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2025 Volume 36 Issue 12
2025, 36(12): 110454
doi: 10.1016/j.cclet.2024.110454
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2025, 36(12): 111635
doi: 10.1016/j.cclet.2025.111635
Abstract:
