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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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期刊内热点文章
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
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Development of electron and hole selective contact materials for perovskite solar cells
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
期刊内下载排行
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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(7): 110975
doi: 10.1016/j.cclet.2025.110975
摘要:
Synthesis of pseudo-mono-coordinate dysprosium(Ⅲ) single-molecule magnets (SMMs) with strong axiality is challenging. Here, by using very basic alkoxides as axial ligands and ether type neutral ligands as ancillary parts two targeted complexes, [Dy(OtBu)(15-C-5)(THF)2][I3]2 1 and [Dy(1-AdO)(15-C-5)(THF)2][I3]2 2 were successfully isolated. Structurally they possess very short Dy–Oalkoxide bonds (2.016(4) Å for 1 and 2.028(3) Å for 2) and very long Dy–Oether bonds (ranging from 2.427(4) Å to 2.523(4) Å for 1 and 2.416(3) Å to 2.509(3) Å for 2). As such, they are very similar to the diatomic model complex [DyO]+and can be magnetically perceived as pseudo-mono-coordinate Dy(Ⅲ) complexes. Both 1 and 2 exhibit high effective magnetic anisotropy barriers (1054(6) K for 1 and 1028(9) K for 2). Consequently, both 1 and 2 demonstrate high opening hysteresis temperatures, namely 14 K for 1 and 10 K for 2. This study provides a new insight into of pseudo-mono-coordinate mode and further emphasizes the excellent potential of this model for constructing high-performance SMMs.
Synthesis of pseudo-mono-coordinate dysprosium(Ⅲ) single-molecule magnets (SMMs) with strong axiality is challenging. Here, by using very basic alkoxides as axial ligands and ether type neutral ligands as ancillary parts two targeted complexes, [Dy(OtBu)(15-C-5)(THF)2][I3]2 1 and [Dy(1-AdO)(15-C-5)(THF)2][I3]2 2 were successfully isolated. Structurally they possess very short Dy–Oalkoxide bonds (2.016(4) Å for 1 and 2.028(3) Å for 2) and very long Dy–Oether bonds (ranging from 2.427(4) Å to 2.523(4) Å for 1 and 2.416(3) Å to 2.509(3) Å for 2). As such, they are very similar to the diatomic model complex [DyO]+and can be magnetically perceived as pseudo-mono-coordinate Dy(Ⅲ) complexes. Both 1 and 2 exhibit high effective magnetic anisotropy barriers (1054(6) K for 1 and 1028(9) K for 2). Consequently, both 1 and 2 demonstrate high opening hysteresis temperatures, namely 14 K for 1 and 10 K for 2. This study provides a new insight into of pseudo-mono-coordinate mode and further emphasizes the excellent potential of this model for constructing high-performance SMMs.
2026, 37(7): 111037
doi: 10.1016/j.cclet.2025.111037
摘要:
The design and exploitation of high-property cathode materials and the exploration of their energy storage mechanism have always been research hotspots in the area of zinc-ion hybrid capacitors (ZHCs). In this study, the new RuO2 nanodots/reduced graphene oxide (RuO2 NDs/rGO) composite is designed, and employed as a cathode for ZHC for the first time. Thanks to the synergism of nanoscale design and composite engineering, the RuO2 NDs/rGO//Zn ZHC delivers large specific capacitance (169.5 mAh/g at 0.1 A/g), splendid rate property (74.4 mAh/g at 20 A/g), eminent cyclic property (up to 10,000 cycles), and high energy and power densities (101.7 Wh/kg and 12 kW/kg). Furthermore, systematic kinetic analyses are used to confirm the rapid ion transport kinetics of the RuO2 NDs/rGO//Zn ZHC. More importantly, systematic ex-situ measurements are employed to illustrate its energy storage mechanism of the coexistence of electric double-layer capacitance (physical adsorption/desorption of SO42-) and pseudocapacitance (insertion/extraction of Zn2+ and H+ and chemical adsorption/desorption between Zn2+ and oxygen-containing functional groups). This study not only offers a good strategy for the design and exploitation of high-performance pseudocapacitive cathode for ZHCs, but also proposes an insight into energy storage mechanism of RuO2-based pseudocapacitive cathode.
The design and exploitation of high-property cathode materials and the exploration of their energy storage mechanism have always been research hotspots in the area of zinc-ion hybrid capacitors (ZHCs). In this study, the new RuO2 nanodots/reduced graphene oxide (RuO2 NDs/rGO) composite is designed, and employed as a cathode for ZHC for the first time. Thanks to the synergism of nanoscale design and composite engineering, the RuO2 NDs/rGO//Zn ZHC delivers large specific capacitance (169.5 mAh/g at 0.1 A/g), splendid rate property (74.4 mAh/g at 20 A/g), eminent cyclic property (up to 10,000 cycles), and high energy and power densities (101.7 Wh/kg and 12 kW/kg). Furthermore, systematic kinetic analyses are used to confirm the rapid ion transport kinetics of the RuO2 NDs/rGO//Zn ZHC. More importantly, systematic ex-situ measurements are employed to illustrate its energy storage mechanism of the coexistence of electric double-layer capacitance (physical adsorption/desorption of SO42-) and pseudocapacitance (insertion/extraction of Zn2+ and H+ and chemical adsorption/desorption between Zn2+ and oxygen-containing functional groups). This study not only offers a good strategy for the design and exploitation of high-performance pseudocapacitive cathode for ZHCs, but also proposes an insight into energy storage mechanism of RuO2-based pseudocapacitive cathode.
2026, 37(7): 111079
doi: 10.1016/j.cclet.2025.111079
摘要:
Ni-rich layered oxides are regarded as one of the most reliable cathode materials for lithium-ion batteries. Modifying the crystal structure through doping with foreign elements and constructing surface coating layers are common modification methods for Ni-rich cathode materials. However, the relationship between the diffusion depth and distribution behavior of foreign elements within the cathode material and the composition of the cathode material has rarely been studied in depth. In this work, by exploring the relationship between element concentration and position in a specially prepared two-substances diffusion couple, the diffusion coefficients between Zr4+ and transition metal elements TMn+ (TM = Ni, Co, Mn; n = 3, 4) were obtained. It was found that the magnitude relationship of their diffusion coefficients is: Zr4+/Mn4+ > Zr4+/Mn3+ > Zr4+/Co3+ > Zr4+/Ni3+. Moreover, through the Arrhenius equation, it was determined that the Zr4+/Mn4+ diffusion couple has the smallest diffusion activation energy of only 0.43 eV, while the Zr4+/Ni3+ diffusion couple has the largest diffusion activation energy, which is 0.63 eV. In addition, this study designed a specific core-shell structure model based on the microscopic morphology of the prepared cathode precursor particles, accurately predicting the distribution differences of Zr4+ in cathode materials with different compositions during the actual sintering process. This work explains the reason for the formation of a Li2ZrO3 secondary phase coating layer on the surface of Ni-rich cathode material particles from the perspective of diffusion kinetics, providing a strong theoretical basis for the future design of high-performance element-modified Ni-rich cathode materials.
Ni-rich layered oxides are regarded as one of the most reliable cathode materials for lithium-ion batteries. Modifying the crystal structure through doping with foreign elements and constructing surface coating layers are common modification methods for Ni-rich cathode materials. However, the relationship between the diffusion depth and distribution behavior of foreign elements within the cathode material and the composition of the cathode material has rarely been studied in depth. In this work, by exploring the relationship between element concentration and position in a specially prepared two-substances diffusion couple, the diffusion coefficients between Zr4+ and transition metal elements TMn+ (TM = Ni, Co, Mn; n = 3, 4) were obtained. It was found that the magnitude relationship of their diffusion coefficients is: Zr4+/Mn4+ > Zr4+/Mn3+ > Zr4+/Co3+ > Zr4+/Ni3+. Moreover, through the Arrhenius equation, it was determined that the Zr4+/Mn4+ diffusion couple has the smallest diffusion activation energy of only 0.43 eV, while the Zr4+/Ni3+ diffusion couple has the largest diffusion activation energy, which is 0.63 eV. In addition, this study designed a specific core-shell structure model based on the microscopic morphology of the prepared cathode precursor particles, accurately predicting the distribution differences of Zr4+ in cathode materials with different compositions during the actual sintering process. This work explains the reason for the formation of a Li2ZrO3 secondary phase coating layer on the surface of Ni-rich cathode material particles from the perspective of diffusion kinetics, providing a strong theoretical basis for the future design of high-performance element-modified Ni-rich cathode materials.
2026, 37(7): 111080
doi: 10.1016/j.cclet.2025.111080
摘要:
The direct utilization of magnesium (Mg) metal as the anode of Mg batteries is significantly susceptible to passivation in conventional electrolytes, which critically hinders Mg plating and stripping. To address this issue, a synergistic effect of the three-dimensional (3D) scaffolds’ dispersive current strategy and the gradient conductivity artificial layer effectively promotes internal reversible Mg plating and stripping. In this study, we have synthesized 3D magnesiophilic gradient conductivity scaffolds (Sn@Ni), featuring an electronic insulation layer, uniform Mg2+ transport channels, and a high specific surface area, through in situ ion-exchange reactions. It is observed that the plate-like metal chloride insulation provides the necessary potential gradient to prevent electrolyte decomposition and Mg deposition on the surface. Furthermore, the magnesiophilic metal tin (Sn) effectively lowers the nucleation barrier of Mg, enhancing the uniform diffusion of Mg. Additionally, the high specific surface area of the nickel foam skeleton effectively mitigates current density and regulates Mg deposition behavior. As a result, the Sn@Ni 3D gradient conductivity scaffolds exhibit an exceptionally low Mg nucleation overpotential (52 mV) under 500 μA/cm2. Moreover, the Sn@Ni-Mg gradient conductivity anode, produced by plating Mg onto Sn@Ni, demonstrates a symmetric cell capable of sustaining an ultra-long stable reversible cycle exceeding 2800 h (5300 cycles). Full cells with Mo6S8 cathode also show an impressive capacity retention of 95.6% after 500 cycles at 1 C. This breakthrough provides a novel approach to anode design, presenting potential advancements for next-generation Mg batteries.
The direct utilization of magnesium (Mg) metal as the anode of Mg batteries is significantly susceptible to passivation in conventional electrolytes, which critically hinders Mg plating and stripping. To address this issue, a synergistic effect of the three-dimensional (3D) scaffolds’ dispersive current strategy and the gradient conductivity artificial layer effectively promotes internal reversible Mg plating and stripping. In this study, we have synthesized 3D magnesiophilic gradient conductivity scaffolds (Sn@Ni), featuring an electronic insulation layer, uniform Mg2+ transport channels, and a high specific surface area, through in situ ion-exchange reactions. It is observed that the plate-like metal chloride insulation provides the necessary potential gradient to prevent electrolyte decomposition and Mg deposition on the surface. Furthermore, the magnesiophilic metal tin (Sn) effectively lowers the nucleation barrier of Mg, enhancing the uniform diffusion of Mg. Additionally, the high specific surface area of the nickel foam skeleton effectively mitigates current density and regulates Mg deposition behavior. As a result, the Sn@Ni 3D gradient conductivity scaffolds exhibit an exceptionally low Mg nucleation overpotential (52 mV) under 500 μA/cm2. Moreover, the Sn@Ni-Mg gradient conductivity anode, produced by plating Mg onto Sn@Ni, demonstrates a symmetric cell capable of sustaining an ultra-long stable reversible cycle exceeding 2800 h (5300 cycles). Full cells with Mo6S8 cathode also show an impressive capacity retention of 95.6% after 500 cycles at 1 C. This breakthrough provides a novel approach to anode design, presenting potential advancements for next-generation Mg batteries.
2026, 37(7): 111081
doi: 10.1016/j.cclet.2025.111081
摘要:
perovskite solar cells have attained exceptional power conversion efficiencies, offering a robust material foundation and device design process for the future of photovoltaics. In addition to optimizing perovskite materials for charge-related properties, it is essential to consider spin-related characteristics, as these could prove to be a pivotal factor in enhancing the photoelectric conversion efficiency. In this study, perovskite solar cells featuring various perovskite/transport layer interfaces were engineered to investigate the interfacial spin polarization’s impact on charge extraction. The intensity of charge extraction correlates directly with the interfacial spin polarization. By applying an external electric field, the interfacial spin polarization can be further amplified, thereby enhancing charge extraction. This amplified charge extraction, resulting from increased interfacial spin polarization, can substantially boost the overall photocurrent, thus enabling a high power conversion efficiency.
perovskite solar cells have attained exceptional power conversion efficiencies, offering a robust material foundation and device design process for the future of photovoltaics. In addition to optimizing perovskite materials for charge-related properties, it is essential to consider spin-related characteristics, as these could prove to be a pivotal factor in enhancing the photoelectric conversion efficiency. In this study, perovskite solar cells featuring various perovskite/transport layer interfaces were engineered to investigate the interfacial spin polarization’s impact on charge extraction. The intensity of charge extraction correlates directly with the interfacial spin polarization. By applying an external electric field, the interfacial spin polarization can be further amplified, thereby enhancing charge extraction. This amplified charge extraction, resulting from increased interfacial spin polarization, can substantially boost the overall photocurrent, thus enabling a high power conversion efficiency.
2026, 37(7): 111083
doi: 10.1016/j.cclet.2025.111083
摘要:
As an indispensable subset of functional materials, quadratic nonlinear optical (NLO) switches have garnered increasing attention owing to their vast potential in next-generation intelligent optoelectronic devices. Despite considerable progress in NLO switches based on solid-state phase transitions, identifying an effective strategy to design high-efficiency NLO switches remains a huge challenge. Herein, we present a molecular engineering approach to develop a high-efficiency lead halide organic-inorganic hybrid NLO switch, (C8H12N)2Pb2Cl6·H2O (NMPTPC). Through the substitution of hydrogen with a methyl group (-CH3) in protonated N-methylaniline, the initial compound (C7H10N)2Pb2Cl6·H2O (NMAPC) transformed into NMPTPC retaining the original space group, which gives rise to a dramatic enhancement of second harmonic generation (SHG) and phase transition temperature. As expected, NMPTPC exhibits high-efficiency modulation of the SHG property (2.6 times that of KH2PO4) and a high phase transition temperature of 372 K. Notably, NMPTPC exhibits a remarkable temperature-dependent SHG behavior, with an impressive "ON/OFF" ratio of approximately 70, underscoring its significant potential as a high-efficient solid-state NLO switch. Based on in-depth crystal structure analysis and theoretical calculations, the modulation of the NLO property is attributed to the asymmetric distortion of the [PbCl6]4− octahedra coupled with π-conjugated aromatic amines with a large dipole moment. This research highlights a promising strategy for advancing the development of high-efficiency NLO switches and provides insights into their applications in next-generation intelligent optoelectronic devices.
As an indispensable subset of functional materials, quadratic nonlinear optical (NLO) switches have garnered increasing attention owing to their vast potential in next-generation intelligent optoelectronic devices. Despite considerable progress in NLO switches based on solid-state phase transitions, identifying an effective strategy to design high-efficiency NLO switches remains a huge challenge. Herein, we present a molecular engineering approach to develop a high-efficiency lead halide organic-inorganic hybrid NLO switch, (C8H12N)2Pb2Cl6·H2O (NMPTPC). Through the substitution of hydrogen with a methyl group (-CH3) in protonated N-methylaniline, the initial compound (C7H10N)2Pb2Cl6·H2O (NMAPC) transformed into NMPTPC retaining the original space group, which gives rise to a dramatic enhancement of second harmonic generation (SHG) and phase transition temperature. As expected, NMPTPC exhibits high-efficiency modulation of the SHG property (2.6 times that of KH2PO4) and a high phase transition temperature of 372 K. Notably, NMPTPC exhibits a remarkable temperature-dependent SHG behavior, with an impressive "ON/OFF" ratio of approximately 70, underscoring its significant potential as a high-efficient solid-state NLO switch. Based on in-depth crystal structure analysis and theoretical calculations, the modulation of the NLO property is attributed to the asymmetric distortion of the [PbCl6]4− octahedra coupled with π-conjugated aromatic amines with a large dipole moment. This research highlights a promising strategy for advancing the development of high-efficiency NLO switches and provides insights into their applications in next-generation intelligent optoelectronic devices.
2026, 37(7): 111110
doi: 10.1016/j.cclet.2025.111110
摘要:
Poly(ethylene oxide)-based polymer all-solid-state lithium-sulfur batteries (ASSLSBs) have been a prominent direction in new generation of energy storage devices due to their safety, low cost and high specific energy. However, the performance degradation arising from the “shuttle effect” and poor ion transport dynamics limit its further development. Herein, for the first time, we introduce the concepts of adsorption and catalysis into polymer ASSLSBs. By combining S@KB with g-C3N4, the polysulfides shuttling is significantly inhibited. Meanwhile, the kinetic process of the cathode is obviously improved, which is confirmed by in situ electrochemical impedance spectroscopy. The battery with g-C3N4 can provide a high reversible capacity 1078.5 mAh/g, and can be stabilized for 150 cycles with a final Coulombic efficiency of 97.47%, implying a superior electrochemical stability than previously reported. Furthermore, the intrinsic mechanisms of adsorption and catalysis are intensively studied by means of XPS, DFT calculations, and galvanostatic intermittent titration technique. Changes in electrode properties before and after cycling have also been used to study battery stability. Overall, this work will open the door to the novel polymer all-solid-state lithium-sulfur battery design for practical realization of high-energy batteries.
Poly(ethylene oxide)-based polymer all-solid-state lithium-sulfur batteries (ASSLSBs) have been a prominent direction in new generation of energy storage devices due to their safety, low cost and high specific energy. However, the performance degradation arising from the “shuttle effect” and poor ion transport dynamics limit its further development. Herein, for the first time, we introduce the concepts of adsorption and catalysis into polymer ASSLSBs. By combining S@KB with g-C3N4, the polysulfides shuttling is significantly inhibited. Meanwhile, the kinetic process of the cathode is obviously improved, which is confirmed by in situ electrochemical impedance spectroscopy. The battery with g-C3N4 can provide a high reversible capacity 1078.5 mAh/g, and can be stabilized for 150 cycles with a final Coulombic efficiency of 97.47%, implying a superior electrochemical stability than previously reported. Furthermore, the intrinsic mechanisms of adsorption and catalysis are intensively studied by means of XPS, DFT calculations, and galvanostatic intermittent titration technique. Changes in electrode properties before and after cycling have also been used to study battery stability. Overall, this work will open the door to the novel polymer all-solid-state lithium-sulfur battery design for practical realization of high-energy batteries.
2026, 37(7): 111111
doi: 10.1016/j.cclet.2025.111111
摘要:
Near-infrared (NIR) light offers significant advantages in photocatalytic reactions due to its excellent penetration ability and low phototoxicity. However, the development and utilization of NIR light for efficient photocatalysis continue to encounter several challenges. In this work, we designed and synthesized two stable iron-oxo clusters functionalized with 1, 1-ferrocene dicarboxylic acid (Fcdc), Fe11-Fcdc and BiFe10-Fcdc, both of which can effectively utilize full-spectrum light to realize efficient oxidative coupling reaction of benzylamine (BA) with a product of selectivity over 90% and a conversion up to 97%. Particularly, under the NIR light, Fe11-Fcdc shows significantly better photocatalytic performance (a conversion of 82.3%) than BiFe10-Fcdc (41.0%), which may be responsible for the stronger metal-ligand charge transfer effect in Fe11-Fcdc. This work reports for the first time the study of ferrocene-modified crystalline clusters achieving effective utilization of NIR light.
Near-infrared (NIR) light offers significant advantages in photocatalytic reactions due to its excellent penetration ability and low phototoxicity. However, the development and utilization of NIR light for efficient photocatalysis continue to encounter several challenges. In this work, we designed and synthesized two stable iron-oxo clusters functionalized with 1, 1-ferrocene dicarboxylic acid (Fcdc), Fe11-Fcdc and BiFe10-Fcdc, both of which can effectively utilize full-spectrum light to realize efficient oxidative coupling reaction of benzylamine (BA) with a product of selectivity over 90% and a conversion up to 97%. Particularly, under the NIR light, Fe11-Fcdc shows significantly better photocatalytic performance (a conversion of 82.3%) than BiFe10-Fcdc (41.0%), which may be responsible for the stronger metal-ligand charge transfer effect in Fe11-Fcdc. This work reports for the first time the study of ferrocene-modified crystalline clusters achieving effective utilization of NIR light.
2026, 37(7): 111112
doi: 10.1016/j.cclet.2025.111112
摘要:
Hard carbon materials are currently the only practical anode materials for commercial sodium-ion battery production, due to their advantages such as high volumetric capacity, low discharge potential, and low production cost. However, hard carbon typically faces issues like low initial Coulombic efficiency (ICE), poor rate performance, and structural instability during cycling, on account of its disordered and porous structure. To address these challenges, this study designs and implements a surface modification strategy to coat hard carbon with a carbon layer derived from the pyrolysis of liquid paraffin. This modified layer significantly reduces the surface defect sites, promotes the ordering of the material's surface structure, and effectively fills the pores of the material. As a result, the ICE of surface-modified hard carbon can be improved from 80% to 90%, with an increased reversible capacity to 310 mAh/g, while also enhancing the rate and cycling performance. This method offers a simple yet efficient approach for structural modification and performance optimization of hard carbon anode materials for developing advanced sodium-ion battery technologies.
Hard carbon materials are currently the only practical anode materials for commercial sodium-ion battery production, due to their advantages such as high volumetric capacity, low discharge potential, and low production cost. However, hard carbon typically faces issues like low initial Coulombic efficiency (ICE), poor rate performance, and structural instability during cycling, on account of its disordered and porous structure. To address these challenges, this study designs and implements a surface modification strategy to coat hard carbon with a carbon layer derived from the pyrolysis of liquid paraffin. This modified layer significantly reduces the surface defect sites, promotes the ordering of the material's surface structure, and effectively fills the pores of the material. As a result, the ICE of surface-modified hard carbon can be improved from 80% to 90%, with an increased reversible capacity to 310 mAh/g, while also enhancing the rate and cycling performance. This method offers a simple yet efficient approach for structural modification and performance optimization of hard carbon anode materials for developing advanced sodium-ion battery technologies.
2026, 37(7): 111113
doi: 10.1016/j.cclet.2025.111113
摘要:
Argyrodite-based all-solid-state batteries exhibit significant potential as energy storage devices across a wide temperature zone. The Li-ion and electronic conductivities in the cathode mixture is crucial factor in determining the corresponding electrochemical performances. Here, an effective charge carrier distribution is tailored by introducing Li3InCl6 electrolyte with wider voltage stability surrounding the bare LiNi0.7Co0.2Mn0.1O2 to promote ionic conductivity and mixing carbon additives to enhance electronic conductivity. The Li3InCl6@LiNi0.7Co0.2Mn0.1O2/Li5.5PS4.5Cl1.5/Li-In battery exhibits superior electrochemical performance at various C-rates over a wide operating temperature range due to the enhanced charge carrier conducting rates. It delivers high charge/discharge capacities, superior rate capability and exceptional cycling performance. Specifically, the battery delivers initial discharge capacities of 202 mAh/g at 0.2 C and retains a discharge capacity of 162 mAh/g at 2 C with a capacity retention of 91.8% over 500 cycles when cycled at room temperature. Moreover, due to the Li3InCl6 coating layer and the carbon additive in the cathode, it exhibits higher discharge capacities and superior cycling performances when operated at -20 and 60 ℃. This work presents a guideline for fabricating high-performance all-climate solid-state lithium batteries via tailoring the charger carriers conducting pathway in the electrode structure.
Argyrodite-based all-solid-state batteries exhibit significant potential as energy storage devices across a wide temperature zone. The Li-ion and electronic conductivities in the cathode mixture is crucial factor in determining the corresponding electrochemical performances. Here, an effective charge carrier distribution is tailored by introducing Li3InCl6 electrolyte with wider voltage stability surrounding the bare LiNi0.7Co0.2Mn0.1O2 to promote ionic conductivity and mixing carbon additives to enhance electronic conductivity. The Li3InCl6@LiNi0.7Co0.2Mn0.1O2/Li5.5PS4.5Cl1.5/Li-In battery exhibits superior electrochemical performance at various C-rates over a wide operating temperature range due to the enhanced charge carrier conducting rates. It delivers high charge/discharge capacities, superior rate capability and exceptional cycling performance. Specifically, the battery delivers initial discharge capacities of 202 mAh/g at 0.2 C and retains a discharge capacity of 162 mAh/g at 2 C with a capacity retention of 91.8% over 500 cycles when cycled at room temperature. Moreover, due to the Li3InCl6 coating layer and the carbon additive in the cathode, it exhibits higher discharge capacities and superior cycling performances when operated at -20 and 60 ℃. This work presents a guideline for fabricating high-performance all-climate solid-state lithium batteries via tailoring the charger carriers conducting pathway in the electrode structure.
Reviving the ionic conductivity of air-instable solid-state electrolytes via a facile heat treatment
2026, 37(7): 111114
doi: 10.1016/j.cclet.2025.111114
摘要:
The quest for sustainable and efficient energy storage solutions has led to significant advancements in the field of solid-state batteries, with a particular focus on solid-state electrolytes (SSEs) especially highly ionic conductive sulfide and halide materials. However, the air instability of these SSEs not only limits their mass production but also poses environmental and safety risks. Herein, the damage of humid-air exposure on the structure and electrochemical properties of Li5.5PS4.5Cl0.8Br0.7 and Li3InCl6 is evaluated, and a subsequent heat treatment is proposed and proven effective to recover the damage, whose mechanisms are pinpointed through XRD data with Retvield refinement. For the exposed samples, a lattice contraction occurs as the hydrolysis reaction caused by H2O from humid air severely damages the structure, which impedes lithium-ion transport. After heat treatment, a lattice rearrangement can rebuild sufficient lithium-ion pathway in the material, leading to the greatly improved ionic conductivity. As a result, the treated electrolytes provide greatly promoted ionic conductivity (from 0.95 mS/cm to 1.8 mS/cm for Li3InCl6, from 1.24 S/cm to 7.04 S/cm for Li5.5PS4.5Cl0.8Br0.7). More importantly, ASSBs employed with the treated electrolytes achieve outstanding long-term cycling and rate performance, even guarantee considerable capacity output of ~217 and ~159 mAh/g under extreme conditions of 60 and –20 ℃, illustrating significantly improved electrochemical reaction kinetics and the impressive reliability of the heat treatment method.
The quest for sustainable and efficient energy storage solutions has led to significant advancements in the field of solid-state batteries, with a particular focus on solid-state electrolytes (SSEs) especially highly ionic conductive sulfide and halide materials. However, the air instability of these SSEs not only limits their mass production but also poses environmental and safety risks. Herein, the damage of humid-air exposure on the structure and electrochemical properties of Li5.5PS4.5Cl0.8Br0.7 and Li3InCl6 is evaluated, and a subsequent heat treatment is proposed and proven effective to recover the damage, whose mechanisms are pinpointed through XRD data with Retvield refinement. For the exposed samples, a lattice contraction occurs as the hydrolysis reaction caused by H2O from humid air severely damages the structure, which impedes lithium-ion transport. After heat treatment, a lattice rearrangement can rebuild sufficient lithium-ion pathway in the material, leading to the greatly improved ionic conductivity. As a result, the treated electrolytes provide greatly promoted ionic conductivity (from 0.95 mS/cm to 1.8 mS/cm for Li3InCl6, from 1.24 S/cm to 7.04 S/cm for Li5.5PS4.5Cl0.8Br0.7). More importantly, ASSBs employed with the treated electrolytes achieve outstanding long-term cycling and rate performance, even guarantee considerable capacity output of ~217 and ~159 mAh/g under extreme conditions of 60 and –20 ℃, illustrating significantly improved electrochemical reaction kinetics and the impressive reliability of the heat treatment method.
2026, 37(7): 111115
doi: 10.1016/j.cclet.2025.111115
摘要:
The development of photosynthetic biological systems (PBSs) presents a promising approach to mitigating global climate change. However, the practical application of PBSs remains hindered by their low product yields. Key determinants of production efficiency include light utilization, electron transfer efficiency, and catalyst stability. To address these challenges, we developed a high-performance Cupriavidus necator/CdS@Au@Poly dimethyl diallyl ammonium chloride (C. necator/CdS@Au@PDDA) biohybrid system for the photocatalytic conversion of CO2 into bioplastic poly(3-hydroxybutyrate) (PHB). The incorporation of Au nanoclusters extends the visible light absorption range and alleviates photocorrosion of CdS, while the PDDA modification enhances electron transfer rates and enables the material to firmly adhere to the bacterial surface. In situ H2 production by CdS@Au@PDDA drives CO2 fixation through bacterial metabolic pathways, achieving a quantum efficiency of 2.76% ± 0.22% and a maximum PHB yield of 53.6 ± 5.2 mg/L, representing the highest yield reported for C. necator-based artificial PBSs. This biohybrid system demonstrates the effective integration of advanced nanomaterials with microbial processes, offering a robust platform for sustainable bioplastic production through carbon-neutral artificial photosynthesis technology and providing a novel perspective for addressing the global challenge of microplastic pollution.
The development of photosynthetic biological systems (PBSs) presents a promising approach to mitigating global climate change. However, the practical application of PBSs remains hindered by their low product yields. Key determinants of production efficiency include light utilization, electron transfer efficiency, and catalyst stability. To address these challenges, we developed a high-performance Cupriavidus necator/CdS@Au@Poly dimethyl diallyl ammonium chloride (C. necator/CdS@Au@PDDA) biohybrid system for the photocatalytic conversion of CO2 into bioplastic poly(3-hydroxybutyrate) (PHB). The incorporation of Au nanoclusters extends the visible light absorption range and alleviates photocorrosion of CdS, while the PDDA modification enhances electron transfer rates and enables the material to firmly adhere to the bacterial surface. In situ H2 production by CdS@Au@PDDA drives CO2 fixation through bacterial metabolic pathways, achieving a quantum efficiency of 2.76% ± 0.22% and a maximum PHB yield of 53.6 ± 5.2 mg/L, representing the highest yield reported for C. necator-based artificial PBSs. This biohybrid system demonstrates the effective integration of advanced nanomaterials with microbial processes, offering a robust platform for sustainable bioplastic production through carbon-neutral artificial photosynthesis technology and providing a novel perspective for addressing the global challenge of microplastic pollution.
2026, 37(7): 111124
doi: 10.1016/j.cclet.2025.111124
摘要:
The disordered structure plays an essential role in high capacity of hard carbon. However, the lack of universal descriptor for characterizing the structural disorder of hard carbon limit advancements in understanding and optimizing its sodium diffusion performance in sodium ion batteries (SIBs). Herein, fractal dimension (D) revealed by small angle X-ray scattering (SAXS) is identified as a descriptor of hard carbon’s structural disorder under the data-driven methods, correlating it with electrochemical and structural features. Porod’s law, TEM and XRD are used to determine the correlation between D and the microstructure of hard carbon. The results reveal that as D increases, pseudo-graphitic domains decrease and carbon layers become more curved, which result in more closed pores. Meanwhile, the diffusion coefficient in different potential below 0.1 V vs. Na+/Na suggest that D are unfavorable to sodium ions diffusion as the diffusion coefficients decrease with D increase and result in a reduce of slope capacity percentage in SIBs. D are used in analyze the sodium ion storage behavior by ex-situ SAXS, which suggests that carbon layers with larger D have more structural defects as nucleation sites. In addition, theoretical plateau capacity utilization (TCU) is proposed based on D and reveal the accessibility of closed pore of hard carbon. This work provides a foundation for bridging the gap between structural characterization and practical performances, and guiding the structural design of hard carbon with high sodium storage and kinetic performance.
The disordered structure plays an essential role in high capacity of hard carbon. However, the lack of universal descriptor for characterizing the structural disorder of hard carbon limit advancements in understanding and optimizing its sodium diffusion performance in sodium ion batteries (SIBs). Herein, fractal dimension (D) revealed by small angle X-ray scattering (SAXS) is identified as a descriptor of hard carbon’s structural disorder under the data-driven methods, correlating it with electrochemical and structural features. Porod’s law, TEM and XRD are used to determine the correlation between D and the microstructure of hard carbon. The results reveal that as D increases, pseudo-graphitic domains decrease and carbon layers become more curved, which result in more closed pores. Meanwhile, the diffusion coefficient in different potential below 0.1 V vs. Na+/Na suggest that D are unfavorable to sodium ions diffusion as the diffusion coefficients decrease with D increase and result in a reduce of slope capacity percentage in SIBs. D are used in analyze the sodium ion storage behavior by ex-situ SAXS, which suggests that carbon layers with larger D have more structural defects as nucleation sites. In addition, theoretical plateau capacity utilization (TCU) is proposed based on D and reveal the accessibility of closed pore of hard carbon. This work provides a foundation for bridging the gap between structural characterization and practical performances, and guiding the structural design of hard carbon with high sodium storage and kinetic performance.
2026, 37(7): 111125
doi: 10.1016/j.cclet.2025.111125
摘要:
Silicon/graphite (Si/C) composites, which combine the advantages of Si anodes and commercial graphite anodes, are promising anode materials for high-energy-density lithium-ion batteries (LIBs). Despite experimental and theoretical studies on the electrochemical characteristics of different silicon crystal surfaces, there have been limited investigations on the electrochemical and mechanical properties of Si composite anode materials with different graphite crystal planes, such as the electrode interfaces between Si(111) and graphite (0001), as well as amorphous Si and graphite (1010). In this study, models of Si/C anode interfaces for LIBs were constructed to explore the mechanical-electrochemical-low-temperature performance by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The calculation results indicate that upon Li intercalation into the graphite (1010) surface, the electrical conductivity, electrochemical adsorption, and interfacial mechanical strength of the Si/C composite are significantly enhanced, with a separation work that is 2.3 times higher than that of Si/C on the graphite (0001) surface. More importantly, AIMD simulations at low temperatures reveal that the interface between graphite (1010) and amorphous Si forms a solid electrolyte interphase (SEI) rich in organic components, which significantly improves the Li-diffusion kinetics. This discovery provides new insights for the design and optimization of Si/C anode materials for low-temperature LIBs.
Silicon/graphite (Si/C) composites, which combine the advantages of Si anodes and commercial graphite anodes, are promising anode materials for high-energy-density lithium-ion batteries (LIBs). Despite experimental and theoretical studies on the electrochemical characteristics of different silicon crystal surfaces, there have been limited investigations on the electrochemical and mechanical properties of Si composite anode materials with different graphite crystal planes, such as the electrode interfaces between Si(111) and graphite (0001), as well as amorphous Si and graphite (1010). In this study, models of Si/C anode interfaces for LIBs were constructed to explore the mechanical-electrochemical-low-temperature performance by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The calculation results indicate that upon Li intercalation into the graphite (1010) surface, the electrical conductivity, electrochemical adsorption, and interfacial mechanical strength of the Si/C composite are significantly enhanced, with a separation work that is 2.3 times higher than that of Si/C on the graphite (0001) surface. More importantly, AIMD simulations at low temperatures reveal that the interface between graphite (1010) and amorphous Si forms a solid electrolyte interphase (SEI) rich in organic components, which significantly improves the Li-diffusion kinetics. This discovery provides new insights for the design and optimization of Si/C anode materials for low-temperature LIBs.
2026, 37(7): 111126
doi: 10.1016/j.cclet.2025.111126
摘要:
The oxidative coupling reaction of methane (OCM) process offers a promising pathway for the direct conversion of methane into high value C2 hydrocarbons (C2H6 and C2H4), albeit facing the challenges of harsh reaction conditions and competing overoxidation reaction. Herein, Ba-doped Eu2O3 synthesized via the spray pyrolysis method was employed as highly active dopant catalyst for the methane oxidative coupling reaction. The prepared Eu0.9Ba0.1Ox catalyst showed satisfactory reactivity and stability, with a C2+ product selectivity of 52.4%, a C2+ yield of 16.2%, and a stabilization time of at least 100 h. The incorporation of Ba atoms into Eu2O3 lattice leads to an increased molar ratio of Eu2+/Eu3+ and a higher oxygen vacancies (Ov) concentration. Such modulation of surface electronic state significantly improves the adsorption and activation behavior of oxygen, thereby accelerating the production of reactive oxygen species (O2−). Meanwhile, the acid-base properties of Eu2O3 substrate also undergo obvious alteration with more basic site generation after Ba doping, which is conducive to the stabilization activated oxygen. O2− substances can promote the activation of methane into methyl radicals, and also facilitate the dehydrogenation of ethane into ethylene, thus improving the catalytic activity.
The oxidative coupling reaction of methane (OCM) process offers a promising pathway for the direct conversion of methane into high value C2 hydrocarbons (C2H6 and C2H4), albeit facing the challenges of harsh reaction conditions and competing overoxidation reaction. Herein, Ba-doped Eu2O3 synthesized via the spray pyrolysis method was employed as highly active dopant catalyst for the methane oxidative coupling reaction. The prepared Eu0.9Ba0.1Ox catalyst showed satisfactory reactivity and stability, with a C2+ product selectivity of 52.4%, a C2+ yield of 16.2%, and a stabilization time of at least 100 h. The incorporation of Ba atoms into Eu2O3 lattice leads to an increased molar ratio of Eu2+/Eu3+ and a higher oxygen vacancies (Ov) concentration. Such modulation of surface electronic state significantly improves the adsorption and activation behavior of oxygen, thereby accelerating the production of reactive oxygen species (O2−). Meanwhile, the acid-base properties of Eu2O3 substrate also undergo obvious alteration with more basic site generation after Ba doping, which is conducive to the stabilization activated oxygen. O2− substances can promote the activation of methane into methyl radicals, and also facilitate the dehydrogenation of ethane into ethylene, thus improving the catalytic activity.
2026, 37(7): 111127
doi: 10.1016/j.cclet.2025.111127
摘要:
Lithium plating and gas evolution during fast charging of graphite-based lithium-ion batteries (LIBs) are among the pivotal challenges contributing to rapid capacity loss. However, the mechanisms underlying gas generation and corresponding mitigation strategies in electrolytes comprising mixed organic molecules and Li salts remain underexplored. Herein, we employed first-principles studies to simulate the lithiation process of electrolytes and predicted gas formation at anode interfaces with Li plating. Our results emphasize the critical role of Li salts in initiating solvent molecule decomposition and the exacerbation of interfacial degradation under conditions of elevated temperature and prolonged annealing, giving rise to the production of CO, C2H4, CH4, and H2, along with a significant increase in SEI's electronic conductivity. Moreover, our computations highlight that ethylene carbonate (EC) in commercial electrolytes is the overarching cause of interface instability and gas evolution. Experimental validations demonstrate that reducing the EC content in electrolytes results in an enhancement of the specific capacity of LiNi0.8Co0.1Mn0.1O2graphite full cells from 158.13 mAh/g to 182.53 mAh/g, and an improvement in capacity retention from 72.0% to 80.4% over 130 cycling at 3 C. This research provides a theoretical framework for designing fast-charging electrolytes with stable interfaces and minimal gas generation.
Lithium plating and gas evolution during fast charging of graphite-based lithium-ion batteries (LIBs) are among the pivotal challenges contributing to rapid capacity loss. However, the mechanisms underlying gas generation and corresponding mitigation strategies in electrolytes comprising mixed organic molecules and Li salts remain underexplored. Herein, we employed first-principles studies to simulate the lithiation process of electrolytes and predicted gas formation at anode interfaces with Li plating. Our results emphasize the critical role of Li salts in initiating solvent molecule decomposition and the exacerbation of interfacial degradation under conditions of elevated temperature and prolonged annealing, giving rise to the production of CO, C2H4, CH4, and H2, along with a significant increase in SEI's electronic conductivity. Moreover, our computations highlight that ethylene carbonate (EC) in commercial electrolytes is the overarching cause of interface instability and gas evolution. Experimental validations demonstrate that reducing the EC content in electrolytes results in an enhancement of the specific capacity of LiNi0.8Co0.1Mn0.1O2graphite full cells from 158.13 mAh/g to 182.53 mAh/g, and an improvement in capacity retention from 72.0% to 80.4% over 130 cycling at 3 C. This research provides a theoretical framework for designing fast-charging electrolytes with stable interfaces and minimal gas generation.
2026, 37(7): 111156
doi: 10.1016/j.cclet.2025.111156
摘要:
Hard carbon with abundant resources and superior sodium storage performance is the most representative anode material for sodium-ion batteries (SIBs), but suffers from unsatisfied reversible capacity and low initial Coulombic efficiency. Herein, brown coal is employed as the precursor to obtain high-performance hard carbon anode materials with the assistance of pre-oxidation treatment for SIBs. The unique pre-oxidation treatment introduces an abundance of oxygen-containing functional groups to regulate the microstructure of hard carbon anode, achieving a more disordered phase structure for improved sodium storage performance. These enable a high reversible specific capacity of 316.1 mAh/g with an initial Coulombic efficiency of 87.6%, significantly higher than those of 236.5 mAh/g and 71.7% in carbonized pristine brown coal. Meanwhile, the adsorption-insertion-pore filling sodium storage mechanism of brown coal-derived hard carbon is demonstrated by in-situ XRD and Raman. This work emphasizes the role of pre-oxidation treatment on boosting the sodium storage performance of brown coal-derived hard carbon for advanced SIBs.
Hard carbon with abundant resources and superior sodium storage performance is the most representative anode material for sodium-ion batteries (SIBs), but suffers from unsatisfied reversible capacity and low initial Coulombic efficiency. Herein, brown coal is employed as the precursor to obtain high-performance hard carbon anode materials with the assistance of pre-oxidation treatment for SIBs. The unique pre-oxidation treatment introduces an abundance of oxygen-containing functional groups to regulate the microstructure of hard carbon anode, achieving a more disordered phase structure for improved sodium storage performance. These enable a high reversible specific capacity of 316.1 mAh/g with an initial Coulombic efficiency of 87.6%, significantly higher than those of 236.5 mAh/g and 71.7% in carbonized pristine brown coal. Meanwhile, the adsorption-insertion-pore filling sodium storage mechanism of brown coal-derived hard carbon is demonstrated by in-situ XRD and Raman. This work emphasizes the role of pre-oxidation treatment on boosting the sodium storage performance of brown coal-derived hard carbon for advanced SIBs.
2026, 37(7): 111157
doi: 10.1016/j.cclet.2025.111157
摘要:
The combination of high-nickel cathodes with poly(ethylene oxide) (PEO)-based solid-state electrolytes represents a promising strategy to achieve both high energy density and enhanced safety. However, existing studies predominantly employ LiFePO4 cathodes due to the inherent limitations of PEO-based electrolytes in high-voltage stability. Even with the improved electrochemical stability window (ESW) of PEO-based electrolytes, current implementations still utilize low-nickel-content (≤80%) cathodes. To further enhance the energy density of PEO-based solid-state batteries (SSBs), this work employs high-nickel-content (> 80%) cathodes in conjunction with PEO-based electrolytes. The influence of nickel content in cathode materials (CAMs) on the electrochemical performance of PEO-based SSBs is systematically investigated through a progressive nickel content optimization approach. This study elucidates the intrinsic relationship between the nickel content and the characteristic capacity activation mechanism observed during the initial cycling phases in solid-state battery systems, revealing a nickel-content-dependent electrochemical activation pattern unique to solid-state configurations. Additionally, through a series of detection schemes, the failure mechanism of high-nickel PEO-based SSBs is systematically studied from the cathode/electrolyte interface, electrolyte, and CAM. Particularly, the degree of PEO decomposition is quantitatively analyzed using differential electrochemical mass spectrometry (DEMS) and gel permeation chromatography (GPC). This work reveals the key issues faced when further increasing the nickel content of CAMs, providing insights for targeted modification designs of high-nickel PEO-based solid-state batteries in the future.
The combination of high-nickel cathodes with poly(ethylene oxide) (PEO)-based solid-state electrolytes represents a promising strategy to achieve both high energy density and enhanced safety. However, existing studies predominantly employ LiFePO4 cathodes due to the inherent limitations of PEO-based electrolytes in high-voltage stability. Even with the improved electrochemical stability window (ESW) of PEO-based electrolytes, current implementations still utilize low-nickel-content (≤80%) cathodes. To further enhance the energy density of PEO-based solid-state batteries (SSBs), this work employs high-nickel-content (> 80%) cathodes in conjunction with PEO-based electrolytes. The influence of nickel content in cathode materials (CAMs) on the electrochemical performance of PEO-based SSBs is systematically investigated through a progressive nickel content optimization approach. This study elucidates the intrinsic relationship between the nickel content and the characteristic capacity activation mechanism observed during the initial cycling phases in solid-state battery systems, revealing a nickel-content-dependent electrochemical activation pattern unique to solid-state configurations. Additionally, through a series of detection schemes, the failure mechanism of high-nickel PEO-based SSBs is systematically studied from the cathode/electrolyte interface, electrolyte, and CAM. Particularly, the degree of PEO decomposition is quantitatively analyzed using differential electrochemical mass spectrometry (DEMS) and gel permeation chromatography (GPC). This work reveals the key issues faced when further increasing the nickel content of CAMs, providing insights for targeted modification designs of high-nickel PEO-based solid-state batteries in the future.
2026, 37(7): 111159
doi: 10.1016/j.cclet.2025.111159
摘要:
Upconversion nanoparticles (UCNPs) have been naturally entangled with surface phonons since their discovery due to their high specific surface area. However, in addition to quenching luminescence at ambient temperatures, surface phonons play a crucial role in activating the dark layer between the sensitizer and the activator to enhance luminescence in thermal environments. Considering that the positive effect of surface phonons may be eliminated under inert cladding, a β-NaGdF4:Yb,Tm@NaYF4@NaGdF4:Yb,Er core-shell-shell upconversion luminescence (UCL) system with two opposite thermo-responsive luminescence behaviors is designed here. The imposition of an inert intermediate shell layer causes the weakening of the blue luminescence of the core Tm ions in the thermal environment, while on the contrary the outermost Er ions realize an effective enhancement of luminescence with the help of surface phonons. In addition, the photoluminescence results show that effective modulation of luminescence color can be achieved by changing the thickness of the inert shell layer, the concentration of Er ions in the activation layer, and the excitation power. Finally, the distinct thermally responsive luminescence behaviors and temperature-dependent color variations enabled moderate temperature sensing and information encryption applications. The maximum relative and absolute sensitivities can be up to 1.62%/K and 0.64%/K from 298 K to 573 K, respectively. These findings provided new insights into optimizing the luminescent properties of fluorides and provided a new platform for the application of multiple properties in a material.
Upconversion nanoparticles (UCNPs) have been naturally entangled with surface phonons since their discovery due to their high specific surface area. However, in addition to quenching luminescence at ambient temperatures, surface phonons play a crucial role in activating the dark layer between the sensitizer and the activator to enhance luminescence in thermal environments. Considering that the positive effect of surface phonons may be eliminated under inert cladding, a β-NaGdF4:Yb,Tm@NaYF4@NaGdF4:Yb,Er core-shell-shell upconversion luminescence (UCL) system with two opposite thermo-responsive luminescence behaviors is designed here. The imposition of an inert intermediate shell layer causes the weakening of the blue luminescence of the core Tm ions in the thermal environment, while on the contrary the outermost Er ions realize an effective enhancement of luminescence with the help of surface phonons. In addition, the photoluminescence results show that effective modulation of luminescence color can be achieved by changing the thickness of the inert shell layer, the concentration of Er ions in the activation layer, and the excitation power. Finally, the distinct thermally responsive luminescence behaviors and temperature-dependent color variations enabled moderate temperature sensing and information encryption applications. The maximum relative and absolute sensitivities can be up to 1.62%/K and 0.64%/K from 298 K to 573 K, respectively. These findings provided new insights into optimizing the luminescent properties of fluorides and provided a new platform for the application of multiple properties in a material.
2026, 37(7): 111176
doi: 10.1016/j.cclet.2025.111176
摘要:
Chiral hybrid metal halides, known for their exceptional piezoelectric properties, facile synthesis, and design flexibility, have become promising candidates for advanced piezoelectric devices. However, most chiral metal halides contain toxic lead and are predominantly restricted to 1D or 2D structures. In contrast, 0D hybrid piezoelectric materials, despite their lower elastic moduli, remain significantly less explored. Here, we report the synthesis of a pair of lead-free chiral 0D hybrid metal halides, R-(APP)2CoBr4 and S-(APP)2CoBr4 (APP = 2-amino-3-phenylpropan-1-ol). First-principles calculations reveal that S-(APP)2CoBr4 exhibits a noticeable shear piezoelectric coefficient while maintaining a relatively low elastic modulus. Furthermore, S-(APP)2CoBr4/PDMS composite films (PDMS = polydimethylsiloxane) were fabricated and their potential for energy harvesting and human motion sensing was investigated. Under a 2 N applied force, a 15 wt% S-(APP)2CoBr4/PDMS composite film exhibits promising performance, generating an open-circuit voltage of 10.21 V and a short-circuit current of 1.02 µA. Additionally, the low acoustic impedance of S-(APP)2CoBr4 (5.80–6.67 MRayl) and its compatibility with water (1.5 MRayl) facilitate efficient ultrasound transmission in composite devices, ensuring precise localization of ultrasound sources. These findings offer valuable insights into the potential of lead-free 0D hybrid metal halides for advanced electromechanical applications.
Chiral hybrid metal halides, known for their exceptional piezoelectric properties, facile synthesis, and design flexibility, have become promising candidates for advanced piezoelectric devices. However, most chiral metal halides contain toxic lead and are predominantly restricted to 1D or 2D structures. In contrast, 0D hybrid piezoelectric materials, despite their lower elastic moduli, remain significantly less explored. Here, we report the synthesis of a pair of lead-free chiral 0D hybrid metal halides, R-(APP)2CoBr4 and S-(APP)2CoBr4 (APP = 2-amino-3-phenylpropan-1-ol). First-principles calculations reveal that S-(APP)2CoBr4 exhibits a noticeable shear piezoelectric coefficient while maintaining a relatively low elastic modulus. Furthermore, S-(APP)2CoBr4/PDMS composite films (PDMS = polydimethylsiloxane) were fabricated and their potential for energy harvesting and human motion sensing was investigated. Under a 2 N applied force, a 15 wt% S-(APP)2CoBr4/PDMS composite film exhibits promising performance, generating an open-circuit voltage of 10.21 V and a short-circuit current of 1.02 µA. Additionally, the low acoustic impedance of S-(APP)2CoBr4 (5.80–6.67 MRayl) and its compatibility with water (1.5 MRayl) facilitate efficient ultrasound transmission in composite devices, ensuring precise localization of ultrasound sources. These findings offer valuable insights into the potential of lead-free 0D hybrid metal halides for advanced electromechanical applications.
2026, 37(7): 111330
doi: 10.1016/j.cclet.2025.111330
摘要:
Lithium–sulfur (Li–S) battery is considered as a promising next-generation high-energy-density battery. However, the cycle life of Li–S batteries is severely plagued by the instability of Li metal anodes. Improving Li deposition uniformity can mitigate the formation of inactive Li and the side reactions between Li polysulfides and Li metal anodes. Herein, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (Py13FSI) is proposed as an additive to improve the uniformity of Li deposition in Li–S batteries. At a low concentration, Py13+ exhibits a lower reduction potential than Li ions. Py13+ can be adsorbed and accumulate on the surface protuberances of Li metal anodes, inducing the deposition of Li towards non-tip sites and improving the uniformity of Li deposition. With a high-loading cathode (4.1 mgS/cm2) and an ultrathin Li metal anode (50 µm), the cycle life of Li–S batteries is prolonged from 61 to 120 cycles via Py13FSI additives. Furthermore, a 401 Wh/kg Li–S pouch cell with Py13FSI additives undergoes 14 cycles. This work demonstrates the potential of improving Li deposition uniformity in Li–S batteries by appropriate electrolyte additives.
Lithium–sulfur (Li–S) battery is considered as a promising next-generation high-energy-density battery. However, the cycle life of Li–S batteries is severely plagued by the instability of Li metal anodes. Improving Li deposition uniformity can mitigate the formation of inactive Li and the side reactions between Li polysulfides and Li metal anodes. Herein, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (Py13FSI) is proposed as an additive to improve the uniformity of Li deposition in Li–S batteries. At a low concentration, Py13+ exhibits a lower reduction potential than Li ions. Py13+ can be adsorbed and accumulate on the surface protuberances of Li metal anodes, inducing the deposition of Li towards non-tip sites and improving the uniformity of Li deposition. With a high-loading cathode (4.1 mgS/cm2) and an ultrathin Li metal anode (50 µm), the cycle life of Li–S batteries is prolonged from 61 to 120 cycles via Py13FSI additives. Furthermore, a 401 Wh/kg Li–S pouch cell with Py13FSI additives undergoes 14 cycles. This work demonstrates the potential of improving Li deposition uniformity in Li–S batteries by appropriate electrolyte additives.
2026, 37(7): 111584
doi: 10.1016/j.cclet.2025.111584
摘要:
A series of highly rearranged labdane diterpenoids featuring previously unreported skeletons, including 9,18-cyclolabdanes (1 and 2), 1,10-seco-9,18-cyclolabdanes (3–5), 7,18-cyclolabdanes (6), and 1,10-seco-1,5-cyclolabdanes (7), along with seven novel labdanes (8–14), two novel halimane diterpenoids (15 and 16), and three known congeners (17–19), were isolated from Chinese liverwort Haplomitrium mnioides. Their structures were unequivocally determined through comprehensive spectroscopic analysis, single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. These diverse diterpenoids were biosynthesized through an aldol-type cascade process, using 19 as the starting material, distinguishing them from compounds generated via conventional carbocation rearrangement. Anti-inflammatory assays revealed that haploide O (15) and haplomitrenolide C (17) significantly inhibited the secretion of proinflammatory cytokines interferon-γ (IFN-γ), tumor necrosis factor-α (TNF-α), and interleukin-6 (IL-6) in vitro in concanavalin A (ConA)-induced murine spleen cells.
A series of highly rearranged labdane diterpenoids featuring previously unreported skeletons, including 9,18-cyclolabdanes (1 and 2), 1,10-seco-9,18-cyclolabdanes (3–5), 7,18-cyclolabdanes (6), and 1,10-seco-1,5-cyclolabdanes (7), along with seven novel labdanes (8–14), two novel halimane diterpenoids (15 and 16), and three known congeners (17–19), were isolated from Chinese liverwort Haplomitrium mnioides. Their structures were unequivocally determined through comprehensive spectroscopic analysis, single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. These diverse diterpenoids were biosynthesized through an aldol-type cascade process, using 19 as the starting material, distinguishing them from compounds generated via conventional carbocation rearrangement. Anti-inflammatory assays revealed that haploide O (15) and haplomitrenolide C (17) significantly inhibited the secretion of proinflammatory cytokines interferon-γ (IFN-γ), tumor necrosis factor-α (TNF-α), and interleukin-6 (IL-6) in vitro in concanavalin A (ConA)-induced murine spleen cells.
2026, 37(7): 111585
doi: 10.1016/j.cclet.2025.111585
摘要:
The application of Arsenic trioxide (ATO) has greatly improved the cure rates in patients with acute promyelocytic leukemia (APL) and has shown therapeutic effects in other leukemia types, as evidenced by an increasing number of preclinical trials. However, its clinical application is still limited due to a lack of understanding of the underlying mechanisms. In this report, we have demonstrated that ATO can induce pyroptosis and release damage-associated molecular patterns (DAMPs), such as high mobility group box 1 (HMGB1) and interleukin-1β (IL-1β). DAMPs can activate the immunogenic cell death (ICD) mechanism. Our study elucidated the pivotal role of pyroptosis and demonstrated the activation of the caspase-3/gasdermin E (GSDME) pathway both in vivo and in vitro upon ATO intervention. Proteomic analysis of cell supernatants revealed the release of the ICD-associated molecule HMGB1. Results from both in vitro and in vivo experiments collectively demonstrated that the release of HMGB1 is contingent upon GSDME-mediated pyroptosis. Furthermore, label-free quantitative proteomics in vivo indicated that ATO-induced pyroptosis activates natural killer cells (NKs) and promotes the release of granzyme B (GZMB). Our study is the first to demonstrate the synergistic interplay between pyroptosis and ICD mechanisms during ATO treatment, providing novel insights into the potential of ATO for immunotherapy and synergistic treatment approaches.
The application of Arsenic trioxide (ATO) has greatly improved the cure rates in patients with acute promyelocytic leukemia (APL) and has shown therapeutic effects in other leukemia types, as evidenced by an increasing number of preclinical trials. However, its clinical application is still limited due to a lack of understanding of the underlying mechanisms. In this report, we have demonstrated that ATO can induce pyroptosis and release damage-associated molecular patterns (DAMPs), such as high mobility group box 1 (HMGB1) and interleukin-1β (IL-1β). DAMPs can activate the immunogenic cell death (ICD) mechanism. Our study elucidated the pivotal role of pyroptosis and demonstrated the activation of the caspase-3/gasdermin E (GSDME) pathway both in vivo and in vitro upon ATO intervention. Proteomic analysis of cell supernatants revealed the release of the ICD-associated molecule HMGB1. Results from both in vitro and in vivo experiments collectively demonstrated that the release of HMGB1 is contingent upon GSDME-mediated pyroptosis. Furthermore, label-free quantitative proteomics in vivo indicated that ATO-induced pyroptosis activates natural killer cells (NKs) and promotes the release of granzyme B (GZMB). Our study is the first to demonstrate the synergistic interplay between pyroptosis and ICD mechanisms during ATO treatment, providing novel insights into the potential of ATO for immunotherapy and synergistic treatment approaches.
2026, 37(7): 111586
doi: 10.1016/j.cclet.2025.111586
摘要:
Multiple myeloma (MM) is the second most common hematological malignancy and still remains incurable. Selinexor (SEL) is the first-in-class exportin 1 (XPO1) inhibitor, and has demonstrated survival benefits in relapsed/refractory MM patients. Despite its therapeutic potential, dose-limiting toxicities frequently compromise SEL’s clinical utility and patients’ quality of life. In this work, to improve therapeutic efficacy and minimize side effects of SEL, we designed the monomethyl poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) micelle-encapsulated nanoformulation for MM therapy. The mPEG-PCL-SEL micelle exhibited controlled release behavior and showed remarkable cytotoxicity in MM cells. Most importantly, in the orthotopic MM model, this micelle system exhibited impressive therapeutic efficacy at low dosages and significantly prolonged the survival of MM-bearing mice. Moreover, the mPEG-PCL-SEL micelle demonstrated a favorable safety profile with fewer gastrointestinal and constitutional symptoms. And we found that compared with the free-SEL, the mPEG-PCL-SEL micelle maintained the integrity of the intestinal barrier, and was more beneficial to the diversity of the intestinal microbiota, which may be related to the improved gastrointestinal tolerability, making it an effective and safe choice for MM treatment.
Multiple myeloma (MM) is the second most common hematological malignancy and still remains incurable. Selinexor (SEL) is the first-in-class exportin 1 (XPO1) inhibitor, and has demonstrated survival benefits in relapsed/refractory MM patients. Despite its therapeutic potential, dose-limiting toxicities frequently compromise SEL’s clinical utility and patients’ quality of life. In this work, to improve therapeutic efficacy and minimize side effects of SEL, we designed the monomethyl poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) micelle-encapsulated nanoformulation for MM therapy. The mPEG-PCL-SEL micelle exhibited controlled release behavior and showed remarkable cytotoxicity in MM cells. Most importantly, in the orthotopic MM model, this micelle system exhibited impressive therapeutic efficacy at low dosages and significantly prolonged the survival of MM-bearing mice. Moreover, the mPEG-PCL-SEL micelle demonstrated a favorable safety profile with fewer gastrointestinal and constitutional symptoms. And we found that compared with the free-SEL, the mPEG-PCL-SEL micelle maintained the integrity of the intestinal barrier, and was more beneficial to the diversity of the intestinal microbiota, which may be related to the improved gastrointestinal tolerability, making it an effective and safe choice for MM treatment.
2026, 37(7): 111589
doi: 10.1016/j.cclet.2025.111589
摘要:
Developing effective strategies to simultaneously suppress tumor thermotolerance and secondary inflammation remains a significant challenge in enhanced photothermal therapy (PTT). In this study, we developed a nitroreductase (NTR)-triggered multifunctional photothermal agent (m-SCy-DCF) by conjugating mitochondria-targeted sulfur-substituted hemicyanine to the anti-inflammatory diclofenac (DCF) through an NTR-cleavable linker. Upon activation in the hypoxic tumor microenvironment, m-SCy-DCF selectively accumulated in mitochondria and generated localized hyperthermia under laser irradiation. This process not only disrupted mitochondrial function but also suppressed the expression of heat shock proteins (HSPs). Simultaneously, the released DCF exerted potent anti-inflammatory effects, effectively reducing the levels of inflammatory cytokines in vivo. This dual suppression of tumor thermotolerance and inflammation induced immunogenic cell death and achieved effective tumor ablation, demonstrating the potential of m-SCy-DCF as a highly promising candidate for enhanced PTT.
Developing effective strategies to simultaneously suppress tumor thermotolerance and secondary inflammation remains a significant challenge in enhanced photothermal therapy (PTT). In this study, we developed a nitroreductase (NTR)-triggered multifunctional photothermal agent (m-SCy-DCF) by conjugating mitochondria-targeted sulfur-substituted hemicyanine to the anti-inflammatory diclofenac (DCF) through an NTR-cleavable linker. Upon activation in the hypoxic tumor microenvironment, m-SCy-DCF selectively accumulated in mitochondria and generated localized hyperthermia under laser irradiation. This process not only disrupted mitochondrial function but also suppressed the expression of heat shock proteins (HSPs). Simultaneously, the released DCF exerted potent anti-inflammatory effects, effectively reducing the levels of inflammatory cytokines in vivo. This dual suppression of tumor thermotolerance and inflammation induced immunogenic cell death and achieved effective tumor ablation, demonstrating the potential of m-SCy-DCF as a highly promising candidate for enhanced PTT.
2026, 37(7): 111641
doi: 10.1016/j.cclet.2025.111641
摘要:
Macrophage-derived exosomes have demonstrated considerable potential for promoting bone regeneration. This study proposes a novel engineered therapeutic strategy that utilizes carbon monoxide releasing prodrugs (TG-Fe CORMs) to selectively induce M2 macrophage polarization, thereby enhancing the production of M2 macrophage-derived exosomes (CO-M2-Exos). These exosomes have been observed to significantly promote osteogenesis and accelerate alveolar bone regeneration through the microRNA-21/Lhx8 signaling pathway. Notably, these exosomes possess several advantageous characteristics, including their capacity for remarkable regenerative effects, low immunogenicity, and high cellular uptake, which renders them promising cell-free therapy for addressing alveolar bone defects. Moreover, the scalable production of CO-M2-Exos successfully overcomes the significant challenges associated with traditional exosome-based therapies, such as the complexity of cell culture processes, the instability of phenotype, and the low yield of exosome production. This engineered approach offers a reliable, efficient, and cost-effective solution for clinical translation, particularly for promoting alveolar bone regeneration in cases of severe bone atrophy following tooth extraction.
Macrophage-derived exosomes have demonstrated considerable potential for promoting bone regeneration. This study proposes a novel engineered therapeutic strategy that utilizes carbon monoxide releasing prodrugs (TG-Fe CORMs) to selectively induce M2 macrophage polarization, thereby enhancing the production of M2 macrophage-derived exosomes (CO-M2-Exos). These exosomes have been observed to significantly promote osteogenesis and accelerate alveolar bone regeneration through the microRNA-21/Lhx8 signaling pathway. Notably, these exosomes possess several advantageous characteristics, including their capacity for remarkable regenerative effects, low immunogenicity, and high cellular uptake, which renders them promising cell-free therapy for addressing alveolar bone defects. Moreover, the scalable production of CO-M2-Exos successfully overcomes the significant challenges associated with traditional exosome-based therapies, such as the complexity of cell culture processes, the instability of phenotype, and the low yield of exosome production. This engineered approach offers a reliable, efficient, and cost-effective solution for clinical translation, particularly for promoting alveolar bone regeneration in cases of severe bone atrophy following tooth extraction.
2026, 37(7): 111642
doi: 10.1016/j.cclet.2025.111642
摘要:
Globo-H is a tumor-associated carbohydrate antigen (TACA) that is overexpressed in various cancers, making it a promising target for anticancer vaccine development. However, traditional conjugate vaccines, such as those linked to keyhole limpet hemocyanin (KLH) or cross-reactive material 197 (CRM197), have demonstrated limited clinical efficacy. To address this limitation, we developed an innovative vaccine candidate by conjugating chemoenzymatically synthesized Globo-H to a mutant of bacteriophage Qβ (mQβ) virus-like particle. The resulting mQβ-Globo-H conjugate elicited significantly higher levels of anti-Globo-H IgG antibodies in mice compared to both KLH-Globo-H and CRM197-Globo-H conjugates. Furthermore, the antibodies produced by the mQβ-Globo-H conjugate exhibited strong binding to MCF-7 breast cancer cells and triggered potent complement-dependent cytotoxicity (CDC) against these cancer cells. In contrast, negligible antibody binding and CDC effects were observed against normal MCF-10A breast epithelial cells. This new conjugate vaccine also produced robust humoral responses in rabbits, with the resulting antibodies exhibiting high selectivity for human breast cancer tissues. These findings underscore the clinical translational potential of the mQβ-Globo-H conjugate vaccine.
Globo-H is a tumor-associated carbohydrate antigen (TACA) that is overexpressed in various cancers, making it a promising target for anticancer vaccine development. However, traditional conjugate vaccines, such as those linked to keyhole limpet hemocyanin (KLH) or cross-reactive material 197 (CRM197), have demonstrated limited clinical efficacy. To address this limitation, we developed an innovative vaccine candidate by conjugating chemoenzymatically synthesized Globo-H to a mutant of bacteriophage Qβ (mQβ) virus-like particle. The resulting mQβ-Globo-H conjugate elicited significantly higher levels of anti-Globo-H IgG antibodies in mice compared to both KLH-Globo-H and CRM197-Globo-H conjugates. Furthermore, the antibodies produced by the mQβ-Globo-H conjugate exhibited strong binding to MCF-7 breast cancer cells and triggered potent complement-dependent cytotoxicity (CDC) against these cancer cells. In contrast, negligible antibody binding and CDC effects were observed against normal MCF-10A breast epithelial cells. This new conjugate vaccine also produced robust humoral responses in rabbits, with the resulting antibodies exhibiting high selectivity for human breast cancer tissues. These findings underscore the clinical translational potential of the mQβ-Globo-H conjugate vaccine.
2026, 37(7): 111645
doi: 10.1016/j.cclet.2025.111645
摘要:
The antioxidant and immune-suppressive microenvironment of tumors has severely limited the efficacy of photodynamic therapy (PDT). To overcome these limitations, we proposed a novel nanoparticle (PEG-PFc/Hyp) that combined hypericin (Hyp) and ferrocene for synergistic anti-tumor therapy within a single system. Briefly, the optimum PEG114-PLL10 was reacted with ferrocene by the carboxylic acid N-succinimidyl ester(ferrocene-NHS), and the subsequent Hyp encapsulated in the above fabricated amphiphilic polymer. When under light irradiation, Hyp generated abundant reactive oxygen species (ROS) that synergized with •OH produced by ferrocene, leading to disrupted redox balance, amplified lethal lipid peroxidation (LPO) and inducing significant ferroptosis. Furthermore, the ferrocene could greatly alleviate hypoxia via O2 production, thereby cascaded enhancing the ROS production efficiency of PDT. As a result, the cascade augmented ROS level, alongside the glutathione (GSH) depletion in tumor cells, caused effective immunogenic cell death (ICD) and potent anti-tumor response. It turned out that the PDT-ferroptosis-ICD strategy enabled significant oxidative damage and tumor cell immunogenicity, offering great potential in cancer immunotherapy.
The antioxidant and immune-suppressive microenvironment of tumors has severely limited the efficacy of photodynamic therapy (PDT). To overcome these limitations, we proposed a novel nanoparticle (PEG-PFc/Hyp) that combined hypericin (Hyp) and ferrocene for synergistic anti-tumor therapy within a single system. Briefly, the optimum PEG114-PLL10 was reacted with ferrocene by the carboxylic acid N-succinimidyl ester(ferrocene-NHS), and the subsequent Hyp encapsulated in the above fabricated amphiphilic polymer. When under light irradiation, Hyp generated abundant reactive oxygen species (ROS) that synergized with •OH produced by ferrocene, leading to disrupted redox balance, amplified lethal lipid peroxidation (LPO) and inducing significant ferroptosis. Furthermore, the ferrocene could greatly alleviate hypoxia via O2 production, thereby cascaded enhancing the ROS production efficiency of PDT. As a result, the cascade augmented ROS level, alongside the glutathione (GSH) depletion in tumor cells, caused effective immunogenic cell death (ICD) and potent anti-tumor response. It turned out that the PDT-ferroptosis-ICD strategy enabled significant oxidative damage and tumor cell immunogenicity, offering great potential in cancer immunotherapy.
2026, 37(7): 111655
doi: 10.1016/j.cclet.2025.111655
摘要:
Copper dysregulation is a critical factor in tumorigenesis and cancer therapy, underscoring the need for in vivo Cu(Ⅰ) imaging in tumors to elucidate its pathological roles. However, developing molecular probes for high-sensitivity and high-resolution in vivo Cu(Ⅰ) imaging remains a significant challenge. Herein, we report a covalently targeted small-molecule probe for dual-modality fluorescence and photoacoustic (PA) imaging of Cu(Ⅰ) in tumors. This probe exhibits highly selective near-infrared fluorescence enhancement and a ratiometric PA response upon coordination with Cu(Ⅰ). Furthermore, it enables precise tumor targeting and sustained imaging through specific recognition and covalent anchoring to the neutral cholesterol ester hydrolase 1 (NCEH1) protein. In vivo experiments demonstrate its capability for dynamic tracking of Cu(Ⅰ) in tumors with high sensitivity via fluorescence imaging and micro resolution via ratiometric PA imaging. We anticipate this Cu(Ⅰ)-responsive dual-modality probe with targeted anchoring capabilities will be a powerful tool for investigating Cu(Ⅰ) dynamics and transport in tumors, thereby deepening our understanding of pathological roles of Cu(Ⅰ) in cancer biology.
Copper dysregulation is a critical factor in tumorigenesis and cancer therapy, underscoring the need for in vivo Cu(Ⅰ) imaging in tumors to elucidate its pathological roles. However, developing molecular probes for high-sensitivity and high-resolution in vivo Cu(Ⅰ) imaging remains a significant challenge. Herein, we report a covalently targeted small-molecule probe for dual-modality fluorescence and photoacoustic (PA) imaging of Cu(Ⅰ) in tumors. This probe exhibits highly selective near-infrared fluorescence enhancement and a ratiometric PA response upon coordination with Cu(Ⅰ). Furthermore, it enables precise tumor targeting and sustained imaging through specific recognition and covalent anchoring to the neutral cholesterol ester hydrolase 1 (NCEH1) protein. In vivo experiments demonstrate its capability for dynamic tracking of Cu(Ⅰ) in tumors with high sensitivity via fluorescence imaging and micro resolution via ratiometric PA imaging. We anticipate this Cu(Ⅰ)-responsive dual-modality probe with targeted anchoring capabilities will be a powerful tool for investigating Cu(Ⅰ) dynamics and transport in tumors, thereby deepening our understanding of pathological roles of Cu(Ⅰ) in cancer biology.
2026, 37(7): 111666
doi: 10.1016/j.cclet.2025.111666
摘要:
Excessive and prolonged inflammatory monocyte activity accelerates left ventricular remodeling after myocardial infarction (MI). After myocardial reperfusion, the CCL2/CCR2 axis is considered to be a key chemokine axis that initiates and modulates tissue inflammatory damage. Effectively blocking the CCL2/CCR2 axis can reduce the chemotaxis of inflammatory monocytes to the infarct area, which has important therapeutic value for the repair of myocardium after reperfusion injury (MI/R). Here, we propose a nanoparticle carrying CCL2 silencing short interfering RNA (siRNA), which is prepared by coating a lipid hybrid CCR2-overexprssion macrophage cell membrane on a siRNA-loaded mesoporous silica nanoparticle. The overexpression of CCR2 and adhesion factors on the macrophage membrane improves its targeting ability, directing nanoparticle to the myocardial infarction area of MI/R-induced mice, the overexpress CCR2 in the macrophage cell membrane also adsorb more CCL2. Then by fusing with the cell membrane, siRNA is released into the injured endothelial cells cytoplasm, silencing the expression of CCL2. In vivo administration of the formula blocked CCL2/CCR2 axis, reduce the chemotaxis of inflammatory cells, regulate the immune microenvironment, further decreasing myocardial infarction area and improving cardiac function. Targeted block of CCL2/CCR2 axis represent a new therapeutic intervention for inflammatory disease.
Excessive and prolonged inflammatory monocyte activity accelerates left ventricular remodeling after myocardial infarction (MI). After myocardial reperfusion, the CCL2/CCR2 axis is considered to be a key chemokine axis that initiates and modulates tissue inflammatory damage. Effectively blocking the CCL2/CCR2 axis can reduce the chemotaxis of inflammatory monocytes to the infarct area, which has important therapeutic value for the repair of myocardium after reperfusion injury (MI/R). Here, we propose a nanoparticle carrying CCL2 silencing short interfering RNA (siRNA), which is prepared by coating a lipid hybrid CCR2-overexprssion macrophage cell membrane on a siRNA-loaded mesoporous silica nanoparticle. The overexpression of CCR2 and adhesion factors on the macrophage membrane improves its targeting ability, directing nanoparticle to the myocardial infarction area of MI/R-induced mice, the overexpress CCR2 in the macrophage cell membrane also adsorb more CCL2. Then by fusing with the cell membrane, siRNA is released into the injured endothelial cells cytoplasm, silencing the expression of CCL2. In vivo administration of the formula blocked CCL2/CCR2 axis, reduce the chemotaxis of inflammatory cells, regulate the immune microenvironment, further decreasing myocardial infarction area and improving cardiac function. Targeted block of CCL2/CCR2 axis represent a new therapeutic intervention for inflammatory disease.
2026, 37(7): 111680
doi: 10.1016/j.cclet.2025.111680
摘要:
Among various smart drug delivery systems (DDSs), redox-responsive systems have emerged as promising platforms for tumor therapy. Herein, we successfully fabricated a tumor microenvironment dual redox-responsive nanoparticle platform (DTX@Cys-0E NPs) assembled from an L-cystine-based biodegradable polymer (Cys-0E) for efficient delivery of docetaxel (DTX). The engineered Cys-0E features a unique structure containing both disulfide bonds and peroxalate ester bonds, synthesized via a one-step reaction. Notably, the strategic incorporation of 6-o-palmitoyl ascorbic acid (PA) not only enhances the stability of DTX@Cys-0E NPs but also generates tumor-specific H2O2. This PA-mediated H2O2 production triggers the degradation of the peroxalate ester bond, followed by CO2 generation, which ultimately results in DTX-controlled release. Simultaneously, the disulfide bonds in Cys-0E react with high concentrations of glutathione (GSH) in tumor cells, increasing the reactive oxygen species (ROS) level, and further facilitating drug release. Both in vitro and in vivo experiment results show that, once DTX@Cys-0E NPs are enriched into tumor cells, the rapid degradation of Cys-0E triggered by these stimuli leads to a burst release of DTX, inducing tumor cell apoptosis and exhibiting significantly better tumor inhibition compared to free DTX. In summary, this novel dual redox-responsive nano platform holds great promise as a controlled drug release system for cancer therapy.
Among various smart drug delivery systems (DDSs), redox-responsive systems have emerged as promising platforms for tumor therapy. Herein, we successfully fabricated a tumor microenvironment dual redox-responsive nanoparticle platform (DTX@Cys-0E NPs) assembled from an L-cystine-based biodegradable polymer (Cys-0E) for efficient delivery of docetaxel (DTX). The engineered Cys-0E features a unique structure containing both disulfide bonds and peroxalate ester bonds, synthesized via a one-step reaction. Notably, the strategic incorporation of 6-o-palmitoyl ascorbic acid (PA) not only enhances the stability of DTX@Cys-0E NPs but also generates tumor-specific H2O2. This PA-mediated H2O2 production triggers the degradation of the peroxalate ester bond, followed by CO2 generation, which ultimately results in DTX-controlled release. Simultaneously, the disulfide bonds in Cys-0E react with high concentrations of glutathione (GSH) in tumor cells, increasing the reactive oxygen species (ROS) level, and further facilitating drug release. Both in vitro and in vivo experiment results show that, once DTX@Cys-0E NPs are enriched into tumor cells, the rapid degradation of Cys-0E triggered by these stimuli leads to a burst release of DTX, inducing tumor cell apoptosis and exhibiting significantly better tumor inhibition compared to free DTX. In summary, this novel dual redox-responsive nano platform holds great promise as a controlled drug release system for cancer therapy.
2026, 37(7): 111692
doi: 10.1016/j.cclet.2025.111692
摘要:
Ferroptosis, a form of programmed cell death driven by iron-dependent lipid peroxidation (LPO), has emerged as a promising therapeutic strategy for cancer. However, challenges such as uncontrolled iron delivery, insufficient ferroptosis induction efficiency, and off-target drug leakage limit its applications. To address these limitations, we developed a biomimetic nanoplatform (Fe-DTX@M) integrating cancer cell membrane-camouflaged Fe-based metallacycles with the chemotherapeutic drug docetaxel (DTX), which synergistically amplifies ferroptosis and apoptosis for precise and effective cervical cancer therapy. The membrane camouflage enabled highly efficient tumor-specific accumulation, achieving a 5.4-fold increase compared to non-targeted controls, and reduced systemic toxicity. Within tumors, Fe2+/Fe3+ cycles attributed to Fe-based metallacycle drove Fenton reactions to convert H2O2 into •OH, inducing LPO, while Fe3+-mediated glutathione depletion inhibited GPX4, amplifying ferroptosis with 2.4-fold malondialdehyde (MDA) increase. Acid-triggered DTX release of nanoplatform further promoted apoptosis, thereby enhancing therapeutic efficacy. Furthermore, Fe-DTX@M exhibited excellent long-term biocompatibility and safety in normal mice over 30 days post-intravenous injection. This combination of biomimetic metallacycles-induced ferroptosis and chemotherapy-induced apoptosis may provide a new paradigm for achieving effective cancer therapy.
Ferroptosis, a form of programmed cell death driven by iron-dependent lipid peroxidation (LPO), has emerged as a promising therapeutic strategy for cancer. However, challenges such as uncontrolled iron delivery, insufficient ferroptosis induction efficiency, and off-target drug leakage limit its applications. To address these limitations, we developed a biomimetic nanoplatform (Fe-DTX@M) integrating cancer cell membrane-camouflaged Fe-based metallacycles with the chemotherapeutic drug docetaxel (DTX), which synergistically amplifies ferroptosis and apoptosis for precise and effective cervical cancer therapy. The membrane camouflage enabled highly efficient tumor-specific accumulation, achieving a 5.4-fold increase compared to non-targeted controls, and reduced systemic toxicity. Within tumors, Fe2+/Fe3+ cycles attributed to Fe-based metallacycle drove Fenton reactions to convert H2O2 into •OH, inducing LPO, while Fe3+-mediated glutathione depletion inhibited GPX4, amplifying ferroptosis with 2.4-fold malondialdehyde (MDA) increase. Acid-triggered DTX release of nanoplatform further promoted apoptosis, thereby enhancing therapeutic efficacy. Furthermore, Fe-DTX@M exhibited excellent long-term biocompatibility and safety in normal mice over 30 days post-intravenous injection. This combination of biomimetic metallacycles-induced ferroptosis and chemotherapy-induced apoptosis may provide a new paradigm for achieving effective cancer therapy.
2026, 37(7): 111694
doi: 10.1016/j.cclet.2025.111694
摘要:
Prodrug nanoassemblies (NPs) have attracted much attention in improving the selectivity of chemotherapy drugs, while most of them suffer from poor targeting efficiency. Biotin, a well-known tumor-targeting ligand, can greatly enhance tumor accumulation. Herein, we construct the biotinylated prodrug (Biotin-PTX) by connecting paclitaxel (PTX) to biotin via a disulfide bond, enabling the prodrug to self-assemble into nanoparticles (Biotin-PTX NPs). However, the pure NPs are observed to be rapidly cleared without polyethylene glycol (PEG) modifying, while excessive PEG can compromise their targeting efficiency, suggesting that it is crucial to optimize the amount of PEG. On this basis, the effect of distearoyl phosphatidylethanolamine-polyethylene glycol2000 (DSPE-PEG2k) ratios (0%, 5%, 10%, 20%, 40% and 60%, WPEG/Wprodrug+PEG) on their performance have been investigated. The results provide evidence that Biotin-PTX NPs containing 20% DSPE-PEG2k (20% NPs) can significantly improve colloidal stability and tumor-targeting efficiency. Moreover, 20% NPs exhibits good antitumor efficacy and safety compared with Taxol, Abraxane and Prodrug Sol. This work highlights the key role of moderate PEGylation in regulating the therapeutic performance of targeting NPs, offering a new way of thinking for tumor-targeting treatment.
Prodrug nanoassemblies (NPs) have attracted much attention in improving the selectivity of chemotherapy drugs, while most of them suffer from poor targeting efficiency. Biotin, a well-known tumor-targeting ligand, can greatly enhance tumor accumulation. Herein, we construct the biotinylated prodrug (Biotin-PTX) by connecting paclitaxel (PTX) to biotin via a disulfide bond, enabling the prodrug to self-assemble into nanoparticles (Biotin-PTX NPs). However, the pure NPs are observed to be rapidly cleared without polyethylene glycol (PEG) modifying, while excessive PEG can compromise their targeting efficiency, suggesting that it is crucial to optimize the amount of PEG. On this basis, the effect of distearoyl phosphatidylethanolamine-polyethylene glycol2000 (DSPE-PEG2k) ratios (0%, 5%, 10%, 20%, 40% and 60%, WPEG/Wprodrug+PEG) on their performance have been investigated. The results provide evidence that Biotin-PTX NPs containing 20% DSPE-PEG2k (20% NPs) can significantly improve colloidal stability and tumor-targeting efficiency. Moreover, 20% NPs exhibits good antitumor efficacy and safety compared with Taxol, Abraxane and Prodrug Sol. This work highlights the key role of moderate PEGylation in regulating the therapeutic performance of targeting NPs, offering a new way of thinking for tumor-targeting treatment.
2026, 37(7): 111714
doi: 10.1016/j.cclet.2025.111714
摘要:
Age-related macular degeneration (AMD) represents a primary cause of vision loss in the elderly population. Reactive oxygen species (ROS) generation constitutes a pivotal pathogenesis mechanism in AMD. Berberine (BBR) shows therapeutic potential for dry AMD through its ability to mitigate cellular senescence and oxidative stress. However, BBR’s low transmembrane permeability severely limits corneal penetration via topic administration, creating an urgent need for novel posterior segment delivery strategies. In this study, we employed biocompatible ionic liquids (ILs) to enhance BBR permeation for posterior AMD treatment. Our approach features ocular surface pretreatment with ILs followed by topical administration of BBR solution. Comprehensive in vitro and in vivo safety assessments confirmed the biocompatibility of monoethanolamine-based IL (Mea-ILs) as ocular penetration enhancers. Trans-monolayer experiments using human corneal epithelial cells (HCECs) demonstrated that ILs enhance paracellular permeability, potentially through tight junction modulation. In vivo studies utilizing a sodium iodate-induced dry AMD mouse model revealed that pretreatment with the [monoethanolamine][citric acid] ([Mea][Ci]) IL significantly potentiated BBR's therapeutic efficacy. These findings not only expand pharmaceutical applications of ILs but also establish a safe, efficient strategy for noninvasive dry AMD therapy with BBR. Furthermore, this work provides critical insights for developing advanced penetration enhancers for posterior ocular drug delivery.
Age-related macular degeneration (AMD) represents a primary cause of vision loss in the elderly population. Reactive oxygen species (ROS) generation constitutes a pivotal pathogenesis mechanism in AMD. Berberine (BBR) shows therapeutic potential for dry AMD through its ability to mitigate cellular senescence and oxidative stress. However, BBR’s low transmembrane permeability severely limits corneal penetration via topic administration, creating an urgent need for novel posterior segment delivery strategies. In this study, we employed biocompatible ionic liquids (ILs) to enhance BBR permeation for posterior AMD treatment. Our approach features ocular surface pretreatment with ILs followed by topical administration of BBR solution. Comprehensive in vitro and in vivo safety assessments confirmed the biocompatibility of monoethanolamine-based IL (Mea-ILs) as ocular penetration enhancers. Trans-monolayer experiments using human corneal epithelial cells (HCECs) demonstrated that ILs enhance paracellular permeability, potentially through tight junction modulation. In vivo studies utilizing a sodium iodate-induced dry AMD mouse model revealed that pretreatment with the [monoethanolamine][citric acid] ([Mea][Ci]) IL significantly potentiated BBR's therapeutic efficacy. These findings not only expand pharmaceutical applications of ILs but also establish a safe, efficient strategy for noninvasive dry AMD therapy with BBR. Furthermore, this work provides critical insights for developing advanced penetration enhancers for posterior ocular drug delivery.
2026, 37(7): 111722
doi: 10.1016/j.cclet.2025.111722
摘要:
Acute respiratory distress syndrome (ARDS) is one of the diseases with a significant mortality rate due to respiratory failure. Yet, malignant microenvironment (MM) composed mainly of inflammatory cytokines (IC) and reactive oxygen species (ROS) limit the therapeutic effect. Herein we construct the nanoparticles (NPs) BSA-MnO2@Tan-IIA/PSLs (BMTPLs) to disrupt the vicious cycle between IC and ROS by suppressing IC production and scavenging ROS, which effectively remodels the MM of ARDS. The BMTPLs composed of the water-dispersible BSA-MnO2 (BM) and phosphatidylserine (PS)-consisting lipid shell containing lipophilic tanshinone IIA (Tan-IIA). After phagocytosed by activated macrophages (M1) in an efferocytosis-like manner originating from the PS effect, the released Tan-IIA inhibit NF-κB pathway and further suppresses the secretion of IC. Concurrently, BM scavenging ROS alleviates the oxidative stress microenvironment, which deeply enhances the anti-inflammation effect of Tan-IIA. Moreover, the low-level ROS and down-regulation IC promote the transformation from pro-inflammatory M1 to anti-inflammatory M2 contributing to restoring tissue homeostasis. The results in vitro and in vivo indicate that the MM of ARDS can be effectively remodeled by BMTPLs, which holds great potential for ARDS treatment.
Acute respiratory distress syndrome (ARDS) is one of the diseases with a significant mortality rate due to respiratory failure. Yet, malignant microenvironment (MM) composed mainly of inflammatory cytokines (IC) and reactive oxygen species (ROS) limit the therapeutic effect. Herein we construct the nanoparticles (NPs) BSA-MnO2@Tan-IIA/PSLs (BMTPLs) to disrupt the vicious cycle between IC and ROS by suppressing IC production and scavenging ROS, which effectively remodels the MM of ARDS. The BMTPLs composed of the water-dispersible BSA-MnO2 (BM) and phosphatidylserine (PS)-consisting lipid shell containing lipophilic tanshinone IIA (Tan-IIA). After phagocytosed by activated macrophages (M1) in an efferocytosis-like manner originating from the PS effect, the released Tan-IIA inhibit NF-κB pathway and further suppresses the secretion of IC. Concurrently, BM scavenging ROS alleviates the oxidative stress microenvironment, which deeply enhances the anti-inflammation effect of Tan-IIA. Moreover, the low-level ROS and down-regulation IC promote the transformation from pro-inflammatory M1 to anti-inflammatory M2 contributing to restoring tissue homeostasis. The results in vitro and in vivo indicate that the MM of ARDS can be effectively remodeled by BMTPLs, which holds great potential for ARDS treatment.
2026, 37(7): 111727
doi: 10.1016/j.cclet.2025.111727
摘要:
Ulcerative colitis (UC) is a chronic inflammatory bowel disease featured by dysregulated immune responses and compromised intestinal barrier function. Current therapies often suffer from limited efficacy and systemic side effects due to non-specific drug distribution. Here, we developed macrophage membrane-camouflaged nanovesicles (mcNVs) for targeted delivery of emodin (Emo) to inflamed colon tissues. The biomimetic nanovesicles were fabricated by fusing J774A.1 macrophage membranes with Emo-loaded liposomes, inheriting the parent cells' chemotactic homing capabilities while maintaining excellent drug loading and colloidal stability. Systematic characterization confirmed successful membrane integration, as evidenced by transmission electron microscope (TEM) imaging, particle size, and ζ potential analyses. In vitro studies demonstrated favorable sustained release and enhanced cellular uptake of Emo-loaded mcNVs (Emo-mcNVs) compared to conventional liposomes. In a sodium dextran sulfate (DSS)-induced murine colitis model, Emo-mcNVs exhibited superior colon-targeting capability through chemokine gradient recognition (C-C motif chemokine ligand (CCL)2/3/5), resulting in significantly improved therapeutic outcomes versus free Emo and 5-aminosalicylic acid controls. Treatment with Emo-mcNVs attenuated disease severity (reduced disease activity index (DAI) score), preserved the colon architecture, and decreased pro-inflammatory cytokines (tumor necrosis factor α (TNF-α), interleukin 1β (IL-1β), IL-6). Biodistribution studies using multimodal imaging confirmed specific accumulation in the inflamed colon tissue with minimal systemic exposure. This study presents a novel biohybrid delivery system that leverages the pathophysiology of UC for targeted therapy, offering a promising translational approach for inflammatory bowel diseases.
Ulcerative colitis (UC) is a chronic inflammatory bowel disease featured by dysregulated immune responses and compromised intestinal barrier function. Current therapies often suffer from limited efficacy and systemic side effects due to non-specific drug distribution. Here, we developed macrophage membrane-camouflaged nanovesicles (mcNVs) for targeted delivery of emodin (Emo) to inflamed colon tissues. The biomimetic nanovesicles were fabricated by fusing J774A.1 macrophage membranes with Emo-loaded liposomes, inheriting the parent cells' chemotactic homing capabilities while maintaining excellent drug loading and colloidal stability. Systematic characterization confirmed successful membrane integration, as evidenced by transmission electron microscope (TEM) imaging, particle size, and ζ potential analyses. In vitro studies demonstrated favorable sustained release and enhanced cellular uptake of Emo-loaded mcNVs (Emo-mcNVs) compared to conventional liposomes. In a sodium dextran sulfate (DSS)-induced murine colitis model, Emo-mcNVs exhibited superior colon-targeting capability through chemokine gradient recognition (C-C motif chemokine ligand (CCL)2/3/5), resulting in significantly improved therapeutic outcomes versus free Emo and 5-aminosalicylic acid controls. Treatment with Emo-mcNVs attenuated disease severity (reduced disease activity index (DAI) score), preserved the colon architecture, and decreased pro-inflammatory cytokines (tumor necrosis factor α (TNF-α), interleukin 1β (IL-1β), IL-6). Biodistribution studies using multimodal imaging confirmed specific accumulation in the inflamed colon tissue with minimal systemic exposure. This study presents a novel biohybrid delivery system that leverages the pathophysiology of UC for targeted therapy, offering a promising translational approach for inflammatory bowel diseases.
2026, 37(7): 111744
doi: 10.1016/j.cclet.2025.111744
摘要:
Phosgene, a highly toxic chemical warfare agent and industrial hazard, poses significant environmental and health risks, necessitating the development of rapid and reliable detection methods. Herein, we present a novel near infrared Ⅱ (NIR-Ⅱ) fluorescent probe based on silicon rhodamine and an o-phenylenediamine-responsive group for the sensitive and selective detection of phosgene. In the presence of phosgene, it generates a distinct color change and lights up NIR-Ⅱ (900 nm) emission, enabling both naked-eye visualization and fluorescence in vivo analysis. The probe shows rapid exceptional selectivity for phosgene and achieves rapid detection in solutions, gases, and soils. Notably, we successfully utilize this probe for in vivo imaging in Arabidopsis thaliana, enabling high signal-to-noise ratio real-time monitoring of phosgene within plant systems with minimal interference from autofluorescence. This work advances the design of reaction-based NIR-Ⅱ probes for hazardous chemical monitoring, combining simple operation, high sensitivity, and broad applicability, thereby contributing to environmental safety and sustainability.
Phosgene, a highly toxic chemical warfare agent and industrial hazard, poses significant environmental and health risks, necessitating the development of rapid and reliable detection methods. Herein, we present a novel near infrared Ⅱ (NIR-Ⅱ) fluorescent probe based on silicon rhodamine and an o-phenylenediamine-responsive group for the sensitive and selective detection of phosgene. In the presence of phosgene, it generates a distinct color change and lights up NIR-Ⅱ (900 nm) emission, enabling both naked-eye visualization and fluorescence in vivo analysis. The probe shows rapid exceptional selectivity for phosgene and achieves rapid detection in solutions, gases, and soils. Notably, we successfully utilize this probe for in vivo imaging in Arabidopsis thaliana, enabling high signal-to-noise ratio real-time monitoring of phosgene within plant systems with minimal interference from autofluorescence. This work advances the design of reaction-based NIR-Ⅱ probes for hazardous chemical monitoring, combining simple operation, high sensitivity, and broad applicability, thereby contributing to environmental safety and sustainability.
2026, 37(7): 111745
doi: 10.1016/j.cclet.2025.111745
摘要:
Nitric oxide (NO), a significant signaling molecule, plays essential roles in diverse physiological and pathological processes including cell senescence. Lysosomes are recognized as pivotal subcellular organelles of cellular senescence, whereas the influence of senescence on lysosomal NO homeostasis remains poorly understood. To explore the potential association between cellular senescence and alterations in lysosomal NO levels, herein, we developed FL-O1, a novel ratiometric fluorescent probe specifically designed for lysosomal NO detection. The probe selectively reacts with NO through the recognition unit of o-phenylenediamine, forming an extended conjugated system that generates a distinct ratiometric optical signal with exceptional sensitivity (detection limit = 95 nmol/L). FL-O1 exhibits versatile applications in both in vitro and in vivo contexts. It successfully visualizes exogenous and endogenous NO dynamics in live zebrafish models and enables specific monitoring of lysosomal NO levels in cellular systems. Importantly, the probe was utilized to quantitatively evaluate NO levels in senescent states of cancer and healthy cells. The results revealed two key insights: (1) Senescent cells consistently maintain higher NO concentrations compared to their non-senescent counterparts, and (2) senescent healthy cells exhibit elevated NO levels relative to senescent cancer cells. This innovative small-molecule probe represents a significant advancement in lysosomal NO imaging technology. Its unique design and capabilities provide a powerful tool for investigating the role of lysosomal NO in cellular senescence, potentially uncovering novel mechanistic insights and facilitating the development of targeted therapeutic strategies for senescence-related disorders.
Nitric oxide (NO), a significant signaling molecule, plays essential roles in diverse physiological and pathological processes including cell senescence. Lysosomes are recognized as pivotal subcellular organelles of cellular senescence, whereas the influence of senescence on lysosomal NO homeostasis remains poorly understood. To explore the potential association between cellular senescence and alterations in lysosomal NO levels, herein, we developed FL-O1, a novel ratiometric fluorescent probe specifically designed for lysosomal NO detection. The probe selectively reacts with NO through the recognition unit of o-phenylenediamine, forming an extended conjugated system that generates a distinct ratiometric optical signal with exceptional sensitivity (detection limit = 95 nmol/L). FL-O1 exhibits versatile applications in both in vitro and in vivo contexts. It successfully visualizes exogenous and endogenous NO dynamics in live zebrafish models and enables specific monitoring of lysosomal NO levels in cellular systems. Importantly, the probe was utilized to quantitatively evaluate NO levels in senescent states of cancer and healthy cells. The results revealed two key insights: (1) Senescent cells consistently maintain higher NO concentrations compared to their non-senescent counterparts, and (2) senescent healthy cells exhibit elevated NO levels relative to senescent cancer cells. This innovative small-molecule probe represents a significant advancement in lysosomal NO imaging technology. Its unique design and capabilities provide a powerful tool for investigating the role of lysosomal NO in cellular senescence, potentially uncovering novel mechanistic insights and facilitating the development of targeted therapeutic strategies for senescence-related disorders.
2026, 37(7): 111748
doi: 10.1016/j.cclet.2025.111748
摘要:
Extracellular vesicles (EVs), mainly comprising microvesicles (MiV) and exosomes (Exo), were successfully isolated from normal human embryonic kidney cells (HEK293T) and demonstrated specific uptake by human tongue squamous cell carcinoma cells (SCC-9). Initial mechanistic investigations revealed that both MiV and Exo were mainly internalized via endocytic pathways and predominantly relied on the surface proteins of SCC-9 cells for specific uptake. Furthermore, Exo, with better stability and uptake efficiency, were chosen as the carriers of the clinical drug cisplatin (CDDP) for the treatment of tongue cancer. Comprehensive in vitro and in vivo evaluations demonstrated that the Exo-CDDP system exhibited remarkable biocompatibility, mitigated drug-related toxicity and minimized CDDP efflux from tumor cells, and displayed potent anti-tumor efficacy. These findings collectively indicated that HEK293T-derived Exo represent a highly promising drug delivery platform for tongue cancer therapy, while simultaneously offering innovative ideas for the development of versatile Exo-based therapeutic delivery systems.
Extracellular vesicles (EVs), mainly comprising microvesicles (MiV) and exosomes (Exo), were successfully isolated from normal human embryonic kidney cells (HEK293T) and demonstrated specific uptake by human tongue squamous cell carcinoma cells (SCC-9). Initial mechanistic investigations revealed that both MiV and Exo were mainly internalized via endocytic pathways and predominantly relied on the surface proteins of SCC-9 cells for specific uptake. Furthermore, Exo, with better stability and uptake efficiency, were chosen as the carriers of the clinical drug cisplatin (CDDP) for the treatment of tongue cancer. Comprehensive in vitro and in vivo evaluations demonstrated that the Exo-CDDP system exhibited remarkable biocompatibility, mitigated drug-related toxicity and minimized CDDP efflux from tumor cells, and displayed potent anti-tumor efficacy. These findings collectively indicated that HEK293T-derived Exo represent a highly promising drug delivery platform for tongue cancer therapy, while simultaneously offering innovative ideas for the development of versatile Exo-based therapeutic delivery systems.
2026, 37(7): 111749
doi: 10.1016/j.cclet.2025.111749
摘要:
Core-shell capsules are excellent carriers, showing good performances in cargo protection and controlled release. However, the controlled encapsulation of solid particles in capsules remains a great challenge, severely limiting their widespread applications. Here, a millifluidic system assisted by periodic vibrations is developed to precisely control the preparation of particle-loaded capsules. A high-frequency low-amplitude vibration is applied to prevent the jamming of solid particles by shaking and a low-frequency high-amplitude vibration is applied to synchronize the feeding of solid particles and the emulsification of capsules by generating a periodic flow pulse. The phase diagrams of particle-loaded capsules are systematically investigated with respect to various experimental parameters to provide guidances for the controlled preparation process. The developed millifluidic system offers a versatile platform to precisely prepare core-shell capsules loaded with different sizes, types and numbers of particles. The prepared particle-loaded capsules possess good biocompatibility, monodispersity, mechanical strength, storage stability and controlled release, paving the way for their widespread applications.
Core-shell capsules are excellent carriers, showing good performances in cargo protection and controlled release. However, the controlled encapsulation of solid particles in capsules remains a great challenge, severely limiting their widespread applications. Here, a millifluidic system assisted by periodic vibrations is developed to precisely control the preparation of particle-loaded capsules. A high-frequency low-amplitude vibration is applied to prevent the jamming of solid particles by shaking and a low-frequency high-amplitude vibration is applied to synchronize the feeding of solid particles and the emulsification of capsules by generating a periodic flow pulse. The phase diagrams of particle-loaded capsules are systematically investigated with respect to various experimental parameters to provide guidances for the controlled preparation process. The developed millifluidic system offers a versatile platform to precisely prepare core-shell capsules loaded with different sizes, types and numbers of particles. The prepared particle-loaded capsules possess good biocompatibility, monodispersity, mechanical strength, storage stability and controlled release, paving the way for their widespread applications.
2026, 37(7): 111750
doi: 10.1016/j.cclet.2025.111750
摘要:
Cysteine (Cys), as a key precursor of glutathione (GSH) and an essential component of the thiol antioxidant system, plays a dual role in the pathological progression of Alzheimer’s disease (AD): it participates in antioxidant defense mechanisms while also potentially exacerbating neurological damage through metabolic dysregulation. Investigating the dynamic regulatory mechanisms of Cys in AD progression serves as a critical bridge linking oxidative stress, metabolic dysregulation, and neurodegenerative degeneration. High-resolution in vivo imaging of Cys dynamics in AD brains remains an unmet need. In view of the instability of the fluorescent probe of acrylyl group and the lack of specificity for Cys. This work introduced chlorine atoms into the probe structure, and achieved dual modifications: (1) Converting the nucleophilic addition mechanism into an SN2 substitution; (2) modulating the conjugation effects between the formyl group and the three-position double bond. In this way, the stability of the probe, the high specificity of Cys, and the crossing of the blood-brain barrier are addressed. Through in situ imaging in AD models, we have demonstrated a pathological reduction in Cys levels during AD. Furthermore, as Cys serves as the core molecule in the regulation of ferroptosis, it was found that ferroptosis can mediate the down-regulation of Cys in AD through ferroptosis inducers and inhibitors. This study is not only to reveal the core pathological mechanism of AD, but to provide theoretical basis and technical support for early diagnosis, targeted therapy and personalized medicine.
Cysteine (Cys), as a key precursor of glutathione (GSH) and an essential component of the thiol antioxidant system, plays a dual role in the pathological progression of Alzheimer’s disease (AD): it participates in antioxidant defense mechanisms while also potentially exacerbating neurological damage through metabolic dysregulation. Investigating the dynamic regulatory mechanisms of Cys in AD progression serves as a critical bridge linking oxidative stress, metabolic dysregulation, and neurodegenerative degeneration. High-resolution in vivo imaging of Cys dynamics in AD brains remains an unmet need. In view of the instability of the fluorescent probe of acrylyl group and the lack of specificity for Cys. This work introduced chlorine atoms into the probe structure, and achieved dual modifications: (1) Converting the nucleophilic addition mechanism into an SN2 substitution; (2) modulating the conjugation effects between the formyl group and the three-position double bond. In this way, the stability of the probe, the high specificity of Cys, and the crossing of the blood-brain barrier are addressed. Through in situ imaging in AD models, we have demonstrated a pathological reduction in Cys levels during AD. Furthermore, as Cys serves as the core molecule in the regulation of ferroptosis, it was found that ferroptosis can mediate the down-regulation of Cys in AD through ferroptosis inducers and inhibitors. This study is not only to reveal the core pathological mechanism of AD, but to provide theoretical basis and technical support for early diagnosis, targeted therapy and personalized medicine.
2026, 37(7): 111775
doi: 10.1016/j.cclet.2025.111775
摘要:
Polymer dielectric capacitors are crucial for advanced power electronics but are often limited by the trade-off among energy density, efficiency, and thermal stability under high electric fields. To overcome these challenges, we propose a multiscale chemical configuration design strategy by constructing a ternary composite comprising high glass transition temperature fluorene polyester (FPE), polyetherimide (PEI), and high-aspect-ratio γ-Al2O3 nanosheets (AO NS). At the molecular scale, the structural compatibility between FPE and PEI enables homogeneous blending, while the incorporation of PEI increases free volume, enhances dipolar mobility, and preserves low dielectric loss. At the nanoscale, AO NS act as ceramic barriers to suppress charge injection, raise interfacial polarization, and stabilize the local electric field. At the device level, this hierarchical design leads to synergistic improvements in dielectric properties, insulation, and energy storage performance. As a result, the optimized composite achieves excellent high-temperature energy-storage capability, characterized by a high energy density of 5.51 J/cm3 with above 80% efficiency at 150 ℃ and 550 MV/m. This study paves a practical and scalable path toward high-performance polymer dielectrics for reliable energy storage under extreme thermal and electrical conditions.
Polymer dielectric capacitors are crucial for advanced power electronics but are often limited by the trade-off among energy density, efficiency, and thermal stability under high electric fields. To overcome these challenges, we propose a multiscale chemical configuration design strategy by constructing a ternary composite comprising high glass transition temperature fluorene polyester (FPE), polyetherimide (PEI), and high-aspect-ratio γ-Al2O3 nanosheets (AO NS). At the molecular scale, the structural compatibility between FPE and PEI enables homogeneous blending, while the incorporation of PEI increases free volume, enhances dipolar mobility, and preserves low dielectric loss. At the nanoscale, AO NS act as ceramic barriers to suppress charge injection, raise interfacial polarization, and stabilize the local electric field. At the device level, this hierarchical design leads to synergistic improvements in dielectric properties, insulation, and energy storage performance. As a result, the optimized composite achieves excellent high-temperature energy-storage capability, characterized by a high energy density of 5.51 J/cm3 with above 80% efficiency at 150 ℃ and 550 MV/m. This study paves a practical and scalable path toward high-performance polymer dielectrics for reliable energy storage under extreme thermal and electrical conditions.
2026, 37(7): 111798
doi: 10.1016/j.cclet.2025.111798
摘要:
Biomolecular self-assembly systems form the cornerstone of biological structures, in which the interactions between carbohydrates and proteins play a crucial role in many life processes. This has driven the development of biomimetic carbohydrate-protein supramolecular assemblies (BCPSAs), which show great potential in biomedical research. We successfully constructed a novel supramolecular hybrid nanocarrier with pH responsiveness and targeting capabilities based on specific interactions between carbohydrates and proteins. This system self-assembles into nanoparticles CA@MP5 in water through the specific binding of mannose clusters on glycosylated pillar[5]arene MP5 with lectin Con A. Additionally, through a host-guest assembly strategy with the synthesized β-d-galactopyranosyl pyridine derivative G, it complexes within the MP5 cavity to form a "double-sweet" supramolecular glyco-nanoprotein (CA@MP5⊃G). This system shows high affinity for the asialoglycoprotein receptor (ASGPR) on HepG2 liver cancer cells. In vitro, the doxorubicin (DOX)-loaded micelles (DCA@MP5⊃G) release drug effectively in acidic environments and significantly inhibit HepG2 cell growth, with reduced toxicity toward normal cells. In vivo, the nanocarrier targets tumors effectively, reducing systemic toxicity and inhibiting tumor growth. This study offers a novel construction strategy for drug delivery systems based on carbohydrate-protein interactions in anti-tumor applications, which is significant for enhancing therapeutic efficacy.
Biomolecular self-assembly systems form the cornerstone of biological structures, in which the interactions between carbohydrates and proteins play a crucial role in many life processes. This has driven the development of biomimetic carbohydrate-protein supramolecular assemblies (BCPSAs), which show great potential in biomedical research. We successfully constructed a novel supramolecular hybrid nanocarrier with pH responsiveness and targeting capabilities based on specific interactions between carbohydrates and proteins. This system self-assembles into nanoparticles CA@MP5 in water through the specific binding of mannose clusters on glycosylated pillar[5]arene MP5 with lectin Con A. Additionally, through a host-guest assembly strategy with the synthesized β-d-galactopyranosyl pyridine derivative G, it complexes within the MP5 cavity to form a "double-sweet" supramolecular glyco-nanoprotein (CA@MP5⊃G). This system shows high affinity for the asialoglycoprotein receptor (ASGPR) on HepG2 liver cancer cells. In vitro, the doxorubicin (DOX)-loaded micelles (DCA@MP5⊃G) release drug effectively in acidic environments and significantly inhibit HepG2 cell growth, with reduced toxicity toward normal cells. In vivo, the nanocarrier targets tumors effectively, reducing systemic toxicity and inhibiting tumor growth. This study offers a novel construction strategy for drug delivery systems based on carbohydrate-protein interactions in anti-tumor applications, which is significant for enhancing therapeutic efficacy.
2026, 37(7): 111816
doi: 10.1016/j.cclet.2025.111816
摘要:
Achieving efficient and sustainable hydrogen production from methanol electrolysis requires significant advances in catalyst design. In this study, we present a novel strategy where nickel selenide, featuring distinct crystal phases, anchors on mesoporous hollow carbon spheres to synergistically enhance the activity of Pt for methanol-assisted water splitting reactions. The heterostructured NiSe/NiSe2 nanosheets modulate the electronic structure of Pt, positioning it closer to an optimal thermodynamic state, and creating a highly oxophilic environment that accelerates charge transfer and optimizes the adsorption and desorption of reaction intermediates. The engineered hybrid catalyst exhibits exceptional enhancements in both mass and specific activity for methanol oxidation, significantly outperforming commercial catalysts. In addition, the catalyst exhibits a high electroactive surface area, an abundance of active sites, fast catalytic kinetics, and excellent stability. Notably, a methanol electrolyzer utilizing this catalyst achieves a current density of 10 mA/cm2 at only 0.67 V, a remarkable 1.08 V reduction compared to the voltage required for conventional water electrolysis (1.75 V). This work provides a transformative strategy for designing high-performance electrocatalysts, offering new pathways for more efficient and sustainable hydrogen production through methanol electrolysis.
Achieving efficient and sustainable hydrogen production from methanol electrolysis requires significant advances in catalyst design. In this study, we present a novel strategy where nickel selenide, featuring distinct crystal phases, anchors on mesoporous hollow carbon spheres to synergistically enhance the activity of Pt for methanol-assisted water splitting reactions. The heterostructured NiSe/NiSe2 nanosheets modulate the electronic structure of Pt, positioning it closer to an optimal thermodynamic state, and creating a highly oxophilic environment that accelerates charge transfer and optimizes the adsorption and desorption of reaction intermediates. The engineered hybrid catalyst exhibits exceptional enhancements in both mass and specific activity for methanol oxidation, significantly outperforming commercial catalysts. In addition, the catalyst exhibits a high electroactive surface area, an abundance of active sites, fast catalytic kinetics, and excellent stability. Notably, a methanol electrolyzer utilizing this catalyst achieves a current density of 10 mA/cm2 at only 0.67 V, a remarkable 1.08 V reduction compared to the voltage required for conventional water electrolysis (1.75 V). This work provides a transformative strategy for designing high-performance electrocatalysts, offering new pathways for more efficient and sustainable hydrogen production through methanol electrolysis.
2026, 37(7): 111819
doi: 10.1016/j.cclet.2025.111819
摘要:
Alkylated arenes, which are prevalent molecular building blocks, are widely applicable across various scientific domains. However, regioselectively alkylating arenes often poses significant challenges, despite their apparent simplicities. Herein, we report the first examples of substrate-controlled photocatalyzed regiodivergent alkylations of aromatic nitriles. The judicious choice of alkyl halide facilitated selection of mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path that proceeds via radical coupling and a Friedel−Crafts-type C–H alkylation via quantum mechanical tunneling, enabled selective access to regioisomeric alkylated arenes. Mechanistic investigations combined with density functional theory (DFT) calculations shed light on the origin of this regioselectivity switch. Remarkably, this process exhibited superior efficiencies, reactivities, and synthetic utilities, and can be performed on the gram scale.
Alkylated arenes, which are prevalent molecular building blocks, are widely applicable across various scientific domains. However, regioselectively alkylating arenes often poses significant challenges, despite their apparent simplicities. Herein, we report the first examples of substrate-controlled photocatalyzed regiodivergent alkylations of aromatic nitriles. The judicious choice of alkyl halide facilitated selection of mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path that proceeds via radical coupling and a Friedel−Crafts-type C–H alkylation via quantum mechanical tunneling, enabled selective access to regioisomeric alkylated arenes. Mechanistic investigations combined with density functional theory (DFT) calculations shed light on the origin of this regioselectivity switch. Remarkably, this process exhibited superior efficiencies, reactivities, and synthetic utilities, and can be performed on the gram scale.
2026, 37(7): 111820
doi: 10.1016/j.cclet.2025.111820
摘要:
The potential use of ammonia (NH3) as a hydrogen energy carrier has generated significant interest in developing efficient catalysts for producing NH3 under mild conditions. The main obstacles for NH3 synthesis are the activation of the N≡N bond and the desorption of NH3 from the catalyst surface. Here, we report the use of C60 to overcome these challenges. Through electron transfer, migration, and feedback between C60 and Ru, there is a balance of electronic density at the Ru active sites and a shift in the d-band center. This simultaneously satisfies the electronic requirements for enhancing N2 activation while weakening NH3 adsorption, thereby circumventing the bottlenecks in NH3 synthesis under mild conditions. Meanwhile, anchoring of C60 accelerates hydrogen spillover and enhances the exchangeability of hydrogen species in the ZrH2 support, as well as expose a greater number of B5 sites of Ru entities, resulting in the co-optimization of hydrogen migration and nitrogen activation. As a consequence, the NH3 synthesis rate of the C60-Ru/ZrH2 catalyst is approximately twice that of the Ru/ZrH2 catalyst at 400 ℃ and 1 MPa. This study shows that doping C60 represents a fundamentally different approach compared to traditional promoters for catalytic NH3 synthesis. We anticipate that this strategy may be generalized to generate widespread interest in the catalysis of NH3 synthesis.
The potential use of ammonia (NH3) as a hydrogen energy carrier has generated significant interest in developing efficient catalysts for producing NH3 under mild conditions. The main obstacles for NH3 synthesis are the activation of the N≡N bond and the desorption of NH3 from the catalyst surface. Here, we report the use of C60 to overcome these challenges. Through electron transfer, migration, and feedback between C60 and Ru, there is a balance of electronic density at the Ru active sites and a shift in the d-band center. This simultaneously satisfies the electronic requirements for enhancing N2 activation while weakening NH3 adsorption, thereby circumventing the bottlenecks in NH3 synthesis under mild conditions. Meanwhile, anchoring of C60 accelerates hydrogen spillover and enhances the exchangeability of hydrogen species in the ZrH2 support, as well as expose a greater number of B5 sites of Ru entities, resulting in the co-optimization of hydrogen migration and nitrogen activation. As a consequence, the NH3 synthesis rate of the C60-Ru/ZrH2 catalyst is approximately twice that of the Ru/ZrH2 catalyst at 400 ℃ and 1 MPa. This study shows that doping C60 represents a fundamentally different approach compared to traditional promoters for catalytic NH3 synthesis. We anticipate that this strategy may be generalized to generate widespread interest in the catalysis of NH3 synthesis.
2026, 37(7): 111821
doi: 10.1016/j.cclet.2025.111821
摘要:
Mechanistic studies of the transmetalation of the trifluoromethyl group from an ionic Cu(Ⅰ) complex Q+[Cu(CF3)2]− to a well-defined chlorinated Cu(Ⅲ) complex trans-[Cu(CF3)2(Cl)(CH2CN)]−Q+ was reported. The combined experimental and computational results including kinetics of the process, reactions in the presence of excess chloride salt, or radical scavengers such as TEMPO or 1, 1-diphenylethene (DPE), 1, 4-dinitrobenzene (DNB), strongly support a concerted metathesis pathway.
Mechanistic studies of the transmetalation of the trifluoromethyl group from an ionic Cu(Ⅰ) complex Q+[Cu(CF3)2]− to a well-defined chlorinated Cu(Ⅲ) complex trans-[Cu(CF3)2(Cl)(CH2CN)]−Q+ was reported. The combined experimental and computational results including kinetics of the process, reactions in the presence of excess chloride salt, or radical scavengers such as TEMPO or 1, 1-diphenylethene (DPE), 1, 4-dinitrobenzene (DNB), strongly support a concerted metathesis pathway.
2026, 37(7): 111822
doi: 10.1016/j.cclet.2025.111822
摘要:
The etiology and pathogenesis of Parkinson's disease (PD) are complex, and its precise pathology remains poorly defined. Emerging evidence suggest that the dysregulation of intracellular copper ion (Cu2+) is tightly associated with PD progression. However, the dynamic interplay between Cu2+ and different stages of PD progression is not fully understood yet. In this study, we developed four Cu2+ fluorescent sensors and evaluated their blood-brain barrier (BBB) penetration efficiency. Among them, PD-Cu-3 exhibited a 62.15% BBB penetration ability and was successfully utilized for real-time monitoring of Cu2+ fluctuations in PD model cells and mice. We first observed an initial increase in Cu2+ level during the early phase PD model cells, followed by a decline in prolonged conditions due to ATP7A-mediated intracellular Cu2+ efflux. Furthermore, in vivo imaging results from PD model mice and brain slices revealed Cu2+ fluctuations across different PD stages, with an elevation in the acute stage and a subsequent reduction in the subacute stage. This study not only provided a new insight into Cu2+ metabolism in PD progression but also help understanding of PD pathology and searching potential therapeutic approaches.
The etiology and pathogenesis of Parkinson's disease (PD) are complex, and its precise pathology remains poorly defined. Emerging evidence suggest that the dysregulation of intracellular copper ion (Cu2+) is tightly associated with PD progression. However, the dynamic interplay between Cu2+ and different stages of PD progression is not fully understood yet. In this study, we developed four Cu2+ fluorescent sensors and evaluated their blood-brain barrier (BBB) penetration efficiency. Among them, PD-Cu-3 exhibited a 62.15% BBB penetration ability and was successfully utilized for real-time monitoring of Cu2+ fluctuations in PD model cells and mice. We first observed an initial increase in Cu2+ level during the early phase PD model cells, followed by a decline in prolonged conditions due to ATP7A-mediated intracellular Cu2+ efflux. Furthermore, in vivo imaging results from PD model mice and brain slices revealed Cu2+ fluctuations across different PD stages, with an elevation in the acute stage and a subsequent reduction in the subacute stage. This study not only provided a new insight into Cu2+ metabolism in PD progression but also help understanding of PD pathology and searching potential therapeutic approaches.
2026, 37(7): 111823
doi: 10.1016/j.cclet.2025.111823
摘要:
Switchable chirality in confined environments is central to biological regulation, yet artificial systems enabling reversible chirality control remain challenging. Herein, we report a redox-responsive supramolecular chirality system constructed from phenylalanine-modified viologen (d/l-PheVio⋅2Br) and cucurbit[8]uril (CB[8]) in aqueous solution. The formation of 1:1 host-guest complex triggers pronounced chirality amplification, evident from characteristic induced circular dichroism (ICD) signals. Upon chemical reduction, these ICD signals vanish abruptly, replaced by unusual CD signals from viologen radical cations, demonstrating chirality transfer enabled by the confined environment. The redox-switchable process exhibits exceptional reversibility and repeatability over multiple cycles. These findings deepen our understanding of supramolecular chirality arising from host-guest complexation in confined spaces at the molecular level, offering new perspectives for designing stimuli-responsive chiral materials.
Switchable chirality in confined environments is central to biological regulation, yet artificial systems enabling reversible chirality control remain challenging. Herein, we report a redox-responsive supramolecular chirality system constructed from phenylalanine-modified viologen (d/l-PheVio⋅2Br) and cucurbit[8]uril (CB[8]) in aqueous solution. The formation of 1:1 host-guest complex triggers pronounced chirality amplification, evident from characteristic induced circular dichroism (ICD) signals. Upon chemical reduction, these ICD signals vanish abruptly, replaced by unusual CD signals from viologen radical cations, demonstrating chirality transfer enabled by the confined environment. The redox-switchable process exhibits exceptional reversibility and repeatability over multiple cycles. These findings deepen our understanding of supramolecular chirality arising from host-guest complexation in confined spaces at the molecular level, offering new perspectives for designing stimuli-responsive chiral materials.
2026, 37(7): 111833
doi: 10.1016/j.cclet.2025.111833
摘要:
Ultra-thick electrodes (UTEs) hold great promise for high-energy-density lithium-ion batteries (LIBs), yet the practical application is hindered by challenges in precise fabrication and reaction kinetics modification. In this contribution, a solvent-free processing method is introduced to tailor UTEs through layer-by-layer fabrication with positive, uniform, and negative gradient porosity from the separator side to the current collector side, denoted as P-UTEs, U-UTEs, and N-UTEs. In contrast to conventional slurry coating, the proposed solvent-free approach effectively circumvents capillary stress, thereby facilitating the fabrication of crack-free UTEs (> 300 µm) while simultaneously mitigating environmental toxicity concerns. The three-layer N-UTEs (> 220 µm) with a gradient porosity of (~34%, ~31%, ~27%) deliver an exceeding areal capacity over 5 mAh/cm2 at 0.29 mA/cm2 and a high-capacity retention over 62% at 2.9 mA/cm2, indicating a favorable balance between the areal capacity and the high-rate behavior. Detailed mechanistic simulations reveal that the multi-center reaction pathways enabled by enhanced ionic accessibility in N-UTEs significantly improve reaction kinetics. This work offers new insights into the gradient porosity tailoring for high-areal-capacity and high-rate UTEs for the next generation LIBs.
Ultra-thick electrodes (UTEs) hold great promise for high-energy-density lithium-ion batteries (LIBs), yet the practical application is hindered by challenges in precise fabrication and reaction kinetics modification. In this contribution, a solvent-free processing method is introduced to tailor UTEs through layer-by-layer fabrication with positive, uniform, and negative gradient porosity from the separator side to the current collector side, denoted as P-UTEs, U-UTEs, and N-UTEs. In contrast to conventional slurry coating, the proposed solvent-free approach effectively circumvents capillary stress, thereby facilitating the fabrication of crack-free UTEs (> 300 µm) while simultaneously mitigating environmental toxicity concerns. The three-layer N-UTEs (> 220 µm) with a gradient porosity of (~34%, ~31%, ~27%) deliver an exceeding areal capacity over 5 mAh/cm2 at 0.29 mA/cm2 and a high-capacity retention over 62% at 2.9 mA/cm2, indicating a favorable balance between the areal capacity and the high-rate behavior. Detailed mechanistic simulations reveal that the multi-center reaction pathways enabled by enhanced ionic accessibility in N-UTEs significantly improve reaction kinetics. This work offers new insights into the gradient porosity tailoring for high-areal-capacity and high-rate UTEs for the next generation LIBs.
2026, 37(7): 111849
doi: 10.1016/j.cclet.2025.111849
摘要:
Developing metal matrix composites with low thermal expansion yet high thermal conductivity (λ) has been an ongoing effort in electronic packaging materials due to the growing demand for high-power applications. However, progress has been hindered by the insufficient thermal expansion suppression of conventional low thermal expansion reinforcements or the low λ of negative thermal expansion reinforcements. In this study, this challenge is overcome via a multiphase design strategy using ZrW2O8 and SiC to co-reinforce the aluminum matrix composites. This approach simultaneously combines the advantages of the ZrW2O8 for controlling the coefficient of thermal expansion (CTE) and SiC for improving λ. A controlled CTE-λ balance (6.22–9.7 × 10–6 K-1, 63.1–131.1 W/mK) can be obtained by varying the volume ratio of ZrW2O8 to SiC. The CTE of this composite is significantly lower than that of the 50 vol% SiC/Al composite, while its CTE is approximately equal to that of the 45 vol% ZrW2O8/Al composite but with a twofold increase in λ. The good thermal performance of this composite can be attributed to the strong interfacial interactions of SiC and the tailored variation in CTE. Furthermore, simulation and experimental results revealed that the residual stress can be effectively relieved through this strategy. This work presents a straightforward structural design and an effective pathway to manufacture composites with excellent integrated properties.
Developing metal matrix composites with low thermal expansion yet high thermal conductivity (λ) has been an ongoing effort in electronic packaging materials due to the growing demand for high-power applications. However, progress has been hindered by the insufficient thermal expansion suppression of conventional low thermal expansion reinforcements or the low λ of negative thermal expansion reinforcements. In this study, this challenge is overcome via a multiphase design strategy using ZrW2O8 and SiC to co-reinforce the aluminum matrix composites. This approach simultaneously combines the advantages of the ZrW2O8 for controlling the coefficient of thermal expansion (CTE) and SiC for improving λ. A controlled CTE-λ balance (6.22–9.7 × 10–6 K-1, 63.1–131.1 W/mK) can be obtained by varying the volume ratio of ZrW2O8 to SiC. The CTE of this composite is significantly lower than that of the 50 vol% SiC/Al composite, while its CTE is approximately equal to that of the 45 vol% ZrW2O8/Al composite but with a twofold increase in λ. The good thermal performance of this composite can be attributed to the strong interfacial interactions of SiC and the tailored variation in CTE. Furthermore, simulation and experimental results revealed that the residual stress can be effectively relieved through this strategy. This work presents a straightforward structural design and an effective pathway to manufacture composites with excellent integrated properties.
2026, 37(7): 111922
doi: 10.1016/j.cclet.2025.111922
摘要:
α-d-Fructofuranoside derivatives are prevalent in natural products, exhibiting diverse bioactivities. Herein, a stereoselective glycosylation method for synthesizing α-d-fructofuranosides using fructofuranosyl fluorides as donors is described. Glycosylation of 1,3,4,6-tetra-O-benzoyl-2-d-fructofuranosyl fluoride, promoted by tris(pentafluorophenyl)borane, proved highly effective, yielding glycosylation products in high yields (up to 98%) with primary alcohols, thiols, N- and C-nucleophiles. Furthermore, β-(2→6) cyclodisaccharide di-d-fructose-2,6′:6,2′-dianhydride (DFA Ⅳ), a disaccharide enzymatically derived from levan, was chemically synthesized through orthogonal glycosylation reactions and hydrogen-bond-mediated aglycone delivery involving thioglycosides and glycosyl fluorides for the first time.
α-d-Fructofuranoside derivatives are prevalent in natural products, exhibiting diverse bioactivities. Herein, a stereoselective glycosylation method for synthesizing α-d-fructofuranosides using fructofuranosyl fluorides as donors is described. Glycosylation of 1,3,4,6-tetra-O-benzoyl-2-d-fructofuranosyl fluoride, promoted by tris(pentafluorophenyl)borane, proved highly effective, yielding glycosylation products in high yields (up to 98%) with primary alcohols, thiols, N- and C-nucleophiles. Furthermore, β-(2→6) cyclodisaccharide di-d-fructose-2,6′:6,2′-dianhydride (DFA Ⅳ), a disaccharide enzymatically derived from levan, was chemically synthesized through orthogonal glycosylation reactions and hydrogen-bond-mediated aglycone delivery involving thioglycosides and glycosyl fluorides for the first time.
2026, 37(7): 111939
doi: 10.1016/j.cclet.2025.111939
摘要:
The carbon-centered radical induced C‒C bond cleavage in strained cyclopropane is a well-known process. However, achieving similar transformations in unstrained rings is still challenging. Herein, a novel inexpensive Cu-catalyzed strategy for the carbon-centered radical-mediated ring-opening/amination or esterification cascade of unstrained α-haloalkyl cycloketone derivatives is presented. Differ from the classical Dowd-Beckwith ring expansion reaction, a ring opening cascade occurred successfully under a simple copper/base catalytic system, yielding useful distal unsaturated amides and esters in good to excellent yields. Mechanistic studies and DFT calculations indicate that the halogen-bonding interaction between halide and base is crucial for the activation of the C‒Br bond. Furthermore, the formation of a bicyclic Cu-complex via bi-dentate coordination, including O–Cu–•CH2, seems to be a crucial factor that promotes ring opening rather than the conventional ring expansion. This work would not only bring new vitality for the radical-mediated C‒C bond cleavage, but also highlight the potential of protocol for synthesizing bioactive molecules.
The carbon-centered radical induced C‒C bond cleavage in strained cyclopropane is a well-known process. However, achieving similar transformations in unstrained rings is still challenging. Herein, a novel inexpensive Cu-catalyzed strategy for the carbon-centered radical-mediated ring-opening/amination or esterification cascade of unstrained α-haloalkyl cycloketone derivatives is presented. Differ from the classical Dowd-Beckwith ring expansion reaction, a ring opening cascade occurred successfully under a simple copper/base catalytic system, yielding useful distal unsaturated amides and esters in good to excellent yields. Mechanistic studies and DFT calculations indicate that the halogen-bonding interaction between halide and base is crucial for the activation of the C‒Br bond. Furthermore, the formation of a bicyclic Cu-complex via bi-dentate coordination, including O–Cu–•CH2, seems to be a crucial factor that promotes ring opening rather than the conventional ring expansion. This work would not only bring new vitality for the radical-mediated C‒C bond cleavage, but also highlight the potential of protocol for synthesizing bioactive molecules.
2026, 37(7): 111940
doi: 10.1016/j.cclet.2025.111940
摘要:
gem–Difluorovinyl compounds and silicon-containing compounds are valuable structural units in organic and medicinal chemistry. However, they are mostly found separately in most compounds. In this study, we present a photocatalytic approach for the synthesis of gem–difluorovinylsilanes, using readily accessible silylboronic pinacol esters as reagents. Through a radical transfer strategy, this method overcomes the limitation of their high oxidation potential. Biological assays further confirmed that several target compounds exhibited moderate to potent antifungal activity against plant pathogens, including Botrytis cinerea, Setosphaeria turcica and Rhizoctonia solani.
gem–Difluorovinyl compounds and silicon-containing compounds are valuable structural units in organic and medicinal chemistry. However, they are mostly found separately in most compounds. In this study, we present a photocatalytic approach for the synthesis of gem–difluorovinylsilanes, using readily accessible silylboronic pinacol esters as reagents. Through a radical transfer strategy, this method overcomes the limitation of their high oxidation potential. Biological assays further confirmed that several target compounds exhibited moderate to potent antifungal activity against plant pathogens, including Botrytis cinerea, Setosphaeria turcica and Rhizoctonia solani.
2026, 37(7): 111941
doi: 10.1016/j.cclet.2025.111941
摘要:
The stereodivergent coupling via photoredox/transition metal catalysis has emerged as a powerful tool to construct diverse alkenes in both E and Z configurations. Despite well-established catalytic systems involving late transition metals, the early transition metal catalyzed stereodivergent synthesis of alkenes still remains underdeveloped. Herein in this work, a stereodivergent reductive C(sp2)-C(sp3) coupling between cycloketone oximes and vinyl halides has been achieved by tunable photoredox/Ti dual catalysis, providing a facile access to a broad scope of cyano-substituted (fluoro)alkenes with high efficiency and controlled E/Z selectivity. Several products exhibited promising antifungal activities.
The stereodivergent coupling via photoredox/transition metal catalysis has emerged as a powerful tool to construct diverse alkenes in both E and Z configurations. Despite well-established catalytic systems involving late transition metals, the early transition metal catalyzed stereodivergent synthesis of alkenes still remains underdeveloped. Herein in this work, a stereodivergent reductive C(sp2)-C(sp3) coupling between cycloketone oximes and vinyl halides has been achieved by tunable photoredox/Ti dual catalysis, providing a facile access to a broad scope of cyano-substituted (fluoro)alkenes with high efficiency and controlled E/Z selectivity. Several products exhibited promising antifungal activities.
2026, 37(7): 111943
doi: 10.1016/j.cclet.2025.111943
摘要:
Functionalized C−N atropisomers has become more and more attractive and found wide applications in natural products, drug molecules, as well as in chiral ligands. As a complement to asymmetric de novo ring formation and cross C−N coupling methods, the resolution approach demonstrates uniquely advantageous, which can progressively introduce the key functional groups and generate enantiomeric excess. Herein, we have developed an enzymatic tool for the construction of difunctionalized C−N atropisomers via lipase-catalyzed desymmetrization and kinetic resolution of N-naphthol-carbazoles. Acetylacetone was found as an efficient proton donor under the catalysis of LPL311-polyester. The enantioselective deacylation process has exhibited good functional group tolerance to produce enantioenriched C−N atropisomers with good to excellent enantioselectivity, in which the pre-installed hydroxyl functionality on the naphthene ring and the hydroxyl functionality on the carbazole ring generated after hydrolysis together provide feasibility for subsequent transformations.
Functionalized C−N atropisomers has become more and more attractive and found wide applications in natural products, drug molecules, as well as in chiral ligands. As a complement to asymmetric de novo ring formation and cross C−N coupling methods, the resolution approach demonstrates uniquely advantageous, which can progressively introduce the key functional groups and generate enantiomeric excess. Herein, we have developed an enzymatic tool for the construction of difunctionalized C−N atropisomers via lipase-catalyzed desymmetrization and kinetic resolution of N-naphthol-carbazoles. Acetylacetone was found as an efficient proton donor under the catalysis of LPL311-polyester. The enantioselective deacylation process has exhibited good functional group tolerance to produce enantioenriched C−N atropisomers with good to excellent enantioselectivity, in which the pre-installed hydroxyl functionality on the naphthene ring and the hydroxyl functionality on the carbazole ring generated after hydrolysis together provide feasibility for subsequent transformations.
2026, 37(7): 111948
doi: 10.1016/j.cclet.2025.111948
摘要:
The pathological protein α-synuclein (α-Syn) aggregates are considered a key toxic substance responsible for the degeneration of dopaminergic neurons in Parkinson's disease (PD). Clearing these pathological aggregates can potentially control PD progression at its source. However, conventional drug delivery systems face significant challenges, including the blood-brain barrier (BBB) and lack of tissue-specific targeting. To address this, we developed a core-shell hybrid system, named RExo-si-TN-T10, for the co-delivery of triptolide (T10) and small interfering RNA targeting α-Syn (siSNCA). This system comprises two components: an outer shell of exosomes (RExo) derived from BV2 microglial cells and modified with rabies virus glycoprotein peptide (RVG), and an inner core of a nanomicelle composed of phenylboronic acid derivatives: 4-Nitrophenyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzyl carbonate (NBC) and trimethyl chitosan (TMC) for co-delivering gene and small-molecule drugs. Furthermore, we utilized cellular nanoporation (CNP) technology to significantly enhance exosome yield and transfection efficiency. This innovative nano-scavenger effectively eliminates α-Syn aggregates and reduces their cytotoxic effects in PD-affected neurons. Following treatment with RExo-si-TN-T10, we observed significant improvement in the motor behavior of PD mice. Our findings suggest that RExo-si-TN-T10 holds promise as a therapeutic platform for PD.
The pathological protein α-synuclein (α-Syn) aggregates are considered a key toxic substance responsible for the degeneration of dopaminergic neurons in Parkinson's disease (PD). Clearing these pathological aggregates can potentially control PD progression at its source. However, conventional drug delivery systems face significant challenges, including the blood-brain barrier (BBB) and lack of tissue-specific targeting. To address this, we developed a core-shell hybrid system, named RExo-si-TN-T10, for the co-delivery of triptolide (T10) and small interfering RNA targeting α-Syn (siSNCA). This system comprises two components: an outer shell of exosomes (RExo) derived from BV2 microglial cells and modified with rabies virus glycoprotein peptide (RVG), and an inner core of a nanomicelle composed of phenylboronic acid derivatives: 4-Nitrophenyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzyl carbonate (NBC) and trimethyl chitosan (TMC) for co-delivering gene and small-molecule drugs. Furthermore, we utilized cellular nanoporation (CNP) technology to significantly enhance exosome yield and transfection efficiency. This innovative nano-scavenger effectively eliminates α-Syn aggregates and reduces their cytotoxic effects in PD-affected neurons. Following treatment with RExo-si-TN-T10, we observed significant improvement in the motor behavior of PD mice. Our findings suggest that RExo-si-TN-T10 holds promise as a therapeutic platform for PD.
2026, 37(7): 111961
doi: 10.1016/j.cclet.2025.111961
摘要:
The fentanyl (Fen) analogs-related drug crisis is a global focus that has badly affected social stability. In view of multitudinous overdose deaths, there is a great need for a portable and sensitive analytical approach that can quickly discriminate these dangerous recreational substances. Herein, an extended biphenarene-based fluorescence displacement sensor assay was constructed by integrating two reporter pairs, where terphen[3]arene sulfate and quaterphen[3]arene sulfate act as receptors, and rhodamine 123 acts as the optimal indicator. The formed supramolecular assay was able to completely classify four analogs, including Fen, 3-methylfentanyl, sufentanil and remifentanil in aqueous phosphate buffered saline, artificial urine, mouse plasma, or even real urine sample from model mice. Moreover, mixed samples containing different proportions of cocaine, heroin and ketamine could also be discriminated with 100% accuracy.
The fentanyl (Fen) analogs-related drug crisis is a global focus that has badly affected social stability. In view of multitudinous overdose deaths, there is a great need for a portable and sensitive analytical approach that can quickly discriminate these dangerous recreational substances. Herein, an extended biphenarene-based fluorescence displacement sensor assay was constructed by integrating two reporter pairs, where terphen[3]arene sulfate and quaterphen[3]arene sulfate act as receptors, and rhodamine 123 acts as the optimal indicator. The formed supramolecular assay was able to completely classify four analogs, including Fen, 3-methylfentanyl, sufentanil and remifentanil in aqueous phosphate buffered saline, artificial urine, mouse plasma, or even real urine sample from model mice. Moreover, mixed samples containing different proportions of cocaine, heroin and ketamine could also be discriminated with 100% accuracy.
2026, 37(7): 111962
doi: 10.1016/j.cclet.2025.111962
摘要:
In this paper, a novel multicolor-responsive fluorescent probe for the rapid and sensitive detection of persulfate ions (S2O82-), KT@Q[8], is constructed via host-guest interactions between cucurbit[8]uril (Q[8]) and 3,6-bis[4-(4-bromophenyl)pyridinium]-carbazole dichloride (KT). Upon interaction with S2O82-, the KT@Q[8] probe exhibits a fluorescence emission blue shift concurrent with a fluorescence color transition gradually from yellow to green. Notably, the probe demonstrates high selectivity for S2O82- even in the presence of competing anions and sulphur-containing metal salts, achieving a detection limit of 0.38 μmol/L. When integrated with smartphone-based RGB analysis, this probe enables rapid visual quantification of S2O82- without requiring sophisticated instrumentation, and can be effectively used to detect S2O82- in tap water, lake water, honey, and white wine. Furthermore, machine learning algorithms enhanced predictive accuracy during data analysis. Overall, this work not only advances a practical approach for persulfate monitoring but also expands the application range of cucurbituril-based fluorescence supramolecular assemblies.
In this paper, a novel multicolor-responsive fluorescent probe for the rapid and sensitive detection of persulfate ions (S2O82-), KT@Q[8], is constructed via host-guest interactions between cucurbit[8]uril (Q[8]) and 3,6-bis[4-(4-bromophenyl)pyridinium]-carbazole dichloride (KT). Upon interaction with S2O82-, the KT@Q[8] probe exhibits a fluorescence emission blue shift concurrent with a fluorescence color transition gradually from yellow to green. Notably, the probe demonstrates high selectivity for S2O82- even in the presence of competing anions and sulphur-containing metal salts, achieving a detection limit of 0.38 μmol/L. When integrated with smartphone-based RGB analysis, this probe enables rapid visual quantification of S2O82- without requiring sophisticated instrumentation, and can be effectively used to detect S2O82- in tap water, lake water, honey, and white wine. Furthermore, machine learning algorithms enhanced predictive accuracy during data analysis. Overall, this work not only advances a practical approach for persulfate monitoring but also expands the application range of cucurbituril-based fluorescence supramolecular assemblies.
Hierarchical confinement achieving cascade phosphorescence resonance energy transfer and application
2026, 37(7): 111964
doi: 10.1016/j.cclet.2025.111964
摘要:
Herein, we report morphology and luminescence tunable supramolecule containing tetracation 6-bromoisoquinoline modified tetraphenylbenzene (TQ), cucurbit[8]uril (CB[8]), β-cyclodextrin grafted hyaluronic acid (HACD), and two dyes (SR101, Cy5), which can lead to cascade efficient phosphorescence resonance energy transfer (PRET) through multi-scale supramolecular space confinement to achieve longlived multi-wavelength emission, especially near-infrared (NIR) luminescence. The initial unit TQ was assembled to form a green phosphorescent 3D supramolecular organic framework (SOF) under the activation of CB[8] confinement and then co-assembled with polysaccharide HACD to form phosphorescence extended long-lifetime (670.3 μs) 3D nanoparticles. This hierarchical confinement boosted phosphorescence supramolecule can act as the donor to achieve efficient energy transfer from phosphor to the dye SR101, giving long-lived luminescence at 615 nm, which can be employed as a transit depot and further encapsulate secondary acceptor Cy5, achieving efficient delayed NIR fluorescence at 680 nm, and was used as phosphorescence logic gate and NIR imaging reagent.
Herein, we report morphology and luminescence tunable supramolecule containing tetracation 6-bromoisoquinoline modified tetraphenylbenzene (TQ), cucurbit[8]uril (CB[8]), β-cyclodextrin grafted hyaluronic acid (HACD), and two dyes (SR101, Cy5), which can lead to cascade efficient phosphorescence resonance energy transfer (PRET) through multi-scale supramolecular space confinement to achieve longlived multi-wavelength emission, especially near-infrared (NIR) luminescence. The initial unit TQ was assembled to form a green phosphorescent 3D supramolecular organic framework (SOF) under the activation of CB[8] confinement and then co-assembled with polysaccharide HACD to form phosphorescence extended long-lifetime (670.3 μs) 3D nanoparticles. This hierarchical confinement boosted phosphorescence supramolecule can act as the donor to achieve efficient energy transfer from phosphor to the dye SR101, giving long-lived luminescence at 615 nm, which can be employed as a transit depot and further encapsulate secondary acceptor Cy5, achieving efficient delayed NIR fluorescence at 680 nm, and was used as phosphorescence logic gate and NIR imaging reagent.
2026, 37(7): 111965
doi: 10.1016/j.cclet.2025.111965
摘要:
Balsalazide disodium is an effective drug for alleviating ulcerative colitis. It slowly releases 5-aminosalicylic acid in the intestine. The traditional synthesis methods of balsalazide disodium exhibit high risk, high pollution and low efficiency concern. Thus, we innovatively develop a four-step route for the large-scale production of balsalazide disodium in continuous flow. In this work, methyl 3-aminopropionate hydrochloride was subjected to acylation and hydrolysis reactions to obtain the nitro intermediate with a selectivity of 99.55%. Micro-hydrogenation reactor filled with Raney Ni catalyzed three-phase reaction improves conversion and selectivity. In the diazotization and azo coupling reactions, the optimal equivalents of salicylic acid and base were determined. With the aid of response surface methodology, the influences of reaction temperature and residence time on yield were systematically investigated. Under the optimum conditions, the experimental yields coincided with the predicted yields. Compared to batch experiments, the continuous process achieved a total yield of 66.1% and a purity of 99.63% in 13.1 min.
Balsalazide disodium is an effective drug for alleviating ulcerative colitis. It slowly releases 5-aminosalicylic acid in the intestine. The traditional synthesis methods of balsalazide disodium exhibit high risk, high pollution and low efficiency concern. Thus, we innovatively develop a four-step route for the large-scale production of balsalazide disodium in continuous flow. In this work, methyl 3-aminopropionate hydrochloride was subjected to acylation and hydrolysis reactions to obtain the nitro intermediate with a selectivity of 99.55%. Micro-hydrogenation reactor filled with Raney Ni catalyzed three-phase reaction improves conversion and selectivity. In the diazotization and azo coupling reactions, the optimal equivalents of salicylic acid and base were determined. With the aid of response surface methodology, the influences of reaction temperature and residence time on yield were systematically investigated. Under the optimum conditions, the experimental yields coincided with the predicted yields. Compared to batch experiments, the continuous process achieved a total yield of 66.1% and a purity of 99.63% in 13.1 min.
2026, 37(7): 111966
doi: 10.1016/j.cclet.2025.111966
摘要:
Efficient macrocycle synthesis remains a persistently pursued objective in supramolecular chemistry. In this work, a series of chiral macrocycles (TBCHMs) incorporating Tröger's base were synthesized via imine condensation reactions from Tröger's base (TB) aldehyde derivatives and cyclohexane-1,2-diamines (CHDA). Gram-scale quantities of crystalline macrocycles were directly obtained during the process of their reaction. Precise modulation of macrocycle structural morphology was achieved by varying the chiral configuration of the components. Notably, chiral self-sorting was realized in these reaction systems, driven by the energy difference between diastereomers and their selective precipitation as crystals. This work might open up new insights for the modular preparation of chiral macrocycles based on dynamic covalent chemistry (DCC).
Efficient macrocycle synthesis remains a persistently pursued objective in supramolecular chemistry. In this work, a series of chiral macrocycles (TBCHMs) incorporating Tröger's base were synthesized via imine condensation reactions from Tröger's base (TB) aldehyde derivatives and cyclohexane-1,2-diamines (CHDA). Gram-scale quantities of crystalline macrocycles were directly obtained during the process of their reaction. Precise modulation of macrocycle structural morphology was achieved by varying the chiral configuration of the components. Notably, chiral self-sorting was realized in these reaction systems, driven by the energy difference between diastereomers and their selective precipitation as crystals. This work might open up new insights for the modular preparation of chiral macrocycles based on dynamic covalent chemistry (DCC).
2026, 37(7): 111967
doi: 10.1016/j.cclet.2025.111967
摘要:
Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials have attracted growing interest for their potential to achieve high color purity and efficiency in organic light-emitting diode (OLED) applications. However, their key performance parameters, including photoluminescence wavelength (PL), full width at half-maximum (FWHM), and photoluminescence quantum yield (PLQY), are highly structure-dependent, presenting challenges for high-throughput screening and efficient design. In this work, we propose a structure-aware ensemble learning model (BNML) that integrates molecular access system (MACCS) fingerprints, fingerprint2 (FP2) fingerprints, and molecular descriptors (MDs) to predict photophysical properties of MR-TADF materials. The model shows strong regression performance under small-data (415) conditions and achieves nearly 100% prediction accuracy (100%, 100%, and 96%, respectively) within a specific range of values. By incorporating SHapley Additive exPlanations (SHAP) analysis, the model reveals interpretable contributions of donor fragments and π-conjugation to the predicted properties. Guided by this analysis, fifteen novel MR-TADF compounds were designed, among which seven were successfully synthesized and validated, showing strong agreement with the predicted values (accuracy: predict/true, 21/20). This work provides a reliable strategy for intelligent design and rapid evaluation of MR-TADF compounds, offering a new approach for structure-property modeling in complex emission systems.
Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials have attracted growing interest for their potential to achieve high color purity and efficiency in organic light-emitting diode (OLED) applications. However, their key performance parameters, including photoluminescence wavelength (PL), full width at half-maximum (FWHM), and photoluminescence quantum yield (PLQY), are highly structure-dependent, presenting challenges for high-throughput screening and efficient design. In this work, we propose a structure-aware ensemble learning model (BNML) that integrates molecular access system (MACCS) fingerprints, fingerprint2 (FP2) fingerprints, and molecular descriptors (MDs) to predict photophysical properties of MR-TADF materials. The model shows strong regression performance under small-data (415) conditions and achieves nearly 100% prediction accuracy (100%, 100%, and 96%, respectively) within a specific range of values. By incorporating SHapley Additive exPlanations (SHAP) analysis, the model reveals interpretable contributions of donor fragments and π-conjugation to the predicted properties. Guided by this analysis, fifteen novel MR-TADF compounds were designed, among which seven were successfully synthesized and validated, showing strong agreement with the predicted values (accuracy: predict/true, 21/20). This work provides a reliable strategy for intelligent design and rapid evaluation of MR-TADF compounds, offering a new approach for structure-property modeling in complex emission systems.
2026, 37(7): 112000
doi: 10.1016/j.cclet.2025.112000
摘要:
Multi-substituted pyrrolidine and piperidine N-heterocycles are the top scaffolds of clinical drugs, but syntheses of these scaffolds are far from trivial. Herein, we report a highly enantioselective protocol for the synthesis of 5- and 6-membered cyclic nitrones via Pd-catalyzed cyclization coupling of alkenyl oximes with aryl, alkenyl and alkynyl (pseudo)halides enabled by chiral sulfonamidephosphine (SadPhos) ligands. These cyclic nitrones products, besides their significance per ser, can be facilely converted to multi-substituted pyrrolidines and piperidines by simple operations. This study also represents the first example of two-component catalytic asymmetric synthesis of cyclic nitrones and provides important insights for further development of enantioselective heterocyclization reaction and processes involving multiple selectivity issues.
Multi-substituted pyrrolidine and piperidine N-heterocycles are the top scaffolds of clinical drugs, but syntheses of these scaffolds are far from trivial. Herein, we report a highly enantioselective protocol for the synthesis of 5- and 6-membered cyclic nitrones via Pd-catalyzed cyclization coupling of alkenyl oximes with aryl, alkenyl and alkynyl (pseudo)halides enabled by chiral sulfonamidephosphine (SadPhos) ligands. These cyclic nitrones products, besides their significance per ser, can be facilely converted to multi-substituted pyrrolidines and piperidines by simple operations. This study also represents the first example of two-component catalytic asymmetric synthesis of cyclic nitrones and provides important insights for further development of enantioselective heterocyclization reaction and processes involving multiple selectivity issues.
2026, 37(7): 112118
doi: 10.1016/j.cclet.2025.112118
摘要:
At present, electromagnetic wave absorbing materials provide an effective solution to the electromagnetic pollution generated by electronic devices. However, materials with a single function can no longer meet practical requirements. Therefore, reduced graphene oxide/Fe3O4 composites were prepared via a combined process involving sol-gel, click chemistry reaction (thiol-ene reaction), and reduction. The results demonstrated that Fe3O4 was covalently grafted onto graphene oxide (GO), which significantly influenced the morphology, electrical conductivity, and electromagnetic wave absorption performance of the composite. When the mass ratio of GO to modified Fe3O4 was 1:1, the composite G2-Fe exhibited optimal impedance matching and the best electromagnetic wave absorption performance. The minimum reflection loss (RLmin) reached -42.0 dB at 4.91 GHz. When the thickness was 2.0 mm, the maximum effective absorption bandwidth (RL < -10 dB) was 4.85 GHz. Moreover, the composite also displayed excellent thermal conductivity and corrosion resistance. The thermal conductivity of the composite material was maintained above 1.486 W m-1 K-1. In a 3.5 wt% saline solution, the composite showed a low corrosion current (3.07 × 10–5 A) and a high corrosion potential (-0.110 V). This study not only achieved structural regulation of the composite through covalent grafting of modified Fe3O4 on GO, but also offered valuable insights for the design of multifunctional materials integrating electromagnetic wave absorption, thermal conduction, and corrosion resistance properties.
At present, electromagnetic wave absorbing materials provide an effective solution to the electromagnetic pollution generated by electronic devices. However, materials with a single function can no longer meet practical requirements. Therefore, reduced graphene oxide/Fe3O4 composites were prepared via a combined process involving sol-gel, click chemistry reaction (thiol-ene reaction), and reduction. The results demonstrated that Fe3O4 was covalently grafted onto graphene oxide (GO), which significantly influenced the morphology, electrical conductivity, and electromagnetic wave absorption performance of the composite. When the mass ratio of GO to modified Fe3O4 was 1:1, the composite G2-Fe exhibited optimal impedance matching and the best electromagnetic wave absorption performance. The minimum reflection loss (RLmin) reached -42.0 dB at 4.91 GHz. When the thickness was 2.0 mm, the maximum effective absorption bandwidth (RL < -10 dB) was 4.85 GHz. Moreover, the composite also displayed excellent thermal conductivity and corrosion resistance. The thermal conductivity of the composite material was maintained above 1.486 W m-1 K-1. In a 3.5 wt% saline solution, the composite showed a low corrosion current (3.07 × 10–5 A) and a high corrosion potential (-0.110 V). This study not only achieved structural regulation of the composite through covalent grafting of modified Fe3O4 on GO, but also offered valuable insights for the design of multifunctional materials integrating electromagnetic wave absorption, thermal conduction, and corrosion resistance properties.
2026, 37(7): 112134
doi: 10.1016/j.cclet.2025.112134
摘要:
Bergenin (BG), a bioactive coumarin derivative, suffers from poor solubility and low oral bioavailability, restricting its clinical potential. To overcome these limitations, we developed a lipid prodrug strategy by conjugating BG with bioactive fatty acids of different chain lengths (6C, 12C, 18C) via ester bonds, formulating the conjugates into solid lipid nanoparticles (SLNs), and systematically investigating the structure–activity relationship. Fatty acid conjugation not only enhanced lipophilicity, lipid matrix compatibility, and enzymatic stability but also imparted distinct biological effects that shaped oral absorption. Stearic acids (18C) conferred strong resistance to enzymatic hydrolysis, whereas lauric acid (12C) offered the most favorable balance in improving drug loading, stability, and membrane permeability. Pharmacokinetic studies in rats demonstrated that 12C-BG SLNs achieved the greatest enhancement in oral bioavailability, with an 8.6-fold increase over BG-SLNs and more than 40-fold improvement relative to reported suspensions and phospholipid solid dispersions. Mechanistic studies indicated that absorption was primarily driven by prodrug monomers released during intestinal lipolysis, with a minor contribution from undigested nanoparticles, and moreover the fatty acid chain length strongly influenced cellular permeability and systemic exposure. Collectively, these results underscore the critical role of bioactive fatty acids as conjugating groups in modulating prodrug fate and highlight a promising platform for enhancing the oral delivery of poorly soluble phytochemicals.
Bergenin (BG), a bioactive coumarin derivative, suffers from poor solubility and low oral bioavailability, restricting its clinical potential. To overcome these limitations, we developed a lipid prodrug strategy by conjugating BG with bioactive fatty acids of different chain lengths (6C, 12C, 18C) via ester bonds, formulating the conjugates into solid lipid nanoparticles (SLNs), and systematically investigating the structure–activity relationship. Fatty acid conjugation not only enhanced lipophilicity, lipid matrix compatibility, and enzymatic stability but also imparted distinct biological effects that shaped oral absorption. Stearic acids (18C) conferred strong resistance to enzymatic hydrolysis, whereas lauric acid (12C) offered the most favorable balance in improving drug loading, stability, and membrane permeability. Pharmacokinetic studies in rats demonstrated that 12C-BG SLNs achieved the greatest enhancement in oral bioavailability, with an 8.6-fold increase over BG-SLNs and more than 40-fold improvement relative to reported suspensions and phospholipid solid dispersions. Mechanistic studies indicated that absorption was primarily driven by prodrug monomers released during intestinal lipolysis, with a minor contribution from undigested nanoparticles, and moreover the fatty acid chain length strongly influenced cellular permeability and systemic exposure. Collectively, these results underscore the critical role of bioactive fatty acids as conjugating groups in modulating prodrug fate and highlight a promising platform for enhancing the oral delivery of poorly soluble phytochemicals.
2026, 37(7): 112150
doi: 10.1016/j.cclet.2025.112150
摘要:
Tandem CO2 electroreduction integrated with carbonylation reactions offers a promising pathway for transforming greenhouse gases into valuable chemical products. The development of efficient CO2–to–CO electrocatalysts operational across wide potential ranges is crucial to address renewable energy fluctuations and facilitate integrated cascade systems. Herein, a Ni single–atom catalyst (SAC) with sulfur doping in the second shell of Ni–N4 is reported. In situ measurements and theoretical calculations demonstrate that the incorporation S atoms not only modulates the electronic configuration of Ni active sites but also enhances H2O adsorption, enabling rapid CO2 hydrogenation into *COOH intermediates even at high potentials. Consequently, the Ni–N–S/CNS catalyst achieves a Faradaic efficiency for CO2–to–CO (FECO) of 99.3% at –0.7 VRHE and maintains over 90% across pH–universal conditions with ultrawide potential windows: 1400 mV (from –0.3 VRHE to –1.7 VRHE) in alkaline media, 1200 mV (from –0.7 VRHE to –1.9 VRHE) in neutral conditions, and 1000 mV (from –1.3 VRHE to –2.3 VRHE) in acidic environments. Remarkably, this catalyst enables the tandem CO2RR and N–alkylaniline carbonylation process for synthesizing o–aminobenzoates and isatoic anhydrides with high yield. Our findings demonstrate an electrothermo–catalytic tandem strategy for cost–effective CO2 conversion and synthesis of high valuable fine chemicals, thereby broadening the scope of its utilization.
Tandem CO2 electroreduction integrated with carbonylation reactions offers a promising pathway for transforming greenhouse gases into valuable chemical products. The development of efficient CO2–to–CO electrocatalysts operational across wide potential ranges is crucial to address renewable energy fluctuations and facilitate integrated cascade systems. Herein, a Ni single–atom catalyst (SAC) with sulfur doping in the second shell of Ni–N4 is reported. In situ measurements and theoretical calculations demonstrate that the incorporation S atoms not only modulates the electronic configuration of Ni active sites but also enhances H2O adsorption, enabling rapid CO2 hydrogenation into *COOH intermediates even at high potentials. Consequently, the Ni–N–S/CNS catalyst achieves a Faradaic efficiency for CO2–to–CO (FECO) of 99.3% at –0.7 VRHE and maintains over 90% across pH–universal conditions with ultrawide potential windows: 1400 mV (from –0.3 VRHE to –1.7 VRHE) in alkaline media, 1200 mV (from –0.7 VRHE to –1.9 VRHE) in neutral conditions, and 1000 mV (from –1.3 VRHE to –2.3 VRHE) in acidic environments. Remarkably, this catalyst enables the tandem CO2RR and N–alkylaniline carbonylation process for synthesizing o–aminobenzoates and isatoic anhydrides with high yield. Our findings demonstrate an electrothermo–catalytic tandem strategy for cost–effective CO2 conversion and synthesis of high valuable fine chemicals, thereby broadening the scope of its utilization.
2026, 37(7): 112153
doi: 10.1016/j.cclet.2025.112153
摘要:
Catalytic oxidation of H2S at room temperature has been regarded as a promising method for removing malodorous H2S pollution. However, most of the existing research has primarily focused on developing catalysts with high sulfur capacity, i.e., high elemental sulfur selectivity, which was unfavored for the catalyst regeneration. The present work prioritizes efficient water wash regeneration as a key objective. A series of activated carbon fibers (ACFs) was synthesized using a synergistic strategy of "nitrogen doping-plasma defect engineering". The certain amount of nitrogen species ensured a certain level of sulfur capacity. The plasma defect engineering can result in the enhancement of surface acidity and defect density, which worked together to make the catalyst with high sulfate selectivity. The O2-plasma modified NH3-ACF-O10 catalyst achieved the best catalytic performance with appropriate sulfur capacity (0.21 g/g) and highest sulfate selectivity (85.40%). Importantly, it can be easily regenerated by water wash, and almost 83.33% sulfur capacity can be recovered. Besides, superoxide radicals (O2•-) were identified as the primary reactive oxygen species for the reaction. And the reaction obeyed a Langmuir-Hinshelwood (L-H) like mechanism, i.e., the reaction was proceeded via chemisorbed H2S and O2•-, which was adsorbed and activated by defect.
Catalytic oxidation of H2S at room temperature has been regarded as a promising method for removing malodorous H2S pollution. However, most of the existing research has primarily focused on developing catalysts with high sulfur capacity, i.e., high elemental sulfur selectivity, which was unfavored for the catalyst regeneration. The present work prioritizes efficient water wash regeneration as a key objective. A series of activated carbon fibers (ACFs) was synthesized using a synergistic strategy of "nitrogen doping-plasma defect engineering". The certain amount of nitrogen species ensured a certain level of sulfur capacity. The plasma defect engineering can result in the enhancement of surface acidity and defect density, which worked together to make the catalyst with high sulfate selectivity. The O2-plasma modified NH3-ACF-O10 catalyst achieved the best catalytic performance with appropriate sulfur capacity (0.21 g/g) and highest sulfate selectivity (85.40%). Importantly, it can be easily regenerated by water wash, and almost 83.33% sulfur capacity can be recovered. Besides, superoxide radicals (O2•-) were identified as the primary reactive oxygen species for the reaction. And the reaction obeyed a Langmuir-Hinshelwood (L-H) like mechanism, i.e., the reaction was proceeded via chemisorbed H2S and O2•-, which was adsorbed and activated by defect.
2026, 37(7): 112158
doi: 10.1016/j.cclet.2025.112158
摘要:
Rare–earth–based perovskite materials, due to their low cost and tunable structure, have been regarded as a promising platform for photoinduced molecular oxygen activation. However, a comprehensive understanding and precise regulation of the surface reconstruction of the active phase in perovskite oxides during molecular oxygen activation remain highly challenging tasks. Herein, a refined A–site management strategy is proposed for perovskite oxides, which provides power for molecular oxygen activation by adjusting the electronic structure of B–site elements. Comprehensive experimental results reveal that the enhanced photocatalytic mechanism is attributed to the substitution of holmium (Ho) at the atomic level, which facilitates an increase in the valence state of iron and shifts the center of the d–band to a more positive energy level, thereby promoting O2 adsorption. Additionally, theoretical calculations demonstrate that the Ho 4f orbital overlaps with the Fe 3d and O 2p orbitals near the Fermi level, significantly enhancing charge transfer between oxygen and metal, thereby facilitating the conversion of oxygen into highly reactive oxygen species. Therefore, the optimized La0.97Ho0.03FeO3 (LHFO) exhibits greatly enhanced catalytic performance for molecular oxygen activation, and the degradation rate constant of tetracycline is 9.5 times higher than LaFeO3, representing one of the most efficient and robust RE–based perovskites.
Rare–earth–based perovskite materials, due to their low cost and tunable structure, have been regarded as a promising platform for photoinduced molecular oxygen activation. However, a comprehensive understanding and precise regulation of the surface reconstruction of the active phase in perovskite oxides during molecular oxygen activation remain highly challenging tasks. Herein, a refined A–site management strategy is proposed for perovskite oxides, which provides power for molecular oxygen activation by adjusting the electronic structure of B–site elements. Comprehensive experimental results reveal that the enhanced photocatalytic mechanism is attributed to the substitution of holmium (Ho) at the atomic level, which facilitates an increase in the valence state of iron and shifts the center of the d–band to a more positive energy level, thereby promoting O2 adsorption. Additionally, theoretical calculations demonstrate that the Ho 4f orbital overlaps with the Fe 3d and O 2p orbitals near the Fermi level, significantly enhancing charge transfer between oxygen and metal, thereby facilitating the conversion of oxygen into highly reactive oxygen species. Therefore, the optimized La0.97Ho0.03FeO3 (LHFO) exhibits greatly enhanced catalytic performance for molecular oxygen activation, and the degradation rate constant of tetracycline is 9.5 times higher than LaFeO3, representing one of the most efficient and robust RE–based perovskites.
2026, 37(7): 112159
doi: 10.1016/j.cclet.2025.112159
摘要:
Achieving point-of-care detection of neutrophil gelatinase-associated lipocalin (NGAL) contributes to the early diagnosis and treatment of acute kidney injury (AKI), but the lack of highly sensitive and long-term stable detection methods is a major challenge. In this work, tetrahedral DNA (tDNA)-functionalized large-sized upconversion nanoparticles (t-UCNP300) were synthesized with high luminescence intensity. Leveraging the dual effects of surface charge density and the rigid structure of tDNA, the developed t-UCNP300 exhibited long-term stability for over 60 days after being stored in phosphate buffer at 25 ℃ and pH 7.4, with no obvious aggregation and only slight luminescence attenuation. By using this developed t-UCNP300, a luminescent lateral flow immunoassay (LFIA) strip was developed for point-of-care detection of NGAL, with a detection linearity range of 2.00–250 ng/mL and limit of detection (LOD) of 1.00 ± 0.07 ng/mL (S/N = 3). Taking advantage of the developed LFIA strip for NGAL with high selectivity and a rapid response time of < 5 min, it was successfully applied for the determination of NGAL in artificial urine samples.
Achieving point-of-care detection of neutrophil gelatinase-associated lipocalin (NGAL) contributes to the early diagnosis and treatment of acute kidney injury (AKI), but the lack of highly sensitive and long-term stable detection methods is a major challenge. In this work, tetrahedral DNA (tDNA)-functionalized large-sized upconversion nanoparticles (t-UCNP300) were synthesized with high luminescence intensity. Leveraging the dual effects of surface charge density and the rigid structure of tDNA, the developed t-UCNP300 exhibited long-term stability for over 60 days after being stored in phosphate buffer at 25 ℃ and pH 7.4, with no obvious aggregation and only slight luminescence attenuation. By using this developed t-UCNP300, a luminescent lateral flow immunoassay (LFIA) strip was developed for point-of-care detection of NGAL, with a detection linearity range of 2.00–250 ng/mL and limit of detection (LOD) of 1.00 ± 0.07 ng/mL (S/N = 3). Taking advantage of the developed LFIA strip for NGAL with high selectivity and a rapid response time of < 5 min, it was successfully applied for the determination of NGAL in artificial urine samples.
2026, 37(7): 112161
doi: 10.1016/j.cclet.2025.112161
摘要:
Understanding the nucleation, growth and structural phase transitions process during the preparation of nanomaterials is crucial for the targeted design and controllable preparation of nanomaterials with specific structures and properties. Herein, a “solid phase transition” behavior is first found in the semiconductor C3N4 material during the conversion process from amorphous bulk C3N4 to high crystallinity C3N4 nanosheets, which usually exists in the process of metals or alloys conversion. A unique C3N4 nanosheet structure with uniform size distribution is successfully synthesized with a simple two-step calcination method, which is totally different from the traditional irregular nanosheets exfoliated from the bulk C3N4. This C3N4 nanosheets also possess high crystallinity and it helps to promote the migration of charge carriers during the catalytic process. By precisely exploring the synthesis process, a new “solid phase transition” mechanism is introduced to help understand the atoms recrystallize and grow to form the uniform high crystallinity nanosheets. The high yield (86%) of this strategy also overcomes the problem of low efficiency in preparing C3N4 nanosheets. Besides, the advantages of this uniform high crystallinity C3N4 nanosheets result in superior long-term stability in 100 CV cycles during the electrochemiluminescence (ECL) test, which is particularly superior to conventional C3N4 nanosheets.
Understanding the nucleation, growth and structural phase transitions process during the preparation of nanomaterials is crucial for the targeted design and controllable preparation of nanomaterials with specific structures and properties. Herein, a “solid phase transition” behavior is first found in the semiconductor C3N4 material during the conversion process from amorphous bulk C3N4 to high crystallinity C3N4 nanosheets, which usually exists in the process of metals or alloys conversion. A unique C3N4 nanosheet structure with uniform size distribution is successfully synthesized with a simple two-step calcination method, which is totally different from the traditional irregular nanosheets exfoliated from the bulk C3N4. This C3N4 nanosheets also possess high crystallinity and it helps to promote the migration of charge carriers during the catalytic process. By precisely exploring the synthesis process, a new “solid phase transition” mechanism is introduced to help understand the atoms recrystallize and grow to form the uniform high crystallinity nanosheets. The high yield (86%) of this strategy also overcomes the problem of low efficiency in preparing C3N4 nanosheets. Besides, the advantages of this uniform high crystallinity C3N4 nanosheets result in superior long-term stability in 100 CV cycles during the electrochemiluminescence (ECL) test, which is particularly superior to conventional C3N4 nanosheets.
2026, 37(7): 112169
doi: 10.1016/j.cclet.2025.112169
摘要:
Electroactive quinone-based compounds have shown great potential as lithium-ion batteries cathodes due to their high capacity, environmental friendliness, and low cost. However, their practical application is severely hindered by high solubility in aprotic electrolytes and low electronic conductivity. Herein, we skillfully utilized the two-dimensional MXene Ti2C2 as a host material to anchor benzoquinone skeleton by a simple coordination chemical reaction, obtaining the composite cathode materials (T@M). Significantly, the MXene not only stabilizes the benzoquinone framework but also shortens ion/electron diffusion pathways. As a result, the T@M cathode delivers a high discharge specific capacity of 300.1 mAh/g at 0.05 A/g and retains 70% of its capacity after 3000 cycles at 1 A/g. This work provides an effective strategy for developing high-performance organic electrodes for rechargeable batteries.
Electroactive quinone-based compounds have shown great potential as lithium-ion batteries cathodes due to their high capacity, environmental friendliness, and low cost. However, their practical application is severely hindered by high solubility in aprotic electrolytes and low electronic conductivity. Herein, we skillfully utilized the two-dimensional MXene Ti2C2 as a host material to anchor benzoquinone skeleton by a simple coordination chemical reaction, obtaining the composite cathode materials (T@M). Significantly, the MXene not only stabilizes the benzoquinone framework but also shortens ion/electron diffusion pathways. As a result, the T@M cathode delivers a high discharge specific capacity of 300.1 mAh/g at 0.05 A/g and retains 70% of its capacity after 3000 cycles at 1 A/g. This work provides an effective strategy for developing high-performance organic electrodes for rechargeable batteries.
2026, 37(7): 112175
doi: 10.1016/j.cclet.2025.112175
摘要:
Marine atmospheric aerosols are pivotal components of the global aerosol system, which can significantly influence global climate and human health. Perfluoroalkyl carboxylic acids (PFCAs), persistent emerging contaminants, exhibit pronounced enrichment in sea spray aerosols (SSAs). However, current gas-particle partitioning models underestimate their particulate-phase ratios in polluted atmospheres. Here, we elucidate the interfacial chemistry driving the enrichment of PFCAs in SSAs under anthropogenic impacts. Through Born-Oppenheimer molecular dynamics simulations, we demonstrated that TFA, a representative of PFCAs, exhibited activity at gas-liquid interfaces. The carbonyl oxygen of TFA protrudes beyond hydration layers, which facilitates collisions with gaseous SO3. Interfacial water molecules can promote simultaneous TFA deprotonation and SO3 collision and then the formation of trifluoroacetic acid sulfuric anhydride ions (TFASA-) and hydronium ions (H3O+). TFASA- displays superior hygroscopicity over precursors, enhancing the growth potential of SSAs to form cloud condensation nuclei (CCN). Given the continuous accumulation of PFCAs in marine environment, the interfacial chemical reactions between PFCAs and reactive pollutants (e.g., SO3) in marine atmospheres need urgent focus to understand the influence of PFCAs on marine particulate matter pollution and global climate.
Marine atmospheric aerosols are pivotal components of the global aerosol system, which can significantly influence global climate and human health. Perfluoroalkyl carboxylic acids (PFCAs), persistent emerging contaminants, exhibit pronounced enrichment in sea spray aerosols (SSAs). However, current gas-particle partitioning models underestimate their particulate-phase ratios in polluted atmospheres. Here, we elucidate the interfacial chemistry driving the enrichment of PFCAs in SSAs under anthropogenic impacts. Through Born-Oppenheimer molecular dynamics simulations, we demonstrated that TFA, a representative of PFCAs, exhibited activity at gas-liquid interfaces. The carbonyl oxygen of TFA protrudes beyond hydration layers, which facilitates collisions with gaseous SO3. Interfacial water molecules can promote simultaneous TFA deprotonation and SO3 collision and then the formation of trifluoroacetic acid sulfuric anhydride ions (TFASA-) and hydronium ions (H3O+). TFASA- displays superior hygroscopicity over precursors, enhancing the growth potential of SSAs to form cloud condensation nuclei (CCN). Given the continuous accumulation of PFCAs in marine environment, the interfacial chemical reactions between PFCAs and reactive pollutants (e.g., SO3) in marine atmospheres need urgent focus to understand the influence of PFCAs on marine particulate matter pollution and global climate.
2026, 37(7): 112193
doi: 10.1016/j.cclet.2025.112193
摘要:
The heterogeneous electro-Fenton (HEF) technology is a promising yet challenging approach for organic pollutant degradation. It is urgent to develop a catalyst for both highly efficient H2O2 and hydroxyl radical (•OH) generation with low energy consumption at neutral conditions. This study presents a bifunctional catalyst (CoPc/OCNTs/FeOF) synthesized by ultrasonic anchoring of FeOF onto cobalt phthalocyanine-modified oxidized carbon nanotubes. The catalyst demonstrated synergistic effects, achieving a 2.94-fold enhancement in H2O2 generation and a 3.85-fold increase in •OH yield compared to its individual components (CoPc/OCNTs and FeOF). At pH 6, the CoPc/OCNTs/FeOF cathode enabled nearly complete phenol removal within 90 min, with a high kinetic rate constant (k) of 0.04848 min-1, driven by cooperative oxidation from singlet oxygen (1O2) and •OH. The system exhibited exceptional stability, inorganic ion tolerance, and broad applicability to real wastewaters, achieving 82.0% total organic carbon (TOC) removal for phenol wastewater at a low energy consumption of 21.9 kWh kg-1 COD-1. Moreover, sodium alginate-immobilized microalgae hydrogel was integrated into the HEF system to supply O2 in situ for the 2e- oxygen reduction reaction (ORR), eliminating energy-intensive mechanical aeration. Subsequent microalgal cultivation further removed 90.6% of total nitrogen and 82.8% of total phosphorus, showcasing a sustainable dual-function strategy for pollutant degradation and nutrient recovery. This work advances the design of efficient HEF catalysts and highlights the potential of microalgae-coupled systems for sustainable wastewater treatment.
The heterogeneous electro-Fenton (HEF) technology is a promising yet challenging approach for organic pollutant degradation. It is urgent to develop a catalyst for both highly efficient H2O2 and hydroxyl radical (•OH) generation with low energy consumption at neutral conditions. This study presents a bifunctional catalyst (CoPc/OCNTs/FeOF) synthesized by ultrasonic anchoring of FeOF onto cobalt phthalocyanine-modified oxidized carbon nanotubes. The catalyst demonstrated synergistic effects, achieving a 2.94-fold enhancement in H2O2 generation and a 3.85-fold increase in •OH yield compared to its individual components (CoPc/OCNTs and FeOF). At pH 6, the CoPc/OCNTs/FeOF cathode enabled nearly complete phenol removal within 90 min, with a high kinetic rate constant (k) of 0.04848 min-1, driven by cooperative oxidation from singlet oxygen (1O2) and •OH. The system exhibited exceptional stability, inorganic ion tolerance, and broad applicability to real wastewaters, achieving 82.0% total organic carbon (TOC) removal for phenol wastewater at a low energy consumption of 21.9 kWh kg-1 COD-1. Moreover, sodium alginate-immobilized microalgae hydrogel was integrated into the HEF system to supply O2 in situ for the 2e- oxygen reduction reaction (ORR), eliminating energy-intensive mechanical aeration. Subsequent microalgal cultivation further removed 90.6% of total nitrogen and 82.8% of total phosphorus, showcasing a sustainable dual-function strategy for pollutant degradation and nutrient recovery. This work advances the design of efficient HEF catalysts and highlights the potential of microalgae-coupled systems for sustainable wastewater treatment.
2026, 37(7): 112196
doi: 10.1016/j.cclet.2025.112196
摘要:
To reduce the pollution of waste heat to the environment and achieve Sustainable Development Goals, recovering and utilizing of low-grade heat is critical. Although various thermal conversion technologies have been extensively developed, research on thermal energy storage materials with dynamically adjustable properties for diverse applications is still lacking. Herein, hydrated salt hydrogel with switchable stiffness and tunable thermal performance was fabricated by simply incorporating sodium acetate trihydrate into hydrogel network. Hydrated salt hydrogel displayed adjustable thermal performance (maximum heat release temperature from 53 ℃ to 20 ℃; enthalpy value from 0 to 179 J/g) by regulated sodium acetate trihydrate concentration of hydrogels. Moreover, the control of variable mechanical strength (0.03–5.21 MPa) and toughness (0.02–420.58 MPa) was accomplished. The study further demonstrates the promising application of hydrated salt hydrogel in thermal management for electronics and controllable soft-rigid coupling thermoelectric devices, opening new opportunities in waste heat recovery and achieving Sustainable Development Goals.
To reduce the pollution of waste heat to the environment and achieve Sustainable Development Goals, recovering and utilizing of low-grade heat is critical. Although various thermal conversion technologies have been extensively developed, research on thermal energy storage materials with dynamically adjustable properties for diverse applications is still lacking. Herein, hydrated salt hydrogel with switchable stiffness and tunable thermal performance was fabricated by simply incorporating sodium acetate trihydrate into hydrogel network. Hydrated salt hydrogel displayed adjustable thermal performance (maximum heat release temperature from 53 ℃ to 20 ℃; enthalpy value from 0 to 179 J/g) by regulated sodium acetate trihydrate concentration of hydrogels. Moreover, the control of variable mechanical strength (0.03–5.21 MPa) and toughness (0.02–420.58 MPa) was accomplished. The study further demonstrates the promising application of hydrated salt hydrogel in thermal management for electronics and controllable soft-rigid coupling thermoelectric devices, opening new opportunities in waste heat recovery and achieving Sustainable Development Goals.
2026, 37(7): 112207
doi: 10.1016/j.cclet.2025.112207
摘要:
Alkaline anion exchange membrane water electrolysis (AEMWE) is a low-cost and sustainable technology for hydrogen production. This study presents the development of high-performance anion exchange membrane (AEM) and ionomers based on quaternized poly(diphenyl carbazole) with rigid ether-bond-free aryl backbone and flexible multination strings in the side chains. The optimized molecular architecture induces pronounced microphase separation, enabling high hydroxide conductivity (159.3 mS/cm at 80 ℃) and exceptional alkaline stability (1 mol/L KOH at 80 ℃, retains 97.5% ionic conductivity and 88.6% tensile strength after 1800 h). By implementing an anode water-fed/cathode water-free configuration and regulating the structure and content of ionomers at anode and cathode electrodes, the AEMWE performance was significantly improved from 1.9 A/cm2 to 4.2 A/cm2 at 2 V (a 2.2-fold increase) using 1 mol/L KOH solution as the electrolyte. Under pure water conditions, the electrolyzer still achieved an excellent electrolysis performance of 1.8 A/cm2 at 2 V. Furthermore, the fabricated AEMWE exhibited an outstanding in-situ durability with a low voltage degradation rate of 0.17 mV/h during a continuous operation of 1185 h at a current density of 0.5 A/cm2.
Alkaline anion exchange membrane water electrolysis (AEMWE) is a low-cost and sustainable technology for hydrogen production. This study presents the development of high-performance anion exchange membrane (AEM) and ionomers based on quaternized poly(diphenyl carbazole) with rigid ether-bond-free aryl backbone and flexible multination strings in the side chains. The optimized molecular architecture induces pronounced microphase separation, enabling high hydroxide conductivity (159.3 mS/cm at 80 ℃) and exceptional alkaline stability (1 mol/L KOH at 80 ℃, retains 97.5% ionic conductivity and 88.6% tensile strength after 1800 h). By implementing an anode water-fed/cathode water-free configuration and regulating the structure and content of ionomers at anode and cathode electrodes, the AEMWE performance was significantly improved from 1.9 A/cm2 to 4.2 A/cm2 at 2 V (a 2.2-fold increase) using 1 mol/L KOH solution as the electrolyte. Under pure water conditions, the electrolyzer still achieved an excellent electrolysis performance of 1.8 A/cm2 at 2 V. Furthermore, the fabricated AEMWE exhibited an outstanding in-situ durability with a low voltage degradation rate of 0.17 mV/h during a continuous operation of 1185 h at a current density of 0.5 A/cm2.
2026, 37(7): 112209
doi: 10.1016/j.cclet.2025.112209
摘要:
The treatment of nitrogen-contained refractory organic wastewater faces challenges due to complex composition and high toxicity. While microscale zero-valent iron (mZVI) based processes enable simultaneous removal of organic contaminants and nitrate (NO3−-N), electron competition and excessive iron sludge generation limit efficiency. This study reveals the dual roles of NO3−-N in the mZVI/O2 process: Inhibiting the oxidative removal of organic contaminants through electron competition and simultaneously enhancing iron dissolution with TFe increased by 17.5% to 65.7% compared to the system without NO3−-N. Nitrogen conversion analysis indicates that NO3−-N is mainly converted to NH4+-N via a direct 8-electron reduction pathway. To increase the utilization efficiency of iron electrons and enhance organic contaminant removal, a two-stage gradient oxidation process (mZVI/O2-Fenton) is designed: 1st stage utilizes NO3−-N to enhance Fe0 corrosion for NO3−-N reduction and Fe(II) release, while 2nd stage achieves efficient organic contaminants degradation via Fenton reaction with addition of H2O2. Actual wastewater validation confirms synergistic high organic contaminants removal (COD removal > 79.5%) and targeted nitrogen conversion (> 66.4% NO3−-N to NH4+-N). The study overcomes electron competition limitations in the mZVI/O2 process and provides a synergistic pollution control-resource recovery strategy for NO3−-N-contained refractory organic wastewaters.
The treatment of nitrogen-contained refractory organic wastewater faces challenges due to complex composition and high toxicity. While microscale zero-valent iron (mZVI) based processes enable simultaneous removal of organic contaminants and nitrate (NO3−-N), electron competition and excessive iron sludge generation limit efficiency. This study reveals the dual roles of NO3−-N in the mZVI/O2 process: Inhibiting the oxidative removal of organic contaminants through electron competition and simultaneously enhancing iron dissolution with TFe increased by 17.5% to 65.7% compared to the system without NO3−-N. Nitrogen conversion analysis indicates that NO3−-N is mainly converted to NH4+-N via a direct 8-electron reduction pathway. To increase the utilization efficiency of iron electrons and enhance organic contaminant removal, a two-stage gradient oxidation process (mZVI/O2-Fenton) is designed: 1st stage utilizes NO3−-N to enhance Fe0 corrosion for NO3−-N reduction and Fe(II) release, while 2nd stage achieves efficient organic contaminants degradation via Fenton reaction with addition of H2O2. Actual wastewater validation confirms synergistic high organic contaminants removal (COD removal > 79.5%) and targeted nitrogen conversion (> 66.4% NO3−-N to NH4+-N). The study overcomes electron competition limitations in the mZVI/O2 process and provides a synergistic pollution control-resource recovery strategy for NO3−-N-contained refractory organic wastewaters.
2026, 37(7): 112210
doi: 10.1016/j.cclet.2025.112210
摘要:
In situ chemical oxidation (ISCO) technology using peroxymonosulfate (PMS) and natural iron-bearing minerals for groundwater remediation has received increasing interest. The interaction between PMS and active Fe sites in minerals significantly influences the effectiveness of groundwater remediation. Nevertheless, there has been limited research investigating the relationship between the minerals active Fe sites and PMS activation. Herein, we distinguished and quantified the active Fe sites of common natural iron-bearing minerals in groundwater aquifers. Lewis acid sites (Fe-OH) were confirmed as the reaction sites in iron oxide/hydroxide/bearing clay minerals. The activation performance of minerals is positively correlated with their Lewis acid content. In iron sulfide minerals, Fe-S sites act as electron transfer mediators, facilitating PMS adsorption and activation. The activation of PMS by Lewis acid and Fe-S sites free radical both led to the generation of free radicals (SO4·- and ·OH) for CPs removal. Moreover, typical ferrihydrite/PMS and pyrite/PMS systems exhibited resistance to environmental interference and broad pH adaptability. A one-dimensional sand column experiment further proved their feasibility and long-term applicability in saturated porous media. These findings highlight the critical influence of active Fe sites of natural iron-bearing minerals and provide technical support for the application of PMS-ISCO strategies for groundwater remediation.
In situ chemical oxidation (ISCO) technology using peroxymonosulfate (PMS) and natural iron-bearing minerals for groundwater remediation has received increasing interest. The interaction between PMS and active Fe sites in minerals significantly influences the effectiveness of groundwater remediation. Nevertheless, there has been limited research investigating the relationship between the minerals active Fe sites and PMS activation. Herein, we distinguished and quantified the active Fe sites of common natural iron-bearing minerals in groundwater aquifers. Lewis acid sites (Fe-OH) were confirmed as the reaction sites in iron oxide/hydroxide/bearing clay minerals. The activation performance of minerals is positively correlated with their Lewis acid content. In iron sulfide minerals, Fe-S sites act as electron transfer mediators, facilitating PMS adsorption and activation. The activation of PMS by Lewis acid and Fe-S sites free radical both led to the generation of free radicals (SO4·- and ·OH) for CPs removal. Moreover, typical ferrihydrite/PMS and pyrite/PMS systems exhibited resistance to environmental interference and broad pH adaptability. A one-dimensional sand column experiment further proved their feasibility and long-term applicability in saturated porous media. These findings highlight the critical influence of active Fe sites of natural iron-bearing minerals and provide technical support for the application of PMS-ISCO strategies for groundwater remediation.
2026, 37(7): 112228
doi: 10.1016/j.cclet.2025.112228
摘要:
This study presents a OH− concentration-regulated one-step hydrothermal synthesis of a novel SrBi4Ti4O15/BiOCl heterojunction for efficient antibiotic degradation. Precise control of alkaline conditions enabled the in-situ generation of Ti–Cl bonds at the heterointerface, with their presence and nature further corroborated by Raman and XPS analyses. The SBTO/BOC heterojunction demonstrated significantly enhanced charge separation, achieving a 91.5% tetracycline degradation rate under illumination, outperforming pure BiOCl (71.9%) and SBTO (54.8%). Radical trapping and EPR studies identified •O2− and •OH as the primary reactive species. The catalyst exhibited robust stability, broad pH tolerance, and resistance to ionic interference. Tetracycline degradation efficiency further improves under combined light and ultrasonic irradiation, leveraging piezoelectric polarization to boost charge separation. LC-MS analysis revealed reduced toxicity of degradation intermediates. This work highlights the strategic role of OH−-mediated interface engineering in designing efficient ferroelectric heterojunctions for wastewater remediation.
This study presents a OH− concentration-regulated one-step hydrothermal synthesis of a novel SrBi4Ti4O15/BiOCl heterojunction for efficient antibiotic degradation. Precise control of alkaline conditions enabled the in-situ generation of Ti–Cl bonds at the heterointerface, with their presence and nature further corroborated by Raman and XPS analyses. The SBTO/BOC heterojunction demonstrated significantly enhanced charge separation, achieving a 91.5% tetracycline degradation rate under illumination, outperforming pure BiOCl (71.9%) and SBTO (54.8%). Radical trapping and EPR studies identified •O2− and •OH as the primary reactive species. The catalyst exhibited robust stability, broad pH tolerance, and resistance to ionic interference. Tetracycline degradation efficiency further improves under combined light and ultrasonic irradiation, leveraging piezoelectric polarization to boost charge separation. LC-MS analysis revealed reduced toxicity of degradation intermediates. This work highlights the strategic role of OH−-mediated interface engineering in designing efficient ferroelectric heterojunctions for wastewater remediation.
2026, 37(7): 112230
doi: 10.1016/j.cclet.2025.112230
摘要:
Iron oxide based magnetic catalytic colorimetric (MCC) nanomaterials have attracted extensive attention as signal labels in lateral flow immunoassays (LFIA). However, the main challenge in this field is its weak catalytic activity leading to relatively low color intensity. Herein, a new strategy of using the metal-organic framework (MOF) as mediate interfacing layer for loading Pt nanoparticles (Pt NPs) on the magnetic nanoparticles (MNPs) was proposed to obtain MCC nanomaterials with high catalytic activity. First, Cu-Co MOF was grown in situ with MNPs as the core, and then the MOF interfacing layer facilitates the uniform growth of Pt NPs on it. The obtained MNPs@MOF@Pt nanocomposite exhibited enhanced color signal intensity, excellent peroxidase-like activity and strong magnetic separation ability. After integration with a dual-antibody sandwich LFIA platform, the highly sensitive detection of interleukin-6 was achieved with a detection limit of 8.3 and 2.8 pg/mL for the pre-catalytic and post-catalytic tests respectively, which were 58-fold and 171-fold higher than that of the LFIA based on gold nanoparticles. Moreover, it exhibited good specificity and high accuracy for detection of clinical serum samples. Therefore, the magnetic nanozyme material proposed in this study demonstrated great potential for application in point-of-care diseases diagnosis.
Iron oxide based magnetic catalytic colorimetric (MCC) nanomaterials have attracted extensive attention as signal labels in lateral flow immunoassays (LFIA). However, the main challenge in this field is its weak catalytic activity leading to relatively low color intensity. Herein, a new strategy of using the metal-organic framework (MOF) as mediate interfacing layer for loading Pt nanoparticles (Pt NPs) on the magnetic nanoparticles (MNPs) was proposed to obtain MCC nanomaterials with high catalytic activity. First, Cu-Co MOF was grown in situ with MNPs as the core, and then the MOF interfacing layer facilitates the uniform growth of Pt NPs on it. The obtained MNPs@MOF@Pt nanocomposite exhibited enhanced color signal intensity, excellent peroxidase-like activity and strong magnetic separation ability. After integration with a dual-antibody sandwich LFIA platform, the highly sensitive detection of interleukin-6 was achieved with a detection limit of 8.3 and 2.8 pg/mL for the pre-catalytic and post-catalytic tests respectively, which were 58-fold and 171-fold higher than that of the LFIA based on gold nanoparticles. Moreover, it exhibited good specificity and high accuracy for detection of clinical serum samples. Therefore, the magnetic nanozyme material proposed in this study demonstrated great potential for application in point-of-care diseases diagnosis.
2026, 37(7): 112231
doi: 10.1016/j.cclet.2025.112231
摘要:
Current environmental and ecological risks associated with plastics are escalating. Cutting-edge research has focused on recycling waste plastics into monomers or energy resources. Fenton-like catalysis exhibits potential for technological development in this field. This study evaluates global warming potential (GWP), non-renewable energy use (NREU), and minimum selling price (MSP) during fuel recovery from waste plastics using Fenton-like processes. Adjusting operational strategies could enhance environmental sustainability and economic viability. Process parameters were optimized through controlled manipulation of catalyst pyrolysis temperature, catalyst concentration, hydrothermal temperature, and peroxymonosulfate (PMS) dosage. The optimization balanced environmental impact and economic returns in plastic recycling. Catalyst expenditure and PMS consumption emerged as primary barriers to sustainable and cost-efficient operations in homogeneous catalysis systems. When the superior-performance heterogeneous catalyst was used, Fenton-like process achieved 78% reduction in GWP, 99% decrease in NREU, and 63% MSP reduction for polypropylene (PP) recycling compared to homogeneous systems. With heterogeneous catalysis, polylactic acid (PLA) conversion demonstrates 29 times greater in terms of energy recovery efficiency for compared to PP processing. Sensitivity analysis revealed a variability of 8%-20% in outcomes due to oxidant loss. And the cost advantage for European operations compared to China was identified. The results underscored the importance of regional energy structures and process control for large-scale application. The system assessment framework has established quantifiable technical operation standards with the goal of environmental-economic benefits for implementing Fenton-like systems in plastic waste management. The results contribute directly to advancing circular economy principles and carbon reduction technologies.
Current environmental and ecological risks associated with plastics are escalating. Cutting-edge research has focused on recycling waste plastics into monomers or energy resources. Fenton-like catalysis exhibits potential for technological development in this field. This study evaluates global warming potential (GWP), non-renewable energy use (NREU), and minimum selling price (MSP) during fuel recovery from waste plastics using Fenton-like processes. Adjusting operational strategies could enhance environmental sustainability and economic viability. Process parameters were optimized through controlled manipulation of catalyst pyrolysis temperature, catalyst concentration, hydrothermal temperature, and peroxymonosulfate (PMS) dosage. The optimization balanced environmental impact and economic returns in plastic recycling. Catalyst expenditure and PMS consumption emerged as primary barriers to sustainable and cost-efficient operations in homogeneous catalysis systems. When the superior-performance heterogeneous catalyst was used, Fenton-like process achieved 78% reduction in GWP, 99% decrease in NREU, and 63% MSP reduction for polypropylene (PP) recycling compared to homogeneous systems. With heterogeneous catalysis, polylactic acid (PLA) conversion demonstrates 29 times greater in terms of energy recovery efficiency for compared to PP processing. Sensitivity analysis revealed a variability of 8%-20% in outcomes due to oxidant loss. And the cost advantage for European operations compared to China was identified. The results underscored the importance of regional energy structures and process control for large-scale application. The system assessment framework has established quantifiable technical operation standards with the goal of environmental-economic benefits for implementing Fenton-like systems in plastic waste management. The results contribute directly to advancing circular economy principles and carbon reduction technologies.
2026, 37(7): 112273
doi: 10.1016/j.cclet.2025.112273
摘要:
The degradation of perfluorocarboxylic acids (PFCAs), persistent organic pollutants, remains a significant environmental challenge. Photolysis represents a key pathway for their degradation, yet the molecular mechanisms driving defluorination and decarboxylation remain unclear. This study investigates the first step of direct PFCA photolysis by analyzing excitation properties using density functional theory (DFT), aiming to elucidate the relationship between electronic structure changes and degradation pathways. To better demonstrate and analyze the impact of internal factors on the first step of PFCAs photolysis, quantum chemical calculations were conducted to quantify and compare the molecule’s properties in the ground state and the excited state, aiming to explore the changes in the molecule’s behavior. Key parameters, including α C–F bond elongation (0.31%–1.62%), α C–C bond contraction (−6.23% to −9.10%), and excitation energy reduction (5.76–5.47 eV), revealed chain-length-dependent trends. The lower bond dissociation energy of α C–C (90–93 kcal/mol) compared to α C–F (116–124 kcal/mol) rationalized the dominance of decarboxylation over defluorination. Charge transfer spectroscopy further indicated localized n → π* excitation at carboxyl groups, promoting decarboxylation. A quantitative structure-activity relationship (QSAR) model linking hole-electron indices to degradation rates (R2 = 0.91) was developed and validated via leave-one-out cross-validation (RMSE = 0.338). These findings not only advance the mechanistic understanding of PFCA photolysis but also provide a predictive tool for optimizing UV-based water treatment systems targeting persistent fluorinated pollutants.
The degradation of perfluorocarboxylic acids (PFCAs), persistent organic pollutants, remains a significant environmental challenge. Photolysis represents a key pathway for their degradation, yet the molecular mechanisms driving defluorination and decarboxylation remain unclear. This study investigates the first step of direct PFCA photolysis by analyzing excitation properties using density functional theory (DFT), aiming to elucidate the relationship between electronic structure changes and degradation pathways. To better demonstrate and analyze the impact of internal factors on the first step of PFCAs photolysis, quantum chemical calculations were conducted to quantify and compare the molecule’s properties in the ground state and the excited state, aiming to explore the changes in the molecule’s behavior. Key parameters, including α C–F bond elongation (0.31%–1.62%), α C–C bond contraction (−6.23% to −9.10%), and excitation energy reduction (5.76–5.47 eV), revealed chain-length-dependent trends. The lower bond dissociation energy of α C–C (90–93 kcal/mol) compared to α C–F (116–124 kcal/mol) rationalized the dominance of decarboxylation over defluorination. Charge transfer spectroscopy further indicated localized n → π* excitation at carboxyl groups, promoting decarboxylation. A quantitative structure-activity relationship (QSAR) model linking hole-electron indices to degradation rates (R2 = 0.91) was developed and validated via leave-one-out cross-validation (RMSE = 0.338). These findings not only advance the mechanistic understanding of PFCA photolysis but also provide a predictive tool for optimizing UV-based water treatment systems targeting persistent fluorinated pollutants.
2026, 37(7): 112275
doi: 10.1016/j.cclet.2025.112275
摘要:
Photocatalytic water oxidation is considered as the bottleneck step for overall artificial photosynthesis, due to the slow photocarrier transfer kinetics and climbing thermodynamics. Developing the electronic structure of catalytic with more dynamic-thermodynamic advantages is crucial to deal with the above dilemma and realize the photocatalytic water oxidation. This work successfully explores an S-induced modification strategy to induce electronic delocalization and non-equilibrium states for unique Bi active sites. The introduction of V4+ species leads to asymmetric coordination of Bi atoms in the S-Bi-V4+ structure to provide more nonlocalized electrons, which initiates a concerted electron transfer in the system. The fine regulation on the local electron density and energy level structure of the Bi active site optimizes the reaction energy barriers to construct thermodynamically more favourable active centers for water oxidation. The optimized 2% S-BVO catalyst achieves outstanding water oxidation rate of 70.25 μmol/h (40 mg catalyst) triggering up to 11.06% apparent quantum efficiency at 420 nm. This work elucidates the influence of synergistic electron interaction of asymmetric coordination structure on both photocarrier transfer kinetics and reaction thermodynamic.
Photocatalytic water oxidation is considered as the bottleneck step for overall artificial photosynthesis, due to the slow photocarrier transfer kinetics and climbing thermodynamics. Developing the electronic structure of catalytic with more dynamic-thermodynamic advantages is crucial to deal with the above dilemma and realize the photocatalytic water oxidation. This work successfully explores an S-induced modification strategy to induce electronic delocalization and non-equilibrium states for unique Bi active sites. The introduction of V4+ species leads to asymmetric coordination of Bi atoms in the S-Bi-V4+ structure to provide more nonlocalized electrons, which initiates a concerted electron transfer in the system. The fine regulation on the local electron density and energy level structure of the Bi active site optimizes the reaction energy barriers to construct thermodynamically more favourable active centers for water oxidation. The optimized 2% S-BVO catalyst achieves outstanding water oxidation rate of 70.25 μmol/h (40 mg catalyst) triggering up to 11.06% apparent quantum efficiency at 420 nm. This work elucidates the influence of synergistic electron interaction of asymmetric coordination structure on both photocarrier transfer kinetics and reaction thermodynamic.
2026, 37(7): 112297
doi: 10.1016/j.cclet.2025.112297
摘要:
Adsorption is the most effective technique for perfluoroalkyl substances removal, owing to its simplicity and cost-effectiveness. However, conventional adsorbents suffer from low capacity, slow kinetics, poor selectivity, and reusability challenge. This study introduced a novel amine and imine functionalized covalent organic frameworks (PDA@COFs) adsorbent. Benefiting from its functional groups and unobstructed channels, PDA@COFs exhibited an ultra-high maximum adsorption capacity (3200 mg/g) and excellent selectivity for perfluorooctanoic (PFOA), which is far more than most adsorbents. Theoretical calculations revealed that electrostatic attraction is the dominant mechanism driving the selective adsorption of PFOA by PDA@COFs. The five-stages analysis of adsorption isotherms revealed that PDA@COFs adsorbed PFOA monomers via electrostatic adsorption at low concentrations and adsorbed PFOA aggregates by electrostatic and hydrophobic synergistic adsorption at high concentrations, which significantly enhanced the adsorption capacity for PFOA. To explore the practical application potential of PDA@COFs, it was evaluated as a promising anode in capacitive deionization (CDI). The recovery of PFOA was as high as 98.2%, highlighting its potential for practical application. This study is the first to demonstrate that PDA@COFs has an ultra-high adsorption capacity toward PFOA and new insights into the PFOA adsorption mechanism with five stages, and explores its practical application potential through CDI.
Adsorption is the most effective technique for perfluoroalkyl substances removal, owing to its simplicity and cost-effectiveness. However, conventional adsorbents suffer from low capacity, slow kinetics, poor selectivity, and reusability challenge. This study introduced a novel amine and imine functionalized covalent organic frameworks (PDA@COFs) adsorbent. Benefiting from its functional groups and unobstructed channels, PDA@COFs exhibited an ultra-high maximum adsorption capacity (3200 mg/g) and excellent selectivity for perfluorooctanoic (PFOA), which is far more than most adsorbents. Theoretical calculations revealed that electrostatic attraction is the dominant mechanism driving the selective adsorption of PFOA by PDA@COFs. The five-stages analysis of adsorption isotherms revealed that PDA@COFs adsorbed PFOA monomers via electrostatic adsorption at low concentrations and adsorbed PFOA aggregates by electrostatic and hydrophobic synergistic adsorption at high concentrations, which significantly enhanced the adsorption capacity for PFOA. To explore the practical application potential of PDA@COFs, it was evaluated as a promising anode in capacitive deionization (CDI). The recovery of PFOA was as high as 98.2%, highlighting its potential for practical application. This study is the first to demonstrate that PDA@COFs has an ultra-high adsorption capacity toward PFOA and new insights into the PFOA adsorption mechanism with five stages, and explores its practical application potential through CDI.
2026, 37(7): 112375
doi: 10.1016/j.cclet.2026.112375
摘要:
Supported catalysts are an effective approach in proton exchange membrane water electrolysis (PEMWE) owing to their enhanced metal-support interfacial interaction. We propose a novel high-temperature shock (HTS) technique by Joule-heating to construct an electronic coupling interface between IrO2 nanoclusters catalysts and TiO2 support (IrO2/TiO2-HTS). The HTS strategy features an ultrafast heating rate and compresses the synthesis time from hours to seconds (2 h to 60 s). The as-prepared catalyst features uniformly embedding the ultrafine IrO2 nanoclusters enrich oxygen vacancies within the redox-active metal oxide matrix, yielding exceptional mass activity and ultrastable performance. The mass activity of the catalyst is 1081 A/gIr at 1.6 V vs. RHE, 13 times higher than of commercial IrO2, and it demonstrates operation time for over 1100 h at 10 mA/cm2 with a voltage decay rate of only 40 μV/h. This HTS strategy offers a scalable route to accelerate vacancy engineering and strong metal oxide-support interaction (SMOSI) formation, enabling high activity at reduced Ir loading and long-term stability under acidic conditions. The approach is general and can be extended to other supported binary oxides, opening opportunities for the development of additional high–performance OER catalysts and PEM–relevant electrolysis systems.
Supported catalysts are an effective approach in proton exchange membrane water electrolysis (PEMWE) owing to their enhanced metal-support interfacial interaction. We propose a novel high-temperature shock (HTS) technique by Joule-heating to construct an electronic coupling interface between IrO2 nanoclusters catalysts and TiO2 support (IrO2/TiO2-HTS). The HTS strategy features an ultrafast heating rate and compresses the synthesis time from hours to seconds (2 h to 60 s). The as-prepared catalyst features uniformly embedding the ultrafine IrO2 nanoclusters enrich oxygen vacancies within the redox-active metal oxide matrix, yielding exceptional mass activity and ultrastable performance. The mass activity of the catalyst is 1081 A/gIr at 1.6 V vs. RHE, 13 times higher than of commercial IrO2, and it demonstrates operation time for over 1100 h at 10 mA/cm2 with a voltage decay rate of only 40 μV/h. This HTS strategy offers a scalable route to accelerate vacancy engineering and strong metal oxide-support interaction (SMOSI) formation, enabling high activity at reduced Ir loading and long-term stability under acidic conditions. The approach is general and can be extended to other supported binary oxides, opening opportunities for the development of additional high–performance OER catalysts and PEM–relevant electrolysis systems.
2026, 37(7): 112611
doi: 10.1016/j.cclet.2026.112611
摘要:
The outer membrane (OM) of Gram-negative bacteria, with its unique and complex structure, serves as a critical structural foundation for their heightened pathogenicity and drug resistance. However, with a thickness of only 7–9 nm, the OM is highly fragile and undergoes continuous remodeling, making it difficult to elucidate its structural dynamics and functional mechanisms during bacterial growth, division, and host invasion. Here, we developed Rho-PMXB as an OM-specific fluorescent probe that incorporates a polymyxin-derived moiety for highly specific recognition of OM lipopolysaccharides (LPS) and a rhodamine fluorophore that confers excellent photostability and high fluorescence brightness. Rho-PMXB enables selective labeling of the OMs of various Gram-negative bacteria and supports super-resolution imaging, allowing real-time visualization of OM dynamics during bacterial growth, division, and antibiotic treatment, thereby providing insight into antimicrobial mechanisms. Furthermore, Rho-PMXB enables dynamic super-resolution imaging of pathogen-host cell interactions, visualizing OM behavior during Porphyromonas gingivalis invasion of human gingival epithelial (HGE) cells and revealing its interplay with the host plasma membrane and actin cytoskeleton.
The outer membrane (OM) of Gram-negative bacteria, with its unique and complex structure, serves as a critical structural foundation for their heightened pathogenicity and drug resistance. However, with a thickness of only 7–9 nm, the OM is highly fragile and undergoes continuous remodeling, making it difficult to elucidate its structural dynamics and functional mechanisms during bacterial growth, division, and host invasion. Here, we developed Rho-PMXB as an OM-specific fluorescent probe that incorporates a polymyxin-derived moiety for highly specific recognition of OM lipopolysaccharides (LPS) and a rhodamine fluorophore that confers excellent photostability and high fluorescence brightness. Rho-PMXB enables selective labeling of the OMs of various Gram-negative bacteria and supports super-resolution imaging, allowing real-time visualization of OM dynamics during bacterial growth, division, and antibiotic treatment, thereby providing insight into antimicrobial mechanisms. Furthermore, Rho-PMXB enables dynamic super-resolution imaging of pathogen-host cell interactions, visualizing OM behavior during Porphyromonas gingivalis invasion of human gingival epithelial (HGE) cells and revealing its interplay with the host plasma membrane and actin cytoskeleton.
In situ real-time imaging of photothermal-induced rupture of self-assembled naphthalimide nanofibers
2026, 37(7): 112627
doi: 10.1016/j.cclet.2026.112627
摘要:
Photoresponsive supramolecular polymers hold great promise for applications in sensing, actuation, and biomedicine. However, the role of photothermal effects in regulating supramolecular assemblies and their dynamic structural evolution at the microscopic level remains poorly understood, as most studies have primarily focused on molecular photochemical mechanisms. Herein, we report a photothermal-responsive supramolecular system based on 1,8-naphthalimide building blocks. By reducing hydrogen-bonding sites through modification of the amide N-substituent of BAze from 4-(hydroxymethyl)benzyl to benzyl, an OH-free derivative, PhAze, was obtained. This subtle structural change endows PhAze assemblies with photoresponsive behavior that markedly differs from that of BAze assemblies. Upon 488 nm laser irradiation, PhAze assemblies undergo nanofiber rupture accompanied by ~40% fluorescence enhancement, whereas BAze assemblies show only a slight fluorescence decrease without morphological change. Real-time in situ observation based on confocal laser scanning microscopy (CLSM) reveals the dynamic photoresponse of PhAze nanofibers. Localized fluorescence enhancement first appears along the fibers, followed by the formation of molten-like microspheres that ultimately lead to fiber rupture. Two distinct modes of microsphere formation, synchronous and asynchronous, are identified during this process. Moreover, thermal imaging further confirms that the response originates from a photothermal effect, where localized temperature rise weakens noncovalent interactions and induces partial melting of the supramolecular fibers. This study provides direct in situ insights into photothermal-driven structural evolution in supramolecular assemblies and offers a new strategy for designing photothermal-responsive supramolecular materials.
Photoresponsive supramolecular polymers hold great promise for applications in sensing, actuation, and biomedicine. However, the role of photothermal effects in regulating supramolecular assemblies and their dynamic structural evolution at the microscopic level remains poorly understood, as most studies have primarily focused on molecular photochemical mechanisms. Herein, we report a photothermal-responsive supramolecular system based on 1,8-naphthalimide building blocks. By reducing hydrogen-bonding sites through modification of the amide N-substituent of BAze from 4-(hydroxymethyl)benzyl to benzyl, an OH-free derivative, PhAze, was obtained. This subtle structural change endows PhAze assemblies with photoresponsive behavior that markedly differs from that of BAze assemblies. Upon 488 nm laser irradiation, PhAze assemblies undergo nanofiber rupture accompanied by ~40% fluorescence enhancement, whereas BAze assemblies show only a slight fluorescence decrease without morphological change. Real-time in situ observation based on confocal laser scanning microscopy (CLSM) reveals the dynamic photoresponse of PhAze nanofibers. Localized fluorescence enhancement first appears along the fibers, followed by the formation of molten-like microspheres that ultimately lead to fiber rupture. Two distinct modes of microsphere formation, synchronous and asynchronous, are identified during this process. Moreover, thermal imaging further confirms that the response originates from a photothermal effect, where localized temperature rise weakens noncovalent interactions and induces partial melting of the supramolecular fibers. This study provides direct in situ insights into photothermal-driven structural evolution in supramolecular assemblies and offers a new strategy for designing photothermal-responsive supramolecular materials.
2026, 37(7): 112645
doi: 10.1016/j.cclet.2026.112645
摘要:
Photocatalytic conversion of polylactic acid (PLA) into high-value-added pyruvic acid (PA) presents a promising strategy for carbon-efficient resource cycling. However, successive dehydrogenation at the α-C of lactic acid (the monomer of PLA) remains a critical challenge. In this study, we fabricated an Au-modified CdS nanosphere photocatalyst (Au-CdS), where the introduction of Au facilitates the activation of the Cα-H bond in lactic acid (LA). Through combined theoretical calculations and in-situ EPR analysis, Au-CdS reduces the Cα-H bond cleavage energy barrier from 1.02 eV to 0.49 eV, substantially elevating the generation of carbon-centered radical intermediates. In addition, Au-CdS demonstrates enhanced separation efficiency of photogenerated electron-hole pairs relative to pristine CdS, thus efficiently activating O2 to generate O2•− radicals and further driving the conversion of O2•− to •OH radicals. The produced •OH radicals facilitate the successive dehydrogenation reactions via interacting with the Cα-H and α-OH bonds on the α-C of LA, thereby promoting the selective conversion of LA to PA. As a result, the Au-CdS catalyst achieves a PA production rate of 1340 ± 25 μmol g-1 h-1, surpassing that of pristine CdS by 8.9-fold. This work presents a novel strategy for the value-added upcycling of plastic waste.
Photocatalytic conversion of polylactic acid (PLA) into high-value-added pyruvic acid (PA) presents a promising strategy for carbon-efficient resource cycling. However, successive dehydrogenation at the α-C of lactic acid (the monomer of PLA) remains a critical challenge. In this study, we fabricated an Au-modified CdS nanosphere photocatalyst (Au-CdS), where the introduction of Au facilitates the activation of the Cα-H bond in lactic acid (LA). Through combined theoretical calculations and in-situ EPR analysis, Au-CdS reduces the Cα-H bond cleavage energy barrier from 1.02 eV to 0.49 eV, substantially elevating the generation of carbon-centered radical intermediates. In addition, Au-CdS demonstrates enhanced separation efficiency of photogenerated electron-hole pairs relative to pristine CdS, thus efficiently activating O2 to generate O2•− radicals and further driving the conversion of O2•− to •OH radicals. The produced •OH radicals facilitate the successive dehydrogenation reactions via interacting with the Cα-H and α-OH bonds on the α-C of LA, thereby promoting the selective conversion of LA to PA. As a result, the Au-CdS catalyst achieves a PA production rate of 1340 ± 25 μmol g-1 h-1, surpassing that of pristine CdS by 8.9-fold. This work presents a novel strategy for the value-added upcycling of plastic waste.
2026, 37(7): 112676
doi: 10.1016/j.cclet.2026.112676
摘要:
To address the challenges of active metal leaching and sluggish redox cycling in heterogeneous metal-catalyzed peroxymonosulfate (PMS) activation, this study proposes a double heteroatom co-anchoring and regulation strategy to design a sulfur-nitrogen co-doped carbon-supported cobalt nanoparticle catalyst (Co-S-CN). This strategy successfully constructs a “S2--Co0” dual micro-reduction environment, significantly accelerating the Co3+/Co2+ redox cycle. Experimental results demonstrate that the Co-S-CN+PMS system achieves 100% phenol degradation within 5 min while exhibiting exceptional resistance to anion interference (SO42−, Cl−, HCO3−, H2PO4−). Low cobalt leaching rate (<1%) across various pH conditions confirms strong metal anchoring via S-N synergy. Structural characterizations verify the existence of S2- and Co0, and co-optimizing cobalt valence cycling. Electron paramagnetic resonance (EPR) and quenching experiments indicate the reaction proceeds primarily via a nonradical pathway, with singlet oxygen (1O2) as the key reactive species. Density functional theory (DFT) calculations reveal that S-N synergy enhances PMS adsorption strength (adsorption energy optimized from −3.51 eV to −3.77 eV), increases charge density (Bader charge increased from 0.75 e to 0.80 e), and optimizes the electronic structure of Co 3d orbitals (d-band center upshifted from −1.341 eV to −1.330 eV). This work provides a strategy for rational design of highly active and stable catalysts.
To address the challenges of active metal leaching and sluggish redox cycling in heterogeneous metal-catalyzed peroxymonosulfate (PMS) activation, this study proposes a double heteroatom co-anchoring and regulation strategy to design a sulfur-nitrogen co-doped carbon-supported cobalt nanoparticle catalyst (Co-S-CN). This strategy successfully constructs a “S2--Co0” dual micro-reduction environment, significantly accelerating the Co3+/Co2+ redox cycle. Experimental results demonstrate that the Co-S-CN+PMS system achieves 100% phenol degradation within 5 min while exhibiting exceptional resistance to anion interference (SO42−, Cl−, HCO3−, H2PO4−). Low cobalt leaching rate (<1%) across various pH conditions confirms strong metal anchoring via S-N synergy. Structural characterizations verify the existence of S2- and Co0, and co-optimizing cobalt valence cycling. Electron paramagnetic resonance (EPR) and quenching experiments indicate the reaction proceeds primarily via a nonradical pathway, with singlet oxygen (1O2) as the key reactive species. Density functional theory (DFT) calculations reveal that S-N synergy enhances PMS adsorption strength (adsorption energy optimized from −3.51 eV to −3.77 eV), increases charge density (Bader charge increased from 0.75 e to 0.80 e), and optimizes the electronic structure of Co 3d orbitals (d-band center upshifted from −1.341 eV to −1.330 eV). This work provides a strategy for rational design of highly active and stable catalysts.
2026, 37(7): 111564
doi: 10.1016/j.cclet.2025.111564
摘要:
The severe threat of heavy metal pollution to ecological sustainability and human health has made the urgent development of efficient and environmentally friendly remediation technologies a necessity. Polyoxometalates (POMs), a class of unique metal-oxygen clusters with regulable structures and excellent properties, have emerged as promising candidates for removal of heavy metal ions. This review summarized the recent advances in POM-based functional materials (e.g., host-guest, heterojunction, and POM-based metal-organic frameworks) for heavy metal ion remediation (such as U(VI), Pb(II), and Cr(VI)). The removal mechanisms, including adsorption, chemical reduction, photocatalytic reduction, adsorption-photocatalysis synergy, as well as the chemical sensor or probe for heavy metal detection, have been highlighted. Additionally, the challenges in improving material recyclability, scaling up synthesis, and understanding the long-term environmental impact of POMs are identified, while future research directions toward sustainable, cost-effective, and multifunctional POM-based systems are proposed. This review provides a comprehensive overview of POM-based functional materials potential in addressing heavy metal pollution, offering insights for designing next-generation environmental remediation materials.
The severe threat of heavy metal pollution to ecological sustainability and human health has made the urgent development of efficient and environmentally friendly remediation technologies a necessity. Polyoxometalates (POMs), a class of unique metal-oxygen clusters with regulable structures and excellent properties, have emerged as promising candidates for removal of heavy metal ions. This review summarized the recent advances in POM-based functional materials (e.g., host-guest, heterojunction, and POM-based metal-organic frameworks) for heavy metal ion remediation (such as U(VI), Pb(II), and Cr(VI)). The removal mechanisms, including adsorption, chemical reduction, photocatalytic reduction, adsorption-photocatalysis synergy, as well as the chemical sensor or probe for heavy metal detection, have been highlighted. Additionally, the challenges in improving material recyclability, scaling up synthesis, and understanding the long-term environmental impact of POMs are identified, while future research directions toward sustainable, cost-effective, and multifunctional POM-based systems are proposed. This review provides a comprehensive overview of POM-based functional materials potential in addressing heavy metal pollution, offering insights for designing next-generation environmental remediation materials.
2026, 37(7): 111597
doi: 10.1016/j.cclet.2025.111597
摘要:
Compared to synthetic chemical compounds, plant extracts derived from natural sources have emerged as the "new favorites" in the treatment and care of skin diseases due to their distinct advantages, including being environmentally friendly, sustainable, and safe. However, challenges such as poor solubility, limited permeability, and the barrier function of the stratum corneum significantly restrict the application of natural products in dermal drug delivery. Fortunately, advancements in nanotechnology offer promising solutions to overcome these challenges. Different skin diseases and treatments require the precise delivery of natural active ingredients to specific skin layers, and the unique structure of nanocarriers enables targeted delivery to achieve desired therapeutic outcomes. This paper begins by exploring the pathogenesis and therapeutic targets of common skin conditions, including atopic dermatitis (AD), psoriasis, decubitus ulcers, diabetic foot ulcers (DFUs), as well as applications in antioxidant therapies and anti-aging strategies. Furthermore, it provides a detailed overview of the depths and locations within the skin where active compounds must be delivered to exert their effects effectively. Subsequently, this review categorizes and examines natural products based on their therapeutic effects on various skin diseases. It then highlights the skin depths and specific sites that can be targeted by different delivery systems designed to enhance skin permeability, tailored to meet the needs of skin disease treatment or care. By addressing these aspects, this review aims to provide a valuable reference for advancing research on nano-delivery systems in the field of topical skin drug delivery for the treatment and management of skin diseases.
Compared to synthetic chemical compounds, plant extracts derived from natural sources have emerged as the "new favorites" in the treatment and care of skin diseases due to their distinct advantages, including being environmentally friendly, sustainable, and safe. However, challenges such as poor solubility, limited permeability, and the barrier function of the stratum corneum significantly restrict the application of natural products in dermal drug delivery. Fortunately, advancements in nanotechnology offer promising solutions to overcome these challenges. Different skin diseases and treatments require the precise delivery of natural active ingredients to specific skin layers, and the unique structure of nanocarriers enables targeted delivery to achieve desired therapeutic outcomes. This paper begins by exploring the pathogenesis and therapeutic targets of common skin conditions, including atopic dermatitis (AD), psoriasis, decubitus ulcers, diabetic foot ulcers (DFUs), as well as applications in antioxidant therapies and anti-aging strategies. Furthermore, it provides a detailed overview of the depths and locations within the skin where active compounds must be delivered to exert their effects effectively. Subsequently, this review categorizes and examines natural products based on their therapeutic effects on various skin diseases. It then highlights the skin depths and specific sites that can be targeted by different delivery systems designed to enhance skin permeability, tailored to meet the needs of skin disease treatment or care. By addressing these aspects, this review aims to provide a valuable reference for advancing research on nano-delivery systems in the field of topical skin drug delivery for the treatment and management of skin diseases.
2026, 37(7): 111610
doi: 10.1016/j.cclet.2025.111610
摘要:
Macrophage membrane-camouflaged nanoparticles (MmNPs) are emerging as efficient nanoplatforms for targeted delivery to inflammatory sites, tumors, and infected tissues due to the innate characteristics of macrophages. This biomimetic strategy effectively addresses several limitations of traditional targeted drug delivery systems, offering improved biocompatibility, extended blood circulation, immune evasion, and site-specific homing. Compared to conventional functionalization methods, MmNPs provide a simplified method for creating multifunctional nanoparticles. In this review, we explore the origins and functions of macrophages, highlighting how MmNP platforms are leveraged for precise drug delivery. The latest applications of MmNPs in targeted delivery are summarized, focusing on their intrinsic targeting properties, membrane surface modifications and designs for environmental stimulus response. Finally, we discuss the prospects and challenges in translating MmNP technology from experimental settings to clinical applications, aiming to inspire continued innovation in the design of MmNP for precise and effective drug delivery strategies against complex diseases.
Macrophage membrane-camouflaged nanoparticles (MmNPs) are emerging as efficient nanoplatforms for targeted delivery to inflammatory sites, tumors, and infected tissues due to the innate characteristics of macrophages. This biomimetic strategy effectively addresses several limitations of traditional targeted drug delivery systems, offering improved biocompatibility, extended blood circulation, immune evasion, and site-specific homing. Compared to conventional functionalization methods, MmNPs provide a simplified method for creating multifunctional nanoparticles. In this review, we explore the origins and functions of macrophages, highlighting how MmNP platforms are leveraged for precise drug delivery. The latest applications of MmNPs in targeted delivery are summarized, focusing on their intrinsic targeting properties, membrane surface modifications and designs for environmental stimulus response. Finally, we discuss the prospects and challenges in translating MmNP technology from experimental settings to clinical applications, aiming to inspire continued innovation in the design of MmNP for precise and effective drug delivery strategies against complex diseases.
2026, 37(7): 111671
doi: 10.1016/j.cclet.2025.111671
摘要:
Cerium oxide nanozymes (CeO2 NZs) exhibit enzyme mimetic activities and great promise for biomedical applications by mediating the dynamic cycling between Ce3+ and Ce4+. However, traditional preparation methods are often expensive and detrimental to the environment. Meanwhile, the problems of easy agglomeration, poor targeting and weak biocompatibility need to be solved. The available literatures have mainly reviewed CeO2 NZs in terms of its material properties, mechanisms and potential clinical applications. The literatures on the limitations of CeO2 NZs and the corresponding improvement methods are fragmented. Consequently, the limitations of CeO2 NZs and the strategies involving green preparation technology and modification mainly summarized, while the biosafety of the modification strategies are compared. Meanwhile, representative studies of potential clinical applications of CeO2 NZs over the past three years are outlined, along with a summary of their clinical translational prospects and challenges. Finally, the challenges of CeO2 NZs promotion technology are discussed.
Cerium oxide nanozymes (CeO2 NZs) exhibit enzyme mimetic activities and great promise for biomedical applications by mediating the dynamic cycling between Ce3+ and Ce4+. However, traditional preparation methods are often expensive and detrimental to the environment. Meanwhile, the problems of easy agglomeration, poor targeting and weak biocompatibility need to be solved. The available literatures have mainly reviewed CeO2 NZs in terms of its material properties, mechanisms and potential clinical applications. The literatures on the limitations of CeO2 NZs and the corresponding improvement methods are fragmented. Consequently, the limitations of CeO2 NZs and the strategies involving green preparation technology and modification mainly summarized, while the biosafety of the modification strategies are compared. Meanwhile, representative studies of potential clinical applications of CeO2 NZs over the past three years are outlined, along with a summary of their clinical translational prospects and challenges. Finally, the challenges of CeO2 NZs promotion technology are discussed.
2026, 37(7): 111695
doi: 10.1016/j.cclet.2025.111695
摘要:
With growing emphasis on drug efficacy, safety, and adverse reactions, many traditional Chinese medicines and their active ingredients, as well as compounds such as antibiotics, immunosuppressants, and hormones often face limited efficacy or give rise to adverse effects during application. To improve therapeutic outcomes and reduce systemic side effects, oral targeted drug delivery systems have become an important research direction. Hydrogels have shown great potential in the field of oral delivery to treat many diseases due to their superior drug protection ability and excellent biocompatibility. This review explores the physiological characteristics of the gastrointestinal tract and the significant advantages of oral hydrogels in drug delivery, and systematically introduces hydrogel carrier design strategies through physical crosslinking, chemical crosslinking, small molecule self-assembly, and metal ion coordination. Furthermore, it emphasizes recent advances in intelligent oral hydrogels and drug loading strategy. Lastly, the review summarizes the innovative applications of oral hydrogels in the treatment of diseases such as esophagitis, GI disorders, metabolic and endocrine diseases, osteoporosis, detoxification, and cardiovascular diseases, offering valuable insights and guidance for optimizing and advancing hydrogel-based drug delivery systems.
With growing emphasis on drug efficacy, safety, and adverse reactions, many traditional Chinese medicines and their active ingredients, as well as compounds such as antibiotics, immunosuppressants, and hormones often face limited efficacy or give rise to adverse effects during application. To improve therapeutic outcomes and reduce systemic side effects, oral targeted drug delivery systems have become an important research direction. Hydrogels have shown great potential in the field of oral delivery to treat many diseases due to their superior drug protection ability and excellent biocompatibility. This review explores the physiological characteristics of the gastrointestinal tract and the significant advantages of oral hydrogels in drug delivery, and systematically introduces hydrogel carrier design strategies through physical crosslinking, chemical crosslinking, small molecule self-assembly, and metal ion coordination. Furthermore, it emphasizes recent advances in intelligent oral hydrogels and drug loading strategy. Lastly, the review summarizes the innovative applications of oral hydrogels in the treatment of diseases such as esophagitis, GI disorders, metabolic and endocrine diseases, osteoporosis, detoxification, and cardiovascular diseases, offering valuable insights and guidance for optimizing and advancing hydrogel-based drug delivery systems.
2026, 37(7): 111831
doi: 10.1016/j.cclet.2025.111831
摘要:
Aqueous zinc-ion batteries (ZIBs) have gained tremendous interests by virtue of their intrinsic safety, low cost and favorable theoretical capacities. As the promising candidates of cathode materials of ZIBs, ammonium vanadates (NVO) have captured widespread attentions owing to their tunable chemical properties and enhanced structural stabilities owing to the existence of NH4+ in the [VO]n layers. However, the pristine NVO fails to meet the expectations due to the strong interlayer electrostatic repulsion and comparatively sluggish transfer kinetics, which necessitates the exploration of appropriate modification strategies to fully dig its potential. Herein, this review systematically summarizes five core molecular engineering strategies, intercalation, defect, interfacial, doping, and structural engineering strategies, and their significances in modulating structural and electrochemical properties of NVO are elaborately discussed. Moreover, the perspectives on the future developments and potential energy-related applications of NVO are presented. This review is anticipated to deepen the researchers' understandings of the potentials of molecular engineering strategies on improving zinc-ion storage capabilities of cathode materials, and further promote the practicality of NVO in ZIBs.
Aqueous zinc-ion batteries (ZIBs) have gained tremendous interests by virtue of their intrinsic safety, low cost and favorable theoretical capacities. As the promising candidates of cathode materials of ZIBs, ammonium vanadates (NVO) have captured widespread attentions owing to their tunable chemical properties and enhanced structural stabilities owing to the existence of NH4+ in the [VO]n layers. However, the pristine NVO fails to meet the expectations due to the strong interlayer electrostatic repulsion and comparatively sluggish transfer kinetics, which necessitates the exploration of appropriate modification strategies to fully dig its potential. Herein, this review systematically summarizes five core molecular engineering strategies, intercalation, defect, interfacial, doping, and structural engineering strategies, and their significances in modulating structural and electrochemical properties of NVO are elaborately discussed. Moreover, the perspectives on the future developments and potential energy-related applications of NVO are presented. This review is anticipated to deepen the researchers' understandings of the potentials of molecular engineering strategies on improving zinc-ion storage capabilities of cathode materials, and further promote the practicality of NVO in ZIBs.
2026, 37(7): 112141
doi: 10.1016/j.cclet.2025.112141
摘要:
Nitrate contamination has prompted global concern due to its far-reaching effects on human health and the ecosystem. As an emerging technology, electrochemical nitrate reduction reaction (eNO3RR) provides a promising approach for converting nitrate to valuable ammonia (NH3) or harmless nitrogen gas (N2). However, the conversion efficiency of eNO3RR is still constrained by the mismatch between catalysts and the reaction microenvironment at lower nitrate concentrations (< 0.1 mol/L). In this review, we have systematically discussed the feasibility of electrochemical methods in treating low-concentration nitrate by summarizing recent advances and their reaction mechanisms. Meanwhile, the selection between NH3 and N2 pathways was evaluated based on the nitrate concentration range and safety considerations associated with each scenario. Finally, the dominant factors for applying eNO3RR to real-world scenarios were also thoroughly discussed. We hope this review can provide comprehensive insights into the design of optimal catalysts and systems for treating low-concentration nitrates in practical scenarios, thereby promoting the environmental sustainability of electrocatalytic technologies.
Nitrate contamination has prompted global concern due to its far-reaching effects on human health and the ecosystem. As an emerging technology, electrochemical nitrate reduction reaction (eNO3RR) provides a promising approach for converting nitrate to valuable ammonia (NH3) or harmless nitrogen gas (N2). However, the conversion efficiency of eNO3RR is still constrained by the mismatch between catalysts and the reaction microenvironment at lower nitrate concentrations (< 0.1 mol/L). In this review, we have systematically discussed the feasibility of electrochemical methods in treating low-concentration nitrate by summarizing recent advances and their reaction mechanisms. Meanwhile, the selection between NH3 and N2 pathways was evaluated based on the nitrate concentration range and safety considerations associated with each scenario. Finally, the dominant factors for applying eNO3RR to real-world scenarios were also thoroughly discussed. We hope this review can provide comprehensive insights into the design of optimal catalysts and systems for treating low-concentration nitrates in practical scenarios, thereby promoting the environmental sustainability of electrocatalytic technologies.
2026, 37(7): 112160
doi: 10.1016/j.cclet.2025.112160
摘要:
The wastewater produced in the antibiotic manufacturing process is a significant source of antibiotic pollution in the aquatic environment, posing a severe threat to ecological health and human well-being. Researchers have explored various methods, including source reduction technologies such as enzymatic engineering and green process control, to enhance antibiotic extraction efficiency. In addition, high-efficiency end-of-line processing technology has also been widely developed. This review first provides a detailed introduction to the characteristics of various antibiotics and their distribution levels in the environment. Then we systematically summarize and analyze the full-chain antibiotic end-of-pipe treatment processes, including conventional treatment processes and typical advanced treatment processes. Especially compares and analyzes the removal efficiency and carbon emissions of different conventional treatment processes, aiming to select efficient and low-carbon treatment processes. We intend to provide effective solutions to tackle the issue of antibiotic pollution while ensuring public health and ecological security.
The wastewater produced in the antibiotic manufacturing process is a significant source of antibiotic pollution in the aquatic environment, posing a severe threat to ecological health and human well-being. Researchers have explored various methods, including source reduction technologies such as enzymatic engineering and green process control, to enhance antibiotic extraction efficiency. In addition, high-efficiency end-of-line processing technology has also been widely developed. This review first provides a detailed introduction to the characteristics of various antibiotics and their distribution levels in the environment. Then we systematically summarize and analyze the full-chain antibiotic end-of-pipe treatment processes, including conventional treatment processes and typical advanced treatment processes. Especially compares and analyzes the removal efficiency and carbon emissions of different conventional treatment processes, aiming to select efficient and low-carbon treatment processes. We intend to provide effective solutions to tackle the issue of antibiotic pollution while ensuring public health and ecological security.
2026, 37(7): 112174
doi: 10.1016/j.cclet.2025.112174
摘要:
As a new wastewater treatment technology, the microalgae-fungi consortia system (MFCS) has attracted much attention because of its high efficiency, environmental protection and energy saving features. Extracellular polymeric substances (EPS) play a key role in MFCS treatment of wastewater and microalgae harvesting. In this review, the definition and formation process of MFCS, thoroughly examines the composition, properties, and influencing factors of EPS, as well as systematically explains the mechanism of action of EPS in wastewater treatment and microalgae harvesting. EPS surface functional groups have negative charge, adsorption, flocculation, and hydrophilicity/hydrophobicity properties. Microalgae and fungi form MFCS through EPS electrostatic attraction and protein bridging. EPS achieves adsorption, aggregation, and degradation of pollutants through targeted binding, chelation, coordination mechanisms, hydrophobic interactions, and complexation degradation mechanisms via functional groups. EPS achieves microalgae harvesting through electrostatic neutralization, surface protein interaction, and polysaccharide adhesion. However, current research still faces the following challenges, the selection of algal strains in the formation process of MFCS is still unclear. The mechanism of EPS removal of new pollutants and internal signaling pathways are still unclear. FSH takes too long, while FPH requires higher costs during harvesting. In the future, MFCS should be explored in combination with actual engineering applications, and different combinations of algae species and strains should be explored. Using genetic engineering to explore the synergistic mechanism of microalgae and fungi EPS in pollutant treatment. Improve the process conditions for harvesting microalgae using fungi, optimizing the two methods of microalgae harvesting, and conduct experiments on the efficient harvesting of microalgae. This review systematically explored the mechanism of action of EPS in MFCS, which is important for wastewater treatment and microalgal biomass harvesting.
As a new wastewater treatment technology, the microalgae-fungi consortia system (MFCS) has attracted much attention because of its high efficiency, environmental protection and energy saving features. Extracellular polymeric substances (EPS) play a key role in MFCS treatment of wastewater and microalgae harvesting. In this review, the definition and formation process of MFCS, thoroughly examines the composition, properties, and influencing factors of EPS, as well as systematically explains the mechanism of action of EPS in wastewater treatment and microalgae harvesting. EPS surface functional groups have negative charge, adsorption, flocculation, and hydrophilicity/hydrophobicity properties. Microalgae and fungi form MFCS through EPS electrostatic attraction and protein bridging. EPS achieves adsorption, aggregation, and degradation of pollutants through targeted binding, chelation, coordination mechanisms, hydrophobic interactions, and complexation degradation mechanisms via functional groups. EPS achieves microalgae harvesting through electrostatic neutralization, surface protein interaction, and polysaccharide adhesion. However, current research still faces the following challenges, the selection of algal strains in the formation process of MFCS is still unclear. The mechanism of EPS removal of new pollutants and internal signaling pathways are still unclear. FSH takes too long, while FPH requires higher costs during harvesting. In the future, MFCS should be explored in combination with actual engineering applications, and different combinations of algae species and strains should be explored. Using genetic engineering to explore the synergistic mechanism of microalgae and fungi EPS in pollutant treatment. Improve the process conditions for harvesting microalgae using fungi, optimizing the two methods of microalgae harvesting, and conduct experiments on the efficient harvesting of microalgae. This review systematically explored the mechanism of action of EPS in MFCS, which is important for wastewater treatment and microalgal biomass harvesting.
2026, 37(7): 112191
doi: 10.1016/j.cclet.2025.112191
摘要:
In heterogeneous Fenton-like systems, the oxidative polymerization pathway is of great significance in the field of sustainable water treatment. Unlike the traditional mineralization pathway, it can convert organic pollutants into polymers, thereby achieving the recovery of carbon resources. This paper focuses on the core content related to this pathway, expounding that the mechanism of oxidative polymerization is influenced by multiple factors (catalysts, oxidants, organic matters). Meanwhile, various methods exist for identifying the polymerization pathway, such as electrochemical experiments, Raman spectroscopy analysis, and mass spectrometry technology, which can infer the reaction process and product structure. Additionally, this paper reveals two pathways for pollutant removal through oxidative polymerization: The radical pathway and the non-radical pathway. In the future, advanced characterization techniques should be used to deeply explore the microscopic mechanism of oxidative polymerization, optimize catalyst design, expand practical application research, and explore comprehensive utilization pathways for its products, so as to promote the development of sustainable water treatment technologies.
In heterogeneous Fenton-like systems, the oxidative polymerization pathway is of great significance in the field of sustainable water treatment. Unlike the traditional mineralization pathway, it can convert organic pollutants into polymers, thereby achieving the recovery of carbon resources. This paper focuses on the core content related to this pathway, expounding that the mechanism of oxidative polymerization is influenced by multiple factors (catalysts, oxidants, organic matters). Meanwhile, various methods exist for identifying the polymerization pathway, such as electrochemical experiments, Raman spectroscopy analysis, and mass spectrometry technology, which can infer the reaction process and product structure. Additionally, this paper reveals two pathways for pollutant removal through oxidative polymerization: The radical pathway and the non-radical pathway. In the future, advanced characterization techniques should be used to deeply explore the microscopic mechanism of oxidative polymerization, optimize catalyst design, expand practical application research, and explore comprehensive utilization pathways for its products, so as to promote the development of sustainable water treatment technologies.
2026, 37(7): 112192
doi: 10.1016/j.cclet.2025.112192
摘要:
Single-atom catalysts (SACs), especially defective-SACs, have been developed into low-cost, high-selectivity and high-performance advanced catalysts due to their unique synergistic effects, and have occupied a place in the energy and environmental fields. However, there is a lack of comprehensive and comprehensive summaries and discussions on the structure-property relationships. Therefore, an exhaustive review on the topic of the synergistic interaction of SACs with defective catalysts is imminent. Firstly, this review offers an overview of the most recent generation pathways of defective-SACs based on SACs and defect formation time differences, with a focus on the important influencing factors in the different synthesis processes. Immediately thereafter, the different roles of defects in the constructed defective-SACs are comprehensively analyzed to unravel the mystery of the high stability and performance of defective-SACs. Subsequently, this article systematically analyzes the synergistic interaction mechanism between defects and SACs from the perspective of reaction mechanisms and explains how this mechanism drives significant performance improvements in various catalytic reactions. The article concludes with limitations of current research and future directions to guide the design of more perfect catalysts for defective-SACs.
Single-atom catalysts (SACs), especially defective-SACs, have been developed into low-cost, high-selectivity and high-performance advanced catalysts due to their unique synergistic effects, and have occupied a place in the energy and environmental fields. However, there is a lack of comprehensive and comprehensive summaries and discussions on the structure-property relationships. Therefore, an exhaustive review on the topic of the synergistic interaction of SACs with defective catalysts is imminent. Firstly, this review offers an overview of the most recent generation pathways of defective-SACs based on SACs and defect formation time differences, with a focus on the important influencing factors in the different synthesis processes. Immediately thereafter, the different roles of defects in the constructed defective-SACs are comprehensively analyzed to unravel the mystery of the high stability and performance of defective-SACs. Subsequently, this article systematically analyzes the synergistic interaction mechanism between defects and SACs from the perspective of reaction mechanisms and explains how this mechanism drives significant performance improvements in various catalytic reactions. The article concludes with limitations of current research and future directions to guide the design of more perfect catalysts for defective-SACs.
2026, 37(7): 112194
doi: 10.1016/j.cclet.2025.112194
摘要:
Micro/nanoplastics (MNPs) have emerged as a global environmental concern, which leads to an urgent need for sensitive and specific MNPs detection technologies. Fluorescence-based methods with high sensitivity and dynamic tracking capabilities have become a significant and promising tool in MNPs analysis. This review systematically summarizes recent developments in fluorescent probes including traditional organic dyes, nanomaterials, aggregation-induced emission (AIE) molecules, binding peptides, and aptamers, for MNPs detection. The fluorescence sensing technology coupled with micro-imaging developed for in situ detection and dynamic tracking is also discussed. The current challenges for MNPs detection including matrix interference and lack of quantification standards are discussed and perspectives including developing multifunctional probes and AI-assisted platforms are proposed. This review provides theoretical reference and innovative ideas for developing new fluorescence probes and methods for MNPs detection and monitoring.
Micro/nanoplastics (MNPs) have emerged as a global environmental concern, which leads to an urgent need for sensitive and specific MNPs detection technologies. Fluorescence-based methods with high sensitivity and dynamic tracking capabilities have become a significant and promising tool in MNPs analysis. This review systematically summarizes recent developments in fluorescent probes including traditional organic dyes, nanomaterials, aggregation-induced emission (AIE) molecules, binding peptides, and aptamers, for MNPs detection. The fluorescence sensing technology coupled with micro-imaging developed for in situ detection and dynamic tracking is also discussed. The current challenges for MNPs detection including matrix interference and lack of quantification standards are discussed and perspectives including developing multifunctional probes and AI-assisted platforms are proposed. This review provides theoretical reference and innovative ideas for developing new fluorescence probes and methods for MNPs detection and monitoring.
2026, 37(7): 112208
doi: 10.1016/j.cclet.2025.112208
摘要:
Mass spectrometry is a highly sensitive and precise analytical technique widely utilized in biomedical research, drug development, and environmental monitoring. Nonetheless, before mass spectrometry analysis, complex matrix samples frequently harbor numerous salts, which may compromise the stability and accuracy of mass spectrometry signals. Hence, it is imperative to employ effective desalting techniques, which serve as critical pretreatment steps in sample preparation for mass spectrometry analysis. While numerous scholars have developed desalting techniques, a comprehensive overview of such techniques is lacking. This paper provides a summary of desalination methods for mass spectrometry analysis developed since the twenty-first century (including extraction techniques, chromatography, ion exchange, crystallography, ambient ionization mass spectrometry and desalting agents, etc.), along with their principles, advantages, and disadvantages. Furthermore, recent research advancements and technological enhancements are discussed to introduce novel ideas and methodologies for sample desalting as a pretreatment step before mass spectrometry analysis. Against the backdrop of the growing importance of precision medicine and environmental monitoring, the continuous improvement of desalination technology will promote its wide application in areas such as clinical diagnosis, food safety testing, and environmental pollution assessment.
Mass spectrometry is a highly sensitive and precise analytical technique widely utilized in biomedical research, drug development, and environmental monitoring. Nonetheless, before mass spectrometry analysis, complex matrix samples frequently harbor numerous salts, which may compromise the stability and accuracy of mass spectrometry signals. Hence, it is imperative to employ effective desalting techniques, which serve as critical pretreatment steps in sample preparation for mass spectrometry analysis. While numerous scholars have developed desalting techniques, a comprehensive overview of such techniques is lacking. This paper provides a summary of desalination methods for mass spectrometry analysis developed since the twenty-first century (including extraction techniques, chromatography, ion exchange, crystallography, ambient ionization mass spectrometry and desalting agents, etc.), along with their principles, advantages, and disadvantages. Furthermore, recent research advancements and technological enhancements are discussed to introduce novel ideas and methodologies for sample desalting as a pretreatment step before mass spectrometry analysis. Against the backdrop of the growing importance of precision medicine and environmental monitoring, the continuous improvement of desalination technology will promote its wide application in areas such as clinical diagnosis, food safety testing, and environmental pollution assessment.
2026, 37(7): 112237
doi: 10.1016/j.cclet.2025.112237
摘要:
Macrocyclic compounds play a fundamental role in supramolecular chemistry, demonstrating significant prospect in functional materials owing to their precise cavities and tunable molecular recognition and assembly capabilities. However, the only cavity of the mono-macrocyclic hosts limited the development of traditional mono-macrocycle-based supramolecular materials in assembly dimensionality, recognition selectivity, and synergistic performance. Therefore, multi-macrocyclic hosts attracted increasing attention due to their unique advantages originated from multi-cavity cooperativity, which include more abundant guest suitability, multiple-dimension assembly, precise collaborative effect, and so on. Based on these merits, introducing multi-macrocyclic hosts into supramolecular materials can efficiently improve and enrich the properties of these kinds of materials. This review summarizes recent innovative design and constructing strategies for multi-macrocyclic hosts, including covalent chain bridged, covalent fused, coordinated, and mechanically interlocked pathway. And their applications in recognition, luminescence, catalysis, biomedical and chiral materials are highlighted, while the advantages of multi-macrocycles in enhancing binding affinity, selectivity, and stimulus-responsive behavior are elucidated. Furthermore, we discuss future directions, such as novel multifunctional hosts design, optimization of assembly strategies, and interdisciplinary applications, providing theoretical insights and practical guidance for the development of multi-macrocycles-based high performance supramolecular materials.
Macrocyclic compounds play a fundamental role in supramolecular chemistry, demonstrating significant prospect in functional materials owing to their precise cavities and tunable molecular recognition and assembly capabilities. However, the only cavity of the mono-macrocyclic hosts limited the development of traditional mono-macrocycle-based supramolecular materials in assembly dimensionality, recognition selectivity, and synergistic performance. Therefore, multi-macrocyclic hosts attracted increasing attention due to their unique advantages originated from multi-cavity cooperativity, which include more abundant guest suitability, multiple-dimension assembly, precise collaborative effect, and so on. Based on these merits, introducing multi-macrocyclic hosts into supramolecular materials can efficiently improve and enrich the properties of these kinds of materials. This review summarizes recent innovative design and constructing strategies for multi-macrocyclic hosts, including covalent chain bridged, covalent fused, coordinated, and mechanically interlocked pathway. And their applications in recognition, luminescence, catalysis, biomedical and chiral materials are highlighted, while the advantages of multi-macrocycles in enhancing binding affinity, selectivity, and stimulus-responsive behavior are elucidated. Furthermore, we discuss future directions, such as novel multifunctional hosts design, optimization of assembly strategies, and interdisciplinary applications, providing theoretical insights and practical guidance for the development of multi-macrocycles-based high performance supramolecular materials.
2026, 37(7): 112274
doi: 10.1016/j.cclet.2025.112274
摘要:
Fe-bearing clay minerals have garnered significant attention in environmental catalysis due to their unique Fe(Ⅱ)/Fe(Ⅲ) redox cycling and high surface area, which enable the effective activation of oxidants such as molecular oxygen (O2), peroxymonosulfate, and other species, and the subsequent generation of reactive oxygen species (ROS). This review offers a comprehensive overview of the structural characteristics and iron coordination environments within these minerals that govern electron transfer processes from Fe(Ⅱ) to oxidant species. It further explores the mechanistic pathways that lead to the formation of superoxide, hydroxyl radicals (•OH), and singlet oxygen, detailing the chemical reactions involved. Additionally, the influence of various co-substrates and chelating agents, such as humic acids and ethylenediaminetetraacetic acid (EDTA), on the enhancement of redox processes and ROS generation is discussed, focusing on their roles in modulating reaction kinetics and improving catalytic efficiency. Furthermore, the review highlights the recent advancements in applying Fe-bearing clay minerals for the degradation of persistent organic pollutants, including dyes, pharmaceuticals, and pesticides, in both aqueous and soil environments. The potential for optimizing these mineral-based catalytic systems by tailoring their composition or creating hybrid materials is also explored to develop more efficient and scalable solutions for environmental remediation. This review outlines future research directions, emphasizing the integration of fundamental mechanistic insights with practical applications for pollutant degradation.
Fe-bearing clay minerals have garnered significant attention in environmental catalysis due to their unique Fe(Ⅱ)/Fe(Ⅲ) redox cycling and high surface area, which enable the effective activation of oxidants such as molecular oxygen (O2), peroxymonosulfate, and other species, and the subsequent generation of reactive oxygen species (ROS). This review offers a comprehensive overview of the structural characteristics and iron coordination environments within these minerals that govern electron transfer processes from Fe(Ⅱ) to oxidant species. It further explores the mechanistic pathways that lead to the formation of superoxide, hydroxyl radicals (•OH), and singlet oxygen, detailing the chemical reactions involved. Additionally, the influence of various co-substrates and chelating agents, such as humic acids and ethylenediaminetetraacetic acid (EDTA), on the enhancement of redox processes and ROS generation is discussed, focusing on their roles in modulating reaction kinetics and improving catalytic efficiency. Furthermore, the review highlights the recent advancements in applying Fe-bearing clay minerals for the degradation of persistent organic pollutants, including dyes, pharmaceuticals, and pesticides, in both aqueous and soil environments. The potential for optimizing these mineral-based catalytic systems by tailoring their composition or creating hybrid materials is also explored to develop more efficient and scalable solutions for environmental remediation. This review outlines future research directions, emphasizing the integration of fundamental mechanistic insights with practical applications for pollutant degradation.
2026, 37(7): 112279
doi: 10.1016/j.cclet.2025.112279
摘要:
Chiral recognition is a central tenet of life sciences and biomolecular interactions. It is indispensable for the enantiomeric analysis of pharmaceuticals and agrochemicals, as well as for the development of chiral materials and devices, with significant implications for biomedical applications. Despite its importance, the creation of efficient and highly selective enantiomer recognition in synthetic systems presents a major challenge. Supramolecular macrocycles address this by providing well-defined cavities and synergistically positioned functional groups, which enhance chiral selectivity and sensitivity beyond the capabilities of traditional small molecules. While the design and synthesis of macrocyclic hosts have advanced considerably, their practical utility is often constrained by their recognition efficiency, binding affinity, and their ability to recognize a diverse range of analytes. This article reviews recent chemical strategies for enhancing chiral complexation and recognition, and discusses the future outlook and obstacles within this field.
Chiral recognition is a central tenet of life sciences and biomolecular interactions. It is indispensable for the enantiomeric analysis of pharmaceuticals and agrochemicals, as well as for the development of chiral materials and devices, with significant implications for biomedical applications. Despite its importance, the creation of efficient and highly selective enantiomer recognition in synthetic systems presents a major challenge. Supramolecular macrocycles address this by providing well-defined cavities and synergistically positioned functional groups, which enhance chiral selectivity and sensitivity beyond the capabilities of traditional small molecules. While the design and synthesis of macrocyclic hosts have advanced considerably, their practical utility is often constrained by their recognition efficiency, binding affinity, and their ability to recognize a diverse range of analytes. This article reviews recent chemical strategies for enhancing chiral complexation and recognition, and discusses the future outlook and obstacles within this field.
2026, 37(7): 112280
doi: 10.1016/j.cclet.2025.112280
摘要:
Imidazole derivatives exhibit broad-spectrum agricultural biological activities and serve as important molecular scaffolds in the discovery of new pesticides, particularly novel herbicides and fungicides. In recent years, there have been rapid developments in the research of imidazole-derived agricultural chemicals, such as the discovery of imidazole herbicides and fungicides. Therefore, it is significant to provide a review and update on the latest advances in the discovery of imidazole derivatives for pesticide development. Based on this, we systematically reviewed the latest research progress of imidazole derivatives in pesticide discovery, summarized the antiviral, insecticidal, nematicidal, and antibacterial activities of imidazole compounds, analyzed the synthetic methods of representative imidazole compounds, and discussed the active moieties, pharmacophores, structure-activity relationships (SAR), and mechanisms of action. This review aims to provide novel insights and inspiration for the discovery of novel imidazole pesticides.
Imidazole derivatives exhibit broad-spectrum agricultural biological activities and serve as important molecular scaffolds in the discovery of new pesticides, particularly novel herbicides and fungicides. In recent years, there have been rapid developments in the research of imidazole-derived agricultural chemicals, such as the discovery of imidazole herbicides and fungicides. Therefore, it is significant to provide a review and update on the latest advances in the discovery of imidazole derivatives for pesticide development. Based on this, we systematically reviewed the latest research progress of imidazole derivatives in pesticide discovery, summarized the antiviral, insecticidal, nematicidal, and antibacterial activities of imidazole compounds, analyzed the synthetic methods of representative imidazole compounds, and discussed the active moieties, pharmacophores, structure-activity relationships (SAR), and mechanisms of action. This review aims to provide novel insights and inspiration for the discovery of novel imidazole pesticides.
2026, 37(7): 112308
doi: 10.1016/j.cclet.2025.112308
摘要:
Broflanilide is the first listed meta-diamide insecticide, which has shown potential in the field of pesticide research and development due to its unique structure and mechanism of action. The key to the development of the meta-diamide insecticides is the derivatization of various sites in the meta-diamide compounds. It is of great research significance to develop highly effective, broad spectrum, safe, and environmentally compatible meta-diamide insecticide using Broflanilide as a lead compound to obtain structurally diverse meta-diamide compounds. An overview of meta-diamide derivatives from the perspectives of insecticidal activities and mechanism of action is offered. Their potentials as a dominant active structure for development of insecticides are also discussed.
Broflanilide is the first listed meta-diamide insecticide, which has shown potential in the field of pesticide research and development due to its unique structure and mechanism of action. The key to the development of the meta-diamide insecticides is the derivatization of various sites in the meta-diamide compounds. It is of great research significance to develop highly effective, broad spectrum, safe, and environmentally compatible meta-diamide insecticide using Broflanilide as a lead compound to obtain structurally diverse meta-diamide compounds. An overview of meta-diamide derivatives from the perspectives of insecticidal activities and mechanism of action is offered. Their potentials as a dominant active structure for development of insecticides are also discussed.
2026, 37(7): 112503
doi: 10.1016/j.cclet.2026.112503
摘要:
Skin aging is a multifactorial biological process driven by oxidative stress (OS), chronic inflammation, cellular senescence, mitochondrial dysfunction, and non-enzymatic glycation (NEG), and is markedly accelerated by environmental stressors such as ultraviolet radiation (UVR) and air pollution. Natural bioactive compounds, including flavonoids, polyphenols, terpenoids, alkaloids, vitamins, polysaccharides, peptides, and indole derivatives, have demonstrated considerable potential in mitigating these processes through multi-target antioxidant, anti-inflammatory, anti-photoaging, and extracellular matrix (ECM)–protective mechanisms. However, their clinical and cosmetic translation is often limited by poor solubility, chemical instability, and insufficient skin penetration. Rather than providing a simple compilation of existing studies, this review offers a mechanism-oriented and delivery-driven synthesis of recent advances in natural anti-skin-aging research. We systematically integrate current knowledge on the molecular drivers of skin aging with a critical comparison of emerging transdermal and nanotechnology-based delivery systems, including lipid-based, polymer-based, inorganic/hybrid, and nucleic acid–assembled nanocarriers. Particular attention is given to how rational carrier design modulates stability, permeability, skin-layer targeting, and controlled release behavior. Furthermore, this review critically discusses current limitations, contradictory findings across studies, and key translational challenges, and identifies promising future research directions, such as stimuli-responsive systems, skin-layer-specific targeting, and mechanism-guided material selection. By bridging biological mechanisms with delivery material innovation, this work provides a forward-looking framework for the development of safer, more effective, and scientifically grounded anti-skin-aging therapeutics and cosmeceuticals.
Skin aging is a multifactorial biological process driven by oxidative stress (OS), chronic inflammation, cellular senescence, mitochondrial dysfunction, and non-enzymatic glycation (NEG), and is markedly accelerated by environmental stressors such as ultraviolet radiation (UVR) and air pollution. Natural bioactive compounds, including flavonoids, polyphenols, terpenoids, alkaloids, vitamins, polysaccharides, peptides, and indole derivatives, have demonstrated considerable potential in mitigating these processes through multi-target antioxidant, anti-inflammatory, anti-photoaging, and extracellular matrix (ECM)–protective mechanisms. However, their clinical and cosmetic translation is often limited by poor solubility, chemical instability, and insufficient skin penetration. Rather than providing a simple compilation of existing studies, this review offers a mechanism-oriented and delivery-driven synthesis of recent advances in natural anti-skin-aging research. We systematically integrate current knowledge on the molecular drivers of skin aging with a critical comparison of emerging transdermal and nanotechnology-based delivery systems, including lipid-based, polymer-based, inorganic/hybrid, and nucleic acid–assembled nanocarriers. Particular attention is given to how rational carrier design modulates stability, permeability, skin-layer targeting, and controlled release behavior. Furthermore, this review critically discusses current limitations, contradictory findings across studies, and key translational challenges, and identifies promising future research directions, such as stimuli-responsive systems, skin-layer-specific targeting, and mechanism-guided material selection. By bridging biological mechanisms with delivery material innovation, this work provides a forward-looking framework for the development of safer, more effective, and scientifically grounded anti-skin-aging therapeutics and cosmeceuticals.
2026, 37(7): 112238
doi: 10.1016/j.cclet.2025.112238
摘要:
2026, 37(7): 112552
doi: 10.1016/j.cclet.2026.112552
摘要:
2026, 37(5): 110827
doi: 10.1016/j.cclet.2025.110827
摘要:
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
2026, 37(5): 110829
doi: 10.1016/j.cclet.2025.110829
摘要:
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
2026, 37(5): 110851
doi: 10.1016/j.cclet.2025.110851
摘要:
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
2026, 37(5): 110852
doi: 10.1016/j.cclet.2025.110852
摘要:
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
2026, 37(5): 110858
doi: 10.1016/j.cclet.2025.110858
摘要:
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
2026, 37(5): 110859
doi: 10.1016/j.cclet.2025.110859
摘要:
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
2026, 37(5): 110862
doi: 10.1016/j.cclet.2025.110862
摘要:
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
2026, 37(5): 110863
doi: 10.1016/j.cclet.2025.110863
摘要:
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
2026, 37(5): 110864
doi: 10.1016/j.cclet.2025.110864
摘要:
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
2026, 37(5): 110889
doi: 10.1016/j.cclet.2025.110889
摘要:
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
2026, 37(5): 110891
doi: 10.1016/j.cclet.2025.110891
摘要:
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
2026, 37(5): 110892
doi: 10.1016/j.cclet.2025.110892
摘要:
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
2026, 37(5): 110893
doi: 10.1016/j.cclet.2025.110893
摘要:
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
2026, 37(5): 110952
doi: 10.1016/j.cclet.2025.110952
摘要:
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
2026, 37(5): 110953
doi: 10.1016/j.cclet.2025.110953
摘要:
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
2026, 37(5): 110954
doi: 10.1016/j.cclet.2025.110954
摘要:
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
2026, 37(5): 110974
doi: 10.1016/j.cclet.2025.110974
摘要:
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
2026, 37(5): 111158
doi: 10.1016/j.cclet.2025.111158
摘要:
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
2026, 37(5): 111236
doi: 10.1016/j.cclet.2025.111236
摘要:
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
2026, 37(5): 111248
doi: 10.1016/j.cclet.2025.111248
摘要:
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
2026, 37(5): 111257
doi: 10.1016/j.cclet.2025.111257
摘要:
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
2026, 37(5): 111274
doi: 10.1016/j.cclet.2025.111274
摘要:
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
2026, 37(5): 111282
doi: 10.1016/j.cclet.2025.111282
摘要:
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
2026, 37(5): 111284
doi: 10.1016/j.cclet.2025.111284
摘要:
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
PROTAC degraders of FSP1 act as potent GPX4 sensitizers to induce ferroptosis for hepatoma treatment
2026, 37(5): 111285
doi: 10.1016/j.cclet.2025.111285
摘要:
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
2026, 37(5): 111291
doi: 10.1016/j.cclet.2025.111291
摘要:
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
2026, 37(5): 111292
doi: 10.1016/j.cclet.2025.111292
摘要:
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
2026, 37(5): 111318
doi: 10.1016/j.cclet.2025.111318
摘要:
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
2026, 37(5): 111324
doi: 10.1016/j.cclet.2025.111324
摘要:
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
2026, 37(5): 111334
doi: 10.1016/j.cclet.2025.111334
摘要:
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
2026, 37(5): 111336
doi: 10.1016/j.cclet.2025.111336
摘要:
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
2026, 37(5): 111337
doi: 10.1016/j.cclet.2025.111337
摘要:
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
2026, 37(5): 111338
doi: 10.1016/j.cclet.2025.111338
摘要:
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
2026, 37(5): 111343
doi: 10.1016/j.cclet.2025.111343
摘要:
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
2026, 37(5): 111347
doi: 10.1016/j.cclet.2025.111347
摘要:
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
2026, 37(5): 111350
doi: 10.1016/j.cclet.2025.111350
摘要:
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
2026, 37(5): 111356
doi: 10.1016/j.cclet.2025.111356
摘要:
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
2026, 37(5): 111381
doi: 10.1016/j.cclet.2025.111381
摘要:
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
2026, 37(5): 111399
doi: 10.1016/j.cclet.2025.111399
摘要:
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
2026, 37(5): 111401
doi: 10.1016/j.cclet.2025.111401
摘要:
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
2026, 37(5): 111403
doi: 10.1016/j.cclet.2025.111403
摘要:
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
2026, 37(5): 111405
doi: 10.1016/j.cclet.2025.111405
摘要:
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
2026, 37(5): 111407
doi: 10.1016/j.cclet.2025.111407
摘要:
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
2026, 37(5): 111419
doi: 10.1016/j.cclet.2025.111419
摘要:
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
2026, 37(5): 111426
doi: 10.1016/j.cclet.2025.111426
摘要:
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
2026, 37(5): 111429
doi: 10.1016/j.cclet.2025.111429
摘要:
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
2026, 37(5): 111430
doi: 10.1016/j.cclet.2025.111430
摘要:
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
2026, 37(5): 111442
doi: 10.1016/j.cclet.2025.111442
摘要:
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
2026, 37(5): 111443
doi: 10.1016/j.cclet.2025.111443
摘要:
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
2026, 37(5): 111454
doi: 10.1016/j.cclet.2025.111454
摘要:
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
2026, 37(5): 111461
doi: 10.1016/j.cclet.2025.111461
摘要:
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
2026, 37(5): 111484
doi: 10.1016/j.cclet.2025.111484
摘要:
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
2026, 37(5): 111499
doi: 10.1016/j.cclet.2025.111499
摘要:
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
2026, 37(5): 111501
doi: 10.1016/j.cclet.2025.111501
摘要:
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
2026, 37(5): 111544
doi: 10.1016/j.cclet.2025.111544
摘要:
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
2026, 37(5): 111555
doi: 10.1016/j.cclet.2025.111555
摘要:
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
2026, 37(5): 111614
doi: 10.1016/j.cclet.2025.111614
摘要:
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
2026, 37(5): 111615
doi: 10.1016/j.cclet.2025.111615
摘要:
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
2026, 37(5): 111616
doi: 10.1016/j.cclet.2025.111616
摘要:
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
2026, 37(5): 111617
doi: 10.1016/j.cclet.2025.111617
摘要:
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
2026, 37(5): 111649
doi: 10.1016/j.cclet.2025.111649
摘要:
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
2026, 37(5): 111706
doi: 10.1016/j.cclet.2025.111706
摘要:
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
2026, 37(5): 111717
doi: 10.1016/j.cclet.2025.111717
摘要:
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
2026, 37(5): 111720
doi: 10.1016/j.cclet.2025.111720
摘要:
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
2026, 37(5): 111789
doi: 10.1016/j.cclet.2025.111789
摘要:
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
2026, 37(5): 111790
doi: 10.1016/j.cclet.2025.111790
摘要:
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
2026, 37(5): 111791
doi: 10.1016/j.cclet.2025.111791
摘要:
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
2026, 37(5): 111811
doi: 10.1016/j.cclet.2025.111811
摘要:
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
2026, 37(5): 111825
doi: 10.1016/j.cclet.2025.111825
摘要:
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
2026, 37(5): 111838
doi: 10.1016/j.cclet.2025.111838
摘要:
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
2026, 37(5): 111839
doi: 10.1016/j.cclet.2025.111839
摘要:
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
2026, 37(5): 111840
doi: 10.1016/j.cclet.2025.111840
摘要:
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
2026, 37(5): 111844
doi: 10.1016/j.cclet.2025.111844
摘要:
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
2026, 37(5): 111851
doi: 10.1016/j.cclet.2025.111851
摘要:
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
2026, 37(5): 111853
doi: 10.1016/j.cclet.2025.111853
摘要:
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
2026, 37(5): 111857
doi: 10.1016/j.cclet.2025.111857
摘要:
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
2026, 37(5): 111858
doi: 10.1016/j.cclet.2025.111858
摘要:
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
2026, 37(5): 111860
doi: 10.1016/j.cclet.2025.111860
摘要:
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
2026, 37(5): 111862
doi: 10.1016/j.cclet.2025.111862
摘要:
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
2026, 37(5): 111864
doi: 10.1016/j.cclet.2025.111864
摘要:
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
2026, 37(5): 111874
doi: 10.1016/j.cclet.2025.111874
摘要:
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
2026, 37(5): 111903
doi: 10.1016/j.cclet.2025.111903
摘要:
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
2026, 37(5): 111914
doi: 10.1016/j.cclet.2025.111914
摘要:
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
2026, 37(5): 111923
doi: 10.1016/j.cclet.2025.111923
摘要:
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
2026, 37(5): 111927
doi: 10.1016/j.cclet.2025.111927
摘要:
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
2026, 37(5): 111931
doi: 10.1016/j.cclet.2025.111931
摘要:
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
2026, 37(5): 111935
doi: 10.1016/j.cclet.2025.111935
摘要:
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
2026, 37(5): 111975
doi: 10.1016/j.cclet.2025.111975
摘要:
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
2026, 37(5): 112064
doi: 10.1016/j.cclet.2025.112064
摘要:
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
2026, 37(5): 112202
doi: 10.1016/j.cclet.2025.112202
摘要:
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
2026, 37(5): 112348
doi: 10.1016/j.cclet.2025.112348
摘要:
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
2026, 37(5): 112373
doi: 10.1016/j.cclet.2026.112373
摘要:
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
2026, 37(5): 112417
doi: 10.1016/j.cclet.2026.112417
摘要:
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
2026, 37(5): 110860
doi: 10.1016/j.cclet.2025.110860
摘要:
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
2026, 37(5): 110973
doi: 10.1016/j.cclet.2025.110973
摘要:
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
2026, 37(5): 111262
doi: 10.1016/j.cclet.2025.111262
摘要:
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
2026, 37(5): 111319
doi: 10.1016/j.cclet.2025.111319
摘要:
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
2026, 37(5): 111390
doi: 10.1016/j.cclet.2025.111390
摘要:
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
2026, 37(5): 111392
doi: 10.1016/j.cclet.2025.111392
摘要:
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
2026, 37(5): 111396
doi: 10.1016/j.cclet.2025.111396
摘要:
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
2026, 37(5): 111707
doi: 10.1016/j.cclet.2025.111707
摘要:
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
2026, 37(5): 111843
doi: 10.1016/j.cclet.2025.111843
摘要:
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
2026, 37(5): 111861
doi: 10.1016/j.cclet.2025.111861
摘要:
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
2026, 37(5): 111902
doi: 10.1016/j.cclet.2025.111902
摘要:
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
2026, 37(5): 111904
doi: 10.1016/j.cclet.2025.111904
摘要:
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
2026, 37(5): 111915
doi: 10.1016/j.cclet.2025.111915
摘要:
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
2026, 37(5): 111929
doi: 10.1016/j.cclet.2025.111929
摘要:
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
2026, 37(5): 111960
doi: 10.1016/j.cclet.2025.111960
摘要:
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
2026, 37(5): 112142
doi: 10.1016/j.cclet.2025.112142
摘要:
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
2026, 37(5): 112235
doi: 10.1016/j.cclet.2025.112235
摘要:
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
2026, 37(5): 111876
doi: 10.1016/j.cclet.2025.111876
摘要:
2026, 37(5): 112260
doi: 10.1016/j.cclet.2025.112260
摘要:
