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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(3): 110623
doi: 10.1016/j.cclet.2024.110623
摘要:
Transition metal sulfides (TMSs) are primitive composition of biocatalysts that are active for molecular hydrogen production. The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation. Herein, super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2 nanosheet/Ni3S4 nanoparticle (Super-NiS/WS2/Ni3S4) with high spatial ordering and abundant plane- and edge-type WS2NiS and WS2Ni3S4 heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid (PW12) as W precursor and nickel foam as Ni precursor in one pot. When evaluated for the electrocatalytic hydrogen evolution reaction (HER), the Super-NiS/WS2/Ni3S4 only required overpotentials of 57, 95, and 151 mV to drive HER in alkaline, acid, and neutral media, respectively, and presented favorable reaction kinetics and test stability. The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces. The Gibbs free energy (ΔGH*) analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER. Moreover, the collaborations of the abundant plane- and edge-type active interfaces, the open nanosheet-based vertical array, and the phosphorus doping in Super-NiS/WS2/Ni3S4 strengthen mass transport and electron transfer in electrocatalysis. The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
Transition metal sulfides (TMSs) are primitive composition of biocatalysts that are active for molecular hydrogen production. The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation. Herein, super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2 nanosheet/Ni3S4 nanoparticle (Super-NiS/WS2/Ni3S4) with high spatial ordering and abundant plane- and edge-type WS2NiS and WS2Ni3S4 heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid (PW12) as W precursor and nickel foam as Ni precursor in one pot. When evaluated for the electrocatalytic hydrogen evolution reaction (HER), the Super-NiS/WS2/Ni3S4 only required overpotentials of 57, 95, and 151 mV to drive HER in alkaline, acid, and neutral media, respectively, and presented favorable reaction kinetics and test stability. The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces. The Gibbs free energy (ΔGH*) analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER. Moreover, the collaborations of the abundant plane- and edge-type active interfaces, the open nanosheet-based vertical array, and the phosphorus doping in Super-NiS/WS2/Ni3S4 strengthen mass transport and electron transfer in electrocatalysis. The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
2026, 37(3): 110625
doi: 10.1016/j.cclet.2024.110625
摘要:
The trithiocyanurate, (H2C3N3S3)-, exhibits a strong optical anisotropy but has a small HOMO-LUMO gap, limiting its application to the higher energy wavelength ranges. Herein, by applying an amino substitution strategy, we report that 2-amino-4,6-dimercapto-S-triazine, (H3C3N4S2)-, generates a series new compound: A2(H2C3N4S2)2•H2O (NH4, Ⅰ; K−Cs, Ⅱ−Ⅳ). Compound Ⅰ crystallizes in P21/n, while compounds Ⅱ–Ⅳ crystallize in P1. Their experimental optical band gaps (Eg) range from 3.52 eV to 3.65 eV, corresponding to a blue shift of 30~60 nm compared to those of the trithiocyanuric containing systems. Moreover, the birefringence of all compounds ranges from 0.440 to 0.510, indicating strong anisotropy. Notably, compound Ⅰ (Eg = 3.65 eV,\begin{document}$ \Delta n_{cal.}^{\max}$\end{document} \begin{document}$ \Delta n_{o b v.}^{(0 \overline{1} \overline{1})} $\end{document}
The trithiocyanurate, (H2C3N3S3)-, exhibits a strong optical anisotropy but has a small HOMO-LUMO gap, limiting its application to the higher energy wavelength ranges. Herein, by applying an amino substitution strategy, we report that 2-amino-4,6-dimercapto-S-triazine, (H3C3N4S2)-, generates a series new compound: A2(H2C3N4S2)2•H2O (NH4, Ⅰ; K−Cs, Ⅱ−Ⅳ). Compound Ⅰ crystallizes in P21/n, while compounds Ⅱ–Ⅳ crystallize in P1. Their experimental optical band gaps (Eg) range from 3.52 eV to 3.65 eV, corresponding to a blue shift of 30~60 nm compared to those of the trithiocyanuric containing systems. Moreover, the birefringence of all compounds ranges from 0.440 to 0.510, indicating strong anisotropy. Notably, compound Ⅰ (Eg = 3.65 eV,
2026, 37(3): 110626
doi: 10.1016/j.cclet.2024.110626
摘要:
Garnet-type ceramic Li7La3Zr2O12 (LLZO) stands out as a potential solid-state electrolyte, offering a promising alternative to conventional flammable liquid electrolytes. However, its large interfacial resistance with electrodes remains a significant challenge. In this research, we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO. By tuning the gel-polymer interphase via fluoroethylene carbonate (FEC), known as FGPE, we have established a rapid Li+ transport channel by enhancing the solid-solid interfacial contact. This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64. Furthermore, FGPE effectively mitigates concentration polarization under high currents, thereby enabling a higher capacity output. In comparison to gel-polymer interphases with dimethyl carbonate (DMC) as the solvent (referred to as GPE), the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over 800 h at a current density of 0.1 mA/cm2. Moreover, the Li|FGPE|LLZO|FGPE|LiFePO4 cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94% at 0.5 C after 200 cycles. This study underscores an innovative approach in advancing in field of solid-state batteries, anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
Garnet-type ceramic Li7La3Zr2O12 (LLZO) stands out as a potential solid-state electrolyte, offering a promising alternative to conventional flammable liquid electrolytes. However, its large interfacial resistance with electrodes remains a significant challenge. In this research, we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO. By tuning the gel-polymer interphase via fluoroethylene carbonate (FEC), known as FGPE, we have established a rapid Li+ transport channel by enhancing the solid-solid interfacial contact. This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64. Furthermore, FGPE effectively mitigates concentration polarization under high currents, thereby enabling a higher capacity output. In comparison to gel-polymer interphases with dimethyl carbonate (DMC) as the solvent (referred to as GPE), the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over 800 h at a current density of 0.1 mA/cm2. Moreover, the Li|FGPE|LLZO|FGPE|LiFePO4 cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94% at 0.5 C after 200 cycles. This study underscores an innovative approach in advancing in field of solid-state batteries, anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
2026, 37(3): 110655
doi: 10.1016/j.cclet.2024.110655
摘要:
Trapping and manipulating microscopic particles (micron or nano) in a liquid environment are of great significance for research and applications in nanoscience, engineering, and biomedicine. Although optical tweezers, magnetic tweezers, acoustic tweezers, etc. have been successfully developed, it is still challenging to separate, select, and manipulate micron and submicron particles with comparable morphologies and sizes in trace amounts of liquids with high viscosity and extremely tiny concentrations. Herein, an electric tweezer with measurable force was introduced in an environmental transmission electron microscope (ETEM) for trapping a single submicron particle in high viscosity liquids. The critical voltages for trapping SiO2 and TiO2 spheres were determined to be 75 V and 25 V, respectively, due to their dielectric characteristics. As a result, although TiO2 particles exhibited a similar size and morphology, they were able to be successfully separated from a mixed suspension of SiO2 and TiO2. Moreover, by applying a reasonable bias voltage to the electric tweezer and customizing the size and shape of the tweezer tip, individual 500, 750, and 1000 nm TiO2 spheres could be easily trapped from the corresponding TiO2 suspension. The displacements of atomic force microscope (AFM) cantilevers indicated that the forces to trapped a single particle gradually increased with the diameter of the particles. Additionally, the electric tweezer could precisely manipulate a single particle, and stack a specific structure on the top of the electric tweezer. When the electric tweezer was combined with an optical microscope, it could successfully transfer a 5 µm SiO2 sphere to a HeLa cell. Precisely trapping and manipulating micron and submicron particles is the foundation for fabricating microdevices to achieve specific functions, and it also show great potential for use in biological applications.
Trapping and manipulating microscopic particles (micron or nano) in a liquid environment are of great significance for research and applications in nanoscience, engineering, and biomedicine. Although optical tweezers, magnetic tweezers, acoustic tweezers, etc. have been successfully developed, it is still challenging to separate, select, and manipulate micron and submicron particles with comparable morphologies and sizes in trace amounts of liquids with high viscosity and extremely tiny concentrations. Herein, an electric tweezer with measurable force was introduced in an environmental transmission electron microscope (ETEM) for trapping a single submicron particle in high viscosity liquids. The critical voltages for trapping SiO2 and TiO2 spheres were determined to be 75 V and 25 V, respectively, due to their dielectric characteristics. As a result, although TiO2 particles exhibited a similar size and morphology, they were able to be successfully separated from a mixed suspension of SiO2 and TiO2. Moreover, by applying a reasonable bias voltage to the electric tweezer and customizing the size and shape of the tweezer tip, individual 500, 750, and 1000 nm TiO2 spheres could be easily trapped from the corresponding TiO2 suspension. The displacements of atomic force microscope (AFM) cantilevers indicated that the forces to trapped a single particle gradually increased with the diameter of the particles. Additionally, the electric tweezer could precisely manipulate a single particle, and stack a specific structure on the top of the electric tweezer. When the electric tweezer was combined with an optical microscope, it could successfully transfer a 5 µm SiO2 sphere to a HeLa cell. Precisely trapping and manipulating micron and submicron particles is the foundation for fabricating microdevices to achieve specific functions, and it also show great potential for use in biological applications.
2026, 37(3): 110666
doi: 10.1016/j.cclet.2024.110666
摘要:
In order to cope with harsh situations without an external power supply, developing high-performance aqueous zinc batteries (AZBs) with chemically self-charging as a self-powered system is of great practical significance. Herein, we present the synthesis of a new porous organic polymer with hexaazatriphenylene hexacarboxylic acid trianhydride (HHAT) and 2,6-diaminoanthraquinone (DAAQ) units (HTAQ). Due to its π-conjugated aromatic structure with abundant redox-active centers and limited solubility in electrolytes, the constructed flexible and coin-type AZBs based on HTAQ cathodes display a superior volume energy density (8.7 mWh/cm3) and a higher energy density (104 Wh/kg), respectively, and excellent cycle life, where both Zn2+ and H+ ions participate in the cathode reaction. Impressively, the electric energy exhausted flexible Zn//HTAQ AZB can be chemically self-recharged by exposing the discharged HTAQ cathode to air, ascribing to the spontaneous redox reaction between O2 and the discharged HTAQ cathode. The exhausted flexible Zn//HTAQ AZB after air-charging for 30 h, can present a high discharge capacity of 294 mAh/g at 0.5 A/g, a higher self-charging cycle stability (15 cycles), a high-rate capability, and work well at hybrid modes (chemical or/and galvanostatic charging). Our work opens a new route to construct high-performance self-powered systems based on AZBs.
In order to cope with harsh situations without an external power supply, developing high-performance aqueous zinc batteries (AZBs) with chemically self-charging as a self-powered system is of great practical significance. Herein, we present the synthesis of a new porous organic polymer with hexaazatriphenylene hexacarboxylic acid trianhydride (HHAT) and 2,6-diaminoanthraquinone (DAAQ) units (HTAQ). Due to its π-conjugated aromatic structure with abundant redox-active centers and limited solubility in electrolytes, the constructed flexible and coin-type AZBs based on HTAQ cathodes display a superior volume energy density (8.7 mWh/cm3) and a higher energy density (104 Wh/kg), respectively, and excellent cycle life, where both Zn2+ and H+ ions participate in the cathode reaction. Impressively, the electric energy exhausted flexible Zn//HTAQ AZB can be chemically self-recharged by exposing the discharged HTAQ cathode to air, ascribing to the spontaneous redox reaction between O2 and the discharged HTAQ cathode. The exhausted flexible Zn//HTAQ AZB after air-charging for 30 h, can present a high discharge capacity of 294 mAh/g at 0.5 A/g, a higher self-charging cycle stability (15 cycles), a high-rate capability, and work well at hybrid modes (chemical or/and galvanostatic charging). Our work opens a new route to construct high-performance self-powered systems based on AZBs.
2026, 37(3): 110667
doi: 10.1016/j.cclet.2024.110667
摘要:
The regulation of guest molecules on the self-assembly system of tetracarboxylic acid derivative (H4BDETP) at the liquid/solid interface was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Coronene (COR) guest molecules induced H4BDETP to transform from linear assembly structure to diversified nanoporous structures in which COR could be captured. And the regulation of pyridine guest molecules (DPE, BPYB, TYPY) on the mono-component assembly structure of H4BDETP was achieved by forming O–H···N hydrogen bonds with H4BDETP. The introduction of both COR and pyridine derivatives could destroy the hydrogen-bonded dimers of H4BDETP, and new O–H···O hydrogen bonds were formed between H4BDETP molecules. In addition, H4BDETP/pyridine co-assembly structures depended on the central bridging units and the number of pyridine groups in pyridine derivatives. Furthermore, H4BDETP/TYPY structure underwent structural transformation induced by COR and multi-component assembly structures with thermodynamic stability were constructed.
The regulation of guest molecules on the self-assembly system of tetracarboxylic acid derivative (H4BDETP) at the liquid/solid interface was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Coronene (COR) guest molecules induced H4BDETP to transform from linear assembly structure to diversified nanoporous structures in which COR could be captured. And the regulation of pyridine guest molecules (DPE, BPYB, TYPY) on the mono-component assembly structure of H4BDETP was achieved by forming O–H···N hydrogen bonds with H4BDETP. The introduction of both COR and pyridine derivatives could destroy the hydrogen-bonded dimers of H4BDETP, and new O–H···O hydrogen bonds were formed between H4BDETP molecules. In addition, H4BDETP/pyridine co-assembly structures depended on the central bridging units and the number of pyridine groups in pyridine derivatives. Furthermore, H4BDETP/TYPY structure underwent structural transformation induced by COR and multi-component assembly structures with thermodynamic stability were constructed.
2026, 37(3): 110668
doi: 10.1016/j.cclet.2024.110668
摘要:
The surficial inherent properties of TiO2 like exposed facet and crystalline state are vital for their surface reactions. However, efficiently controlling the specific crystal structure and the exposed crystal surface still faces big challenge. Here, the controlled solid phase transition of amorphous TiO2 to crystalline phase with exposed crystal facet (001) is achieved by photo-assisted atomic layer deposition (ALD) Pt process. Significantly, the obtained Pt/TiO2 film via photo-assisted treatment exhibits high sensing performance to NO and HF, and shows a lower optimized working temperature. The enhanced sensing performance is attributed to the metal-support strong interaction under oxidative atmosphere (O-SMSI). The facet effects leading to the unique distribution of charges at the interface combined with the catalytic effects result in the high sensing performance. This work provides a novel phase transition engineering strategy for regulating TiO2 from amorphous to crystalline phase, and the controllable synthesis of high Pt monatomic loading on TiO2 via ALD, which are critical for the accurate synthesis of efficient sensing and catalytic nanomaterials.
The surficial inherent properties of TiO2 like exposed facet and crystalline state are vital for their surface reactions. However, efficiently controlling the specific crystal structure and the exposed crystal surface still faces big challenge. Here, the controlled solid phase transition of amorphous TiO2 to crystalline phase with exposed crystal facet (001) is achieved by photo-assisted atomic layer deposition (ALD) Pt process. Significantly, the obtained Pt/TiO2 film via photo-assisted treatment exhibits high sensing performance to NO and HF, and shows a lower optimized working temperature. The enhanced sensing performance is attributed to the metal-support strong interaction under oxidative atmosphere (O-SMSI). The facet effects leading to the unique distribution of charges at the interface combined with the catalytic effects result in the high sensing performance. This work provides a novel phase transition engineering strategy for regulating TiO2 from amorphous to crystalline phase, and the controllable synthesis of high Pt monatomic loading on TiO2 via ALD, which are critical for the accurate synthesis of efficient sensing and catalytic nanomaterials.
2026, 37(3): 110681
doi: 10.1016/j.cclet.2024.110681
摘要:
The emerging anode-free lithium metal battery (AFLMB) is very promising for the next-generation electrochemical energy storage technology due to its remarkable high-energy density. However, the current development of AFLMB is seriously hampered by the low Coulombic efficiency and limited lifespan caused mainly by the uncontrolled dendritic lithium growth and significant volume change during Li plating/stripping on the traditional current collector. Here, we report the design of a “breathable” three-dimensional (3D) lithium host with MnO2 nanoflake array for long-lifespan AFLMB. Specifically, a dense MnO2 nanoflake array stretchably grown on carbon cloth by an easy solution dipping method is constructed as a 3D current collector for AFLMBs. Both experimental and theoretical studies underlined that the Li2O/Mn nanoflake arrays produced spontaneously upon the initial lithiation can effectively guide uniform lithium nucleation and growth. Moreover, this unique 3D hierarchical structure expands/shrinks along with the lithium plating/stripping, accommodating the large volume expansion/shrinkage over the subsequent charge/discharge processes. As such, a dendrite-free lithium structure was achieved even at a high capacity of 10 mAh/cm2. More importantly, the as-constructed AFLMB with this current collector exhibits impressive cycling stability with 64% capacity retained after 200 cycles. This study offers new insights into constructing highly efficient 3D protective layers for metal anodes toward the practical feasibility of anode-free batteries.
The emerging anode-free lithium metal battery (AFLMB) is very promising for the next-generation electrochemical energy storage technology due to its remarkable high-energy density. However, the current development of AFLMB is seriously hampered by the low Coulombic efficiency and limited lifespan caused mainly by the uncontrolled dendritic lithium growth and significant volume change during Li plating/stripping on the traditional current collector. Here, we report the design of a “breathable” three-dimensional (3D) lithium host with MnO2 nanoflake array for long-lifespan AFLMB. Specifically, a dense MnO2 nanoflake array stretchably grown on carbon cloth by an easy solution dipping method is constructed as a 3D current collector for AFLMBs. Both experimental and theoretical studies underlined that the Li2O/Mn nanoflake arrays produced spontaneously upon the initial lithiation can effectively guide uniform lithium nucleation and growth. Moreover, this unique 3D hierarchical structure expands/shrinks along with the lithium plating/stripping, accommodating the large volume expansion/shrinkage over the subsequent charge/discharge processes. As such, a dendrite-free lithium structure was achieved even at a high capacity of 10 mAh/cm2. More importantly, the as-constructed AFLMB with this current collector exhibits impressive cycling stability with 64% capacity retained after 200 cycles. This study offers new insights into constructing highly efficient 3D protective layers for metal anodes toward the practical feasibility of anode-free batteries.
2026, 37(3): 110682
doi: 10.1016/j.cclet.2024.110682
摘要:
Lead-free perovskite has become a shining pearl in the field of direct X-ray detection due to its non-toxicity and excellent optoelectronic properties. However, the high limit of detection (LoD) of X-ray detectors due to high current noise caused by high operating voltages is a major challenge to overcome. Here, we utilized a zero-dimensional lead-free perovskite ferroelectric material (NMP)3Sb2Br9 (1, NMP = N-methylpyrrolidine) to achieve ultra-low LoD self-driven X-ray detection. The self-driven detection mode without external bias has been proven to be an effective means of reducing LoD due to its low current noise characteristics. Additionally, the zero-dimensional distinctive isolated framework results in a high resistivity of 1.39 × 1011 Ω cm, which effectively reduces the current noise and suppresses ion migration. By further combining the ferroelectric-induced bulk photovoltaic effect, the 1-based detector achieves an ultra-low LoD X-ray detection of 84.1 nGyair/s under the self-driven mode, which represents a quite advanced level in the lead-free perovskite X-ray detection region. Our work successfully achieved ultra-low LoD self-driven X-ray detection by combining ferroelectricity with high resistance, providing a promising avenue for the development of low LoD X-ray detectors.
Lead-free perovskite has become a shining pearl in the field of direct X-ray detection due to its non-toxicity and excellent optoelectronic properties. However, the high limit of detection (LoD) of X-ray detectors due to high current noise caused by high operating voltages is a major challenge to overcome. Here, we utilized a zero-dimensional lead-free perovskite ferroelectric material (NMP)3Sb2Br9 (1, NMP = N-methylpyrrolidine) to achieve ultra-low LoD self-driven X-ray detection. The self-driven detection mode without external bias has been proven to be an effective means of reducing LoD due to its low current noise characteristics. Additionally, the zero-dimensional distinctive isolated framework results in a high resistivity of 1.39 × 1011 Ω cm, which effectively reduces the current noise and suppresses ion migration. By further combining the ferroelectric-induced bulk photovoltaic effect, the 1-based detector achieves an ultra-low LoD X-ray detection of 84.1 nGyair/s under the self-driven mode, which represents a quite advanced level in the lead-free perovskite X-ray detection region. Our work successfully achieved ultra-low LoD self-driven X-ray detection by combining ferroelectricity with high resistance, providing a promising avenue for the development of low LoD X-ray detectors.
2026, 37(3): 110702
doi: 10.1016/j.cclet.2024.110702
摘要:
Rechargeable aqueous zinc-ion batteries (AZIBs) draw intensive attention due to their high security, low price and the abundant zinc source. However, the electrochemical behaviors of AZIBs are seriously affected by the cathode materials. Mn-based oxide cathodes have been extensively investigated owing to the superior electrochemical performances such as large theoretical capacity and high working voltage. In this work, we rationally design a high-performance cathode material using organic-inorganic co-modification strategy. The inorganic Al3+ ions and organic poly-vinylpyrrolidone (PVP) are successfully incorporated into the tunnel α-MnO2 structure. Structural characterizations and DFT calculations indicates that the Zn2+ adsorption energy in the Al3+/PVP co-intercalated tunnel α-MnO2 is effectively lowered when compared with the original material, facilitating fast ion diffusion and stable Zn2+ ion storage. Electrochemical tests indicate that the PVP-Al-MnO2 electrode exhibits excellent electrochemical performances, a capacity of 306.8 mAh/g at 0.3 A/g and 93.1% capacity retention over 2000 cycles at 1.0 A/g. In addition, the aqueous PVP-Al-MnO2||ZnClO4||Zn battery is able to operate properly at low temperature (-45 ℃). This work shows an encouraging strategy to the modification of materials for AZIBs and other multivalent ion systems.
Rechargeable aqueous zinc-ion batteries (AZIBs) draw intensive attention due to their high security, low price and the abundant zinc source. However, the electrochemical behaviors of AZIBs are seriously affected by the cathode materials. Mn-based oxide cathodes have been extensively investigated owing to the superior electrochemical performances such as large theoretical capacity and high working voltage. In this work, we rationally design a high-performance cathode material using organic-inorganic co-modification strategy. The inorganic Al3+ ions and organic poly-vinylpyrrolidone (PVP) are successfully incorporated into the tunnel α-MnO2 structure. Structural characterizations and DFT calculations indicates that the Zn2+ adsorption energy in the Al3+/PVP co-intercalated tunnel α-MnO2 is effectively lowered when compared with the original material, facilitating fast ion diffusion and stable Zn2+ ion storage. Electrochemical tests indicate that the PVP-Al-MnO2 electrode exhibits excellent electrochemical performances, a capacity of 306.8 mAh/g at 0.3 A/g and 93.1% capacity retention over 2000 cycles at 1.0 A/g. In addition, the aqueous PVP-Al-MnO2||ZnClO4||Zn battery is able to operate properly at low temperature (-45 ℃). This work shows an encouraging strategy to the modification of materials for AZIBs and other multivalent ion systems.
2026, 37(3): 110709
doi: 10.1016/j.cclet.2024.110709
摘要:
The gas separation performance of metal-organic framework (MOF) adsorbents could be enhanced by tuning the pores, whereas the presence of moisture usually compromises the efficiency. Herein, two MOFs, Fe-BDC-TPT-BF4, Ni-BDC-TPT-TMA (TMA+ = (CH3)4N+), were synthesized by exchanging countering ions in parent MOFs, Fe-BDC-TPT-Cl and Ni-BDC-TPT-Me2NH2, respectively. Fe-BDC-TPT-BF4 and Ni-BDC-TPT-TMA exhibited a high C2H2 adsorption uptake of 203.1 cm3/g and 200.1 cm3/g at 298 K and 1 bar, and high C2H2/CO2 selectivity of 4.6 and 4.4. Humid breakthrough experiments revealed that high C2H2 productivity of high C2H2 purity was achieved on Ni-BDC-TPT-TMA at 35% relative humidity. Cycling dynamic breakthrough experiments demonstrate good recyclability of Ni-BDC-TPT-TMA for humid C2H2/CO2 separation. The alteration of countering ions changed the pore size and chemistry, leading to high C2H2 uptake, high C2H2 selectivity, and retained performance in the presence of moisture, making it a promising candidate for practical applications. This work highlights that ion exchange modification of MOFs has been developed as a facile and powerful strategy to optimize the inner pores for better performance in challenging separations.
The gas separation performance of metal-organic framework (MOF) adsorbents could be enhanced by tuning the pores, whereas the presence of moisture usually compromises the efficiency. Herein, two MOFs, Fe-BDC-TPT-BF4, Ni-BDC-TPT-TMA (TMA+ = (CH3)4N+), were synthesized by exchanging countering ions in parent MOFs, Fe-BDC-TPT-Cl and Ni-BDC-TPT-Me2NH2, respectively. Fe-BDC-TPT-BF4 and Ni-BDC-TPT-TMA exhibited a high C2H2 adsorption uptake of 203.1 cm3/g and 200.1 cm3/g at 298 K and 1 bar, and high C2H2/CO2 selectivity of 4.6 and 4.4. Humid breakthrough experiments revealed that high C2H2 productivity of high C2H2 purity was achieved on Ni-BDC-TPT-TMA at 35% relative humidity. Cycling dynamic breakthrough experiments demonstrate good recyclability of Ni-BDC-TPT-TMA for humid C2H2/CO2 separation. The alteration of countering ions changed the pore size and chemistry, leading to high C2H2 uptake, high C2H2 selectivity, and retained performance in the presence of moisture, making it a promising candidate for practical applications. This work highlights that ion exchange modification of MOFs has been developed as a facile and powerful strategy to optimize the inner pores for better performance in challenging separations.
2026, 37(3): 110710
doi: 10.1016/j.cclet.2024.110710
摘要:
In this paper, a new series of donor-acceptor coordination polymers (DACPs), [Cd(dppz)(R-ndc)(H2O)]n (R = none, DZU-400; R = F, DZU-400-F; R = Br, DZU-400-Br; DZU is short for Dezhou University), [Cd(dppz)(adc)(H2O)]n (DZU-401), and {[Cd(dppz)(adb)0.5(HCOO)(H2O)]}n (DZU-402), have been successfully constructed through the combination of electron-deficient dipyrido[3,2-a: 2′,3′-c]phenazine (dppz) as an acceptor and various dicarboxylic ligands (H2ndc = 2,3-naphthalenedicarboxylic acid, F-H2ndc = 6,7-difluoronaphthalene-2,3-dicarboxylic acid, Br-H2ndc = 6,7-dibromonaphthalene-2,3-dicarboxylic acid, H2adc = 9,10-anthracenedicarboxylic acid, and H2adb = 4,4′-(anthracene-9,10-diyl)dibenzoic acid) with electron-rich planar aromatic rings as donors. Structural analyses reveal closely parallel arrangement of the planar acceptor and donor units in these DACPs, which could facilitate the through-space charge transfer (TSCT) interactions of the D-A systems and the corresponding luminescent properties. Interestingly, the DACPs show highly regulable donor dependent photoluminescence from blue to orange. Based on the TSCT based luminescence and the high thermal stability of the DACPs, their thermal-stimuli responsive emission properties were further studied. Photoluminescence intensity of the DACPs all present good linearity with temperature (298–473 K), as proved by variable temperature fluorescence spectra. Importantly, the temperature sensing process is reversible and recyclable, suggesting the promising applications of the DACPs as thermal-stimuli responsive materials.
In this paper, a new series of donor-acceptor coordination polymers (DACPs), [Cd(dppz)(R-ndc)(H2O)]n (R = none, DZU-400; R = F, DZU-400-F; R = Br, DZU-400-Br; DZU is short for Dezhou University), [Cd(dppz)(adc)(H2O)]n (DZU-401), and {[Cd(dppz)(adb)0.5(HCOO)(H2O)]}n (DZU-402), have been successfully constructed through the combination of electron-deficient dipyrido[3,2-a: 2′,3′-c]phenazine (dppz) as an acceptor and various dicarboxylic ligands (H2ndc = 2,3-naphthalenedicarboxylic acid, F-H2ndc = 6,7-difluoronaphthalene-2,3-dicarboxylic acid, Br-H2ndc = 6,7-dibromonaphthalene-2,3-dicarboxylic acid, H2adc = 9,10-anthracenedicarboxylic acid, and H2adb = 4,4′-(anthracene-9,10-diyl)dibenzoic acid) with electron-rich planar aromatic rings as donors. Structural analyses reveal closely parallel arrangement of the planar acceptor and donor units in these DACPs, which could facilitate the through-space charge transfer (TSCT) interactions of the D-A systems and the corresponding luminescent properties. Interestingly, the DACPs show highly regulable donor dependent photoluminescence from blue to orange. Based on the TSCT based luminescence and the high thermal stability of the DACPs, their thermal-stimuli responsive emission properties were further studied. Photoluminescence intensity of the DACPs all present good linearity with temperature (298–473 K), as proved by variable temperature fluorescence spectra. Importantly, the temperature sensing process is reversible and recyclable, suggesting the promising applications of the DACPs as thermal-stimuli responsive materials.
2026, 37(3): 110711
doi: 10.1016/j.cclet.2024.110711
摘要:
Electrochemical two-electron oxygen reduction reaction (2e- ORR) is a green and attractive method for hydrogen peroxide synthesis. However, rapid and efficient development of high-performance catalyst remains a great challenge. Different from traditional trial and error methods, this study employs density functional theory and machine learning method to efficiently screen the promising main-group metal single-atom catalysts (SACs) and systematically investigate the influence of electronegativity of coordination atoms on the adsorption behavior of key intermediates in ORR process. It is found that the K SAC with N/B in the first coordination sphere and Sn SAC with N/C in the first coordination sphere and O in the second coordination sphere exhibit both excellent 2e- ORR activity and selectivity by showing extremely low overpotentials of 0.029 V and 0.064 V, respectively, as well as barrier-free processes from *OOH to H2O2. Bagging displays prominent advantages among seven popular algorithms because of its ensemble strategy. This provides a low-cost approach for designing and screening electrocatalyst candidates, and it will be informative for experimental study in the future to accelerate the development of catalysts for oxygen reduction and other types of reactions.
Electrochemical two-electron oxygen reduction reaction (2e- ORR) is a green and attractive method for hydrogen peroxide synthesis. However, rapid and efficient development of high-performance catalyst remains a great challenge. Different from traditional trial and error methods, this study employs density functional theory and machine learning method to efficiently screen the promising main-group metal single-atom catalysts (SACs) and systematically investigate the influence of electronegativity of coordination atoms on the adsorption behavior of key intermediates in ORR process. It is found that the K SAC with N/B in the first coordination sphere and Sn SAC with N/C in the first coordination sphere and O in the second coordination sphere exhibit both excellent 2e- ORR activity and selectivity by showing extremely low overpotentials of 0.029 V and 0.064 V, respectively, as well as barrier-free processes from *OOH to H2O2. Bagging displays prominent advantages among seven popular algorithms because of its ensemble strategy. This provides a low-cost approach for designing and screening electrocatalyst candidates, and it will be informative for experimental study in the future to accelerate the development of catalysts for oxygen reduction and other types of reactions.
2026, 37(3): 110728
doi: 10.1016/j.cclet.2024.110728
摘要:
Cutting-edge high/pulsed power capacitors with satisfactory power density are fundamental units in modern power storage systems. However, a persistent challenge is how to overcome the trade-off between recoverable energy storage density (Wrec) and efficiency (η) for meeting the miniaturization and integration of advanced applications. Here, multiple local distortions including inhomogeneous functional nanoclusters, (anti)ferro-distortions and highly dynamic polar nanoregions are modulated through a high-entropy strategy to design a stable ergodic-relaxor-state-dominated structure. Of great importance, this strategy delay polarization saturation, reduces hysteresis and improves breakdown strength, so that an ultrahigh Wrec ~11.94 J/cm3 with a η ~ 82.4% is realized in Pb-free ergodic-relaxors. Moreover, a significant Vickers hardness of 10.04 GPa as well as superior temperature, cycling and frequency stabilities are also obtained. This work demonstrates that designing multiple local distortions via a high-entropy strategy is a promising way to realize superior comprehensive energy storage properties in high/pulsed power capacitors.
Cutting-edge high/pulsed power capacitors with satisfactory power density are fundamental units in modern power storage systems. However, a persistent challenge is how to overcome the trade-off between recoverable energy storage density (Wrec) and efficiency (η) for meeting the miniaturization and integration of advanced applications. Here, multiple local distortions including inhomogeneous functional nanoclusters, (anti)ferro-distortions and highly dynamic polar nanoregions are modulated through a high-entropy strategy to design a stable ergodic-relaxor-state-dominated structure. Of great importance, this strategy delay polarization saturation, reduces hysteresis and improves breakdown strength, so that an ultrahigh Wrec ~11.94 J/cm3 with a η ~ 82.4% is realized in Pb-free ergodic-relaxors. Moreover, a significant Vickers hardness of 10.04 GPa as well as superior temperature, cycling and frequency stabilities are also obtained. This work demonstrates that designing multiple local distortions via a high-entropy strategy is a promising way to realize superior comprehensive energy storage properties in high/pulsed power capacitors.
2026, 37(3): 110729
doi: 10.1016/j.cclet.2024.110729
摘要:
Nickel-rich layered oxides are considered highly promising cathode materials for all-solid-state batteries (ASSBs) due to their high theoretical specific capacity and energy density. In this study, a comparison between polycrystalline and single-crystalline cathode materials was conducted. It was found that, during the charging process, ion transport at the interface of polycrystalline cathodes is significantly influenced by phase transitions and side reactions with the electrolyte, resulting in an irreversible increase in impedance after cycling. Furthermore, the structural stability of the cathode material affects internal ion diffusion kinetics, thereby influencing its electrochemical performance. Unlike single-crystalline materials, ion migration in polycrystalline materials must traverse anisotropic grain boundaries, which, due to anisotropic lattice contraction, evolve into intergranular cracks, leading to reduced ion diffusion kinetics and degraded electrochemical performance. In contrast, single-crystalline cathodes exhibit more stable interfacial resistance and uniform ion transport during charging, ensuring structural stability over long-term cycling. Consequently, at a 0.5 C rate, the single-crystalline cathode maintains a specific capacity of 143 mAh/g after 500 cycles, with a capacity retention of 89.2%, while preserving its intact single-crystal morphology. This study provides valuable new insights into the localized lithium-ion transport behavior in single-crystalline and polycrystalline cathode materials for sulfide-based all-solid-state batteries.
Nickel-rich layered oxides are considered highly promising cathode materials for all-solid-state batteries (ASSBs) due to their high theoretical specific capacity and energy density. In this study, a comparison between polycrystalline and single-crystalline cathode materials was conducted. It was found that, during the charging process, ion transport at the interface of polycrystalline cathodes is significantly influenced by phase transitions and side reactions with the electrolyte, resulting in an irreversible increase in impedance after cycling. Furthermore, the structural stability of the cathode material affects internal ion diffusion kinetics, thereby influencing its electrochemical performance. Unlike single-crystalline materials, ion migration in polycrystalline materials must traverse anisotropic grain boundaries, which, due to anisotropic lattice contraction, evolve into intergranular cracks, leading to reduced ion diffusion kinetics and degraded electrochemical performance. In contrast, single-crystalline cathodes exhibit more stable interfacial resistance and uniform ion transport during charging, ensuring structural stability over long-term cycling. Consequently, at a 0.5 C rate, the single-crystalline cathode maintains a specific capacity of 143 mAh/g after 500 cycles, with a capacity retention of 89.2%, while preserving its intact single-crystal morphology. This study provides valuable new insights into the localized lithium-ion transport behavior in single-crystalline and polycrystalline cathode materials for sulfide-based all-solid-state batteries.
2026, 37(3): 111033
doi: 10.1016/j.cclet.2025.111033
摘要:
Interleukin-1 receptor-associated kinase 4 (IRAK4), a key target with both enzymatic and non-enzymatic functions, plays a pivotal role in autoimmune diseases. Previous studies have demonstrated that proteolysis-targeting chimera (PROTAC) molecules targeting IRAK4 can effectively eliminate both its enzymatic and non-enzymatic functions, showing promising therapeutic potential. However, the development of highly potent, synthetically accessible IRAK4-targeting degraders remains a challenge. In this work, through three rounds of PROTAC library construction, screening, and optimization, we successfully identified a representative compound, LZ-07, which proved to be a highly potent degrader with a half-maximal degradation concentration (DC50) value of 1.14 nmol/L. Notably, compared with KT-474, LZ-07 demonstrated comparable degradation activity and superior inhibition of cytokine production, while featuring a simpler synthetic route with optimized IRAK4 and cereblon (CRBN) ligands. LZ-07-induced degradation of IRAK4 led to marked suppression of key cytokines, including interleukin-6 (IL-6), IL-1β, tumor necrosis factor alpha (TNF-α), and IL-10. This study presents LZ-07 as a novel, highly efficient, and synthetically straightforward IRAK4-targeting degrader, offering a promising tool compound for the study of the potential treatment of autoimmune diseases.
Interleukin-1 receptor-associated kinase 4 (IRAK4), a key target with both enzymatic and non-enzymatic functions, plays a pivotal role in autoimmune diseases. Previous studies have demonstrated that proteolysis-targeting chimera (PROTAC) molecules targeting IRAK4 can effectively eliminate both its enzymatic and non-enzymatic functions, showing promising therapeutic potential. However, the development of highly potent, synthetically accessible IRAK4-targeting degraders remains a challenge. In this work, through three rounds of PROTAC library construction, screening, and optimization, we successfully identified a representative compound, LZ-07, which proved to be a highly potent degrader with a half-maximal degradation concentration (DC50) value of 1.14 nmol/L. Notably, compared with KT-474, LZ-07 demonstrated comparable degradation activity and superior inhibition of cytokine production, while featuring a simpler synthetic route with optimized IRAK4 and cereblon (CRBN) ligands. LZ-07-induced degradation of IRAK4 led to marked suppression of key cytokines, including interleukin-6 (IL-6), IL-1β, tumor necrosis factor alpha (TNF-α), and IL-10. This study presents LZ-07 as a novel, highly efficient, and synthetically straightforward IRAK4-targeting degrader, offering a promising tool compound for the study of the potential treatment of autoimmune diseases.
2026, 37(3): 111041
doi: 10.1016/j.cclet.2025.111041
摘要:
Classic near-infrared dyes typically enhance their maxima absorption wavelength through the D-A system. Herein, introducing p-trifluoromethylphenyl group at 1,7-sites as electron-withdrawing group and julolidine at 3,5-sites as electron-donating group in aza-borondipyrromethene (aza-BODIPY) system, CF3-JLD with the donor-acceptor-acceptor (D-A-A’) system was prepared, which absorbs at 952 nm and emits at 1069 nm in dimethyl sulfoxide (DMSO) in the near infrared-Ⅱ (NIR-Ⅱ) region. According to the experimental observation and theoretical calculation, the D-A-A’ system for enhancing redshift of maxima absorption is found to be more effective than that of donor-acceptor-donor (D-A-D’) system. NIR-Ⅱ absorbing CF3-JLD was type Ⅰ photodynamic therapy/photothermal therapy (PDT/PTT) co-therapy reagent, with high photothermal conversion efficiency (η = 81%). Self-assembled nanoparticles (CF3-JLD NPs) can effectively induce 4T1 cell death in vitro, and the cellular morphology of tumor was destroyed and the proliferation-related protein was decreased in vivo under NIR irradiation by phototherapy. This strategy of the D-A-A’ system provides a guideline for developing organic fluorophores with enhanced NIR-Ⅱ absorption and type Ⅰ PDT/PTT co-therapy for 4T1 breast tumors.
Classic near-infrared dyes typically enhance their maxima absorption wavelength through the D-A system. Herein, introducing p-trifluoromethylphenyl group at 1,7-sites as electron-withdrawing group and julolidine at 3,5-sites as electron-donating group in aza-borondipyrromethene (aza-BODIPY) system, CF3-JLD with the donor-acceptor-acceptor (D-A-A’) system was prepared, which absorbs at 952 nm and emits at 1069 nm in dimethyl sulfoxide (DMSO) in the near infrared-Ⅱ (NIR-Ⅱ) region. According to the experimental observation and theoretical calculation, the D-A-A’ system for enhancing redshift of maxima absorption is found to be more effective than that of donor-acceptor-donor (D-A-D’) system. NIR-Ⅱ absorbing CF3-JLD was type Ⅰ photodynamic therapy/photothermal therapy (PDT/PTT) co-therapy reagent, with high photothermal conversion efficiency (η = 81%). Self-assembled nanoparticles (CF3-JLD NPs) can effectively induce 4T1 cell death in vitro, and the cellular morphology of tumor was destroyed and the proliferation-related protein was decreased in vivo under NIR irradiation by phototherapy. This strategy of the D-A-A’ system provides a guideline for developing organic fluorophores with enhanced NIR-Ⅱ absorption and type Ⅰ PDT/PTT co-therapy for 4T1 breast tumors.
2026, 37(3): 111061
doi: 10.1016/j.cclet.2025.111061
摘要:
Quantitative visualization of pivotal biomarkers and accurate delineation of tumor lesion boundary are highly significant to assist surgeon precisely resect the tumors and reduce the risk of recurrence. Activatable fluorescent probes hold great promise for intraoperative guidance of tumor surgery with high signal-to-background ratio (SBR). Here, we report a γ-glutamyl transpeptidase (GGT)-activated fluorogenic probe Indol-Glu for quantitative visualization of GGT and fluorescence-guided tumor resection. The fluorescence of Indol-Glu was initially “off” state but was specifically activated by GGT to produce enhanced near-infrared (NIR) fluorescence (~37-fold at 741 nm). It is also accompanied by the formation of self-assemblies in the tumor microenvironment resulting in prolonged retention in tumor tissues, which was demonstrated to be able to apply for NIR imaging-guided surgical resection of GGT-overexpressed luciferase-transfected hepatocellular carcinoma (HCC/Luc) tumor. More notably, taking advantage of the ratiometric photoacoustic signal (PA690/PA800) characteristic of Indol-Glu under the digestion of GGT, quantitative visual assessment of GGT activities in various tumor models was achieved in living mice. We believe that this research work may offer a powerful tool for precise diagnosis and surgical resection of malignant tumors.
Quantitative visualization of pivotal biomarkers and accurate delineation of tumor lesion boundary are highly significant to assist surgeon precisely resect the tumors and reduce the risk of recurrence. Activatable fluorescent probes hold great promise for intraoperative guidance of tumor surgery with high signal-to-background ratio (SBR). Here, we report a γ-glutamyl transpeptidase (GGT)-activated fluorogenic probe Indol-Glu for quantitative visualization of GGT and fluorescence-guided tumor resection. The fluorescence of Indol-Glu was initially “off” state but was specifically activated by GGT to produce enhanced near-infrared (NIR) fluorescence (~37-fold at 741 nm). It is also accompanied by the formation of self-assemblies in the tumor microenvironment resulting in prolonged retention in tumor tissues, which was demonstrated to be able to apply for NIR imaging-guided surgical resection of GGT-overexpressed luciferase-transfected hepatocellular carcinoma (HCC/Luc) tumor. More notably, taking advantage of the ratiometric photoacoustic signal (PA690/PA800) characteristic of Indol-Glu under the digestion of GGT, quantitative visual assessment of GGT activities in various tumor models was achieved in living mice. We believe that this research work may offer a powerful tool for precise diagnosis and surgical resection of malignant tumors.
2026, 37(3): 111087
doi: 10.1016/j.cclet.2025.111087
摘要:
The employment of low-frequency electrical stimulation therapy has been shown to elicit a pronounced depolarization of neurons, thereby initiating the regenerative signaling cascades within neural cells, which is favorable for the regeneration of neural cells. In this study, we designed the flexible triboelectric nanogenerator device (TENG) to treat injury of peripheral nerve, which is combined with mesoporous silica (H-SiO2), high dielectric performance of polydimethylsiloxane (PDMS), and connected to biocompatible and conductive polycaprolactone (PCL) conduit materials for limited power generation to neuro-bioelectric response adaptation. By adjusting the content of H-SiO2 and the amount of PDMS monomers, the electrical performance of the device is optimized. Through the charge collection effect of silica molecular sieve, the endogenous neural electric field in nerve injury was stabilized, ensuring the consistency of the electrical stimulation level that is crucial for maintaining resting membrane potential. In vitro experiments clearly demonstrated that electrical stimulation derived from the triboelectric nanogenerator significantly promotes cell proliferation. Further animal experiments confirmed that electrical stimulation can effectively treat sciatic nerve injury and accelerate axonal regeneration. Based on experimental outcomes, we have developed an implantable sciatic nerve system that can stably generate effective electrical pulses in response to rat movement through charge collection. This system regulates the electric field around the injured sciatic nerve, maintains the electric field threshold required for rapid nerve tissue repair, and accelerates the recovery of nerve function.
The employment of low-frequency electrical stimulation therapy has been shown to elicit a pronounced depolarization of neurons, thereby initiating the regenerative signaling cascades within neural cells, which is favorable for the regeneration of neural cells. In this study, we designed the flexible triboelectric nanogenerator device (TENG) to treat injury of peripheral nerve, which is combined with mesoporous silica (H-SiO2), high dielectric performance of polydimethylsiloxane (PDMS), and connected to biocompatible and conductive polycaprolactone (PCL) conduit materials for limited power generation to neuro-bioelectric response adaptation. By adjusting the content of H-SiO2 and the amount of PDMS monomers, the electrical performance of the device is optimized. Through the charge collection effect of silica molecular sieve, the endogenous neural electric field in nerve injury was stabilized, ensuring the consistency of the electrical stimulation level that is crucial for maintaining resting membrane potential. In vitro experiments clearly demonstrated that electrical stimulation derived from the triboelectric nanogenerator significantly promotes cell proliferation. Further animal experiments confirmed that electrical stimulation can effectively treat sciatic nerve injury and accelerate axonal regeneration. Based on experimental outcomes, we have developed an implantable sciatic nerve system that can stably generate effective electrical pulses in response to rat movement through charge collection. This system regulates the electric field around the injured sciatic nerve, maintains the electric field threshold required for rapid nerve tissue repair, and accelerates the recovery of nerve function.
2026, 37(3): 111151
doi: 10.1016/j.cclet.2025.111151
摘要:
The design and synthesis of fully conjugated covalent organic cages (cCOCs) featuring sp2 carbon connections pose significant challenges due to the difficulties associated with forming stable CC bonds. In this study, we present a novel anthracene-based cCOC linked by CC bonds, synthesized directly through Knoevenagel condensation. Remarkably, this sp2c COC has shown exceptional performance as an n-type semiconductor, characterized by strong electronic delocalization, an optimized band structure, and extensive light absorption capabilities. It efficiently catalyzes the photodegradation of organic dyes and promotes the photoinduced aerobic oxidation of amines to imines. In comparison to imine-linked cCOCs with the same skeleton, the sp2c COC demonstrates distinct advantages as a next-generation photocatalyst, including enhanced chemical stability and superior photocatalytic performance. This research underscores the potential of Knoevenagel condensation in the development of innovative cCOCs, offering valuable insights for their applications in optoelectronic materials and catalysis.
The design and synthesis of fully conjugated covalent organic cages (cCOCs) featuring sp2 carbon connections pose significant challenges due to the difficulties associated with forming stable CC bonds. In this study, we present a novel anthracene-based cCOC linked by CC bonds, synthesized directly through Knoevenagel condensation. Remarkably, this sp2c COC has shown exceptional performance as an n-type semiconductor, characterized by strong electronic delocalization, an optimized band structure, and extensive light absorption capabilities. It efficiently catalyzes the photodegradation of organic dyes and promotes the photoinduced aerobic oxidation of amines to imines. In comparison to imine-linked cCOCs with the same skeleton, the sp2c COC demonstrates distinct advantages as a next-generation photocatalyst, including enhanced chemical stability and superior photocatalytic performance. This research underscores the potential of Knoevenagel condensation in the development of innovative cCOCs, offering valuable insights for their applications in optoelectronic materials and catalysis.
2026, 37(3): 111188
doi: 10.1016/j.cclet.2025.111188
摘要:
Electrochemically converting nitrate to ammonia under ambient conditions is a hot topic. However, it suffers from low efficiency because of the multi-electron/proton transfer. Herein, high-load atomic Fe (16.45 wt%) in-situ grown on carbon fiber cloth (Fe1@MoS2/CFC) demonstrates super high activity and selectivity in electrochemical nitrate reduction to ammonia at -0.73 V vs. RHE. The maximum NH3 yield is 28.59 mg h-1 cm-2, and the corresponding NH3-Faradaic efficiency is 96.65% at 360 mA/cm2 partial current density. The electrode exhibits good durability during ten cycled tests of 1 h each. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), in-situ Raman analysis, and electron paramagnetic resonance (EPR) measurements reveal that the super high activity derives from the rich presence of active sites related to Fe-S and surrounding unsaturated Mo-S. Density functional theory (DFT) calculations show that the atomic Fe facilitates the water dissociation and provides sufficient active hydrogen for the edge Mo to boost nitrate reduction reaction (NO3-RR) activity, enhances NH3 selectivity, and decreases the energy barrier of NH3 desorption (rate-determining step) by regulating the coordination environment and electronic structure of the active Mo site. This stable and binder-free electrode with high dosage atomic Fe and rich edge Mo active sites is an attractive cathode for NO3-RR.
Electrochemically converting nitrate to ammonia under ambient conditions is a hot topic. However, it suffers from low efficiency because of the multi-electron/proton transfer. Herein, high-load atomic Fe (16.45 wt%) in-situ grown on carbon fiber cloth (Fe1@MoS2/CFC) demonstrates super high activity and selectivity in electrochemical nitrate reduction to ammonia at -0.73 V vs. RHE. The maximum NH3 yield is 28.59 mg h-1 cm-2, and the corresponding NH3-Faradaic efficiency is 96.65% at 360 mA/cm2 partial current density. The electrode exhibits good durability during ten cycled tests of 1 h each. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), in-situ Raman analysis, and electron paramagnetic resonance (EPR) measurements reveal that the super high activity derives from the rich presence of active sites related to Fe-S and surrounding unsaturated Mo-S. Density functional theory (DFT) calculations show that the atomic Fe facilitates the water dissociation and provides sufficient active hydrogen for the edge Mo to boost nitrate reduction reaction (NO3-RR) activity, enhances NH3 selectivity, and decreases the energy barrier of NH3 desorption (rate-determining step) by regulating the coordination environment and electronic structure of the active Mo site. This stable and binder-free electrode with high dosage atomic Fe and rich edge Mo active sites is an attractive cathode for NO3-RR.
2026, 37(3): 111195
doi: 10.1016/j.cclet.2025.111195
摘要:
Photodynamic therapy (PDT) has attracted various attentions for cancer treatment, yet current strategies suffer many limitations including short retention time of photosensitizers, exacerbation of hypoxia due to oxygen consumption and restricted release of singlet oxygen under hypoxic conditions or in the absence of light. We present here a promising cancer therapy which not only reduces the frequency of drug administration and overall drug dosage through near-infrared (NIR) light-triggered drug immobilization in tumor sites, but also enhances anticancer efficacy by synergistic treatments through PDT and chemotherapeutic drug camptothecin. More importantly, endoperoxides generated in situ can not only persistently release singlet oxygen even in the absence of light, thereby augmenting PDT efficacy, but also release triplet oxygen to alleviate tumor hypoxia exacerbated by PDT. Its enhanced retention time was demonstrated both in vitro (96 h) and in vivo (240 h), with the duration adjustable by varying the light source. Notably, a single administration (3 mg/mL, 300 µL) during the entire treatment under low-power red light irradiation (11 mW/cm2) resulted in efficient suppression of the tumor growth and pulmonary metastasis. This NIR light-triggered long-acting platforms could be utilized for design of long-term disease imaging and therapy tools, and the in situ generated endoperoxide is promising for self-regulation of tumor hypoxia.
Photodynamic therapy (PDT) has attracted various attentions for cancer treatment, yet current strategies suffer many limitations including short retention time of photosensitizers, exacerbation of hypoxia due to oxygen consumption and restricted release of singlet oxygen under hypoxic conditions or in the absence of light. We present here a promising cancer therapy which not only reduces the frequency of drug administration and overall drug dosage through near-infrared (NIR) light-triggered drug immobilization in tumor sites, but also enhances anticancer efficacy by synergistic treatments through PDT and chemotherapeutic drug camptothecin. More importantly, endoperoxides generated in situ can not only persistently release singlet oxygen even in the absence of light, thereby augmenting PDT efficacy, but also release triplet oxygen to alleviate tumor hypoxia exacerbated by PDT. Its enhanced retention time was demonstrated both in vitro (96 h) and in vivo (240 h), with the duration adjustable by varying the light source. Notably, a single administration (3 mg/mL, 300 µL) during the entire treatment under low-power red light irradiation (11 mW/cm2) resulted in efficient suppression of the tumor growth and pulmonary metastasis. This NIR light-triggered long-acting platforms could be utilized for design of long-term disease imaging and therapy tools, and the in situ generated endoperoxide is promising for self-regulation of tumor hypoxia.
2026, 37(3): 111204
doi: 10.1016/j.cclet.2025.111204
摘要:
Estrogen sulfotransferase (SULT1E1), an essential conjugative enzyme in mammals, plays a crucial role in both estrogen homeostasis and xenobiotic metabolism. Deciphering the dynamic changes in SULT1E1 function under specific physiological or pathological conditions and discovering SULT1E1 modulators require practical and highly efficient tools for sensing SULT1E1 in biological context. Herein, we showcase a scaffold-seeking and structural optimization strategy for the rational engineering of isoform-specific fluorescent substrates for SULT1E1. First, docking-based virtual screening coupled with biochemical assays suggested that N-butyl-4-hydroxyphenyl-1,8-naphthalimide (HPN) was a suitable scaffold for constructing the fluorescent substrates for SULT1E1, but this fluorophore could be metabolized by multiple SULT isoforms. To develop isoform-specific substrates for SULT1E1, various substituents were introduced on the north part of HPN to explore the structure-enzyme specificity relationships of HPN derivatives as SULT1E1 substrates. After molecular docking and experimental validation, an isoform-specific fluorescent substrate (HPN10) for SULT1E1 was successfully engineered. HPN10 demonstrated exceptional isoform-specificity, ultra-high sensitivity, and favorable signal-to-noise ratio (212). HPN10 excelled in the precise sensing of SULT1E1 activities in complex biological matrices, including cellular specimens and liver preparations. HPN10 immensely facilitated the discovery and characterization of SULT1E1 inhibitors, while tetrabromobisphenol A (TBBPA, half inhibitory concentration (IC50) = 31.5 ± 3.4 nmol/L) was identified as a potent SULT1E1 inhibitor that could strongly block SULT1E1 activities in living cells. Collectively, this work presents a practical and efficient strategy for the rational engineering of isoform-specific fluorescent substrates for target conjugative enzyme(s), while HPN10 emerges as a reliable SULT1E1-activatable tool for functional sensing and drug discovery.
Estrogen sulfotransferase (SULT1E1), an essential conjugative enzyme in mammals, plays a crucial role in both estrogen homeostasis and xenobiotic metabolism. Deciphering the dynamic changes in SULT1E1 function under specific physiological or pathological conditions and discovering SULT1E1 modulators require practical and highly efficient tools for sensing SULT1E1 in biological context. Herein, we showcase a scaffold-seeking and structural optimization strategy for the rational engineering of isoform-specific fluorescent substrates for SULT1E1. First, docking-based virtual screening coupled with biochemical assays suggested that N-butyl-4-hydroxyphenyl-1,8-naphthalimide (HPN) was a suitable scaffold for constructing the fluorescent substrates for SULT1E1, but this fluorophore could be metabolized by multiple SULT isoforms. To develop isoform-specific substrates for SULT1E1, various substituents were introduced on the north part of HPN to explore the structure-enzyme specificity relationships of HPN derivatives as SULT1E1 substrates. After molecular docking and experimental validation, an isoform-specific fluorescent substrate (HPN10) for SULT1E1 was successfully engineered. HPN10 demonstrated exceptional isoform-specificity, ultra-high sensitivity, and favorable signal-to-noise ratio (212). HPN10 excelled in the precise sensing of SULT1E1 activities in complex biological matrices, including cellular specimens and liver preparations. HPN10 immensely facilitated the discovery and characterization of SULT1E1 inhibitors, while tetrabromobisphenol A (TBBPA, half inhibitory concentration (IC50) = 31.5 ± 3.4 nmol/L) was identified as a potent SULT1E1 inhibitor that could strongly block SULT1E1 activities in living cells. Collectively, this work presents a practical and efficient strategy for the rational engineering of isoform-specific fluorescent substrates for target conjugative enzyme(s), while HPN10 emerges as a reliable SULT1E1-activatable tool for functional sensing and drug discovery.
2026, 37(3): 111214
doi: 10.1016/j.cclet.2025.111214
摘要:
Given the immense potential of sonodynamic therapy (SDT) in cancer treatment, designing effective sonosensitizers (SNSs) and elucidating their mechanisms are crucial for advancing the field and enhancing anti-tumor responses. However, there are still several limitations that hinder the application of SDT, such as the activation of the hypoxia-inducible factor-1 (HIF-1) pathway. Herein, we designed an endoplasmic reticulum (ER)-targeted iridium(Ⅲ) SNS, C6IrAC, which exhibits specific toxicity towards tumor cells and excellent performance as a SNS. C6IrAC specifically targets the ER, causing ER stress, and under ultrasound (US) stimulation, the increased stress intensity enhances therapeutic efficacy. C6IrAC induces the degradation of HIF-1α and suppresses the HIF-1 pathway, thereby enhancing SDT. Furthermore, C6IrAC-induced ER stress leads to mitochondrial calcium overload, which subsequently results in the release of a large amount of mitochondrial DNA (mtDNA) into the cytoplasm, thereby activating the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway. Significant anti-tumor effects have been consistently observed both in vitro and in vivo. C6IrAC can effectively activate both the innate and adaptive immune systems, highlighting its substantial therapeutic potential. Taken together, this study provides a feasible method to overcome the limitations of SDT, and opens up new avenues for the design of SNSs.
Given the immense potential of sonodynamic therapy (SDT) in cancer treatment, designing effective sonosensitizers (SNSs) and elucidating their mechanisms are crucial for advancing the field and enhancing anti-tumor responses. However, there are still several limitations that hinder the application of SDT, such as the activation of the hypoxia-inducible factor-1 (HIF-1) pathway. Herein, we designed an endoplasmic reticulum (ER)-targeted iridium(Ⅲ) SNS, C6IrAC, which exhibits specific toxicity towards tumor cells and excellent performance as a SNS. C6IrAC specifically targets the ER, causing ER stress, and under ultrasound (US) stimulation, the increased stress intensity enhances therapeutic efficacy. C6IrAC induces the degradation of HIF-1α and suppresses the HIF-1 pathway, thereby enhancing SDT. Furthermore, C6IrAC-induced ER stress leads to mitochondrial calcium overload, which subsequently results in the release of a large amount of mitochondrial DNA (mtDNA) into the cytoplasm, thereby activating the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway. Significant anti-tumor effects have been consistently observed both in vitro and in vivo. C6IrAC can effectively activate both the innate and adaptive immune systems, highlighting its substantial therapeutic potential. Taken together, this study provides a feasible method to overcome the limitations of SDT, and opens up new avenues for the design of SNSs.
2026, 37(3): 111254
doi: 10.1016/j.cclet.2025.111254
摘要:
Glioma, a highly aggressive brain tumor with a dismal prognosis, faces significant treatment hurdles due to the blood-brain barrier, which limits the efficient delivery of most medications. Diphtheria toxin receptor (DTR) is a specific receptor expressed both on brain microvascular endothelial cells and glioma, emerging as a potentially valuable target for targeted drug delivery system for glioma treatment. In this work, a short peptide (designated DTX) derived from diphtheria toxin, was rational designed and chemical synthesized based on the binding domain to DTR. The function of DTX as a ligand of DTR and the brain/glioma dual targeting efficacy were evaluated in vitro and in vivo. Furthermore, DTX was conjugated to vorinostat (SAHA) to enable its anti-glioma efficacy. The results demonstrated that DTX-SAHA can effectively cross the blood-brain barrier, exhibiting promising anti-glioma efficacy with good biocompatibility. This research confirmed the potential of DTX as the ligand for DTR-mediated intracranial drug delivery.
Glioma, a highly aggressive brain tumor with a dismal prognosis, faces significant treatment hurdles due to the blood-brain barrier, which limits the efficient delivery of most medications. Diphtheria toxin receptor (DTR) is a specific receptor expressed both on brain microvascular endothelial cells and glioma, emerging as a potentially valuable target for targeted drug delivery system for glioma treatment. In this work, a short peptide (designated DTX) derived from diphtheria toxin, was rational designed and chemical synthesized based on the binding domain to DTR. The function of DTX as a ligand of DTR and the brain/glioma dual targeting efficacy were evaluated in vitro and in vivo. Furthermore, DTX was conjugated to vorinostat (SAHA) to enable its anti-glioma efficacy. The results demonstrated that DTX-SAHA can effectively cross the blood-brain barrier, exhibiting promising anti-glioma efficacy with good biocompatibility. This research confirmed the potential of DTX as the ligand for DTR-mediated intracranial drug delivery.
2026, 37(3): 111258
doi: 10.1016/j.cclet.2025.111258
摘要:
A new type of C2-symmetric chiral spirobiindole structure is developed, and excellent diastereoselectivities and enantioselectivities (>20:1 dr & >99% ee for all examples) were obtained via an asymmetric rhodium catalysis-intramolecular spirocyclization sequence. Selective synthesis of both spirobiindole enantiomers could be achieved using the same catalyst by simply switching the substrate combination.
A new type of C2-symmetric chiral spirobiindole structure is developed, and excellent diastereoselectivities and enantioselectivities (>20:1 dr & >99% ee for all examples) were obtained via an asymmetric rhodium catalysis-intramolecular spirocyclization sequence. Selective synthesis of both spirobiindole enantiomers could be achieved using the same catalyst by simply switching the substrate combination.
2026, 37(3): 111288
doi: 10.1016/j.cclet.2025.111288
摘要:
Fluorine locates a pivotal position in modern medicinal chemistry due to its distinctive impact on the properties of organic molecules. This work described an efficient divergent palladium/XPhos-catalyzed ring-opening defluorinative cross-coupling of gem-difluorocyclopropanes with less nucleophilic fluorinated malonates or fluorobis(phenylsulfonyl)methane. The corresponding difluoro malonates and 2,4-difluorobutadienyl sulfones were obtained in good yields, respectively. Besides, this protocol also enabled the modification of structurally diverse complex molecules.
Fluorine locates a pivotal position in modern medicinal chemistry due to its distinctive impact on the properties of organic molecules. This work described an efficient divergent palladium/XPhos-catalyzed ring-opening defluorinative cross-coupling of gem-difluorocyclopropanes with less nucleophilic fluorinated malonates or fluorobis(phenylsulfonyl)methane. The corresponding difluoro malonates and 2,4-difluorobutadienyl sulfones were obtained in good yields, respectively. Besides, this protocol also enabled the modification of structurally diverse complex molecules.
2026, 37(3): 111299
doi: 10.1016/j.cclet.2025.111299
摘要:
Immunosuppressive tumor microenvironment (TME) is a key regulator in the high recurrence and metastasis rate of breast cancer after microwave (MW) thermal therapy. Pyroptosis, a form of programmed cell death initiated by inflammasomes, which can activate tumor immunogenicity and reprogram immune TME. Here, we report an extremely simple Al-based metal-organic frameworks nano-immunoadjuvants (AM NIAs) that programmatically activate nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 (NLRP3)-mediated pyroptosis to enhance MW-immunotherapy (MW-ICB). After entering the TME, AM NIAs programmed activation of NLRP3-mediated pyroptosis by inducing mitochondrial dysfunction, upregulating HSP90 and promoting lysosomal stress. Consequently, substantial amounts of lactate dehydrogenase, interleukin-18 (IL-18), and calreticulin are released, which improves immunosuppressive TME and hinders tumor cell proliferation by facilitating T-cell infiltration. The integration of immune checkpoint inhibitors with MW elicits potent immune responses, demonstrating high inhibition of both primary and distant tumors. Thus, a simple yet effective nano-immunoadjuvant is developed to enhance MW-ICB in breast cancer simply by NLRP3-mediated pyroptosis and immunosuppression reversal.
Immunosuppressive tumor microenvironment (TME) is a key regulator in the high recurrence and metastasis rate of breast cancer after microwave (MW) thermal therapy. Pyroptosis, a form of programmed cell death initiated by inflammasomes, which can activate tumor immunogenicity and reprogram immune TME. Here, we report an extremely simple Al-based metal-organic frameworks nano-immunoadjuvants (AM NIAs) that programmatically activate nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 (NLRP3)-mediated pyroptosis to enhance MW-immunotherapy (MW-ICB). After entering the TME, AM NIAs programmed activation of NLRP3-mediated pyroptosis by inducing mitochondrial dysfunction, upregulating HSP90 and promoting lysosomal stress. Consequently, substantial amounts of lactate dehydrogenase, interleukin-18 (IL-18), and calreticulin are released, which improves immunosuppressive TME and hinders tumor cell proliferation by facilitating T-cell infiltration. The integration of immune checkpoint inhibitors with MW elicits potent immune responses, demonstrating high inhibition of both primary and distant tumors. Thus, a simple yet effective nano-immunoadjuvant is developed to enhance MW-ICB in breast cancer simply by NLRP3-mediated pyroptosis and immunosuppression reversal.
2026, 37(3): 111314
doi: 10.1016/j.cclet.2025.111314
摘要:
Four novel Daphniphyllum alkaloids with highly rearranged skeletons involving a 6/5/7/7/5 pentacyclic scaffold (1), a 6/5/7/5/6/5/6 heptacyclic scaffold (2 and 4), and a 6/5/7/5/6/5 hexacyclic scaffold (3), were isolated from Daphniphyllum calycinum. Particularly, compound 1 contains a unique 13-oxa-17-aza-pentacyclo[7.6.4.112,15.04,8.09,15] eicosane core. Their structures were elucidated by comprehensive spectroscopic analyses, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Putative biosynthetic pathways for compounds 1–4 were discussed with caldaphnidine C (5) as their biosynthetic precursor. Compound 2 markedly enhanced the survival of H9c2 cardiomyocytes under oxygen glucose deprivation and reoxygenation conditions. Mechanistic study revealed that 2 exerted its cardioprotective effects by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase-1 (Nrf2/HO-1) antioxidant pathway, thereby enhancing cellular antioxidant capacity and alleviating oxidative stress induced by hypoxia.
Four novel Daphniphyllum alkaloids with highly rearranged skeletons involving a 6/5/7/7/5 pentacyclic scaffold (1), a 6/5/7/5/6/5/6 heptacyclic scaffold (2 and 4), and a 6/5/7/5/6/5 hexacyclic scaffold (3), were isolated from Daphniphyllum calycinum. Particularly, compound 1 contains a unique 13-oxa-17-aza-pentacyclo[7.6.4.112,15.04,8.09,15] eicosane core. Their structures were elucidated by comprehensive spectroscopic analyses, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Putative biosynthetic pathways for compounds 1–4 were discussed with caldaphnidine C (5) as their biosynthetic precursor. Compound 2 markedly enhanced the survival of H9c2 cardiomyocytes under oxygen glucose deprivation and reoxygenation conditions. Mechanistic study revealed that 2 exerted its cardioprotective effects by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase-1 (Nrf2/HO-1) antioxidant pathway, thereby enhancing cellular antioxidant capacity and alleviating oxidative stress induced by hypoxia.
2026, 37(3): 111339
doi: 10.1016/j.cclet.2025.111339
摘要:
Chemodynamic therapy (CDT) represents a novel strategy for the safe treatment of malignant melanoma. It capitalizes on transition metal-catalyzed Fenton-like reactions to generate hydroxyl radicals (•OH) that directly eradicate tumor cells. However, its efficacy is hindered in the tumor microenvironment (TME) by low endogenous hydrogen peroxide (H2O2) levels and high glutathione (GSH) content. To overcome these limitations, an injectable self-healing adipic dihydrazide (ADH)-modified hyaluronic acid (HA) (HA-ADH)/aldehyde terminated polyethylene glycol (PEG-CHO)/PVP-cupric peroxide (CuO2) nanoparticles (HPC) hydrogel was developed. This hydrogel system is injectable, pH-responsive, self-healing, and enables sustained GSH depletion through dual Cu2+/•OH-mediated mechanisms. The HPC hydrogel system not only compensates for the TME's endogenous H2O2 deficiency through self-generated H2O2 but also disrupts redox homeostasis via GSH oxidation, thereby inactivating glutathione peroxidase 4 (GPX4) and promoting lipid peroxide accumulation to trigger ferroptosis in melanoma cells. Such a strategy represents a promising approach to achieve enhanced CDT and potent ferroptosis induction by synergizing dual GSH-depleting cycling and self-sufficient H2O2 generation.
Chemodynamic therapy (CDT) represents a novel strategy for the safe treatment of malignant melanoma. It capitalizes on transition metal-catalyzed Fenton-like reactions to generate hydroxyl radicals (•OH) that directly eradicate tumor cells. However, its efficacy is hindered in the tumor microenvironment (TME) by low endogenous hydrogen peroxide (H2O2) levels and high glutathione (GSH) content. To overcome these limitations, an injectable self-healing adipic dihydrazide (ADH)-modified hyaluronic acid (HA) (HA-ADH)/aldehyde terminated polyethylene glycol (PEG-CHO)/PVP-cupric peroxide (CuO2) nanoparticles (HPC) hydrogel was developed. This hydrogel system is injectable, pH-responsive, self-healing, and enables sustained GSH depletion through dual Cu2+/•OH-mediated mechanisms. The HPC hydrogel system not only compensates for the TME's endogenous H2O2 deficiency through self-generated H2O2 but also disrupts redox homeostasis via GSH oxidation, thereby inactivating glutathione peroxidase 4 (GPX4) and promoting lipid peroxide accumulation to trigger ferroptosis in melanoma cells. Such a strategy represents a promising approach to achieve enhanced CDT and potent ferroptosis induction by synergizing dual GSH-depleting cycling and self-sufficient H2O2 generation.
2026, 37(3): 111341
doi: 10.1016/j.cclet.2025.111341
摘要:
Photocatalytic H2O2 production has emerged as a promising strategy for solar-to-H2O2 energy conversion. However, the inevitable requirement for aeration or sacrificial agents poses great challenges for its further application, particularly in environmental remediation process. Previous works often struggles to simultaneously balance the antibiotics degradation and H2O2 production. Herein, bifunctional TiO2 mesocrystal with oxygen vacancy (meso–TiO2-x) was prepared through a facile pyromellitic diimide assisted hydrothermal process. The well-aligned meso–TiO2-x superstructures with unique oxygen vacancies on the surface collectively facilitated the direct h+ oxidation and oxygen reduction reaction (ORR). The ciprofloxacin degradation through direct h+ oxidation boosted the separation of photogenerated carriers, which enhances the e- participation in ORR, resulting H2O2 production rate up to 904.2 µmol g−1 h−1. This work provides an ingenious strategy of constructing bifunctional catalyst to achieve synergistic antibiotics degradation and H2O2 production without the addition of exogenous reagents.
Photocatalytic H2O2 production has emerged as a promising strategy for solar-to-H2O2 energy conversion. However, the inevitable requirement for aeration or sacrificial agents poses great challenges for its further application, particularly in environmental remediation process. Previous works often struggles to simultaneously balance the antibiotics degradation and H2O2 production. Herein, bifunctional TiO2 mesocrystal with oxygen vacancy (meso–TiO2-x) was prepared through a facile pyromellitic diimide assisted hydrothermal process. The well-aligned meso–TiO2-x superstructures with unique oxygen vacancies on the surface collectively facilitated the direct h+ oxidation and oxygen reduction reaction (ORR). The ciprofloxacin degradation through direct h+ oxidation boosted the separation of photogenerated carriers, which enhances the e- participation in ORR, resulting H2O2 production rate up to 904.2 µmol g−1 h−1. This work provides an ingenious strategy of constructing bifunctional catalyst to achieve synergistic antibiotics degradation and H2O2 production without the addition of exogenous reagents.
2026, 37(3): 111358
doi: 10.1016/j.cclet.2025.111358
摘要:
Probes that can undergo photoconversion in situ within cells are advantageous tools for live cell imaging in terms of precise spatial and temporal control. We herein present a new concept to construct photoconvertible probes based on intramolecular oxygen direct arylation within cells. Xanthones bearing aryls (XO-Ars) were designed and prepared. XO-Ars undergo oxygen direct arylation under visible light irradiation in cells to afford xanthene derivatives (XE-Ars). XO-Ars initially accumulate in the endoplasmic reticulum (ER) with green emission and then migrate to the mitochondria with bright red emission. Sequential single-cell lighting up experiments show high spatiotemporal control ability and utility in single or multi-cell tracking. In addition, the photoproducts irradiated with optimized wavelength light source show excellent photodynamic therapy effects. As the duration of light exposure increases, the cells begin to undergo apoptosis. These innovative photoconvertible probes capable of migrating from ER to mitochondria driven by light provide a feasible approach for the in-situ monitoring of subcellular physiological events and cell apoptosis.
Probes that can undergo photoconversion in situ within cells are advantageous tools for live cell imaging in terms of precise spatial and temporal control. We herein present a new concept to construct photoconvertible probes based on intramolecular oxygen direct arylation within cells. Xanthones bearing aryls (XO-Ars) were designed and prepared. XO-Ars undergo oxygen direct arylation under visible light irradiation in cells to afford xanthene derivatives (XE-Ars). XO-Ars initially accumulate in the endoplasmic reticulum (ER) with green emission and then migrate to the mitochondria with bright red emission. Sequential single-cell lighting up experiments show high spatiotemporal control ability and utility in single or multi-cell tracking. In addition, the photoproducts irradiated with optimized wavelength light source show excellent photodynamic therapy effects. As the duration of light exposure increases, the cells begin to undergo apoptosis. These innovative photoconvertible probes capable of migrating from ER to mitochondria driven by light provide a feasible approach for the in-situ monitoring of subcellular physiological events and cell apoptosis.
2026, 37(3): 111370
doi: 10.1016/j.cclet.2025.111370
摘要:
To enhance the suitability of noble metal-based electrocatalysts for acidic overall water splitting, a Pt/Ir-based electrocatalyst incorporating Co and Pd anchored on Ti3C2Tx MXene (Ir/Co Pt Pd@MX) has been successfully synthesized. The incorporation of Co during the synthesis process increases the valence states of Ir and Pt, resulting in improved electrocatalytic performance. The Ir/Co Pt Pd@MX exhibits a low HER overpotential of 38 mV and an OER overpotential of 230 mV, outperforming commercial catalysts. The low noble metal containing electrocatalyst shows nearly 10 times the mass activity of Pt/C for HER and 35 times that of Ir/C for OER. The water splitting cell voltage is 1.46 V, with no observable decay after a 24-h stability test at 10 mA/cm2, establishing it as a top-tier noble metal-based electrocatalyst in acidic environments. Density functional theory (DFT) calculations indicate that Co facilitates the deposition of Ir, enhancing OER performance, while Pd restrict H+absorption of Ir, ensuring the stability. The energy barrier of the rate-determining steps for both the HER and OER decreases.
To enhance the suitability of noble metal-based electrocatalysts for acidic overall water splitting, a Pt/Ir-based electrocatalyst incorporating Co and Pd anchored on Ti3C2Tx MXene (Ir/Co Pt Pd@MX) has been successfully synthesized. The incorporation of Co during the synthesis process increases the valence states of Ir and Pt, resulting in improved electrocatalytic performance. The Ir/Co Pt Pd@MX exhibits a low HER overpotential of 38 mV and an OER overpotential of 230 mV, outperforming commercial catalysts. The low noble metal containing electrocatalyst shows nearly 10 times the mass activity of Pt/C for HER and 35 times that of Ir/C for OER. The water splitting cell voltage is 1.46 V, with no observable decay after a 24-h stability test at 10 mA/cm2, establishing it as a top-tier noble metal-based electrocatalyst in acidic environments. Density functional theory (DFT) calculations indicate that Co facilitates the deposition of Ir, enhancing OER performance, while Pd restrict H+absorption of Ir, ensuring the stability. The energy barrier of the rate-determining steps for both the HER and OER decreases.
2026, 37(3): 111375
doi: 10.1016/j.cclet.2025.111375
摘要:
Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η6-p-cymene)(µ2-m-bitmb)Cl]2·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl- (1·2Cl), NO3- (1·2NO3), CF3SO3- (1·2CF3SO3), PF6- (1·2PF6), or BF4- (1·2BF4). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO3 in twist-boat and chair conformations, and 1·2CF3SO3 in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF3SO3 or 1·2NO3 in DMSO/H2O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η6-p-cymene)(µ2-m-bitmb)Cl]2·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl- (1·2Cl), NO3- (1·2NO3), CF3SO3- (1·2CF3SO3), PF6- (1·2PF6), or BF4- (1·2BF4). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO3 in twist-boat and chair conformations, and 1·2CF3SO3 in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF3SO3 or 1·2NO3 in DMSO/H2O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
2026, 37(3): 111376
doi: 10.1016/j.cclet.2025.111376
摘要:
Polycyclic pyrrole fused indolo[2,1-a]isoquinolins were efficiently generated from alkene-tethered indole derivatives and di–tert-butyldiaziridinone in up to 99% yield in the presence of Pd catalyst. The reaction likely proceeded via sequential Heck, CH activation, and amination process. Varying N-substituents of indole substrates led to indolo[3,2-b]indoles in up to 98% yields.
Polycyclic pyrrole fused indolo[2,1-a]isoquinolins were efficiently generated from alkene-tethered indole derivatives and di–tert-butyldiaziridinone in up to 99% yield in the presence of Pd catalyst. The reaction likely proceeded via sequential Heck, CH activation, and amination process. Varying N-substituents of indole substrates led to indolo[3,2-b]indoles in up to 98% yields.
2026, 37(3): 111378
doi: 10.1016/j.cclet.2025.111378
摘要:
The extraction of uranium from seawater is essential for the sustainable development of the nuclear industry. Covalent organic frameworks (COFs) exhibit significant potential in uranium extraction from seawater due to their high stability, designability, and large specific surface area. Herein, a vinyl-decorated covalent organic framework, designated as COF-IHEP5, was synthesized through acid-catalyzed solvothermal method. COF-IHEP5-COOH was constructed by post-modification strategy through the "thiol-ene" click reaction, where COF-IHEP5-COOH contains hydrazone-carbonyl and flexible carboxylic acid chelating sites on pore wall. This modification facilitates synergistic adsorption of uranium by utilizing a "nano trap" that is embedded within the COF framework. The maximum adsorption capacity of the post-modified COF-IHEP5-COOH for UO22+ has reached 543.8 mg/g, representing a 1.5-fold increase compared to the unmodified COF-IHEP5. Additionally, COF-IHEP5-COOH demonstrates an extraction efficiency of approximately 80% for uranium from spiked natural seawater, featuring 4.5 times higher selectivity than vanadium. The DFT calculation results show that the adsorption of uranium orginated from the synergistic coordination of the skeleton in COF-IHEP5-COOH and carboxyl group on the side arm. This research highlights the remarkable potential of pore surface engineering in customizing active adsorption sites and offers new insights for the design of functionalized uranium adsorbents with superior binding affinity and adsorption capacities.
The extraction of uranium from seawater is essential for the sustainable development of the nuclear industry. Covalent organic frameworks (COFs) exhibit significant potential in uranium extraction from seawater due to their high stability, designability, and large specific surface area. Herein, a vinyl-decorated covalent organic framework, designated as COF-IHEP5, was synthesized through acid-catalyzed solvothermal method. COF-IHEP5-COOH was constructed by post-modification strategy through the "thiol-ene" click reaction, where COF-IHEP5-COOH contains hydrazone-carbonyl and flexible carboxylic acid chelating sites on pore wall. This modification facilitates synergistic adsorption of uranium by utilizing a "nano trap" that is embedded within the COF framework. The maximum adsorption capacity of the post-modified COF-IHEP5-COOH for UO22+ has reached 543.8 mg/g, representing a 1.5-fold increase compared to the unmodified COF-IHEP5. Additionally, COF-IHEP5-COOH demonstrates an extraction efficiency of approximately 80% for uranium from spiked natural seawater, featuring 4.5 times higher selectivity than vanadium. The DFT calculation results show that the adsorption of uranium orginated from the synergistic coordination of the skeleton in COF-IHEP5-COOH and carboxyl group on the side arm. This research highlights the remarkable potential of pore surface engineering in customizing active adsorption sites and offers new insights for the design of functionalized uranium adsorbents with superior binding affinity and adsorption capacities.
2026, 37(3): 111391
doi: 10.1016/j.cclet.2025.111391
摘要:
In this study, we successfully construct a non-noble metal-based Schottky photocatalyst MX@MIL-125 (MX is shorted for Ti3C2 MXene) by combining the Ti-based metal-organic framework MIL-125(Ti) with Ti3C2 MXene. Leveraging the unique surface properties of MXene, a close and uniform distribution of nano-cake-like MIL-125(Ti) was achieved on the two-dimensional Ti3C2 MXene layers. The introduction of Ti3C2 MXene not only broadens the light absorption range but also adjusts the local coordination structure between the interfaces. This heterojunction significantly promotes the separation and transfer of photogenerated carriers. The photocatalytic N2 reduction efficiency of MX@MIL-125-20 is 11-fold higher than that of pristine MIL-125(Ti) (48.8 vs. 4.6 µmol gcat−1 h−1), and the photodegradation efficiency of tetracycline hydrochloride (TCH) is increased by about 18% (92.95% vs. 74.67%). This work may provide new insights for the design of innovative photocatalysts for various chemical redox reactions.
In this study, we successfully construct a non-noble metal-based Schottky photocatalyst MX@MIL-125 (MX is shorted for Ti3C2 MXene) by combining the Ti-based metal-organic framework MIL-125(Ti) with Ti3C2 MXene. Leveraging the unique surface properties of MXene, a close and uniform distribution of nano-cake-like MIL-125(Ti) was achieved on the two-dimensional Ti3C2 MXene layers. The introduction of Ti3C2 MXene not only broadens the light absorption range but also adjusts the local coordination structure between the interfaces. This heterojunction significantly promotes the separation and transfer of photogenerated carriers. The photocatalytic N2 reduction efficiency of MX@MIL-125-20 is 11-fold higher than that of pristine MIL-125(Ti) (48.8 vs. 4.6 µmol gcat−1 h−1), and the photodegradation efficiency of tetracycline hydrochloride (TCH) is increased by about 18% (92.95% vs. 74.67%). This work may provide new insights for the design of innovative photocatalysts for various chemical redox reactions.
2026, 37(3): 111397
doi: 10.1016/j.cclet.2025.111397
摘要:
While TiO2 is a promising catalyst for electrocatalytic nitrate (NO3--N) reduction to NH3 (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (Ov) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO2 catalysts with controlled phase composition and Ov number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO2-x, x = 450–750 ℃). Generally, higher temperatures lead to increased R-TiO2 content but decreased Ov number. The ENRR performances of these N-TiO2 are higher than that of pure A- and R-TiO2, and vary in volcano-like trends against both the R-TiO2 content and Ov number. Combined control experiments and theoretical simulation demonstrate that Ovs are the active sites for ENRR, but their functions differ between A-TiO2 and R-TiO2. Specifically, the Ovs on R-TiO2 are more active in NO3- conversion and renew more easily during reaction, while those on A-TiO2 perform better in proton adsorption. The synergy between Ovs on R-TiO2 and A-TiO2 promotes the ENRR on the phase-mixed N-TiO2. Furthermore, as the catalyst varies from N-TiO2–450 to -750, the overall efficacy of Ovs in proton transfer decreases due to the decreased number of Ovs on A-TiO2, while the mean activity and renewability of them improve as a higher proportion of Ovs are distributed on R-TiO2. The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO2–650 (mass activity: 22.2 mgN h-1 gcat.-1; NH3-N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO2, and provide new insights for the design of efficient catalysts.
While TiO2 is a promising catalyst for electrocatalytic nitrate (NO3--N) reduction to NH3 (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (Ov) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO2 catalysts with controlled phase composition and Ov number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO2-x, x = 450–750 ℃). Generally, higher temperatures lead to increased R-TiO2 content but decreased Ov number. The ENRR performances of these N-TiO2 are higher than that of pure A- and R-TiO2, and vary in volcano-like trends against both the R-TiO2 content and Ov number. Combined control experiments and theoretical simulation demonstrate that Ovs are the active sites for ENRR, but their functions differ between A-TiO2 and R-TiO2. Specifically, the Ovs on R-TiO2 are more active in NO3- conversion and renew more easily during reaction, while those on A-TiO2 perform better in proton adsorption. The synergy between Ovs on R-TiO2 and A-TiO2 promotes the ENRR on the phase-mixed N-TiO2. Furthermore, as the catalyst varies from N-TiO2–450 to -750, the overall efficacy of Ovs in proton transfer decreases due to the decreased number of Ovs on A-TiO2, while the mean activity and renewability of them improve as a higher proportion of Ovs are distributed on R-TiO2. The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO2–650 (mass activity: 22.2 mgN h-1 gcat.-1; NH3-N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO2, and provide new insights for the design of efficient catalysts.
2026, 37(3): 111398
doi: 10.1016/j.cclet.2025.111398
摘要:
Photocatalysis shows promising application in efficient reduction of nitrogen oxides (NOx). However, the sluggish selectivity in nitric oxide removal with reductants, resulting in the formation of undesired N2O byproducts, presents a great challenge. In this work, complete prohibition of nitric oxide generation in photo-removal of NO with carbon particulate is successfully achieved through the rational regulation of electron-trapping centers on TiO2 nanosheets (TNS) surface achieved by the surface reduction treatment with NaBH4. The efficient suppression (100%) of N2O generation is ascribed to the more stable N2O adsorption on the active (001) crystalline plane of TNS and the electron-capturing ability around oxygen vacancies based on the density functional theory (DFT) and experimental investigations. The existence of O2 and H2O effectively promote the photocatalytic activity of NO reduction but demonstrate no adverse effect on N2O suppression. The optimal photocatalytic NO reduction activity with the highest CO2 formation rate of 5.54 mg g−1 h−1 without N2O formation is achieved over the optimized 0.135-TNS. These investigations guide the development of feasible photocatalytic treatment of air pollutants, emphasizing the significance of managing electron capture and gas adsorption for efficient byproduct control in pollutants removal.
Photocatalysis shows promising application in efficient reduction of nitrogen oxides (NOx). However, the sluggish selectivity in nitric oxide removal with reductants, resulting in the formation of undesired N2O byproducts, presents a great challenge. In this work, complete prohibition of nitric oxide generation in photo-removal of NO with carbon particulate is successfully achieved through the rational regulation of electron-trapping centers on TiO2 nanosheets (TNS) surface achieved by the surface reduction treatment with NaBH4. The efficient suppression (100%) of N2O generation is ascribed to the more stable N2O adsorption on the active (001) crystalline plane of TNS and the electron-capturing ability around oxygen vacancies based on the density functional theory (DFT) and experimental investigations. The existence of O2 and H2O effectively promote the photocatalytic activity of NO reduction but demonstrate no adverse effect on N2O suppression. The optimal photocatalytic NO reduction activity with the highest CO2 formation rate of 5.54 mg g−1 h−1 without N2O formation is achieved over the optimized 0.135-TNS. These investigations guide the development of feasible photocatalytic treatment of air pollutants, emphasizing the significance of managing electron capture and gas adsorption for efficient byproduct control in pollutants removal.
2026, 37(3): 111404
doi: 10.1016/j.cclet.2025.111404
摘要:
In situ therapeutic agent production strategy is promising to overcome the drawbacks of direct drug delivery. Hypoxia provides a great target for precise treatment of tumor. Here we report a copper ion competition-based nanoparticle (NP) for hypoxia-activated formation of diethyldithiocarbamate (DTC)-copper complex, an immunogenic cell death (ICD) inducer. The NP is composed of an amphiphilic hypoxia-responsive DTC precursor and a fluorescence quenched copper ion-chelated squaric acid. In hypoxic tumor cells, the azobenzene linker in DTC precursor can be cleaved through bioreduction, leading to DTC release and subsequent copper ion exchange between DTC and squaric acid. Simultaneous formation of toxic DTC-copper complexes and fluorescence recovery will allow for visualization of in situ therapeutic agents production. Furthermore, the DTC-copper complexes can induce ICD and promote cytotoxic T lymphocyte infiltration for cancer immunotherapy. This study not only provides a promising hypoxia-activated nanomedicine for precision cancer therapy, but also a visualization strategy for evaluating the treatment process.
In situ therapeutic agent production strategy is promising to overcome the drawbacks of direct drug delivery. Hypoxia provides a great target for precise treatment of tumor. Here we report a copper ion competition-based nanoparticle (NP) for hypoxia-activated formation of diethyldithiocarbamate (DTC)-copper complex, an immunogenic cell death (ICD) inducer. The NP is composed of an amphiphilic hypoxia-responsive DTC precursor and a fluorescence quenched copper ion-chelated squaric acid. In hypoxic tumor cells, the azobenzene linker in DTC precursor can be cleaved through bioreduction, leading to DTC release and subsequent copper ion exchange between DTC and squaric acid. Simultaneous formation of toxic DTC-copper complexes and fluorescence recovery will allow for visualization of in situ therapeutic agents production. Furthermore, the DTC-copper complexes can induce ICD and promote cytotoxic T lymphocyte infiltration for cancer immunotherapy. This study not only provides a promising hypoxia-activated nanomedicine for precision cancer therapy, but also a visualization strategy for evaluating the treatment process.
2026, 37(3): 111420
doi: 10.1016/j.cclet.2025.111420
摘要:
Mechanosensitive channel proteins serve important physiological functions in biological systems. Building artificial transmembrane channels to mimic the function of natural channels would provide a new strategy for treating channel-related diseases. In this paper, we describe the design and construction of artificial channels derived from pillar[5]arene backbones with different flexibilities, which are determined by the alkyl chain length. Importantly, the ion transport activities of the channels can be activated by increasing the membrane curvature and tension, which endows the channel with mechano-gating behavior.
Mechanosensitive channel proteins serve important physiological functions in biological systems. Building artificial transmembrane channels to mimic the function of natural channels would provide a new strategy for treating channel-related diseases. In this paper, we describe the design and construction of artificial channels derived from pillar[5]arene backbones with different flexibilities, which are determined by the alkyl chain length. Importantly, the ion transport activities of the channels can be activated by increasing the membrane curvature and tension, which endows the channel with mechano-gating behavior.
2026, 37(3): 111427
doi: 10.1016/j.cclet.2025.111427
摘要:
The development of advanced anti-counterfeiting technology using photochromic inorganic materials with dynamic optical signals has garnered significant interest, but the limited color response and un-controlled photochromic kinetics largely restrict their practical application. In this work, we report the design of photochromic supramolecular assembly based on host-guest chemistry, enabling kinetics-tunable time-encoded anti-counterfeiting. By co-assembling of photochromic tungsten oxide quantum dots (WO3 QDs) with cucurbit[7]uril (CB[7]), we developed a kinetics-tunable photochromic supramolecular assembly (WO3CB[7]). The WO3CB[7] assembly exhibits distinct photochromic kinetics compared to free WO3 QDs due to efficient suppression of photogenerated decomposition of water adsorbed on WO3 QDs, as verified by spectral and photophysical analysis. The photochromic kinetics can be readily modulated by adjusting the WO3 QDs to CB[7] ratio. The kinetics-tunable photochromic WO3CB[7] assembly has been successfully applied as innovative anti-counterfeiting materials for fabricating time-encoded anti-counterfeiting arrays and information encryption system. The irradiation time serves as a key parameter for decrypting the final information, thereby enhancing the complexity of replication and counterfeiting. This approach offers a simple, scalable and generalizable strategy for designing advanced optical anti-counterfeiting materials by integrating inorganic photochromic materials with the supramolecular strategy.
The development of advanced anti-counterfeiting technology using photochromic inorganic materials with dynamic optical signals has garnered significant interest, but the limited color response and un-controlled photochromic kinetics largely restrict their practical application. In this work, we report the design of photochromic supramolecular assembly based on host-guest chemistry, enabling kinetics-tunable time-encoded anti-counterfeiting. By co-assembling of photochromic tungsten oxide quantum dots (WO3 QDs) with cucurbit[7]uril (CB[7]), we developed a kinetics-tunable photochromic supramolecular assembly (WO3CB[7]). The WO3CB[7] assembly exhibits distinct photochromic kinetics compared to free WO3 QDs due to efficient suppression of photogenerated decomposition of water adsorbed on WO3 QDs, as verified by spectral and photophysical analysis. The photochromic kinetics can be readily modulated by adjusting the WO3 QDs to CB[7] ratio. The kinetics-tunable photochromic WO3CB[7] assembly has been successfully applied as innovative anti-counterfeiting materials for fabricating time-encoded anti-counterfeiting arrays and information encryption system. The irradiation time serves as a key parameter for decrypting the final information, thereby enhancing the complexity of replication and counterfeiting. This approach offers a simple, scalable and generalizable strategy for designing advanced optical anti-counterfeiting materials by integrating inorganic photochromic materials with the supramolecular strategy.
2026, 37(3): 111445
doi: 10.1016/j.cclet.2025.111445
摘要:
The electrostatic repulsion between the anode and ammonia (NH4+) can cause chlorine radicals (Cl•) at the interface to self-compounding into low oxidating species, weakening the treatment performance of ammonia-nitrogen (NH4+-N) wastewater. This study introduces electron-rich elements into the tetrahedral sites (ATd2+) of spinel cobalt oxide (Co3O4) for efficient and selective NH4+-N mineralization induced by interfacial Cl•. Batch experiments, in-situ characterizations, and theoretical calculations confirm that CuTd2+ have moderate energy level matching and strong binding energy with NH4+ compared to NiTd2+ and ZnTd2+. NH4+ can effectively overcome electrostatic repulsion and enrich on CuxCo3-xO4 anode. More importantly, the interaction of CuTd2+-O-CoOh3+ weakens the binding of Cl• at CoOh3+ sites, promoting the desorption of Cl• from the anodic interface. As a result, NH4+-N is mineralized by Cl• into N2 with a rate of 4.4 × 10–2 min-1, superior to Co3O4 and commercial dimensionally stable anodes. Finally, the scale-up experiment using a continuous flow reactor realizes long-term stability for NH4+-N wastewater treatment, in which 100% of NH4+-N and 88.3% of total nitrogen can be continuously eliminated in 96 h. This study offers an in-depth understanding of interfacial reactions in the EC system and guides the design and synthesis of superior anodes for environmental remediation.
The electrostatic repulsion between the anode and ammonia (NH4+) can cause chlorine radicals (Cl•) at the interface to self-compounding into low oxidating species, weakening the treatment performance of ammonia-nitrogen (NH4+-N) wastewater. This study introduces electron-rich elements into the tetrahedral sites (ATd2+) of spinel cobalt oxide (Co3O4) for efficient and selective NH4+-N mineralization induced by interfacial Cl•. Batch experiments, in-situ characterizations, and theoretical calculations confirm that CuTd2+ have moderate energy level matching and strong binding energy with NH4+ compared to NiTd2+ and ZnTd2+. NH4+ can effectively overcome electrostatic repulsion and enrich on CuxCo3-xO4 anode. More importantly, the interaction of CuTd2+-O-CoOh3+ weakens the binding of Cl• at CoOh3+ sites, promoting the desorption of Cl• from the anodic interface. As a result, NH4+-N is mineralized by Cl• into N2 with a rate of 4.4 × 10–2 min-1, superior to Co3O4 and commercial dimensionally stable anodes. Finally, the scale-up experiment using a continuous flow reactor realizes long-term stability for NH4+-N wastewater treatment, in which 100% of NH4+-N and 88.3% of total nitrogen can be continuously eliminated in 96 h. This study offers an in-depth understanding of interfacial reactions in the EC system and guides the design and synthesis of superior anodes for environmental remediation.
2026, 37(3): 111446
doi: 10.1016/j.cclet.2025.111446
摘要:
It is still challenging to develop nanomedicines with full-active and simple components to tackle osteoarthritis (OA) through restoration of inflammation and cartilage homeostasis. Here, we report the synthesis of a bioactive asymmetric phosphorus dendrimer bearing an azabisphosphonate (ABP) group, termed as G0.PD-ABP, by a divergent method for intracellular bromelain (Bro) delivery. The formed G0.PD-ABP/Bro nanocomplexes (NCs) exhibit a uniformly dispersed spherical shape with a mean size of 148.4 nm and can achieve more significant intracellular Bro delivery than symmetric phosphorus dendrimer (G0.PD) without ABP via the clathrin-mediated endocytosis pathway. Importantly, the NCs efficiently block the activation of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), and nuclear factor kappa-B (NF-κB) by amplifying the anti-inflammatory function of Bro and synergizing with the immunomodulatory activity of dendrimers, thereby facilitating the polarization of macrophages towards M2 phenotype and down-regulating inflammatory cytokine secretion to lead to suppressed chondrocyte apoptosis. Compared with G0.PD/Bro NCs, an OA mouse model treated with G0.PD-ABP/Bro NCs demonstrates more remarkable alleviation of pathological features such as cartilage degradation, bone erosion, and synovial inflammation. This study emphasizes the positive contribution of structural asymmetry of phosphorus dendrimers in protein delivery and provides a viable strategy for the treatment of OA or other inflammatory diseases through enhanced immune modulation of macrophages.
It is still challenging to develop nanomedicines with full-active and simple components to tackle osteoarthritis (OA) through restoration of inflammation and cartilage homeostasis. Here, we report the synthesis of a bioactive asymmetric phosphorus dendrimer bearing an azabisphosphonate (ABP) group, termed as G0.PD-ABP, by a divergent method for intracellular bromelain (Bro) delivery. The formed G0.PD-ABP/Bro nanocomplexes (NCs) exhibit a uniformly dispersed spherical shape with a mean size of 148.4 nm and can achieve more significant intracellular Bro delivery than symmetric phosphorus dendrimer (G0.PD) without ABP via the clathrin-mediated endocytosis pathway. Importantly, the NCs efficiently block the activation of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), and nuclear factor kappa-B (NF-κB) by amplifying the anti-inflammatory function of Bro and synergizing with the immunomodulatory activity of dendrimers, thereby facilitating the polarization of macrophages towards M2 phenotype and down-regulating inflammatory cytokine secretion to lead to suppressed chondrocyte apoptosis. Compared with G0.PD/Bro NCs, an OA mouse model treated with G0.PD-ABP/Bro NCs demonstrates more remarkable alleviation of pathological features such as cartilage degradation, bone erosion, and synovial inflammation. This study emphasizes the positive contribution of structural asymmetry of phosphorus dendrimers in protein delivery and provides a viable strategy for the treatment of OA or other inflammatory diseases through enhanced immune modulation of macrophages.
2026, 37(3): 111459
doi: 10.1016/j.cclet.2025.111459
摘要:
Chronic kidney disease (CKD) is a progressive disease characterized by high rates of morbidity and mortality, often leading to various complications. Early home diagnosis and point-of-care prognosis are therefore crucial for monitoring CKD progression and managing patient outcomes. β2-microglobulin (B2M) levels offer a valuable indicator of renal function changes, however, their quantitative detection typically relies on sophisticated and costly laboratory instrumentation. Here, we present a universal and adaptable strategy for efficiently conjugating rare-earth-based nanoparticles with antibodies via a carboxymethyl β-cyclodextrin-mediated "self-assembly-followed-by-conjugation" approach. Cyclodextrin modification enhances the rigidity, hydrophilicity, and electrostatic repulsion of nanoparticles, significantly improving their colloidal stability and upconversion luminescence in aqueous solution. Moreover, the ample carboxyl groups on cyclodextrin offer multiple sites for covalent conjugation, resulting in a substantial enhancement in antibody loading capacity and improved immunoaffinity for biomarkers. Employing this methodology, we developed an antibody-conjugated nanoprobe for B2M and fabricated a fluorescent lateral flow strip. Subsequently, image acquisition and data analysis using a smartphone enabled sensitive and quantitative detection of B2M in artificial urine, achieving a detection limit of 2.7 ng/mL. This study provides a versatile strategy for the development of nanoparticle-based colorimetric/luminescent immunoassay probes.
Chronic kidney disease (CKD) is a progressive disease characterized by high rates of morbidity and mortality, often leading to various complications. Early home diagnosis and point-of-care prognosis are therefore crucial for monitoring CKD progression and managing patient outcomes. β2-microglobulin (B2M) levels offer a valuable indicator of renal function changes, however, their quantitative detection typically relies on sophisticated and costly laboratory instrumentation. Here, we present a universal and adaptable strategy for efficiently conjugating rare-earth-based nanoparticles with antibodies via a carboxymethyl β-cyclodextrin-mediated "self-assembly-followed-by-conjugation" approach. Cyclodextrin modification enhances the rigidity, hydrophilicity, and electrostatic repulsion of nanoparticles, significantly improving their colloidal stability and upconversion luminescence in aqueous solution. Moreover, the ample carboxyl groups on cyclodextrin offer multiple sites for covalent conjugation, resulting in a substantial enhancement in antibody loading capacity and improved immunoaffinity for biomarkers. Employing this methodology, we developed an antibody-conjugated nanoprobe for B2M and fabricated a fluorescent lateral flow strip. Subsequently, image acquisition and data analysis using a smartphone enabled sensitive and quantitative detection of B2M in artificial urine, achieving a detection limit of 2.7 ng/mL. This study provides a versatile strategy for the development of nanoparticle-based colorimetric/luminescent immunoassay probes.
2026, 37(3): 111496
doi: 10.1016/j.cclet.2025.111496
摘要:
Traditional enzyme-nanozymes cascade assays for glucose detection are usually limited by pH incompatibility and operational complexity. Herein, we present a strategy based on hollow mesoporous Prussian blue (HMPB) nanozymes for one-step, dual-modal glucose sensing under neutral conditions. The rationally designed HMPB nanozymes exhibit intrinsic peroxidase-like activity at physiological pH (~7.4), inherent chromogenic properties and superior photothermal conversion efficiency. These features directly enable integration with glucose oxidase (GOx) for one-step glucose detection without intermediate pH adjustment. Additionally, the catalytic coupling of 4-aminoantipyrine/phenol oxidation products, enhanced by the intrinsic blue coloration of HMPB, generates vivid multicolorimetric responses for smartphone-based quantitative analysis. To enhance signal reliability, the photothermal properties of HMPB nanozymes are further ingeniously coupled with the thermal-responsive characteristics of oxidized 3,3′,5,5′-tetramethylbenzidine (oxTMB), establishing a dual-amplified thermal imaging platform through portable infrared thermal imager detection. HMPB nanozymes serve as both a catalytic activator and an intrinsic signal reporter, establish a new platform in dual-modal glucose monitoring. The platform demonstrates remarkable clinical adaptability through its smartphone-compatible colorimetric readout and portable thermal imaging capabilities, achieving a detection limit of 1.39 µmol/L (multicolorimetric modal) and 3.05 µmol/L (photothermometric modal) for glucose with robust reliability in human serum samples. This research overcomes the pH mismatch barrier in enzyme-nanozymes cascade system, and providing a cost-effective, instrument-flexible detection strategy that bridges laboratory research and point-of-care diagnostics.
Traditional enzyme-nanozymes cascade assays for glucose detection are usually limited by pH incompatibility and operational complexity. Herein, we present a strategy based on hollow mesoporous Prussian blue (HMPB) nanozymes for one-step, dual-modal glucose sensing under neutral conditions. The rationally designed HMPB nanozymes exhibit intrinsic peroxidase-like activity at physiological pH (~7.4), inherent chromogenic properties and superior photothermal conversion efficiency. These features directly enable integration with glucose oxidase (GOx) for one-step glucose detection without intermediate pH adjustment. Additionally, the catalytic coupling of 4-aminoantipyrine/phenol oxidation products, enhanced by the intrinsic blue coloration of HMPB, generates vivid multicolorimetric responses for smartphone-based quantitative analysis. To enhance signal reliability, the photothermal properties of HMPB nanozymes are further ingeniously coupled with the thermal-responsive characteristics of oxidized 3,3′,5,5′-tetramethylbenzidine (oxTMB), establishing a dual-amplified thermal imaging platform through portable infrared thermal imager detection. HMPB nanozymes serve as both a catalytic activator and an intrinsic signal reporter, establish a new platform in dual-modal glucose monitoring. The platform demonstrates remarkable clinical adaptability through its smartphone-compatible colorimetric readout and portable thermal imaging capabilities, achieving a detection limit of 1.39 µmol/L (multicolorimetric modal) and 3.05 µmol/L (photothermometric modal) for glucose with robust reliability in human serum samples. This research overcomes the pH mismatch barrier in enzyme-nanozymes cascade system, and providing a cost-effective, instrument-flexible detection strategy that bridges laboratory research and point-of-care diagnostics.
2026, 37(3): 111498
doi: 10.1016/j.cclet.2025.111498
摘要:
Multi-substituted azetidines have been an under-utilized bioisosteres in modern drug entities, due to the scarcity of mild and stereo-controllable synthetic methods. The state-of-art aza-[2 + 2] cycloaddition suffers from two drawbacks, namely limited C=N scope and the dearth of stereochemical control. Herein, we extend a photocatalytic direct N-heteroarene dearomative aza-[2 + 2] cycloaddition under white light via energy transfer mechanism. A key protonic solvent triggered retro aza-[2 + 2] cycloaddition process was discovered and utilized as a stereochemical editing logic to address the challenge of diastereomeric control (controlling three contiguous stereocenters).
Multi-substituted azetidines have been an under-utilized bioisosteres in modern drug entities, due to the scarcity of mild and stereo-controllable synthetic methods. The state-of-art aza-[2 + 2] cycloaddition suffers from two drawbacks, namely limited C=N scope and the dearth of stereochemical control. Herein, we extend a photocatalytic direct N-heteroarene dearomative aza-[2 + 2] cycloaddition under white light via energy transfer mechanism. A key protonic solvent triggered retro aza-[2 + 2] cycloaddition process was discovered and utilized as a stereochemical editing logic to address the challenge of diastereomeric control (controlling three contiguous stereocenters).
2026, 37(3): 111502
doi: 10.1016/j.cclet.2025.111502
摘要:
Multiple myeloma (MM) is a highly aggressive hematologic malignancy characterized by abnormal proliferation of malignant plasma cells. CD38, a transmembrane glycoprotein, is highly expressed on the surface of plasma cells and serves as a critical diagnostic and therapeutic target for MM. However, the masking of CD38 epitopes caused by therapeutic interventions often leads to false-negative results in clinical detection of CD38, compromising diagnostic accuracy and underscoring the urgent need for novel specific molecular tools. Herein, we reported a novel aptamer, CD38jd4a, specifically targeting CD38 with potential clinical applications. A series of high-affinity aptamers specifically binding CD38 were selected and identified through a highly efficient aptamer selection method with CD38 as the target. Among them, aptamer CD38jd4a exhibited the best performance, with a dissociation constant (Kd) value as low as 5.4 ± 0.6 nmol/L. Through siRNA-mediated knockdown experiments, CD38jd4a was further validated to specifically recognize native CD38 expressed on surface of cells. Furthermore, binding epitopes of CD38jd4a were confirmed to be distinct from those recognized by any of current therapeutic antibodies. This unique characteristic enabled the simultaneous application of CD38jd4a with therapeutic antibodies for CD38 detection on CD38-positive Ramos cells by flow cytometry without cross-interference. Importantly, clinical blood sample analysis revealed that CD38jd4a was capable of effectively detecting CD38 despite epitope masking, thereby overcoming limitations of conventional antibody-based detection methods. Given the small molecular size and excellent performance, CD38jd4a is expected to be a robust diagnostic tool for CD38 detection, offering a promising alternative for clinical diagnostics of CD38.
Multiple myeloma (MM) is a highly aggressive hematologic malignancy characterized by abnormal proliferation of malignant plasma cells. CD38, a transmembrane glycoprotein, is highly expressed on the surface of plasma cells and serves as a critical diagnostic and therapeutic target for MM. However, the masking of CD38 epitopes caused by therapeutic interventions often leads to false-negative results in clinical detection of CD38, compromising diagnostic accuracy and underscoring the urgent need for novel specific molecular tools. Herein, we reported a novel aptamer, CD38jd4a, specifically targeting CD38 with potential clinical applications. A series of high-affinity aptamers specifically binding CD38 were selected and identified through a highly efficient aptamer selection method with CD38 as the target. Among them, aptamer CD38jd4a exhibited the best performance, with a dissociation constant (Kd) value as low as 5.4 ± 0.6 nmol/L. Through siRNA-mediated knockdown experiments, CD38jd4a was further validated to specifically recognize native CD38 expressed on surface of cells. Furthermore, binding epitopes of CD38jd4a were confirmed to be distinct from those recognized by any of current therapeutic antibodies. This unique characteristic enabled the simultaneous application of CD38jd4a with therapeutic antibodies for CD38 detection on CD38-positive Ramos cells by flow cytometry without cross-interference. Importantly, clinical blood sample analysis revealed that CD38jd4a was capable of effectively detecting CD38 despite epitope masking, thereby overcoming limitations of conventional antibody-based detection methods. Given the small molecular size and excellent performance, CD38jd4a is expected to be a robust diagnostic tool for CD38 detection, offering a promising alternative for clinical diagnostics of CD38.
2026, 37(3): 111526
doi: 10.1016/j.cclet.2025.111526
摘要:
According to the "New Coronavirus Pneumonia (COVID-19) Tenth Edition Diagnosis and Treatment Plan", residues from three prescriptions including Qingfei-Paidu Formula, Huashi-Baidu Formula, and Xuanfei-Zhixue Formula were selected as precursors for biochar preparation. The resulting Chinese medicine residue-derived biochars (CMR-BCs), prepared using different prescriptions and pyrolysis temperatures, were used to activate peracetic acid (PAA) for sulfamethoxazole (SMX) removal. Biochar (q800) produced from 800 ℃-treated Qingfei-Paidu Formula residue achieved ~60% SMX adsorption removal efficiency, outperforming other CMR-BCs. All prepared CMR-BC samples demonstrated oxidative degradation of SMX via activating PAA, with efficiencies ranging from ~20.8% to 45.5%, which might be ascribed to their abundant oxygen-containing functional groups and graphitic structures. Electro-chemical analysis and quenching tests indicated that the direct electron-transfer (DET) process was identified as the primary non-radical degradation mechanism. The formation of CMR-BCs-PAA* interfacial complexes enhanced the overall oxidation potential, facilitating the redox reaction between CMR-BCs-PAA* and SMX. In total, this study offers new insights into the non-radical mechanism of CMR-BC/PAA systems, presenting a potential solution for the resource utilization of Chinese medicine residue wastes.
According to the "New Coronavirus Pneumonia (COVID-19) Tenth Edition Diagnosis and Treatment Plan", residues from three prescriptions including Qingfei-Paidu Formula, Huashi-Baidu Formula, and Xuanfei-Zhixue Formula were selected as precursors for biochar preparation. The resulting Chinese medicine residue-derived biochars (CMR-BCs), prepared using different prescriptions and pyrolysis temperatures, were used to activate peracetic acid (PAA) for sulfamethoxazole (SMX) removal. Biochar (q800) produced from 800 ℃-treated Qingfei-Paidu Formula residue achieved ~60% SMX adsorption removal efficiency, outperforming other CMR-BCs. All prepared CMR-BC samples demonstrated oxidative degradation of SMX via activating PAA, with efficiencies ranging from ~20.8% to 45.5%, which might be ascribed to their abundant oxygen-containing functional groups and graphitic structures. Electro-chemical analysis and quenching tests indicated that the direct electron-transfer (DET) process was identified as the primary non-radical degradation mechanism. The formation of CMR-BCs-PAA* interfacial complexes enhanced the overall oxidation potential, facilitating the redox reaction between CMR-BCs-PAA* and SMX. In total, this study offers new insights into the non-radical mechanism of CMR-BC/PAA systems, presenting a potential solution for the resource utilization of Chinese medicine residue wastes.
2026, 37(3): 111536
doi: 10.1016/j.cclet.2025.111536
摘要:
To deal with the problem of NO3− enrichment in water environment, electrochemical catalysis of nitrate reduction reaction (NO3RR) provides a possibility. However, this catalytic process requires efficient and highly selective NO3RR electrocatalysts to catalyze NO3− conversion. Consequently, the objective of this work is to search highly active NO3RR electrocatalysts by employing an efficient screening strategy using density functional theory methods. The catalytic activity is assessed by calculating limiting potential UL(NO3RR) and UL(HER). The research results indicate that Os2_C19N3 not only has excellent catalytic activity (UL(NO3RR) = −0.15 V), but also can effectively avoid the occurrence of competitive hydrogen evolution reaction. The NO3RR process of Os2_C19N3 is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *N → *NH → *NH2 → *NH3 → * + NH3. When Os2_C19N3 is in the condition of DFT-Sol, DFT-D, and DFT-D-Sol, the NO3RR process is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *NHOH → *NH2OH → *NH2 → *NH3 → * + NH3, and the UL(NO3RR) values are −0.06, −0.15, and −0.06 V, respectively. This research may offer potential reference values for the development of innovative NO3RR catalysts and the synthesis of NH3.
To deal with the problem of NO3− enrichment in water environment, electrochemical catalysis of nitrate reduction reaction (NO3RR) provides a possibility. However, this catalytic process requires efficient and highly selective NO3RR electrocatalysts to catalyze NO3− conversion. Consequently, the objective of this work is to search highly active NO3RR electrocatalysts by employing an efficient screening strategy using density functional theory methods. The catalytic activity is assessed by calculating limiting potential UL(NO3RR) and UL(HER). The research results indicate that Os2_C19N3 not only has excellent catalytic activity (UL(NO3RR) = −0.15 V), but also can effectively avoid the occurrence of competitive hydrogen evolution reaction. The NO3RR process of Os2_C19N3 is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *N → *NH → *NH2 → *NH3 → * + NH3. When Os2_C19N3 is in the condition of DFT-Sol, DFT-D, and DFT-D-Sol, the NO3RR process is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *NHOH → *NH2OH → *NH2 → *NH3 → * + NH3, and the UL(NO3RR) values are −0.06, −0.15, and −0.06 V, respectively. This research may offer potential reference values for the development of innovative NO3RR catalysts and the synthesis of NH3.
2026, 37(3): 111537
doi: 10.1016/j.cclet.2025.111537
摘要:
Quenching experiments play an essential role in the probing of reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, inappropriate choice of quencher type and concentration will affect the judgement of the contribution of ROS. Herein, we systematically explored the direct reaction of quenchers with oxidants commonly used in AOPs (e.g., hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS)). The experimental results showed that PMS had a noticeable reaction with methyl phenyl sulfoxide, dimethyl sulfoxide and furfuryl alcohol, and the second-order reaction rate constants between them were measured. Meanwhile, PDS and H2O2 were hardly consumed in the presence of various quenchers. Moreover, high-performance liquid chromatography measurements demonstrated that L-histidine, benzoquinone, and phenol would have the artifact of rapid PMS depletion due to the limitations of the test method. Furthermore, in response to the problems with the quenching experiments, some suggestions for the selection of quencher type and concentration were presented. This work is of great reference value in guiding the appropriate selection of quenchers in AOPs, which in turn facilitates the accurate investigation of ROS and reaction mechanisms.
Quenching experiments play an essential role in the probing of reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, inappropriate choice of quencher type and concentration will affect the judgement of the contribution of ROS. Herein, we systematically explored the direct reaction of quenchers with oxidants commonly used in AOPs (e.g., hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS)). The experimental results showed that PMS had a noticeable reaction with methyl phenyl sulfoxide, dimethyl sulfoxide and furfuryl alcohol, and the second-order reaction rate constants between them were measured. Meanwhile, PDS and H2O2 were hardly consumed in the presence of various quenchers. Moreover, high-performance liquid chromatography measurements demonstrated that L-histidine, benzoquinone, and phenol would have the artifact of rapid PMS depletion due to the limitations of the test method. Furthermore, in response to the problems with the quenching experiments, some suggestions for the selection of quencher type and concentration were presented. This work is of great reference value in guiding the appropriate selection of quenchers in AOPs, which in turn facilitates the accurate investigation of ROS and reaction mechanisms.
2026, 37(3): 111542
doi: 10.1016/j.cclet.2025.111542
摘要:
Antibiotic contamination in aquatic environments poses serious risks to ecosystems and public health, necessitating the development of effective removal technologies. In this study, a novel biochar-supported ferric oxyhydroxide (FeOOH/BC) composite catalyst was developed for the activation of peracetic acid (PAA) to degrade cefapirin (CFP), a widely used and persistent cephalosporin antibiotic. The catalyst featured highly dispersed FeOOH nanoparticles and enhanced interfacial electron transfer, enabling efficient activation of PAA through dual pathways involving both radical and non-radical species. FeOOH/BC-1 exhibited the highest catalytic activity, where high-valent iron, singlet oxygen, and surface-bound reactive species played the primary roles in CFP degradation. Fe(Ⅲ) active sites generate high-valent iron oxo, while N active sites in biochar accounted for the direct electron transfer. This work provides a new approach for activating PAA in the degradation of emerging contaminants and offers a feasible method for catalyst regeneration in wastewater treatment applications.
Antibiotic contamination in aquatic environments poses serious risks to ecosystems and public health, necessitating the development of effective removal technologies. In this study, a novel biochar-supported ferric oxyhydroxide (FeOOH/BC) composite catalyst was developed for the activation of peracetic acid (PAA) to degrade cefapirin (CFP), a widely used and persistent cephalosporin antibiotic. The catalyst featured highly dispersed FeOOH nanoparticles and enhanced interfacial electron transfer, enabling efficient activation of PAA through dual pathways involving both radical and non-radical species. FeOOH/BC-1 exhibited the highest catalytic activity, where high-valent iron, singlet oxygen, and surface-bound reactive species played the primary roles in CFP degradation. Fe(Ⅲ) active sites generate high-valent iron oxo, while N active sites in biochar accounted for the direct electron transfer. This work provides a new approach for activating PAA in the degradation of emerging contaminants and offers a feasible method for catalyst regeneration in wastewater treatment applications.
2026, 37(3): 111546
doi: 10.1016/j.cclet.2025.111546
摘要:
Microplastics (MPs), which originate from plastic degradation, are becoming a significant environmental pollutant, and their prevalence is increasing rapidly. Humans can ingest MPs through various pathways and their presence has been detected in multiple human organs, raising concerns about the potential toxic effects associated with plastic consumption. Epigenetic modifications of nucleic acids play crucial roles in various biological processes, including gene expression and tumorigenesis. Previous studies have demonstrated that exposure to certain environmental pollutants can influence disease pathogenesis by affecting epigenetic factors, including modifications of nucleic acids. However, the impact of MPs on epigenetic modifications of nucleic acids remains largely unexplored. In this study, we systematically investigated the alterations in epigenetic modifications of DNA and RNA following exposure to polystyrene microplastics (PS-MPs). We utilized liquid chromatography-tandem mass spectrometry (LC-MS/MS) to simultaneously analyze two DNA epigenetic modifications of 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (5hmC), along with twenty RNA epigenetic modifications from small RNA and nine epigenetic modifications from mRNA. We measured changes in the levels of DNA and RNA modifications across six tissues (heart, liver, spleen, lung, kidney, and intestine) in mice after PS-MPs exposure. The results indicated that exposure to PS-MPs significantly altered the landscape of epigenetic modifications in nucleic acids. Furthermore, we observed tissue-specific effects, suggesting that different organs respond uniquely to PS-MPs exposure. Additionally, the correlation patterns between DNA and RNA modifications changed following PS-MPs exposure. These findings provide valuable insights suggesting that PS-MPs exposure may alter the patterns of epigenetic modifications in nucleic acids, potentially leading to adverse health effects.
Microplastics (MPs), which originate from plastic degradation, are becoming a significant environmental pollutant, and their prevalence is increasing rapidly. Humans can ingest MPs through various pathways and their presence has been detected in multiple human organs, raising concerns about the potential toxic effects associated with plastic consumption. Epigenetic modifications of nucleic acids play crucial roles in various biological processes, including gene expression and tumorigenesis. Previous studies have demonstrated that exposure to certain environmental pollutants can influence disease pathogenesis by affecting epigenetic factors, including modifications of nucleic acids. However, the impact of MPs on epigenetic modifications of nucleic acids remains largely unexplored. In this study, we systematically investigated the alterations in epigenetic modifications of DNA and RNA following exposure to polystyrene microplastics (PS-MPs). We utilized liquid chromatography-tandem mass spectrometry (LC-MS/MS) to simultaneously analyze two DNA epigenetic modifications of 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (5hmC), along with twenty RNA epigenetic modifications from small RNA and nine epigenetic modifications from mRNA. We measured changes in the levels of DNA and RNA modifications across six tissues (heart, liver, spleen, lung, kidney, and intestine) in mice after PS-MPs exposure. The results indicated that exposure to PS-MPs significantly altered the landscape of epigenetic modifications in nucleic acids. Furthermore, we observed tissue-specific effects, suggesting that different organs respond uniquely to PS-MPs exposure. Additionally, the correlation patterns between DNA and RNA modifications changed following PS-MPs exposure. These findings provide valuable insights suggesting that PS-MPs exposure may alter the patterns of epigenetic modifications in nucleic acids, potentially leading to adverse health effects.
2026, 37(3): 111548
doi: 10.1016/j.cclet.2025.111548
摘要:
Nanomedicine preparation is a promising approach for the effective utilization of natural bioactive products. However, the successful fortification of natural products into nanocarriers in a host-guest manner remains a great challenge. Here, a 96-WP TFH/TM strategy integrating 96-well plate mediated thin-film hydration, turbidity measurement, stability evaluation, and relative quantification, was proposed to screen host-guest complexes. As a proof-of-concept, biomimetic bile acid-lecithin nanomicelles (BA-L NMs) were used as nanocarriers and 51 natural products were assayed for guest molecules. Muscone came out as the fit-for-purpose candidate to produce stable NMs, namely M-NMs. Following spectroscopic characterization and molecular dynamics calculation, hydrophobic interactions, hydrogen bonding, and salt bridges were demonstrated as the primary correlations amongst taurocholic acid, lecithin, and muscone. M-NMs exhibited significant in vitro and in vivo anti-inflammation features. Together, we developed a 96-WP TFH/TM strategy to achieve high-throughput host-guest complex screening, facilitating the development of natural product nanomicelles.
Nanomedicine preparation is a promising approach for the effective utilization of natural bioactive products. However, the successful fortification of natural products into nanocarriers in a host-guest manner remains a great challenge. Here, a 96-WP TFH/TM strategy integrating 96-well plate mediated thin-film hydration, turbidity measurement, stability evaluation, and relative quantification, was proposed to screen host-guest complexes. As a proof-of-concept, biomimetic bile acid-lecithin nanomicelles (BA-L NMs) were used as nanocarriers and 51 natural products were assayed for guest molecules. Muscone came out as the fit-for-purpose candidate to produce stable NMs, namely M-NMs. Following spectroscopic characterization and molecular dynamics calculation, hydrophobic interactions, hydrogen bonding, and salt bridges were demonstrated as the primary correlations amongst taurocholic acid, lecithin, and muscone. M-NMs exhibited significant in vitro and in vivo anti-inflammation features. Together, we developed a 96-WP TFH/TM strategy to achieve high-throughput host-guest complex screening, facilitating the development of natural product nanomicelles.
2026, 37(3): 111554
doi: 10.1016/j.cclet.2025.111554
摘要:
In this study, two chiral cationic cage-shaped hosts were successfully self-assembled via imine condensation, achieving near-quantitative yields. Compared with the counterparts bearing a single imine bond, the intrinsic multivalency of the cage frameworks confers significant robustness to the cages, even when exposed to aqueous environments. Each cage features three relatively acidic CH protons oriented towards the interior cavity or clefts, enabling the efficient recognition of anionic guests through cooperative hydrogen bonding. The cage containing pyridinium functions adopts a pseudo face-in conformation, thus it accommodates anionic guests in its peripheral windows in a 1:2 stoichiometry. As a comparison, the cage containing imidazolium functions adopts an edge-in conformation, and thus recognizes the anions within the cavity in a 1:1 binding stoichiometry.
In this study, two chiral cationic cage-shaped hosts were successfully self-assembled via imine condensation, achieving near-quantitative yields. Compared with the counterparts bearing a single imine bond, the intrinsic multivalency of the cage frameworks confers significant robustness to the cages, even when exposed to aqueous environments. Each cage features three relatively acidic CH protons oriented towards the interior cavity or clefts, enabling the efficient recognition of anionic guests through cooperative hydrogen bonding. The cage containing pyridinium functions adopts a pseudo face-in conformation, thus it accommodates anionic guests in its peripheral windows in a 1:2 stoichiometry. As a comparison, the cage containing imidazolium functions adopts an edge-in conformation, and thus recognizes the anions within the cavity in a 1:1 binding stoichiometry.
2026, 37(3): 111566
doi: 10.1016/j.cclet.2025.111566
摘要:
Immunogenic cell death (ICD) represents a specific form of tumor cell death that has the potential to elicit a tumor-specific immune response, resulting in a systemic anti-tumor effect and providing therapeutic benefits for metastatic lesions. The extensive research in this field has led to numerous studies confirming that during the induction of ICD, tumor cells can release damage-associated molecular patterns (DAMPs), which can be used as biomarkers to predict anti-cancer efficiency. However, few ratiometric fluorescent probes have been developed to tackle this fluctuation in living cells. In this study, we present a novel ratiometric fluorescence probe based on semiconducting polymer nanoparticles (SPNs) and carbon dots (CDs) for the sensing of DAMPs fluctuation in the ICD process by choosing adenosine triphosphate as a model. In this design, the fluorescence intensity of SPNs could not be affected by the change of target, while CDs could selectively respond to target, therefore realizing the ratiometric sensing of DAMPs. The ratiometric probe was successfully applied in real-time monitoring of the fluctuating concentration of DAMPs induced by doxorubicin in living cells. These results demonstrate that the ratiometric probe may become a promising agent for predicting anti-cancer efficiency.
Immunogenic cell death (ICD) represents a specific form of tumor cell death that has the potential to elicit a tumor-specific immune response, resulting in a systemic anti-tumor effect and providing therapeutic benefits for metastatic lesions. The extensive research in this field has led to numerous studies confirming that during the induction of ICD, tumor cells can release damage-associated molecular patterns (DAMPs), which can be used as biomarkers to predict anti-cancer efficiency. However, few ratiometric fluorescent probes have been developed to tackle this fluctuation in living cells. In this study, we present a novel ratiometric fluorescence probe based on semiconducting polymer nanoparticles (SPNs) and carbon dots (CDs) for the sensing of DAMPs fluctuation in the ICD process by choosing adenosine triphosphate as a model. In this design, the fluorescence intensity of SPNs could not be affected by the change of target, while CDs could selectively respond to target, therefore realizing the ratiometric sensing of DAMPs. The ratiometric probe was successfully applied in real-time monitoring of the fluctuating concentration of DAMPs induced by doxorubicin in living cells. These results demonstrate that the ratiometric probe may become a promising agent for predicting anti-cancer efficiency.
2026, 37(3): 111569
doi: 10.1016/j.cclet.2025.111569
摘要:
Nanozymes-mediated catalytic therapy is an emerging approach for tumor treatment, but the performance of the nanozymes is limited by low enzyme catalytic efficiency, low reaction substrate concentration, and immunosuppressive features of the tumor microenvironment. Herein, a hollow gold nanorods loaded with oxygen-carrying hemoglobin (HAuHbO2) nanozyme with high enzyme catalytic efficiency is reported. In the tumor microenvironment, HAuHbO2 shows dual enzyme activities of glucose oxidase (GOD) and peroxidase (POD) for spontaneous cascade catalytic reactions to realize chemodynamic therapy (CDT). Meanwhile, it exerts excellent photothermal conversion ability for photothermal therapy (PTT). This study also reports the antitumor ability of HAuHbO2, including its mechanism of action in vivo. HAuHbO2 can induce the occurrence of immunogenic cell death (ICD) with the involvement of near-infrared light, which in turn induces the immune response of the organism. Overall, a simple, ingenious, and multifunctional nanozyme is designed in this study, which can provide a basis for applying nanozymes in antitumor therapy.
Nanozymes-mediated catalytic therapy is an emerging approach for tumor treatment, but the performance of the nanozymes is limited by low enzyme catalytic efficiency, low reaction substrate concentration, and immunosuppressive features of the tumor microenvironment. Herein, a hollow gold nanorods loaded with oxygen-carrying hemoglobin (HAuHbO2) nanozyme with high enzyme catalytic efficiency is reported. In the tumor microenvironment, HAuHbO2 shows dual enzyme activities of glucose oxidase (GOD) and peroxidase (POD) for spontaneous cascade catalytic reactions to realize chemodynamic therapy (CDT). Meanwhile, it exerts excellent photothermal conversion ability for photothermal therapy (PTT). This study also reports the antitumor ability of HAuHbO2, including its mechanism of action in vivo. HAuHbO2 can induce the occurrence of immunogenic cell death (ICD) with the involvement of near-infrared light, which in turn induces the immune response of the organism. Overall, a simple, ingenious, and multifunctional nanozyme is designed in this study, which can provide a basis for applying nanozymes in antitumor therapy.
2026, 37(3): 111598
doi: 10.1016/j.cclet.2025.111598
摘要:
The heavy biofouling on electrochemical sensor surface poses a formidable challenge for biosensing in human blood. Herein, we designed a multilayer filtering-sensing sandwich patch that served as a versatile platform to surmount the substantial fouling constraints for detection in human blood. The patch integrated two functional layers: (i) Inspired by dialysis phenomenon, a filtering-mass transfer hydrophilic membrane with heterogeneous nanostructure was used to filter large-size substances (like cells, bacteria and microorganisms, etc.) and continuously pass through the rest of the biological fluid (like proteins, metabolites and inorganic salts, etc.). (ii) the polypeptide composite hydrogel (rGO/PEPG) on the screen-printed electrode (SPE) surface, with the modulation of -COOH and -NH2 groups, endowed a strong hydrophilic layer with electric neutrality to further facilitate the antifouling ability. Notably, the integration of the filtering porous membrane with the antifouling hydrogel ensures the strong antifouling ability of the electrochemical sensor in complex human blood. Furthermore, the self-healing property of the rGO/PEPG, relying on the physical π-π stacking forces, aligns the electrochemical sensor with practical needs. The constructed antifouling biosensor based on the filtering-sensing sandwich patch was successfully applied for the sensitive detection of cortisol in human blood, with an acceptable accuracy comparable to the enzyme-linked immunosorbent assay (ELISA) method. The strategy presented herein represent a promising advance along the road to construct effective antifouling biosensing devices with robust operation in diverse complex body fluids.
The heavy biofouling on electrochemical sensor surface poses a formidable challenge for biosensing in human blood. Herein, we designed a multilayer filtering-sensing sandwich patch that served as a versatile platform to surmount the substantial fouling constraints for detection in human blood. The patch integrated two functional layers: (i) Inspired by dialysis phenomenon, a filtering-mass transfer hydrophilic membrane with heterogeneous nanostructure was used to filter large-size substances (like cells, bacteria and microorganisms, etc.) and continuously pass through the rest of the biological fluid (like proteins, metabolites and inorganic salts, etc.). (ii) the polypeptide composite hydrogel (rGO/PEPG) on the screen-printed electrode (SPE) surface, with the modulation of -COOH and -NH2 groups, endowed a strong hydrophilic layer with electric neutrality to further facilitate the antifouling ability. Notably, the integration of the filtering porous membrane with the antifouling hydrogel ensures the strong antifouling ability of the electrochemical sensor in complex human blood. Furthermore, the self-healing property of the rGO/PEPG, relying on the physical π-π stacking forces, aligns the electrochemical sensor with practical needs. The constructed antifouling biosensor based on the filtering-sensing sandwich patch was successfully applied for the sensitive detection of cortisol in human blood, with an acceptable accuracy comparable to the enzyme-linked immunosorbent assay (ELISA) method. The strategy presented herein represent a promising advance along the road to construct effective antifouling biosensing devices with robust operation in diverse complex body fluids.
2026, 37(3): 111631
doi: 10.1016/j.cclet.2025.111631
摘要:
To implement the principle of utilizing waste to address waste issues, porous carbon catalytic materials, prepared through a straightforward process involving NaOH-assisted microwave pyrolysis of ubiquitous waste plastics, were employed to degrade pollutants via peroxymonosulfate (PMS) activation. Polyethylene terephthalate (PET) derived P1S2 exhibited characteristics of defects enrichment and CO formation, while H1S2, prepared by carbonization of high-density polyethylene (HDPE), possessed a large number of COH and defects. Metal-free catalysts P1S2 and H1S2 exhibited excellent tetracycline (TC) degradation performance, with the rate constants up to 0.303 min-1 and 0.235 min-1. Interestingly, mechanism studies demonstrated that the types of waste plastic precursor had a significant impact on the pathways involved in TC degradation. Specifically, carbon defects in P1S2 dominated the electron transfer nonradial degradation pathway of TC; However, COH in H1S2 served as the reactive site for main active species SO4•−/•OH generation, initiating a free radical pathway. In addition, by combining Fukui function calculation and LC-MS test during the TC degradation process, the vulnerable sites attacked by active species were identified; different degradation routes of TC in nonradial and radial pathways were proposed and discussed. Furthermore, the toxicity of all intermediates was analyzed using the toxicity assessment software. This study offers fresh insights into the critical role of carbocatalysts derived from various waste plastics in both nonradical and radical activation processes of PMS.
To implement the principle of utilizing waste to address waste issues, porous carbon catalytic materials, prepared through a straightforward process involving NaOH-assisted microwave pyrolysis of ubiquitous waste plastics, were employed to degrade pollutants via peroxymonosulfate (PMS) activation. Polyethylene terephthalate (PET) derived P1S2 exhibited characteristics of defects enrichment and CO formation, while H1S2, prepared by carbonization of high-density polyethylene (HDPE), possessed a large number of COH and defects. Metal-free catalysts P1S2 and H1S2 exhibited excellent tetracycline (TC) degradation performance, with the rate constants up to 0.303 min-1 and 0.235 min-1. Interestingly, mechanism studies demonstrated that the types of waste plastic precursor had a significant impact on the pathways involved in TC degradation. Specifically, carbon defects in P1S2 dominated the electron transfer nonradial degradation pathway of TC; However, COH in H1S2 served as the reactive site for main active species SO4•−/•OH generation, initiating a free radical pathway. In addition, by combining Fukui function calculation and LC-MS test during the TC degradation process, the vulnerable sites attacked by active species were identified; different degradation routes of TC in nonradial and radial pathways were proposed and discussed. Furthermore, the toxicity of all intermediates was analyzed using the toxicity assessment software. This study offers fresh insights into the critical role of carbocatalysts derived from various waste plastics in both nonradical and radical activation processes of PMS.
2026, 37(3): 111693
doi: 10.1016/j.cclet.2025.111693
摘要:
Nanozymes, particularly single-atom nanozymes (SAzymes), have gained attention as potential ferroptosis inducers for cancer therapy due to their high catalytic efficiency and selectivity. However, the catalytic activity of SAzymes is often limited by the symmetrical electronic structure at their active sites. To enhance their performance, heteroatom doping strategies have been applied to modulate the electronic properties of SAzyme catalysts. In this study, we synthesized sulfur-doped FNS SAzymes with an Fe-N-S-C asymmetric coordination structure through pyrolysis. Enzyme kinetics analysis and density functional theory calculations revealed that FNS SAzymes exhibit highly efficient peroxidase-like and glutathione oxidase-like activities. These nanozymes are capable of catalyzing the decomposition of H2O2 to produce reactive oxygen species and depleting glutathione (GSH), thereby inducing ferroptosis. The FNS SAzymes were combined with an alkyl radical (•R) initiator, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIPH), and assembled into microneedle patches for enhanced ferroptosis therapy (FNSA-MN). Beyond the dual enzyme activities of FNS SAzymes, 808 nm laser activation induced a photothermal effect that facilitated the rapid dissociation of AIPH to generate •R. This FNSA-MN significantly enhanced lipid peroxidation within cells, thereby promoting ferroptosis. In vivo studies demonstrated significant suppression of tumor growth and strong anti-metastatic effects, highlighting a promising strategy for localized cancer therapy.
Nanozymes, particularly single-atom nanozymes (SAzymes), have gained attention as potential ferroptosis inducers for cancer therapy due to their high catalytic efficiency and selectivity. However, the catalytic activity of SAzymes is often limited by the symmetrical electronic structure at their active sites. To enhance their performance, heteroatom doping strategies have been applied to modulate the electronic properties of SAzyme catalysts. In this study, we synthesized sulfur-doped FNS SAzymes with an Fe-N-S-C asymmetric coordination structure through pyrolysis. Enzyme kinetics analysis and density functional theory calculations revealed that FNS SAzymes exhibit highly efficient peroxidase-like and glutathione oxidase-like activities. These nanozymes are capable of catalyzing the decomposition of H2O2 to produce reactive oxygen species and depleting glutathione (GSH), thereby inducing ferroptosis. The FNS SAzymes were combined with an alkyl radical (•R) initiator, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIPH), and assembled into microneedle patches for enhanced ferroptosis therapy (FNSA-MN). Beyond the dual enzyme activities of FNS SAzymes, 808 nm laser activation induced a photothermal effect that facilitated the rapid dissociation of AIPH to generate •R. This FNSA-MN significantly enhanced lipid peroxidation within cells, thereby promoting ferroptosis. In vivo studies demonstrated significant suppression of tumor growth and strong anti-metastatic effects, highlighting a promising strategy for localized cancer therapy.
2026, 37(3): 111863
doi: 10.1016/j.cclet.2025.111863
摘要:
Based on recently reported high-performance doubly concerted companion (DCC) dye XW96 constructed by covalently linking a porphyrin dye and an organic dye with hexyl chain protected phenothiazine and fluorenyl indoline donors, respectively, we herein employ a branched 2-ethylhexyl chain to realize better anti-charge-recombination and anti-aggregation abilities, achieving improved photovoltaic behavior. Thus, based on XW96, dye XW98 has been synthesized by introducing branched chains to the donors. As a result, the bulkier donors on both sub-dye units cause spatial repulsion, resulting in more severe twisting, decreased adsorption amount and lowered efficiency, compared to XW96. To reduce the steric hindrance, the linker between the two subdye units has been extended on the basis of XW98 (seven bonds) to give XW99 (eight bonds) and XW100 (nine bonds), affording considerably improved adsorption. Notably, XW99 affords an open-circuit voltage (VOC) of 784 mV, a short-circuit current density (JSC) of 22.08 mA/cm2, and a high power conversion efficiency (PCE) of 12.54%. Compared with XW99, dye XW100 exhibits a larger percentage of single anchoring despite its larger adsorption amount, leading to a lowered efficiency of 12.25%. This work indicates that combination of bulky branched chains on the donors with optimized linker length is essential for developing efficient DCC sensitizers.
Based on recently reported high-performance doubly concerted companion (DCC) dye XW96 constructed by covalently linking a porphyrin dye and an organic dye with hexyl chain protected phenothiazine and fluorenyl indoline donors, respectively, we herein employ a branched 2-ethylhexyl chain to realize better anti-charge-recombination and anti-aggregation abilities, achieving improved photovoltaic behavior. Thus, based on XW96, dye XW98 has been synthesized by introducing branched chains to the donors. As a result, the bulkier donors on both sub-dye units cause spatial repulsion, resulting in more severe twisting, decreased adsorption amount and lowered efficiency, compared to XW96. To reduce the steric hindrance, the linker between the two subdye units has been extended on the basis of XW98 (seven bonds) to give XW99 (eight bonds) and XW100 (nine bonds), affording considerably improved adsorption. Notably, XW99 affords an open-circuit voltage (VOC) of 784 mV, a short-circuit current density (JSC) of 22.08 mA/cm2, and a high power conversion efficiency (PCE) of 12.54%. Compared with XW99, dye XW100 exhibits a larger percentage of single anchoring despite its larger adsorption amount, leading to a lowered efficiency of 12.25%. This work indicates that combination of bulky branched chains on the donors with optimized linker length is essential for developing efficient DCC sensitizers.
2026, 37(3): 111893
doi: 10.1016/j.cclet.2025.111893
摘要:
Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.
Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.
2026, 37(3): 111916
doi: 10.1016/j.cclet.2025.111916
摘要:
Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr3+-doped Sr9Ga1-x(PO4)7 (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr9Ga0.5(PO4)7:0.5Cr3+ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr9Ga0.5(PO4)7:0.5Cr3+ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.
Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr3+-doped Sr9Ga1-x(PO4)7 (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr9Ga0.5(PO4)7:0.5Cr3+ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr9Ga0.5(PO4)7:0.5Cr3+ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.
2026, 37(3): 111921
doi: 10.1016/j.cclet.2025.111921
摘要:
Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization
Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization
2026, 37(3): 111928
doi: 10.1016/j.cclet.2025.111928
摘要:
Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.
Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.
2026, 37(3): 111947
doi: 10.1016/j.cclet.2025.111947
摘要:
Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C3F6) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO2 aerogel-embedded polyethylene oxide (PEO/SiO2 aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 µm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 ℃ under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.
Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C3F6) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO2 aerogel-embedded polyethylene oxide (PEO/SiO2 aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 µm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 ℃ under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.
2026, 37(3): 111958
doi: 10.1016/j.cclet.2025.111958
摘要:
Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO2 reduction reaction (CO2RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO2 than H2O on Pd NPs surface, and induced more CO linear configuration intermediate (*COL), indicative of ease CO2 transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FECO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FECO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO2 reduction reaction (CO2RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO2 than H2O on Pd NPs surface, and induced more CO linear configuration intermediate (*COL), indicative of ease CO2 transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FECO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FECO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
2026, 37(3): 111963
doi: 10.1016/j.cclet.2025.111963
摘要:
Given the emerging demand to “escape from flatland” for modern medicinal chemistry, both the catalytic construction of complex three-dimensional molecular architectures from planar aromatics and the bioisosteric substitution of aromatic ring with bicyclo[2.1.1]hexanes (BCHs) become increasingly valuable. Despite notable advancements in the cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) and 2π-components, the application of easily accessible aromatic compounds in these transformations, particularly in an asymmetric manner, is still relatively unexplored. Herein, we report a nickel-catalyzed enantioselective polar dearomative (3 + 2) cycloaddition of BCBs with benzazoles and indoles. This protocol offers an efficient route for the synthesis of N,S- or N,N-heterocycles decorated fused aza-BCHs bearing two quaternary carbon centers. This approach stands out for its practicality and appeal due to the utilization of easily accessible starting materials and catalysts, broad substrate scope, easy scalability, and the employment of mild reaction conditions. Density functional theory (DFT) calculations offer crucial insights into the reaction mechanism and elucidate the factors governing the enantioselectivity within the dearomative cycloaddition process.
Given the emerging demand to “escape from flatland” for modern medicinal chemistry, both the catalytic construction of complex three-dimensional molecular architectures from planar aromatics and the bioisosteric substitution of aromatic ring with bicyclo[2.1.1]hexanes (BCHs) become increasingly valuable. Despite notable advancements in the cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) and 2π-components, the application of easily accessible aromatic compounds in these transformations, particularly in an asymmetric manner, is still relatively unexplored. Herein, we report a nickel-catalyzed enantioselective polar dearomative (3 + 2) cycloaddition of BCBs with benzazoles and indoles. This protocol offers an efficient route for the synthesis of N,S- or N,N-heterocycles decorated fused aza-BCHs bearing two quaternary carbon centers. This approach stands out for its practicality and appeal due to the utilization of easily accessible starting materials and catalysts, broad substrate scope, easy scalability, and the employment of mild reaction conditions. Density functional theory (DFT) calculations offer crucial insights into the reaction mechanism and elucidate the factors governing the enantioselectivity within the dearomative cycloaddition process.
2026, 37(3): 112003
doi: 10.1016/j.cclet.2025.112003
摘要:
A novel method for carbonylation of tertiary C(sp3)–H bonds in 2-aminophenyl-alkyl methanones with CO2 has been developed, enabling the synthesis of 2,4-quinolinediones featuring quaternary carbon centres. Building on this approach, a promising iridium(Ⅲ) complex involving carbon from CO2 was designed and synthesized. This complex, exhibiting a high photoluminescent quantum yield, was successfully applied in organic light-emitting diodes (OLEDs), achieving a high maximum luminance up to 12,010 cd/m2 and a maximum external quantum efficiency (EQE) of 13.95%.
A novel method for carbonylation of tertiary C(sp3)–H bonds in 2-aminophenyl-alkyl methanones with CO2 has been developed, enabling the synthesis of 2,4-quinolinediones featuring quaternary carbon centres. Building on this approach, a promising iridium(Ⅲ) complex involving carbon from CO2 was designed and synthesized. This complex, exhibiting a high photoluminescent quantum yield, was successfully applied in organic light-emitting diodes (OLEDs), achieving a high maximum luminance up to 12,010 cd/m2 and a maximum external quantum efficiency (EQE) of 13.95%.
2026, 37(3): 112018
doi: 10.1016/j.cclet.2025.112018
摘要:
The α,β-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of γ-butyrolactones—a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of α,β-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing γ-butyrolactone moiety.
The α,β-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of γ-butyrolactones—a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of α,β-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing γ-butyrolactone moiety.
2026, 37(3): 112042
doi: 10.1016/j.cclet.2025.112042
摘要:
Organic electrochemical transistor (OECT)-based inverters hold great promise for neural-machine interfaces due to their low operating voltage and compatibility with aqueous environments. However, unbalanced p-/n-channel characteristics hinder the inverter's voltage gain and fast switching. Here, a rational inverter design is presented, leveraging ion concentration to equilibrate p-n channel conductivity and kinetic doping in the OECT inverter, achieving an extremely high gain value of over 370 V/V under optimized driving conditions. Furthermore, a 3-stage ring oscillator constructed from these ion-equilibrated OECT inverters exhibits a rapid response time (stage delay < 0.6 ms) and a broad frequency response exceeding 300 Hz, matching the mechanoreceptor signals in human skin. The biocompatible output displays a sublinear reaction to static pressure pulses, indicating successful tactile recognition in live neurons. This work presents a practical strategy for constructing neural-compatible artificial logics through ion-concentration engineering, providing a platform for seamless neural-machine integration.
Organic electrochemical transistor (OECT)-based inverters hold great promise for neural-machine interfaces due to their low operating voltage and compatibility with aqueous environments. However, unbalanced p-/n-channel characteristics hinder the inverter's voltage gain and fast switching. Here, a rational inverter design is presented, leveraging ion concentration to equilibrate p-n channel conductivity and kinetic doping in the OECT inverter, achieving an extremely high gain value of over 370 V/V under optimized driving conditions. Furthermore, a 3-stage ring oscillator constructed from these ion-equilibrated OECT inverters exhibits a rapid response time (stage delay < 0.6 ms) and a broad frequency response exceeding 300 Hz, matching the mechanoreceptor signals in human skin. The biocompatible output displays a sublinear reaction to static pressure pulses, indicating successful tactile recognition in live neurons. This work presents a practical strategy for constructing neural-compatible artificial logics through ion-concentration engineering, providing a platform for seamless neural-machine integration.
2026, 37(3): 112114
doi: 10.1016/j.cclet.2025.112114
摘要:
Supported noble‐metal catalysts often suffer from nanoparticle sintering, resulting in rapid deactivation under high‐temperature conditions. We report hierarchically porous spinel type high-entropy oxide (S-HEO) nanofibers, (CrMnFeCoMg)3O4, as robust supports for Pt nanoparticles. The porous structure (38.5 m2/g) endows thermal stability, preserving porosity after 880 ℃ calcination. The porous Pt/S-HEO-500 exhibits exceptional sinter-resistance. Under 500 ℃ calcination, Pt exhibits only a 0.2 nm growth increment, owing to the physical confinement and strong metal–support interactions. For Pt/S-HEO-500, the T50 (50% conversion temperature) for CO oxidation was merely 9 ℃ higher than that without calcination, with 100% conversion retained over 100 h of steady-state operation. These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in high-temperature applications.
Supported noble‐metal catalysts often suffer from nanoparticle sintering, resulting in rapid deactivation under high‐temperature conditions. We report hierarchically porous spinel type high-entropy oxide (S-HEO) nanofibers, (CrMnFeCoMg)3O4, as robust supports for Pt nanoparticles. The porous structure (38.5 m2/g) endows thermal stability, preserving porosity after 880 ℃ calcination. The porous Pt/S-HEO-500 exhibits exceptional sinter-resistance. Under 500 ℃ calcination, Pt exhibits only a 0.2 nm growth increment, owing to the physical confinement and strong metal–support interactions. For Pt/S-HEO-500, the T50 (50% conversion temperature) for CO oxidation was merely 9 ℃ higher than that without calcination, with 100% conversion retained over 100 h of steady-state operation. These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in high-temperature applications.
2026, 37(3): 110665
doi: 10.1016/j.cclet.2024.110665
摘要:
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) holds great promise in producing value-added chemicals, and achieving carbon neutrality. However, the efficiency of eCO2RR is often hindered by the sluggish oxygen evolution reaction (OER) at the anode. Thereby, various strategies have been developed to boost anode reaction, aiming to realize economic viability and reduce energy consumption in an eCO2RR electrolyzer. To give a comprehensive overview of anode engineering for optimizing eCO2RR, this review summarizes and discusses the cutting-edge anodic design strategies from recent research progress. They mainly include the direct substitution of OER to the value-added oxidation reaction of other small molecules, the introduction of photo/bio-assistance anodes, and the construction of metal-CO2 batteries. Furthermore, the emerging challenges and a forward-looking perspective on anode development by coupling renewable energy, sewage treatment and eCO2RR are also proposed.
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) holds great promise in producing value-added chemicals, and achieving carbon neutrality. However, the efficiency of eCO2RR is often hindered by the sluggish oxygen evolution reaction (OER) at the anode. Thereby, various strategies have been developed to boost anode reaction, aiming to realize economic viability and reduce energy consumption in an eCO2RR electrolyzer. To give a comprehensive overview of anode engineering for optimizing eCO2RR, this review summarizes and discusses the cutting-edge anodic design strategies from recent research progress. They mainly include the direct substitution of OER to the value-added oxidation reaction of other small molecules, the introduction of photo/bio-assistance anodes, and the construction of metal-CO2 batteries. Furthermore, the emerging challenges and a forward-looking perspective on anode development by coupling renewable energy, sewage treatment and eCO2RR are also proposed.
2026, 37(3): 111170
doi: 10.1016/j.cclet.2025.111170
摘要:
Peptides are increasingly favored as therapeutic agents due to their high efficacy, selectivity, and minimal side effects. However, they often face challenges related to poor stability and limited permeability through the gastrointestinal tract (GIT) and epithelia, necessitating parenteral administration. Despite this, there is a considerable demand for oral administration in clinical practice. To address the urgent clinical need for oral delivery, researchers have developed various technologies to surmount these challenges, including device-related systems, permeation enhancers (PEs), nanocarrier-based systems, and more. This review systematically explores the physiological barriers impacting peptide permeability and discusses the permeation-enhancing technologies designed to overcome them. It also reviews the oral peptide delivery systems currently available or under clinical investigation, offering insights into future developments in this field.
Peptides are increasingly favored as therapeutic agents due to their high efficacy, selectivity, and minimal side effects. However, they often face challenges related to poor stability and limited permeability through the gastrointestinal tract (GIT) and epithelia, necessitating parenteral administration. Despite this, there is a considerable demand for oral administration in clinical practice. To address the urgent clinical need for oral delivery, researchers have developed various technologies to surmount these challenges, including device-related systems, permeation enhancers (PEs), nanocarrier-based systems, and more. This review systematically explores the physiological barriers impacting peptide permeability and discusses the permeation-enhancing technologies designed to overcome them. It also reviews the oral peptide delivery systems currently available or under clinical investigation, offering insights into future developments in this field.
2026, 37(3): 111213
doi: 10.1016/j.cclet.2025.111213
摘要:
Mucosal vaccines would be game-changing for blocking pathogenic transmission, prompting protection where microorganism first enters that those intramuscular ones could not be able to achieve. The exploration of the vaccines at mucosal surfaces is gaining momentum due to the unique immune reservoir they offer in a minimally invasive manner. Nevertheless, the application of mucosal vaccines faces challenges, including barriers such as degrading enzymes, mucus interference, and clearance mechanisms. The field of mucosal vaccination is still in its early stages, and its advancement will significantly benefit from foundational inquiries into immune activation mechanisms and the innovation of delivery technologies for optimal efficacy. It is highly central to design efficient systems for mucosal vaccine development, herein, this article offers the insights towards the status, bottlenecks and solutions in this field, the intricacies of the immune response, fundamental mechanisms, applications of the delivery strategies for various forms of mucosal vaccines are explored. Collectively, this review conducts systematical analysis on biological and chemical strategies designed to augment vaccine uptake across mucosal tissues, antigen design and delivery methods strengthening vaccination efficacy, with emphasis on the emerging mRNA mucosal vaccines, offering new insights into recent advancements, trends and future scenarios, aiming to harness mucosal immunity (MI) for comprehensive protection against infections and other diseases.
Mucosal vaccines would be game-changing for blocking pathogenic transmission, prompting protection where microorganism first enters that those intramuscular ones could not be able to achieve. The exploration of the vaccines at mucosal surfaces is gaining momentum due to the unique immune reservoir they offer in a minimally invasive manner. Nevertheless, the application of mucosal vaccines faces challenges, including barriers such as degrading enzymes, mucus interference, and clearance mechanisms. The field of mucosal vaccination is still in its early stages, and its advancement will significantly benefit from foundational inquiries into immune activation mechanisms and the innovation of delivery technologies for optimal efficacy. It is highly central to design efficient systems for mucosal vaccine development, herein, this article offers the insights towards the status, bottlenecks and solutions in this field, the intricacies of the immune response, fundamental mechanisms, applications of the delivery strategies for various forms of mucosal vaccines are explored. Collectively, this review conducts systematical analysis on biological and chemical strategies designed to augment vaccine uptake across mucosal tissues, antigen design and delivery methods strengthening vaccination efficacy, with emphasis on the emerging mRNA mucosal vaccines, offering new insights into recent advancements, trends and future scenarios, aiming to harness mucosal immunity (MI) for comprehensive protection against infections and other diseases.
2026, 37(3): 111298
doi: 10.1016/j.cclet.2025.111298
摘要:
As an essential micronutrient, selenium (Se) plays crucial roles in maintaining cutaneous homeostasis through multifaceted mechanisms including redox regulation, immunomodulation, and anti-tumorigenic activity. While epidemiological and preclinical studies substantiate the therapeutic promise of Se in managing dermatological pathologies such as psoriasis, atopic dermatitis, and cutaneous malignancies, conventional Se formulations face translational challenges due to suboptimal bioavailability and dose-limiting hepatotoxicity. Recent advancements in nanobiotechnology have catalyzed the emergence of Se nanoparticles (SeNPs) as next-generation therapeutic platforms. These engineered nanostructures exhibit superior pharmacokinetic profiles characterized by enhanced epithelial permeability, stimuli-responsive drug release kinetics, and targeted biodistribution. This comprehensive review systematically examines: (1) pathophysiological barriers in dermatologic therapy; (2) Se-mediated molecular circuitry; (3) nano-enabled theranostic breakthroughs; (4) preclinical validation of SeNPs-based combinatorial regimens. By critically evaluating structure-activity relationships of various nanoformulations, we delineate a translational roadmap bridging nanomaterial design principles with clinical needs in precision dermatology. This synthesis aims to accelerate the clinical deployment of Se nanotechnology while addressing key regulatory and manufacturing challenges.
As an essential micronutrient, selenium (Se) plays crucial roles in maintaining cutaneous homeostasis through multifaceted mechanisms including redox regulation, immunomodulation, and anti-tumorigenic activity. While epidemiological and preclinical studies substantiate the therapeutic promise of Se in managing dermatological pathologies such as psoriasis, atopic dermatitis, and cutaneous malignancies, conventional Se formulations face translational challenges due to suboptimal bioavailability and dose-limiting hepatotoxicity. Recent advancements in nanobiotechnology have catalyzed the emergence of Se nanoparticles (SeNPs) as next-generation therapeutic platforms. These engineered nanostructures exhibit superior pharmacokinetic profiles characterized by enhanced epithelial permeability, stimuli-responsive drug release kinetics, and targeted biodistribution. This comprehensive review systematically examines: (1) pathophysiological barriers in dermatologic therapy; (2) Se-mediated molecular circuitry; (3) nano-enabled theranostic breakthroughs; (4) preclinical validation of SeNPs-based combinatorial regimens. By critically evaluating structure-activity relationships of various nanoformulations, we delineate a translational roadmap bridging nanomaterial design principles with clinical needs in precision dermatology. This synthesis aims to accelerate the clinical deployment of Se nanotechnology while addressing key regulatory and manufacturing challenges.
2026, 37(3): 111431
doi: 10.1016/j.cclet.2025.111431
摘要:
Sewage sludge (SS) is a by-product of wastewater treatment. Recovering resources from SS, particularly nitrogen (N) and phosphorus (P), is emerging as a crucial approach to promoting carbon neutrality within the treatment sector. This need necessitates developing methods that not only recover these vital nutrients but also mitigate the release of nitrogenous pollutants. Our review addresses the recovery of N and P from SS, aiming to reduce the dissemination of harmful nitrogen compounds into the environment. We provide a comprehensive analysis of techniques ranging from ultrasonic treatment and aerobic/anaerobic digestion to thermochemical conversion methods such as incineration, pyrolysis, and gasification. We also evaluate strategies like bio-enhanced phosphorus recovery and electrochemical methods, with the dual goal of diminishing nitrogen emissions and reclaiming phosphorus from SS. The review synthesizes advanced techniques and strategies to support emission control and resource recovery, offering a comprehensive guide for advancing SS treatment technologies.
Sewage sludge (SS) is a by-product of wastewater treatment. Recovering resources from SS, particularly nitrogen (N) and phosphorus (P), is emerging as a crucial approach to promoting carbon neutrality within the treatment sector. This need necessitates developing methods that not only recover these vital nutrients but also mitigate the release of nitrogenous pollutants. Our review addresses the recovery of N and P from SS, aiming to reduce the dissemination of harmful nitrogen compounds into the environment. We provide a comprehensive analysis of techniques ranging from ultrasonic treatment and aerobic/anaerobic digestion to thermochemical conversion methods such as incineration, pyrolysis, and gasification. We also evaluate strategies like bio-enhanced phosphorus recovery and electrochemical methods, with the dual goal of diminishing nitrogen emissions and reclaiming phosphorus from SS. The review synthesizes advanced techniques and strategies to support emission control and resource recovery, offering a comprehensive guide for advancing SS treatment technologies.
2026, 37(3): 111549
doi: 10.1016/j.cclet.2025.111549
摘要:
Residual ions introduced during catalyst synthesis can significantly impact both the structure and performance of the catalyst. Despite their crucial role, the effects of these residual ions are frequently overlooked in catalyst design and optimization. This review systematically surveys the characteristics and sources of typical residual ions in catalytic systems, including halogen anions, acidic anions, and alkali metal cations. It also examines their impact on both the supports and active metals of supported catalysts, as well as the alterations in surface, crystal structure, and chemical states of non-supported catalysts. The effects of residual ions on the performance of these catalysts in catalytic reactions such as oxidation and hydrogenation are discussed in detail. Additionally, the influence mechanism of residual ions on the catalysts is further explored, with a focus on their promotion and inhibition roles in catalytic processes, thus providing insights for the development of more efficient and durable catalysts. A summary finally provides an outlook on future approaches to advance catalyst preparation and mitigate the adverse effects of residual ions in catalysis.
Residual ions introduced during catalyst synthesis can significantly impact both the structure and performance of the catalyst. Despite their crucial role, the effects of these residual ions are frequently overlooked in catalyst design and optimization. This review systematically surveys the characteristics and sources of typical residual ions in catalytic systems, including halogen anions, acidic anions, and alkali metal cations. It also examines their impact on both the supports and active metals of supported catalysts, as well as the alterations in surface, crystal structure, and chemical states of non-supported catalysts. The effects of residual ions on the performance of these catalysts in catalytic reactions such as oxidation and hydrogenation are discussed in detail. Additionally, the influence mechanism of residual ions on the catalysts is further explored, with a focus on their promotion and inhibition roles in catalytic processes, thus providing insights for the development of more efficient and durable catalysts. A summary finally provides an outlook on future approaches to advance catalyst preparation and mitigate the adverse effects of residual ions in catalysis.
2026, 37(3): 111628
doi: 10.1016/j.cclet.2025.111628
摘要:
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by complex pathological features such as amyloid-β plaques and tau tangles. Early and accurate diagnosis is crucial for effective intervention, yet remains challenging. This review focuses on current and emerging imaging modalities used in AD detection, including positron emission tomography, single-photon emission computed tomography, magnetic resonance imaging (MRI), fluorescence imaging, photoacoustic imaging, and mass spectrometry imaging, with an emphasis on their mechanisms, advantages, and limitations. Special attention is given to the integration of nanotechnology with imaging platforms, highlighting how nanomaterials enhance diagnostic specificity, sensitivity, stability and therapeutic potential. The review also explores recent advances in multimodal imaging, artificial intelligence-assisted diagnostics, and future directions toward personalized and other non-invasive strategies for early AD diagnosis.
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by complex pathological features such as amyloid-β plaques and tau tangles. Early and accurate diagnosis is crucial for effective intervention, yet remains challenging. This review focuses on current and emerging imaging modalities used in AD detection, including positron emission tomography, single-photon emission computed tomography, magnetic resonance imaging (MRI), fluorescence imaging, photoacoustic imaging, and mass spectrometry imaging, with an emphasis on their mechanisms, advantages, and limitations. Special attention is given to the integration of nanotechnology with imaging platforms, highlighting how nanomaterials enhance diagnostic specificity, sensitivity, stability and therapeutic potential. The review also explores recent advances in multimodal imaging, artificial intelligence-assisted diagnostics, and future directions toward personalized and other non-invasive strategies for early AD diagnosis.
2026, 37(3): 111723
doi: 10.1016/j.cclet.2025.111723
摘要:
Osteoarthritis (OA), as a multifactorial degenerative joint disorder, is pathologically characterized by structural joint destruction and functional impairment, ultimately leading to chronic locomotor dysfunction. Clinically, intra-articular (IA) injection remains the preferred approach for localized OA treatment due to its advantages of high bioavailability, precise dosing, and minimal systemic side effects. However, frequent IA interventions may induce complications such as patient discomfort, pain, or even infection. Hydrogel materials, with their unique hydrophilic network structures and viscoelastic mechanical properties, are regarded as ideal joint cavity supplements and efficient drug carriers, making them a promising platform for localized therapy. This article systematically reviews recent advances in injectable hydrogel-based OA treatments. First, from a materials science perspective, it comprehensively analyzes the classification of injectable hydrogels (natural/synthetic polymers), their crosslinking mechanisms (chemical/physical/ionic), and environmental responsiveness (temperature/pH/ion triggers). Subsequently, it delves into their therapeutic potential in OA management, covering three major applications: controlled release of small-molecule drugs, cell delivery, and gene therapy. Despite the demonstrated prospects of hydrogels in OA therapy, attributed to their mechanical adaptability, biodegradability, and biocompatibility, key scientific challenges persist, particularly in maintaining IA mechanical homeostasis and long-term structural integrity. The review emphasizes that future research should focus on optimizing hydrogel architectures and enhancing delivery system functionalities to achieve sustained therapeutic efficacy in OA.
Osteoarthritis (OA), as a multifactorial degenerative joint disorder, is pathologically characterized by structural joint destruction and functional impairment, ultimately leading to chronic locomotor dysfunction. Clinically, intra-articular (IA) injection remains the preferred approach for localized OA treatment due to its advantages of high bioavailability, precise dosing, and minimal systemic side effects. However, frequent IA interventions may induce complications such as patient discomfort, pain, or even infection. Hydrogel materials, with their unique hydrophilic network structures and viscoelastic mechanical properties, are regarded as ideal joint cavity supplements and efficient drug carriers, making them a promising platform for localized therapy. This article systematically reviews recent advances in injectable hydrogel-based OA treatments. First, from a materials science perspective, it comprehensively analyzes the classification of injectable hydrogels (natural/synthetic polymers), their crosslinking mechanisms (chemical/physical/ionic), and environmental responsiveness (temperature/pH/ion triggers). Subsequently, it delves into their therapeutic potential in OA management, covering three major applications: controlled release of small-molecule drugs, cell delivery, and gene therapy. Despite the demonstrated prospects of hydrogels in OA therapy, attributed to their mechanical adaptability, biodegradability, and biocompatibility, key scientific challenges persist, particularly in maintaining IA mechanical homeostasis and long-term structural integrity. The review emphasizes that future research should focus on optimizing hydrogel architectures and enhancing delivery system functionalities to achieve sustained therapeutic efficacy in OA.
2026, 37(3): 111739
doi: 10.1016/j.cclet.2025.111739
摘要:
Organoboron compounds have garnered significant attention in the fields of organic synthesis, materials science, medicinal chemistry and fine chemicals. In the past few decades, transition metal-catalyzed C–H borylation has been developed rapidly and efficiently. In recent years, in order to explore eco-friendly, economical and efficient method for constructing C–B bond, chemists are dedicated to developing metal-free BX3-mediated borylation. In this review, we present a systematic and comprehensive overview of the borylation driven by BX3 with different directing group auxiliary in the fields of organic synthesis and boron-containing organic materials since 2010, including (1) nitrogen directed C–H borylation, (2) oxygen directed C–H borylation, (3) sulfur directed C–H borylation and (4) phosphorus directed C–H borylation. The methods of borylation processes as well as the substance scopes, limits, and mechanisms of these routes are also discussed.
Organoboron compounds have garnered significant attention in the fields of organic synthesis, materials science, medicinal chemistry and fine chemicals. In the past few decades, transition metal-catalyzed C–H borylation has been developed rapidly and efficiently. In recent years, in order to explore eco-friendly, economical and efficient method for constructing C–B bond, chemists are dedicated to developing metal-free BX3-mediated borylation. In this review, we present a systematic and comprehensive overview of the borylation driven by BX3 with different directing group auxiliary in the fields of organic synthesis and boron-containing organic materials since 2010, including (1) nitrogen directed C–H borylation, (2) oxygen directed C–H borylation, (3) sulfur directed C–H borylation and (4) phosphorus directed C–H borylation. The methods of borylation processes as well as the substance scopes, limits, and mechanisms of these routes are also discussed.
2026, 37(3): 111793
doi: 10.1016/j.cclet.2025.111793
摘要:
The asymmetric catalytic synthesis of planar chiral ferrocene derivatives has received dramatic attention in recent years. Transition metal-catalyzed asymmetric cross-coupling reactions and CH functionalization reactions have played significant roles in the stereoselective construction of planar chiral ferrocene derivatives. Transition metals such as copper, palladium, rhodium, iridium, gold, and platinum have been adopted as the effective catalysts in combination with various chiral ligands to achieve satisfactory yields and stereoselectivity. Organic catalysts have also shown great potential in the synthesis of planar chiral ferrocenes. Chiral amines and N-heterocyclic carbenes (NHCs) have been the key catalysts for facile access to multi-functional ferrocene derivatives. Some of the planar chiral ferrocene molecules obtained from the above methods have demonstrated promising applications in the development of novel ligands for asymmetric synthesis and pesticides for plant protection. This review provides an overview on the key progresses in the catalytic synthesis of planar chiral ferrocene derivatives using transition metal catalysts and organic catalysts. The merits, challenges and potential directions in the future development within this highly active research field are also discussed at the end of this review.
The asymmetric catalytic synthesis of planar chiral ferrocene derivatives has received dramatic attention in recent years. Transition metal-catalyzed asymmetric cross-coupling reactions and CH functionalization reactions have played significant roles in the stereoselective construction of planar chiral ferrocene derivatives. Transition metals such as copper, palladium, rhodium, iridium, gold, and platinum have been adopted as the effective catalysts in combination with various chiral ligands to achieve satisfactory yields and stereoselectivity. Organic catalysts have also shown great potential in the synthesis of planar chiral ferrocenes. Chiral amines and N-heterocyclic carbenes (NHCs) have been the key catalysts for facile access to multi-functional ferrocene derivatives. Some of the planar chiral ferrocene molecules obtained from the above methods have demonstrated promising applications in the development of novel ligands for asymmetric synthesis and pesticides for plant protection. This review provides an overview on the key progresses in the catalytic synthesis of planar chiral ferrocene derivatives using transition metal catalysts and organic catalysts. The merits, challenges and potential directions in the future development within this highly active research field are also discussed at the end of this review.
2026, 37(3): 111842
doi: 10.1016/j.cclet.2025.111842
摘要:
Nanozymes are nanomaterials with enzyme-like catalytic activities that have rapidly advanced in the biomedical field in recent years due to their high stability, low cost, and catalytic versatility. As promising alternatives to natural enzymes, nanozymes have demonstrated unique advantages in infection control, cancer therapy, and tissue regeneration. This review systematically summarizes key advances in recent years in nanozyme-based catalytic therapeutics. We focus on their mechanisms and applications in combating bacterial, viral, and fungal infections via membrane lipid peroxidation, protein/genome damage, and biofilm disruption; in cancer treatment through chemodynamic therapy (CDT), tumor microenvironment modulation, and multimodal synergistic strategies; and in bone regeneration through antioxidant, anti-inflammatory, and osteoinductive functions. Moreover, we highlight the integration of nanozymes with hydrogels, scaffolds, and microrobotic systems to enhance therapeutic outcomes. Finally, current challenges such as targeting specificity, in vivo catalytic control, biosafety, and clinical translation are discussed to provide a comprehensive roadmap for future research and clinical development in catalytic nanomedicine.
Nanozymes are nanomaterials with enzyme-like catalytic activities that have rapidly advanced in the biomedical field in recent years due to their high stability, low cost, and catalytic versatility. As promising alternatives to natural enzymes, nanozymes have demonstrated unique advantages in infection control, cancer therapy, and tissue regeneration. This review systematically summarizes key advances in recent years in nanozyme-based catalytic therapeutics. We focus on their mechanisms and applications in combating bacterial, viral, and fungal infections via membrane lipid peroxidation, protein/genome damage, and biofilm disruption; in cancer treatment through chemodynamic therapy (CDT), tumor microenvironment modulation, and multimodal synergistic strategies; and in bone regeneration through antioxidant, anti-inflammatory, and osteoinductive functions. Moreover, we highlight the integration of nanozymes with hydrogels, scaffolds, and microrobotic systems to enhance therapeutic outcomes. Finally, current challenges such as targeting specificity, in vivo catalytic control, biosafety, and clinical translation are discussed to provide a comprehensive roadmap for future research and clinical development in catalytic nanomedicine.
2026, 37(3): 111905
doi: 10.1016/j.cclet.2025.111905
摘要:
The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.
The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.
2026, 37(3): 111944
doi: 10.1016/j.cclet.2025.111944
摘要:
Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.
Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.
2026, 37(3): 112021
doi: 10.1016/j.cclet.2025.112021
摘要:
The hydrogen evolution reaction (HER) is a pivotal process for clean energy conversion, yet the development of efficient and cost-effective electrocatalysts remains a major challenge. Alloy catalysts, with their tunable electronic properties and promising catalytic performance, have shown great potential for HER. However, the design of component types and ratios, along with structural optimization, has largely relied on traditional trial-and-error approaches, which are very complex and time-consuming. The rise of machine learning (ML) provides an efficient strategy for discovering and optimizing alloy catalysts by enabling rapid analysis of extensive experimental and simulation datasets. This review highlights the recent advances in applying ML techniques for the design and optimization of alloy electrocatalysts for HER, covering binary and multinary (ternary, quaternary and high-entropy alloys). In particular, by employing supervised learning and deep learning techniques, ML has achieved remarkable success in the rapid screening of alloy catalysts and in improving prediction accuracy. It also demonstrates the merit and capability of ML in accelerating this process. In the end, we discuss current challenges and future prospects for integrating ML into advanced HER catalysis, highlighting its potential to revolutionize catalyst development and promote sustainable hydrogen energy solutions.
The hydrogen evolution reaction (HER) is a pivotal process for clean energy conversion, yet the development of efficient and cost-effective electrocatalysts remains a major challenge. Alloy catalysts, with their tunable electronic properties and promising catalytic performance, have shown great potential for HER. However, the design of component types and ratios, along with structural optimization, has largely relied on traditional trial-and-error approaches, which are very complex and time-consuming. The rise of machine learning (ML) provides an efficient strategy for discovering and optimizing alloy catalysts by enabling rapid analysis of extensive experimental and simulation datasets. This review highlights the recent advances in applying ML techniques for the design and optimization of alloy electrocatalysts for HER, covering binary and multinary (ternary, quaternary and high-entropy alloys). In particular, by employing supervised learning and deep learning techniques, ML has achieved remarkable success in the rapid screening of alloy catalysts and in improving prediction accuracy. It also demonstrates the merit and capability of ML in accelerating this process. In the end, we discuss current challenges and future prospects for integrating ML into advanced HER catalysis, highlighting its potential to revolutionize catalyst development and promote sustainable hydrogen energy solutions.
2026, 37(3): 112040
doi: 10.1016/j.cclet.2025.112040
摘要:
Transforming sunlight into renewable energy sources like hydrogen and methane through photocatalytic water splitting and the CO2 conversion presents a promising prospect to tackle energy scarcity and environmental pollution caused by burning fossil fuels. As the core of the photocatalytic technique, photocatalysts design is most significant for acquiring the desirable catalytic performance and target products. Photonic crystals, also denoted as inverse opals and three-dimensionally ordered macroporous materials (3DOM), have been extensively applied in photocatalytic fields due to their distinct advantages. Specifically, photonic crystal possesses slow photons effect, rich reactive sites, and well-interconnected inner channels. Among the above advantages, the slow photons effect contributes the most essential role for accelerating photocatalytic reaction. However, how to design materials with maximized slow photons effect upon specific wavelength illumination is still in the infancy. Although some reviews about 3DOM photocatalysts have been published, a critical review focusing on tunable slow photons effects for efficient photocatalysis is still lacking. In this review, we highlighted recent advances in slow photons effect in boosting solar energy conversion. Meanwhile, the relevant mechanism and fundamentals of the slow photons effect are discussed. Finally, we present our vision of the future developments and challenges in this exciting research field.
Transforming sunlight into renewable energy sources like hydrogen and methane through photocatalytic water splitting and the CO2 conversion presents a promising prospect to tackle energy scarcity and environmental pollution caused by burning fossil fuels. As the core of the photocatalytic technique, photocatalysts design is most significant for acquiring the desirable catalytic performance and target products. Photonic crystals, also denoted as inverse opals and three-dimensionally ordered macroporous materials (3DOM), have been extensively applied in photocatalytic fields due to their distinct advantages. Specifically, photonic crystal possesses slow photons effect, rich reactive sites, and well-interconnected inner channels. Among the above advantages, the slow photons effect contributes the most essential role for accelerating photocatalytic reaction. However, how to design materials with maximized slow photons effect upon specific wavelength illumination is still in the infancy. Although some reviews about 3DOM photocatalysts have been published, a critical review focusing on tunable slow photons effects for efficient photocatalysis is still lacking. In this review, we highlighted recent advances in slow photons effect in boosting solar energy conversion. Meanwhile, the relevant mechanism and fundamentals of the slow photons effect are discussed. Finally, we present our vision of the future developments and challenges in this exciting research field.
2026, 37(3): 112049
doi: 10.1016/j.cclet.2025.112049
摘要:
Essential oils (EOs) are widely present in aromatic plants and possess a wide range of significant pharmacological activities such as antibacterial, antioxidant and anti-tumor properties. They have broad application prospects in medical care, food, agriculture and other fields. However, their poor stability poses substantial challenges that significantly hinder their development and practical application. Metal-organic framework materials (MOFs), characterized by highly controllable structures, large specific surface areas, and stimuli-responsive release properties, have been extensively utilized in various fields such as drug delivery and food preservation. Due to their capacity to encapsulate and deliver EOs, MOFs have garnered considerable attention. In this review, we systematically summarize the structural features, types, and characteristics of MOFs, as well as the recent advancements in their application for controlled EO release. Furthermore, we focus on discussing engineering strategies aimed at enhancing the encapsulation, release, and delivery of EOs using MOFs. Finally, we briefly outline the existing challenges in the delivery of EOs using MOFs and present well-reasoned insights into prospective directions for future research.
Essential oils (EOs) are widely present in aromatic plants and possess a wide range of significant pharmacological activities such as antibacterial, antioxidant and anti-tumor properties. They have broad application prospects in medical care, food, agriculture and other fields. However, their poor stability poses substantial challenges that significantly hinder their development and practical application. Metal-organic framework materials (MOFs), characterized by highly controllable structures, large specific surface areas, and stimuli-responsive release properties, have been extensively utilized in various fields such as drug delivery and food preservation. Due to their capacity to encapsulate and deliver EOs, MOFs have garnered considerable attention. In this review, we systematically summarize the structural features, types, and characteristics of MOFs, as well as the recent advancements in their application for controlled EO release. Furthermore, we focus on discussing engineering strategies aimed at enhancing the encapsulation, release, and delivery of EOs using MOFs. Finally, we briefly outline the existing challenges in the delivery of EOs using MOFs and present well-reasoned insights into prospective directions for future research.
2026, 37(3): 112179
doi: 10.1016/j.cclet.2025.112179
摘要:
Electrochemical reduction of carbon dioxide (CO2RR) into formate and related products is a crucial strategy for sustainable carbon utilization, yet the development of catalysts with both high efficiency and durability remains a central challenge. Among available candidates, two-dimensional (2D) bismuth (Bi) nanosheets stand out because of their earth abundance, low toxicity, and unique ability to stabilize *OCHO intermediates. In this review, we systematically summarize recent advances in the controlled synthesis of 2D Bi nanosheets, covering bottom-up chemical and electrochemical routes, top-down exfoliation, and physical/thermal methods, and highlight the application strategies that enable performance optimization, including defect/strain engineering, heteroatom doping, interface construction, heterostructure coupling, in situ reconstruction, and microenvironment regulation. We further integrate mechanistic insights from in situ/operando characterizations and density functional theory, which clarify the real active sites, dynamic reconstruction, and structure–activity relationships. Finally, we provide a forward-looking perspective on atomic-level structural control, understanding and regulating reconstruction, multi-scale architecture integration, expanding product selectivity beyond formate, device-level optimization, and data-driven catalyst discovery. By bridging synthesis, application strategies, and mechanistic understanding, this timely review establishes a comprehensive framework to guide the rational design of 2D Bi nanosheets and accelerate their translation toward industrially relevant CO2 electroreduction.
Electrochemical reduction of carbon dioxide (CO2RR) into formate and related products is a crucial strategy for sustainable carbon utilization, yet the development of catalysts with both high efficiency and durability remains a central challenge. Among available candidates, two-dimensional (2D) bismuth (Bi) nanosheets stand out because of their earth abundance, low toxicity, and unique ability to stabilize *OCHO intermediates. In this review, we systematically summarize recent advances in the controlled synthesis of 2D Bi nanosheets, covering bottom-up chemical and electrochemical routes, top-down exfoliation, and physical/thermal methods, and highlight the application strategies that enable performance optimization, including defect/strain engineering, heteroatom doping, interface construction, heterostructure coupling, in situ reconstruction, and microenvironment regulation. We further integrate mechanistic insights from in situ/operando characterizations and density functional theory, which clarify the real active sites, dynamic reconstruction, and structure–activity relationships. Finally, we provide a forward-looking perspective on atomic-level structural control, understanding and regulating reconstruction, multi-scale architecture integration, expanding product selectivity beyond formate, device-level optimization, and data-driven catalyst discovery. By bridging synthesis, application strategies, and mechanistic understanding, this timely review establishes a comprehensive framework to guide the rational design of 2D Bi nanosheets and accelerate their translation toward industrially relevant CO2 electroreduction.
2026, 37(3): 112181
doi: 10.1016/j.cclet.2025.112181
摘要:
Porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), aerogels, and porous metal oxides, have been extensively explored as versatile platforms for energy conversion, storage, and environmental applications. Over the past five years, remarkable advances have been achieved in the design, synthesis, and functional optimization of these materials, opening new opportunities for practical implementation. In this roadmap, we focus on several key subtopics, including MOFs and COFs for supercapacitors and batteries, electrocatalysis and photocatalysis, heterojunction materials for charge separation, advanced electrocatalysts and photocatalysts based on aerogels, carbon aerogels for environmental remediation, and porous metal oxide nanomaterials for electrocatalysis. The current status, challenges, and opportunities in these areas are systematically summarized. Special attention is given to mechanistic insights, stability enhancement, conductivity improvement, and scalable fabrication strategies that are essential for bridging fundamental research and real-world applications. We believe this roadmap will provide valuable suggestions and updated knowledge for researchers, and offer useful inspiration to accelerate the development of porous materials for sustainable energy and environmental technologies toward 2030.
Porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), aerogels, and porous metal oxides, have been extensively explored as versatile platforms for energy conversion, storage, and environmental applications. Over the past five years, remarkable advances have been achieved in the design, synthesis, and functional optimization of these materials, opening new opportunities for practical implementation. In this roadmap, we focus on several key subtopics, including MOFs and COFs for supercapacitors and batteries, electrocatalysis and photocatalysis, heterojunction materials for charge separation, advanced electrocatalysts and photocatalysts based on aerogels, carbon aerogels for environmental remediation, and porous metal oxide nanomaterials for electrocatalysis. The current status, challenges, and opportunities in these areas are systematically summarized. Special attention is given to mechanistic insights, stability enhancement, conductivity improvement, and scalable fabrication strategies that are essential for bridging fundamental research and real-world applications. We believe this roadmap will provide valuable suggestions and updated knowledge for researchers, and offer useful inspiration to accelerate the development of porous materials for sustainable energy and environmental technologies toward 2030.
2026, 37(3): 112242
doi: 10.1016/j.cclet.2025.112242
摘要:
Two-dimensional (2D) materials have rapidly emerged as transformative platforms for energy storage and conversion, owing to their atomic-scale thickness, tunable electronic structures, and versatile chemical functionalities. Over the past five years, remarkable advances in material synthesis, interface engineering, and device integration have unlocked new opportunities, yet challenges in stability, scalability, and performance optimization remain. In this roadmap, we provide an updated perspective toward 2030, systematically reviewing eleven representative 2D material classes, which can be broadly grouped into carbon-based materials, inorganic semiconductors, framework materials, and layered nanosheet systems. Their opportunities and challenges in electrochemical energy storage, photocatalysis, and electrocatalysis are highlighted. We believe this roadmap can enrich the development of 2D materials for sustainable energy technologies, and provide useful guidance for both fundamental studies and practical applications in the coming decade.
Two-dimensional (2D) materials have rapidly emerged as transformative platforms for energy storage and conversion, owing to their atomic-scale thickness, tunable electronic structures, and versatile chemical functionalities. Over the past five years, remarkable advances in material synthesis, interface engineering, and device integration have unlocked new opportunities, yet challenges in stability, scalability, and performance optimization remain. In this roadmap, we provide an updated perspective toward 2030, systematically reviewing eleven representative 2D material classes, which can be broadly grouped into carbon-based materials, inorganic semiconductors, framework materials, and layered nanosheet systems. Their opportunities and challenges in electrochemical energy storage, photocatalysis, and electrocatalysis are highlighted. We believe this roadmap can enrich the development of 2D materials for sustainable energy technologies, and provide useful guidance for both fundamental studies and practical applications in the coming decade.
2026, 37(3): 112243
doi: 10.1016/j.cclet.2025.112243
摘要:
This review comprehensively summarizes the latest advancements in the synthesis and multifaceted applications of metal-organic frameworks (MOFs) for clean water. It systematically explores scalable synthesis methods, from solvothermal to green mechanochemical routes, and highlights the innovative transformation of waste into high-value MOFs. The article delves into the diverse functionalities of MOFs in water remediation, including the adsorptive and catalytic removal of heavy metals, organic pollutants, pharmaceuticals, PFASs, and micro/nano-plastics. Applications in sensing, radionuclide separation, oil-water separation, and advanced membrane technologies are also detailed. Furthermore, emerging roles in water capture, algal inhibition and resource recovery are discussed. Finally, the review provides a critical perspective on future challenges and opportunities, emphasizing sustainable synthesis, life-cycle assessment, and the integration of AI for the intelligent design of next-generation MOFs, paving the way for their transition from laboratory research to real-world water treatment solutions.
This review comprehensively summarizes the latest advancements in the synthesis and multifaceted applications of metal-organic frameworks (MOFs) for clean water. It systematically explores scalable synthesis methods, from solvothermal to green mechanochemical routes, and highlights the innovative transformation of waste into high-value MOFs. The article delves into the diverse functionalities of MOFs in water remediation, including the adsorptive and catalytic removal of heavy metals, organic pollutants, pharmaceuticals, PFASs, and micro/nano-plastics. Applications in sensing, radionuclide separation, oil-water separation, and advanced membrane technologies are also detailed. Furthermore, emerging roles in water capture, algal inhibition and resource recovery are discussed. Finally, the review provides a critical perspective on future challenges and opportunities, emphasizing sustainable synthesis, life-cycle assessment, and the integration of AI for the intelligent design of next-generation MOFs, paving the way for their transition from laboratory research to real-world water treatment solutions.
2026, 37(3): 112037
doi: 10.1016/j.cclet.2025.112037
摘要:
2026, 37(3): 112132
doi: 10.1016/j.cclet.2025.112132
摘要:
2026, 37(1): 110064
doi: 10.1016/j.cclet.2024.110064
摘要:
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
2026, 37(1): 110071
doi: 10.1016/j.cclet.2024.110071
摘要:
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
2026, 37(1): 110414
doi: 10.1016/j.cclet.2024.110414
摘要:
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
2026, 37(1): 110572
doi: 10.1016/j.cclet.2024.110572
摘要:
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
2026, 37(1): 110576
doi: 10.1016/j.cclet.2024.110576
摘要:
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
2026, 37(1): 110752
doi: 10.1016/j.cclet.2024.110752
摘要:
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
2026, 37(1): 110903
doi: 10.1016/j.cclet.2025.110903
摘要:
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
2026, 37(1): 110919
doi: 10.1016/j.cclet.2025.110919
摘要:
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
2026, 37(1): 110956
doi: 10.1016/j.cclet.2025.110956
摘要:
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
2026, 37(1): 110959
doi: 10.1016/j.cclet.2025.110959
摘要:
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
2026, 37(1): 110964
doi: 10.1016/j.cclet.2025.110964
摘要:
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
2026, 37(1): 110966
doi: 10.1016/j.cclet.2025.110966
摘要:
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
2026, 37(1): 110970
doi: 10.1016/j.cclet.2025.110970
摘要:
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
2026, 37(1): 110971
doi: 10.1016/j.cclet.2025.110971
摘要:
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
2026, 37(1): 110979
doi: 10.1016/j.cclet.2025.110979
摘要:
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
2026, 37(1): 110981
doi: 10.1016/j.cclet.2025.110981
摘要:
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
2026, 37(1): 111042
doi: 10.1016/j.cclet.2025.111042
摘要:
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
2026, 37(1): 111072
doi: 10.1016/j.cclet.2025.111072
摘要:
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
2026, 37(1): 111082
doi: 10.1016/j.cclet.2025.111082
摘要:
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
2026, 37(1): 111085
doi: 10.1016/j.cclet.2025.111085
摘要:
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
2026, 37(1): 111095
doi: 10.1016/j.cclet.2025.111095
摘要:
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
2026, 37(1): 111116
doi: 10.1016/j.cclet.2025.111116
摘要:
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
2026, 37(1): 111131
doi: 10.1016/j.cclet.2025.111131
摘要:
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
2026, 37(1): 111132
doi: 10.1016/j.cclet.2025.111132
摘要:
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
2026, 37(1): 111134
doi: 10.1016/j.cclet.2025.111134
摘要:
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
2026, 37(1): 111142
doi: 10.1016/j.cclet.2025.111142
摘要:
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
2026, 37(1): 111146
doi: 10.1016/j.cclet.2025.111146
摘要:
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
2026, 37(1): 111147
doi: 10.1016/j.cclet.2025.111147
摘要:
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
2026, 37(1): 111153
doi: 10.1016/j.cclet.2025.111153
摘要:
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
2026, 37(1): 111154
doi: 10.1016/j.cclet.2025.111154
摘要:
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
2026, 37(1): 111165
doi: 10.1016/j.cclet.2025.111165
摘要:
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
2026, 37(1): 111168
doi: 10.1016/j.cclet.2025.111168
摘要:
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
2026, 37(1): 111177
doi: 10.1016/j.cclet.2025.111177
摘要:
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
2026, 37(1): 111184
doi: 10.1016/j.cclet.2025.111184
摘要:
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
2026, 37(1): 111186
doi: 10.1016/j.cclet.2025.111186
摘要:
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
2026, 37(1): 111187
doi: 10.1016/j.cclet.2025.111187
摘要:
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
2026, 37(1): 111197
doi: 10.1016/j.cclet.2025.111197
摘要:
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
2026, 37(1): 111207
doi: 10.1016/j.cclet.2025.111207
摘要:
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
2026, 37(1): 111219
doi: 10.1016/j.cclet.2025.111219
摘要:
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
2026, 37(1): 111222
doi: 10.1016/j.cclet.2025.111222
摘要:
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
2026, 37(1): 111237
doi: 10.1016/j.cclet.2025.111237
摘要:
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
2026, 37(1): 111251
doi: 10.1016/j.cclet.2025.111251
摘要:
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
2026, 37(1): 111252
doi: 10.1016/j.cclet.2025.111252
摘要:
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
2026, 37(1): 111253
doi: 10.1016/j.cclet.2025.111253
摘要:
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
2026, 37(1): 111260
doi: 10.1016/j.cclet.2025.111260
摘要:
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Beyond superhalogen assembly: Field-driven hyperhalogen design via dual-external-field cooperativity
2026, 37(1): 111265
doi: 10.1016/j.cclet.2025.111265
摘要:
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
2026, 37(1): 111270
doi: 10.1016/j.cclet.2025.111270
摘要:
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
2026, 37(1): 111283
doi: 10.1016/j.cclet.2025.111283
摘要:
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
2026, 37(1): 111307
doi: 10.1016/j.cclet.2025.111307
摘要:
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
2026, 37(1): 111308
doi: 10.1016/j.cclet.2025.111308
摘要:
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
2026, 37(1): 111321
doi: 10.1016/j.cclet.2025.111321
摘要:
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
2026, 37(1): 111353
doi: 10.1016/j.cclet.2025.111353
摘要:
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
2026, 37(1): 111385
doi: 10.1016/j.cclet.2025.111385
摘要:
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
2026, 37(1): 111415
doi: 10.1016/j.cclet.2025.111415
摘要:
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
2026, 37(1): 111425
doi: 10.1016/j.cclet.2025.111425
摘要:
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
2026, 37(1): 111450
doi: 10.1016/j.cclet.2025.111450
摘要:
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
2026, 37(1): 111458
doi: 10.1016/j.cclet.2025.111458
摘要:
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
2026, 37(1): 111476
doi: 10.1016/j.cclet.2025.111476
摘要:
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
2026, 37(1): 111486
doi: 10.1016/j.cclet.2025.111486
摘要:
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
2026, 37(1): 111500
doi: 10.1016/j.cclet.2025.111500
摘要:
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
2026, 37(1): 111520
doi: 10.1016/j.cclet.2025.111520
摘要:
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
2026, 37(1): 111551
doi: 10.1016/j.cclet.2025.111551
摘要:
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
2026, 37(1): 111582
doi: 10.1016/j.cclet.2025.111582
摘要:
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
2026, 37(1): 111609
doi: 10.1016/j.cclet.2025.111609
摘要:
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
2026, 37(1): 111622
doi: 10.1016/j.cclet.2025.111622
摘要:
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
2026, 37(1): 111623
doi: 10.1016/j.cclet.2025.111623
摘要:
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
2026, 37(1): 111659
doi: 10.1016/j.cclet.2025.111659
摘要:
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
2026, 37(1): 111660
doi: 10.1016/j.cclet.2025.111660
摘要:
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
2026, 37(1): 111679
doi: 10.1016/j.cclet.2025.111679
摘要:
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
2026, 37(1): 111721
doi: 10.1016/j.cclet.2025.111721
摘要:
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
2026, 37(1): 111724
doi: 10.1016/j.cclet.2025.111724
摘要:
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
2026, 37(1): 111736
doi: 10.1016/j.cclet.2025.111736
摘要:
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
2026, 37(1): 111740
doi: 10.1016/j.cclet.2025.111740
摘要:
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
2026, 37(1): 111741
doi: 10.1016/j.cclet.2025.111741
摘要:
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
2026, 37(1): 111756
doi: 10.1016/j.cclet.2025.111756
摘要:
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
2026, 37(1): 111779
doi: 10.1016/j.cclet.2025.111779
摘要:
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
2026, 37(1): 111787
doi: 10.1016/j.cclet.2025.111787
摘要:
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
2026, 37(1): 111804
doi: 10.1016/j.cclet.2025.111804
摘要:
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
2026, 37(1): 111806
doi: 10.1016/j.cclet.2025.111806
摘要:
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
2026, 37(1): 111826
doi: 10.1016/j.cclet.2025.111826
摘要:
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
2026, 37(1): 111926
doi: 10.1016/j.cclet.2025.111926
摘要:
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
2026, 37(1): 111930
doi: 10.1016/j.cclet.2025.111930
摘要:
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
2026, 37(1): 110967
doi: 10.1016/j.cclet.2025.110967
摘要:
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
2026, 37(1): 111120
doi: 10.1016/j.cclet.2025.111120
摘要:
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
2026, 37(1): 111183
doi: 10.1016/j.cclet.2025.111183
摘要:
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
2026, 37(1): 111232
doi: 10.1016/j.cclet.2025.111232
摘要:
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
2026, 37(1): 111249
doi: 10.1016/j.cclet.2025.111249
摘要:
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
2026, 37(1): 111273
doi: 10.1016/j.cclet.2025.111273
摘要:
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
2026, 37(1): 111512
doi: 10.1016/j.cclet.2025.111512
摘要:
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
2026, 37(1): 111513
doi: 10.1016/j.cclet.2025.111513
摘要:
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
2026, 37(1): 111524
doi: 10.1016/j.cclet.2025.111524
摘要:
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
2026, 37(1): 111543
doi: 10.1016/j.cclet.2025.111543
摘要:
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
2026, 37(1): 111545
doi: 10.1016/j.cclet.2025.111545
摘要:
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
2026, 37(1): 111596
doi: 10.1016/j.cclet.2025.111596
摘要:
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
2026, 37(1): 111604
doi: 10.1016/j.cclet.2025.111604
摘要:
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
2026, 37(1): 111661
doi: 10.1016/j.cclet.2025.111661
摘要:
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
2026, 37(1): 111673
doi: 10.1016/j.cclet.2025.111673
摘要:
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
2026, 37(1): 111886
doi: 10.1016/j.cclet.2025.111886
摘要:
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
2026, 37(1): 111894
doi: 10.1016/j.cclet.2025.111894
摘要:
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
2026, 37(1): 111638
doi: 10.1016/j.cclet.2025.111638
摘要:
2026, 37(1): 111796
doi: 10.1016/j.cclet.2025.111796
摘要:
