizon; 3D printing holds immense prospects for revolutionizing the means by which infectious bone defects are repaired.
2025, 36(9): 110698
doi: 10.1016/j.cclet.2024.110698
摘要:
Rare earth metal elements include lanthanide elements as well as scandium and yttrium, totaling seventeen metal elements. Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials, magnetic materials, catalytic materials, electronic devices, they have an important strategic position. In the field of electrocatalysis, rare earth metal elements have great potential for development due to their unique 4f electron layer structure, spin orbit coupling, high reactivity, controllable coordination number, and rich optical properties. However, there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis. Therefore, in order to stimulate the enthusiasm of researchers, this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment, hydrogen peroxide synthesis, hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR) and machine learning assisted research. In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance. This review is of great significance for further developing high-performance and multifunctional electrocatalysts, and is expected to provide strong support for the development of energy, environment, and chemical industries.
Rare earth metal elements include lanthanide elements as well as scandium and yttrium, totaling seventeen metal elements. Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials, magnetic materials, catalytic materials, electronic devices, they have an important strategic position. In the field of electrocatalysis, rare earth metal elements have great potential for development due to their unique 4f electron layer structure, spin orbit coupling, high reactivity, controllable coordination number, and rich optical properties. However, there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis. Therefore, in order to stimulate the enthusiasm of researchers, this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment, hydrogen peroxide synthesis, hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR) and machine learning assisted research. In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance. This review is of great significance for further developing high-performance and multifunctional electrocatalysts, and is expected to provide strong support for the development of energy, environment, and chemical industries.
2025, 36(9): 110722
doi: 10.1016/j.cclet.2024.110722
摘要:
To develop more efficient catalysts and discover new materials to work towards efficient solutions to the growing environmental problems, machine learning (ML) offers viable new ideas. Due to its ability to process large-scale data and mine underlying patterns, ML has been widely used in the design and development of materials in recent years. The purpose of this manuscript is to summarize the research progress of ML to guide the development of materials in the environmental field and open new horizons for environmental pollution control. This manuscript firstly details the basic ML definitions and operational procedures. Secondly, it summarizes the main ways of applying ML in materials. Then it unfolds to introduce the specific application examples of ML in different materials. Finally, we summarize the shortcomings and research trends of ML in predicting material design.
To develop more efficient catalysts and discover new materials to work towards efficient solutions to the growing environmental problems, machine learning (ML) offers viable new ideas. Due to its ability to process large-scale data and mine underlying patterns, ML has been widely used in the design and development of materials in recent years. The purpose of this manuscript is to summarize the research progress of ML to guide the development of materials in the environmental field and open new horizons for environmental pollution control. This manuscript firstly details the basic ML definitions and operational procedures. Secondly, it summarizes the main ways of applying ML in materials. Then it unfolds to introduce the specific application examples of ML in different materials. Finally, we summarize the shortcomings and research trends of ML in predicting material design.
2025, 36(9): 110725
doi: 10.1016/j.cclet.2024.110725
摘要:
Urbanization and industrialization have escalated water pollution, threatening ecosystems and human health. Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain. The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard. Carbon dots (CDs), as emerging carbon-based nanomaterials, exhibit properties such as biocompatibility, photoluminescence (PL), water solubility, and strong adsorption, positioning them as promising candidates for environmental monitoring and management. Particularly in wastewater treatment, their optical and electron transfer properties make them ideal for pollutant detection and removal. Despite their potential, comprehensive reviews on CDs' role in wastewater treatment are scarce, often lacking detailed insights into their synthesis, PL mechanisms, and practical applications. This review systematically addresses the synthesis, PL mechanisms, and wastewater treatment applications of CDs, aiming to bridge existing research gaps. It begins with an overview of CDs structure and classification, essential for grasping their properties and uses. The paper then explores the pivotal PL mechanisms of CDs, crucial for their sensing capabilities. Next, comprehensive synthesis strategies are presented, encompassing both top-down and bottom-up strategies such as arc discharge, chemical oxidation, and hydrothermal/solvothermal synthesis. The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications. Furthermore, the review systematically discusses the applications of CDs in wastewater treatment, including sensing, inorganic removal, and organic degradation. Finally, it delves into the research prospects and challenges of CDs, proposing future directions to enhance their role in wastewater treatment.
Urbanization and industrialization have escalated water pollution, threatening ecosystems and human health. Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain. The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard. Carbon dots (CDs), as emerging carbon-based nanomaterials, exhibit properties such as biocompatibility, photoluminescence (PL), water solubility, and strong adsorption, positioning them as promising candidates for environmental monitoring and management. Particularly in wastewater treatment, their optical and electron transfer properties make them ideal for pollutant detection and removal. Despite their potential, comprehensive reviews on CDs' role in wastewater treatment are scarce, often lacking detailed insights into their synthesis, PL mechanisms, and practical applications. This review systematically addresses the synthesis, PL mechanisms, and wastewater treatment applications of CDs, aiming to bridge existing research gaps. It begins with an overview of CDs structure and classification, essential for grasping their properties and uses. The paper then explores the pivotal PL mechanisms of CDs, crucial for their sensing capabilities. Next, comprehensive synthesis strategies are presented, encompassing both top-down and bottom-up strategies such as arc discharge, chemical oxidation, and hydrothermal/solvothermal synthesis. The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications. Furthermore, the review systematically discusses the applications of CDs in wastewater treatment, including sensing, inorganic removal, and organic degradation. Finally, it delves into the research prospects and challenges of CDs, proposing future directions to enhance their role in wastewater treatment.
2025, 36(9): 110736
doi: 10.1016/j.cclet.2024.110736
摘要:
Small interfering RNAs (siRNA) provide a novel and highly specific therapy due to their ability to effectively silence target genes, to date six siRNA therapeutics are approved for clinical use. Even so, some critical challenges remain to overcome in the therapeutic application of siRNAs, with delivery issues at the forefront. Among them, endo/lysosomal barrier is one of the important but often-neglected limitations hindering the delivery of siRNA therapeutics. In this review, we summarize the promising strategies that facilitate siRNAs overcoming endo/lysosomal barriers based on the cellular uptake and intracellular transport pathways, including promoting escape once endocytosis into the endo/lysosomes and bypassing lysosomes via endosome-Golgi-endoplasmic reticulum (ER) pathway or nonendocytosis pathway, and discuss the principal considerations and the future directions of promoting endo/lysosomal escape in the development of therapeutic siRNAs.
Small interfering RNAs (siRNA) provide a novel and highly specific therapy due to their ability to effectively silence target genes, to date six siRNA therapeutics are approved for clinical use. Even so, some critical challenges remain to overcome in the therapeutic application of siRNAs, with delivery issues at the forefront. Among them, endo/lysosomal barrier is one of the important but often-neglected limitations hindering the delivery of siRNA therapeutics. In this review, we summarize the promising strategies that facilitate siRNAs overcoming endo/lysosomal barriers based on the cellular uptake and intracellular transport pathways, including promoting escape once endocytosis into the endo/lysosomes and bypassing lysosomes via endosome-Golgi-endoplasmic reticulum (ER) pathway or nonendocytosis pathway, and discuss the principal considerations and the future directions of promoting endo/lysosomal escape in the development of therapeutic siRNAs.
2025, 36(9): 110813
doi: 10.1016/j.cclet.2024.110813
摘要:
Untreated water environments encourage the emergence of pathogenic microorganisms, which pose a significant risk to human health and sustainable development. Antimicrobial technologies in advanced photothermal materials offer a promising alternative strategy for solving water disinfection challenges. This technology effectively destroys bacterial biofilms by designing materials with controlled photothermal properties. Despite the potential of this technology, there is a lack of comprehensive reviews on the application of photothermal materials in water disinfection. The aim of this paper is to provide a comprehensive and up-to-date overview of the research and application of photothermal materials in water disinfection. It focuses on composites in photothermal materials, elucidates their basic mechanisms and sterilization properties, and provides a systematic and detailed overview of their recent progress in the field. The goal of this review is to offer insights into the future design of photothermal materials and to propose strategies for their practical application in disinfection processes.
Untreated water environments encourage the emergence of pathogenic microorganisms, which pose a significant risk to human health and sustainable development. Antimicrobial technologies in advanced photothermal materials offer a promising alternative strategy for solving water disinfection challenges. This technology effectively destroys bacterial biofilms by designing materials with controlled photothermal properties. Despite the potential of this technology, there is a lack of comprehensive reviews on the application of photothermal materials in water disinfection. The aim of this paper is to provide a comprehensive and up-to-date overview of the research and application of photothermal materials in water disinfection. It focuses on composites in photothermal materials, elucidates their basic mechanisms and sterilization properties, and provides a systematic and detailed overview of their recent progress in the field. The goal of this review is to offer insights into the future design of photothermal materials and to propose strategies for their practical application in disinfection processes.
2025, 36(9): 110857
doi: 10.1016/j.cclet.2025.110857
摘要:
The development of efficient green energy technology is imperative in the face of energy crises and environmental concerns. Photocatalysis, which utilizes solar energy for processes such as carbon dioxide (CO2) reduction, organic pollutants degradation, and hydrogen (H2) production through water splitting, is a promising approach. The key to high-efficiency photocatalysis lies in the design of superior photocatalysts. Graphene quantum dots (GQDs) have sparked significant interest in photocatalysis due to their exceptional up conversion photoluminescence (UCPL), strong light-capturing capability, and unique photoinduced charge transfer properties. However, their standalone use is limited by stability and activity. By integrating GQDs into composite photocatalysts, the separation of photogenerated electron-hole pairs is enhanced, boosting photocatalytic performance. This review provides the first overview and summary of the preparation methods of GQDs in photocatalysts, encompassing top-down and bottom-up strategy. Subsequently, a pioneering detailed summary was made on the applications of GQDs-semiconductor composites (metal organic frameworks, CdS, and bismuth-based oxides, etc.) in photocatalytic reactions such as CO2 reduction, organic pollutant degradation, and H2 generation. Furthermore, the corresponding representative examples and mechanisms are also elaborated and discussed respectively. Finally, the challenges and prospects for GQDs-based photocatalysts in the field of photocatalysis are proposed. This review provides inspiration and guidance for the development of efficient GQDs-based photocatalysts.
The development of efficient green energy technology is imperative in the face of energy crises and environmental concerns. Photocatalysis, which utilizes solar energy for processes such as carbon dioxide (CO2) reduction, organic pollutants degradation, and hydrogen (H2) production through water splitting, is a promising approach. The key to high-efficiency photocatalysis lies in the design of superior photocatalysts. Graphene quantum dots (GQDs) have sparked significant interest in photocatalysis due to their exceptional up conversion photoluminescence (UCPL), strong light-capturing capability, and unique photoinduced charge transfer properties. However, their standalone use is limited by stability and activity. By integrating GQDs into composite photocatalysts, the separation of photogenerated electron-hole pairs is enhanced, boosting photocatalytic performance. This review provides the first overview and summary of the preparation methods of GQDs in photocatalysts, encompassing top-down and bottom-up strategy. Subsequently, a pioneering detailed summary was made on the applications of GQDs-semiconductor composites (metal organic frameworks, CdS, and bismuth-based oxides, etc.) in photocatalytic reactions such as CO2 reduction, organic pollutant degradation, and H2 generation. Furthermore, the corresponding representative examples and mechanisms are also elaborated and discussed respectively. Finally, the challenges and prospects for GQDs-based photocatalysts in the field of photocatalysis are proposed. This review provides inspiration and guidance for the development of efficient GQDs-based photocatalysts.
2025, 36(9): 110912
doi: 10.1016/j.cclet.2025.110912
摘要:
Pyrazole derivatives have made impressive achievements in the discovery of new pesticides, especially novel fungicides, insecticides, and herbicides. The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment, which showed broad-spectrum and efficient biological activities. With the great interest and focus on pyrazoles, it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides. Based on this, we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides, antibacterial agents, insecticides, herbicides, antiviral agents, and nematicides in the past decade, summarized the fungicidal, antibacterial, insecticidal, herbicidal, antiviral, and nematicidal activities of pyrazoles, as well as the synthetic methods of the representative compounds. We also discussed the structure-activity relationship (SAR) and mechanism of action of the active compounds, aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency, low toxicity, and unique mechanism of action.
Pyrazole derivatives have made impressive achievements in the discovery of new pesticides, especially novel fungicides, insecticides, and herbicides. The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment, which showed broad-spectrum and efficient biological activities. With the great interest and focus on pyrazoles, it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides. Based on this, we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides, antibacterial agents, insecticides, herbicides, antiviral agents, and nematicides in the past decade, summarized the fungicidal, antibacterial, insecticidal, herbicidal, antiviral, and nematicidal activities of pyrazoles, as well as the synthetic methods of the representative compounds. We also discussed the structure-activity relationship (SAR) and mechanism of action of the active compounds, aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency, low toxicity, and unique mechanism of action.
2025, 36(9): 110988
doi: 10.1016/j.cclet.2025.110988
摘要:
Environmental catalysis has been considered one of the important research topics. Some technologies (e.g., photocatalysis and electrocatalysis) have been intensively developed with the advance of synthetic technologies of catalytical materials. In 2019, we discussed the development trend of this field, and wrote a roadmap on this topic in Chinese Chemical Letters (30 (2019) 2065–2088). Nowadays, we discuss it again from a new viewpoint along this road. In this paper, several subtopics are discussed, e.g., photocatalysis based on titanium dioxide, violet phosphorus, graphitic carbon and covalent organic frameworks, electrocatalysts based on carbon, metal- and covalent-organic framework. Finally, we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding, and give useful inspiration to explore new catalysts for practical applications.
Environmental catalysis has been considered one of the important research topics. Some technologies (e.g., photocatalysis and electrocatalysis) have been intensively developed with the advance of synthetic technologies of catalytical materials. In 2019, we discussed the development trend of this field, and wrote a roadmap on this topic in Chinese Chemical Letters (30 (2019) 2065–2088). Nowadays, we discuss it again from a new viewpoint along this road. In this paper, several subtopics are discussed, e.g., photocatalysis based on titanium dioxide, violet phosphorus, graphitic carbon and covalent organic frameworks, electrocatalysts based on carbon, metal- and covalent-organic framework. Finally, we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding, and give useful inspiration to explore new catalysts for practical applications.
2025, 36(9): 111052
doi: 10.1016/j.cclet.2025.111052
摘要:
P-stereogenic compounds play pivotal roles in natural products, pharmaceuticals, bioactive molecules, and catalysts/ligands, making their synthesis a highly researched area. Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species, despite the fact that many therapeutically relevant compounds feature P-O, P-N, or P-S bonds. The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds, offering significant potential for further development. This review provides an overview of advancements in the construction of P-stereogenic centers based on P-centered nucleophilic substitution, highlighting key challenges, breakthroughs, and future opportunities in the field.
P-stereogenic compounds play pivotal roles in natural products, pharmaceuticals, bioactive molecules, and catalysts/ligands, making their synthesis a highly researched area. Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species, despite the fact that many therapeutically relevant compounds feature P-O, P-N, or P-S bonds. The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds, offering significant potential for further development. This review provides an overview of advancements in the construction of P-stereogenic centers based on P-centered nucleophilic substitution, highlighting key challenges, breakthroughs, and future opportunities in the field.
2025, 36(9): 111093
doi: 10.1016/j.cclet.2025.111093
摘要:
Immunotherapy offers the promise of a potential cure for cancer, yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments (TMEs) present in some tumors. Therefore, robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications. Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses. Engineered bacteria, modified through chemical or biological methods, can be endowed with specific physiological properties, such as diverse surface antigens, metabolites, and improved biocompatibility. These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses. This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.
Immunotherapy offers the promise of a potential cure for cancer, yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments (TMEs) present in some tumors. Therefore, robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications. Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses. Engineered bacteria, modified through chemical or biological methods, can be endowed with specific physiological properties, such as diverse surface antigens, metabolites, and improved biocompatibility. These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses. This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.
2025, 36(9): 111178
doi: 10.1016/j.cclet.2025.111178
摘要:
Two-dimensional (2D) nanomaterials have always been regarded as having great development potential in the field of oil-based lubrication due to their designable structures, functional groups, and abundant active sites. However, understanding the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance from a comprehensive perspective is crucial for guiding their future development. This review provides a timely and comprehensive overview of the applications of 2D nanomaterials in oil-based lubrication. First, the bottlenecks and mechanisms of action of 2D nanomaterials are outlined, including adsorption protective films, charge adsorption effects, tribochemical reaction films, interlayer slip, and synergistic effects. On this basis, the review summarizes recent structural regulation strategies for 2D nanomaterials, including doping engineering, surface modification, structural optimization, and interfacial mixing engineering. Then, the focus was on analyzing the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance. The effects of thickness, number of layers, sheet diameter, interlayer spacing, Moiré patterns, wettability, functional groups, concentration, as well as interfacial compatibility and dispersion behavior of 2D nanomaterials were systematically investigated in oil-based lubrication, with the intrinsic correlations resolved through computational simulations. Finally, the review offers a preliminary summary of the significant challenges and future directions for 2D nanomaterials in oil-based lubrication. This review aims to provide valuable insights and development strategies for the rational design of high-performance oil-based lubrication materials.
Two-dimensional (2D) nanomaterials have always been regarded as having great development potential in the field of oil-based lubrication due to their designable structures, functional groups, and abundant active sites. However, understanding the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance from a comprehensive perspective is crucial for guiding their future development. This review provides a timely and comprehensive overview of the applications of 2D nanomaterials in oil-based lubrication. First, the bottlenecks and mechanisms of action of 2D nanomaterials are outlined, including adsorption protective films, charge adsorption effects, tribochemical reaction films, interlayer slip, and synergistic effects. On this basis, the review summarizes recent structural regulation strategies for 2D nanomaterials, including doping engineering, surface modification, structural optimization, and interfacial mixing engineering. Then, the focus was on analyzing the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance. The effects of thickness, number of layers, sheet diameter, interlayer spacing, Moiré patterns, wettability, functional groups, concentration, as well as interfacial compatibility and dispersion behavior of 2D nanomaterials were systematically investigated in oil-based lubrication, with the intrinsic correlations resolved through computational simulations. Finally, the review offers a preliminary summary of the significant challenges and future directions for 2D nanomaterials in oil-based lubrication. This review aims to provide valuable insights and development strategies for the rational design of high-performance oil-based lubrication materials.
2025, 36(9): 111297
doi: 10.1016/j.cclet.2025.111297
摘要:
Introducing functional polar groups into polyolefins can significantly improve the material properties, but there are still challenges in achieving this goal, with the core difficulty being that polar groups are prone to interact with metal active species, affecting the efficiency of the copolymerization. With the rapid advancement in catalyst, a variety of copolymerization strategies are developed aimed at producing more versatile polyolefin materials. Although early transition metal catalysts play an indispensable role in the traditional polyolefin industry, their inherent strong oxophilicity becomes a significant constraint in copolymerization involving polar olefins, limiting their application scope. This review summarizes the progress made in recent years in the efficient copolymerization of non-polar olefins with polar comonomers catalyzed by groups 3 and 4 single-site catalysts. We classify the catalysts into four categories, Sc-, Ti-, Zr-, Hf-, based on the type of metal centers, and provide insights into the influence of catalyst structures and the type of comonomers on the copolymerization behavior. The introduction of polar monomers fundamentally improves the comprehensive performance of the products, greatly broadens the application scope of polyolefin materials, and meets the growing market demand for multifunctional and high-performance materials.
Introducing functional polar groups into polyolefins can significantly improve the material properties, but there are still challenges in achieving this goal, with the core difficulty being that polar groups are prone to interact with metal active species, affecting the efficiency of the copolymerization. With the rapid advancement in catalyst, a variety of copolymerization strategies are developed aimed at producing more versatile polyolefin materials. Although early transition metal catalysts play an indispensable role in the traditional polyolefin industry, their inherent strong oxophilicity becomes a significant constraint in copolymerization involving polar olefins, limiting their application scope. This review summarizes the progress made in recent years in the efficient copolymerization of non-polar olefins with polar comonomers catalyzed by groups 3 and 4 single-site catalysts. We classify the catalysts into four categories, Sc-, Ti-, Zr-, Hf-, based on the type of metal centers, and provide insights into the influence of catalyst structures and the type of comonomers on the copolymerization behavior. The introduction of polar monomers fundamentally improves the comprehensive performance of the products, greatly broadens the application scope of polyolefin materials, and meets the growing market demand for multifunctional and high-performance materials.
2025, 36(9): 111383
doi: 10.1016/j.cclet.2025.111383
摘要:
Solid-state lithium-ion batteries (SSLIBs) offer significant advantages over traditional liquid-electrolyte-based batteries, including improved safety, higher energy density, and better thermal stability. Among various anode materials, silicon (Si)-based anodes have attracted significant attention due to their ultrahigh theoretical capacity (~4200 mAh/g) and abundant resources. However, widespread adoption of Si-based anodes in SSLIBs is still restricted by some critical challenges such as severe volume expansion, low electronic and ionic conductivity, high interfacial impedance, and low initial Coulombic efficiency (ICE). This review mainly focuses on the design strategies of Si-based anode for SSLIBs at the material, electrode and cell levels including nanostructuring, Si alloys, Si-carbon composites, conductive additives, advanced binder, external pressure, electrolyte infiltration, and prelithiation. The insights provided here aim to inspire future research and accelerate commercialization of high-performance Si-based anodes in next-generation SSLIBs.
Solid-state lithium-ion batteries (SSLIBs) offer significant advantages over traditional liquid-electrolyte-based batteries, including improved safety, higher energy density, and better thermal stability. Among various anode materials, silicon (Si)-based anodes have attracted significant attention due to their ultrahigh theoretical capacity (~4200 mAh/g) and abundant resources. However, widespread adoption of Si-based anodes in SSLIBs is still restricted by some critical challenges such as severe volume expansion, low electronic and ionic conductivity, high interfacial impedance, and low initial Coulombic efficiency (ICE). This review mainly focuses on the design strategies of Si-based anode for SSLIBs at the material, electrode and cell levels including nanostructuring, Si alloys, Si-carbon composites, conductive additives, advanced binder, external pressure, electrolyte infiltration, and prelithiation. The insights provided here aim to inspire future research and accelerate commercialization of high-performance Si-based anodes in next-generation SSLIBs.
2025, 36(9): 110679
doi: 10.1016/j.cclet.2024.110679
摘要:
2025, 36(9): 110924
doi: 10.1016/j.cclet.2025.110924
摘要:
Element Transfer Reaction (ETR) theory is a new fundamental theory guiding the design of synthetic routes. It analyses problems from a brand-new perspective of element circulation, decomposing the factors affecting synthetic efficiency into three elements: element sources, driving force, and output. Different from the retrosynthetic analysis method and the atom economy theory, the ETR theory places more emphasis on examining the problem as a whole and comprehensively considering various factors involved in industrial applications. This perspective intends to elaborate on the scientific connotation of the ETR theory and explore its characteristics by discussing the practical application cases.
Element Transfer Reaction (ETR) theory is a new fundamental theory guiding the design of synthetic routes. It analyses problems from a brand-new perspective of element circulation, decomposing the factors affecting synthetic efficiency into three elements: element sources, driving force, and output. Different from the retrosynthetic analysis method and the atom economy theory, the ETR theory places more emphasis on examining the problem as a whole and comprehensively considering various factors involved in industrial applications. This perspective intends to elaborate on the scientific connotation of the ETR theory and explore its characteristics by discussing the practical application cases.
2025, 36(9): 111160
doi: 10.1016/j.cclet.2025.111160
摘要:
Linear mRNA vaccines are constrained by exonuclease susceptibility and instability, leading to compromised antigen expression. Circular RNA (circRNA) lacking canonical 5′ and 3′ untranslated regions demonstrates intrinsic exonuclease resistance. Current circularization strategies face three principal limitations: chemical methods produce non-native 2′, 5′-phosphodiester bonds; ribozyme-mediated approaches are restricted to RNA fragments shorter than 500 nucleotides; the Anabaena Group Ⅰ intron system retains immunogenic exon sequences. In contrast, the self-splicing Group Ⅰ intron ribozyme from Tetrahymena enables precisely controlled circularization through autonomous structural rearrangement, yielding exon-free constructs. Through optimized purification protocols, historical scalability challenges are systematically addressed. This Perspective establishes the mechanistic rationale and therapeutic superiority of this engineered RNA circularization platform.
Linear mRNA vaccines are constrained by exonuclease susceptibility and instability, leading to compromised antigen expression. Circular RNA (circRNA) lacking canonical 5′ and 3′ untranslated regions demonstrates intrinsic exonuclease resistance. Current circularization strategies face three principal limitations: chemical methods produce non-native 2′, 5′-phosphodiester bonds; ribozyme-mediated approaches are restricted to RNA fragments shorter than 500 nucleotides; the Anabaena Group Ⅰ intron system retains immunogenic exon sequences. In contrast, the self-splicing Group Ⅰ intron ribozyme from Tetrahymena enables precisely controlled circularization through autonomous structural rearrangement, yielding exon-free constructs. Through optimized purification protocols, historical scalability challenges are systematically addressed. This Perspective establishes the mechanistic rationale and therapeutic superiority of this engineered RNA circularization platform.
2025, 36(5): 109726
doi: 10.1016/j.cclet.2024.109726
摘要:
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
2025, 36(5): 109853
doi: 10.1016/j.cclet.2024.109853
摘要:
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
2025, 36(5): 109870
doi: 10.1016/j.cclet.2024.109870
摘要:
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
2025, 36(5): 109873
doi: 10.1016/j.cclet.2024.109873
摘要:
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
2025, 36(5): 109919
doi: 10.1016/j.cclet.2024.109919
摘要:
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
2025, 36(5): 109920
doi: 10.1016/j.cclet.2024.109920
摘要:
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
2025, 36(5): 109935
doi: 10.1016/j.cclet.2024.109935
摘要:
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
2025, 36(5): 109936
doi: 10.1016/j.cclet.2024.109936
摘要:
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
2025, 36(5): 109937
doi: 10.1016/j.cclet.2024.109937
摘要:
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
2025, 36(5): 109939
doi: 10.1016/j.cclet.2024.109939
摘要:
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
2025, 36(5): 109940
doi: 10.1016/j.cclet.2024.109940
摘要:
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
2025, 36(5): 110015
doi: 10.1016/j.cclet.2024.110015
摘要:
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
2025, 36(5): 110034
doi: 10.1016/j.cclet.2024.110034
摘要:
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
2025, 36(5): 110043
doi: 10.1016/j.cclet.2024.110043
摘要:
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
2025, 36(5): 110045
doi: 10.1016/j.cclet.2024.110045
摘要:
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
2025, 36(5): 110053
doi: 10.1016/j.cclet.2024.110053
摘要:
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
2025, 36(5): 110067
doi: 10.1016/j.cclet.2024.110067
摘要:
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
2025, 36(5): 110069
doi: 10.1016/j.cclet.2024.110069
摘要:
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
2025, 36(5): 110073
doi: 10.1016/j.cclet.2024.110073
摘要:
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
2025, 36(5): 110082
doi: 10.1016/j.cclet.2024.110082
摘要:
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
2025, 36(5): 110084
doi: 10.1016/j.cclet.2024.110084
摘要:
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
2025, 36(5): 110097
doi: 10.1016/j.cclet.2024.110097
摘要:
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
2025, 36(5): 110098
doi: 10.1016/j.cclet.2024.110098
摘要:
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
2025, 36(5): 110105
doi: 10.1016/j.cclet.2024.110105
摘要:
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
2025, 36(5): 110106
doi: 10.1016/j.cclet.2024.110106
摘要:
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
2025, 36(5): 110116
doi: 10.1016/j.cclet.2024.110116
摘要:
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
2025, 36(5): 110119
doi: 10.1016/j.cclet.2024.110119
摘要:
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
2025, 36(5): 110128
doi: 10.1016/j.cclet.2024.110128
摘要:
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
2025, 36(5): 110130
doi: 10.1016/j.cclet.2024.110130
摘要:
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
2025, 36(5): 110133
doi: 10.1016/j.cclet.2024.110133
摘要:
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
2025, 36(5): 110135
doi: 10.1016/j.cclet.2024.110135
摘要:
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
2025, 36(5): 110140
doi: 10.1016/j.cclet.2024.110140
摘要:
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
2025, 36(5): 110141
doi: 10.1016/j.cclet.2024.110141
摘要:
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
2025, 36(5): 110146
doi: 10.1016/j.cclet.2024.110146
摘要:
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
2025, 36(5): 110147
doi: 10.1016/j.cclet.2024.110147
摘要:
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
2025, 36(5): 110149
doi: 10.1016/j.cclet.2024.110149
摘要:
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
2025, 36(5): 110166
doi: 10.1016/j.cclet.2024.110166
摘要:
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
2025, 36(5): 110168
doi: 10.1016/j.cclet.2024.110168
摘要:
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
2025, 36(5): 110178
doi: 10.1016/j.cclet.2024.110178
摘要:
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
2025, 36(5): 110179
doi: 10.1016/j.cclet.2024.110179
摘要:
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
2025, 36(5): 110183
doi: 10.1016/j.cclet.2024.110183
摘要:
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
2025, 36(5): 110190
doi: 10.1016/j.cclet.2024.110190
摘要:
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
2025, 36(5): 110191
doi: 10.1016/j.cclet.2024.110191
摘要:
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
2025, 36(5): 110192
doi: 10.1016/j.cclet.2024.110192
摘要:
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
2025, 36(5): 110195
doi: 10.1016/j.cclet.2024.110195
摘要:
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
2025, 36(5): 110196
doi: 10.1016/j.cclet.2024.110196
摘要:
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
2025, 36(5): 110200
doi: 10.1016/j.cclet.2024.110200
摘要:
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
2025, 36(5): 110201
doi: 10.1016/j.cclet.2024.110201
摘要:
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
2025, 36(5): 110202
doi: 10.1016/j.cclet.2024.110202
摘要:
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
2025, 36(5): 110203
doi: 10.1016/j.cclet.2024.110203
摘要:
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
2025, 36(5): 110206
doi: 10.1016/j.cclet.2024.110206
摘要:
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
2025, 36(5): 110207
doi: 10.1016/j.cclet.2024.110207
摘要:
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
2025, 36(5): 110209
doi: 10.1016/j.cclet.2024.110209
摘要:
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
2025, 36(5): 110213
doi: 10.1016/j.cclet.2024.110213
摘要:
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
2025, 36(5): 110227
doi: 10.1016/j.cclet.2024.110227
摘要:
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
2025, 36(5): 110230
doi: 10.1016/j.cclet.2024.110230
摘要:
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
2025, 36(5): 110231
doi: 10.1016/j.cclet.2024.110231
摘要:
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
2025, 36(5): 110237
doi: 10.1016/j.cclet.2024.110237
摘要:
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
2025, 36(5): 110238
doi: 10.1016/j.cclet.2024.110238
摘要:
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
2025, 36(5): 110239
doi: 10.1016/j.cclet.2024.110239
摘要:
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
2025, 36(5): 110240
doi: 10.1016/j.cclet.2024.110240
摘要:
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
2025, 36(5): 110241
doi: 10.1016/j.cclet.2024.110241
摘要:
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
2025, 36(5): 110243
doi: 10.1016/j.cclet.2024.110243
摘要:
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
2025, 36(5): 110244
doi: 10.1016/j.cclet.2024.110244
摘要:
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
2025, 36(5): 110249
doi: 10.1016/j.cclet.2024.110249
摘要:
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
2025, 36(5): 110253
doi: 10.1016/j.cclet.2024.110253
摘要:
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
2025, 36(5): 110258
doi: 10.1016/j.cclet.2024.110258
摘要:
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
2025, 36(5): 110260
doi: 10.1016/j.cclet.2024.110260
摘要:
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
2025, 36(5): 110282
doi: 10.1016/j.cclet.2024.110282
摘要:
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
2025, 36(5): 110291
doi: 10.1016/j.cclet.2024.110291
摘要:
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
2025, 36(5): 110293
doi: 10.1016/j.cclet.2024.110293
摘要:
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
2025, 36(5): 110295
doi: 10.1016/j.cclet.2024.110295
摘要:
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
2025, 36(5): 110306
doi: 10.1016/j.cclet.2024.110306
摘要:
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
2025, 36(5): 110310
doi: 10.1016/j.cclet.2024.110310
摘要:
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
2025, 36(5): 110311
doi: 10.1016/j.cclet.2024.110311
摘要:
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
2025, 36(5): 110312
doi: 10.1016/j.cclet.2024.110312
摘要:
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
2025, 36(5): 110334
doi: 10.1016/j.cclet.2024.110334
摘要:
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
2025, 36(5): 110432
doi: 10.1016/j.cclet.2024.110432
摘要:
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
2025, 36(5): 110437
doi: 10.1016/j.cclet.2024.110437
摘要:
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
2025, 36(5): 110508
doi: 10.1016/j.cclet.2024.110508
摘要:
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
2025, 36(5): 110561
doi: 10.1016/j.cclet.2024.110561
摘要:
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
2025, 36(5): 110629
doi: 10.1016/j.cclet.2024.110629
摘要:
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
2025, 36(5): 110663
doi: 10.1016/j.cclet.2024.110663
摘要:
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
2025, 36(5): 110672
doi: 10.1016/j.cclet.2024.110672
摘要:
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
2025, 36(5): 110699
doi: 10.1016/j.cclet.2024.110699
摘要:
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
2025, 36(5): 110700
doi: 10.1016/j.cclet.2024.110700
摘要:
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
2025, 36(5): 110719
doi: 10.1016/j.cclet.2024.110719
摘要:
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
2025, 36(5): 110724
doi: 10.1016/j.cclet.2024.110724
摘要:
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
2025, 36(5): 110760
doi: 10.1016/j.cclet.2024.110760
摘要:
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
2025, 36(5): 110762
doi: 10.1016/j.cclet.2024.110762
摘要:
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
2025, 36(5): 110765
doi: 10.1016/j.cclet.2024.110765
摘要:
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
2025, 36(5): 109871
doi: 10.1016/j.cclet.2024.109871
摘要:
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
2025, 36(5): 109898
doi: 10.1016/j.cclet.2024.109898
摘要:
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis
2025, 36(5): 109906
doi: 10.1016/j.cclet.2024.109906
摘要:
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
2025, 36(5): 109938
doi: 10.1016/j.cclet.2024.109938
摘要:
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
2025, 36(5): 110059
doi: 10.1016/j.cclet.2024.110059
摘要:
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
2025, 36(5): 110072
doi: 10.1016/j.cclet.2024.110072
摘要:
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
2025, 36(5): 110126
doi: 10.1016/j.cclet.2024.110126
摘要:
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
2025, 36(5): 110226
doi: 10.1016/j.cclet.2024.110226
摘要:
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
2025, 36(5): 110277
doi: 10.1016/j.cclet.2024.110277
摘要:
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
2025, 36(5): 110284
doi: 10.1016/j.cclet.2024.110284
摘要:
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
2025, 36(5): 110423
doi: 10.1016/j.cclet.2024.110423
摘要:
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
2025, 36(5): 110503
doi: 10.1016/j.cclet.2024.110503
摘要:
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
2025, 36(5): 110521
doi: 10.1016/j.cclet.2024.110521
摘要:
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
2025, 36(5): 110529
doi: 10.1016/j.cclet.2024.110529
摘要:
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
2025, 36(5): 110618
doi: 10.1016/j.cclet.2024.110618
摘要:
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
2025, 36(5): 110628
doi: 10.1016/j.cclet.2024.110628
摘要:
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
2025, 36(5): 110764
doi: 10.1016/j.cclet.2024.110764
摘要:
2025, 36(5): 110869
doi: 10.1016/j.cclet.2025.110869
摘要:
2025, 36(5): 110936
doi: 10.1016/j.cclet.2025.110936
摘要:
