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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2025, 36(12): 110454
doi: 10.1016/j.cclet.2024.110454
摘要:
Cobalt phosphide has been successfully used as a catalyst in the production of ammonia from nitric acid. Substituting appropriate atoms is expected to further improve its catalytic performance. Owing to the diversity of substituting elements, substitution sites, adsorption sites, and adsorption configurations, extensive time-consuming simulation calculations are required for the high-throughput screening method. Additionally, multi-objective attributes should be considered simultaneously in catalytic design. To tackle this challenge, this paper suggests a multi-objective cobalt phosphide catalytic material design method based on surrogate models. And the effectiveness of the proposed method was validated through comparative experiments. The proposed method led to the discovery of fifteen promising cobalt phosphide catalyst configurations. This study provides a new avenue for expediting the design of catalyst, with the potential for application in other systems.
Cobalt phosphide has been successfully used as a catalyst in the production of ammonia from nitric acid. Substituting appropriate atoms is expected to further improve its catalytic performance. Owing to the diversity of substituting elements, substitution sites, adsorption sites, and adsorption configurations, extensive time-consuming simulation calculations are required for the high-throughput screening method. Additionally, multi-objective attributes should be considered simultaneously in catalytic design. To tackle this challenge, this paper suggests a multi-objective cobalt phosphide catalytic material design method based on surrogate models. And the effectiveness of the proposed method was validated through comparative experiments. The proposed method led to the discovery of fifteen promising cobalt phosphide catalyst configurations. This study provides a new avenue for expediting the design of catalyst, with the potential for application in other systems.
2025, 36(12): 110534
doi: 10.1016/j.cclet.2024.110534
摘要:
Photo-responsive metal-organic frameworks (MOFs) have evoked considerable attention due to their potential application in inkless printing paper. However, the poor cycling performance and low printing resolution greatly inhibit their practical application. Herein, a novel MOF based on naphthalenediimide derivate moiety, [La(H2O)(BINDI)0.5(DMF)3][NO3] (1, H4BINDI = N, N'-bis(5-isophthalic acid)naphthalenediimide), was successfully synthesized for inkless erasable printing. This material exhibits reversible photochromic behavior and good stability. The inkless printing paper coated with 1 delivers high resolution reaching up to 0.2 mm, comparable to commercial printers. Furthermore, the stable framework and suitable reversibility enable excellent cycling performance with 197 cycles, surpassing almost all reported MOFs. This work sheds light on new opportunities in designing outstanding photochromic MOFs for ink-free printing.
Photo-responsive metal-organic frameworks (MOFs) have evoked considerable attention due to their potential application in inkless printing paper. However, the poor cycling performance and low printing resolution greatly inhibit their practical application. Herein, a novel MOF based on naphthalenediimide derivate moiety, [La(H2O)(BINDI)0.5(DMF)3][NO3] (1, H4BINDI = N, N'-bis(5-isophthalic acid)naphthalenediimide), was successfully synthesized for inkless erasable printing. This material exhibits reversible photochromic behavior and good stability. The inkless printing paper coated with 1 delivers high resolution reaching up to 0.2 mm, comparable to commercial printers. Furthermore, the stable framework and suitable reversibility enable excellent cycling performance with 197 cycles, surpassing almost all reported MOFs. This work sheds light on new opportunities in designing outstanding photochromic MOFs for ink-free printing.
2025, 36(12): 110535
doi: 10.1016/j.cclet.2024.110535
摘要:
Electrochemical water splitting has attracted tremendous interest as a promising approach for generating sustainable hydrogen for transportation and other industrial applications. However, the oxygen evolution reaction (OER) significantly limits the efficiency of electrochemical water splitting because of the sluggish reaction kinetics derived from the intrinsic four-electron-transfer process. In addition, the stability of OER electrocatalysts encounters significant challenges during long-term operation under harsh conditions. To overcome these challenges, we demonstrate that monolithic electrodes composed of medium-entropy alloys (MEAs) containing Fe, Co, Cr, and Ni can be used as efficient and stable OER catalysts in alkaline solutions. The monolithic FeCoCrNi alloy electrode exhibited a remarkably low overpotential of 237 mV at a current density of 10 mA/cm2 in a 1 mol/L KOH solution. Significantly, the monolithic alloy electrode can operate stably for more than 2000 h at a practical current density of 1 A/cm2. The enhanced activity and stability of the alloy electrode are ascribed to surface reconstruction. This work presents a novel and effective approach for fabricating high-performance electrodes with excellent stability for the oxygen evolution reaction.
Electrochemical water splitting has attracted tremendous interest as a promising approach for generating sustainable hydrogen for transportation and other industrial applications. However, the oxygen evolution reaction (OER) significantly limits the efficiency of electrochemical water splitting because of the sluggish reaction kinetics derived from the intrinsic four-electron-transfer process. In addition, the stability of OER electrocatalysts encounters significant challenges during long-term operation under harsh conditions. To overcome these challenges, we demonstrate that monolithic electrodes composed of medium-entropy alloys (MEAs) containing Fe, Co, Cr, and Ni can be used as efficient and stable OER catalysts in alkaline solutions. The monolithic FeCoCrNi alloy electrode exhibited a remarkably low overpotential of 237 mV at a current density of 10 mA/cm2 in a 1 mol/L KOH solution. Significantly, the monolithic alloy electrode can operate stably for more than 2000 h at a practical current density of 1 A/cm2. The enhanced activity and stability of the alloy electrode are ascribed to surface reconstruction. This work presents a novel and effective approach for fabricating high-performance electrodes with excellent stability for the oxygen evolution reaction.
2025, 36(12): 110536
doi: 10.1016/j.cclet.2024.110536
摘要:
Two-dimensional (2D) metal-organic frameworks (MOFs) have emerged as promising photosensitizers in photodynamic therapy in recent years. In comparison to bulk MOFs, constructing 2D MOFs can increase the presence of active sites through increasing the surface area ratio. Herein, we report a simple solvent-mediated synthesis method for preparation of 2D porphyrin-based MOF (In-TCPP) nanosheets without the addition of any surfactants as an efficient photosensitizer for enhancing photodynamic antibacterial therapy. The accurate regulation of the morphology and size of 2D In-TCPP nanosheets can be achieved by varying the ratio of water to N,N-dimethylformamide solvent with the appropriate assistance of pyridine. The optimal synthesized 2D In-TCPP nanosheets exhibit a diameter of 70–120 nm and a thickness of 21.5–27.4 nm. Promisingly, 2D In-TCPP nanosheets produce a higher amount of 1O2 when exposed to 660 nm laser compared to the In-TCPP bulk, indicating that the smaller nanosheets possess more active sites for reactive oxygen species generation and can greatly improve the antibacterial photodynamic therapeutic effect. Both the in vitro and in vivo results prove that the In-TCPP nanosheets can be used as a photosensitizer for efficient photodynamic antibacterial therapy to kill S. aureus and promote wound healing.
Two-dimensional (2D) metal-organic frameworks (MOFs) have emerged as promising photosensitizers in photodynamic therapy in recent years. In comparison to bulk MOFs, constructing 2D MOFs can increase the presence of active sites through increasing the surface area ratio. Herein, we report a simple solvent-mediated synthesis method for preparation of 2D porphyrin-based MOF (In-TCPP) nanosheets without the addition of any surfactants as an efficient photosensitizer for enhancing photodynamic antibacterial therapy. The accurate regulation of the morphology and size of 2D In-TCPP nanosheets can be achieved by varying the ratio of water to N,N-dimethylformamide solvent with the appropriate assistance of pyridine. The optimal synthesized 2D In-TCPP nanosheets exhibit a diameter of 70–120 nm and a thickness of 21.5–27.4 nm. Promisingly, 2D In-TCPP nanosheets produce a higher amount of 1O2 when exposed to 660 nm laser compared to the In-TCPP bulk, indicating that the smaller nanosheets possess more active sites for reactive oxygen species generation and can greatly improve the antibacterial photodynamic therapeutic effect. Both the in vitro and in vivo results prove that the In-TCPP nanosheets can be used as a photosensitizer for efficient photodynamic antibacterial therapy to kill S. aureus and promote wound healing.
2025, 36(12): 110537
doi: 10.1016/j.cclet.2024.110537
摘要:
Bimetallic sulfide anodes offer promising stability and high capacity in sodium-ion batteries (SIBs) but face significant challenges, including low electronic conductivity, limited ionic diffusion, and substantial volume expansion during conversion and alloying processes. These issues significantly impair the performance. To effectively address these challenges, we employed a systematic design approach to develop a bimetallic ZnS/MoS2 hierarchical heterostructure coated with nitrogen-doped carbon (T-MS/C). This advanced structure was synthesized using a metal-organic framework (MOF) as a template, followed by hydrothermal synthesis. The resulting heterostructure features multiple layers arranged hierarchically, incorporating various phase interfaces and smaller crystal domains due to the MOF templating process. This design significantly enhances reactivity, electrical conductivity, and ionic diffusion, ultimately leading to the development of an optimized Na-storage performance T-MS/C anode. The T-MS/C anode exhibits remarkable Na-storage capability, with capacities of 690.8 mAh/g after 100 cycles at 0.2 A/g and 306 mAh/g at 10 A/g. This carefully synthesized T-MS/C anode exhibits highly promising features for Na-storage, making it an excellent contender for the next generation of high-performance SIBs.
Bimetallic sulfide anodes offer promising stability and high capacity in sodium-ion batteries (SIBs) but face significant challenges, including low electronic conductivity, limited ionic diffusion, and substantial volume expansion during conversion and alloying processes. These issues significantly impair the performance. To effectively address these challenges, we employed a systematic design approach to develop a bimetallic ZnS/MoS2 hierarchical heterostructure coated with nitrogen-doped carbon (T-MS/C). This advanced structure was synthesized using a metal-organic framework (MOF) as a template, followed by hydrothermal synthesis. The resulting heterostructure features multiple layers arranged hierarchically, incorporating various phase interfaces and smaller crystal domains due to the MOF templating process. This design significantly enhances reactivity, electrical conductivity, and ionic diffusion, ultimately leading to the development of an optimized Na-storage performance T-MS/C anode. The T-MS/C anode exhibits remarkable Na-storage capability, with capacities of 690.8 mAh/g after 100 cycles at 0.2 A/g and 306 mAh/g at 10 A/g. This carefully synthesized T-MS/C anode exhibits highly promising features for Na-storage, making it an excellent contender for the next generation of high-performance SIBs.
2025, 36(12): 110550
doi: 10.1016/j.cclet.2024.110550
摘要:
Compounds with 1,3,5-triazine ring such as melamine derivatives, known for their low cost and high stability, offer potential for affordable, stable metal organic framework (MOF) synthesis. However, reported such frameworks are facing issues like low stability and reduced porosity. To overcome such problems, we explored organic ligands with protonated nitrogen atoms on the 1,3,5-triazine ring, facilitated by introducing hydroxyl groups on carbon atoms of the triazine ring to construct MOFs. By using 5-azacytosine, we have successfully synthesized SXU-121, a neutral ultramicroporous MOF with eta-topology and high density of open Cu(Ⅰ) sites. SXU-121 features robust structural stability and significant CO2 adsorption capacity with high selectivity over N2 under ambient conditions. We believe SXU-121's development opens new avenues for creating a class of stable and low cost metal-triazine frameworks with potential diverse functionalities.
Compounds with 1,3,5-triazine ring such as melamine derivatives, known for their low cost and high stability, offer potential for affordable, stable metal organic framework (MOF) synthesis. However, reported such frameworks are facing issues like low stability and reduced porosity. To overcome such problems, we explored organic ligands with protonated nitrogen atoms on the 1,3,5-triazine ring, facilitated by introducing hydroxyl groups on carbon atoms of the triazine ring to construct MOFs. By using 5-azacytosine, we have successfully synthesized SXU-121, a neutral ultramicroporous MOF with eta-topology and high density of open Cu(Ⅰ) sites. SXU-121 features robust structural stability and significant CO2 adsorption capacity with high selectivity over N2 under ambient conditions. We believe SXU-121's development opens new avenues for creating a class of stable and low cost metal-triazine frameworks with potential diverse functionalities.
2025, 36(12): 110551
doi: 10.1016/j.cclet.2024.110551
摘要:
Many catalysts have shown excellent activity for the sulfur reduction reaction (SRR), but sluggish electrochemistry kinetics have hindered the development of lithium–sulfur batteries. It has been found that the activity of catalysts for the sulfur evolution reaction (SER) plays a crucial role in determining the overall reaction kinetics. To address this issue, the rational design of catalysts is crucial. Here, we proposed a popular rule to accelerate SER by using chip–like high–entropy perovskite oxide La0.7Sr0.3(Fe0.2Co0.2Ni0.2Zn0.2Mn0.2)O3-δ (LMO–HEO) as advanced electrocatalysts. The strong interaction between the adjacent metal atoms in different metals of LMO–HEO electrocatalysts could lead to a "cocktail effect", which not only greatly improved the catalytic capacity toward sulfur species, but also accelerated the oxidation reaction kinetics of Li2S. As a result, the S/La0.7Sr0.3(Fe0.2Co0.2Ni0.2Zn0.2Mn0.2)O3-δ cathodes delivered excellent cyclic stability with a capacity decay of only 0.025% after 1200 cycles at 2 C. This work has provided a rational design idea for new multifunctional electrocatalysts with high catalytic capacity.
Many catalysts have shown excellent activity for the sulfur reduction reaction (SRR), but sluggish electrochemistry kinetics have hindered the development of lithium–sulfur batteries. It has been found that the activity of catalysts for the sulfur evolution reaction (SER) plays a crucial role in determining the overall reaction kinetics. To address this issue, the rational design of catalysts is crucial. Here, we proposed a popular rule to accelerate SER by using chip–like high–entropy perovskite oxide La0.7Sr0.3(Fe0.2Co0.2Ni0.2Zn0.2Mn0.2)O3-δ (LMO–HEO) as advanced electrocatalysts. The strong interaction between the adjacent metal atoms in different metals of LMO–HEO electrocatalysts could lead to a "cocktail effect", which not only greatly improved the catalytic capacity toward sulfur species, but also accelerated the oxidation reaction kinetics of Li2S. As a result, the S/La0.7Sr0.3(Fe0.2Co0.2Ni0.2Zn0.2Mn0.2)O3-δ cathodes delivered excellent cyclic stability with a capacity decay of only 0.025% after 1200 cycles at 2 C. This work has provided a rational design idea for new multifunctional electrocatalysts with high catalytic capacity.
2025, 36(12): 110556
doi: 10.1016/j.cclet.2024.110556
摘要:
The propylene/propane (C3H6/C3H8) separation is particularly challenging due to their highly similar physical properties, but of industrial importance. Herein, we report a bifunctional ultramicroporous metal-organic framework (Co-aip-pyz) with customized pore environment and selective binding sites for the challenging C3H6/C3H8 separation. Co-aip-pyz exhibits a good C3H6 uptake with an ultrahigh C3H6 packing density (931 g/L), as well as possesses a remarkable C3H6/C3H8 uptake ratio with 911% and distinguished C3H6/C3H8 selectivity (>104) at 298 K and 1.0 bar. Furthermore, Co-aip-pyz possesses a record high C3H6 packing density with 859 g/L at 313 K and 1.0 bar, which is unprecedented in the C3H6/C3H8 separation. Its high performance for the C3H6/C3H8 separation has been further confirmed by breakthrough experiments and molecular simulations. Combined with good stability, facilely synthesized procedure by low-cost precursors, record-high C3H6 packing density, as well as good C3H6/C3H8 separation performance, it highlights Co-aip-pyz as a benchmark adsorbent to address daunting challenge for industrial C3H6/C3H8 separation. This work provides valuable insights into constructing top-performing MOF materials for addressing the industrial separation challenges.
The propylene/propane (C3H6/C3H8) separation is particularly challenging due to their highly similar physical properties, but of industrial importance. Herein, we report a bifunctional ultramicroporous metal-organic framework (Co-aip-pyz) with customized pore environment and selective binding sites for the challenging C3H6/C3H8 separation. Co-aip-pyz exhibits a good C3H6 uptake with an ultrahigh C3H6 packing density (931 g/L), as well as possesses a remarkable C3H6/C3H8 uptake ratio with 911% and distinguished C3H6/C3H8 selectivity (>104) at 298 K and 1.0 bar. Furthermore, Co-aip-pyz possesses a record high C3H6 packing density with 859 g/L at 313 K and 1.0 bar, which is unprecedented in the C3H6/C3H8 separation. Its high performance for the C3H6/C3H8 separation has been further confirmed by breakthrough experiments and molecular simulations. Combined with good stability, facilely synthesized procedure by low-cost precursors, record-high C3H6 packing density, as well as good C3H6/C3H8 separation performance, it highlights Co-aip-pyz as a benchmark adsorbent to address daunting challenge for industrial C3H6/C3H8 separation. This work provides valuable insights into constructing top-performing MOF materials for addressing the industrial separation challenges.
2025, 36(12): 110557
doi: 10.1016/j.cclet.2024.110557
摘要:
The insulating nature and dissolution of vanadium-based oxides in aqueous electrolytes result in low capacity and lifespan during charge/discharge process, which is unable to meet the demands for the development and application of high-energy-density aqueous zinc-ion batteries (AZIBs). Herein, a novel V2O5-x@C composite cathode consisting of conductive carbon coatings with abundant oxygen vacancies is specifically designed through plasma-enhanced chemical vapor deposition (PECVD) method. As expected, the ideal microstructure of V2O5-x@C cathode enables large specific surface areas, fast electron/ion diffusion kinetics, and superior interfacial stability, which can realize outstanding cycling stability and electrochemical performance. Consequently, the V2O5-x@C composite cathode delivers a high reversible rate capacity of 130.6 mAh/g at 10 A/g and remains 277.6 mAh/g when returned to 1 A/g. In addition, the Zn//V2O5-x@C full cell can stably cycle for 1000 cycles with a high initial specific capacity of 149.2 mAh/g, possessing 83.8% capacity retention at 5 A/g. The process of constructing a conductive layer on the surface of cathode materials while increasing oxygen vacancies in the structure through PECVD provides new insight into the design of high-performance cathode materials for AZIBs.
The insulating nature and dissolution of vanadium-based oxides in aqueous electrolytes result in low capacity and lifespan during charge/discharge process, which is unable to meet the demands for the development and application of high-energy-density aqueous zinc-ion batteries (AZIBs). Herein, a novel V2O5-x@C composite cathode consisting of conductive carbon coatings with abundant oxygen vacancies is specifically designed through plasma-enhanced chemical vapor deposition (PECVD) method. As expected, the ideal microstructure of V2O5-x@C cathode enables large specific surface areas, fast electron/ion diffusion kinetics, and superior interfacial stability, which can realize outstanding cycling stability and electrochemical performance. Consequently, the V2O5-x@C composite cathode delivers a high reversible rate capacity of 130.6 mAh/g at 10 A/g and remains 277.6 mAh/g when returned to 1 A/g. In addition, the Zn//V2O5-x@C full cell can stably cycle for 1000 cycles with a high initial specific capacity of 149.2 mAh/g, possessing 83.8% capacity retention at 5 A/g. The process of constructing a conductive layer on the surface of cathode materials while increasing oxygen vacancies in the structure through PECVD provides new insight into the design of high-performance cathode materials for AZIBs.
2025, 36(12): 110573
doi: 10.1016/j.cclet.2024.110573
摘要:
The design and development of high-performance electrocatalysts for the hydrogen evolution reaction (HER) are essential for advancing the hydrogen economy. The electronic structure and core size of an electrocatalyst are pivotal for determining the intrinsic activity of the catalytic sites. Interfacial engineering, particularly the formation of well-controlled core-shell heterostructures, has emerged as a promising strategy, although significant challenges remain. Here, we present a series of Ru@NC heterostructures with size-controlled Ru cores encapsulated in N-doped graphene layers. Among these, Ru@NC-3h, with the best holistic effects, has superior durability and mass activity 7.03 times that of Pt/C. This high performance is attributed to the open porous structure, which enhances active site exposure and mass transfer, and the optimized adsorption and desorption of reaction intermediates by the strengthened hetero-interfacial interaction between the smaller Ru cores and thin N-doped shells. Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals reinforced interfacial water interaction and reduced hydrogen adsorption. Density functional theory (DFT) calculations indicate that the size effect promotes interfacial H2O adsorption, whereas the electronic effect governs *H adsorption to collectively accelerate the HER kinetics. This novel strategy, introduced to regulate heterostructures through size and electronic effects, offers significant potential for various energy material applications.
The design and development of high-performance electrocatalysts for the hydrogen evolution reaction (HER) are essential for advancing the hydrogen economy. The electronic structure and core size of an electrocatalyst are pivotal for determining the intrinsic activity of the catalytic sites. Interfacial engineering, particularly the formation of well-controlled core-shell heterostructures, has emerged as a promising strategy, although significant challenges remain. Here, we present a series of Ru@NC heterostructures with size-controlled Ru cores encapsulated in N-doped graphene layers. Among these, Ru@NC-3h, with the best holistic effects, has superior durability and mass activity 7.03 times that of Pt/C. This high performance is attributed to the open porous structure, which enhances active site exposure and mass transfer, and the optimized adsorption and desorption of reaction intermediates by the strengthened hetero-interfacial interaction between the smaller Ru cores and thin N-doped shells. Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals reinforced interfacial water interaction and reduced hydrogen adsorption. Density functional theory (DFT) calculations indicate that the size effect promotes interfacial H2O adsorption, whereas the electronic effect governs *H adsorption to collectively accelerate the HER kinetics. This novel strategy, introduced to regulate heterostructures through size and electronic effects, offers significant potential for various energy material applications.
2025, 36(12): 110656
doi: 10.1016/j.cclet.2024.110656
摘要:
The electrochemical nitric oxide reduction reaction (NORR) to NH3 represents a promising avenue for NO removal and NH3 synthesis. It is essential to develop catalysts with superior performance for this process. We systematically studied a series of single-atom alloy catalysts (SAACs) with Pd single-atom dopants using density functional theory (DFT) calculations and machine learning (ML). Based on the energetic span model, we take Gmax(η) as a descriptor to evaluate the reaction activity of SAACs. After comprehensively considering the stability, activity, and NH3 selectivity of SAACs, Cu and Pd/Cu SAAC are screened out as candidate NORR to NH3 catalysts. To predict the Gmax(η) descriptor, the extreme gradient boosting regression (XGBR) ML algorithm was adopted with geometric/electronic properties of the SAACs as input features. Additionally, we proposed a mathematical formula to correlate the crucial features and the Gmax(η) descriptor using the sure independence screening and sparsifying operator (SISSO) approach. This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.
The electrochemical nitric oxide reduction reaction (NORR) to NH3 represents a promising avenue for NO removal and NH3 synthesis. It is essential to develop catalysts with superior performance for this process. We systematically studied a series of single-atom alloy catalysts (SAACs) with Pd single-atom dopants using density functional theory (DFT) calculations and machine learning (ML). Based on the energetic span model, we take Gmax(η) as a descriptor to evaluate the reaction activity of SAACs. After comprehensively considering the stability, activity, and NH3 selectivity of SAACs, Cu and Pd/Cu SAAC are screened out as candidate NORR to NH3 catalysts. To predict the Gmax(η) descriptor, the extreme gradient boosting regression (XGBR) ML algorithm was adopted with geometric/electronic properties of the SAACs as input features. Additionally, we proposed a mathematical formula to correlate the crucial features and the Gmax(η) descriptor using the sure independence screening and sparsifying operator (SISSO) approach. This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.
2025, 36(12): 110683
doi: 10.1016/j.cclet.2024.110683
摘要:
Anti-perovskite cathodes, typified by Li2FeSO, hold great promise for Li-ion batteries due to their high specific capacity, cost-effectiveness, and ease of production. However, their utilization in high-energy-density batteries is hindered by low Li intercalation voltage and limited rate performance. This study employs first-principles calculations to assess the impact of element substitutions and doping on the voltage and Li-ion migration energy barrier in Li2TMSO (TM = Cu, Ni, Co, Fe, V, Cr, Ti) anti-perovskite materials. Our findings reveal that replacing the S element with Se or Te in Li2FeSO and Li2MnSO can reduce the voltage. For Li2TMSO (TM = Cu, Ni, Co, Fe, V, Cr, Ti), the voltage increases as TM changes from Ti to Ni. This process closely related to the downward shift of the TM-3d electron orbital energy level. When the energy level difference between TM-3d and S-3p orbital energy levels is large, the voltage is determined by TM-3d orbitals. When the difference is small, S-3p participates in the reaction. Additionally, doping with the inactive element Mg could allow deeper energy level electrons to participate in the reaction, thus increasing the voltage. To simultaneously enhance intercalation voltage and rate performance, we investigated multi-element doping strategies for anti-perovskite cathode materials. Our study establishes a solid foundation the development of high-voltage anti-perovskite cathodes, holding promise for significant advancements in energy storage technology.
Anti-perovskite cathodes, typified by Li2FeSO, hold great promise for Li-ion batteries due to their high specific capacity, cost-effectiveness, and ease of production. However, their utilization in high-energy-density batteries is hindered by low Li intercalation voltage and limited rate performance. This study employs first-principles calculations to assess the impact of element substitutions and doping on the voltage and Li-ion migration energy barrier in Li2TMSO (TM = Cu, Ni, Co, Fe, V, Cr, Ti) anti-perovskite materials. Our findings reveal that replacing the S element with Se or Te in Li2FeSO and Li2MnSO can reduce the voltage. For Li2TMSO (TM = Cu, Ni, Co, Fe, V, Cr, Ti), the voltage increases as TM changes from Ti to Ni. This process closely related to the downward shift of the TM-3d electron orbital energy level. When the energy level difference between TM-3d and S-3p orbital energy levels is large, the voltage is determined by TM-3d orbitals. When the difference is small, S-3p participates in the reaction. Additionally, doping with the inactive element Mg could allow deeper energy level electrons to participate in the reaction, thus increasing the voltage. To simultaneously enhance intercalation voltage and rate performance, we investigated multi-element doping strategies for anti-perovskite cathode materials. Our study establishes a solid foundation the development of high-voltage anti-perovskite cathodes, holding promise for significant advancements in energy storage technology.
2025, 36(12): 110865
doi: 10.1016/j.cclet.2025.110865
摘要:
The inherent low immunogenicity and immunosuppressive metabolism of solid tumors significantly attenuate the immunotherapeutic effect and restrict the immune response. In this work, an endoplasmic reticulum (ER) targeting photodynamic oxidizer (designated as PhotoOx) is fabricated to boost the anti-tumor immunity by integrating photodynamic therapy (PDT) induced immunogenic cell death (ICD) with indoleamine 2,3-dioxygenase 1 (IDO1) inhibition. Among which, an ER targeting photosensitizer-peptide conjugate called PhotoPe is rationally designed for optimal functionality and amphiphilicity, which could self-assemble into nano-micelles co-delivering chlorin e6 and NLG919. PhotoOx exhibits a good stability to enable ER targeting drug delivery, which could induce ER rupture to intensify PDT induced ICD and release damage associated molecular patterns (DAMPs). Furthermore, PhotoOx could effectively initiate immunological cascades, leading to the suppression of regulatory T cells (Tregs) and activation of CD8+ T cells when combines with IDO inhibition. Furthermore, the multi-synergistic effects of PhotoOx activate a robust systemic anti-tumor immune response, resulting in the eradication of lung and liver metastases. Such a medication strategy might inspire the rational design of biomedicine for precise drug delivery, which also provides a sophisticated mechanism for addressing the challenges of solid tumor treatment.
The inherent low immunogenicity and immunosuppressive metabolism of solid tumors significantly attenuate the immunotherapeutic effect and restrict the immune response. In this work, an endoplasmic reticulum (ER) targeting photodynamic oxidizer (designated as PhotoOx) is fabricated to boost the anti-tumor immunity by integrating photodynamic therapy (PDT) induced immunogenic cell death (ICD) with indoleamine 2,3-dioxygenase 1 (IDO1) inhibition. Among which, an ER targeting photosensitizer-peptide conjugate called PhotoPe is rationally designed for optimal functionality and amphiphilicity, which could self-assemble into nano-micelles co-delivering chlorin e6 and NLG919. PhotoOx exhibits a good stability to enable ER targeting drug delivery, which could induce ER rupture to intensify PDT induced ICD and release damage associated molecular patterns (DAMPs). Furthermore, PhotoOx could effectively initiate immunological cascades, leading to the suppression of regulatory T cells (Tregs) and activation of CD8+ T cells when combines with IDO inhibition. Furthermore, the multi-synergistic effects of PhotoOx activate a robust systemic anti-tumor immune response, resulting in the eradication of lung and liver metastases. Such a medication strategy might inspire the rational design of biomedicine for precise drug delivery, which also provides a sophisticated mechanism for addressing the challenges of solid tumor treatment.
2025, 36(12): 110866
doi: 10.1016/j.cclet.2025.110866
摘要:
Liver cancer is a major killer threatening human health worldwide. At this stage the clinical choice to the treatment of liver cancer is a combination of surgery, chemotherapy and radiotherapy. Alternatively, using hydrogen to treat cancer has great prospects and development space. Herein, we fabricated a hierarchical and flexible electrode that being able to continuously generate hydrogen in vivo in the deep abdominal liver through efficient water electrolysis to kill tumor cells and regulate the tumor microenvironment. The flexibility of the electrode facilitated to fit the tumor surface and thus improved the contact area of hydrogen therapy. By in situ growth of molybdenum disulfide on a hierarchical carbon skeleton, improved reaction kinetics and smaller impedance with a low overpotential of 1.02 V at −10 mA/cm2 in cell culture medium and Tafel slope of 73 mV/dec were achieved. Animal experiments showed that the electrode could effectively inhibit the growth of human hepatocellular carcinoma cells in nude mice by efficient H2-production in vivo. The apoptosis rate of cancer cells reached 81.8%, and the proliferation rate decreased to 3.39%. Moreover, this treatment does not affect the growth of normal hepatocytes according to the results of cell experiments. This study demonstrated that the in vivo hydrogen production by our flexible electrode is a safe and effective treatment for liver cancer, with the advantages of minimal invasiveness, simple operation, low side effects and low cost.
Liver cancer is a major killer threatening human health worldwide. At this stage the clinical choice to the treatment of liver cancer is a combination of surgery, chemotherapy and radiotherapy. Alternatively, using hydrogen to treat cancer has great prospects and development space. Herein, we fabricated a hierarchical and flexible electrode that being able to continuously generate hydrogen in vivo in the deep abdominal liver through efficient water electrolysis to kill tumor cells and regulate the tumor microenvironment. The flexibility of the electrode facilitated to fit the tumor surface and thus improved the contact area of hydrogen therapy. By in situ growth of molybdenum disulfide on a hierarchical carbon skeleton, improved reaction kinetics and smaller impedance with a low overpotential of 1.02 V at −10 mA/cm2 in cell culture medium and Tafel slope of 73 mV/dec were achieved. Animal experiments showed that the electrode could effectively inhibit the growth of human hepatocellular carcinoma cells in nude mice by efficient H2-production in vivo. The apoptosis rate of cancer cells reached 81.8%, and the proliferation rate decreased to 3.39%. Moreover, this treatment does not affect the growth of normal hepatocytes according to the results of cell experiments. This study demonstrated that the in vivo hydrogen production by our flexible electrode is a safe and effective treatment for liver cancer, with the advantages of minimal invasiveness, simple operation, low side effects and low cost.
2025, 36(12): 110895
doi: 10.1016/j.cclet.2025.110895
摘要:
Camptothecin, a plant-derived pentacyclic pyrroloquinoline alkaloid, and its derivatives like topotecan and irinotecan have been used as clinical anticancer agents for decades. However, the complete biosynthetic pathway of camptothecin still remains unelucidated due to the unknown complex formation processes and corresponding enzymes for the downstream biosynthetic pathway including the committed hydrolysis of glycosides. Herein, a novel glycoside hydrolase (CaGH1) responsible for the deglycosylation of biosynthetic glycoside intermediates including both quinoline-type alkaloids pumiloside (1), (3S)-deoxypumiloside (2) and indole-type alkaloid strictosamide (3) has been functionally identified. Moreover, CaGH1 exhibits the highly strict stereoselectivity towards the substrates with 3S configuration. Furthermore, a combined strategy for the discovery of the unknown biosynthetic enzyme by employing activity-guided enzyme verification, transcriptome-based gene mining, biochemical assay in vitro, and structurally characterizing the unstable enzymatic products by derivatization, is reported. These findings not only provide a better understanding of the deglycosylation in camptothecin biosynthesis, also lay the foundation for the complete elucidation of camptothecin biosynthetic pathway and biological production of camptothecin.
Camptothecin, a plant-derived pentacyclic pyrroloquinoline alkaloid, and its derivatives like topotecan and irinotecan have been used as clinical anticancer agents for decades. However, the complete biosynthetic pathway of camptothecin still remains unelucidated due to the unknown complex formation processes and corresponding enzymes for the downstream biosynthetic pathway including the committed hydrolysis of glycosides. Herein, a novel glycoside hydrolase (CaGH1) responsible for the deglycosylation of biosynthetic glycoside intermediates including both quinoline-type alkaloids pumiloside (1), (3S)-deoxypumiloside (2) and indole-type alkaloid strictosamide (3) has been functionally identified. Moreover, CaGH1 exhibits the highly strict stereoselectivity towards the substrates with 3S configuration. Furthermore, a combined strategy for the discovery of the unknown biosynthetic enzyme by employing activity-guided enzyme verification, transcriptome-based gene mining, biochemical assay in vitro, and structurally characterizing the unstable enzymatic products by derivatization, is reported. These findings not only provide a better understanding of the deglycosylation in camptothecin biosynthesis, also lay the foundation for the complete elucidation of camptothecin biosynthetic pathway and biological production of camptothecin.
2025, 36(12): 110904
doi: 10.1016/j.cclet.2025.110904
摘要:
Bipolarpenoids A–J (1–10), ten undescribed ophiobolin-derived sesterterpenoids, were identified from the fungus Bipolaris oryzae. Their structures were elucidated by high resolution electrospray ionization mass spectrometry (HRESIMS), spectroscopic analyses, quantum chemical 13C nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analyses. Notably, compounds 1 and 2 were uniquely characterized by a multicyclic caged pentacyclo[8.4.0.01,5.04,9.07,11]tetradecane-bridged system; compounds 4–6 featured unprecedented 5/8/5/6 and 5/8/5/5 fused cores, respectively; compound 7 represented the first example of 3,4-seco-ophiobolin-alkaloid hybrid with a modified 5/6/8/5/5 fused carbon skeleton. Compound 9 showed potential anti-inflammatory effect in RAW264.7 macrophages and ulcerative colitis mice.
Bipolarpenoids A–J (1–10), ten undescribed ophiobolin-derived sesterterpenoids, were identified from the fungus Bipolaris oryzae. Their structures were elucidated by high resolution electrospray ionization mass spectrometry (HRESIMS), spectroscopic analyses, quantum chemical 13C nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analyses. Notably, compounds 1 and 2 were uniquely characterized by a multicyclic caged pentacyclo[8.4.0.01,5.04,9.07,11]tetradecane-bridged system; compounds 4–6 featured unprecedented 5/8/5/6 and 5/8/5/5 fused cores, respectively; compound 7 represented the first example of 3,4-seco-ophiobolin-alkaloid hybrid with a modified 5/6/8/5/5 fused carbon skeleton. Compound 9 showed potential anti-inflammatory effect in RAW264.7 macrophages and ulcerative colitis mice.
2025, 36(12): 110908
doi: 10.1016/j.cclet.2025.110908
摘要:
Cancer vaccines are a notable area of immunotherapy due to their capacity to elicit specific antitumor immune responses and to create immune memory. However, they encounter challenges in clinical practice due to several bottlenecks, including tumor heterogeneity, low immunogenicity, immunosuppressive tumor environment, and delivery obstacles, which collectively impact their clinical effectiveness. In this study, we developed nanocomposites containing positively charged melittin (MEL) and negatively charged photosensitizer indocyanine green (ICG), embedded in dissolving microneedles (MEL/ICG-HA@DMNs). This approach allows precise drug delivery by creating microchannels that bypass the stratum corneum barrier, targeting superficial lesions directly. Our results demonstrated that the complexation of MEL and ICG significantly reduced the hemolytic activity of MEL while maintaining its ability to disrupt cell membranes. After loading MEL/ICG-HA into the microneedle, MEL/ICG-HA@DMNs not only effectively concentrated the drug at the tumor site, inducing localized hyperthermia and successfully ablating the tumor, but also formed an in situ whole-cell vaccine containing a rich source of tumor-associated antigens. Moreover, the system promoted dendritic cell maturation and increased the M1/M2 macrophage ratio, enhancing the immune response. By overcoming the limitations of traditional cancer vaccines, this system ensures precise drug delivery and robust immune activation. This innovative approach holds the potential to revolutionize cancer treatment, offering a new paradigm in precision oncology.
Cancer vaccines are a notable area of immunotherapy due to their capacity to elicit specific antitumor immune responses and to create immune memory. However, they encounter challenges in clinical practice due to several bottlenecks, including tumor heterogeneity, low immunogenicity, immunosuppressive tumor environment, and delivery obstacles, which collectively impact their clinical effectiveness. In this study, we developed nanocomposites containing positively charged melittin (MEL) and negatively charged photosensitizer indocyanine green (ICG), embedded in dissolving microneedles (MEL/ICG-HA@DMNs). This approach allows precise drug delivery by creating microchannels that bypass the stratum corneum barrier, targeting superficial lesions directly. Our results demonstrated that the complexation of MEL and ICG significantly reduced the hemolytic activity of MEL while maintaining its ability to disrupt cell membranes. After loading MEL/ICG-HA into the microneedle, MEL/ICG-HA@DMNs not only effectively concentrated the drug at the tumor site, inducing localized hyperthermia and successfully ablating the tumor, but also formed an in situ whole-cell vaccine containing a rich source of tumor-associated antigens. Moreover, the system promoted dendritic cell maturation and increased the M1/M2 macrophage ratio, enhancing the immune response. By overcoming the limitations of traditional cancer vaccines, this system ensures precise drug delivery and robust immune activation. This innovative approach holds the potential to revolutionize cancer treatment, offering a new paradigm in precision oncology.
2025, 36(12): 110917
doi: 10.1016/j.cclet.2025.110917
摘要:
Outer-surface functionalized solid-state nanochannels have emerged as a new powerful tool for label-free and sensitive detection of biotargets, owing to the unique advantages, such as the target's size is not limited by the nanochannel size, probes on the outer surface are easier to modify and characterize. Despite the advancements, the current outer-surface functionalized nanochannels can only achieve single target detection, which is insufficient for understanding disease pathogenesis and clinical diagnosis. Herein, we develop an ordered mesoporous carbon-silicon/anodic aluminum oxide hybrid membrane (MCS/AAO) with outer surface probes for in situ detecting living cells released secretions with a wide size range (from nano-scale to micron-scale). Due to asymmetric nanochannel structure and charge distribution, the hybrid membrane exhibits cation selectivity and a high ionic current rectification value of 29.21. By taking advantage of this mechanism, different cell secretions can be selectively and sensitively detected through replacing the modified aptamers on the outer surface of hybrid membrane. ATP (adenosine triphosphate), VEGF (vascular endothelial growth factor), and HepG2-MVs (micro vesicles) are chosen as model secretions representing different sizes. The detection limits are 0.64 fmol/L for ATP, 3.31 fg/mL for VEGF, and 5.37 × 104 particles/mL for HepG2-MVs, which was over 10-fold higher than that of commercial assay kits. In addition, the prepared hybrid membrane has exceptional mechanical stability, the detection interface could be regenerated at least 5 times. This work provides a promising platform for in situ detection of cell secretions with different types and sizes by one sensing device and facilitates the clinical diagnosis of secretion-related diseases.
Outer-surface functionalized solid-state nanochannels have emerged as a new powerful tool for label-free and sensitive detection of biotargets, owing to the unique advantages, such as the target's size is not limited by the nanochannel size, probes on the outer surface are easier to modify and characterize. Despite the advancements, the current outer-surface functionalized nanochannels can only achieve single target detection, which is insufficient for understanding disease pathogenesis and clinical diagnosis. Herein, we develop an ordered mesoporous carbon-silicon/anodic aluminum oxide hybrid membrane (MCS/AAO) with outer surface probes for in situ detecting living cells released secretions with a wide size range (from nano-scale to micron-scale). Due to asymmetric nanochannel structure and charge distribution, the hybrid membrane exhibits cation selectivity and a high ionic current rectification value of 29.21. By taking advantage of this mechanism, different cell secretions can be selectively and sensitively detected through replacing the modified aptamers on the outer surface of hybrid membrane. ATP (adenosine triphosphate), VEGF (vascular endothelial growth factor), and HepG2-MVs (micro vesicles) are chosen as model secretions representing different sizes. The detection limits are 0.64 fmol/L for ATP, 3.31 fg/mL for VEGF, and 5.37 × 104 particles/mL for HepG2-MVs, which was over 10-fold higher than that of commercial assay kits. In addition, the prepared hybrid membrane has exceptional mechanical stability, the detection interface could be regenerated at least 5 times. This work provides a promising platform for in situ detection of cell secretions with different types and sizes by one sensing device and facilitates the clinical diagnosis of secretion-related diseases.
2025, 36(12): 110918
doi: 10.1016/j.cclet.2025.110918
摘要:
The supramolecular assemblies of luminescent metallohelicates play a crucial role in ion transport, thanks to their tunable three-dimensional molecular architecture and advantageous fluorescence properties. In this study, we synthesized a series of benzo[c][1,2,5]thiadiazole (BTZ)-based metallohelicates specifically designed for ion transport applications. These carefully crafted metallohelicates possess internal cavities and varying lengths of alkyl side chains, which enable modulation of their compatibility with phospholipid membranes and enhance ion transport efficiency. Moreover, their high fluorescence quantum yields allow for characterization via fluorescence microscopy following successful incorporation into the membranes. Importantly, due to their strong affinity for anions and the smaller ionic radius of chloride, these metallohelicates exhibit selective transport activity for chloride ions.
The supramolecular assemblies of luminescent metallohelicates play a crucial role in ion transport, thanks to their tunable three-dimensional molecular architecture and advantageous fluorescence properties. In this study, we synthesized a series of benzo[c][1,2,5]thiadiazole (BTZ)-based metallohelicates specifically designed for ion transport applications. These carefully crafted metallohelicates possess internal cavities and varying lengths of alkyl side chains, which enable modulation of their compatibility with phospholipid membranes and enhance ion transport efficiency. Moreover, their high fluorescence quantum yields allow for characterization via fluorescence microscopy following successful incorporation into the membranes. Importantly, due to their strong affinity for anions and the smaller ionic radius of chloride, these metallohelicates exhibit selective transport activity for chloride ions.
2025, 36(12): 110940
doi: 10.1016/j.cclet.2025.110940
摘要:
Superior neutral or cationic dinuclear gold(I) N-heterocyclic carbene (NHC) complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom. The novel cationic dinuclear gold(I) complex 4a (BF5-Au) with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo. The Hyper7 sensor was first used to analyze the sites of reactive oxygen species (ROS) generation by BF5-Au, showing that ROS were preferably generated in mitochondria and endoplasmic reticulum. Mechanism studies showed that BF5-Au could induce immunogenic cell death (ICD) via ROS-driven endoplasmic reticulum stress (ERS). However, targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances. Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types. Overall, BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis, which is expected to be a promising chemoimmunotherapy for cancer treatment.
Superior neutral or cationic dinuclear gold(I) N-heterocyclic carbene (NHC) complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom. The novel cationic dinuclear gold(I) complex 4a (BF5-Au) with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo. The Hyper7 sensor was first used to analyze the sites of reactive oxygen species (ROS) generation by BF5-Au, showing that ROS were preferably generated in mitochondria and endoplasmic reticulum. Mechanism studies showed that BF5-Au could induce immunogenic cell death (ICD) via ROS-driven endoplasmic reticulum stress (ERS). However, targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances. Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types. Overall, BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis, which is expected to be a promising chemoimmunotherapy for cancer treatment.
2025, 36(12): 110941
doi: 10.1016/j.cclet.2025.110941
摘要:
Upon encountering external challenges, immune cell recognition of response to pathogens constitutes a pivotal physiological process. Here, we designed and engineering an artificial immune signal transduction system utilizing DNA strands and liposomes to simulate antigen signals presentation, i.e., the uptake and processing of antigens by antigen-presenting cells (APCs). Through controlled DNA strand displacement reactions, we engineered artificial antigen-presenting cells (mAPCs) that display antigen signals on their surface and mimic phagocytosis. To further simulate antigen presentation, we constructed mimic naïve T cells (mTCs). Then, deoxyribonucleic acid (DNA) ion channels across mTCs membranes, simulating T-cell receptors, were opened by DNA strands on mAPCs mimicking the major histocompatibility complex (MHC), i.e., MHC molecules that present peptides to the T-cell receptor (TCR) on mTCs (recognition). This allowed Ca2+ ions to enter mTCs, increasing calcein fluorescence as activated mTC response indicator. The DNA strands on the surface of A-mAPCs and the Ca2+ ions in the solution together act like costimulatory molecules on APCs to trigger responses of mTCs. This simulation of immune signal transduction provides a significant reference value for the construction of bioinspired signal transduction systems and the design of more realistic artificial biological systems.
Upon encountering external challenges, immune cell recognition of response to pathogens constitutes a pivotal physiological process. Here, we designed and engineering an artificial immune signal transduction system utilizing DNA strands and liposomes to simulate antigen signals presentation, i.e., the uptake and processing of antigens by antigen-presenting cells (APCs). Through controlled DNA strand displacement reactions, we engineered artificial antigen-presenting cells (mAPCs) that display antigen signals on their surface and mimic phagocytosis. To further simulate antigen presentation, we constructed mimic naïve T cells (mTCs). Then, deoxyribonucleic acid (DNA) ion channels across mTCs membranes, simulating T-cell receptors, were opened by DNA strands on mAPCs mimicking the major histocompatibility complex (MHC), i.e., MHC molecules that present peptides to the T-cell receptor (TCR) on mTCs (recognition). This allowed Ca2+ ions to enter mTCs, increasing calcein fluorescence as activated mTC response indicator. The DNA strands on the surface of A-mAPCs and the Ca2+ ions in the solution together act like costimulatory molecules on APCs to trigger responses of mTCs. This simulation of immune signal transduction provides a significant reference value for the construction of bioinspired signal transduction systems and the design of more realistic artificial biological systems.
2025, 36(12): 110942
doi: 10.1016/j.cclet.2025.110942
摘要:
The efficient and safe strategy is highly desirable for effective tumor treatment, yet the development is still unsatisfied. In this work, we develop a photo-accelerated nanoplatform for image-guided synergistic chemo-photodynamic therapy. We first synthesize an aggregation-induced emission luminogen (AIEgen) with outstanding type-Ⅰ and type-Ⅱ photodynamic therapy (PDT) properties. By integrating the high-performance AIEgen with a hypoxia-responsive prodrug and camouflaging with M1 macrophage membrane, a tumor-targeting theranostic agent is created. Upon light trigger, the type-Ⅱ PDT process depletes oxygen in the tumor microenvironment, exacerbating hypoxia and promoting prodrug activation. Meanwhile, the type-Ⅰ PDT mechanism, being less reliant on oxygen, ensures that the overall PDT efficacy remains largely unaffected. Consequently, this light-triggered synergistic PDT-chemotherapy system demonstrates enhanced therapeutic performance. In vivo fluorescence imaging precisely delineates tumor sites, guiding subsequent treatment. The photo-triggered prodrug activation and PDT significantly boost the therapeutic outcomes of the tumor. This approach presents a compelling solution for targeted and efficient tumor treatment.
The efficient and safe strategy is highly desirable for effective tumor treatment, yet the development is still unsatisfied. In this work, we develop a photo-accelerated nanoplatform for image-guided synergistic chemo-photodynamic therapy. We first synthesize an aggregation-induced emission luminogen (AIEgen) with outstanding type-Ⅰ and type-Ⅱ photodynamic therapy (PDT) properties. By integrating the high-performance AIEgen with a hypoxia-responsive prodrug and camouflaging with M1 macrophage membrane, a tumor-targeting theranostic agent is created. Upon light trigger, the type-Ⅱ PDT process depletes oxygen in the tumor microenvironment, exacerbating hypoxia and promoting prodrug activation. Meanwhile, the type-Ⅰ PDT mechanism, being less reliant on oxygen, ensures that the overall PDT efficacy remains largely unaffected. Consequently, this light-triggered synergistic PDT-chemotherapy system demonstrates enhanced therapeutic performance. In vivo fluorescence imaging precisely delineates tumor sites, guiding subsequent treatment. The photo-triggered prodrug activation and PDT significantly boost the therapeutic outcomes of the tumor. This approach presents a compelling solution for targeted and efficient tumor treatment.
2025, 36(12): 110957
doi: 10.1016/j.cclet.2025.110957
摘要:
Perfluorooctanoic acid (PFOA) is a highly bioaccumulative environmental endocrine disruptor and a persistent organic pollutant. Epigenetic modifications in DNA and RNA are crucial for regulating gene expression and are involved in numerous physiological processes. However, research on the effects of PFOA on epigenetic modifications is still limited. In this study, we systematically investigated the alterations in epigenetic modifications in both DNA and RNA from the heart, liver, spleen, lung, kidney, and brain of C57BL/6N mice following exposure to PFOA at doses of 0, 0.5, and 5 mg kg−1 d−1, utilizing liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results indicated that exposure to PFOA inhibited weight gain in mice, and significant changes were observed in the organ coefficients of the liver, spleen, lungs, and heart in the high PFOA exposure group. Modifications in DNA and RNA exhibited tissue specificity. Orthogonal partial least squares discriminant analysis revealed that the control group and the high PFOA exposure group clustered well, suggesting that PFOA exposure significantly impacts epigenetic modifications in DNA and RNA. Specifically, PFOA exposure significantly affected the levels of 5-hydroxymethylcytosine (5hmC) in genomic DNA in the heart, lung, kidney, and liver tissues. For RNA modifications, significant changes were observed, with the levels of 12, 13, 10, 6, 12, and 14 modifications in the heart, liver, spleen, lung, kidney, and brain, respectively, altered in response to PFOA exposure. Our study highlights the significance of PFOA exposure in altering DNA and RNA modifications, providing a new perspective on understanding the toxicology of PFOA from an epigenetic standpoint.
Perfluorooctanoic acid (PFOA) is a highly bioaccumulative environmental endocrine disruptor and a persistent organic pollutant. Epigenetic modifications in DNA and RNA are crucial for regulating gene expression and are involved in numerous physiological processes. However, research on the effects of PFOA on epigenetic modifications is still limited. In this study, we systematically investigated the alterations in epigenetic modifications in both DNA and RNA from the heart, liver, spleen, lung, kidney, and brain of C57BL/6N mice following exposure to PFOA at doses of 0, 0.5, and 5 mg kg−1 d−1, utilizing liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results indicated that exposure to PFOA inhibited weight gain in mice, and significant changes were observed in the organ coefficients of the liver, spleen, lungs, and heart in the high PFOA exposure group. Modifications in DNA and RNA exhibited tissue specificity. Orthogonal partial least squares discriminant analysis revealed that the control group and the high PFOA exposure group clustered well, suggesting that PFOA exposure significantly impacts epigenetic modifications in DNA and RNA. Specifically, PFOA exposure significantly affected the levels of 5-hydroxymethylcytosine (5hmC) in genomic DNA in the heart, lung, kidney, and liver tissues. For RNA modifications, significant changes were observed, with the levels of 12, 13, 10, 6, 12, and 14 modifications in the heart, liver, spleen, lung, kidney, and brain, respectively, altered in response to PFOA exposure. Our study highlights the significance of PFOA exposure in altering DNA and RNA modifications, providing a new perspective on understanding the toxicology of PFOA from an epigenetic standpoint.
2025, 36(12): 110962
doi: 10.1016/j.cclet.2025.110962
摘要:
Rheumatoid arthritis, being a chronic autoimmune malady, may culminate in joint malformation and incapacitation in severe instances. Nevertheless, monitoring the heterogeneity of the viscosity microenvironment in local joint areas remains challenging. Hence, we have developed a near-infrared (NIR)-emitting fluorescence lifetime probe WY-V for dual fluorescence lifetime imaging microscopy (FLIM)/NIR optical imaging, featuring precise targeting capabilities to the endoplasmic reticulum (ER) and lipid droplets (LD). This probe modulates distinct fluorescence lifetimes in the varying viscosity environments of these organelles, allowing for the quantification of their respective viscosities. Using FLIM/NIR optical imaging of joint tissues from arthritic mice, the probe accurately discerned the viscosity of inflamed cells at diverse sites, reveals the viscosity heterogeneity present within the arthritic tissues. Therefore, this research offers a potent biological instrument for clinical diagnosis and pathological examination of rheumatoid arthritis.
Rheumatoid arthritis, being a chronic autoimmune malady, may culminate in joint malformation and incapacitation in severe instances. Nevertheless, monitoring the heterogeneity of the viscosity microenvironment in local joint areas remains challenging. Hence, we have developed a near-infrared (NIR)-emitting fluorescence lifetime probe WY-V for dual fluorescence lifetime imaging microscopy (FLIM)/NIR optical imaging, featuring precise targeting capabilities to the endoplasmic reticulum (ER) and lipid droplets (LD). This probe modulates distinct fluorescence lifetimes in the varying viscosity environments of these organelles, allowing for the quantification of their respective viscosities. Using FLIM/NIR optical imaging of joint tissues from arthritic mice, the probe accurately discerned the viscosity of inflamed cells at diverse sites, reveals the viscosity heterogeneity present within the arthritic tissues. Therefore, this research offers a potent biological instrument for clinical diagnosis and pathological examination of rheumatoid arthritis.
2025, 36(12): 110980
doi: 10.1016/j.cclet.2025.110980
摘要:
Fluorogen-activating proteins (FAPs) selectively bind to specific fluorophores, inducing fluorescence activation through the inhibition of torsion of fluorophores. This binding-activation mechanism provides a highly specific and efficient fluorescence system that minimizes background signals, significantly enhancing the signal-to-noise ratio (SNR) and making it a powerful tool in live-cell imaging. The principle of binding-activation fluorescence is fundamental to point accumulation for imaging in nanoscale topography (PAINT) super-resolution imaging. However, the high binding affinity between traditional FAP-fluorophore pairs limits their application in PAINT, thus hindering the rapid and dynamic imaging necessary for high-resolution cellular studies. In this work, we designed malachite green (MG) derivatives with bulky N-substituents to modulate the binding affinity of the MG-dL5** fluorophore-FAP pair. This modification introduces steric hindrance in MG-dL5** system, resulting in reduced binding affinity and practicability for fast, high-resolution PAINT imaging. Among the synthesized derivatives, MG-Pen showed optimal properties, enabling rapid and high-resolution PAINT imaging of dL5** in living cells. This study highlights the potential of MG derivatives optimization in overcoming the limitations of fluorophore-FAP pairs for super-resolution imaging and provides a new approach for enhancing the performance of PAINT in living cell applications.
Fluorogen-activating proteins (FAPs) selectively bind to specific fluorophores, inducing fluorescence activation through the inhibition of torsion of fluorophores. This binding-activation mechanism provides a highly specific and efficient fluorescence system that minimizes background signals, significantly enhancing the signal-to-noise ratio (SNR) and making it a powerful tool in live-cell imaging. The principle of binding-activation fluorescence is fundamental to point accumulation for imaging in nanoscale topography (PAINT) super-resolution imaging. However, the high binding affinity between traditional FAP-fluorophore pairs limits their application in PAINT, thus hindering the rapid and dynamic imaging necessary for high-resolution cellular studies. In this work, we designed malachite green (MG) derivatives with bulky N-substituents to modulate the binding affinity of the MG-dL5** fluorophore-FAP pair. This modification introduces steric hindrance in MG-dL5** system, resulting in reduced binding affinity and practicability for fast, high-resolution PAINT imaging. Among the synthesized derivatives, MG-Pen showed optimal properties, enabling rapid and high-resolution PAINT imaging of dL5** in living cells. This study highlights the potential of MG derivatives optimization in overcoming the limitations of fluorophore-FAP pairs for super-resolution imaging and provides a new approach for enhancing the performance of PAINT in living cell applications.
2025, 36(12): 110991
doi: 10.1016/j.cclet.2025.110991
摘要:
The adsorption and separation of antibody drugs are of great significance, but the promising hydrophobic charge induction chromatography (HCIC) and boronate affinity chromatography (BAC) suffer from low specific due to the limitations of single-site adsorption mechanism as well as low adsorption capacity of adsorbents, resulting in a lower purity and recovery of antibodies. To address this issue, this work proposes a two-site synergistic binding strategy integrating HCIC and BAC mechanism on a polymer brushes-grafted adsorbent. Five adsorbents were easily created by polymerizing the mixed monomers of 5-acryloylaminobenzimidazole, 3-acryloylamide phenylboronic acid and acrylamide on surface of agarose gel via activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). The molecular docking implies that the two-site synergistic binding towards immunoglobulin G (IgG) originates from the closely adjacent boronic and benzimidazole side groups in the polymer chains with monomer ratio of 1:1:0. The inference was verified by the effect of three monomer ratios and adsorption conditions on the adsorption performance of IgG. The adsorbent with two-site synergy possesses an excellent specific, enhanced affinity (Kd = 3.9 × 10−6 mol/L) and adsorption capacity (Qm = 253 mg/g) towards IgG. Benefiting from the advantages, IgG from serum and monoclonal antibody (mAb) from cell culture achieve purities of 95.8% and 98.3%, and recoveries of 95.7% and 97.5%, respectively. The results are comparable to those with protein A adsorbent considered to have the best specific so far, indicating the potential of the two-site synergistic binding strategy in the purification of antibody drugs.
The adsorption and separation of antibody drugs are of great significance, but the promising hydrophobic charge induction chromatography (HCIC) and boronate affinity chromatography (BAC) suffer from low specific due to the limitations of single-site adsorption mechanism as well as low adsorption capacity of adsorbents, resulting in a lower purity and recovery of antibodies. To address this issue, this work proposes a two-site synergistic binding strategy integrating HCIC and BAC mechanism on a polymer brushes-grafted adsorbent. Five adsorbents were easily created by polymerizing the mixed monomers of 5-acryloylaminobenzimidazole, 3-acryloylamide phenylboronic acid and acrylamide on surface of agarose gel via activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). The molecular docking implies that the two-site synergistic binding towards immunoglobulin G (IgG) originates from the closely adjacent boronic and benzimidazole side groups in the polymer chains with monomer ratio of 1:1:0. The inference was verified by the effect of three monomer ratios and adsorption conditions on the adsorption performance of IgG. The adsorbent with two-site synergy possesses an excellent specific, enhanced affinity (Kd = 3.9 × 10−6 mol/L) and adsorption capacity (Qm = 253 mg/g) towards IgG. Benefiting from the advantages, IgG from serum and monoclonal antibody (mAb) from cell culture achieve purities of 95.8% and 98.3%, and recoveries of 95.7% and 97.5%, respectively. The results are comparable to those with protein A adsorbent considered to have the best specific so far, indicating the potential of the two-site synergistic binding strategy in the purification of antibody drugs.
2025, 36(12): 111006
doi: 10.1016/j.cclet.2025.111006
摘要:
An efficient synthesis of α-thioenamine compounds via a K2S2O8-promoted cross-dehydrogenative coupling reaction between heterocyclic thiols and enamine esters in an aqueous medium has been developed. The reaction showed good tolerance for enamine esters and heterocyclic thiols with various functional groups, producing α-thioenamine derivatives in moderate to high yields. Mechanistic studies revealed that heterocyclic thiols react with K2S2O8 in water to form reactive disulfides in situ, which then react with enamine esters to generate a series of α-thioenamines. Building on the proposed mechanism, we developed a sulfenylation reaction of enamine esters with disulfides without the need for an oxidant. This oxidant-free approach has been successfully employed to synthesize DNA-tagged α-thioenamine, demonstrating its considerable potential for various synthetic applications.
An efficient synthesis of α-thioenamine compounds via a K2S2O8-promoted cross-dehydrogenative coupling reaction between heterocyclic thiols and enamine esters in an aqueous medium has been developed. The reaction showed good tolerance for enamine esters and heterocyclic thiols with various functional groups, producing α-thioenamine derivatives in moderate to high yields. Mechanistic studies revealed that heterocyclic thiols react with K2S2O8 in water to form reactive disulfides in situ, which then react with enamine esters to generate a series of α-thioenamines. Building on the proposed mechanism, we developed a sulfenylation reaction of enamine esters with disulfides without the need for an oxidant. This oxidant-free approach has been successfully employed to synthesize DNA-tagged α-thioenamine, demonstrating its considerable potential for various synthetic applications.
Machine learning-assisted construction of C=O and pyridinic N active sites in sludge-based catalysts
2025, 36(12): 111019
doi: 10.1016/j.cclet.2025.111019
摘要:
The type and quantity of active sites on a catalyst surface determine catalytic activity. In this study, machine learning was employed to assist in the construction of C=O and pyridine N active sites using sludge waste. Reactive descriptors, including C%, N%, O%, Fe%, pyrolysis temperature, heating rate, and pyrolysis time were proposed. Decision tree, extra tree, extreme gradient boosting (XGB), automatic relevance determination, and Bayesian ridge regression models were constructed and optimized. Among these, the XGB model was demonstrated with superior accuracy for prediction of C=O sites on the catalyst surface. Additionally, an ensemble model combining extra trees and XGB was developed to predict pyridine N, with R2 value as high as 0.80 and minimum root mean square error (RMSE) of 0.1386. The ensemble model demonstrated a 17% improvement in accuracy compared to individual models. The model enables high-throughput screening of construction conditions for C=O and pyridine N. The study found that a pyrolysis temperature above of 500–800 ℃, a heating rate of 10–20 ℃/min, and a heating time of 120–200 min favor the generation of C=O active sites. For pyridine N sites, a pyrolysis temperature between 400 ℃ and 600 ℃, a heating rate of 5–10 ℃/min, and a pyrolysis time of around 150 min are optimal. Experimental validation demonstrated that both models exhibit excellent predictive performance, with prediction errors below 10% in all cases. This research provides a method to assist in the construction of C=O and pyridine N active sites, which is beneficial for guiding the design of sludge catalysts.
The type and quantity of active sites on a catalyst surface determine catalytic activity. In this study, machine learning was employed to assist in the construction of C=O and pyridine N active sites using sludge waste. Reactive descriptors, including C%, N%, O%, Fe%, pyrolysis temperature, heating rate, and pyrolysis time were proposed. Decision tree, extra tree, extreme gradient boosting (XGB), automatic relevance determination, and Bayesian ridge regression models were constructed and optimized. Among these, the XGB model was demonstrated with superior accuracy for prediction of C=O sites on the catalyst surface. Additionally, an ensemble model combining extra trees and XGB was developed to predict pyridine N, with R2 value as high as 0.80 and minimum root mean square error (RMSE) of 0.1386. The ensemble model demonstrated a 17% improvement in accuracy compared to individual models. The model enables high-throughput screening of construction conditions for C=O and pyridine N. The study found that a pyrolysis temperature above of 500–800 ℃, a heating rate of 10–20 ℃/min, and a heating time of 120–200 min favor the generation of C=O active sites. For pyridine N sites, a pyrolysis temperature between 400 ℃ and 600 ℃, a heating rate of 5–10 ℃/min, and a pyrolysis time of around 150 min are optimal. Experimental validation demonstrated that both models exhibit excellent predictive performance, with prediction errors below 10% in all cases. This research provides a method to assist in the construction of C=O and pyridine N active sites, which is beneficial for guiding the design of sludge catalysts.
2025, 36(12): 111027
doi: 10.1016/j.cclet.2025.111027
摘要:
Cardiolipins (CLs), the mitochondria-specific class of phospholipids, are crucial to energy metabolism, cristae structure, and cell apoptosis. CLs present significant challenges in lipidomics analysis due to their structural diversity with up to four fatty acyl side chains. In this study, we developed CLAN (CardioLipin ANalysis), a comprehensive computational pipeline designed to improve the accuracy and coverage of cardiolipin identification. CLAN integrates three innovative modules: A cardiolipin identification module that utilizes specific fragmentation rules for precise characterization of CLs and their acyl side chains; a false positives detection module that employs retention time (RT) criteria to reduce false positives; and a prediction module that constructs regression models to identify CLs lacking authentic MS/MS spectra. CLAN achieved better identification accuracy and the highest recall rate for potential CL identification compared to the existing lipid identification tools. Furthermore, we applied CLAN program to an intermittent fasting mouse model, delineating tissue-specific CL alterations across 10 tissues. Every-other-day fasting (EODF) can partially counteract the disruption of the CL atlas across multiple tissues caused by high-fat-high-sugar diet feeding, providing novel insights into mitochondrial lipid metabolism under dietary interventions. Taken together, this work not only advances CL identification methodology but also underscores CLAN's potential in comprehensive analysis of CL atlas in the EODF animal model. CLAN is freely accessible on GitHub.
Cardiolipins (CLs), the mitochondria-specific class of phospholipids, are crucial to energy metabolism, cristae structure, and cell apoptosis. CLs present significant challenges in lipidomics analysis due to their structural diversity with up to four fatty acyl side chains. In this study, we developed CLAN (CardioLipin ANalysis), a comprehensive computational pipeline designed to improve the accuracy and coverage of cardiolipin identification. CLAN integrates three innovative modules: A cardiolipin identification module that utilizes specific fragmentation rules for precise characterization of CLs and their acyl side chains; a false positives detection module that employs retention time (RT) criteria to reduce false positives; and a prediction module that constructs regression models to identify CLs lacking authentic MS/MS spectra. CLAN achieved better identification accuracy and the highest recall rate for potential CL identification compared to the existing lipid identification tools. Furthermore, we applied CLAN program to an intermittent fasting mouse model, delineating tissue-specific CL alterations across 10 tissues. Every-other-day fasting (EODF) can partially counteract the disruption of the CL atlas across multiple tissues caused by high-fat-high-sugar diet feeding, providing novel insights into mitochondrial lipid metabolism under dietary interventions. Taken together, this work not only advances CL identification methodology but also underscores CLAN's potential in comprehensive analysis of CL atlas in the EODF animal model. CLAN is freely accessible on GitHub.
2025, 36(12): 111035
doi: 10.1016/j.cclet.2025.111035
摘要:
Inflammation is often accompanied by glioblastoma cells (GBMs) and is considered a key factor for GBM growth. This feature is believed to be connected with the tryptophan pathway mainly affected by intestinal microbes since the concept of gut-brain axis (GBA) has been proposed. Here we present a microchip model co-culturing intestinal cells (Caco2), microbes (E. coli), and GBM cells (U87) to study inflammatory responses of GBM by investigating the tryptophan metabolism. E. coli after encapsulating with alginate hydrogel microparticles (AHMPs) was seeded in the microchip where Caco2 was located, forming the simulated system of intestinal physiology and avoiding excessive reproduction of microbes. Continuous flow was applied to maintain the cell viability, induce the morphogenesis, and simulate the tryptophan transportation in GBA. The morphological alterations of Caco2 and U87 were characterized by fluorescence imaging and the tryptophan metabolism, especially the tryptophan-kynurenine pathway, was analyzed by LC-MS. Above these results of molecular analysis and cell behavior, we can conclude that GBM inflammation is induced by tryptophan accumulation. This microchip-based model generally provides an alternative method for in vitro research of interactions in GBA.
Inflammation is often accompanied by glioblastoma cells (GBMs) and is considered a key factor for GBM growth. This feature is believed to be connected with the tryptophan pathway mainly affected by intestinal microbes since the concept of gut-brain axis (GBA) has been proposed. Here we present a microchip model co-culturing intestinal cells (Caco2), microbes (E. coli), and GBM cells (U87) to study inflammatory responses of GBM by investigating the tryptophan metabolism. E. coli after encapsulating with alginate hydrogel microparticles (AHMPs) was seeded in the microchip where Caco2 was located, forming the simulated system of intestinal physiology and avoiding excessive reproduction of microbes. Continuous flow was applied to maintain the cell viability, induce the morphogenesis, and simulate the tryptophan transportation in GBA. The morphological alterations of Caco2 and U87 were characterized by fluorescence imaging and the tryptophan metabolism, especially the tryptophan-kynurenine pathway, was analyzed by LC-MS. Above these results of molecular analysis and cell behavior, we can conclude that GBM inflammation is induced by tryptophan accumulation. This microchip-based model generally provides an alternative method for in vitro research of interactions in GBA.
2025, 36(12): 111051
doi: 10.1016/j.cclet.2025.111051
摘要:
The active Cu(Ⅰ) species Q+ [CuⅠ(CF2CO2Et)(Cl)]- 1a and Q+ [CuⅠ(CF2CO2Et)2]- 1b (Q = Ph4P), which played an important role in the copper mediated ethoxycarbonyl difluoromethylation of organic halides, have been isolated and characterized for the first time. Stoichiometric reaction showed complex 1b is much more reactive than 1a. Furthermore, while oxidative addition of complex 1b with aryl iodide resulted in the formation of the reductive elimination product without the observation of the Cu(Ⅲ) intermediate, the oxidative addition of iodoacetronitrile to 1b successfully generated Cu(Ⅲ) intermediates that reductively eliminate to give the products. Building on the stoichiometric reaction, a copper-catalyzed ethoxycarbonyl difluoromethylation of benzylic, allylic halides was developed. Additionally, it has been found that complex 1b serves as a powerful ethoxycarbonyl difluoromethylation reagent capable of ethoxycarbonyl difluoromethylating a variety of electrophiles including (hetero)aryl electrophiles, alkyl electrophiles and acid chloride, disulfide. Moreover, the oxidative ethoxycarbonyl difluoromethylation of complex 1b with various lithium n–butyl (hetero)aryl boronic acid pinacol esters has been achieved in the presence of an oxidant.
The active Cu(Ⅰ) species Q+ [CuⅠ(CF2CO2Et)(Cl)]- 1a and Q+ [CuⅠ(CF2CO2Et)2]- 1b (Q = Ph4P), which played an important role in the copper mediated ethoxycarbonyl difluoromethylation of organic halides, have been isolated and characterized for the first time. Stoichiometric reaction showed complex 1b is much more reactive than 1a. Furthermore, while oxidative addition of complex 1b with aryl iodide resulted in the formation of the reductive elimination product without the observation of the Cu(Ⅲ) intermediate, the oxidative addition of iodoacetronitrile to 1b successfully generated Cu(Ⅲ) intermediates that reductively eliminate to give the products. Building on the stoichiometric reaction, a copper-catalyzed ethoxycarbonyl difluoromethylation of benzylic, allylic halides was developed. Additionally, it has been found that complex 1b serves as a powerful ethoxycarbonyl difluoromethylation reagent capable of ethoxycarbonyl difluoromethylating a variety of electrophiles including (hetero)aryl electrophiles, alkyl electrophiles and acid chloride, disulfide. Moreover, the oxidative ethoxycarbonyl difluoromethylation of complex 1b with various lithium n–butyl (hetero)aryl boronic acid pinacol esters has been achieved in the presence of an oxidant.
2025, 36(12): 111053
doi: 10.1016/j.cclet.2025.111053
摘要:
With advances in organoboron chemistry, boron-centered functional groups, especially alkyl boronic acids, which are widely available, bench stable, easy to prepare, minimally toxic, and structurally diverse, have become increasingly attractive. However, their utility is limited by their high oxidation potentials. In this study, we overcame this limitation by complexing an inorganic base (K3PO4) with alkyl boronic acids to decrease their oxidation potentials. Specifically, we present a powerful method for light-mediated deboronative cross-coupling reactions between alkyl boronic acids and aryl halides to afford products. This method demonstrated good functional group tolerance, and the mild conditions enabled the functionalization of drug molecules. In addition, the method could be extended to three-component carboacylation/carboarylation reactions of olefins to give products with high enantiomeric excess. Moreover, the reactions could be carried out under continuous-flow conditions, which enhanced the scalability, safety, and overall efficiency of the method.
With advances in organoboron chemistry, boron-centered functional groups, especially alkyl boronic acids, which are widely available, bench stable, easy to prepare, minimally toxic, and structurally diverse, have become increasingly attractive. However, their utility is limited by their high oxidation potentials. In this study, we overcame this limitation by complexing an inorganic base (K3PO4) with alkyl boronic acids to decrease their oxidation potentials. Specifically, we present a powerful method for light-mediated deboronative cross-coupling reactions between alkyl boronic acids and aryl halides to afford products. This method demonstrated good functional group tolerance, and the mild conditions enabled the functionalization of drug molecules. In addition, the method could be extended to three-component carboacylation/carboarylation reactions of olefins to give products with high enantiomeric excess. Moreover, the reactions could be carried out under continuous-flow conditions, which enhanced the scalability, safety, and overall efficiency of the method.
2025, 36(12): 111062
doi: 10.1016/j.cclet.2025.111062
摘要:
It is hard to achieve efficient photoelectrochemical (PEC) water splitting with BiVO4 due to the severe electron/hole recombination and slow carrier migration. In this work, BiVO4/BNQDs/CoBi photoanode was rationally designed and prepared for efficient PEC water splitting, utilizing boron nitride quantum dots (BNQDs) as hole extractors and cobalt borate (CoBi) as a cocatalyst. The BiVO4/BNQDs/CoBi exhibits an excellent photocurrent density of 5.1 mA/cm2 at 1.23 V vs. RHE, which is 3.4 times that of the pure BiVO4. Systematic studies show that BNQDs and CoBi can simultaneously promote charge separation and migration, with a charge injection and separation efficiency of 82% and 93% at 1.23 V vs. RHE, respectively. The enhanced dynamic behavior at the BiVO4/BNQDs/CoBi interface was systematically and quantitatively evaluated by intensity modulated photocurrent spectroscopy (IMPS) and transient surface photovoltage (TPV) spectroscopy. It is found that BNQDs and CoBi play a similar role for inhibiting charge recombination while BNQDs play significant role for improving the charge transfer rate than CoBi.
It is hard to achieve efficient photoelectrochemical (PEC) water splitting with BiVO4 due to the severe electron/hole recombination and slow carrier migration. In this work, BiVO4/BNQDs/CoBi photoanode was rationally designed and prepared for efficient PEC water splitting, utilizing boron nitride quantum dots (BNQDs) as hole extractors and cobalt borate (CoBi) as a cocatalyst. The BiVO4/BNQDs/CoBi exhibits an excellent photocurrent density of 5.1 mA/cm2 at 1.23 V vs. RHE, which is 3.4 times that of the pure BiVO4. Systematic studies show that BNQDs and CoBi can simultaneously promote charge separation and migration, with a charge injection and separation efficiency of 82% and 93% at 1.23 V vs. RHE, respectively. The enhanced dynamic behavior at the BiVO4/BNQDs/CoBi interface was systematically and quantitatively evaluated by intensity modulated photocurrent spectroscopy (IMPS) and transient surface photovoltage (TPV) spectroscopy. It is found that BNQDs and CoBi play a similar role for inhibiting charge recombination while BNQDs play significant role for improving the charge transfer rate than CoBi.
2025, 36(12): 111063
doi: 10.1016/j.cclet.2025.111063
摘要:
The photo-assisted Fenton-like method is an effective and sustainable way to remove organic pollutants from water. Herein, a series of three-dimensional composites containing MIL-88A(Fe)-derived α-Fe2O3 and graphene aerogel (GA-Fe-X) were designed and used as catalysts to degrade ciprofloxacin (CIP) by peroxymonosulfate (PMS) activated photo-Fenton-like technology. The as-prepared GA-Fe-1 displayed remarkable enhancement with a CIP degradation rate constant (0.017 min−1) higher than that of graphene aerogel (0.0031 min−1) and MIL-88A(Fe) (0.0039 min−1). Experimental results demonstrated that the combination of MIL-88A(Fe)-derived α-Fe2O3 and graphene aerogel forming GA-Fe-X enhanced the separation efficiency of electron-hole pairs, activating PMS to produce SO4•−, •OH and 1O2 for enhanced CIP degradation through radical and non-radical pathways. The factors affecting CIP degradation during the photo-Fenton-like process were thoroughly investigated. The possible CIP degradation pathways and ecotoxicity of the intermediates were also analyzed. This work enhances our understanding of the photo-Fenton-like effect in three-dimensional graphene aerogel composites.
The photo-assisted Fenton-like method is an effective and sustainable way to remove organic pollutants from water. Herein, a series of three-dimensional composites containing MIL-88A(Fe)-derived α-Fe2O3 and graphene aerogel (GA-Fe-X) were designed and used as catalysts to degrade ciprofloxacin (CIP) by peroxymonosulfate (PMS) activated photo-Fenton-like technology. The as-prepared GA-Fe-1 displayed remarkable enhancement with a CIP degradation rate constant (0.017 min−1) higher than that of graphene aerogel (0.0031 min−1) and MIL-88A(Fe) (0.0039 min−1). Experimental results demonstrated that the combination of MIL-88A(Fe)-derived α-Fe2O3 and graphene aerogel forming GA-Fe-X enhanced the separation efficiency of electron-hole pairs, activating PMS to produce SO4•−, •OH and 1O2 for enhanced CIP degradation through radical and non-radical pathways. The factors affecting CIP degradation during the photo-Fenton-like process were thoroughly investigated. The possible CIP degradation pathways and ecotoxicity of the intermediates were also analyzed. This work enhances our understanding of the photo-Fenton-like effect in three-dimensional graphene aerogel composites.
2025, 36(12): 111066
doi: 10.1016/j.cclet.2025.111066
摘要:
Electrocatalytic reduction of nitrate to ammonia offers an environmentally friendly and sustainable approach for ammonia production, but it involves a multi-step reaction process with complex intermediates, and still faces the challenge of high activity and high selectivity. Herein, a high-entropy nanoalloy was synthesized via high-temperature annealing of metal salt with dopamine as a carbon source for electrocatalytic reduction of nitrate to ammonia. The FeCoNiCuRu1.5/C catalyst displays a conversion rate of 90.2% and an ammonia selectivity of 92.2% at -0.74 V (vs. RHE), significantly surpassing the performance of low-entropy alloys such as FeCo/C by 1.5–2 times. Moreover, FeCoNiCuRu1.5/C maintains a consistent nitrate conversion rate of about 90.0% after 120 h of continuous operation (10 cycles), indicating high stability. The superior performance of FeCoNiCuRu1.5/C can be attributed to the synergetic relay catalysis among Fe, Co, Ni, Cu, and Ru sites. This synergy enhances nitrate adsorption due to the optimized electronic structure of multiple active sites, which facilitates the nitrate reduction to intermediates. Subsequently, the effective active hydrogen produced at the Ru site, in conjunction with adjustments at other metal sites, promotes the selective transformation of the intermediates into ammonia. This work not only highlights the efficacy of synergetic relay electrocatalysis but also opens new avenues for developing highly efficient multi-site catalysts.
Electrocatalytic reduction of nitrate to ammonia offers an environmentally friendly and sustainable approach for ammonia production, but it involves a multi-step reaction process with complex intermediates, and still faces the challenge of high activity and high selectivity. Herein, a high-entropy nanoalloy was synthesized via high-temperature annealing of metal salt with dopamine as a carbon source for electrocatalytic reduction of nitrate to ammonia. The FeCoNiCuRu1.5/C catalyst displays a conversion rate of 90.2% and an ammonia selectivity of 92.2% at -0.74 V (vs. RHE), significantly surpassing the performance of low-entropy alloys such as FeCo/C by 1.5–2 times. Moreover, FeCoNiCuRu1.5/C maintains a consistent nitrate conversion rate of about 90.0% after 120 h of continuous operation (10 cycles), indicating high stability. The superior performance of FeCoNiCuRu1.5/C can be attributed to the synergetic relay catalysis among Fe, Co, Ni, Cu, and Ru sites. This synergy enhances nitrate adsorption due to the optimized electronic structure of multiple active sites, which facilitates the nitrate reduction to intermediates. Subsequently, the effective active hydrogen produced at the Ru site, in conjunction with adjustments at other metal sites, promotes the selective transformation of the intermediates into ammonia. This work not only highlights the efficacy of synergetic relay electrocatalysis but also opens new avenues for developing highly efficient multi-site catalysts.
2025, 36(12): 111067
doi: 10.1016/j.cclet.2025.111067
摘要:
In contrast to the well-established synthetic protocols for monoalkenyl halides, a general approach to access diverse distal bisalkenyl halides with high synthetic fidelity has not yet been established, which are found in various biologically active natural products and may also serve as useful building blocks in organic synthesis. We herein report a cobalt-catalyzed regio- and stereoselective deoxygenative hydrohalogenation of propargyl alcohols to access Z-configurated alkenyl halides and the analogous distal bisalkenyl chlorides, bromides, and iodides. Mechanistic investigation suggests that the regio- and stereoselective stepwise hydrogenation of in situ generated chloroallenes is the key step wherein the commercially available halodimethylsilane, or a surrogate combination of hydrosilane and halosilane, serves both as the hydrogen and chlorine sources.
In contrast to the well-established synthetic protocols for monoalkenyl halides, a general approach to access diverse distal bisalkenyl halides with high synthetic fidelity has not yet been established, which are found in various biologically active natural products and may also serve as useful building blocks in organic synthesis. We herein report a cobalt-catalyzed regio- and stereoselective deoxygenative hydrohalogenation of propargyl alcohols to access Z-configurated alkenyl halides and the analogous distal bisalkenyl chlorides, bromides, and iodides. Mechanistic investigation suggests that the regio- and stereoselective stepwise hydrogenation of in situ generated chloroallenes is the key step wherein the commercially available halodimethylsilane, or a surrogate combination of hydrosilane and halosilane, serves both as the hydrogen and chlorine sources.
2025, 36(12): 111069
doi: 10.1016/j.cclet.2025.111069
摘要:
Polyanilines (PANIs) are easily accessible materials that can be employed to prepare catalysts for a variety of useful reactions. Investigations in the field are of profound academic and industrial values. In this work, we unexpectedly found that, calcium-doping could enhance the specific surface area and pore volume of poly-p-anisidine (PANI-OMe), so that the catalytic activity of the material could be significantly improved. It is notable that Ca-doping significantly enhanced the pore size of the material to 291.5 nm, making it a macroporous material that can allow even more sufficient contact of the catalytically active sites of nitrogen to contact with the macromolecules such as the PLA oligomer. Thus, the Ca-doped PANI-OMe (PANI-OMe/Ca) could well catalyse the condensation reaction of L-lactic acid to synthesize L-lactide in 75.0% yield with 98.2% optical purity at kilogram reaction scale. Since Ca is a biocompatible element that widely exists in both human and animal bodies, the Ca-doping protocol provides a biocompatible catalyst for L-lactide production. This is an important progress because L-lactide is widely employed as the basic raw material to produce the environment-friendly bio-degradable materials and the biomedical polymers. It may also inspire new strategies for designing the catalyst for the reactions involving macromolecular intermediates.
Polyanilines (PANIs) are easily accessible materials that can be employed to prepare catalysts for a variety of useful reactions. Investigations in the field are of profound academic and industrial values. In this work, we unexpectedly found that, calcium-doping could enhance the specific surface area and pore volume of poly-p-anisidine (PANI-OMe), so that the catalytic activity of the material could be significantly improved. It is notable that Ca-doping significantly enhanced the pore size of the material to 291.5 nm, making it a macroporous material that can allow even more sufficient contact of the catalytically active sites of nitrogen to contact with the macromolecules such as the PLA oligomer. Thus, the Ca-doped PANI-OMe (PANI-OMe/Ca) could well catalyse the condensation reaction of L-lactic acid to synthesize L-lactide in 75.0% yield with 98.2% optical purity at kilogram reaction scale. Since Ca is a biocompatible element that widely exists in both human and animal bodies, the Ca-doping protocol provides a biocompatible catalyst for L-lactide production. This is an important progress because L-lactide is widely employed as the basic raw material to produce the environment-friendly bio-degradable materials and the biomedical polymers. It may also inspire new strategies for designing the catalyst for the reactions involving macromolecular intermediates.
2025, 36(12): 111071
doi: 10.1016/j.cclet.2025.111071
摘要:
The development of cost-effective, environmentally sustainable narrowband near-infrared (NIR) organic light-emitting diodes (OLEDs) remains challenging due to low intrinsic quantum yields of NIR emitters, as constrained by the energy gap law and inefficient triplet exciton utilization. In this study, we present a conformation-locking strategy combined with donor engineering to enhance NIR emitters based on a boron-dipyrromethene (BODIPY) scaffold for high-performance solution-processed OLEDs. Two NIR emitters, Ph-BDP-Cz and Ph-BDP-PY, were synthesized by introducing a donor at the α-position of the BODIPY core via a vinyl bridge. This design increases molecular rigidity by promoting HF interactions between vinyl hydrogens and the BF2 group, suppressing twisting and scissoring motions, which results in narrow emission and high photoluminescence quantum yields. Donor engineering also enables fine-tuning of emission wavelengths without broadening the full-width at half-maximum (FWHM), maintaining a narrow emission profile. Using these BODIPY emitters in thermally activated delayed fluorescence (TADF)-sensitized hyperfluorescent OLEDs, we achieved a maximum external quantum efficiency (EQE) of 6.9% with an emission peak at 702 nm and a narrow FWHM of < 45 nm. To our knowledge, this represents one of the highest efficiencies among TADF sensitized solution-processed NIR OLEDs, offering a promising path toward the development of sustainable and high-performance NIR optoelectronic devices.
The development of cost-effective, environmentally sustainable narrowband near-infrared (NIR) organic light-emitting diodes (OLEDs) remains challenging due to low intrinsic quantum yields of NIR emitters, as constrained by the energy gap law and inefficient triplet exciton utilization. In this study, we present a conformation-locking strategy combined with donor engineering to enhance NIR emitters based on a boron-dipyrromethene (BODIPY) scaffold for high-performance solution-processed OLEDs. Two NIR emitters, Ph-BDP-Cz and Ph-BDP-PY, were synthesized by introducing a donor at the α-position of the BODIPY core via a vinyl bridge. This design increases molecular rigidity by promoting HF interactions between vinyl hydrogens and the BF2 group, suppressing twisting and scissoring motions, which results in narrow emission and high photoluminescence quantum yields. Donor engineering also enables fine-tuning of emission wavelengths without broadening the full-width at half-maximum (FWHM), maintaining a narrow emission profile. Using these BODIPY emitters in thermally activated delayed fluorescence (TADF)-sensitized hyperfluorescent OLEDs, we achieved a maximum external quantum efficiency (EQE) of 6.9% with an emission peak at 702 nm and a narrow FWHM of < 45 nm. To our knowledge, this represents one of the highest efficiencies among TADF sensitized solution-processed NIR OLEDs, offering a promising path toward the development of sustainable and high-performance NIR optoelectronic devices.
2025, 36(12): 111073
doi: 10.1016/j.cclet.2025.111073
摘要:
A novel hydrangea-like boron and nitrogen co-doped carbon material synthesised by the cross-linking reaction of spiny spherical polymers and co-doped with boron and nitrogen (B/N) via high-temperature calcination was used to construct an electrochemical sensor for the detection of aristolochic acid. Under optimal conditions, the sensor showed good electrochemical response to aristolochic acid, with a theoretical detection limit of 47.3 nmol/L and the sensitivity reaching 0.31 µA L µmol-1 cm-2. Moreover, the sensor was successfully applied to the detection of aristolochic acid in the extracts of Chinese herbal medicine samples, and the detection results were consistent with those of high-performance liquid chromatography. With a strong selectivity for substances to be measured in complex environments, this study provides a new and efficient method by which to detect aristolochic acid in Chinese herbal medicine, which greatly expands the application field of B/N heteroatom-doped carbon materials.
A novel hydrangea-like boron and nitrogen co-doped carbon material synthesised by the cross-linking reaction of spiny spherical polymers and co-doped with boron and nitrogen (B/N) via high-temperature calcination was used to construct an electrochemical sensor for the detection of aristolochic acid. Under optimal conditions, the sensor showed good electrochemical response to aristolochic acid, with a theoretical detection limit of 47.3 nmol/L and the sensitivity reaching 0.31 µA L µmol-1 cm-2. Moreover, the sensor was successfully applied to the detection of aristolochic acid in the extracts of Chinese herbal medicine samples, and the detection results were consistent with those of high-performance liquid chromatography. With a strong selectivity for substances to be measured in complex environments, this study provides a new and efficient method by which to detect aristolochic acid in Chinese herbal medicine, which greatly expands the application field of B/N heteroatom-doped carbon materials.
2025, 36(12): 111088
doi: 10.1016/j.cclet.2025.111088
摘要:
Photocatalytic H2 evolution from wastewater exhibits fascinating prospects in environment and energy fields. Here, we propose a novel 3D cross-linked g-C3N4 network (SCN) assembling with 1D nanowires. This network structure endows SCN with abundant carbon defects, creating a defect energy level and shallow charge trapping centres, which significantly prolongs the photocarrier lifetime, suppresses their recombination and facilitates the mass transfer process during the dye photodegradation. Consequently, in photocatalytic H2 evolution coupled with Rhodamine B (RhB) photodegradation under visible light, the H2 production rate of SCN is 283 µmol h−1 g−1, accompanying by 97% RhB photodegradation efficiency, much higher than UCN’s 31 µmol h−1 g−1 and 64%. In particular, AQY of SCN for H2 evolution from RhB solution reaches 23.7% at 380 nm. Furthermore, the calculated transition states demonstrate that the N1 site connected to the defect in SCN has a minimum Gibbs free energy ∆G (H*), indicating that H+ undergoes an H+ → H* → H2 evolution process.
Photocatalytic H2 evolution from wastewater exhibits fascinating prospects in environment and energy fields. Here, we propose a novel 3D cross-linked g-C3N4 network (SCN) assembling with 1D nanowires. This network structure endows SCN with abundant carbon defects, creating a defect energy level and shallow charge trapping centres, which significantly prolongs the photocarrier lifetime, suppresses their recombination and facilitates the mass transfer process during the dye photodegradation. Consequently, in photocatalytic H2 evolution coupled with Rhodamine B (RhB) photodegradation under visible light, the H2 production rate of SCN is 283 µmol h−1 g−1, accompanying by 97% RhB photodegradation efficiency, much higher than UCN’s 31 µmol h−1 g−1 and 64%. In particular, AQY of SCN for H2 evolution from RhB solution reaches 23.7% at 380 nm. Furthermore, the calculated transition states demonstrate that the N1 site connected to the defect in SCN has a minimum Gibbs free energy ∆G (H*), indicating that H+ undergoes an H+ → H* → H2 evolution process.
2025, 36(12): 111090
doi: 10.1016/j.cclet.2025.111090
摘要:
Reducing the highly toxic Cr(Ⅵ) to safe levels is a critical challenge in water treatment, essential for protecting both ecosystems and human health. In this study, we present a facile in situ polymerization approach to prepare polypyrrole-coated layered double hydroxide composites (PPy/NiFe LDHs). Compared with other LDHs and polypyrrole-based materials, the synthesized PPy/LDHs exhibit excellent adsorption performance under mildly acidic conditions, achieving a maximum Cr(Ⅵ) adsorption capacity of 440.4 mg/g at pH 5. Notably, PPy/LDH effectively reduces Cr(Ⅵ) concentration from 10 mg/L to 0.028 mg/L, well below the maximum permissible level of 0.05 mg/L for drinking water. Additionally, PPy/LDH demonstrates durable stability; at pH 5, nickel and iron ions are not detected after adsorption, and trivalent chromium remains fixed on the material without re-release into the solution following reduction. The adsorption behavior and mechanistic analysis indicate that a combination of adsorption and reduction drives Cr(Ⅵ) removal by PPy/LDHs. This work offers an innovative approach to effectively remove the low concentrations of Cr(Ⅵ) from water, showing significant potential for efficient Cr(Ⅵ) remediation.
Reducing the highly toxic Cr(Ⅵ) to safe levels is a critical challenge in water treatment, essential for protecting both ecosystems and human health. In this study, we present a facile in situ polymerization approach to prepare polypyrrole-coated layered double hydroxide composites (PPy/NiFe LDHs). Compared with other LDHs and polypyrrole-based materials, the synthesized PPy/LDHs exhibit excellent adsorption performance under mildly acidic conditions, achieving a maximum Cr(Ⅵ) adsorption capacity of 440.4 mg/g at pH 5. Notably, PPy/LDH effectively reduces Cr(Ⅵ) concentration from 10 mg/L to 0.028 mg/L, well below the maximum permissible level of 0.05 mg/L for drinking water. Additionally, PPy/LDH demonstrates durable stability; at pH 5, nickel and iron ions are not detected after adsorption, and trivalent chromium remains fixed on the material without re-release into the solution following reduction. The adsorption behavior and mechanistic analysis indicate that a combination of adsorption and reduction drives Cr(Ⅵ) removal by PPy/LDHs. This work offers an innovative approach to effectively remove the low concentrations of Cr(Ⅵ) from water, showing significant potential for efficient Cr(Ⅵ) remediation.
2025, 36(12): 111091
doi: 10.1016/j.cclet.2025.111091
摘要:
Characterization of the distribution and accurate counting of RNA molecules in the context of tissues is necessary to understand their complexity and heterogeneity. Single-molecule fluorescence in situ hybridization reveals the abundance and distribution of RNA and resolves different cell types in complex tissues. Especially, off-target binding and nonspecific adsorption of probes are prone to producing nonspecific amplification. Herein, we present highly de-noising amplified imaging, which leverages a site-specific cleavage-amplifying design to achieve accurate counting of RNA in tissues. Our method avoids adding probe as primer, decreases nonspecific spots of single cells from 7 to nearly zero, and enables RNA imaging in uncleared tissue sections with nearly zero noise. We demonstrate the efficacy of this method on various thickness of mouse tissue sections. We envision this approach will serve as a tool to revealing the information content from patient samples for biomedical purpose.
Characterization of the distribution and accurate counting of RNA molecules in the context of tissues is necessary to understand their complexity and heterogeneity. Single-molecule fluorescence in situ hybridization reveals the abundance and distribution of RNA and resolves different cell types in complex tissues. Especially, off-target binding and nonspecific adsorption of probes are prone to producing nonspecific amplification. Herein, we present highly de-noising amplified imaging, which leverages a site-specific cleavage-amplifying design to achieve accurate counting of RNA in tissues. Our method avoids adding probe as primer, decreases nonspecific spots of single cells from 7 to nearly zero, and enables RNA imaging in uncleared tissue sections with nearly zero noise. We demonstrate the efficacy of this method on various thickness of mouse tissue sections. We envision this approach will serve as a tool to revealing the information content from patient samples for biomedical purpose.
2025, 36(12): 111094
doi: 10.1016/j.cclet.2025.111094
摘要:
A strategy based on local spin-state manipulation was achieved through S-modification on single-Fe-atom catalysts (Fe1NSC). Spectral analyses and theoretical calculations elucidated that a medium-spin reconfiguration of Fe species in Fe1NSC endowed an increased orbital overlap between Fe 3d and O 2p, reinforcing the peroxymonosulfate (PMS) dissociation kinetics. Consequently, Fe1NSC delivered excellent performance in PMS conversion and pollutant degradation. The specific activity of PMS activation over Fe1NSC reached 36.1 × 10–3 L min-1 m-2, 4.2-folds that of Fe1NC (8.61 × 10–3 L min-1 m-2) and superior to the state-of-the-art catalysts reported to date. Importantly, the atomic spin-state modulation via S-modification can extend to other metals (Mn, Co and Cu) for improved PMS activation with > 3 times higher than those without S-modification. This work provides a universal scheme for electronic configuration regulation and highlights the significance of local environment modulation in designing high-performance catalysts for PMS activation.
A strategy based on local spin-state manipulation was achieved through S-modification on single-Fe-atom catalysts (Fe1NSC). Spectral analyses and theoretical calculations elucidated that a medium-spin reconfiguration of Fe species in Fe1NSC endowed an increased orbital overlap between Fe 3d and O 2p, reinforcing the peroxymonosulfate (PMS) dissociation kinetics. Consequently, Fe1NSC delivered excellent performance in PMS conversion and pollutant degradation. The specific activity of PMS activation over Fe1NSC reached 36.1 × 10–3 L min-1 m-2, 4.2-folds that of Fe1NC (8.61 × 10–3 L min-1 m-2) and superior to the state-of-the-art catalysts reported to date. Importantly, the atomic spin-state modulation via S-modification can extend to other metals (Mn, Co and Cu) for improved PMS activation with > 3 times higher than those without S-modification. This work provides a universal scheme for electronic configuration regulation and highlights the significance of local environment modulation in designing high-performance catalysts for PMS activation.
2025, 36(12): 111130
doi: 10.1016/j.cclet.2025.111130
摘要:
The reductive cyclocoupling of isocyanides is a pivotal reaction that facilitates the rapid construction of intricate cyclic compounds in a single-step process. In this work, treatment of simple precursor 1 (Cp#CrLCl, L = CAAC, NHC, PCy3, or PPh2Et; Cp# = Cp* or Cp*TMS) with XylNC (2,6-dimethylphenyl isocyanide) led to the reductive coupling of isocyanides, yielding either complex 2 {(Cp*TMSCr)2[μ-C4(NXyl)4]} or complex 6 {(Cp*CrCl)2[μ-C4(NXyl)4]}, corresponding to the tetramerization of isocyanides. Control experiments and in-situ monitoring were carried out to understand the reaction mechanism, revealing various side reaction pathways during the isocyanide tetramerization. SQUID and DFT calculations provided insights into the electronic structures. In complex 2, the energies of nonet and broken-symmetry singlet states are close and significantly lower than other spin states, indicating two independent high-spin Cr(Ⅱ) centers with weak antiferromagnetic coupling. A similar situation is observed in complex 6, where two independent high-spin Cr(Ⅲ) centers are coupled antiferromagnetically. In both complexes 2 and 6, the tetrameric isocyanide rings, receiving two electrons from Cr centers, show averaged bond lengths and display moderate aromatic characteristics.
The reductive cyclocoupling of isocyanides is a pivotal reaction that facilitates the rapid construction of intricate cyclic compounds in a single-step process. In this work, treatment of simple precursor 1 (Cp#CrLCl, L = CAAC, NHC, PCy3, or PPh2Et; Cp# = Cp* or Cp*TMS) with XylNC (2,6-dimethylphenyl isocyanide) led to the reductive coupling of isocyanides, yielding either complex 2 {(Cp*TMSCr)2[μ-C4(NXyl)4]} or complex 6 {(Cp*CrCl)2[μ-C4(NXyl)4]}, corresponding to the tetramerization of isocyanides. Control experiments and in-situ monitoring were carried out to understand the reaction mechanism, revealing various side reaction pathways during the isocyanide tetramerization. SQUID and DFT calculations provided insights into the electronic structures. In complex 2, the energies of nonet and broken-symmetry singlet states are close and significantly lower than other spin states, indicating two independent high-spin Cr(Ⅱ) centers with weak antiferromagnetic coupling. A similar situation is observed in complex 6, where two independent high-spin Cr(Ⅲ) centers are coupled antiferromagnetically. In both complexes 2 and 6, the tetrameric isocyanide rings, receiving two electrons from Cr centers, show averaged bond lengths and display moderate aromatic characteristics.
2025, 36(12): 111149
doi: 10.1016/j.cclet.2025.111149
摘要:
Machine learning methodologies have been extensively leveraged across diverse domains of chemical research, yielding remarkable outcomes, and exhibit substantial potential for impactful future applications within the field of supramolecular chemistry. The recognition of alkali metal ions by crown ethers is one of the most classic and widely applied host-guest interactions in supramolecular chemistry. Due to the numerous factors affecting the host-guest interaction, it remains a great challenge to achieve fast and accurate prediction of the binding constants between crown ethers and alkali metal ions. Herein, we report a highly accurate machine learning model that can effectively predict the binding constants between crown ethers and alkali metal ions, i.e., CrownBind-IA, with a low RMSE of 0.68 logK units. Moreover, this model proves robust extrapolative capabilities by accurately predicting out-of-sample data. The establishment of CrownBind-IA demonstrates the promising application potentials of data-driven machine learning methods in supramolecular chemistry, and it will substantially reduce the time and expense of experimental trials and characterizations, promote the exploration of the mechanism of host-guest interactions, as well as the rational design of novel functional supramolecular host molecules.
Machine learning methodologies have been extensively leveraged across diverse domains of chemical research, yielding remarkable outcomes, and exhibit substantial potential for impactful future applications within the field of supramolecular chemistry. The recognition of alkali metal ions by crown ethers is one of the most classic and widely applied host-guest interactions in supramolecular chemistry. Due to the numerous factors affecting the host-guest interaction, it remains a great challenge to achieve fast and accurate prediction of the binding constants between crown ethers and alkali metal ions. Herein, we report a highly accurate machine learning model that can effectively predict the binding constants between crown ethers and alkali metal ions, i.e., CrownBind-IA, with a low RMSE of 0.68 logK units. Moreover, this model proves robust extrapolative capabilities by accurately predicting out-of-sample data. The establishment of CrownBind-IA demonstrates the promising application potentials of data-driven machine learning methods in supramolecular chemistry, and it will substantially reduce the time and expense of experimental trials and characterizations, promote the exploration of the mechanism of host-guest interactions, as well as the rational design of novel functional supramolecular host molecules.
2025, 36(12): 111164
doi: 10.1016/j.cclet.2025.111164
摘要:
Simultaneously suppressing tumor growth and metastasis is a pivotal strategy in the treatment of cutaneous melanoma (CM). Towards this end, we first developed a novel PtCu nanozyme (PtCu-zyme) integrating single-atom Pt and Pt subnanoclusters, which was further functionalized with triphenylphosphine (TPP) to yield PtCu-TPP and confer the nanozyme mitochondria-targeting capabilities. By combining PtCu-TPP with a hyaluronic acid (HA) analog, isoliquiritigenin-grafted HA (HA-ISL), we later formulated PtCu-TPP loaded microneedles (PtCu-TPP@MNs) for potent CM treatment. Our findings indicated that PtCu-zyme exhibited exceptional oxidative enzyme-like properties and PtCu-TPP@MNs significantly inhibited the tumor growth and pulmonary metastasis. Furthermore, PtCu-TPP@MNs not only prolonged the survival of CM-bearing mice but also retained the nanozymes in the tumor, continually catalyzing reactive oxygen species (ROS) generation for sustained nanocatalytic therapy. In vitro studies revealed that PtCu-TPP specifically localized within mitochondria, increasing ROS levels and causing mitochondrial damage, which in turn enhanced the cytotoxicity towards tumor cells. These findings suggest that PtCu-TPP@MN delivery system holds significant promise for the effective treatment of CM, potentially offering a valuable alternative to existing therapeutic strategies.
Simultaneously suppressing tumor growth and metastasis is a pivotal strategy in the treatment of cutaneous melanoma (CM). Towards this end, we first developed a novel PtCu nanozyme (PtCu-zyme) integrating single-atom Pt and Pt subnanoclusters, which was further functionalized with triphenylphosphine (TPP) to yield PtCu-TPP and confer the nanozyme mitochondria-targeting capabilities. By combining PtCu-TPP with a hyaluronic acid (HA) analog, isoliquiritigenin-grafted HA (HA-ISL), we later formulated PtCu-TPP loaded microneedles (PtCu-TPP@MNs) for potent CM treatment. Our findings indicated that PtCu-zyme exhibited exceptional oxidative enzyme-like properties and PtCu-TPP@MNs significantly inhibited the tumor growth and pulmonary metastasis. Furthermore, PtCu-TPP@MNs not only prolonged the survival of CM-bearing mice but also retained the nanozymes in the tumor, continually catalyzing reactive oxygen species (ROS) generation for sustained nanocatalytic therapy. In vitro studies revealed that PtCu-TPP specifically localized within mitochondria, increasing ROS levels and causing mitochondrial damage, which in turn enhanced the cytotoxicity towards tumor cells. These findings suggest that PtCu-TPP@MN delivery system holds significant promise for the effective treatment of CM, potentially offering a valuable alternative to existing therapeutic strategies.
2025, 36(12): 111169
doi: 10.1016/j.cclet.2025.111169
摘要:
Here, we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO2, characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids. Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates, facilitating the synthesis of mono-, di-, tri-, and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions. Mechanistic investigations indicate that the in situ generated Ni(Ⅰ) complex might serve as the active species to react with propargylic esters, forming the allenyl-Ni(Ⅰ) complex under electro-reductive conditions. A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ) complex on CO2 is likely involved in the formation of the desired 2,3-allenoic acids.
Here, we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO2, characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids. Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates, facilitating the synthesis of mono-, di-, tri-, and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions. Mechanistic investigations indicate that the in situ generated Ni(Ⅰ) complex might serve as the active species to react with propargylic esters, forming the allenyl-Ni(Ⅰ) complex under electro-reductive conditions. A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ) complex on CO2 is likely involved in the formation of the desired 2,3-allenoic acids.
Enantioselective synthesis of bulky planar-chiral pillar[n]arenes through dynamic kinetic resolution
2025, 36(12): 111201
doi: 10.1016/j.cclet.2025.111201
摘要:
The precise synthesis of planar chiral pillar[n]arenes (PAs) faces significant challenges due to their inherent dynamic racemization induced by rapid molecular flipping. To address this issue and enhance conformational stability of these macrocycles, we have developed a strategic approach involving the introduction of sterically bulky aryl (sp2) substituents at the molecular rims through dynamic kinetic resolution (DKR). A series of robust and chirality-aligned homo- and hetero-diaryl PAs (n = 5, 6) were achieved with excellent enantioselectivity (>95% ee) via Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions. Mechanism study revealed axial steric hindrance, rather than radial substitution, governs conformational chirality-locking in pillar[n]arenes. This work not only provides an attractive protocol for the enantioselective synthesis of planar chiral pillar[n]arenes, but also enriches the library of macrocycles for promising applications in chiral molecular machines, enantioselective sensors, and chiral luminescent materials.
The precise synthesis of planar chiral pillar[n]arenes (PAs) faces significant challenges due to their inherent dynamic racemization induced by rapid molecular flipping. To address this issue and enhance conformational stability of these macrocycles, we have developed a strategic approach involving the introduction of sterically bulky aryl (sp2) substituents at the molecular rims through dynamic kinetic resolution (DKR). A series of robust and chirality-aligned homo- and hetero-diaryl PAs (n = 5, 6) were achieved with excellent enantioselectivity (>95% ee) via Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions. Mechanism study revealed axial steric hindrance, rather than radial substitution, governs conformational chirality-locking in pillar[n]arenes. This work not only provides an attractive protocol for the enantioselective synthesis of planar chiral pillar[n]arenes, but also enriches the library of macrocycles for promising applications in chiral molecular machines, enantioselective sensors, and chiral luminescent materials.
2025, 36(12): 111202
doi: 10.1016/j.cclet.2025.111202
摘要:
Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.02,7]octane are prevalent in natural products known for their significant biological activities. However, strategies for efficiently synthesizing these complex frameworks from simple starting materials via de novo synthesis remain underexplored. This article presents an efficient strategy that combines phosphine catalysis and photocatalysis to execute a stepwise tandem reaction involving allenoates and α-cyano cinnamaldehydes, including [3 + 2] cyclization, [5 + 2] cyclization, acyl transfer, and decarboxylation reactions, synthesizing a series of functional bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.02,7]oct–3-ene skeleton derivatives with excellent chemoselectivity demonstrated throughout the process. Meanwhile, the reaction can also be performed via a one-pot, scalable phosphine/photocatalytic cascade process, efficiently yielding the bridged products which can serve as versatile intermediates for further applications.
Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.02,7]octane are prevalent in natural products known for their significant biological activities. However, strategies for efficiently synthesizing these complex frameworks from simple starting materials via de novo synthesis remain underexplored. This article presents an efficient strategy that combines phosphine catalysis and photocatalysis to execute a stepwise tandem reaction involving allenoates and α-cyano cinnamaldehydes, including [3 + 2] cyclization, [5 + 2] cyclization, acyl transfer, and decarboxylation reactions, synthesizing a series of functional bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.02,7]oct–3-ene skeleton derivatives with excellent chemoselectivity demonstrated throughout the process. Meanwhile, the reaction can also be performed via a one-pot, scalable phosphine/photocatalytic cascade process, efficiently yielding the bridged products which can serve as versatile intermediates for further applications.
2025, 36(12): 111233
doi: 10.1016/j.cclet.2025.111233
摘要:
Calcium carbide, a bulky and cheap raw chemical, is traditionally depolymerized by water to release acetylene, allowing the downstream organic transformation. In this study, hydrogen sulfide (H2S), an industrial waste gas, has been exploited to depolymerize calcium carbide, which represents a strategy for the comprehensive utilization of both hydrogen sulfide and calcium carbide. As a proof of concept, a three-component condensation reaction was established to prepare thioamides directly from hydrogen sulfide and calcium carbide in high yields. Leveraging the unique properties of thioamides that possess both nucleophilic sulfur and electrophilic carbon sites, a series of novel tandem reactions were further developed to construct structurally diverse heterocyclic compounds. Our strategy not only provides a new chemical pathway for calcium carbide depolymerization, but also offers a solution for the utilization of hazardous hydrogen sulfide gas. More importantly, this approach facilitates the comprehensive and sustainable utilization of the calcium carbide resource.
Calcium carbide, a bulky and cheap raw chemical, is traditionally depolymerized by water to release acetylene, allowing the downstream organic transformation. In this study, hydrogen sulfide (H2S), an industrial waste gas, has been exploited to depolymerize calcium carbide, which represents a strategy for the comprehensive utilization of both hydrogen sulfide and calcium carbide. As a proof of concept, a three-component condensation reaction was established to prepare thioamides directly from hydrogen sulfide and calcium carbide in high yields. Leveraging the unique properties of thioamides that possess both nucleophilic sulfur and electrophilic carbon sites, a series of novel tandem reactions were further developed to construct structurally diverse heterocyclic compounds. Our strategy not only provides a new chemical pathway for calcium carbide depolymerization, but also offers a solution for the utilization of hazardous hydrogen sulfide gas. More importantly, this approach facilitates the comprehensive and sustainable utilization of the calcium carbide resource.
2025, 36(12): 111261
doi: 10.1016/j.cclet.2025.111261
摘要:
Despite the promising potential of organic nanoscintillator-mediated radiodynamic therapy (RDT) in enhancing the effectiveness of immunotherapy, their cutaneous phototoxicity exacerbates the risk for immune-related adverse events (irAEs). Herein, we demonstrate that organic nanoscintillators, when combined with checkpoint blockade immunotherapy and exposed to X-ray-induced RDT, can trigger cutaneous irAEs. To address this challenge, we engineered diselenide-bridged silicon coatings on organic nanoscintillators, fine-tuning the steric hindrance of the protective layer by varying its thickness. This strategy enables radiation-triggered reactive oxygen species (ROS) generation while mitigating off-target phototoxicity through neutralizing ROS. By optimizing the steric hindrance to precisely control energy transfer between the organic nanoscintillators and surrounding oxygen molecules, we effectively reduce phototoxicity and mitigate off-tumor effects through engineered surface protection. Under X-ray irradiation exposure, the steric hindrance is rapidly deactivated through the dissociation of the silicon coating, activating RDT and inducing abundant ROS generation within tumor cells. In an orthotopic 4T1 breast cancer model, intravenous administration of these surface-engineered nanoscintillators, combined with anti-programmed death-1 (anti-PD-1) antibodies, results in robust anti-tumor immune responses, while minimizing cutaneous irAEs. This work offers valuable insights into how surface engineering can modulate the delicate balance between anti-tumor efficacy and off-tumor toxicity in nanoscintillator-mediated RDT.
Despite the promising potential of organic nanoscintillator-mediated radiodynamic therapy (RDT) in enhancing the effectiveness of immunotherapy, their cutaneous phototoxicity exacerbates the risk for immune-related adverse events (irAEs). Herein, we demonstrate that organic nanoscintillators, when combined with checkpoint blockade immunotherapy and exposed to X-ray-induced RDT, can trigger cutaneous irAEs. To address this challenge, we engineered diselenide-bridged silicon coatings on organic nanoscintillators, fine-tuning the steric hindrance of the protective layer by varying its thickness. This strategy enables radiation-triggered reactive oxygen species (ROS) generation while mitigating off-target phototoxicity through neutralizing ROS. By optimizing the steric hindrance to precisely control energy transfer between the organic nanoscintillators and surrounding oxygen molecules, we effectively reduce phototoxicity and mitigate off-tumor effects through engineered surface protection. Under X-ray irradiation exposure, the steric hindrance is rapidly deactivated through the dissociation of the silicon coating, activating RDT and inducing abundant ROS generation within tumor cells. In an orthotopic 4T1 breast cancer model, intravenous administration of these surface-engineered nanoscintillators, combined with anti-programmed death-1 (anti-PD-1) antibodies, results in robust anti-tumor immune responses, while minimizing cutaneous irAEs. This work offers valuable insights into how surface engineering can modulate the delicate balance between anti-tumor efficacy and off-tumor toxicity in nanoscintillator-mediated RDT.
2025, 36(12): 111290
doi: 10.1016/j.cclet.2025.111290
摘要:
The coating material is considered as the key of solid-phase microextraction (SPME) due to the fact that which has much effect on the selectivity and sensitivity of the analytical method. Herein, the porous hollow carbon nanospheres (PHCNs) were synthesized by selectively removing the interior part of solid inhomogeneous nanospheres with acetone. Using PHCNs as new coating material, a SPME fiber was prepared. To the best of our knowledge, PHCNs was utilized as a SPME fiber coating for the first time. The fiber coating material PHCNs demonstrated excellent thermal stability (> 800 ℃) and long usage lifespan (≥60 times). A headspace SPME (HS-SPME) was established to non-contact extract and enrich polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The HS-SPME not only can eliminate non-volatile interferences from matrix, but also be able to protect fiber coating and prolong lifespan of fiber prober. The linearity in the linear range of 0.01–30 ng/mL and limits of detection from 0.003 ng/mL to 0.006 ng/mL were obtained by HS-SPME-GC-FID with PHCNs as fiber coating. The enrichment factors were calculated as 5420–9211 compared with conventional direct introduce analysis. The spiked recoveries of real samples including campus lake water and lime tree honey were obtained from 80.93% to 118.0% with relative standard deviation no higher than 10.6%. The π-π stacking interaction, CH/π interaction, and unique built-in cavities significantly enhance the extraction performance of PHCNs coating fiber to PAHs. This work demonstrated that the PHCNs as fiber coating materials present good application prospects for the extraction and enrichment of trace PAHs from complex matrixes.
The coating material is considered as the key of solid-phase microextraction (SPME) due to the fact that which has much effect on the selectivity and sensitivity of the analytical method. Herein, the porous hollow carbon nanospheres (PHCNs) were synthesized by selectively removing the interior part of solid inhomogeneous nanospheres with acetone. Using PHCNs as new coating material, a SPME fiber was prepared. To the best of our knowledge, PHCNs was utilized as a SPME fiber coating for the first time. The fiber coating material PHCNs demonstrated excellent thermal stability (> 800 ℃) and long usage lifespan (≥60 times). A headspace SPME (HS-SPME) was established to non-contact extract and enrich polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The HS-SPME not only can eliminate non-volatile interferences from matrix, but also be able to protect fiber coating and prolong lifespan of fiber prober. The linearity in the linear range of 0.01–30 ng/mL and limits of detection from 0.003 ng/mL to 0.006 ng/mL were obtained by HS-SPME-GC-FID with PHCNs as fiber coating. The enrichment factors were calculated as 5420–9211 compared with conventional direct introduce analysis. The spiked recoveries of real samples including campus lake water and lime tree honey were obtained from 80.93% to 118.0% with relative standard deviation no higher than 10.6%. The π-π stacking interaction, CH/π interaction, and unique built-in cavities significantly enhance the extraction performance of PHCNs coating fiber to PAHs. This work demonstrated that the PHCNs as fiber coating materials present good application prospects for the extraction and enrichment of trace PAHs from complex matrixes.
2025, 36(12): 111322
doi: 10.1016/j.cclet.2025.111322
摘要:
Photocatalytic hydrogen evolution is a promising method for sustainable fuel production, but the efficiency of metal-organic complexes (MOCs) as photocatalysts is often limited by their poor light absorption, rapid exciton recombination, and aggregation. To address these challenges, we encapsulated Pt-based MOCs within porphyrin-based metallacages, which not only prevent the aggregation of catalysts but also enable effective electron transfer from the photosensitive metallacages to the photocatalysts. The structures of the host-guest complexes were confirmed by single-crystal X-ray diffraction, and one complex achieved a hydrogen generation rate of 19,786.5 µmol g−1 h−1, which was among the highest values in metallacage-based photocatalytic systems. Femtosecond transient absorption and DFT calculations revealed that the enhanced performance is due to efficient photoinduced electron transfer from the porphyrin units to the Pt catalytic centers. This work demonstrates a new approach to integrating photosensitizers and photocatalysts via host-guest complexation, offering an effective pathway to improve photocatalytic hydrogen production.
Photocatalytic hydrogen evolution is a promising method for sustainable fuel production, but the efficiency of metal-organic complexes (MOCs) as photocatalysts is often limited by their poor light absorption, rapid exciton recombination, and aggregation. To address these challenges, we encapsulated Pt-based MOCs within porphyrin-based metallacages, which not only prevent the aggregation of catalysts but also enable effective electron transfer from the photosensitive metallacages to the photocatalysts. The structures of the host-guest complexes were confirmed by single-crystal X-ray diffraction, and one complex achieved a hydrogen generation rate of 19,786.5 µmol g−1 h−1, which was among the highest values in metallacage-based photocatalytic systems. Femtosecond transient absorption and DFT calculations revealed that the enhanced performance is due to efficient photoinduced electron transfer from the porphyrin units to the Pt catalytic centers. This work demonstrates a new approach to integrating photosensitizers and photocatalysts via host-guest complexation, offering an effective pathway to improve photocatalytic hydrogen production.
2025, 36(12): 111402
doi: 10.1016/j.cclet.2025.111402
摘要:
Herein, the Nd@g-C3N4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with RfSO2Cl under visible-light and ultrasound conditions was firstly reported. The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation. A wide range of N-heteroarenes, alkenes and RfSO2Cl, were well compatible for this reaction to access valuable fluoroalkylated N-heteroarenes with diverse structural features. The antitumor potential of synthesized fluoroalkylated N-heterocycles against Glioma 261 cells was evaluated by CCK8 assay. Notably, compound 4aka demonstrated remarkable efficacy, exhibiting approximately sevenfold greater potency than temozolomide, a widely used chemotherapeutic agent.
Herein, the Nd@g-C3N4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with RfSO2Cl under visible-light and ultrasound conditions was firstly reported. The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation. A wide range of N-heteroarenes, alkenes and RfSO2Cl, were well compatible for this reaction to access valuable fluoroalkylated N-heteroarenes with diverse structural features. The antitumor potential of synthesized fluoroalkylated N-heterocycles against Glioma 261 cells was evaluated by CCK8 assay. Notably, compound 4aka demonstrated remarkable efficacy, exhibiting approximately sevenfold greater potency than temozolomide, a widely used chemotherapeutic agent.
2025, 36(12): 111437
doi: 10.1016/j.cclet.2025.111437
摘要:
Direct seawater electrolysis is a promising way for hydrogen energy production. However, developing efficient and cost-effective electrocatalysts remains a significant challenge for seawater electrolysis with industrial-level current density due to high concentration of salts and compete reaction of chlorine evolution. Herein, a 1D NiFe2O4/NiMoO4 heterostructure as a bifunctional electrocatalyst for overall seawater splitting is constructed by combining NiMoO4 nanowires with NiFe2O4 nanoparticles on carbon felt (CF) by a simple hydrothermal, impregnation and calcination method. The electrocatalyst exhibits low overpotential of 237 and 292 mV for oxygen evolution reaction and hydrogen evolution reaction at 400 mA/cm2 in the alkaline seawater (1 mol/L KOH + 0.5 mol/L NaCl) due to the plentiful interfaces of NiFe2O4/NiMoO4 which exposes more active sites and expands the active surface area, thereby enhancing its intrinsic activity and promoting the reaction kinetics. Notably, it displays low voltages of 1.95 V to drive current density of 400 mA/cm2 in alkaline seawater with its excellent stability of 200 h at above 100 mA/cm2, exhibiting outstanding performance and good corrosion resistance. This work provides an effective strategy for constructing efficient and cost-effective electrocatalysts for industrial seawater electrolysis, underscoring its potential for sustainable energy applications.
Direct seawater electrolysis is a promising way for hydrogen energy production. However, developing efficient and cost-effective electrocatalysts remains a significant challenge for seawater electrolysis with industrial-level current density due to high concentration of salts and compete reaction of chlorine evolution. Herein, a 1D NiFe2O4/NiMoO4 heterostructure as a bifunctional electrocatalyst for overall seawater splitting is constructed by combining NiMoO4 nanowires with NiFe2O4 nanoparticles on carbon felt (CF) by a simple hydrothermal, impregnation and calcination method. The electrocatalyst exhibits low overpotential of 237 and 292 mV for oxygen evolution reaction and hydrogen evolution reaction at 400 mA/cm2 in the alkaline seawater (1 mol/L KOH + 0.5 mol/L NaCl) due to the plentiful interfaces of NiFe2O4/NiMoO4 which exposes more active sites and expands the active surface area, thereby enhancing its intrinsic activity and promoting the reaction kinetics. Notably, it displays low voltages of 1.95 V to drive current density of 400 mA/cm2 in alkaline seawater with its excellent stability of 200 h at above 100 mA/cm2, exhibiting outstanding performance and good corrosion resistance. This work provides an effective strategy for constructing efficient and cost-effective electrocatalysts for industrial seawater electrolysis, underscoring its potential for sustainable energy applications.
2025, 36(12): 111449
doi: 10.1016/j.cclet.2025.111449
摘要:
Constrained by severe bulk charge recombination, the actual photocurrent density of tantalum nitride (Ta3N5) photoanode is much lower than the theoretical maximum value. Herein, we report the doping of phosphorus, a non-metallic element distinct from oxygen, into Ta3N5, resulting in a photocurrent density 9 times higher than that of pristine Ta3N5. Systematic characterization reveals that the phosphorus doping simultaneously enhances the bulk charge separation efficiency and surface charge injection efficiency of Ta3N5, and induces favorable band energy restructuring. Specifically, a type-Ⅱ homojunction formed between phosphorus-doped near-surface region and bulk Ta3N5 effectively promotes the separation and transfer of photogenerated holes and electrons. Further modification with a NiFe-based cocatalyst enables the optimized photoanode to deliver a photocurrent density of 10 mA/cm2 at 1.23 V versus the reversible hydrogen electrode (RHE) and an applied bias photo-to-current efficiency of 1.78% at 0.95 V versus RHE. Our work provides a foundation for the development of a broader range of non-metal doped semiconductors.
Constrained by severe bulk charge recombination, the actual photocurrent density of tantalum nitride (Ta3N5) photoanode is much lower than the theoretical maximum value. Herein, we report the doping of phosphorus, a non-metallic element distinct from oxygen, into Ta3N5, resulting in a photocurrent density 9 times higher than that of pristine Ta3N5. Systematic characterization reveals that the phosphorus doping simultaneously enhances the bulk charge separation efficiency and surface charge injection efficiency of Ta3N5, and induces favorable band energy restructuring. Specifically, a type-Ⅱ homojunction formed between phosphorus-doped near-surface region and bulk Ta3N5 effectively promotes the separation and transfer of photogenerated holes and electrons. Further modification with a NiFe-based cocatalyst enables the optimized photoanode to deliver a photocurrent density of 10 mA/cm2 at 1.23 V versus the reversible hydrogen electrode (RHE) and an applied bias photo-to-current efficiency of 1.78% at 0.95 V versus RHE. Our work provides a foundation for the development of a broader range of non-metal doped semiconductors.
2025, 36(12): 111460
doi: 10.1016/j.cclet.2025.111460
摘要:
The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades. Nevertheless, the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge. Herein, we introduce a new dipyridinyl ligand L1 featuring two methoxy groups, which act as electron-donating species and provide electrons to the central benzene ring, resulting in an enhanced electron rich effect. Previous research indicates that this feature significantly contributes to forming π-stacking interactions. Furthermore, four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of [2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect. Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis, NMR spectroscopy, and ESI-TOF-MS. In addition, dynamic structural transformation between [2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect. Photothermal conversion abilities of the isolated complexes were studied and we observed that [2]catenane 3a displayed significant temperature changes (from 25.8 ℃ to 50.3 ℃) under laser irradiation of 1.5 W/cm2, thereby reaching a photothermal conversion efficiency of 40.42%. Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of [2]catenanes most likely generated photothermal conversion.
The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades. Nevertheless, the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge. Herein, we introduce a new dipyridinyl ligand L1 featuring two methoxy groups, which act as electron-donating species and provide electrons to the central benzene ring, resulting in an enhanced electron rich effect. Previous research indicates that this feature significantly contributes to forming π-stacking interactions. Furthermore, four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of [2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect. Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis, NMR spectroscopy, and ESI-TOF-MS. In addition, dynamic structural transformation between [2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect. Photothermal conversion abilities of the isolated complexes were studied and we observed that [2]catenane 3a displayed significant temperature changes (from 25.8 ℃ to 50.3 ℃) under laser irradiation of 1.5 W/cm2, thereby reaching a photothermal conversion efficiency of 40.42%. Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of [2]catenanes most likely generated photothermal conversion.
2025, 36(12): 111462
doi: 10.1016/j.cclet.2025.111462
摘要:
Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions. Herein, we investigated the cascade hydrolysis and intramolecular cyclization reactions of three guests with varying lengths within the well-defined nanocavities of cavitands in aqueous solution. Driven by hydrophobic effect, these guests were encapsulated within the dimeric capsules, adopting distinct conformations and orientations due to spatial constraints. Specifically, the shorter guest maintained an extended linear geometry, whereas the longer guests adopted a folded binding mode. Upon initiating the reaction, the terminal residue of the shorter guest displayed lower reactivity, while the longer guests, preorganized within the cavity, underwent efficient cyclization, resulting in significant differences in reaction kinetics. Furthermore, electrostatic potential fields played a critical role in modulating reaction rates, with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart, likely due to stabilization of the anionic transition state. This study provides an effective strategy for designing enzyme-mimetic nanoreactors through the utilization of well-defined nanospaces.
Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions. Herein, we investigated the cascade hydrolysis and intramolecular cyclization reactions of three guests with varying lengths within the well-defined nanocavities of cavitands in aqueous solution. Driven by hydrophobic effect, these guests were encapsulated within the dimeric capsules, adopting distinct conformations and orientations due to spatial constraints. Specifically, the shorter guest maintained an extended linear geometry, whereas the longer guests adopted a folded binding mode. Upon initiating the reaction, the terminal residue of the shorter guest displayed lower reactivity, while the longer guests, preorganized within the cavity, underwent efficient cyclization, resulting in significant differences in reaction kinetics. Furthermore, electrostatic potential fields played a critical role in modulating reaction rates, with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart, likely due to stabilization of the anionic transition state. This study provides an effective strategy for designing enzyme-mimetic nanoreactors through the utilization of well-defined nanospaces.
2025, 36(12): 111495
doi: 10.1016/j.cclet.2025.111495
摘要:
Aggregation-induced emission luminogens (AIEgens) exhibit viscosity-responsive behavior resembling those of molecular rotors; however, their response mechanisms are more complex and cannot be adequately described using simple rotational models. AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures. In this study, we synthesized water-soluble derivatives of representative AIEgens, including tetraphenylethene (TPE), bis(N, N-dialkylamino)anthracene (BDAA), and bridged stilbene, and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity. To elucidate the origin of their viscosity responsiveness, quantum chemical calculations were conducted to analyze their potential energy surfaces (PESs). The results revealed that compared to typical molecular rotors, these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions. Notably, for TPE and BDAA derivatives, the viscosity responsiveness was found to be governed not by the activation energy barrier (ΔEa) based on the PES, but rather by the viscosity-dependent constraints on molecular structural changes. Furthermore, molecules possessing multiple aromatic rings or large, flexible, rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions. This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens, thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscosity-sensitive probes.
Aggregation-induced emission luminogens (AIEgens) exhibit viscosity-responsive behavior resembling those of molecular rotors; however, their response mechanisms are more complex and cannot be adequately described using simple rotational models. AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures. In this study, we synthesized water-soluble derivatives of representative AIEgens, including tetraphenylethene (TPE), bis(N, N-dialkylamino)anthracene (BDAA), and bridged stilbene, and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity. To elucidate the origin of their viscosity responsiveness, quantum chemical calculations were conducted to analyze their potential energy surfaces (PESs). The results revealed that compared to typical molecular rotors, these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions. Notably, for TPE and BDAA derivatives, the viscosity responsiveness was found to be governed not by the activation energy barrier (ΔEa) based on the PES, but rather by the viscosity-dependent constraints on molecular structural changes. Furthermore, molecules possessing multiple aromatic rings or large, flexible, rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions. This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens, thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscosity-sensitive probes.
2025, 36(12): 111540
doi: 10.1016/j.cclet.2025.111540
摘要:
Synchronously achieving morphological and electronic engineering control is crucial but challenging for enhancing the oxygen evolution reaction (OER) performance of nickel-iron based catalysts. Herein, a ruthenium and sulfur co-modified nickel-iron hydroxide (SARuT-FeNiOHx-5h) was synthesized by a distributed room-temperature impregnation method. It was found that the solubility product difference between ruthenium and nickel-iron hydroxide can promote the rapid nucleation of the catalyst and form finer nanosheet structures, thereby increasing 1.25 times for the contact area between the catalyst and the electrolyte. Meanwhile, the subsequent deposition of sulfur can act as an electronic modulator, promoting the transfer of surface charge at nickel sites and increasing the oxidation state of nickel. Theoretical calculations indicate that the combination of ruthenium and sulfur can effectively optimize the OER reaction pathway and lower the activation energy barrier of the rate-determining step, endowing SARuT-FeNiOHx-5h an excellent OER performance with a low overpotential of 253 mV at 1000 mA/cm2 and long-term stability (500 h). In the future, it is hoped that this strategy of synergistic control of morphology and electronic structure can be applied to the development of other highly active catalysts.
Synchronously achieving morphological and electronic engineering control is crucial but challenging for enhancing the oxygen evolution reaction (OER) performance of nickel-iron based catalysts. Herein, a ruthenium and sulfur co-modified nickel-iron hydroxide (SARuT-FeNiOHx-5h) was synthesized by a distributed room-temperature impregnation method. It was found that the solubility product difference between ruthenium and nickel-iron hydroxide can promote the rapid nucleation of the catalyst and form finer nanosheet structures, thereby increasing 1.25 times for the contact area between the catalyst and the electrolyte. Meanwhile, the subsequent deposition of sulfur can act as an electronic modulator, promoting the transfer of surface charge at nickel sites and increasing the oxidation state of nickel. Theoretical calculations indicate that the combination of ruthenium and sulfur can effectively optimize the OER reaction pathway and lower the activation energy barrier of the rate-determining step, endowing SARuT-FeNiOHx-5h an excellent OER performance with a low overpotential of 253 mV at 1000 mA/cm2 and long-term stability (500 h). In the future, it is hoped that this strategy of synergistic control of morphology and electronic structure can be applied to the development of other highly active catalysts.
2025, 36(12): 111621
doi: 10.1016/j.cclet.2025.111621
摘要:
Poly(heptazine imide) (PHI), a new allotrope of heptazine-based carbon nitride, is usually synthesized in the presence of binary molten salts (e.g., LiCl/NaCl, LiCl/KCl, NaCl/KCl) with diverse melting points and solvation abilities. However, the quantum efficiency of PHI for photocatalytic hydrogen production is still extremely restrained. Herein, a series of ternary molten salt mixtures (LiCl/NaCl/KCl) with varying compositions and properties, were employed for the rational control of the polymerization process of PHI and thus optimization in the optical properties, charge separation behaviors, and also photocatalytic performance. The results indicate that the ternary molten salts provide suitable environment for the development of a nanorod morphology, which significantly improves separation of photo-induced charge carriers. Hence, the optimized PHI presents a high apparent quantum yield (AQY = 52.9%) for visible-light driven hydrogen production.
Poly(heptazine imide) (PHI), a new allotrope of heptazine-based carbon nitride, is usually synthesized in the presence of binary molten salts (e.g., LiCl/NaCl, LiCl/KCl, NaCl/KCl) with diverse melting points and solvation abilities. However, the quantum efficiency of PHI for photocatalytic hydrogen production is still extremely restrained. Herein, a series of ternary molten salt mixtures (LiCl/NaCl/KCl) with varying compositions and properties, were employed for the rational control of the polymerization process of PHI and thus optimization in the optical properties, charge separation behaviors, and also photocatalytic performance. The results indicate that the ternary molten salts provide suitable environment for the development of a nanorod morphology, which significantly improves separation of photo-induced charge carriers. Hence, the optimized PHI presents a high apparent quantum yield (AQY = 52.9%) for visible-light driven hydrogen production.
2025, 36(12): 111646
doi: 10.1016/j.cclet.2025.111646
摘要:
The construction of electrocatalysts with exceptional intrinsic activity and rich active sites has proven to be an effective strategy for remarkably enhancing the activity of the hydrogen evolution reaction (HER). Here, self-supporting cerium (Ce) and nitrogen (N)-doped rhenium disulfide nanosheets (denoted Ce, N-ReS2) grown on carbon fiber paper have been successfully synthesized. Ce and N doping modulates the lattice irregularity and adjusts the electronic configuration of rhenium disulfide, resulting in reduced hydrogen adsorption/desorption energy and enhanced catalytic stability. The optimized Ce, N-ReS2 electrocatalysts exhibit superior catalytic activities of 44/130 and 79/139 mV at 10/100 mA/cm2 for HER in alkaline and acidic media, respectively, along with robust durability. Both experimental results and density functional theory calculations indicate that the electronic structure of ReS2 can be significantly altered by strategically incorporating Ce and N into the lattice, which in turn optimizes the Gibbs free energy of HER intermediates and accelerates the electrochemical kinetics. This study provides a potentially effective approach for the design and optimization of innovative electrocatalysts involving the regulation of anion and cation dual-doping and architectural engineering.
The construction of electrocatalysts with exceptional intrinsic activity and rich active sites has proven to be an effective strategy for remarkably enhancing the activity of the hydrogen evolution reaction (HER). Here, self-supporting cerium (Ce) and nitrogen (N)-doped rhenium disulfide nanosheets (denoted Ce, N-ReS2) grown on carbon fiber paper have been successfully synthesized. Ce and N doping modulates the lattice irregularity and adjusts the electronic configuration of rhenium disulfide, resulting in reduced hydrogen adsorption/desorption energy and enhanced catalytic stability. The optimized Ce, N-ReS2 electrocatalysts exhibit superior catalytic activities of 44/130 and 79/139 mV at 10/100 mA/cm2 for HER in alkaline and acidic media, respectively, along with robust durability. Both experimental results and density functional theory calculations indicate that the electronic structure of ReS2 can be significantly altered by strategically incorporating Ce and N into the lattice, which in turn optimizes the Gibbs free energy of HER intermediates and accelerates the electrochemical kinetics. This study provides a potentially effective approach for the design and optimization of innovative electrocatalysts involving the regulation of anion and cation dual-doping and architectural engineering.
2025, 36(12): 111647
doi: 10.1016/j.cclet.2025.111647
摘要:
Orthodontic appliances are essential for dentofacial deformity corrections. However, orthodontic appliances inadvertently increase the risk of bacterial colonization and dental calculus formation, which may lead to dental caries and gingivitis. Herein, this study developed a pH-responsive antifouling coating by integrating a zwitterionic hydrogel (ZH) with pH-responsive microcapsules (PRMs) encapsulating bactericide, displaying excellent synergies of anti-bacteria and anti-calculus for orthodontic appliances. The excellent antifouling properties can be attributed to two following points: ZH provides anti-adhesion properties via electrostatically induced hydration layers, while the PRMs can kill bacteria by on-demand bactericide release under acidic conditions. Results demonstrated that ZH+PRMs coating significantly reduced bacterial adhesion and inhibited calculus formation while maintaining excellent biocompatibility. By optimizing PRMs concentrations (0–15 wt%), compared with ZH, the antibacterial efficiency of ZH+PRMs (optimal concentration 10 wt%) increased from 49.8% ± 7.3% to 95.2% ± 1.1% for E. coli and from 85.7% ± 3.5% to 91.3% ± 1.4% for S. mutans. Compared with pristine steel (SS), ZH+PRMs coating showed ca. 97.0% reduction for calcium carbonate and ca. 87.3% reduction for calcium phosphate. In an in vitro model, compared with SS, our coating extended the crystal biofilm inhibition effect from one day to five days. Therefore, this study can provide promising strategies for reducing the risk of dental caries and gingivitis during orthodontic treatment.
Orthodontic appliances are essential for dentofacial deformity corrections. However, orthodontic appliances inadvertently increase the risk of bacterial colonization and dental calculus formation, which may lead to dental caries and gingivitis. Herein, this study developed a pH-responsive antifouling coating by integrating a zwitterionic hydrogel (ZH) with pH-responsive microcapsules (PRMs) encapsulating bactericide, displaying excellent synergies of anti-bacteria and anti-calculus for orthodontic appliances. The excellent antifouling properties can be attributed to two following points: ZH provides anti-adhesion properties via electrostatically induced hydration layers, while the PRMs can kill bacteria by on-demand bactericide release under acidic conditions. Results demonstrated that ZH+PRMs coating significantly reduced bacterial adhesion and inhibited calculus formation while maintaining excellent biocompatibility. By optimizing PRMs concentrations (0–15 wt%), compared with ZH, the antibacterial efficiency of ZH+PRMs (optimal concentration 10 wt%) increased from 49.8% ± 7.3% to 95.2% ± 1.1% for E. coli and from 85.7% ± 3.5% to 91.3% ± 1.4% for S. mutans. Compared with pristine steel (SS), ZH+PRMs coating showed ca. 97.0% reduction for calcium carbonate and ca. 87.3% reduction for calcium phosphate. In an in vitro model, compared with SS, our coating extended the crystal biofilm inhibition effect from one day to five days. Therefore, this study can provide promising strategies for reducing the risk of dental caries and gingivitis during orthodontic treatment.
2025, 36(12): 111658
doi: 10.1016/j.cclet.2025.111658
摘要:
The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction (OER/HER) electrocatalysts; customarily catalyzed by platinum (Pt) and ruthenium/iridium oxides (RuO2/IrO2). In this work, we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO2 with Pt. Pt dopants in ruthenium oxides (Pt-RuO2) create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates, evidenced by downshifted d band center and increment in eg orbital filling of Ru atom; thereby, the acidic OER performance of Pt-RuO2 is enhanced by 3.5-fold than commercial RuO2 by mean of turnover frequency at 1.6 V vs. RHE. Moreover, Pt-RuO2 exhibits a similar HER performance to commercial Pt/C. The potential for overall water splitting is decreased by 0.18 V at 100 mA/cm2; besides, an excellent stability is also recorded after the incorporation of Pt dopants. The Δεd-p value of Pt-RuO2 was 1.76 eV, which is lower than the counterpart of RuO2, suggesting easy electron transition between d and p orbitals, suppressing the over-oxidation of RuO2; thereby, a higher stability is achieved for Pt-RuO2. The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO2.
The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction (OER/HER) electrocatalysts; customarily catalyzed by platinum (Pt) and ruthenium/iridium oxides (RuO2/IrO2). In this work, we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO2 with Pt. Pt dopants in ruthenium oxides (Pt-RuO2) create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates, evidenced by downshifted d band center and increment in eg orbital filling of Ru atom; thereby, the acidic OER performance of Pt-RuO2 is enhanced by 3.5-fold than commercial RuO2 by mean of turnover frequency at 1.6 V vs. RHE. Moreover, Pt-RuO2 exhibits a similar HER performance to commercial Pt/C. The potential for overall water splitting is decreased by 0.18 V at 100 mA/cm2; besides, an excellent stability is also recorded after the incorporation of Pt dopants. The Δεd-p value of Pt-RuO2 was 1.76 eV, which is lower than the counterpart of RuO2, suggesting easy electron transition between d and p orbitals, suppressing the over-oxidation of RuO2; thereby, a higher stability is achieved for Pt-RuO2. The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO2.
2025, 36(12): 111662
doi: 10.1016/j.cclet.2025.111662
摘要:
Layered sodium cobaltate (NaxCoO2), characterized by CoO2 slabs and intralayer edge-shared CoO6 octahedra, holds promising potential as an electrocatalyst for chlorine evolution reaction (CER). However, the suboptimal adsorption of the intermediate on NaxCoO2 resulted in unsatisfactory activity. Herein, NaxCoO2 flakes with varying sodium densities (x = 0.6, 0.7, 0.9) were engineered for efficient CER. Excitingly, the optimal Na0.7CoO2 achieves an ultralow overpotential (55.47 mV) outperforming commercial RuO2 at 10 mA/cm2, while remaining inactive toward the competing OER. Experimental and theoretical calculations demonstrate that appropriate interlayer sodium density has optimized the d-band center level of Co atoms in NaxCoO2, thereby weakening the strength of Co-Cl bonds. This modulation facilitates the adsorption-desorption equilibrium of Cl species (∆GCl* = -0.109 eV) on the surface and kinetically accelerating Cl2 release. This work is anticipated to elucidate the mechanism by which interlayer sodium density modifies the catalytic performance of NaxCoO2, and present new insights for the rational design of advanced CER electrocatalysts.
Layered sodium cobaltate (NaxCoO2), characterized by CoO2 slabs and intralayer edge-shared CoO6 octahedra, holds promising potential as an electrocatalyst for chlorine evolution reaction (CER). However, the suboptimal adsorption of the intermediate on NaxCoO2 resulted in unsatisfactory activity. Herein, NaxCoO2 flakes with varying sodium densities (x = 0.6, 0.7, 0.9) were engineered for efficient CER. Excitingly, the optimal Na0.7CoO2 achieves an ultralow overpotential (55.47 mV) outperforming commercial RuO2 at 10 mA/cm2, while remaining inactive toward the competing OER. Experimental and theoretical calculations demonstrate that appropriate interlayer sodium density has optimized the d-band center level of Co atoms in NaxCoO2, thereby weakening the strength of Co-Cl bonds. This modulation facilitates the adsorption-desorption equilibrium of Cl species (∆GCl* = -0.109 eV) on the surface and kinetically accelerating Cl2 release. This work is anticipated to elucidate the mechanism by which interlayer sodium density modifies the catalytic performance of NaxCoO2, and present new insights for the rational design of advanced CER electrocatalysts.
2025, 36(12): 111716
doi: 10.1016/j.cclet.2025.111716
摘要:
Intrinsically stretchable semiconducting polymers play a vital role in the development of wearable electronics, featuring low-cost, large-area and high-density fabrication. Only single-stage dynamic chemical bond has been widely incorporated into polymer backbones to afford stretchability while multiple dynamic bonds have not been investigated, making a formidable challenge to achieve high stretchability without compromising charge transport properties. Herein, we synthesize a series of stretchable polymer semiconductors incorporating urethane and bipyridine units, which can provide dynamic interconnected polymer network by combination of hydrogen bonds with metal coordination, simultaneously obtaining excellent stretchability and carrier mobilities. Compared with single-stage hydrogen bonds, multiple dynamic chemical bonds constructed by 10% hydrogen bonds and 0.25 equiv. metal coordination endowed the polymer semiconductors with an 58% enhancement in carrier mobility and a two-fold increase in crack-onset strain. Notably, the polymer exhibited stable carrier mobilities parallel to the stretching direction, with 91% of initial values even under 150% strain, which is the unprecedented value for intrinsically stretchable semiconducting polymers without blending of elastomers. Therefore, the introduction of multiple dynamic bonds provides an effective and promising approach for intrinsically stretchable and high-performance polymer semiconductor.
Intrinsically stretchable semiconducting polymers play a vital role in the development of wearable electronics, featuring low-cost, large-area and high-density fabrication. Only single-stage dynamic chemical bond has been widely incorporated into polymer backbones to afford stretchability while multiple dynamic bonds have not been investigated, making a formidable challenge to achieve high stretchability without compromising charge transport properties. Herein, we synthesize a series of stretchable polymer semiconductors incorporating urethane and bipyridine units, which can provide dynamic interconnected polymer network by combination of hydrogen bonds with metal coordination, simultaneously obtaining excellent stretchability and carrier mobilities. Compared with single-stage hydrogen bonds, multiple dynamic chemical bonds constructed by 10% hydrogen bonds and 0.25 equiv. metal coordination endowed the polymer semiconductors with an 58% enhancement in carrier mobility and a two-fold increase in crack-onset strain. Notably, the polymer exhibited stable carrier mobilities parallel to the stretching direction, with 91% of initial values even under 150% strain, which is the unprecedented value for intrinsically stretchable semiconducting polymers without blending of elastomers. Therefore, the introduction of multiple dynamic bonds provides an effective and promising approach for intrinsically stretchable and high-performance polymer semiconductor.
2025, 36(12): 111795
doi: 10.1016/j.cclet.2025.111795
摘要:
Herein, we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte. This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated N-heteroarenes, features high atom- and step-economy, excellent energy efficiency, operational simplicity, good functional group tolerance, mild conditions and no requirement of sacrifice reagent and base additive. Importantly, the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment. We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.
Herein, we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte. This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated N-heteroarenes, features high atom- and step-economy, excellent energy efficiency, operational simplicity, good functional group tolerance, mild conditions and no requirement of sacrifice reagent and base additive. Importantly, the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment. We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.
2025, 36(12): 111809
doi: 10.1016/j.cclet.2025.111809
摘要:
The uncontrollable dendrite growth of lithium anode and active material dissolution of transition metal oxides cathodes severely hinder the development of lithium metal batteries. An effective strategy to address these issues is optimizing the separator to regulate ion transport and trap the lost active component. Herein, a crosslinked gelatin nonwoven (CGN) separator is elaborately fabricated through electrospinning and in-situ vapor phase crosslinking process to manipulate the dual electrode interface. Benefitting from the characteristic composition of gelatin, and porous structure of electrospun nonwoven, the CGN separator exhibits excellent interface wettability and low interface resistance, featuring a high Li+ transference number of 0.70 and high ionic conductivity of 3.75 mS/cm. As expected, the symmetrical Li/Li cells present stable cycling behavior for 1900 h at 0.5 mA/cm2 with low overpotential of 20 mV. The optimized LiMn2O4/Li cells deliver high reversible capacity of 103 mAh/g as well as high capacity-retention ratio of 83.7% after 100 cycles at 0.3 C, which can be effectively attributed to the strong interaction between CGN separator and Mn ions to prevent the loss of active Mn component. This study indicates the application potential of protein-based electrospun membrane for high-performance lithium metal batteries.
The uncontrollable dendrite growth of lithium anode and active material dissolution of transition metal oxides cathodes severely hinder the development of lithium metal batteries. An effective strategy to address these issues is optimizing the separator to regulate ion transport and trap the lost active component. Herein, a crosslinked gelatin nonwoven (CGN) separator is elaborately fabricated through electrospinning and in-situ vapor phase crosslinking process to manipulate the dual electrode interface. Benefitting from the characteristic composition of gelatin, and porous structure of electrospun nonwoven, the CGN separator exhibits excellent interface wettability and low interface resistance, featuring a high Li+ transference number of 0.70 and high ionic conductivity of 3.75 mS/cm. As expected, the symmetrical Li/Li cells present stable cycling behavior for 1900 h at 0.5 mA/cm2 with low overpotential of 20 mV. The optimized LiMn2O4/Li cells deliver high reversible capacity of 103 mAh/g as well as high capacity-retention ratio of 83.7% after 100 cycles at 0.3 C, which can be effectively attributed to the strong interaction between CGN separator and Mn ions to prevent the loss of active Mn component. This study indicates the application potential of protein-based electrospun membrane for high-performance lithium metal batteries.
2025, 36(12): 110574
doi: 10.1016/j.cclet.2024.110574
摘要:
Sodium-ion batteries (SIBs) are the promising rechargeable batteries in large-scale energy storage systems for their low cost, high safety, wide temperature range adaptability, environmental friendliness and excellent fast-charging capabilities. Significant research endeavors in SIBs have focused on the exploration of high-performance electrode materials and thorough investigation of their mechanisms. Na2FePO4F (NFPF) is one of potential cathode materials because of low cost, minimal volume strain and extended cycle performance. This review summarizes the crystal structure, sodium ion migration pathways, and synthesis methods of NFPF and discusses the effect of various strategies including hybridization with carbon materials, ion doping, morphology control and electrolyte optimization on its electrochemical performance. Additionally, the application of the NFPF in different batteries is summarized. Finally, the challenges and future directions of NFPF are proposed. This review is both timely and important for promoting the applications of cost-effective NFPF.
Sodium-ion batteries (SIBs) are the promising rechargeable batteries in large-scale energy storage systems for their low cost, high safety, wide temperature range adaptability, environmental friendliness and excellent fast-charging capabilities. Significant research endeavors in SIBs have focused on the exploration of high-performance electrode materials and thorough investigation of their mechanisms. Na2FePO4F (NFPF) is one of potential cathode materials because of low cost, minimal volume strain and extended cycle performance. This review summarizes the crystal structure, sodium ion migration pathways, and synthesis methods of NFPF and discusses the effect of various strategies including hybridization with carbon materials, ion doping, morphology control and electrolyte optimization on its electrochemical performance. Additionally, the application of the NFPF in different batteries is summarized. Finally, the challenges and future directions of NFPF are proposed. This review is both timely and important for promoting the applications of cost-effective NFPF.
2025, 36(12): 110577
doi: 10.1016/j.cclet.2024.110577
摘要:
The dynamic regulation of single-molecule magnet (SMM) behavior remains challenging but extremely critical to practical applications. Efficient manipulation of magnetization of complexes via external stimulus, like solvent, pressure, electric potential or light may further extend the scope of applications for these magnetic molecules. Among these, light is highly desirable because it can provide high-contrast, sensitive and remote control of magnetic behavior at relatively high spatial and temporal resolution. Lanthanide (Ln) complexes represent a distinctive platform for constructing photo-responsive SMMs owing to their extreme sensitivity to subtle change of crystal field (CF) environment. Despite the numerous potential benefits and unique advantages outlined above, light control of magnetism of Ln-SMMs still faces several challenges. This review briefly summarizes recent advancements of photo-responsive Ln-SMMs with photochromic characteristic, highlighting the significance of photoinduced structural changes or electronic distribution alterations to modulate the magnetic properties, which may throw light on the future improvements of photo-responsive molecular materials.
The dynamic regulation of single-molecule magnet (SMM) behavior remains challenging but extremely critical to practical applications. Efficient manipulation of magnetization of complexes via external stimulus, like solvent, pressure, electric potential or light may further extend the scope of applications for these magnetic molecules. Among these, light is highly desirable because it can provide high-contrast, sensitive and remote control of magnetic behavior at relatively high spatial and temporal resolution. Lanthanide (Ln) complexes represent a distinctive platform for constructing photo-responsive SMMs owing to their extreme sensitivity to subtle change of crystal field (CF) environment. Despite the numerous potential benefits and unique advantages outlined above, light control of magnetism of Ln-SMMs still faces several challenges. This review briefly summarizes recent advancements of photo-responsive Ln-SMMs with photochromic characteristic, highlighting the significance of photoinduced structural changes or electronic distribution alterations to modulate the magnetic properties, which may throw light on the future improvements of photo-responsive molecular materials.
2025, 36(12): 110603
doi: 10.1016/j.cclet.2024.110603
摘要:
The rising level of CO2 concentration in the atmosphere poses major threats to the global climate and environment. Various technologies have been developed to mitigate its negative effects through non-conversion and conversion routes. Particularly, solid oxide electrolysis cells (SOECs), as a promising technology with the highest energy efficiency, have garnered considerable attention for their effectiveness to electrochemically convert CO2 into high-value fuels. However, the insufficient catalytic activity, poor long-term stability, and high costs have significantly hindered the industrial-scale application of SOECs. To this end, substantial efforts, with an emphasis on the smart design of targeting electrode materials for specific applications have been devoted to advancing the electrosynthesis of high-value fuels from CO2 in various SOECs, but there still lacks a critical and comprehensive review in-depth discussing the fundamentals, and summarizing the latest advances in various applications and electrode materials for electrochemically converting CO2 to high-value fuels in SOECs. This review thus aims to fill this gap by focusing on the fundamentals (i.e., SOEC working principles, thermodynamics, kinetics and representative evaluation parameters), specific applications (i.e., pure CO2 electrolysis, CO2-H2O co-electrolysis, fuel-assisted CO2 conversion), and material selection criteria (i.e., cathodic materials for CO2 conversion, and anodic materials for fuel-assisted CO2 conversion). In addition, the challenges that this technology is currently facing, and our perspectives on electrochemical CO2 conversion in SOECs are proposed to guide the smart design of high-performance electrocatalysts and future industrial-scale application of SOECs for electrosynthesizing high-value fuels from CO2.
The rising level of CO2 concentration in the atmosphere poses major threats to the global climate and environment. Various technologies have been developed to mitigate its negative effects through non-conversion and conversion routes. Particularly, solid oxide electrolysis cells (SOECs), as a promising technology with the highest energy efficiency, have garnered considerable attention for their effectiveness to electrochemically convert CO2 into high-value fuels. However, the insufficient catalytic activity, poor long-term stability, and high costs have significantly hindered the industrial-scale application of SOECs. To this end, substantial efforts, with an emphasis on the smart design of targeting electrode materials for specific applications have been devoted to advancing the electrosynthesis of high-value fuels from CO2 in various SOECs, but there still lacks a critical and comprehensive review in-depth discussing the fundamentals, and summarizing the latest advances in various applications and electrode materials for electrochemically converting CO2 to high-value fuels in SOECs. This review thus aims to fill this gap by focusing on the fundamentals (i.e., SOEC working principles, thermodynamics, kinetics and representative evaluation parameters), specific applications (i.e., pure CO2 electrolysis, CO2-H2O co-electrolysis, fuel-assisted CO2 conversion), and material selection criteria (i.e., cathodic materials for CO2 conversion, and anodic materials for fuel-assisted CO2 conversion). In addition, the challenges that this technology is currently facing, and our perspectives on electrochemical CO2 conversion in SOECs are proposed to guide the smart design of high-performance electrocatalysts and future industrial-scale application of SOECs for electrosynthesizing high-value fuels from CO2.
2025, 36(12): 110921
doi: 10.1016/j.cclet.2025.110921
摘要:
Immune evasion is a hallmark of cancer. Recent advancements suggest that targeting cholesterol metabolism to regulate stimulator of interferon genes (STING) signaling offers a promising approach to overcome this challenge. While STING pathway activation is critical for enhancing anti-tumor immunity, its excessive or prolonged activation can lead to chronic inflammation and immune suppression. This review examines how cholesterol-lowering nanomedicines can balance STING activation to promote effective immune responses. Nanoparticles (NPs) enable precise delivery of cholesterol-lowering agents, reducing chronic STING activation and transforming the tumor microenvironment (TME) into an immunostimulatory state. Furthermore, NPs can co-deliver STING agonists to synergize innate immune activation, providing enhanced anti-tumor responses while mitigating the risks of inflammation. By integrating cholesterol metabolism modulation with advanced nanotechnologies, this approach holds significant translational potential for developing next-generation immunotherapies. Future research should focus on optimizing NP design and exploring combination strategies with existing cancer immunotherapies to improve clinical outcomes and address immune resistance.
Immune evasion is a hallmark of cancer. Recent advancements suggest that targeting cholesterol metabolism to regulate stimulator of interferon genes (STING) signaling offers a promising approach to overcome this challenge. While STING pathway activation is critical for enhancing anti-tumor immunity, its excessive or prolonged activation can lead to chronic inflammation and immune suppression. This review examines how cholesterol-lowering nanomedicines can balance STING activation to promote effective immune responses. Nanoparticles (NPs) enable precise delivery of cholesterol-lowering agents, reducing chronic STING activation and transforming the tumor microenvironment (TME) into an immunostimulatory state. Furthermore, NPs can co-deliver STING agonists to synergize innate immune activation, providing enhanced anti-tumor responses while mitigating the risks of inflammation. By integrating cholesterol metabolism modulation with advanced nanotechnologies, this approach holds significant translational potential for developing next-generation immunotherapies. Future research should focus on optimizing NP design and exploring combination strategies with existing cancer immunotherapies to improve clinical outcomes and address immune resistance.
2025, 36(12): 110943
doi: 10.1016/j.cclet.2025.110943
摘要:
The intricate pathological mechanisms of ischemia-reperfusion injury (IRI) are intimately associated with the imbalance of metabolic substance supply and demand. Investigation of the fluctuated molecules reveals the progression of reperfusion injury, facilitating earlier diagnosis and treatments. Fluorescence imaging is a powerful technique in fluorescent optical diagnosis, essential for detecting biomarker levels both in vitro and in vivo. By integrating multifunctional scaffolds with specific recognition groups, small-molecule fluorescent probes (SMFPs) effectively monitor biomarkers related to IRI, providing valuable insights into pathological mechanisms and enhancing early diagnostic capabilities. This review systemically summarizes the recent developments of SMFPs, focusing on design strategies and their applications in the main types of IRI. Furthermore, we discuss the challenges and propose prospects based on existing SMFP applications in this area. We aim to provide a comprehensive analysis of SMFPs for disease diagnosis and inspire researchers to further innovate and develop effective tools for clinical applications.
The intricate pathological mechanisms of ischemia-reperfusion injury (IRI) are intimately associated with the imbalance of metabolic substance supply and demand. Investigation of the fluctuated molecules reveals the progression of reperfusion injury, facilitating earlier diagnosis and treatments. Fluorescence imaging is a powerful technique in fluorescent optical diagnosis, essential for detecting biomarker levels both in vitro and in vivo. By integrating multifunctional scaffolds with specific recognition groups, small-molecule fluorescent probes (SMFPs) effectively monitor biomarkers related to IRI, providing valuable insights into pathological mechanisms and enhancing early diagnostic capabilities. This review systemically summarizes the recent developments of SMFPs, focusing on design strategies and their applications in the main types of IRI. Furthermore, we discuss the challenges and propose prospects based on existing SMFP applications in this area. We aim to provide a comprehensive analysis of SMFPs for disease diagnosis and inspire researchers to further innovate and develop effective tools for clinical applications.
2025, 36(12): 110944
doi: 10.1016/j.cclet.2025.110944
摘要:
Ice-assisted synthesis is a facile, effective, and eco-friendly approach for preparing environmental functional materials. The quasi-liquid layer (QLL) or ice grain boundary (IGB) of the ice provides ideal interface-confined environments for preparing two-dimensional (2D) sheet-like, three-dimensional (3D) hierarchical porous, polymeric hybrid, and atomically dispersed materials via the in-situ interfacial chemical reactions. Ice-templating physical pretreatment allows directional assembly of preformed materials, sheet exfoliation from bulk materials, transfer or cleaning of 2D materials, uniform dispersion of precursors, and self-assembly of nanoparticles. Additionally, the ice-melting process offers a novel way to prepare nanomaterials of uniform size due to the ultraslow release of reactants from the ice crystals. Furthermore, environmental applications of ice-assisted synthetic materials have been concluded. Advanced membrane materials synthesized based on ice chemistry exhibit superior water permeance, ion selectivity, and disinfection. Also, ice-assisted synthesis has innate advantages for designing environmental functional catalysts or adsorbents dedicated to environmental remediation. Finally, the challenges of the current progress in this field are discussed.
Ice-assisted synthesis is a facile, effective, and eco-friendly approach for preparing environmental functional materials. The quasi-liquid layer (QLL) or ice grain boundary (IGB) of the ice provides ideal interface-confined environments for preparing two-dimensional (2D) sheet-like, three-dimensional (3D) hierarchical porous, polymeric hybrid, and atomically dispersed materials via the in-situ interfacial chemical reactions. Ice-templating physical pretreatment allows directional assembly of preformed materials, sheet exfoliation from bulk materials, transfer or cleaning of 2D materials, uniform dispersion of precursors, and self-assembly of nanoparticles. Additionally, the ice-melting process offers a novel way to prepare nanomaterials of uniform size due to the ultraslow release of reactants from the ice crystals. Furthermore, environmental applications of ice-assisted synthetic materials have been concluded. Advanced membrane materials synthesized based on ice chemistry exhibit superior water permeance, ion selectivity, and disinfection. Also, ice-assisted synthesis has innate advantages for designing environmental functional catalysts or adsorbents dedicated to environmental remediation. Finally, the challenges of the current progress in this field are discussed.
2025, 36(12): 110963
doi: 10.1016/j.cclet.2025.110963
摘要:
Interleukin-1 receptor-associated kinase 4 (IRAK4) is a key kinase downstream of the interleukin-1 receptor (IL-1R) and Toll-like receptors (TLRs) signaling pathway, whose overexpression and hyperactivation have been associated with several inflammatory diseases or cancer. Therefore, targeting IRAK4 has emerged as a promising therapeutic strategy. A range of potent and selective IRAK4 inhibitors and degraders based on draggability have been designed and developed. This article provides a comprehensive summary of the IRAK4 inhibitors and degraders that have been developed and discusses the challenges and opportunities for research in this area.
Interleukin-1 receptor-associated kinase 4 (IRAK4) is a key kinase downstream of the interleukin-1 receptor (IL-1R) and Toll-like receptors (TLRs) signaling pathway, whose overexpression and hyperactivation have been associated with several inflammatory diseases or cancer. Therefore, targeting IRAK4 has emerged as a promising therapeutic strategy. A range of potent and selective IRAK4 inhibitors and degraders based on draggability have been designed and developed. This article provides a comprehensive summary of the IRAK4 inhibitors and degraders that have been developed and discusses the challenges and opportunities for research in this area.
2025, 36(12): 110994
doi: 10.1016/j.cclet.2025.110994
摘要:
Renal cell carcinoma (RCC) as one of the most commonly diagnosed cancers threatens human health. The treatment of RCC demands more advanced protocols for better prognosis and higher quality of life. In recent years, the blooming of nanomaterials in various fields demonstrates its critical role as one of the most important components in constructing a smart therapeutic platform against RCC. Herein, focusing on the therapeutic inorganic nanomaterials (such as carbon nanomaterials, metal nanomaterials, oxide nanomaterials), their functions as drug carriers, external field sensitizers, and/or RCC microenvironment sensitizers are analyzed. In combination with the advantages of nanomaterial and RCC characteristics, the trends in integrating nanomaterial to construct multifunctional theranostic platforms for RCC treatment are highlighted. Also, possible solutions concerning the life trajectory and long-term toxicity of nanomaterials are put forward. These perspectives may promote the development of smarter and more effective systems for comprehensive RCC treatment.
Renal cell carcinoma (RCC) as one of the most commonly diagnosed cancers threatens human health. The treatment of RCC demands more advanced protocols for better prognosis and higher quality of life. In recent years, the blooming of nanomaterials in various fields demonstrates its critical role as one of the most important components in constructing a smart therapeutic platform against RCC. Herein, focusing on the therapeutic inorganic nanomaterials (such as carbon nanomaterials, metal nanomaterials, oxide nanomaterials), their functions as drug carriers, external field sensitizers, and/or RCC microenvironment sensitizers are analyzed. In combination with the advantages of nanomaterial and RCC characteristics, the trends in integrating nanomaterial to construct multifunctional theranostic platforms for RCC treatment are highlighted. Also, possible solutions concerning the life trajectory and long-term toxicity of nanomaterials are put forward. These perspectives may promote the development of smarter and more effective systems for comprehensive RCC treatment.
2025, 36(12): 110995
doi: 10.1016/j.cclet.2025.110995
摘要:
Recent insights into the immune landscape of the brain tumor microenvironment shed new light on immunotherapy for various brain tumors. This study provides comprehensive overviews of the development trends of immunotherapy for four common brain tumors (brain metastasis, glioma, meningioma, and pituitary adenoma), for which immunotherapy-related clinical trials have been conducted. Publications spanning from January 1, 2011, to December 31, 2023, were retrieved from the Web of Science Core Collection for a bibliometric analysis aimed at visualizing research trends and hotspots in immunotherapy for brain metastases, gliomas, meningiomas, and pituitary adenomas. Additionally, ongoing clinical trials were reviewed to identify the frontiers of immunotherapy in brain tumors. Research activity has significantly increased for brain metastasis and glioma, while studies on meningioma and pituitary adenoma remain in the nascent stages. The United States and China are the leading countries in these four research areas. Keyword analysis and ongoing trials underscore the crucial role of immune checkpoint inhibitors, which are currently a focal point in the treatment of various brain tumors. This review outlines the knowledge structures and research priorities in immunotherapy over the past 13 years, providing valuable insights for researchers in these fields.
Recent insights into the immune landscape of the brain tumor microenvironment shed new light on immunotherapy for various brain tumors. This study provides comprehensive overviews of the development trends of immunotherapy for four common brain tumors (brain metastasis, glioma, meningioma, and pituitary adenoma), for which immunotherapy-related clinical trials have been conducted. Publications spanning from January 1, 2011, to December 31, 2023, were retrieved from the Web of Science Core Collection for a bibliometric analysis aimed at visualizing research trends and hotspots in immunotherapy for brain metastases, gliomas, meningiomas, and pituitary adenomas. Additionally, ongoing clinical trials were reviewed to identify the frontiers of immunotherapy in brain tumors. Research activity has significantly increased for brain metastasis and glioma, while studies on meningioma and pituitary adenoma remain in the nascent stages. The United States and China are the leading countries in these four research areas. Keyword analysis and ongoing trials underscore the crucial role of immune checkpoint inhibitors, which are currently a focal point in the treatment of various brain tumors. This review outlines the knowledge structures and research priorities in immunotherapy over the past 13 years, providing valuable insights for researchers in these fields.
2025, 36(12): 110996
doi: 10.1016/j.cclet.2025.110996
摘要:
Antibiotic-contaminated wastewater poses a global threat to aquatic ecosystems. Fenton-like oxidative processes effectively decompose recalcitrant pollutants. While these oxidative processes effectively break down target contaminants, they may also produce uncontrolled intermediates, potentially resulting in unexpected combined toxicities. This review explores the chemical mechanisms behind Fenton-like reactions, particularly in antibiotic removal, and evaluates the formation of byproducts and their potential toxicological effects. Furthermore, recommendations for optimizing catalyst design and treatment conditions are provided to enhance degradation performance while minimizing ecological risks. This study highlights critical concerns regarding the toxicity of degradation byproducts and their impact on ecosystems by integrating chemical and biological risk assessments. By integrating chemical and biological risk assessments with computational toxicology, particularly quantitative structure-activity relationship (QSAR) modeling, this study proposes a comprehensive approach to evaluate degradation and toxicity. This work highlights the importance of a comprehensive framework for evaluating degradation efficiency and toxicity, contributing to safer and more effective antibiotic wastewater treatment strategies. The findings underscore the importance of balancing degradation efficiency with environmental safety in wastewater treatment processes involving advanced oxidative technologies.
Antibiotic-contaminated wastewater poses a global threat to aquatic ecosystems. Fenton-like oxidative processes effectively decompose recalcitrant pollutants. While these oxidative processes effectively break down target contaminants, they may also produce uncontrolled intermediates, potentially resulting in unexpected combined toxicities. This review explores the chemical mechanisms behind Fenton-like reactions, particularly in antibiotic removal, and evaluates the formation of byproducts and their potential toxicological effects. Furthermore, recommendations for optimizing catalyst design and treatment conditions are provided to enhance degradation performance while minimizing ecological risks. This study highlights critical concerns regarding the toxicity of degradation byproducts and their impact on ecosystems by integrating chemical and biological risk assessments. By integrating chemical and biological risk assessments with computational toxicology, particularly quantitative structure-activity relationship (QSAR) modeling, this study proposes a comprehensive approach to evaluate degradation and toxicity. This work highlights the importance of a comprehensive framework for evaluating degradation efficiency and toxicity, contributing to safer and more effective antibiotic wastewater treatment strategies. The findings underscore the importance of balancing degradation efficiency with environmental safety in wastewater treatment processes involving advanced oxidative technologies.
2025, 36(12): 111008
doi: 10.1016/j.cclet.2025.111008
摘要:
Multi-components landfill leachate is one type of wastewater that is challenging to deal with. The excellent degrading ability and low secondary pollution of electrochemical oxidation make it a promising technology for leachate treatment. However, the commercial application of this method is restricted by some technical barriers such as limited anode activity and intricate operating conditions. To improve the efficiency of electrochemical leachate treatment, many researchers commit to developing efficient electrode and optimizing operation process for eliminating these limitations. This review summarized the recently studied countermeasures for accelerating the performance of electrochemical oxidation of leachate with respect to the electron transfer, active sites and stability of electrode. The performance of electrochemical leachate treatment with different anode and the corresponding underlying mechanisms were summarized and discussed. Besides, the effects of critical parameters including temperature, pH, current density and electrolyte on reaction were discussed. With these in mind, this work offers recommendations for the improvement of electrooxidation performance as well as direction for the design of leachate treatment engineering.
Multi-components landfill leachate is one type of wastewater that is challenging to deal with. The excellent degrading ability and low secondary pollution of electrochemical oxidation make it a promising technology for leachate treatment. However, the commercial application of this method is restricted by some technical barriers such as limited anode activity and intricate operating conditions. To improve the efficiency of electrochemical leachate treatment, many researchers commit to developing efficient electrode and optimizing operation process for eliminating these limitations. This review summarized the recently studied countermeasures for accelerating the performance of electrochemical oxidation of leachate with respect to the electron transfer, active sites and stability of electrode. The performance of electrochemical leachate treatment with different anode and the corresponding underlying mechanisms were summarized and discussed. Besides, the effects of critical parameters including temperature, pH, current density and electrolyte on reaction were discussed. With these in mind, this work offers recommendations for the improvement of electrooxidation performance as well as direction for the design of leachate treatment engineering.
2025, 36(12): 111135
doi: 10.1016/j.cclet.2025.111135
摘要:
In recent years, stimulus-responsive metal-organic cages (MOCs) have attracted significant attention due to their dynamic structures and properties, which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies. Among various external stimuli, light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units, such as azobenzene, thereby enabling precise photoresponsive behavior. Substantial progress has been made in the development of azobenzene-containing MOCs, underscoring their research significance and broad application potential across multiple fields. Given these advancements, it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs. This review will highlight key developments and explore their functional applications.
In recent years, stimulus-responsive metal-organic cages (MOCs) have attracted significant attention due to their dynamic structures and properties, which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies. Among various external stimuli, light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units, such as azobenzene, thereby enabling precise photoresponsive behavior. Substantial progress has been made in the development of azobenzene-containing MOCs, underscoring their research significance and broad application potential across multiple fields. Given these advancements, it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs. This review will highlight key developments and explore their functional applications.
2025, 36(12): 111224
doi: 10.1016/j.cclet.2025.111224
摘要:
Oxalic acid salts (oxalate) were recently developed as C1 synthon, potent single-electron-transfer (SET) reductant, and hole scavengers via generation of CO2 and CO2 radical anion (CO2•−) under mild photochemical conditions. A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor (EDA) complex formation process. As a chemical intermediate for carbon capture and utilization (also a cheap and readily available reagent), oxalate salts could release one electron easily (Eox = +0.06 V vs. SCE) via visible-light irradiation to give CO2 and CO2•− and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation, alkenes cross coupling, and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way. This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.
Oxalic acid salts (oxalate) were recently developed as C1 synthon, potent single-electron-transfer (SET) reductant, and hole scavengers via generation of CO2 and CO2 radical anion (CO2•−) under mild photochemical conditions. A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor (EDA) complex formation process. As a chemical intermediate for carbon capture and utilization (also a cheap and readily available reagent), oxalate salts could release one electron easily (Eox = +0.06 V vs. SCE) via visible-light irradiation to give CO2 and CO2•− and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation, alkenes cross coupling, and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way. This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.
2025, 36(12): 111267
doi: 10.1016/j.cclet.2025.111267
摘要:
With the development of lithium-ion batteries, people are no longer confined to portable electronic products. Large-scale energy storage systems and electric vehicles have emerged as significant areas of development, with many of these systems and vehicles intended for operation in low-temperature environments. Compared with lithium-ion batteries, sodium-ion batteries possess abundant resources and exhibit superior electrochemical performance under extreme conditions. However, their performance at low temperatures remains suboptimal. In this review, we comprehensively examined the reasons for the performance decline of sodium-ion batteries at low temperatures and elucidated their storage mechanisms. Additionally, we explored modification strategies and specific applications for low-temperature sodium-ion batteries from multiple perspectives, including electrodes, electrolytes, and interphases. Finally, we summarized the key factors influencing the performance of low-temperature sodium-ion batteries and provided an outlook on their future development.
With the development of lithium-ion batteries, people are no longer confined to portable electronic products. Large-scale energy storage systems and electric vehicles have emerged as significant areas of development, with many of these systems and vehicles intended for operation in low-temperature environments. Compared with lithium-ion batteries, sodium-ion batteries possess abundant resources and exhibit superior electrochemical performance under extreme conditions. However, their performance at low temperatures remains suboptimal. In this review, we comprehensively examined the reasons for the performance decline of sodium-ion batteries at low temperatures and elucidated their storage mechanisms. Additionally, we explored modification strategies and specific applications for low-temperature sodium-ion batteries from multiple perspectives, including electrodes, electrolytes, and interphases. Finally, we summarized the key factors influencing the performance of low-temperature sodium-ion batteries and provided an outlook on their future development.
2025, 36(12): 111421
doi: 10.1016/j.cclet.2025.111421
摘要:
The efficient utilization of light energy is fundamental to sustainable energy solutions, driving extensive research into artificial light-harvesting systems (LHSs) inspired by natural photosynthesis. Among various approaches, supramolecular polymer materials have emerged as a versatile platform for constructing high-performance LHSs due to their dynamic self-assembly and tunable optical properties. This review comprehensively examines their design principles, synthesis, and functionalization for light-harvesting applications. Key strategies for enhancing light absorption, energy transfer efficiency, and photostability are analyzed, along with the integration of supramolecular polymers with nanomaterials to create multifunctional hybrid systems. Despite significant advancements, challenges remain in optimizing performance and scalability. Future research should focus on novel supramolecular motifs, bio-inspired architectures, and environmentally benign synthesis methods to advance practical applications in solar energy conversion and beyond.
The efficient utilization of light energy is fundamental to sustainable energy solutions, driving extensive research into artificial light-harvesting systems (LHSs) inspired by natural photosynthesis. Among various approaches, supramolecular polymer materials have emerged as a versatile platform for constructing high-performance LHSs due to their dynamic self-assembly and tunable optical properties. This review comprehensively examines their design principles, synthesis, and functionalization for light-harvesting applications. Key strategies for enhancing light absorption, energy transfer efficiency, and photostability are analyzed, along with the integration of supramolecular polymers with nanomaterials to create multifunctional hybrid systems. Despite significant advancements, challenges remain in optimizing performance and scalability. Future research should focus on novel supramolecular motifs, bio-inspired architectures, and environmentally benign synthesis methods to advance practical applications in solar energy conversion and beyond.
2025, 36(12): 111588
doi: 10.1016/j.cclet.2025.111588
摘要:
Photothermal therapy (PTT), characterized by its minimally invasive nature and highly selective tumor-killing ability, holds great potential for tumor therapy. Due to the outstanding photothermal performance and tumor targeting ability, nanomaterial-based photothermal agents (nano-PTAs) have further expanded the therapeutic horizons of PTT. However, the dense and complicated network of the tumor extracellular matrix (ECM) severely restricts the penetration of nano-PTAs into deep tumor tissues. Since elevated temperatures are only generated in the vicinity of nano-PTAs upon laser irradiation, the uneven distribution of these agents leads to incomplete tumor coverage across the tumor. Consequently, overcoming ECM barriers and enhancing tumor permeability are critical for the success of tumor PTT. To address this challenge, researchers have explored strategies that combine tumor ECM regulation with PTT to facilitate the deep diffusion of nano-PTAs. This review summarizes the latest advancements in designing nano-PTAs with ECM-remodeling capabilities, aiming to enable their uniform penetration throughout tumors. Additionally, we discuss the remaining obstacles and challenges in elucidating the mechanisms of ECM manipulation and understanding the interactions between nano-PTAs and ECM components during the penetration process.
Photothermal therapy (PTT), characterized by its minimally invasive nature and highly selective tumor-killing ability, holds great potential for tumor therapy. Due to the outstanding photothermal performance and tumor targeting ability, nanomaterial-based photothermal agents (nano-PTAs) have further expanded the therapeutic horizons of PTT. However, the dense and complicated network of the tumor extracellular matrix (ECM) severely restricts the penetration of nano-PTAs into deep tumor tissues. Since elevated temperatures are only generated in the vicinity of nano-PTAs upon laser irradiation, the uneven distribution of these agents leads to incomplete tumor coverage across the tumor. Consequently, overcoming ECM barriers and enhancing tumor permeability are critical for the success of tumor PTT. To address this challenge, researchers have explored strategies that combine tumor ECM regulation with PTT to facilitate the deep diffusion of nano-PTAs. This review summarizes the latest advancements in designing nano-PTAs with ECM-remodeling capabilities, aiming to enable their uniform penetration throughout tumors. Additionally, we discuss the remaining obstacles and challenges in elucidating the mechanisms of ECM manipulation and understanding the interactions between nano-PTAs and ECM components during the penetration process.
2025, 36(12): 111746
doi: 10.1016/j.cclet.2025.111746
摘要:
Ni-based materials, widely recognized for their exceptional catalytic properties, experience structural transformations that profoundly influence their performance characteristics and operational stability. To deeply understand the reconstruction mechanism of Ni-based catalysts, this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process, including electrochemical activation, defect engineering, partial etching, ionic doping, and heterostructure construction. Furthermore, we discuss the implications of these surface transformations on catalytic activity, highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions, such as oxygen evolution reaction (OER), urea oxidation reaction (UOR), glycerol oxidation reaction (GOR), hydroxymethylfurfural oxidation reaction (HMFOR), and ammonia oxidation reaction (AOR). By summarizing recent research findings, this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications, paving the way for advancements in energy conversion and storage technologies.
Ni-based materials, widely recognized for their exceptional catalytic properties, experience structural transformations that profoundly influence their performance characteristics and operational stability. To deeply understand the reconstruction mechanism of Ni-based catalysts, this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process, including electrochemical activation, defect engineering, partial etching, ionic doping, and heterostructure construction. Furthermore, we discuss the implications of these surface transformations on catalytic activity, highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions, such as oxygen evolution reaction (OER), urea oxidation reaction (UOR), glycerol oxidation reaction (GOR), hydroxymethylfurfural oxidation reaction (HMFOR), and ammonia oxidation reaction (AOR). By summarizing recent research findings, this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications, paving the way for advancements in energy conversion and storage technologies.
2025, 36(12): 111527
doi: 10.1016/j.cclet.2025.111527
摘要:
2025, 36(12): 111635
doi: 10.1016/j.cclet.2025.111635
摘要:
2025, 36(5): 109726
doi: 10.1016/j.cclet.2024.109726
摘要:
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
2025, 36(5): 109853
doi: 10.1016/j.cclet.2024.109853
摘要:
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
2025, 36(5): 109870
doi: 10.1016/j.cclet.2024.109870
摘要:
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
2025, 36(5): 109873
doi: 10.1016/j.cclet.2024.109873
摘要:
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
2025, 36(5): 109919
doi: 10.1016/j.cclet.2024.109919
摘要:
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
2025, 36(5): 109920
doi: 10.1016/j.cclet.2024.109920
摘要:
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
2025, 36(5): 109935
doi: 10.1016/j.cclet.2024.109935
摘要:
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
2025, 36(5): 109936
doi: 10.1016/j.cclet.2024.109936
摘要:
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
2025, 36(5): 109937
doi: 10.1016/j.cclet.2024.109937
摘要:
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
2025, 36(5): 109939
doi: 10.1016/j.cclet.2024.109939
摘要:
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
2025, 36(5): 109940
doi: 10.1016/j.cclet.2024.109940
摘要:
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
2025, 36(5): 110015
doi: 10.1016/j.cclet.2024.110015
摘要:
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
2025, 36(5): 110034
doi: 10.1016/j.cclet.2024.110034
摘要:
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
2025, 36(5): 110043
doi: 10.1016/j.cclet.2024.110043
摘要:
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
2025, 36(5): 110045
doi: 10.1016/j.cclet.2024.110045
摘要:
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
2025, 36(5): 110053
doi: 10.1016/j.cclet.2024.110053
摘要:
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
2025, 36(5): 110067
doi: 10.1016/j.cclet.2024.110067
摘要:
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
2025, 36(5): 110069
doi: 10.1016/j.cclet.2024.110069
摘要:
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
2025, 36(5): 110073
doi: 10.1016/j.cclet.2024.110073
摘要:
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
2025, 36(5): 110082
doi: 10.1016/j.cclet.2024.110082
摘要:
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
2025, 36(5): 110084
doi: 10.1016/j.cclet.2024.110084
摘要:
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
2025, 36(5): 110097
doi: 10.1016/j.cclet.2024.110097
摘要:
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
2025, 36(5): 110098
doi: 10.1016/j.cclet.2024.110098
摘要:
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
2025, 36(5): 110105
doi: 10.1016/j.cclet.2024.110105
摘要:
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
2025, 36(5): 110106
doi: 10.1016/j.cclet.2024.110106
摘要:
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
2025, 36(5): 110116
doi: 10.1016/j.cclet.2024.110116
摘要:
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
2025, 36(5): 110119
doi: 10.1016/j.cclet.2024.110119
摘要:
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
2025, 36(5): 110128
doi: 10.1016/j.cclet.2024.110128
摘要:
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
2025, 36(5): 110130
doi: 10.1016/j.cclet.2024.110130
摘要:
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
2025, 36(5): 110133
doi: 10.1016/j.cclet.2024.110133
摘要:
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
2025, 36(5): 110135
doi: 10.1016/j.cclet.2024.110135
摘要:
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
2025, 36(5): 110140
doi: 10.1016/j.cclet.2024.110140
摘要:
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
2025, 36(5): 110141
doi: 10.1016/j.cclet.2024.110141
摘要:
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
2025, 36(5): 110146
doi: 10.1016/j.cclet.2024.110146
摘要:
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
2025, 36(5): 110147
doi: 10.1016/j.cclet.2024.110147
摘要:
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
2025, 36(5): 110149
doi: 10.1016/j.cclet.2024.110149
摘要:
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
2025, 36(5): 110166
doi: 10.1016/j.cclet.2024.110166
摘要:
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
2025, 36(5): 110168
doi: 10.1016/j.cclet.2024.110168
摘要:
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
2025, 36(5): 110178
doi: 10.1016/j.cclet.2024.110178
摘要:
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
2025, 36(5): 110179
doi: 10.1016/j.cclet.2024.110179
摘要:
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
2025, 36(5): 110183
doi: 10.1016/j.cclet.2024.110183
摘要:
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
2025, 36(5): 110190
doi: 10.1016/j.cclet.2024.110190
摘要:
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
2025, 36(5): 110191
doi: 10.1016/j.cclet.2024.110191
摘要:
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
2025, 36(5): 110192
doi: 10.1016/j.cclet.2024.110192
摘要:
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
2025, 36(5): 110195
doi: 10.1016/j.cclet.2024.110195
摘要:
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
2025, 36(5): 110196
doi: 10.1016/j.cclet.2024.110196
摘要:
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
2025, 36(5): 110200
doi: 10.1016/j.cclet.2024.110200
摘要:
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
2025, 36(5): 110201
doi: 10.1016/j.cclet.2024.110201
摘要:
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
2025, 36(5): 110202
doi: 10.1016/j.cclet.2024.110202
摘要:
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
2025, 36(5): 110203
doi: 10.1016/j.cclet.2024.110203
摘要:
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
2025, 36(5): 110206
doi: 10.1016/j.cclet.2024.110206
摘要:
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
2025, 36(5): 110207
doi: 10.1016/j.cclet.2024.110207
摘要:
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
2025, 36(5): 110209
doi: 10.1016/j.cclet.2024.110209
摘要:
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
2025, 36(5): 110213
doi: 10.1016/j.cclet.2024.110213
摘要:
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
2025, 36(5): 110227
doi: 10.1016/j.cclet.2024.110227
摘要:
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
2025, 36(5): 110230
doi: 10.1016/j.cclet.2024.110230
摘要:
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
2025, 36(5): 110231
doi: 10.1016/j.cclet.2024.110231
摘要:
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
2025, 36(5): 110237
doi: 10.1016/j.cclet.2024.110237
摘要:
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
2025, 36(5): 110238
doi: 10.1016/j.cclet.2024.110238
摘要:
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
2025, 36(5): 110239
doi: 10.1016/j.cclet.2024.110239
摘要:
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
2025, 36(5): 110240
doi: 10.1016/j.cclet.2024.110240
摘要:
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
2025, 36(5): 110241
doi: 10.1016/j.cclet.2024.110241
摘要:
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
2025, 36(5): 110243
doi: 10.1016/j.cclet.2024.110243
摘要:
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
2025, 36(5): 110244
doi: 10.1016/j.cclet.2024.110244
摘要:
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
2025, 36(5): 110249
doi: 10.1016/j.cclet.2024.110249
摘要:
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
2025, 36(5): 110253
doi: 10.1016/j.cclet.2024.110253
摘要:
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
2025, 36(5): 110258
doi: 10.1016/j.cclet.2024.110258
摘要:
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
2025, 36(5): 110260
doi: 10.1016/j.cclet.2024.110260
摘要:
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
2025, 36(5): 110282
doi: 10.1016/j.cclet.2024.110282
摘要:
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
2025, 36(5): 110291
doi: 10.1016/j.cclet.2024.110291
摘要:
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
2025, 36(5): 110293
doi: 10.1016/j.cclet.2024.110293
摘要:
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
2025, 36(5): 110295
doi: 10.1016/j.cclet.2024.110295
摘要:
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
2025, 36(5): 110306
doi: 10.1016/j.cclet.2024.110306
摘要:
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
2025, 36(5): 110310
doi: 10.1016/j.cclet.2024.110310
摘要:
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
2025, 36(5): 110311
doi: 10.1016/j.cclet.2024.110311
摘要:
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
2025, 36(5): 110312
doi: 10.1016/j.cclet.2024.110312
摘要:
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
2025, 36(5): 110334
doi: 10.1016/j.cclet.2024.110334
摘要:
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
2025, 36(5): 110432
doi: 10.1016/j.cclet.2024.110432
摘要:
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
2025, 36(5): 110437
doi: 10.1016/j.cclet.2024.110437
摘要:
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
2025, 36(5): 110508
doi: 10.1016/j.cclet.2024.110508
摘要:
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
2025, 36(5): 110561
doi: 10.1016/j.cclet.2024.110561
摘要:
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
2025, 36(5): 110629
doi: 10.1016/j.cclet.2024.110629
摘要:
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
2025, 36(5): 110663
doi: 10.1016/j.cclet.2024.110663
摘要:
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
2025, 36(5): 110672
doi: 10.1016/j.cclet.2024.110672
摘要:
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
2025, 36(5): 110699
doi: 10.1016/j.cclet.2024.110699
摘要:
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
2025, 36(5): 110700
doi: 10.1016/j.cclet.2024.110700
摘要:
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
2025, 36(5): 110719
doi: 10.1016/j.cclet.2024.110719
摘要:
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
2025, 36(5): 110724
doi: 10.1016/j.cclet.2024.110724
摘要:
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
2025, 36(5): 110760
doi: 10.1016/j.cclet.2024.110760
摘要:
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
2025, 36(5): 110762
doi: 10.1016/j.cclet.2024.110762
摘要:
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
2025, 36(5): 110765
doi: 10.1016/j.cclet.2024.110765
摘要:
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
2025, 36(5): 109871
doi: 10.1016/j.cclet.2024.109871
摘要:
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
2025, 36(5): 109898
doi: 10.1016/j.cclet.2024.109898
摘要:
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis
2025, 36(5): 109906
doi: 10.1016/j.cclet.2024.109906
摘要:
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
2025, 36(5): 109938
doi: 10.1016/j.cclet.2024.109938
摘要:
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
2025, 36(5): 110059
doi: 10.1016/j.cclet.2024.110059
摘要:
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
2025, 36(5): 110072
doi: 10.1016/j.cclet.2024.110072
摘要:
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
2025, 36(5): 110126
doi: 10.1016/j.cclet.2024.110126
摘要:
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
2025, 36(5): 110226
doi: 10.1016/j.cclet.2024.110226
摘要:
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
2025, 36(5): 110277
doi: 10.1016/j.cclet.2024.110277
摘要:
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
2025, 36(5): 110284
doi: 10.1016/j.cclet.2024.110284
摘要:
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
2025, 36(5): 110423
doi: 10.1016/j.cclet.2024.110423
摘要:
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
2025, 36(5): 110503
doi: 10.1016/j.cclet.2024.110503
摘要:
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
2025, 36(5): 110521
doi: 10.1016/j.cclet.2024.110521
摘要:
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
2025, 36(5): 110529
doi: 10.1016/j.cclet.2024.110529
摘要:
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
2025, 36(5): 110618
doi: 10.1016/j.cclet.2024.110618
摘要:
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
2025, 36(5): 110628
doi: 10.1016/j.cclet.2024.110628
摘要:
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
2025, 36(5): 110764
doi: 10.1016/j.cclet.2024.110764
摘要:
2025, 36(5): 110869
doi: 10.1016/j.cclet.2025.110869
摘要:
2025, 36(5): 110936
doi: 10.1016/j.cclet.2025.110936
摘要:
