Login In
Browse Articles
The first issue is scheduled to be published in Dec. 2018.
Call for Papers
CCS Chemistry is the flagship general journal for the cutting edge and fundamental research in the areas of chemica research facing global audiences published by Chinese Chemical Society. We call for excellent papers cover but not limited to synthetic chemistry, catalysis & surface chemistry, chemical theory and mechanism, chemical metrology, materials & energy chemistry, environmental chemistry, chemical biology, chemical engineering and industrial chemistry. Professional arrangement ensures that all papers can be reviewed and published online quickly and efficiently (one or two weeks).
Contact information:
Dr. Hao Linxiao, haolinxiao@iccas.ac.cn; +86-10-82449177-888
Display Method: |
2026, 37(12): 110978
doi: 10.1016/j.cclet.2025.110978
Abstract:
Enzymes can catalyze corresponding biochemical reactions efficiently under mild conditions, and plays a crucial role in maintaining normal physiological processes. Therefore, the development of enzyme activity detection methods is of great significance. Fluorescent probes for enzyme activity detection have attracted an increasing interest due to their excellent selectivity, high sensitivity and good cell permeability recently. Especially in the last few years, probes based on Förster resonance energy transfer (FRET) mechanism have been successively used for the quantitative analysis of enzyme activity, which has promoted the application of enzyme activity probes in vivo. In this review, we summarized the recent progress on fluorescence probes for quantitative detection of enzyme activity based on azo-quencher involving FRET mechanism. It concluded the design strategies of fluorescent probes, enzyme-responsiveness, and their application in biological systems. These fluorescence probes show the ability of in situ visualization and can achieve the quantitative detection of enzyme activity. We believe it will be useful for designing in situ enzyme activity fluorescent probes for quantitative analysis in vivo.
Enzymes can catalyze corresponding biochemical reactions efficiently under mild conditions, and plays a crucial role in maintaining normal physiological processes. Therefore, the development of enzyme activity detection methods is of great significance. Fluorescent probes for enzyme activity detection have attracted an increasing interest due to their excellent selectivity, high sensitivity and good cell permeability recently. Especially in the last few years, probes based on Förster resonance energy transfer (FRET) mechanism have been successively used for the quantitative analysis of enzyme activity, which has promoted the application of enzyme activity probes in vivo. In this review, we summarized the recent progress on fluorescence probes for quantitative detection of enzyme activity based on azo-quencher involving FRET mechanism. It concluded the design strategies of fluorescent probes, enzyme-responsiveness, and their application in biological systems. These fluorescence probes show the ability of in situ visualization and can achieve the quantitative detection of enzyme activity. We believe it will be useful for designing in situ enzyme activity fluorescent probes for quantitative analysis in vivo.
2026, 37(12): 111590
doi: 10.1016/j.cclet.2025.111590
Abstract:
Hard carbon stands out among commercial anode materials for sodium-ion batteries (SIBs) due to its low redox potential, high safety, and significant cost advantages, making it a viable candidate for large-scale applications. While hard carbon can be derived from various precursors, coal offers the most economically viable and abundant resource, with a significantly higher carbonization yield, making it an attractive functional carbon precursor. Nevertheless, the electrochemical Na-storage performance of coal-based carbons is limited by structural constraints, including regular microcrystalline arrangements and a restricted number of active sites. To address the challenges associated with the practical application of coal-derived carbon in SIBs, advanced structural modifications strategies such as microcrystalline regulation, heteroatom doping, and pore structure engineering have been developed. This review offers a thorough analysis of the latest advancements in the structure design of coal-based carbons in terms of their effect on the electrochemical performance, especially the Na-storage capacity, initial coulombic efficiency, and rate capability. The existing challenges for the coal-based carbon anode are also discussed alongside future development prospects. This discussion aims to guide future research efforts toward advancing the development of cost-efficient, high-performance coal-derived carbon materials, thereby facilitating the SIBs’ commercialization as a viable, sustainable energy storage solution.
Hard carbon stands out among commercial anode materials for sodium-ion batteries (SIBs) due to its low redox potential, high safety, and significant cost advantages, making it a viable candidate for large-scale applications. While hard carbon can be derived from various precursors, coal offers the most economically viable and abundant resource, with a significantly higher carbonization yield, making it an attractive functional carbon precursor. Nevertheless, the electrochemical Na-storage performance of coal-based carbons is limited by structural constraints, including regular microcrystalline arrangements and a restricted number of active sites. To address the challenges associated with the practical application of coal-derived carbon in SIBs, advanced structural modifications strategies such as microcrystalline regulation, heteroatom doping, and pore structure engineering have been developed. This review offers a thorough analysis of the latest advancements in the structure design of coal-based carbons in terms of their effect on the electrochemical performance, especially the Na-storage capacity, initial coulombic efficiency, and rate capability. The existing challenges for the coal-based carbon anode are also discussed alongside future development prospects. This discussion aims to guide future research efforts toward advancing the development of cost-efficient, high-performance coal-derived carbon materials, thereby facilitating the SIBs’ commercialization as a viable, sustainable energy storage solution.
2026, 37(12): 111897
doi: 10.1016/j.cclet.2025.111897
Abstract:
Photocatalytic organic synthesis offers a green, sustainable approach for manufacturing high-value chemicals, addressing critical energy and environmental challenges. Polyoxometalates (POMs)-based photocatalysts, known for their structural tunability, robust redox properties, and thermal stability, have emerged as key players in selective oxidation and coupling reactions. This review highlights recent advances in POMs-based photocatalysts, focusing on strategic modifications such as transition metal doping, hybridization with metal-organic frameworks (MOFs), and integration with semiconductor materials to enhance light absorption, charge separation, and electron transfer efficiency. Applications in controlled oxidation of aromatic alcohols, toluene, and amines are explored, along with discussions on stability and recyclability challenges. Emerging perspectives on optimizing POMs-based photocatalysts for scalable, cost-effective, and durable use in sustainable chemical synthesis are also presented.
Photocatalytic organic synthesis offers a green, sustainable approach for manufacturing high-value chemicals, addressing critical energy and environmental challenges. Polyoxometalates (POMs)-based photocatalysts, known for their structural tunability, robust redox properties, and thermal stability, have emerged as key players in selective oxidation and coupling reactions. This review highlights recent advances in POMs-based photocatalysts, focusing on strategic modifications such as transition metal doping, hybridization with metal-organic frameworks (MOFs), and integration with semiconductor materials to enhance light absorption, charge separation, and electron transfer efficiency. Applications in controlled oxidation of aromatic alcohols, toluene, and amines are explored, along with discussions on stability and recyclability challenges. Emerging perspectives on optimizing POMs-based photocatalysts for scalable, cost-effective, and durable use in sustainable chemical synthesis are also presented.
2026, 37(12): 111906
doi: 10.1016/j.cclet.2025.111906
Abstract:
Cobalt single-atom nanozymes (Co-SANs) have emerged as a class of high-performance catalysts with atomic-level precision, offering promising solutions for environmental remediation and energy sustainability. This review systematically elaborates on the rational design principles of Co-SANs, focusing on coordination environment engineering (e.g., N/C coordination, defect engineering) and their structure-activity relationships. Specifically, we highlight their catalytic mechanisms in environmental remediation, encompassing efficient activation of oxidants (peroxymonosulfate, persulfate) for aqueous pollutant degradation (e.g., 4-nitrophenol, bisphenol A, pesticides) and catalytic oxidation of gaseous pollutants (formaldehyde, CO2). In energy storage and conversion, we discuss applications in advanced energy storage and conversion systems, including Li-S batteries, Zn-air batteries, green hydrogen production, and sustainable H2O2 synthesis, emphasizing how atomic-level sites optimize redox kinetics. Finally, we address key challenges, such as synthesis scalability, stability under harsh reaction conditions, and mechanistic ambiguities at the atomic scale, and propose future directions such as machine learning-guided design and hybrid system integration for industrial deployment. This review establishes a comprehensive framework to leverage Co-SANs as catalytic bridges between environmental remediation and energy sustainability.
Cobalt single-atom nanozymes (Co-SANs) have emerged as a class of high-performance catalysts with atomic-level precision, offering promising solutions for environmental remediation and energy sustainability. This review systematically elaborates on the rational design principles of Co-SANs, focusing on coordination environment engineering (e.g., N/C coordination, defect engineering) and their structure-activity relationships. Specifically, we highlight their catalytic mechanisms in environmental remediation, encompassing efficient activation of oxidants (peroxymonosulfate, persulfate) for aqueous pollutant degradation (e.g., 4-nitrophenol, bisphenol A, pesticides) and catalytic oxidation of gaseous pollutants (formaldehyde, CO2). In energy storage and conversion, we discuss applications in advanced energy storage and conversion systems, including Li-S batteries, Zn-air batteries, green hydrogen production, and sustainable H2O2 synthesis, emphasizing how atomic-level sites optimize redox kinetics. Finally, we address key challenges, such as synthesis scalability, stability under harsh reaction conditions, and mechanistic ambiguities at the atomic scale, and propose future directions such as machine learning-guided design and hybrid system integration for industrial deployment. This review establishes a comprehensive framework to leverage Co-SANs as catalytic bridges between environmental remediation and energy sustainability.
2026, 37(12): 112264
doi: 10.1016/j.cclet.2025.112264
Abstract:
Chronic wounds represent a significant healthcare challenge, particularly for populations such as the elderly, diabetics, and individuals with poor immune function. Various factors contribute to the failure of chronic wound healing, including oxidative stress, impaired vascularization, infection, and prolonged inflammation. Traditional wound care methods, such as routine dressing changes, antibiotics, and debridement, primarily focus on infection control and basic protection, but reckoning without balanced coordination of complex pathological factors and difficulty handling intricate problems such as antibiotic resistance. In this review, we will mainly introduce the emerging advanced therapeutic strategies based on nanomaterials and smart wound dressings that target the underlying pathological causes to accelerate the chronic wound healing process, and will also discuss the current limitations and future perspectives of chronic wound management.
Chronic wounds represent a significant healthcare challenge, particularly for populations such as the elderly, diabetics, and individuals with poor immune function. Various factors contribute to the failure of chronic wound healing, including oxidative stress, impaired vascularization, infection, and prolonged inflammation. Traditional wound care methods, such as routine dressing changes, antibiotics, and debridement, primarily focus on infection control and basic protection, but reckoning without balanced coordination of complex pathological factors and difficulty handling intricate problems such as antibiotic resistance. In this review, we will mainly introduce the emerging advanced therapeutic strategies based on nanomaterials and smart wound dressings that target the underlying pathological causes to accelerate the chronic wound healing process, and will also discuss the current limitations and future perspectives of chronic wound management.
2026, 37(12): 112312
doi: 10.1016/j.cclet.2025.112312
Abstract:
The proven clinical efficacy of messenger RNA (mRNA) vaccines against corona virus disease 2019 (COVID-19) has accelerated the development of mRNA nanomedicines for diverse therapeutic applications. Nevertheless, knowledge gaps persist, constraining the development of next-generation mRNA therapeutics with enhanced potency and safety. Deeper insights into the mechanisms of mRNA vaccine effects, coupled with rational antigen design, innovative delivery strategies, and optimized vaccination regimens, are essential for producing highly effective therapies against a broad spectrum of diseases. This review commences by outlining current advances in mRNA modification, synthesis, novel lipids design, and alternative nanoparticles development for mRNA-based vaccines. Subsequently, it covers targeted delivery systems, emphasizing endosomal escape and cell- or organ-specific targeting. Additionally, we deliberate on the potential challenges mRNA drugs face in disease treatment, current improvement endeavors, and future application prospects. Furthermore, we highlight emerging systems immunology approaches that integrate multi-omic and computational analyses to elucidate human immune responses to vaccination and enhance predictive modeling. Finally, we summarize key points pertaining to the preclinical and clinical development of mRNA therapeutics. Overall, this review strives to provide a comprehensive understanding of mRNA-based therapies while illuminating prospective development and clinical applications.
The proven clinical efficacy of messenger RNA (mRNA) vaccines against corona virus disease 2019 (COVID-19) has accelerated the development of mRNA nanomedicines for diverse therapeutic applications. Nevertheless, knowledge gaps persist, constraining the development of next-generation mRNA therapeutics with enhanced potency and safety. Deeper insights into the mechanisms of mRNA vaccine effects, coupled with rational antigen design, innovative delivery strategies, and optimized vaccination regimens, are essential for producing highly effective therapies against a broad spectrum of diseases. This review commences by outlining current advances in mRNA modification, synthesis, novel lipids design, and alternative nanoparticles development for mRNA-based vaccines. Subsequently, it covers targeted delivery systems, emphasizing endosomal escape and cell- or organ-specific targeting. Additionally, we deliberate on the potential challenges mRNA drugs face in disease treatment, current improvement endeavors, and future application prospects. Furthermore, we highlight emerging systems immunology approaches that integrate multi-omic and computational analyses to elucidate human immune responses to vaccination and enhance predictive modeling. Finally, we summarize key points pertaining to the preclinical and clinical development of mRNA therapeutics. Overall, this review strives to provide a comprehensive understanding of mRNA-based therapies while illuminating prospective development and clinical applications.
2026, 37(12): 112338
doi: 10.1016/j.cclet.2025.112338
Abstract:
Proteolysis-targeting chimeras (PROTACs) represent a transformative therapeutic approach but face clinical translation hurdles due to high molecular weight, poor physicochemical properties, and off-target risks. We present a comprehensive review and analysis of various current PROTAC delivery strategies. These strategies fall into three main categories: Nanocarrier-based systems utilizing polymers, liposomes, and other materials, often with stimuli-responsive control; biomacromolecular platforms based on antibodies, peptides, or nucleic acids; and novel chemical methods such as prodrug modifications through esterification or photocaging. All three approaches have been developed to enhance delivery efficiency and specificity. Finally, this review outlines prospective future directions toward intelligent and precise delivery systems. These systems hold promise for expanding the spectrum of degradable undruggable targets and facilitate novel combination therapies. Collectively, these advancements provide valuable theoretical insights and practical guidance for the clinical translation of PROTACs.
Proteolysis-targeting chimeras (PROTACs) represent a transformative therapeutic approach but face clinical translation hurdles due to high molecular weight, poor physicochemical properties, and off-target risks. We present a comprehensive review and analysis of various current PROTAC delivery strategies. These strategies fall into three main categories: Nanocarrier-based systems utilizing polymers, liposomes, and other materials, often with stimuli-responsive control; biomacromolecular platforms based on antibodies, peptides, or nucleic acids; and novel chemical methods such as prodrug modifications through esterification or photocaging. All three approaches have been developed to enhance delivery efficiency and specificity. Finally, this review outlines prospective future directions toward intelligent and precise delivery systems. These systems hold promise for expanding the spectrum of degradable undruggable targets and facilitate novel combination therapies. Collectively, these advancements provide valuable theoretical insights and practical guidance for the clinical translation of PROTACs.
2026, 37(12): 112358
doi: 10.1016/j.cclet.2026.112358
Abstract:
This paper explores the application of messenger RNA (mRNA) therapy in skin regeneration and rejuvenation. It highlights the unique advantages of mRNA therapeutics, including transient protein expression, non-genomic integration, and scalable manufacturing. Facing challenges, progress in chemical modifications, delivery systems, and biomaterial scaffolds have significantly enhanced mRNA stability, delivery efficiency, and safety, paving the way for clinical applications. Innovative transdermal delivery platforms, particularly lipid nanoparticles (LNPs) and microneedles (MNs) offer enhanced skin penetration, prolonged retention, and controlled release of mRNA cargo. LNPs provide structural stability and efficient cellular uptake, while MNs enable minimally invasive, pain-free delivery, overcoming skin barriers. The applications section reviews recent advances in mRNA therapies to promote wound healing and combat skin aging. Preclinical studies demonstrate that nanocarriers loaded with mRNAs have shown efficacy and safety in accelerating wound healing by stimulating angiogenesis and epidermal cell migration. mRNA-based therapeutics have also shown great potential in increasing collagen and elastin synthesis. Although challenges remain in the regulation of long-term efficacy and standardization of mass production, the field is offering solutions ranging from acute wound healing to chronic photoaging reversal. By focusing on the potential of mRNA therapy in skin regeneration applications, this review discusses its impacts on dermatology and prospects in regenerative medicine.
This paper explores the application of messenger RNA (mRNA) therapy in skin regeneration and rejuvenation. It highlights the unique advantages of mRNA therapeutics, including transient protein expression, non-genomic integration, and scalable manufacturing. Facing challenges, progress in chemical modifications, delivery systems, and biomaterial scaffolds have significantly enhanced mRNA stability, delivery efficiency, and safety, paving the way for clinical applications. Innovative transdermal delivery platforms, particularly lipid nanoparticles (LNPs) and microneedles (MNs) offer enhanced skin penetration, prolonged retention, and controlled release of mRNA cargo. LNPs provide structural stability and efficient cellular uptake, while MNs enable minimally invasive, pain-free delivery, overcoming skin barriers. The applications section reviews recent advances in mRNA therapies to promote wound healing and combat skin aging. Preclinical studies demonstrate that nanocarriers loaded with mRNAs have shown efficacy and safety in accelerating wound healing by stimulating angiogenesis and epidermal cell migration. mRNA-based therapeutics have also shown great potential in increasing collagen and elastin synthesis. Although challenges remain in the regulation of long-term efficacy and standardization of mass production, the field is offering solutions ranging from acute wound healing to chronic photoaging reversal. By focusing on the potential of mRNA therapy in skin regeneration applications, this review discusses its impacts on dermatology and prospects in regenerative medicine.
2026, 37(12): 112362
doi: 10.1016/j.cclet.2026.112362
Abstract:
The oral administration of anticancer drugs emerged as a promising approach, offering improved patient acceptability, convenience for chronic treatment regimens, and the potential for optimized therapeutic outcomes. However, the clinical translation of oral anticancer agents remains hindered by gastrointestinal tract barriers, including poor aqueous solubility, variable pH, enzymatic degradation, mucus layer, limited intestinal epithelial permeation, and the influence of gut microbiota. To address these challenges, a wide range of innovative strategies have been explored, such as pH modifiers, enzyme inhibitors, permeation enhancers, prodrug design, and nanoparticle-based drug delivery systems. In addition, the integration of artificial intelligence and machine learning with nanomedicine offers new opportunities to accelerate formulation development, optimize drug design, and overcome existing absorption barriers. This review provides a comprehensive analysis of the current landscape of oral anticancer drug delivery and explores advanced strategies to enhance bioavailability, offering insights into future directions for improved therapeutic efficacy.
The oral administration of anticancer drugs emerged as a promising approach, offering improved patient acceptability, convenience for chronic treatment regimens, and the potential for optimized therapeutic outcomes. However, the clinical translation of oral anticancer agents remains hindered by gastrointestinal tract barriers, including poor aqueous solubility, variable pH, enzymatic degradation, mucus layer, limited intestinal epithelial permeation, and the influence of gut microbiota. To address these challenges, a wide range of innovative strategies have been explored, such as pH modifiers, enzyme inhibitors, permeation enhancers, prodrug design, and nanoparticle-based drug delivery systems. In addition, the integration of artificial intelligence and machine learning with nanomedicine offers new opportunities to accelerate formulation development, optimize drug design, and overcome existing absorption barriers. This review provides a comprehensive analysis of the current landscape of oral anticancer drug delivery and explores advanced strategies to enhance bioavailability, offering insights into future directions for improved therapeutic efficacy.
2026, 37(12): 112465
doi: 10.1016/j.cclet.2026.112465
Abstract:
Essential oils (EOs), extracted from various aromatic plants, have numerous health benefits and are widely used in medicine. However, their low yields, complex composition, poor solubility, limited bioavailability, and sensitivity to environmental factors such as light, heat, and oxidation pose challenges that hinder their applications. This review provides a comprehensive overview of the plant biosynthetic pathways involved in the production of EOs and discusses strategies to enhance their production through metabolic and process regulation. Additionally, it meticulously examines the development of diverse techniques for the extraction, separation, and purification of EOs, as well as sophisticated analytical methods for the identification of their components. The bioactivities of EOs and the biomedical applications of both native and encapsulated EOs in various in vitro and in vivo models are discussed. Moreover, the encapsulation-induced enhancement of the efficacy and stability of EOs is highlighted. Finally, this review details the current clinical trials involving EOs and their encapsulated formulations. Overall, the review seeks to provide a comprehensive overview of the current state of EOs research and promote future innovations and advancements in their production, characterization, and clinical utilization.
Essential oils (EOs), extracted from various aromatic plants, have numerous health benefits and are widely used in medicine. However, their low yields, complex composition, poor solubility, limited bioavailability, and sensitivity to environmental factors such as light, heat, and oxidation pose challenges that hinder their applications. This review provides a comprehensive overview of the plant biosynthetic pathways involved in the production of EOs and discusses strategies to enhance their production through metabolic and process regulation. Additionally, it meticulously examines the development of diverse techniques for the extraction, separation, and purification of EOs, as well as sophisticated analytical methods for the identification of their components. The bioactivities of EOs and the biomedical applications of both native and encapsulated EOs in various in vitro and in vivo models are discussed. Moreover, the encapsulation-induced enhancement of the efficacy and stability of EOs is highlighted. Finally, this review details the current clinical trials involving EOs and their encapsulated formulations. Overall, the review seeks to provide a comprehensive overview of the current state of EOs research and promote future innovations and advancements in their production, characterization, and clinical utilization.
2026, 37(12): 112722
doi: 10.1016/j.cclet.2026.112722
Abstract:
The efficient utilization of biomass energy serves as an effective approach to replace fossil fuels and advance sustainable social development. Among these, alcohols and aldehydes derived from biomass represent crucial basic raw materials in industrial synthesis. Photoelectrocatalysis (PEC) technology has opened a highly competitive pathway for producing high-value-added chemicals, comprehensively meeting requirements for controllable selectivity, green processes, and synergistic systems. These advantages are unparalleled by other methods. However, insufficient product selectivity remains the primary bottleneck before industrialization. This review summarizes the fundamental mechanisms of PEC upgrading of biomass-derived alcohols/aldehydes, along with the selection and design of photoanode materials. It focuses on the role of photoanodes in regulating oxidation pathways: Regulating oxidized depth, selecting oxidized functional group at different positions, controlling oxidized quantity of functional groups, and the C-C bond breakage. Finally, the future development and potential challenges in this field are envisioned on the basis of existing technologies.
The efficient utilization of biomass energy serves as an effective approach to replace fossil fuels and advance sustainable social development. Among these, alcohols and aldehydes derived from biomass represent crucial basic raw materials in industrial synthesis. Photoelectrocatalysis (PEC) technology has opened a highly competitive pathway for producing high-value-added chemicals, comprehensively meeting requirements for controllable selectivity, green processes, and synergistic systems. These advantages are unparalleled by other methods. However, insufficient product selectivity remains the primary bottleneck before industrialization. This review summarizes the fundamental mechanisms of PEC upgrading of biomass-derived alcohols/aldehydes, along with the selection and design of photoanode materials. It focuses on the role of photoanodes in regulating oxidation pathways: Regulating oxidized depth, selecting oxidized functional group at different positions, controlling oxidized quantity of functional groups, and the C-C bond breakage. Finally, the future development and potential challenges in this field are envisioned on the basis of existing technologies.
2026, 37(12): 112736
doi: 10.1016/j.cclet.2026.112736
Abstract:
Emerging contaminants (ECs), due to their high biological activity and environmental persistence, pose a potential and long-term significant threat to the ecosystem and human health, even in trace amounts. The efficient removal of environmentally persistent and biologically active ECs by conventional wastewater treatment remains challenging. Peracetic acid-based advanced oxidation processes (PAA-AOPs) have been considered as promising technologies, which can offer high removal efficiency. However, no related review about PAA-AOPs has been reported. This review begins by examining recent developments in different strategies for activating peracetic acid (PAA) and outlines the corresponding mechanistic pathways. It then offers an in-depth discussion of how major reactive species, such as hydroxyl radicals, carbon-centered radicals, and singlet oxygen, are produced and transformed within these systems. Because real aquatic environments are chemically complex, the review also considers how operational factors and water quality parameters, including pH, oxidant concentration, catalyst dosage, and the presence of coexisting ions or organic matter, affect pollutant degradation and influence the underlying reaction mechanisms. Subsequent sections address the main technical barriers that currently limit large-scale application of PAA-based oxidation systems and propose practical solutions and future research directions to enhance their environmental performance. Altogether, the article seeks to advance understanding of PAA-AOP mechanisms and to provide useful guidance for designing more effective processes for water purification.
Emerging contaminants (ECs), due to their high biological activity and environmental persistence, pose a potential and long-term significant threat to the ecosystem and human health, even in trace amounts. The efficient removal of environmentally persistent and biologically active ECs by conventional wastewater treatment remains challenging. Peracetic acid-based advanced oxidation processes (PAA-AOPs) have been considered as promising technologies, which can offer high removal efficiency. However, no related review about PAA-AOPs has been reported. This review begins by examining recent developments in different strategies for activating peracetic acid (PAA) and outlines the corresponding mechanistic pathways. It then offers an in-depth discussion of how major reactive species, such as hydroxyl radicals, carbon-centered radicals, and singlet oxygen, are produced and transformed within these systems. Because real aquatic environments are chemically complex, the review also considers how operational factors and water quality parameters, including pH, oxidant concentration, catalyst dosage, and the presence of coexisting ions or organic matter, affect pollutant degradation and influence the underlying reaction mechanisms. Subsequent sections address the main technical barriers that currently limit large-scale application of PAA-based oxidation systems and propose practical solutions and future research directions to enhance their environmental performance. Altogether, the article seeks to advance understanding of PAA-AOP mechanisms and to provide useful guidance for designing more effective processes for water purification.
2026, 37(12): 112737
doi: 10.1016/j.cclet.2026.112737
Abstract:
The inappropriate use of antibiotics has accelerated antimicrobial resistance development. Antimicrobial susceptibility testing (AST) is a critical tool for guiding clinical antibiotic administration and mitigating the progression of antimicrobial resistance. A major limitation of conventional AST methods is their prolonged duration, which severely restricts their clinical utility. Recent advances in micro/nano technology have offered innovative solutions to this longstanding bottleneck. By leveraging nanomaterials and micro/nano devices, novel AST platforms have been developed that dramatically reduce detection time. This review summarizes recent progress in micro/nano technology-based AST platforms, highlights the outstanding performance of nanomaterials and micro/nano devices in accelerating AST, and discusses future prospects for their clinical translation.
The inappropriate use of antibiotics has accelerated antimicrobial resistance development. Antimicrobial susceptibility testing (AST) is a critical tool for guiding clinical antibiotic administration and mitigating the progression of antimicrobial resistance. A major limitation of conventional AST methods is their prolonged duration, which severely restricts their clinical utility. Recent advances in micro/nano technology have offered innovative solutions to this longstanding bottleneck. By leveraging nanomaterials and micro/nano devices, novel AST platforms have been developed that dramatically reduce detection time. This review summarizes recent progress in micro/nano technology-based AST platforms, highlights the outstanding performance of nanomaterials and micro/nano devices in accelerating AST, and discusses future prospects for their clinical translation.
2026, 37(12): 112742
doi: 10.1016/j.cclet.2026.112742
Abstract:
The highly selective and effective separation of radioactive uranium from wastewater containing uranium and seawater through photocatalytic technique holds great significance for alleviating the energy crisis and protecting the environment, yet it also presents great challenges. Covalent organic frameworks (COFs) are considered desirable photocatalytic candidates for separating hexavalent uranium (U(Ⅵ)) on account of their tunable and programmable structure. Herein, the crucial advances in COF-based photocatalysts for U(Ⅵ) photocatalytic reduction from radioactive wastewater and seawater are presented, emphasizing particularly the relationship between structure-property-activity. A detailed discussion is conducted on the design of linkage of COF for important factors affecting photocatalysis. Subsequently, the performance enhancement strategies (such as morphology control, skeleton functionalization, hybrid materials, metalized, elemental doping and piezo-photocatalysis) are systematically highlighted. The experimental parameters of COF photocatalysts for practical application in radioactive wastewater or seawater are discussed, and the underlying mechanisms of U(Ⅵ) photocatalytic reduction by COF materials carefully analyzed. Finally, the challenges and prospects of COFs-based photocatalysts on separation U(Ⅵ) are envisaged, and a variety of strategies for improving the performance are elaborated. This review establishes the structure-activity relationship between COF linkages, band structure, and uranium reduction efficiency, which aims to and affords guidance for the design and synthesis of diverse COF-based photocatalyst with excellent photocatalytic performance to achieve the high-efficiency photoreduction U(Ⅵ) from radioactive wastewater and seawater.
The highly selective and effective separation of radioactive uranium from wastewater containing uranium and seawater through photocatalytic technique holds great significance for alleviating the energy crisis and protecting the environment, yet it also presents great challenges. Covalent organic frameworks (COFs) are considered desirable photocatalytic candidates for separating hexavalent uranium (U(Ⅵ)) on account of their tunable and programmable structure. Herein, the crucial advances in COF-based photocatalysts for U(Ⅵ) photocatalytic reduction from radioactive wastewater and seawater are presented, emphasizing particularly the relationship between structure-property-activity. A detailed discussion is conducted on the design of linkage of COF for important factors affecting photocatalysis. Subsequently, the performance enhancement strategies (such as morphology control, skeleton functionalization, hybrid materials, metalized, elemental doping and piezo-photocatalysis) are systematically highlighted. The experimental parameters of COF photocatalysts for practical application in radioactive wastewater or seawater are discussed, and the underlying mechanisms of U(Ⅵ) photocatalytic reduction by COF materials carefully analyzed. Finally, the challenges and prospects of COFs-based photocatalysts on separation U(Ⅵ) are envisaged, and a variety of strategies for improving the performance are elaborated. This review establishes the structure-activity relationship between COF linkages, band structure, and uranium reduction efficiency, which aims to and affords guidance for the design and synthesis of diverse COF-based photocatalyst with excellent photocatalytic performance to achieve the high-efficiency photoreduction U(Ⅵ) from radioactive wastewater and seawater.
2026, 37(12): 112747
doi: 10.1016/j.cclet.2026.112747
Abstract:
Metal halide perovskites have become very promising optoelectronic materials because of their excellent photophysical features such as wide absorption spectra, adjustable band structures and long diffusion lengths of charge carriers. However, the conventional lead-based perovskites cannot be deployed in practice because of their intrinsic toxicity and lack of stability at room temperature. These drawbacks have triggered a series of studies on lead-free perovskite substitutes, which can be more environmentally friendly and structurally resilient. Specifically, new developments in lead-free halide perovskites have created new possibilities in photocatalysis, allowing their use in solar-to-chemical energy conversion and photocatalytic organic reactions. The present review is a systematic overview of the current advancements in lead-free perovskite photocatalysts and outlines some of the challenges faced and the fundamental constraints in the current state, as well as provides some insight into the future research directions and possible applications.
Metal halide perovskites have become very promising optoelectronic materials because of their excellent photophysical features such as wide absorption spectra, adjustable band structures and long diffusion lengths of charge carriers. However, the conventional lead-based perovskites cannot be deployed in practice because of their intrinsic toxicity and lack of stability at room temperature. These drawbacks have triggered a series of studies on lead-free perovskite substitutes, which can be more environmentally friendly and structurally resilient. Specifically, new developments in lead-free halide perovskites have created new possibilities in photocatalysis, allowing their use in solar-to-chemical energy conversion and photocatalytic organic reactions. The present review is a systematic overview of the current advancements in lead-free perovskite photocatalysts and outlines some of the challenges faced and the fundamental constraints in the current state, as well as provides some insight into the future research directions and possible applications.
2026, 37(12): 112748
doi: 10.1016/j.cclet.2026.112748
Abstract:
gem-Diboron compounds have attracted considerable attention in synthetic chemistry owing to their remarkable versatility and broad range of transformations. While the reactivity of gem-diboron compounds, such as anions and carbocation equivalents, has been extensively studied, the chemistry of gem-diboryl radicals remains comparatively underexplored. Nonetheless, this emerging field is developing rapidly and shows great promise for applications in both organic synthesis and medicinal chemistry. However, a comprehensive review of this field is still missing. This review summarizes recent advances in the chemistry of gem-diboryl radicals, highlighting their growing importance as highly versatile synthons in radical-mediated transformations. The manuscript systematically classifies the generation of gem-diboryl radicals into several pathways, including single-electron transfer (SET), energy transfer (EnT), and halogen-atom transfer (XAT). Furthermore, it discusses the underlying mechanisms, representative synthetic applications, and existing challenges associated with these reactions. Finally, the review provides an outlook on future directions for effectively harnessing gem-diboryl radicals in modern synthesis.
gem-Diboron compounds have attracted considerable attention in synthetic chemistry owing to their remarkable versatility and broad range of transformations. While the reactivity of gem-diboron compounds, such as anions and carbocation equivalents, has been extensively studied, the chemistry of gem-diboryl radicals remains comparatively underexplored. Nonetheless, this emerging field is developing rapidly and shows great promise for applications in both organic synthesis and medicinal chemistry. However, a comprehensive review of this field is still missing. This review summarizes recent advances in the chemistry of gem-diboryl radicals, highlighting their growing importance as highly versatile synthons in radical-mediated transformations. The manuscript systematically classifies the generation of gem-diboryl radicals into several pathways, including single-electron transfer (SET), energy transfer (EnT), and halogen-atom transfer (XAT). Furthermore, it discusses the underlying mechanisms, representative synthetic applications, and existing challenges associated with these reactions. Finally, the review provides an outlook on future directions for effectively harnessing gem-diboryl radicals in modern synthesis.
2026, 37(12): 112751
doi: 10.1016/j.cclet.2026.112751
Abstract:
Core-shell structured materials, with their distinctive physical and chemical properties, have demonstrated significant potential for a wide range of applications in the field of photocatalysis. However, the relationship between the core-shell structured materials and their performance in photocatalysis reactions remains unclear. In this review, the recent advancements in the controlled synthesis of core-shell structured materials are discussed, as well as various optimization strategies of core-shell structured materials with regard to photocatalysis application. Fabrication strategies for sophisticated core-shell structured materials can be categorized into two primary types, including templating methods and template-free methods. Furthermore, the study discusses optimization strategies such as embedding heterojunctions, engineering exposed facet, constructing defect, and modulating morphology to enhance the efficiency and stability of catalytic reactions. Niche applications of core-shell structured materials in photocatalytic pollutant degradation, photocatalytic CO2 reduction, photocatalytic hydrogen evolution are discussed in detail. To conclude, this study summarizes the structure-performance correlation between core-shell structured materials and photocatalysis and offers insights into future research directions and development opportunities for sophisticated core-shell structured materials. This comprehensive review aims to serve as a valuable guide for the rational design and application of core-shell structured materials, which are essential for the advancement of high-performance catalytic systems.
Core-shell structured materials, with their distinctive physical and chemical properties, have demonstrated significant potential for a wide range of applications in the field of photocatalysis. However, the relationship between the core-shell structured materials and their performance in photocatalysis reactions remains unclear. In this review, the recent advancements in the controlled synthesis of core-shell structured materials are discussed, as well as various optimization strategies of core-shell structured materials with regard to photocatalysis application. Fabrication strategies for sophisticated core-shell structured materials can be categorized into two primary types, including templating methods and template-free methods. Furthermore, the study discusses optimization strategies such as embedding heterojunctions, engineering exposed facet, constructing defect, and modulating morphology to enhance the efficiency and stability of catalytic reactions. Niche applications of core-shell structured materials in photocatalytic pollutant degradation, photocatalytic CO2 reduction, photocatalytic hydrogen evolution are discussed in detail. To conclude, this study summarizes the structure-performance correlation between core-shell structured materials and photocatalysis and offers insights into future research directions and development opportunities for sophisticated core-shell structured materials. This comprehensive review aims to serve as a valuable guide for the rational design and application of core-shell structured materials, which are essential for the advancement of high-performance catalytic systems.
2026, 37(12): 112773
doi: 10.1016/j.cclet.2026.112773
Abstract:
Adhesive flexible bioelectronics play an important role in the field of bioelectronic medicine. For example, adhesive flexible bioelectronics can not only be used to monitor electrophysiological signals to diagnose neurological diseases, but also to treat neurological diseases or promote wound healing through electrical stimulation. Existing reviews on adhesive flexible bioelectronics only focuses on conductive hydrogel adhesive. In fact, in addition to the conductive hydrogel adhesive used to enhance the adhesion between flexible bioelectronics and tissues, polymer elastomer substrates with adhesion and hydrogel adhesives are employed as the substrate of flexible electronics, endowing flexible electronics with adhesion to tissue. In this paper, polymer elastomer with adhesion as the substrate of bioelectronics, the hydrogel adhesive as the substrate, and the conductive hydrogel adhesive as the bioelectronics are discussed. respectively. Among them, the strategies for endowing polymer elastomers with adhesion include constructing micro nano structures and modifying hydrophilic groups; the hydrogel adhesive as substrates does not need to consider the conductivity and swelling because it only needs to adjust adhesion and swelling performance, and cannot be used for transmission signal; conductive hydrogel adhesive as flexible bioelectronics not only needs to regulate adhesion, but also enhance conductivity, swell resistance, achieve anti-adhesion, and self-healing properties. Finally, the challenges and future opportunities of adhesive flexible bioelectronics are considered.
Adhesive flexible bioelectronics play an important role in the field of bioelectronic medicine. For example, adhesive flexible bioelectronics can not only be used to monitor electrophysiological signals to diagnose neurological diseases, but also to treat neurological diseases or promote wound healing through electrical stimulation. Existing reviews on adhesive flexible bioelectronics only focuses on conductive hydrogel adhesive. In fact, in addition to the conductive hydrogel adhesive used to enhance the adhesion between flexible bioelectronics and tissues, polymer elastomer substrates with adhesion and hydrogel adhesives are employed as the substrate of flexible electronics, endowing flexible electronics with adhesion to tissue. In this paper, polymer elastomer with adhesion as the substrate of bioelectronics, the hydrogel adhesive as the substrate, and the conductive hydrogel adhesive as the bioelectronics are discussed. respectively. Among them, the strategies for endowing polymer elastomers with adhesion include constructing micro nano structures and modifying hydrophilic groups; the hydrogel adhesive as substrates does not need to consider the conductivity and swelling because it only needs to adjust adhesion and swelling performance, and cannot be used for transmission signal; conductive hydrogel adhesive as flexible bioelectronics not only needs to regulate adhesion, but also enhance conductivity, swell resistance, achieve anti-adhesion, and self-healing properties. Finally, the challenges and future opportunities of adhesive flexible bioelectronics are considered.
2026, 37(12): 112819
doi: 10.1016/j.cclet.2026.112819
Abstract:
Carbon nanomaterials have emerged as promising electrocatalysts for sustainable energy storage and conversion. As a unique allotrope, fullerenes offer distinct advantages, including high reactivity and a highly curved structure. However, their electrocatalytic application is limited by inherently low electrical conductivity, limited specific surface area, and insufficient intrinsic activity. Pyrolytic transformation of fullerenes provides an effective strategy to overcome these limitations, yielding carbon materials that are rich in defects, feature porous architectures with high surface areas, and possess tunable surface chemistry. These attributes meet the critical requirements for electrocatalysis—abundant active sites and efficient mass/charge transport—establishing pyrolyzed fullerene-derived carbons as a highly promising platform for advanced electrocatalysis. This review summarizes the structural evolution mechanisms during pyrolysis, the advantages of the resulting carbons, and their characterization methods. It then analyzes key modification strategies, such as hierarchical engineering, heteroatom doping, and metal composites, to clarify the structure-performance relationships. The representative applications and performance of these derived carbon materials in diverse electrocatalytic reactions are then highlighted. Finally, future opportunities and core challenges are discussed, providing scientific guidance for the rational design of next-generation electrocatalysts from pyrolyzed fullerenes.
Carbon nanomaterials have emerged as promising electrocatalysts for sustainable energy storage and conversion. As a unique allotrope, fullerenes offer distinct advantages, including high reactivity and a highly curved structure. However, their electrocatalytic application is limited by inherently low electrical conductivity, limited specific surface area, and insufficient intrinsic activity. Pyrolytic transformation of fullerenes provides an effective strategy to overcome these limitations, yielding carbon materials that are rich in defects, feature porous architectures with high surface areas, and possess tunable surface chemistry. These attributes meet the critical requirements for electrocatalysis—abundant active sites and efficient mass/charge transport—establishing pyrolyzed fullerene-derived carbons as a highly promising platform for advanced electrocatalysis. This review summarizes the structural evolution mechanisms during pyrolysis, the advantages of the resulting carbons, and their characterization methods. It then analyzes key modification strategies, such as hierarchical engineering, heteroatom doping, and metal composites, to clarify the structure-performance relationships. The representative applications and performance of these derived carbon materials in diverse electrocatalytic reactions are then highlighted. Finally, future opportunities and core challenges are discussed, providing scientific guidance for the rational design of next-generation electrocatalysts from pyrolyzed fullerenes.
2026, 37(12): 112836
doi: 10.1016/j.cclet.2026.112836
Abstract:
Potassium-ion batteries (PIBs) are promising energy storage technologies due to their low-temperature performance, fast-charging capabilities, suitable voltage, and cost-effectiveness. However, challenges such as limited capacity, slow kinetics, and volume expansion hinder their practical application. Existing conventional modification strategies, such as surface coating, elemental doping, and structural nanostructuring, primarily focus on optimizing individual properties and struggle to fundamentally resolve the coupled effects of the aforementioned multidimensional bottlenecks. During the research and development of PIBs, researchers discovered that the microstructure of certain electrode materials exhibits a high degree of similarity to natural biological structures, providing a novel breakthrough approach for optimizing electrode performance. This review first summarizes the fundamental principles of quasi-biomimetic structures, focusing on the mechanisms by which rapid ion transport, exceptional structural stability, and abundant active sites significantly enhance the performance of energy storage materials. Subsequently, the review provides a comprehensive overview of research progress in quasi-biomimetic design for PIBs electrode materials, proposing corresponding quasi-biomimetic design optimization schemes to address challenges posed by different potassium storage mechanisms. Finally, this review discusses the challenges and future development directions that key materials for quasi-biomimetic PIBs may face, providing some insights into linking quasi-biomimetic design principles with energy storage materials.
Potassium-ion batteries (PIBs) are promising energy storage technologies due to their low-temperature performance, fast-charging capabilities, suitable voltage, and cost-effectiveness. However, challenges such as limited capacity, slow kinetics, and volume expansion hinder their practical application. Existing conventional modification strategies, such as surface coating, elemental doping, and structural nanostructuring, primarily focus on optimizing individual properties and struggle to fundamentally resolve the coupled effects of the aforementioned multidimensional bottlenecks. During the research and development of PIBs, researchers discovered that the microstructure of certain electrode materials exhibits a high degree of similarity to natural biological structures, providing a novel breakthrough approach for optimizing electrode performance. This review first summarizes the fundamental principles of quasi-biomimetic structures, focusing on the mechanisms by which rapid ion transport, exceptional structural stability, and abundant active sites significantly enhance the performance of energy storage materials. Subsequently, the review provides a comprehensive overview of research progress in quasi-biomimetic design for PIBs electrode materials, proposing corresponding quasi-biomimetic design optimization schemes to address challenges posed by different potassium storage mechanisms. Finally, this review discusses the challenges and future development directions that key materials for quasi-biomimetic PIBs may face, providing some insights into linking quasi-biomimetic design principles with energy storage materials.
2026, 37(12): 113079
doi: 10.1016/j.cclet.2026.113079
Abstract:
Impaired diabetic wound healing is a major complication of diabetes, primarily driven by persistent inflammation resulting from dysregulated macrophage polarization. Exosomes are cell-derived extracellular vesicles carrying diverse active cargoes. Exosomes from specific origins represent a promising cell-free option for diabetic wound healing, with their capacity to induce M2 macrophage polarization serving as a key therapeutic mechanism to resolve the chronic inflammation. However, the therapeutic efficacy of naïve exosomes is constrained by inherent limitations, including suboptimal levels of active cargo, poor stability in the wound microenvironment, and insufficient targeting specificity. To address these challenges, transdermal delivery of engineered exosomes had recently been developed. This review provides a comprehensive overview of recent advances in the application of these systems for promoting diabetic wound healing through precise regulation of macrophage polarization. Key strategies discussed include cargo loading techniques, surface modification for enhanced targeting, and integration with localized delivery platforms such as hydrogels, microneedles, porous sponges, three dimensions (3D)-printed scaffolds and metal-organic framework (MOF)-based scaffolds. By improving exosome stability, retention, targeting ability, and controlled release combined with the co-delivery of therapeutic cargo, these platforms collectively facilitate M2 macrophage polarization, optimize the wound microenvironment, and accelerate healing. Finally, we highlight current challenges and outline future directions, aiming to establish a theoretical foundation for next-generation immunomodulatory therapies leveraging engineered exosomes to induce M2 macrophage polarization for diabetic wound treatment.
Impaired diabetic wound healing is a major complication of diabetes, primarily driven by persistent inflammation resulting from dysregulated macrophage polarization. Exosomes are cell-derived extracellular vesicles carrying diverse active cargoes. Exosomes from specific origins represent a promising cell-free option for diabetic wound healing, with their capacity to induce M2 macrophage polarization serving as a key therapeutic mechanism to resolve the chronic inflammation. However, the therapeutic efficacy of naïve exosomes is constrained by inherent limitations, including suboptimal levels of active cargo, poor stability in the wound microenvironment, and insufficient targeting specificity. To address these challenges, transdermal delivery of engineered exosomes had recently been developed. This review provides a comprehensive overview of recent advances in the application of these systems for promoting diabetic wound healing through precise regulation of macrophage polarization. Key strategies discussed include cargo loading techniques, surface modification for enhanced targeting, and integration with localized delivery platforms such as hydrogels, microneedles, porous sponges, three dimensions (3D)-printed scaffolds and metal-organic framework (MOF)-based scaffolds. By improving exosome stability, retention, targeting ability, and controlled release combined with the co-delivery of therapeutic cargo, these platforms collectively facilitate M2 macrophage polarization, optimize the wound microenvironment, and accelerate healing. Finally, we highlight current challenges and outline future directions, aiming to establish a theoretical foundation for next-generation immunomodulatory therapies leveraging engineered exosomes to induce M2 macrophage polarization for diabetic wound treatment.
2026, 37(12): 113100
doi: 10.1016/j.cclet.2026.113100
Abstract:
Lithium-ion batteries (LIBs), featuring high energy density and long cycle life, have evolved into a critical technological pillar for global energy transition and dual-carbon target achievement, with fast-growing demand in electric transportation and grid-scale energy storage. High-nickel layered oxides (HNLOs) are widely recognized as one of the most promising cathode candidates for next-generation high-energy-density LIBs, owing to their superior reversible capacity, moderate operating voltage and low material cost. Nevertheless, the continuous increase in nickel content and cutting-off voltage triggers severe chemical, structural and mechanical instability, creating an inherent contradiction between high specific energy and long-term durability, which has become the core bottleneck for their large-scale commercialization. In this review, we systematically elaborate the multi-scale coupled failure mechanisms of HNLOs from a chemical-structural-mechanical perspective, including interfacial parasitic side reactions, irreversible lattice oxygen release, cation mixing-induced phase transformation, and chemo-mechanical failure. We comprehensively summarize state-of-the-art modification strategies, clarify their regulatory mechanisms and evolution from empirical optimization to rational design, identify critical gaps between lab-scale research and industrial application, and propose a holistic design philosophy for high-performance HNLOs. This review provides systematic theoretical and practical guidance for developing durable high-energy-density LIB cathodes.
Lithium-ion batteries (LIBs), featuring high energy density and long cycle life, have evolved into a critical technological pillar for global energy transition and dual-carbon target achievement, with fast-growing demand in electric transportation and grid-scale energy storage. High-nickel layered oxides (HNLOs) are widely recognized as one of the most promising cathode candidates for next-generation high-energy-density LIBs, owing to their superior reversible capacity, moderate operating voltage and low material cost. Nevertheless, the continuous increase in nickel content and cutting-off voltage triggers severe chemical, structural and mechanical instability, creating an inherent contradiction between high specific energy and long-term durability, which has become the core bottleneck for their large-scale commercialization. In this review, we systematically elaborate the multi-scale coupled failure mechanisms of HNLOs from a chemical-structural-mechanical perspective, including interfacial parasitic side reactions, irreversible lattice oxygen release, cation mixing-induced phase transformation, and chemo-mechanical failure. We comprehensively summarize state-of-the-art modification strategies, clarify their regulatory mechanisms and evolution from empirical optimization to rational design, identify critical gaps between lab-scale research and industrial application, and propose a holistic design philosophy for high-performance HNLOs. This review provides systematic theoretical and practical guidance for developing durable high-energy-density LIB cathodes.
2026, 37(12): 113188
doi: 10.1016/j.cclet.2026.113188
Abstract:
This review critically examines the rapidly developing field of heterogeneous material-microbe hybrid systems for advanced wastewater remediation. To address the inherent limitations of conventional physico-chemical and biological methods, such as low efficiency and poor stability, these systems combine conductive or photoactive materials (e.g., zero-valent iron, magnetite, graphitic carbon nitride) with functional microorganisms to construct synergistic interfaces. These interfaces facilitate crucial direct or indirect electron transfer, significantly enhance microbial metabolic activity, and provide protective microenvironments. Recent advances underscore their remarkable effectiveness in the degradation of refractory organic pollutants, enhanced nitrogen removal and bioreduction of heavy metal, even under challenging low-substrate conditions. Despite promising progress, significant challenges persist, including a limited mechanistic understanding of interfacial electron transfer at the molecular level and a notable gap in the design of efficient reactor configurations. This work provides a systematic analysis of interfacial electron transfer mechanisms in heterogeneous material-microorganism hybrid systems, categorizes the photocatalytic biohybrid systems and non-photocatalytic biohybrid systems for enhanced water remediation, and evaluates reactor design strategies. Finally, it outlines future research priorities, emphasizing the development of stable and cost-effective heterogeneous materials, advanced microbial protection strategies, integration with reactor engineering and real-world scenarios, as well as long-term economic and environmental assessment.
This review critically examines the rapidly developing field of heterogeneous material-microbe hybrid systems for advanced wastewater remediation. To address the inherent limitations of conventional physico-chemical and biological methods, such as low efficiency and poor stability, these systems combine conductive or photoactive materials (e.g., zero-valent iron, magnetite, graphitic carbon nitride) with functional microorganisms to construct synergistic interfaces. These interfaces facilitate crucial direct or indirect electron transfer, significantly enhance microbial metabolic activity, and provide protective microenvironments. Recent advances underscore their remarkable effectiveness in the degradation of refractory organic pollutants, enhanced nitrogen removal and bioreduction of heavy metal, even under challenging low-substrate conditions. Despite promising progress, significant challenges persist, including a limited mechanistic understanding of interfacial electron transfer at the molecular level and a notable gap in the design of efficient reactor configurations. This work provides a systematic analysis of interfacial electron transfer mechanisms in heterogeneous material-microorganism hybrid systems, categorizes the photocatalytic biohybrid systems and non-photocatalytic biohybrid systems for enhanced water remediation, and evaluates reactor design strategies. Finally, it outlines future research priorities, emphasizing the development of stable and cost-effective heterogeneous materials, advanced microbial protection strategies, integration with reactor engineering and real-world scenarios, as well as long-term economic and environmental assessment.
2026, 37(12): 113340
doi: 10.1016/j.cclet.2026.113340
Abstract:
Covalent organic frameworks (COFs) are crystalline photocatalytic materials with tunable structures, but their light-to-chemical energy conversion efficiency is limited by severe carrier recombination and inadequate light harvesting. Asymmetric defect engineering relies on lattice distortion, vacancy creation, and asymmetric grafting to induce symmetry breaking of the framework, which serves as an effective means to modulate the electronic structure. This review attempts to systematically demonstrate that this strategy can facilitate the clarification of charge-transfer dynamics through band reconstruction and internal electric field construction, and may further provide insight into energy superposition and sequential electron transfer pathways under multiphoton excitation based on existing theoretical mechanisms. We also summarize strategies for improving photocatalytic performance and discuss recent advances in COF-based materials for photocatalytic energy conversion. Existing challenges, including the precise controllability of defect structures, framework stability, and in-situ quantitative characterization, are critically analyzed, with the aim of offering theoretical guidance for the rational design of efficient COF-based photocatalytic systems.
Covalent organic frameworks (COFs) are crystalline photocatalytic materials with tunable structures, but their light-to-chemical energy conversion efficiency is limited by severe carrier recombination and inadequate light harvesting. Asymmetric defect engineering relies on lattice distortion, vacancy creation, and asymmetric grafting to induce symmetry breaking of the framework, which serves as an effective means to modulate the electronic structure. This review attempts to systematically demonstrate that this strategy can facilitate the clarification of charge-transfer dynamics through band reconstruction and internal electric field construction, and may further provide insight into energy superposition and sequential electron transfer pathways under multiphoton excitation based on existing theoretical mechanisms. We also summarize strategies for improving photocatalytic performance and discuss recent advances in COF-based materials for photocatalytic energy conversion. Existing challenges, including the precise controllability of defect structures, framework stability, and in-situ quantitative characterization, are critically analyzed, with the aim of offering theoretical guidance for the rational design of efficient COF-based photocatalytic systems.
2026, 37(12): 113390
doi: 10.1016/j.cclet.2026.113390
Abstract:
Immunotherapy has been the most attractive and promising strategy to conquer tumors. However, tumor immunotherapy faces many challenges, such as the immunosuppressive tumor microenvironment (TME), poor T cell infiltration, and low immune response. Recently, numerous studies have been published to overcome these barriers, and many emerging immunotherapies have been developed. In this review, we first analyze the key barriers that compromise tumor immunotherapy, focusing on the immunosuppressive TME. Next, we summarize strategies to overcome these barriers, including inducing immunogenic cell death, promoting antigen presentation, improving T cell infiltration, and blocking immune checkpoints. We then highlight emerging new strategies for tumor immunotherapy, such as regulating tumor immune microenvironment network, engineering cell therapies, utilizing microbial-based therapies, and applying targeted protein degradation. The aforementioned innovative therapeutic strategies are expected to propel tumor immunotherapy into a completely new phase of development.
Immunotherapy has been the most attractive and promising strategy to conquer tumors. However, tumor immunotherapy faces many challenges, such as the immunosuppressive tumor microenvironment (TME), poor T cell infiltration, and low immune response. Recently, numerous studies have been published to overcome these barriers, and many emerging immunotherapies have been developed. In this review, we first analyze the key barriers that compromise tumor immunotherapy, focusing on the immunosuppressive TME. Next, we summarize strategies to overcome these barriers, including inducing immunogenic cell death, promoting antigen presentation, improving T cell infiltration, and blocking immune checkpoints. We then highlight emerging new strategies for tumor immunotherapy, such as regulating tumor immune microenvironment network, engineering cell therapies, utilizing microbial-based therapies, and applying targeted protein degradation. The aforementioned innovative therapeutic strategies are expected to propel tumor immunotherapy into a completely new phase of development.
2026, 37(12): 111559
doi: 10.1016/j.cclet.2025.111559
Abstract:
Ferroelectrics are highly desirable for their potential applications in the fields of optoelectronic sensors, energy conversion, and memorizers. The discovery of two-dimensional ferroelectrics with vertical polarization presents an ideal platform to miniaturize the smart devices. Herein, we demonstrate a new two-dimensional organic–inorganic hybrid layered perovskite, (2-F-C6H4CH2CH2NH3)2[CdCl4], which exhibits a rare flipping and twisting ferroelectric phase transition at near room temperature (295/298 K), accompany by an unusual frequency-dependent dielectric behaviour, strong second harmonic generation intensity (2.75 times of KH2PO4), and a large vertical spontaneous polarization (9.45 μC/cm2) with a low coercive electric field (1.07 kV/cm). This work throws light on the exploration of two-dimensional hybrid layered perovskite ferroelectrics for applications in the field of multifunctional devices.
Ferroelectrics are highly desirable for their potential applications in the fields of optoelectronic sensors, energy conversion, and memorizers. The discovery of two-dimensional ferroelectrics with vertical polarization presents an ideal platform to miniaturize the smart devices. Herein, we demonstrate a new two-dimensional organic–inorganic hybrid layered perovskite, (2-F-C6H4CH2CH2NH3)2[CdCl4], which exhibits a rare flipping and twisting ferroelectric phase transition at near room temperature (295/298 K), accompany by an unusual frequency-dependent dielectric behaviour, strong second harmonic generation intensity (2.75 times of KH2PO4), and a large vertical spontaneous polarization (9.45 μC/cm2) with a low coercive electric field (1.07 kV/cm). This work throws light on the exploration of two-dimensional hybrid layered perovskite ferroelectrics for applications in the field of multifunctional devices.
2026, 37(12): 111565
doi: 10.1016/j.cclet.2025.111565
Abstract:
The development of green and scientific recycling of spent lithium-ion batteries is closely intertwined with the sustained advancement of the new energy industry chain. However, direct regeneration has emerged as a superior alternative owing to its streamlined processes and high added-value advantages. In response to the pronounced grain boundary effects, poor structural stability, and severe interfacial side reactions in regenerated polycrystalline particles, this work proposes a synergistic strategy of thermodynamic regulation in sub-molten state and in situ self-formed modification with fast ionic conductor Li3N phases for single-crystallization regeneration of spent LiNi0.8CoxMn0.2-xO2 materials. Based on thermodynamic regulation, the decomposition product NH3 reacts with a lithium compensation agent, forming the fast ionic conductor Li3N interface on the surface of regenerated single-crystal particles. Through the regulation of urea's thermodynamic behavior, urea penetrates along grain boundaries in the sub-molten state, thereby weakening the grain boundary bonding strength and inducing directional fracture. This process enables the fragmentation of spent polycrystalline materials into submicron-sized particles, ultimately achieving single-crystallization regeneration. This strategy has effectively restored and optimized the crystal structure of ternary materials, recovered their electrochemical performance, and enhanced the conductivity of regenerated materials while suppressing transition metal dissolution. Electrochemical tests demonstrate that the regenerated material delivers an initial capacity of 194.42 mAh/g and retains a discharge specific capacity of 158.9 mAh/g after 200 cycles. This effective strategy provides valuable insights into the single-crystallization regeneration of spent NCM cathodes from lithium-ion batteries
The development of green and scientific recycling of spent lithium-ion batteries is closely intertwined with the sustained advancement of the new energy industry chain. However, direct regeneration has emerged as a superior alternative owing to its streamlined processes and high added-value advantages. In response to the pronounced grain boundary effects, poor structural stability, and severe interfacial side reactions in regenerated polycrystalline particles, this work proposes a synergistic strategy of thermodynamic regulation in sub-molten state and in situ self-formed modification with fast ionic conductor Li3N phases for single-crystallization regeneration of spent LiNi0.8CoxMn0.2-xO2 materials. Based on thermodynamic regulation, the decomposition product NH3 reacts with a lithium compensation agent, forming the fast ionic conductor Li3N interface on the surface of regenerated single-crystal particles. Through the regulation of urea's thermodynamic behavior, urea penetrates along grain boundaries in the sub-molten state, thereby weakening the grain boundary bonding strength and inducing directional fracture. This process enables the fragmentation of spent polycrystalline materials into submicron-sized particles, ultimately achieving single-crystallization regeneration. This strategy has effectively restored and optimized the crystal structure of ternary materials, recovered their electrochemical performance, and enhanced the conductivity of regenerated materials while suppressing transition metal dissolution. Electrochemical tests demonstrate that the regenerated material delivers an initial capacity of 194.42 mAh/g and retains a discharge specific capacity of 158.9 mAh/g after 200 cycles. This effective strategy provides valuable insights into the single-crystallization regeneration of spent NCM cathodes from lithium-ion batteries
2026, 37(12): 111700
doi: 10.1016/j.cclet.2025.111700
Abstract:
Li+/Na+ ion exchange has made a breakthrough in the synthesis of Ni-rich layered cathode oxide, which can effectively mitigate the severe Li/Ni disorder that occurs in the traditional solid-phase sintering method. However, the comparative study of the cations presents in the Li layer as pillars is rarely reported. Herein, a series of Ni2+/Na+ co-substituted Ni-rich materials are designed by ion exchange at ∼200 °C with varying Li+/Na+ molar ratios (4, 8, 12, 16), which is used as a platform to quantitatively decipher the pillar effect contributed by Ni2+ and Na+ in the Li layer. We found that Ni2+ is approximately 3.5 times more effective as pillar than Na+. Theoretical calculations further reveal that Ni2+ in Li slab provides the higher mechanical strength than Na+ in the deeply delithiated state of Ni-rich materials. Besides, the results of structural evolution over cycling reveals that Ni2+ plays a greater role of pillar in stabilizing the structure with higher lattice energy compared to Na+, attributed to its higher mechanical strength (bulk modulus: 56.9 vs. 43.8 GPa). The PL-4 cathode (Li+/Na+ molar ratios = 4) exhibited optimal electrochemical performance, retaining 90.4% capacity after 70 cycles at 1 C and delivering a high specific capacity of 141.7 mAh/g at 10 C. This work provides design principles for the synthesis of layered oxides with high structural stability via ion exchange, potentially leading to the development of advanced cathode materials for high-energy lithium-ion batteries.
Li+/Na+ ion exchange has made a breakthrough in the synthesis of Ni-rich layered cathode oxide, which can effectively mitigate the severe Li/Ni disorder that occurs in the traditional solid-phase sintering method. However, the comparative study of the cations presents in the Li layer as pillars is rarely reported. Herein, a series of Ni2+/Na+ co-substituted Ni-rich materials are designed by ion exchange at ∼200 °C with varying Li+/Na+ molar ratios (4, 8, 12, 16), which is used as a platform to quantitatively decipher the pillar effect contributed by Ni2+ and Na+ in the Li layer. We found that Ni2+ is approximately 3.5 times more effective as pillar than Na+. Theoretical calculations further reveal that Ni2+ in Li slab provides the higher mechanical strength than Na+ in the deeply delithiated state of Ni-rich materials. Besides, the results of structural evolution over cycling reveals that Ni2+ plays a greater role of pillar in stabilizing the structure with higher lattice energy compared to Na+, attributed to its higher mechanical strength (bulk modulus: 56.9 vs. 43.8 GPa). The PL-4 cathode (Li+/Na+ molar ratios = 4) exhibited optimal electrochemical performance, retaining 90.4% capacity after 70 cycles at 1 C and delivering a high specific capacity of 141.7 mAh/g at 10 C. This work provides design principles for the synthesis of layered oxides with high structural stability via ion exchange, potentially leading to the development of advanced cathode materials for high-energy lithium-ion batteries.
2026, 37(12): 111810
doi: 10.1016/j.cclet.2025.111810
Abstract:
Lithium-sulfur batteries (LSBs) have attracted extensive research interest due to their high theoretical capacity, low cost, and environmental friendliness. However, the practical application of LSBs is hindered by the severe shuttle effect and slow conversion kinetics of lithium polysulfides (LiPSs). In this manuscript, dual catalytic active sites Ru@Nb2O5@NC heterostructure was successfully synthesized through ion exchange and the subsequent high temperature annealing of the ZIF-8 precursor. The obtained Ru@Nb2O5@NC heterostructure provides enough channels to accelerate Li+ diffusion and the dual active sites of ruthenium (Ru) and niobium oxide (Nb2O5) nanocrystals effectively promote the chemical trapping and catalytic conversion of lithium polysulfide (LiPSs). When applied as the modifier of the LSBs separator, the modified Ru@Nb2O5@NC separator equipped battery exhibits excellent high initial specific capacity, outstanding rate capability (651.7 mAh/g at 3 C) and excellent cyclic stability with a capacity decline rate of only 0.099% after 500 cycles. It is worth noting that even at high sulfur loading (2.048, 2.432, and 2.944 mg/cm2), the cell still exhibited excellent electrochemical and battery properties. This work provides a feasible strategy for the LSBs separator modification through catalytic conversion and chemisorption of polysulfides.
Lithium-sulfur batteries (LSBs) have attracted extensive research interest due to their high theoretical capacity, low cost, and environmental friendliness. However, the practical application of LSBs is hindered by the severe shuttle effect and slow conversion kinetics of lithium polysulfides (LiPSs). In this manuscript, dual catalytic active sites Ru@Nb2O5@NC heterostructure was successfully synthesized through ion exchange and the subsequent high temperature annealing of the ZIF-8 precursor. The obtained Ru@Nb2O5@NC heterostructure provides enough channels to accelerate Li+ diffusion and the dual active sites of ruthenium (Ru) and niobium oxide (Nb2O5) nanocrystals effectively promote the chemical trapping and catalytic conversion of lithium polysulfide (LiPSs). When applied as the modifier of the LSBs separator, the modified Ru@Nb2O5@NC separator equipped battery exhibits excellent high initial specific capacity, outstanding rate capability (651.7 mAh/g at 3 C) and excellent cyclic stability with a capacity decline rate of only 0.099% after 500 cycles. It is worth noting that even at high sulfur loading (2.048, 2.432, and 2.944 mg/cm2), the cell still exhibited excellent electrochemical and battery properties. This work provides a feasible strategy for the LSBs separator modification through catalytic conversion and chemisorption of polysulfides.
2026, 37(12): 111869
doi: 10.1016/j.cclet.2025.111869
Abstract:
Organic polymers have been widely employed as electrode materials for secondary batteries due to their tunable structural flexibility and tailorable electrochemical properties. However, their inherent steric hindrance and dense molecular packing inevitably lower the utilization of active sites, thus resulting in unsatisfactory capacity. Hence, we designed and synthesized a para-substituted triazine-based polyamine (PAN-p) featuring both minimal steric hindrance and a highly porous architecture through rational molecular engineering. The reduced steric hindrance and increased porosity affords a significant improvement in redox reaction kinetics, thereby boosting the Li-storage performance. As a result, the PAN-p anode delivers a high reversible capacity of 780 mAh/g at 0.3 A/g and long life-span over 500 cycles without significant decay. Furthermore, theoretical calculations were conducted to unravel the relationships between steric hindrance and electrochemical performance of PAN derivatives based on the different substitution patterns (para-, meta-, and ortho-positions), offering insights into their distinct electrochemical behaviors. The work provides a promising design of high-performance organic electrode materials for efficient Li-storage.
Organic polymers have been widely employed as electrode materials for secondary batteries due to their tunable structural flexibility and tailorable electrochemical properties. However, their inherent steric hindrance and dense molecular packing inevitably lower the utilization of active sites, thus resulting in unsatisfactory capacity. Hence, we designed and synthesized a para-substituted triazine-based polyamine (PAN-p) featuring both minimal steric hindrance and a highly porous architecture through rational molecular engineering. The reduced steric hindrance and increased porosity affords a significant improvement in redox reaction kinetics, thereby boosting the Li-storage performance. As a result, the PAN-p anode delivers a high reversible capacity of 780 mAh/g at 0.3 A/g and long life-span over 500 cycles without significant decay. Furthermore, theoretical calculations were conducted to unravel the relationships between steric hindrance and electrochemical performance of PAN derivatives based on the different substitution patterns (para-, meta-, and ortho-positions), offering insights into their distinct electrochemical behaviors. The work provides a promising design of high-performance organic electrode materials for efficient Li-storage.
2026, 37(12): 111870
doi: 10.1016/j.cclet.2025.111870
Abstract:
Aqueous zinc-iodine batteries (AZIBs) are promising and sustainable batteries due to their safety, low cost, and high storage. However, their application has been severely hindered by the notorious shuttle effect of polyiodide species during repeated charge/discharge cycles. Here, we report a novel cathode material by reacting poly(diallyl dimethylammonium) with iodine solution (containing triiodide ions) to form PDDA/I3 hybrid. Experimental and theoretical analyses reveal that the cationic polymer skeleton exhibits strong interaction with iodine species to suppress the shuttle effect of polyiodide ions. Therefore, the assembled PDDA/I3-based AZIBs deliver a large specific capacity of 271.2 mAh/g and high Coulombic efficiency exceeding 98.5% at current density of 0.1 A/g. Furthermore, the optimized AZIBs cell shows an outstanding cycling stability (91.0% capacity retention after 46,000 cycles at current density of 3.0 A/g). This study offers a new strategy for designing high-performance, long-cycling-life AZIBs through effective mitigation of the iodine shuttle behavior, opening an avenue for their practical application in large-scale energy storage systems.
Aqueous zinc-iodine batteries (AZIBs) are promising and sustainable batteries due to their safety, low cost, and high storage. However, their application has been severely hindered by the notorious shuttle effect of polyiodide species during repeated charge/discharge cycles. Here, we report a novel cathode material by reacting poly(diallyl dimethylammonium) with iodine solution (containing triiodide ions) to form PDDA/I3 hybrid. Experimental and theoretical analyses reveal that the cationic polymer skeleton exhibits strong interaction with iodine species to suppress the shuttle effect of polyiodide ions. Therefore, the assembled PDDA/I3-based AZIBs deliver a large specific capacity of 271.2 mAh/g and high Coulombic efficiency exceeding 98.5% at current density of 0.1 A/g. Furthermore, the optimized AZIBs cell shows an outstanding cycling stability (91.0% capacity retention after 46,000 cycles at current density of 3.0 A/g). This study offers a new strategy for designing high-performance, long-cycling-life AZIBs through effective mitigation of the iodine shuttle behavior, opening an avenue for their practical application in large-scale energy storage systems.
2026, 37(12): 111871
doi: 10.1016/j.cclet.2025.111871
Abstract:
In this study, sulfonic acid group was incorporated into the covalent organic framework (COF) to synthesize TpPa-SO3H, which was subsequently lithiated to obtain TpPa-SO3Li. And then a solid composite electrolyte (SCE), integrating PVDF-HFP, TpPa-SO3Li, and LiTFSI was prepared. The SCE exhibited a high lithium-ion transference number (0.72), as well as a high ionic conductivity at 30 °C (2.15 × 10–4 S/cm). Electrochemical tests revealed that the Li symmetric cell achieved remarkable cycling stability, sustaining operation for ＞ 500 h at 60 °C (0.2 mA/cm2) and ＞ 1000 h at room temperature (0.1 mA/cm2). The assembled LFP//Li battery exhibited a stable discharge capacity of 129.33 mAh/g after 110 cycles at 0.2 C under room temperature. This COF-based composite electrolyte significantly enhances lithium-ion conduction and interfacial stability, offering a novel material choice and design strategy for advancing next-generation solid-state lithium-ion batteries.
In this study, sulfonic acid group was incorporated into the covalent organic framework (COF) to synthesize TpPa-SO3H, which was subsequently lithiated to obtain TpPa-SO3Li. And then a solid composite electrolyte (SCE), integrating PVDF-HFP, TpPa-SO3Li, and LiTFSI was prepared. The SCE exhibited a high lithium-ion transference number (0.72), as well as a high ionic conductivity at 30 °C (2.15 × 10–4 S/cm). Electrochemical tests revealed that the Li symmetric cell achieved remarkable cycling stability, sustaining operation for ＞ 500 h at 60 °C (0.2 mA/cm2) and ＞ 1000 h at room temperature (0.1 mA/cm2). The assembled LFP//Li battery exhibited a stable discharge capacity of 129.33 mAh/g after 110 cycles at 0.2 C under room temperature. This COF-based composite electrolyte significantly enhances lithium-ion conduction and interfacial stability, offering a novel material choice and design strategy for advancing next-generation solid-state lithium-ion batteries.
2026, 37(12): 111872
doi: 10.1016/j.cclet.2025.111872
Abstract:
Chiral induction is an effective strategy for synthesizing chiral metal-organic cages (CMOCs), where understanding chiral transfer mechanisms is critical for advancing their assembly and applications. Herein, we report an electrostatic-driven enantioselective resolution of racemic tetrahedral MⅡ4L4 cages into enantiomerically excess products. Two cages (1-Fe and 1-Zn) were synthesized via coordination-driven self-assembly of guanidinium-based ligands with Fe2+/Zn2+ ions. Protonated guanidinium units impart positive charges, enabling strong electrostatic interactions with anions. Using chiral BINOL-derived phosphates as anionic inducers, we achieved efficient resolution of racemic cages. Mechanistic studies confirm electrostatic interactions as the dominant driver of chiral transfer, while anions served as a chiral origin to promote stereoselective assembly. This work establishes a foundation for precise stereochemical control in supramolecular systems and offers new insights into designing functional chiral materials.
Chiral induction is an effective strategy for synthesizing chiral metal-organic cages (CMOCs), where understanding chiral transfer mechanisms is critical for advancing their assembly and applications. Herein, we report an electrostatic-driven enantioselective resolution of racemic tetrahedral MⅡ4L4 cages into enantiomerically excess products. Two cages (1-Fe and 1-Zn) were synthesized via coordination-driven self-assembly of guanidinium-based ligands with Fe2+/Zn2+ ions. Protonated guanidinium units impart positive charges, enabling strong electrostatic interactions with anions. Using chiral BINOL-derived phosphates as anionic inducers, we achieved efficient resolution of racemic cages. Mechanistic studies confirm electrostatic interactions as the dominant driver of chiral transfer, while anions served as a chiral origin to promote stereoselective assembly. This work establishes a foundation for precise stereochemical control in supramolecular systems and offers new insights into designing functional chiral materials.
2026, 37(12): 111873
doi: 10.1016/j.cclet.2025.111873
Abstract:
Carbon-supported nitrogen-coordinated single metal-site (M-N-C) catalysts are considered ideal platinum group metal (PGM)-free cathode catalysts for zinc-air batteries (ZABs) due to their high metal utilization efficiency, unique size-dependent quantum effects, and excellent catalytic activity. However, large-scale, sustainable preparation of M-N-C catalysts remains a significant challenge owing to the complex synthesis procedures and the difficulty in achieving an optimal coordination environment between metal atoms and the carbon matrix. In this study, we develop a large-scale preparation method for Fe-N-C catalysts, which directly utilizes lignocellulosic materials through in situ etching and carbonization, without the need for pickling. During the in situ etching process, chloride ions (Cl−) weaken the hydrogen bonds in lignocellulose, facilitating the dissolution of cellulose, hemicellulose, and lignin, thus creating abundant micropores. The Fe-N4 active site is successfully formed during the subsequent carbonization process. The resulting SA-FeN4/PC catalyst, benefiting from its porous structure and homogeneous dispersion of Fe-N4 sites, exhibits enhanced oxygen reduction and evolution reaction (ORR/OER) performance and superior stability. When used as the cathode in ZABs, SA-FeN4/PC demonstrates long-term stability, maintaining 520 h of operation at a current density of 5 mA/cm2. Furthermore, by varying the metal cation, we successfully prepare other metal-nitrogen-carbon catalysts (SA-MN4/PC, where M refers to Co, Ni, and Cu). This scalable synthesis strategy shows significant potential for the preparation of wood-based single-atom catalysts for high-temperature applications.
Carbon-supported nitrogen-coordinated single metal-site (M-N-C) catalysts are considered ideal platinum group metal (PGM)-free cathode catalysts for zinc-air batteries (ZABs) due to their high metal utilization efficiency, unique size-dependent quantum effects, and excellent catalytic activity. However, large-scale, sustainable preparation of M-N-C catalysts remains a significant challenge owing to the complex synthesis procedures and the difficulty in achieving an optimal coordination environment between metal atoms and the carbon matrix. In this study, we develop a large-scale preparation method for Fe-N-C catalysts, which directly utilizes lignocellulosic materials through in situ etching and carbonization, without the need for pickling. During the in situ etching process, chloride ions (Cl−) weaken the hydrogen bonds in lignocellulose, facilitating the dissolution of cellulose, hemicellulose, and lignin, thus creating abundant micropores. The Fe-N4 active site is successfully formed during the subsequent carbonization process. The resulting SA-FeN4/PC catalyst, benefiting from its porous structure and homogeneous dispersion of Fe-N4 sites, exhibits enhanced oxygen reduction and evolution reaction (ORR/OER) performance and superior stability. When used as the cathode in ZABs, SA-FeN4/PC demonstrates long-term stability, maintaining 520 h of operation at a current density of 5 mA/cm2. Furthermore, by varying the metal cation, we successfully prepare other metal-nitrogen-carbon catalysts (SA-MN4/PC, where M refers to Co, Ni, and Cu). This scalable synthesis strategy shows significant potential for the preparation of wood-based single-atom catalysts for high-temperature applications.
2026, 37(12): 111882
doi: 10.1016/j.cclet.2025.111882
Abstract:
The synthesis of zirconium-based polyoxometalates (POMs) has always been an attractive yet challenging research objective, especially for POMs with high nuclear zirconium cluster. Herein, by introduction of pyrazine-2,3-dicarboxylic acid into the reaction system of K12[H2P2W12O48]·24H2O and ZrOCl2·8H2O, a novel threaded phosphotungstate wheel anchored by a heptanuclear zirconium cluster [N(CH3)4]18K2[(Zr7(OH)4(PO4)2(Pzdc)4(H2O)16)(P6W39O147(H2O)3)]·43H2O (H2Pzdc = pyrazine-2,3-dicarboxylic acid) (Zr7) has been successfully synthesized via one-pot method and characterized by PXRD pattern, IR spectra and TGA. The analysis of X-ray crystallography reveals that compound Zr7 crystallizes in the orthorhombic space group Pnma. Notably, compound Zr7 is currently the largest odd-nuclearity pure zirconium cluster based on POMs. Furthermore, compound Zr7 exhibits remarkable catalytic activity as a Lewis acid-base catalyst for the cyclization reaction of benzenediamines and 1,3-diketones, affording the valuable 3H-benzo[b][1,4]diazepines up to 99% yield.
The synthesis of zirconium-based polyoxometalates (POMs) has always been an attractive yet challenging research objective, especially for POMs with high nuclear zirconium cluster. Herein, by introduction of pyrazine-2,3-dicarboxylic acid into the reaction system of K12[H2P2W12O48]·24H2O and ZrOCl2·8H2O, a novel threaded phosphotungstate wheel anchored by a heptanuclear zirconium cluster [N(CH3)4]18K2[(Zr7(OH)4(PO4)2(Pzdc)4(H2O)16)(P6W39O147(H2O)3)]·43H2O (H2Pzdc = pyrazine-2,3-dicarboxylic acid) (Zr7) has been successfully synthesized via one-pot method and characterized by PXRD pattern, IR spectra and TGA. The analysis of X-ray crystallography reveals that compound Zr7 crystallizes in the orthorhombic space group Pnma. Notably, compound Zr7 is currently the largest odd-nuclearity pure zirconium cluster based on POMs. Furthermore, compound Zr7 exhibits remarkable catalytic activity as a Lewis acid-base catalyst for the cyclization reaction of benzenediamines and 1,3-diketones, affording the valuable 3H-benzo[b][1,4]diazepines up to 99% yield.
2026, 37(12): 111884
doi: 10.1016/j.cclet.2025.111884
Abstract:
Protonic ceramic electrolysis cells (PCECs) are promising for energy conversion and hydrogen production. Developing air electrodes with high reaction kinetics and durability is crucial for their broad applications. In this study, a novel triple-conducting oxide air electrode is developed by incorporating Ta5+ ions into the Sr2Fe1.5Mo0.5O6-δ substrate. This modification ensures the lattice matching due to compatible ionic radii, while simultaneously modulating oxygen vacancy concentration. The hydration capacity of SFMTa material is enhanced, leading to an increase in proton defects and improving proton mobility. When tested in air with 3 vol% H2O at 1.3 V and 700 ℃, the Sr2Fe1.5Mo0.4Ta0.1O6-δ single cell demonstrates a relatively high current density of 2.17 A/cm2. Furthermore, the cell exhibits stable operation for 120 h without significant degradation, indicating the chemical stability of the material. The ionic radius matching strategy offers a practical approach for the development of highly efficient and durable air electrodes for PCECs.
Protonic ceramic electrolysis cells (PCECs) are promising for energy conversion and hydrogen production. Developing air electrodes with high reaction kinetics and durability is crucial for their broad applications. In this study, a novel triple-conducting oxide air electrode is developed by incorporating Ta5+ ions into the Sr2Fe1.5Mo0.5O6-δ substrate. This modification ensures the lattice matching due to compatible ionic radii, while simultaneously modulating oxygen vacancy concentration. The hydration capacity of SFMTa material is enhanced, leading to an increase in proton defects and improving proton mobility. When tested in air with 3 vol% H2O at 1.3 V and 700 ℃, the Sr2Fe1.5Mo0.4Ta0.1O6-δ single cell demonstrates a relatively high current density of 2.17 A/cm2. Furthermore, the cell exhibits stable operation for 120 h without significant degradation, indicating the chemical stability of the material. The ionic radius matching strategy offers a practical approach for the development of highly efficient and durable air electrodes for PCECs.
2026, 37(12): 111885
doi: 10.1016/j.cclet.2025.111885
Abstract:
Dual-mode temperature management technologies based on passive radiative cooling (PRC) and solar heating (SH) have garnered significant attention to adapt to seasonal temperature fluctuations. Yet, the development of switchable dual-mode temperature management materials featuring simple fabrication processes and superior thermal conductivity remains a challenge. Here, we demonstrate a dual-mode thermal regulator by assembling of Al2O3 and black Al nanoparticles directly on a high-thermal-conductivity Al sheet with laser surface direct writing (LSDW) and further spraying polytetrafluoroethylene (PTFE) as the self-cleaning layer. The thermal regulator has a high overall thermal conductivity of 32.1 W m−1 K−1. The black Al/PTFE side exhibits high solar absorptivity (~90%) and achieves an 11.3 °C temperature elevation in winter. The Al2O3/PTFE demonstrates excellent infrared emissivity (>96%) and high solar reflectivity (~90%), enabling 4.4 °C sub-ambient cooling in summer. PRC and SH can be switched by flipping to adapt to seasonal temperature variations. We envision this dual-mode thermal regulator has great potential for indoor energy-saving when integrated with buildings, offering a viable solution to address energy crises and reduce greenhouse gas emissions.
Dual-mode temperature management technologies based on passive radiative cooling (PRC) and solar heating (SH) have garnered significant attention to adapt to seasonal temperature fluctuations. Yet, the development of switchable dual-mode temperature management materials featuring simple fabrication processes and superior thermal conductivity remains a challenge. Here, we demonstrate a dual-mode thermal regulator by assembling of Al2O3 and black Al nanoparticles directly on a high-thermal-conductivity Al sheet with laser surface direct writing (LSDW) and further spraying polytetrafluoroethylene (PTFE) as the self-cleaning layer. The thermal regulator has a high overall thermal conductivity of 32.1 W m−1 K−1. The black Al/PTFE side exhibits high solar absorptivity (~90%) and achieves an 11.3 °C temperature elevation in winter. The Al2O3/PTFE demonstrates excellent infrared emissivity (>96%) and high solar reflectivity (~90%), enabling 4.4 °C sub-ambient cooling in summer. PRC and SH can be switched by flipping to adapt to seasonal temperature variations. We envision this dual-mode thermal regulator has great potential for indoor energy-saving when integrated with buildings, offering a viable solution to address energy crises and reduce greenhouse gas emissions.
2026, 37(12): 111895
doi: 10.1016/j.cclet.2025.111895
Abstract:
The rare-earth calcium oxyborate ReCa4O(BO3)3 based crystals possess the outstanding performance in high-temperature piezoelectricity causing the industrial application extensively, quantitatively analyzing the intrinsic contribution of piezo-units is critical key for the further enhancement of piezo-performance as well as its thermal stability. In this work, we combine the deep-learning interatomic potential and first-principles calculation to clarify the dynamics and static properties, and the stress-strain method is utilized to measure the piezoelectricity and decompose the contribution of each piezo-unit. The quantitative analysis results show that the phonon localized behavior and the nature of chemical bonds, especially for the rare earth elements in oxygen octahedrons, are identified as the main reason for the difference of piezoelectricity as well as its thermal stability. This work may provide the brand-new strategy and perspective to investigate the unique function in sub-cells quantitatively and the reference to guide high performance materials design.
The rare-earth calcium oxyborate ReCa4O(BO3)3 based crystals possess the outstanding performance in high-temperature piezoelectricity causing the industrial application extensively, quantitatively analyzing the intrinsic contribution of piezo-units is critical key for the further enhancement of piezo-performance as well as its thermal stability. In this work, we combine the deep-learning interatomic potential and first-principles calculation to clarify the dynamics and static properties, and the stress-strain method is utilized to measure the piezoelectricity and decompose the contribution of each piezo-unit. The quantitative analysis results show that the phonon localized behavior and the nature of chemical bonds, especially for the rare earth elements in oxygen octahedrons, are identified as the main reason for the difference of piezoelectricity as well as its thermal stability. This work may provide the brand-new strategy and perspective to investigate the unique function in sub-cells quantitatively and the reference to guide high performance materials design.
2026, 37(12): 111898
doi: 10.1016/j.cclet.2025.111898
Abstract:
Spin-crossover (SCO) materials exhibit reversible transitions between high-spin (HS) and low-spin (LS) states and are potentially multifunctional; however their practical deployment is hindered by limited operating-temperature windows. While metal-ion dilution using molecular solid solutions has emerged as a powerful strategy for modulating Fe(Ⅱ) SCO systems, analogous approaches for Fe(Ⅲ) systems remain unexplored. Herein, we report the first successful incorporation of paramagnetic Cr(Ⅲ) into the [FeⅢ(HLCl)(LCl)]·H2O Fe(Ⅲ) SCO complex and the construction of isostructural {[FeⅢ(HLCl)(LCl)]1-x[CrⅢ(HLCl)(LCl)]x}·H2O (x = 0.1–0.9) molecular solid solutions. Variable-temperature magnetic susceptibility and differential scanning calorimetry (DSC) studies revealed that increasing the Cr(Ⅲ) concentration led to a systematic reduction in spin-transition temperature (Tc). Single-crystal X-ray diffractometry confirmed that the monoclinic P21/n symmetry is conserved across the solid-solution series, while structural analysis revealed Cr-induced octahedral distortion at the metal centers. Density functional theory (DFT) calculations establish that Cr(Ⅲ) doping stabilizes the HS state and diminishes Fe···Fe cooperativity through site-specific perturbations, resulting in lower Tc values and slower spin-transition kinetics. This study provides a novel pathway for precise Tc engineering in Fe(Ⅲ) SCO systems, thereby significantly advancing their use in data-storage and sensing-technology applications.
Spin-crossover (SCO) materials exhibit reversible transitions between high-spin (HS) and low-spin (LS) states and are potentially multifunctional; however their practical deployment is hindered by limited operating-temperature windows. While metal-ion dilution using molecular solid solutions has emerged as a powerful strategy for modulating Fe(Ⅱ) SCO systems, analogous approaches for Fe(Ⅲ) systems remain unexplored. Herein, we report the first successful incorporation of paramagnetic Cr(Ⅲ) into the [FeⅢ(HLCl)(LCl)]·H2O Fe(Ⅲ) SCO complex and the construction of isostructural {[FeⅢ(HLCl)(LCl)]1-x[CrⅢ(HLCl)(LCl)]x}·H2O (x = 0.1–0.9) molecular solid solutions. Variable-temperature magnetic susceptibility and differential scanning calorimetry (DSC) studies revealed that increasing the Cr(Ⅲ) concentration led to a systematic reduction in spin-transition temperature (Tc). Single-crystal X-ray diffractometry confirmed that the monoclinic P21/n symmetry is conserved across the solid-solution series, while structural analysis revealed Cr-induced octahedral distortion at the metal centers. Density functional theory (DFT) calculations establish that Cr(Ⅲ) doping stabilizes the HS state and diminishes Fe···Fe cooperativity through site-specific perturbations, resulting in lower Tc values and slower spin-transition kinetics. This study provides a novel pathway for precise Tc engineering in Fe(Ⅲ) SCO systems, thereby significantly advancing their use in data-storage and sensing-technology applications.
2026, 37(12): 111909
doi: 10.1016/j.cclet.2025.111909
Abstract:
The efficient photothermal catalytic methanation of CO2 offers a sustainable approach to carbon valorization, yet its practical implementation is hindered by suboptimal methane yields due to the complex interplay of multi-physical parameters. In this work, a comprehensive dataset was assembled from the literature to capture the diversity of reaction conditions, catalyst properties, and metal loading elements. Fourteen machine learning models were systematically compared for methane yield prediction, with CatBoost outperforming others (test R2 = 0.946), demonstrating both exceptional accuracy and generalization. Interpretable modeling via SHapley Additive exPlanations (SHAP) and partial dependence analyses identified reaction temperature, pore size, gas flow rate, and Ru loading as critical factors, with pronounced nonlinear and synergistic effects. Notably, bivariate analysis uncovered optimal parameter regimes inaccessible through traditional uni-variable experimentation. This study provides a robust, interpretable machine-learning framework for mechanistically deciphering and optimizing photothermal CO2 methanation, paving the way for rational catalyst and process development in green energy applications.
The efficient photothermal catalytic methanation of CO2 offers a sustainable approach to carbon valorization, yet its practical implementation is hindered by suboptimal methane yields due to the complex interplay of multi-physical parameters. In this work, a comprehensive dataset was assembled from the literature to capture the diversity of reaction conditions, catalyst properties, and metal loading elements. Fourteen machine learning models were systematically compared for methane yield prediction, with CatBoost outperforming others (test R2 = 0.946), demonstrating both exceptional accuracy and generalization. Interpretable modeling via SHapley Additive exPlanations (SHAP) and partial dependence analyses identified reaction temperature, pore size, gas flow rate, and Ru loading as critical factors, with pronounced nonlinear and synergistic effects. Notably, bivariate analysis uncovered optimal parameter regimes inaccessible through traditional uni-variable experimentation. This study provides a robust, interpretable machine-learning framework for mechanistically deciphering and optimizing photothermal CO2 methanation, paving the way for rational catalyst and process development in green energy applications.
2026, 37(12): 111911
doi: 10.1016/j.cclet.2025.111911
Abstract:
The rational design of high-performance alloy materials requires a deep understanding of electronic structures, which governs key material properties. The electronic density of states (DOS) is an expression of the electronic structure, normally derived from conventional first principle calculation. However, simulation of multi-component alloy requires consideration of a huge phase space, which is computationally prohibitive. Here, we present a machine learning (ML) combining a modified crystal graph convolutional neural network (CGCNN) and a convolutional neural network (CNN) to predict DOS and related surface features in CuAgAu alloy system. The CGCNN model, trained on 800 calculated structures, predicts site-resolved DOS with mean absolute error below 0.1 and median R2 values approaching 0.98. By integrating predicted DOS with a CNN model, CO adsorption energies on various surface sites were predicted, achieving MAE < 0.05 eV. The integrated model generalizes well to ternary and binary alloy compositions, demonstrating utility in high-throughput screening. This work bridges ML with physical insights, enabling rapid exploration of alloy surfaces for catalytic applications while circumventing computational costs of ab initio methods.
The rational design of high-performance alloy materials requires a deep understanding of electronic structures, which governs key material properties. The electronic density of states (DOS) is an expression of the electronic structure, normally derived from conventional first principle calculation. However, simulation of multi-component alloy requires consideration of a huge phase space, which is computationally prohibitive. Here, we present a machine learning (ML) combining a modified crystal graph convolutional neural network (CGCNN) and a convolutional neural network (CNN) to predict DOS and related surface features in CuAgAu alloy system. The CGCNN model, trained on 800 calculated structures, predicts site-resolved DOS with mean absolute error below 0.1 and median R2 values approaching 0.98. By integrating predicted DOS with a CNN model, CO adsorption energies on various surface sites were predicted, achieving MAE < 0.05 eV. The integrated model generalizes well to ternary and binary alloy compositions, demonstrating utility in high-throughput screening. This work bridges ML with physical insights, enabling rapid exploration of alloy surfaces for catalytic applications while circumventing computational costs of ab initio methods.
2026, 37(12): 111912
doi: 10.1016/j.cclet.2025.111912
Abstract:
The dielectric response of materials can be generated through temperature induced dipole polarization. However, the response is typically weak at gigahertz, because the external electric field change is too fast for the dipole orientation motion, and thermal molecular motion further diminishes dipole polarization. Herein, we explored a novel type of metal-organic frameworks using dipole amine as the guest molecule to create a hydrogen bonding system that cyclic break and reconstruction under moderate thermal stimulation. The dipoles transition between constrained and dissociated states, achieving a fourfold reduction in reorientation relaxation time. Meanwhile, the confined space of the metal-formate framework inhibits thermal molecular motion, allowing for independent control of dipole polarization. Consequently, the MOF shows a maximum change of nearly two orders of magnitude of reversible dielectric properties at gigahertz.
The dielectric response of materials can be generated through temperature induced dipole polarization. However, the response is typically weak at gigahertz, because the external electric field change is too fast for the dipole orientation motion, and thermal molecular motion further diminishes dipole polarization. Herein, we explored a novel type of metal-organic frameworks using dipole amine as the guest molecule to create a hydrogen bonding system that cyclic break and reconstruction under moderate thermal stimulation. The dipoles transition between constrained and dissociated states, achieving a fourfold reduction in reorientation relaxation time. Meanwhile, the confined space of the metal-formate framework inhibits thermal molecular motion, allowing for independent control of dipole polarization. Consequently, the MOF shows a maximum change of nearly two orders of magnitude of reversible dielectric properties at gigahertz.
2026, 37(12): 111913
doi: 10.1016/j.cclet.2025.111913
Abstract:
Sensors based on metal oxide semiconductor (MOS) for chlorine (Cl2) usually have a very high operating temperature (≥200 °C). It is imperative to develop the high-performance room-temperature Cl2 sensors. In this study, a high-sensitivity VO-In2O3/MXene heterojunction sensor with abundant oxygen vacancies was fabricated for Cl2 detection at room temperature. To prepare In2O3 nanoparticles with abundant oxygen vacancies (VO-In2O3), the precursors were treated in an argon atmosphere. Cetyltrimethylammonium bromide (CTAB) was then used as a surfactant to facilitate the electrostatic assembly of the V2CTx MXene nanosheets and VO-In2O3 nanoparticles, thereby forming a unique heterostructure. The heterojunction enables the sensor to reduce its operating temperature to room temperature, while the abundant oxygen vacancies guarantee the high gas response of the sensor. Results of the gas-sensing performance tests indicate that the VO-In2O3/MXene heterojunction sensor exhibits a high response of 22.85% toward 0.5 ppm Cl2 at 25 °C, with a detection limit as low as 1.05 ppb and good stability. Such exceptional performance indicates that the use of VO-In2O3/MXene heterojunction sensor for Cl2 detecting at room temperature has great application prospects.
Sensors based on metal oxide semiconductor (MOS) for chlorine (Cl2) usually have a very high operating temperature (≥200 °C). It is imperative to develop the high-performance room-temperature Cl2 sensors. In this study, a high-sensitivity VO-In2O3/MXene heterojunction sensor with abundant oxygen vacancies was fabricated for Cl2 detection at room temperature. To prepare In2O3 nanoparticles with abundant oxygen vacancies (VO-In2O3), the precursors were treated in an argon atmosphere. Cetyltrimethylammonium bromide (CTAB) was then used as a surfactant to facilitate the electrostatic assembly of the V2CTx MXene nanosheets and VO-In2O3 nanoparticles, thereby forming a unique heterostructure. The heterojunction enables the sensor to reduce its operating temperature to room temperature, while the abundant oxygen vacancies guarantee the high gas response of the sensor. Results of the gas-sensing performance tests indicate that the VO-In2O3/MXene heterojunction sensor exhibits a high response of 22.85% toward 0.5 ppm Cl2 at 25 °C, with a detection limit as low as 1.05 ppb and good stability. Such exceptional performance indicates that the use of VO-In2O3/MXene heterojunction sensor for Cl2 detecting at room temperature has great application prospects.
2026, 37(12): 111919
doi: 10.1016/j.cclet.2025.111919
Abstract:
The methylidyne radical (CH·) and oxygen-bearing complex organic molecules (COMs), such as dimethyl ether (DME, CH3OCH3), are recognized to be of great importance in interstellar chemistry. However, despite its potential role in the growth and evolution of interstellar COMs, the reaction between CH· and DME has not yet been studied experimentally or theoretically. In this work, we measured the rate coefficients using the pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique, and characterized reaction product via vacuum ultraviolet (VUV) photoionization reflectron time-of-flight mass spectrometry (Re-TOFMS) under uniform supersonic low-temperature flow conditions. The rate coefficients were determined to range from 3.7 × 10–10 cm3 molecule-1 s-1 to 1.6 × 10–10 cm3 molecule-1 s-1 at temperatures of 25–100 K. By combining mass spectroscopy results and the newly calculated potential energy surface, we identified the dominate reaction pathway, which leads to the formation of CH3O· + C2H4. Astrochemical modelling further revealed that this reaction serves as a gas-phase reaction source for CH3O· in the cold interstellar environments.
The methylidyne radical (CH·) and oxygen-bearing complex organic molecules (COMs), such as dimethyl ether (DME, CH3OCH3), are recognized to be of great importance in interstellar chemistry. However, despite its potential role in the growth and evolution of interstellar COMs, the reaction between CH· and DME has not yet been studied experimentally or theoretically. In this work, we measured the rate coefficients using the pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique, and characterized reaction product via vacuum ultraviolet (VUV) photoionization reflectron time-of-flight mass spectrometry (Re-TOFMS) under uniform supersonic low-temperature flow conditions. The rate coefficients were determined to range from 3.7 × 10–10 cm3 molecule-1 s-1 to 1.6 × 10–10 cm3 molecule-1 s-1 at temperatures of 25–100 K. By combining mass spectroscopy results and the newly calculated potential energy surface, we identified the dominate reaction pathway, which leads to the formation of CH3O· + C2H4. Astrochemical modelling further revealed that this reaction serves as a gas-phase reaction source for CH3O· in the cold interstellar environments.
2026, 37(12): 111950
doi: 10.1016/j.cclet.2025.111950
Abstract:
Industrialization and agricultural development urgently require sustainable energy solutions and pollutant removal strategies. Semiconductor photocatalysts can simultaneously achieve hydrogen production and environmental remediation. Building on previous studies, CdS0.25Se0.75 was combined with diethylenetriamine (DETA) to construct a novel organic–inorganic hybrid material (CdS0.25Se0.75–DETA (CSE)), thereby improving structural stability, suppressing photocorrosion, and enhancing interfacial charge transfer. Compared with conventional CdS-based inorganic photocatalysts, this hybridization strategy provides stronger interfacial coupling and more efficient carrier dynamics, underscoring the distinctiveness of this work. Subsequently, a Schottky-structured Bi/CSE nanocomposite was fabricated by in-situ reducing BiOBr to metallic Bi and integrating with CSE, combining the advantages of organic–inorganic hybridization and Schottky junctions. Experimental results reveal that this structure effectively promotes electron transfer and charge separation while suppressing recombination. The Bi/CSE nanocomposite exhibits excellent performance in hydrogen evolution and dichlorvos degradation. With 1% Bi precursor loading, 1-Bi/CSE achieves a hydrogen evolution rate of 5.6 mmol g-1 h-1, 3.1 times higher than pristine CSE (1.8 mmol g-1 h-1), while maintaining stable performance over five cycles (10 h). 20-Bi/CSE (20% Bi precursor loading) degrades 85.2% of dichlorvos within 80 min, outperforming pristine Bi (58.9%) and CSE (47.6%), and remains highly active throughout five cycles (400 min). The enhanced performance arises from the synergistic effect of the organic–inorganic hybrid matrix and the Bi–CSE Schottky junction, as verified by Kelvin probe force microscopy (KPFM), X-ray photoelectron spectroscopy (XPS), femtosecond transient absorption spectroscopy (fs-TAS), and theoretical calculations. This study demonstrates, for the first time, that integrating Schottky structures with DETA modification enables a dual-functional photocatalyst for both hydrogen evolution and organophosphorus pesticide degradation, providing a new strategy for the design of multifunctional photocatalysts.
Industrialization and agricultural development urgently require sustainable energy solutions and pollutant removal strategies. Semiconductor photocatalysts can simultaneously achieve hydrogen production and environmental remediation. Building on previous studies, CdS0.25Se0.75 was combined with diethylenetriamine (DETA) to construct a novel organic–inorganic hybrid material (CdS0.25Se0.75–DETA (CSE)), thereby improving structural stability, suppressing photocorrosion, and enhancing interfacial charge transfer. Compared with conventional CdS-based inorganic photocatalysts, this hybridization strategy provides stronger interfacial coupling and more efficient carrier dynamics, underscoring the distinctiveness of this work. Subsequently, a Schottky-structured Bi/CSE nanocomposite was fabricated by in-situ reducing BiOBr to metallic Bi and integrating with CSE, combining the advantages of organic–inorganic hybridization and Schottky junctions. Experimental results reveal that this structure effectively promotes electron transfer and charge separation while suppressing recombination. The Bi/CSE nanocomposite exhibits excellent performance in hydrogen evolution and dichlorvos degradation. With 1% Bi precursor loading, 1-Bi/CSE achieves a hydrogen evolution rate of 5.6 mmol g-1 h-1, 3.1 times higher than pristine CSE (1.8 mmol g-1 h-1), while maintaining stable performance over five cycles (10 h). 20-Bi/CSE (20% Bi precursor loading) degrades 85.2% of dichlorvos within 80 min, outperforming pristine Bi (58.9%) and CSE (47.6%), and remains highly active throughout five cycles (400 min). The enhanced performance arises from the synergistic effect of the organic–inorganic hybrid matrix and the Bi–CSE Schottky junction, as verified by Kelvin probe force microscopy (KPFM), X-ray photoelectron spectroscopy (XPS), femtosecond transient absorption spectroscopy (fs-TAS), and theoretical calculations. This study demonstrates, for the first time, that integrating Schottky structures with DETA modification enables a dual-functional photocatalyst for both hydrogen evolution and organophosphorus pesticide degradation, providing a new strategy for the design of multifunctional photocatalysts.
A dual-functional polyoxomolybdate@COF nanoplatform for synergistic chemo-photodynamic tumor therapy
2026, 37(12): 111953
doi: 10.1016/j.cclet.2025.111953
Abstract:
The development of innovative drug delivery systems for POMs-based nanomedicines with enhanced targeting and efficient multi-modal therapeutic capabilities is crucial for tumor therapy. Herein, a novel POMo@COF-PEG nanoplatform by integrating mixed-valence polyoxomolybdate (POMo) into a photosensitive covalent organic framework (COF) has been successfully developed. This nanoplatform exhibited a synergistic COF-based photodynamic therapy effect and a POMo-based chemotherapy effect to induce cancer cell apoptosis. Various in vitro and in vivo studies including proteomic analysis and Western blot experiments demonstrated for the first time that the POMo could regulate the apoptosis signaling pathway by inhibiting the 4T1 cell proliferation via an apoptosis pathway. The present study provides valuable insights in developing novel polyoxometalate (POM)-based anti-tumor nanodrugs.
The development of innovative drug delivery systems for POMs-based nanomedicines with enhanced targeting and efficient multi-modal therapeutic capabilities is crucial for tumor therapy. Herein, a novel POMo@COF-PEG nanoplatform by integrating mixed-valence polyoxomolybdate (POMo) into a photosensitive covalent organic framework (COF) has been successfully developed. This nanoplatform exhibited a synergistic COF-based photodynamic therapy effect and a POMo-based chemotherapy effect to induce cancer cell apoptosis. Various in vitro and in vivo studies including proteomic analysis and Western blot experiments demonstrated for the first time that the POMo could regulate the apoptosis signaling pathway by inhibiting the 4T1 cell proliferation via an apoptosis pathway. The present study provides valuable insights in developing novel polyoxometalate (POM)-based anti-tumor nanodrugs.
2026, 37(12): 112121
doi: 10.1016/j.cclet.2025.112121
Abstract:
Three regioisomeric dodecanuclear cuprofullerenes with six Cu2LF2 (HLF= trifluoracetic acid) units arranged on the six hexagons around the equatorial belt of C60 molecules were achieved. Supramolecular interactions arising from pyridine and pyrazole auxiliary ligands result in distinct 6α and 6β regioisomeric C60@(Cu2)6 architectures with well-defined coordination environments and supramolecular packing motifs. Photophysical studies combined with density functional theory calculations demonstrate that the optical absorptions are dominated by charge transfer from Cu(Ⅰ) and O from LF to the fullerene π* orbitals. This work highlights the critical role of weak interactions in modulating the regioselectivity of high-nuclearity metallofullerenes, providing new insights for the design of functional fullerene-based materials.
Three regioisomeric dodecanuclear cuprofullerenes with six Cu2LF2 (HLF= trifluoracetic acid) units arranged on the six hexagons around the equatorial belt of C60 molecules were achieved. Supramolecular interactions arising from pyridine and pyrazole auxiliary ligands result in distinct 6α and 6β regioisomeric C60@(Cu2)6 architectures with well-defined coordination environments and supramolecular packing motifs. Photophysical studies combined with density functional theory calculations demonstrate that the optical absorptions are dominated by charge transfer from Cu(Ⅰ) and O from LF to the fullerene π* orbitals. This work highlights the critical role of weak interactions in modulating the regioselectivity of high-nuclearity metallofullerenes, providing new insights for the design of functional fullerene-based materials.
2026, 37(12): 112291
doi: 10.1016/j.cclet.2025.112291
Abstract:
Photon-activated immunogenic cell death (ICD) is a promising anti-tumor immunotherapy strategy, offering a new avenue for combating cancer recurrence and metastasis. Nevertheless, the poor tumor retention of ICD inducers, such as photosensitizers (PSs), which results in insufficient immune activation, hinders both immediate efficacy and long-term outcomes. To address this challenge, we designed a series of PSs via structural engineering of the thiophenopyridine-based donor-acceptor (D-A) framework, optimizing water solubility and molecular charge. The structure-activity relationship revealed that increasing water solubility and reducing positive charge minimized protein adsorption, thereby evading immune clearance and prolonging tumor retention. Notably, LTD-PEG7 exhibited prolonged retention exceeding 96 h. The oligomerized glycol unit formed a “protective hydration layer” that shields the PS from protein adsorption, while its amphiphilic character enhances cellular uptake. Giving the excellent type I reactive oxygen species (ROS) generation efficiency, LTD-PEG7 could efficiently overcome hypoxia-induced immunosuppression in the tumor microenvironment. Furthermore, the ROS mediated mitochondrial damage, triggering potent anti-tumor immune responses through ICD and ultimately eliciting a robust systemic anti-tumor immune response that significantly curbs the proliferation of 4T1 tumors in vivo. This study provides a valuable design principle for developing long-term tumor-retentive PS and advances photoimmunotherapy strategies.
Photon-activated immunogenic cell death (ICD) is a promising anti-tumor immunotherapy strategy, offering a new avenue for combating cancer recurrence and metastasis. Nevertheless, the poor tumor retention of ICD inducers, such as photosensitizers (PSs), which results in insufficient immune activation, hinders both immediate efficacy and long-term outcomes. To address this challenge, we designed a series of PSs via structural engineering of the thiophenopyridine-based donor-acceptor (D-A) framework, optimizing water solubility and molecular charge. The structure-activity relationship revealed that increasing water solubility and reducing positive charge minimized protein adsorption, thereby evading immune clearance and prolonging tumor retention. Notably, LTD-PEG7 exhibited prolonged retention exceeding 96 h. The oligomerized glycol unit formed a “protective hydration layer” that shields the PS from protein adsorption, while its amphiphilic character enhances cellular uptake. Giving the excellent type I reactive oxygen species (ROS) generation efficiency, LTD-PEG7 could efficiently overcome hypoxia-induced immunosuppression in the tumor microenvironment. Furthermore, the ROS mediated mitochondrial damage, triggering potent anti-tumor immune responses through ICD and ultimately eliciting a robust systemic anti-tumor immune response that significantly curbs the proliferation of 4T1 tumors in vivo. This study provides a valuable design principle for developing long-term tumor-retentive PS and advances photoimmunotherapy strategies.
2026, 37(12): 112292
doi: 10.1016/j.cclet.2025.112292
Abstract:
The application of nano-encapsulation-based drug delivery systems has become increasingly prevalent in oncological therapy. However, the suboptimal accumulation and retention of nanomedicines within tumor cells pose significant challenges to enhance therapeutic efficacy. Herein, we engineered peptide-capped mesoporous silica nanoparticles (MSNs) capable of intracellular self-aggregation into micron-sized clusters, thereby facilitating specific accumulation and retention of encapsulated drugs within tumor cells. In this innovative design, polydopamine (PDA) was in situ polymerized on the surface of MSNs loaded with berberine (BBR) and evodiamine (EVO), respectively. A peptide was conjugated to PDA via esterification. The coating of the colon cancer cell membrane could further enhance the drug encapsulation and targeting ability of MSNs. The resultant nanomedicine could assemble into micron-sized MSN clusters through peptide self-assembly, resulting in a heightened concentration and prolonged retention of nano-herb medicine. The combination of acid-responsive, sustainable release of nano-herb medicine from these nanocarriers and immunotherapy with an immune checkpoint inhibitor (anti-programmed death-ligand 1 (anti-PD-L1)) had been demonstrated to be effective in the treatment of colon cancer. This study not only presents a pragmatic approach to the treatment of colon cancer but also contributes novel perspectives to the development of intelligent drug delivery systems.
The application of nano-encapsulation-based drug delivery systems has become increasingly prevalent in oncological therapy. However, the suboptimal accumulation and retention of nanomedicines within tumor cells pose significant challenges to enhance therapeutic efficacy. Herein, we engineered peptide-capped mesoporous silica nanoparticles (MSNs) capable of intracellular self-aggregation into micron-sized clusters, thereby facilitating specific accumulation and retention of encapsulated drugs within tumor cells. In this innovative design, polydopamine (PDA) was in situ polymerized on the surface of MSNs loaded with berberine (BBR) and evodiamine (EVO), respectively. A peptide was conjugated to PDA via esterification. The coating of the colon cancer cell membrane could further enhance the drug encapsulation and targeting ability of MSNs. The resultant nanomedicine could assemble into micron-sized MSN clusters through peptide self-assembly, resulting in a heightened concentration and prolonged retention of nano-herb medicine. The combination of acid-responsive, sustainable release of nano-herb medicine from these nanocarriers and immunotherapy with an immune checkpoint inhibitor (anti-programmed death-ligand 1 (anti-PD-L1)) had been demonstrated to be effective in the treatment of colon cancer. This study not only presents a pragmatic approach to the treatment of colon cancer but also contributes novel perspectives to the development of intelligent drug delivery systems.
2026, 37(12): 112293
doi: 10.1016/j.cclet.2025.112293
Abstract:
Lipounguisins (LPUs) A‒K (9‒19), eleven novel lipopeptides were isolated from the sponge-associated fungus Aspergillus sp. SCSIO 40435. LPUs represent a rare class of lipopeptides (LPs), featuring cyclic heptapeptides conjugated to diverse octadecadienoic acids (either trans Δ10, Δ12 or trans Δ9, Δ11) via a C‒C or C‒N bond, and showed bioactivities including anti-Gram-positive bacteria, inhibitory activity of α-glucosidase, and cytotoxicity to Huh-7 (half-maximal inhibitory concentration (IC50) = 5.42 µmol/L). A radical-mediated coupling reaction between unguisins and octadecadienoic acids was proposed to account for LPU formation.
Lipounguisins (LPUs) A‒K (9‒19), eleven novel lipopeptides were isolated from the sponge-associated fungus Aspergillus sp. SCSIO 40435. LPUs represent a rare class of lipopeptides (LPs), featuring cyclic heptapeptides conjugated to diverse octadecadienoic acids (either trans Δ10, Δ12 or trans Δ9, Δ11) via a C‒C or C‒N bond, and showed bioactivities including anti-Gram-positive bacteria, inhibitory activity of α-glucosidase, and cytotoxicity to Huh-7 (half-maximal inhibitory concentration (IC50) = 5.42 µmol/L). A radical-mediated coupling reaction between unguisins and octadecadienoic acids was proposed to account for LPU formation.
2026, 37(12): 112295
doi: 10.1016/j.cclet.2025.112295
Abstract:
Two racemic pairs of unprecedented stilbenolignan-stilbene hybrids, (±)–heterosmilphanols A and B [(+)/(–)–1 and (+)/(–)–2], with a rare 1,4-benzodioxane core and C(sp3)–C(sp2) bond, were isolated from the roots of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic methods and quantum chemical calculations. Furthermore, our proposed biogenetic pathway led to their synthesis in seven concise steps by using a protecting-group-free strategy. The p-toluenesulfonic acid (p-TSA)-catalyzed Friedel-Crafts alkylation and Ag2O-mediated oxidative cross-coupling reactions are essential steps for the constructions of C(sp3)–C(sp2) bond and the 1,4-benzodioxane core, proceeding with high regioselectivity and stereoselectivity. Interestingly, both 1 and 2 exerted potent anti-fibrotic effects in transforming growth factor-β1 (TGF-β1)-induced HL-1 cells through inhibiting cytoskeletal remodeling, cell migration and expression of fibrotic markers. A preliminary mechanism exploration demonstrated that (+)–2 could dose-dependently and significantly suppress the TGF-β1-induced upregulation of macrophage migration inhibitory factor (MIF) protein expression in HL-1 cells. Overall, this study not only enriches the library of stilbenolignan-derived molecules but also offers potential inhibitors for myocardial fibrosis therapy. Moreover, the established synthesis ensures a sufficient supply for subsequent druggability research.
Two racemic pairs of unprecedented stilbenolignan-stilbene hybrids, (±)–heterosmilphanols A and B [(+)/(–)–1 and (+)/(–)–2], with a rare 1,4-benzodioxane core and C(sp3)–C(sp2) bond, were isolated from the roots of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic methods and quantum chemical calculations. Furthermore, our proposed biogenetic pathway led to their synthesis in seven concise steps by using a protecting-group-free strategy. The p-toluenesulfonic acid (p-TSA)-catalyzed Friedel-Crafts alkylation and Ag2O-mediated oxidative cross-coupling reactions are essential steps for the constructions of C(sp3)–C(sp2) bond and the 1,4-benzodioxane core, proceeding with high regioselectivity and stereoselectivity. Interestingly, both 1 and 2 exerted potent anti-fibrotic effects in transforming growth factor-β1 (TGF-β1)-induced HL-1 cells through inhibiting cytoskeletal remodeling, cell migration and expression of fibrotic markers. A preliminary mechanism exploration demonstrated that (+)–2 could dose-dependently and significantly suppress the TGF-β1-induced upregulation of macrophage migration inhibitory factor (MIF) protein expression in HL-1 cells. Overall, this study not only enriches the library of stilbenolignan-derived molecules but also offers potential inhibitors for myocardial fibrosis therapy. Moreover, the established synthesis ensures a sufficient supply for subsequent druggability research.
2026, 37(12): 112300
doi: 10.1016/j.cclet.2025.112300
Abstract:
WD repeat domain 5 (WDR5), a WD40 repeat protein, promotes oncogenic processes in various human cancers through dynamic interactions with key partners such as the mixed lineage leukemia (MLL) complex and cellular Myc (c-Myc). Although small-molecule inhibitors targeting WDR5–protein interfaces hold therapeutic potential, the lack of specific molecular probes for real-time monitoring has limited the mechanistic investigation of WDR5 dynamics. Here, we report the rational design of P3, a first-in-class fluorescent probe derived from the WDR5 inhibitor OICR-9429 scaffold. Structural characterization via X-ray crystallography and surface plasmon resonance (SPR) confirmed micromolar binding affinity with WDR5, while systematic linker optimization elucidated structure–optical property relationships essential for bioimaging. P3 enabled in situ visualization of WDR5 distribution in cancer cells and facilitated tumor-selective intravital imaging in xenograft models. This probe offers high spatiotemporal resolution for tracking WDR5 pathobiology, directly linking its dysregulated localization to malignant progression through multimodal imaging validation.
WD repeat domain 5 (WDR5), a WD40 repeat protein, promotes oncogenic processes in various human cancers through dynamic interactions with key partners such as the mixed lineage leukemia (MLL) complex and cellular Myc (c-Myc). Although small-molecule inhibitors targeting WDR5–protein interfaces hold therapeutic potential, the lack of specific molecular probes for real-time monitoring has limited the mechanistic investigation of WDR5 dynamics. Here, we report the rational design of P3, a first-in-class fluorescent probe derived from the WDR5 inhibitor OICR-9429 scaffold. Structural characterization via X-ray crystallography and surface plasmon resonance (SPR) confirmed micromolar binding affinity with WDR5, while systematic linker optimization elucidated structure–optical property relationships essential for bioimaging. P3 enabled in situ visualization of WDR5 distribution in cancer cells and facilitated tumor-selective intravital imaging in xenograft models. This probe offers high spatiotemporal resolution for tracking WDR5 pathobiology, directly linking its dysregulated localization to malignant progression through multimodal imaging validation.
2026, 37(12): 112309
doi: 10.1016/j.cclet.2025.112309
Abstract:
Visible-light induced multi-component carbonthioesterification reaction of alkenes with quinoxalin-2(1H)-ones, elemental sulfur and α-ketoacids has been developed. The present transformation is conducted under mild conditions to afford a wide range of biologically important quinoxalin-2(1H)-one-containing thioesters in moderate to good yields. Interestingly, the formed products show the potency of antitumor activities against HepG2. A mechanistic investigation indicates that carbonyl thiyl radical is formed through the coupling of photocatalytic activated elemental sulphur with acyl radical derived from decarboxylation of α-ketoacids.
Visible-light induced multi-component carbonthioesterification reaction of alkenes with quinoxalin-2(1H)-ones, elemental sulfur and α-ketoacids has been developed. The present transformation is conducted under mild conditions to afford a wide range of biologically important quinoxalin-2(1H)-one-containing thioesters in moderate to good yields. Interestingly, the formed products show the potency of antitumor activities against HepG2. A mechanistic investigation indicates that carbonyl thiyl radical is formed through the coupling of photocatalytic activated elemental sulphur with acyl radical derived from decarboxylation of α-ketoacids.
2026, 37(12): 112311
doi: 10.1016/j.cclet.2025.112311
Abstract:
Single-modality cancer therapies face limitations from tumor heterogeneity, drug resistance, and immune evasion. Combination therapies, particularly those that merge nucleic acid-based and immune-based therapeutics, offer promise by leveraging synergy; however, both face delivery challenges. This study reports a liquid-liquid phase separation (LLPS)-driven therapeutic coacervate system designed to simultaneously deliver nucleic acid drugs and immunostimulators for synergistic antitumor treatment. Short elastin-like polypeptide-antisense oligonucleotide (E-ASO) conjugates are synthesized to form membraneless coacervates via LLPS. These E-ASO coacervates directly internalize into cells and potently silence anti-apoptotic gene, Bcl-2, across six distinct cancer cell lines. By incorporating the stimulator of interferon gene (STING) agonist cyclic GMP-AMP (cGAMP), E-ASO-cGAMP coacervates are generated, which simultaneously downregulate Bcl-2 and activate the STING pathway, triggering cytokine production and immune activation. In melanoma and hypopharyngeal carcinoma mouse models, E-ASO-cGAMP coacervates demonstrate significantly enhanced antitumor efficacy compared to monotherapies, with potent and consistent tumor suppression across both immunologically distinct tumor types. The platform shows no observable systemic toxicity in vital organs. This LLPS-driven coacervate system establishes a new model for combined anticancer therapy, overcoming delivery barriers to synergistically integrate gene silencing and immune activation and provide a translatable strategy for solid tumor treatment.
Single-modality cancer therapies face limitations from tumor heterogeneity, drug resistance, and immune evasion. Combination therapies, particularly those that merge nucleic acid-based and immune-based therapeutics, offer promise by leveraging synergy; however, both face delivery challenges. This study reports a liquid-liquid phase separation (LLPS)-driven therapeutic coacervate system designed to simultaneously deliver nucleic acid drugs and immunostimulators for synergistic antitumor treatment. Short elastin-like polypeptide-antisense oligonucleotide (E-ASO) conjugates are synthesized to form membraneless coacervates via LLPS. These E-ASO coacervates directly internalize into cells and potently silence anti-apoptotic gene, Bcl-2, across six distinct cancer cell lines. By incorporating the stimulator of interferon gene (STING) agonist cyclic GMP-AMP (cGAMP), E-ASO-cGAMP coacervates are generated, which simultaneously downregulate Bcl-2 and activate the STING pathway, triggering cytokine production and immune activation. In melanoma and hypopharyngeal carcinoma mouse models, E-ASO-cGAMP coacervates demonstrate significantly enhanced antitumor efficacy compared to monotherapies, with potent and consistent tumor suppression across both immunologically distinct tumor types. The platform shows no observable systemic toxicity in vital organs. This LLPS-driven coacervate system establishes a new model for combined anticancer therapy, overcoming delivery barriers to synergistically integrate gene silencing and immune activation and provide a translatable strategy for solid tumor treatment.
2026, 37(12): 112314
doi: 10.1016/j.cclet.2025.112314
Abstract:
Hepatic fibrosis (HF) is critical for immune evasion in hepatocellular carcinoma (HCC), mainly driven by hepatic stellate cell (HSCs) activation, though the underlying molecular mechanisms linking HSCs activation to immune evasion remain unclear. Here, we report a targeted fluorescent nanoprobe platform for visualizing and dissecting oxidative stress dynamics driving HCC immune evasion in fibrotic tumor microenvironments. We develop a dual-channel fluorescent probe (FP-CP) enabling crosstalk-free detection of superoxide anion (O2•−) and nitric oxide (NO) with high sensitivity and spectral separation. To achieve HSCs-specific targeting, FP-CP is encapsulated into nanoparticles surface-functionalized with the HSCs-targeting peptide HTP, yielding HTP-FP-CP nanoprobes that selectively accumulate in fibrotic niches. Using this nanoplatform, in situ imaging reveals coordinated O2•−/NO elevation during HSCs activation, directly linked to oxidative inactivation of the tumor suppressor phosphatase and tensin homolog (Pten). Mechanistically, cyclooxygenase-2 (COX-2) elevation drives O2•−/NO accumulation, with O2•− and their products peroxynitrite (ONOO−) directly oxidizing/nitrifying residues in Pten. This oxidative-mediated Pten suppression activates the protein kinase B (AKT)- mammalian target of rapamycin (mTOR)-programmed cell death ligand 1 (PD-L1) axis, facilitating HCC immune evasion. Our study identifies the COX-2-O2•−/NO-Pten-Akt-mTOR-PD-L1 pathway as a critical oxidative stress-mediated molecular bridge between HF and HCC, and establishes HTP-FP-CP as a powerful nanoplatform for probing these oxidative stress dynamics in vivo, providing insights into potential therapeutic strategies for intercepting HCC in fibrotic patients.
Hepatic fibrosis (HF) is critical for immune evasion in hepatocellular carcinoma (HCC), mainly driven by hepatic stellate cell (HSCs) activation, though the underlying molecular mechanisms linking HSCs activation to immune evasion remain unclear. Here, we report a targeted fluorescent nanoprobe platform for visualizing and dissecting oxidative stress dynamics driving HCC immune evasion in fibrotic tumor microenvironments. We develop a dual-channel fluorescent probe (FP-CP) enabling crosstalk-free detection of superoxide anion (O2•−) and nitric oxide (NO) with high sensitivity and spectral separation. To achieve HSCs-specific targeting, FP-CP is encapsulated into nanoparticles surface-functionalized with the HSCs-targeting peptide HTP, yielding HTP-FP-CP nanoprobes that selectively accumulate in fibrotic niches. Using this nanoplatform, in situ imaging reveals coordinated O2•−/NO elevation during HSCs activation, directly linked to oxidative inactivation of the tumor suppressor phosphatase and tensin homolog (Pten). Mechanistically, cyclooxygenase-2 (COX-2) elevation drives O2•−/NO accumulation, with O2•− and their products peroxynitrite (ONOO−) directly oxidizing/nitrifying residues in Pten. This oxidative-mediated Pten suppression activates the protein kinase B (AKT)- mammalian target of rapamycin (mTOR)-programmed cell death ligand 1 (PD-L1) axis, facilitating HCC immune evasion. Our study identifies the COX-2-O2•−/NO-Pten-Akt-mTOR-PD-L1 pathway as a critical oxidative stress-mediated molecular bridge between HF and HCC, and establishes HTP-FP-CP as a powerful nanoplatform for probing these oxidative stress dynamics in vivo, providing insights into potential therapeutic strategies for intercepting HCC in fibrotic patients.
2026, 37(12): 112315
doi: 10.1016/j.cclet.2025.112315
Abstract:
Photoacoustic imaging (PAI) and photothermal therapy (PTT) require contrast agents that combine strong near-infrared (NIR) absorption, high photothermal conversion efficiency, and exceptional photostability. Despite the proliferation of PAI/PTT contrast agents, most have been developed empirically, with limited mechanistic understanding guiding design. Here, we introduce the NIR–barrierless access to conical-intersection thermocycling (NIR-BLACIT) model as a guiding photophysical framework for high-performance PAI/PTT agents. In this model, strong NIR absorption couples to ultrafast, barrierless transitions to conical intersection (CI) formation and rapid nonradiative decay, minimizing excited-state lifetimes and maximizing heat release. Using combined computational and experimental analysis, we identify structural determinants of NIR-BLACIT behavior in positive examples (T-AzHCy series and QC-1) and negative controls (indocyanine green (ICG) and E-AzCy7). We demonstrate that backbone-integrated azo linkages enhance the TICT propensity, lower rotational barriers, and increase the driving energies toward CI access. Guided by this principle, we designed NN7Cy and NNBDP, two novel azo-cyanine derivatives, that achieve strong NIR absorption, high oscillator strengths, and (nearly) barrierless CI access. This strategy extends beyond azo linkages; other low-energy-gap systems, such as BAF dyes, also meet the NIR-BLACIT criteria. Our findings establish NIR-BLACIT as a predictive and generalizable design principle for next-generation optoacoustic and photothermal agents.
Photoacoustic imaging (PAI) and photothermal therapy (PTT) require contrast agents that combine strong near-infrared (NIR) absorption, high photothermal conversion efficiency, and exceptional photostability. Despite the proliferation of PAI/PTT contrast agents, most have been developed empirically, with limited mechanistic understanding guiding design. Here, we introduce the NIR–barrierless access to conical-intersection thermocycling (NIR-BLACIT) model as a guiding photophysical framework for high-performance PAI/PTT agents. In this model, strong NIR absorption couples to ultrafast, barrierless transitions to conical intersection (CI) formation and rapid nonradiative decay, minimizing excited-state lifetimes and maximizing heat release. Using combined computational and experimental analysis, we identify structural determinants of NIR-BLACIT behavior in positive examples (T-AzHCy series and QC-1) and negative controls (indocyanine green (ICG) and E-AzCy7). We demonstrate that backbone-integrated azo linkages enhance the TICT propensity, lower rotational barriers, and increase the driving energies toward CI access. Guided by this principle, we designed NN7Cy and NNBDP, two novel azo-cyanine derivatives, that achieve strong NIR absorption, high oscillator strengths, and (nearly) barrierless CI access. This strategy extends beyond azo linkages; other low-energy-gap systems, such as BAF dyes, also meet the NIR-BLACIT criteria. Our findings establish NIR-BLACIT as a predictive and generalizable design principle for next-generation optoacoustic and photothermal agents.
2026, 37(12): 112316
doi: 10.1016/j.cclet.2025.112316
Abstract:
Traditional trimethine cyanines (Cy3) dyes with the emission wavelength range of 550–700 nm face multiple limitations in practical applications. Herein, we propose a photoactivation strategy to make benzo[cd]indolium-containing Cy3, which exhibit favorable fluorescence in the near infrared (NIR) region (750–1200 nm). The eco-friendly synthetic method demonstrates excellent air tolerance while requiring no photosensitizers, metals, or condensation agents. Computational results indicate that the synthesized cyanines exhibit a highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy bandgap between 2.029 eV and 2.063 eV, and the pure functional BP86 shows relatively small errors in predicting the maximum absorption wavelength. Besides, the synthesized Cy3 dyes display comparable photophysical characteristics to indocyanine green (ICG) while demonstrating improved photostability. Moreover, using benzo[cd]indolium derivatives as the sole exogenous precursor, the NIR Cy3 dyes were in situ synthesized in living cells using the photoactivation method, demonstrating significant potential for spatiotemporally controlled mitochondria-specific imaging.
Traditional trimethine cyanines (Cy3) dyes with the emission wavelength range of 550–700 nm face multiple limitations in practical applications. Herein, we propose a photoactivation strategy to make benzo[cd]indolium-containing Cy3, which exhibit favorable fluorescence in the near infrared (NIR) region (750–1200 nm). The eco-friendly synthetic method demonstrates excellent air tolerance while requiring no photosensitizers, metals, or condensation agents. Computational results indicate that the synthesized cyanines exhibit a highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy bandgap between 2.029 eV and 2.063 eV, and the pure functional BP86 shows relatively small errors in predicting the maximum absorption wavelength. Besides, the synthesized Cy3 dyes display comparable photophysical characteristics to indocyanine green (ICG) while demonstrating improved photostability. Moreover, using benzo[cd]indolium derivatives as the sole exogenous precursor, the NIR Cy3 dyes were in situ synthesized in living cells using the photoactivation method, demonstrating significant potential for spatiotemporally controlled mitochondria-specific imaging.
2026, 37(12): 112317
doi: 10.1016/j.cclet.2025.112317
Abstract:
Carbon dots (CDs) have garnered considerable attention owing to their distinctive characteristics, including excellent photoluminescence properties, inherent low toxicity and superior biocompatibility. In this study, methotrexate (MTX)-derived carbon dots (M-CDs) were synthesized via a hydrothermal method. This approach not only leverages the distinctive structural features of MTX but also allows for exploring the potential applications of M-CDs. The synthesized M-CDs exhibit excellent photoluminescence while maintaining MTX bioactivity, enabling their application in both bioimaging and cancer therapy. Notably, M-CDs display selective cytotoxicity toward A20 cells while showing minimal effects on normal human umbilical vein endothelial cells (HUVECs). Subsequently, further investigation revealed that the inhibitory effect of A20 cells is attributed to cell cycle arrest. In vivo fluorescence imaging of mice demonstrated the efficient blood-brain barrier (BBB) penetration of M-CDs, highlighting their potential candidates as a theranostic agent for central nervous system (CNS) diseases, particularly central lymphoma. The study illustrates that the converting therapeutic drugs into CDs via carbonization offers a promising strategy for developing multifunctional nanoplatforms capable of simultaneous diagnosis and therapy.
Carbon dots (CDs) have garnered considerable attention owing to their distinctive characteristics, including excellent photoluminescence properties, inherent low toxicity and superior biocompatibility. In this study, methotrexate (MTX)-derived carbon dots (M-CDs) were synthesized via a hydrothermal method. This approach not only leverages the distinctive structural features of MTX but also allows for exploring the potential applications of M-CDs. The synthesized M-CDs exhibit excellent photoluminescence while maintaining MTX bioactivity, enabling their application in both bioimaging and cancer therapy. Notably, M-CDs display selective cytotoxicity toward A20 cells while showing minimal effects on normal human umbilical vein endothelial cells (HUVECs). Subsequently, further investigation revealed that the inhibitory effect of A20 cells is attributed to cell cycle arrest. In vivo fluorescence imaging of mice demonstrated the efficient blood-brain barrier (BBB) penetration of M-CDs, highlighting their potential candidates as a theranostic agent for central nervous system (CNS) diseases, particularly central lymphoma. The study illustrates that the converting therapeutic drugs into CDs via carbonization offers a promising strategy for developing multifunctional nanoplatforms capable of simultaneous diagnosis and therapy.
2026, 37(12): 112319
doi: 10.1016/j.cclet.2025.112319
Abstract:
The advancement of intelligent packaging systems that integrate real-time freshness monitoring with active preservation capabilities is critically important for enhancing food safety. Beyond traditional single-function packaging materials, we synthesized sulfur/selenium-substituted Nile blue (NBS/NBSe) dyes for fabricating multifunctional films (SA/NBS, SA/NBSe) using sodium alginate (SA) via an extended-flow casting method. The obtained films exhibited dual functionality of freshness monitoring and antibacterial preservation, with excellent mechanical properties and stability. Compared with SA/NBS, SA/NBSe films demonstrated high sensitivity in monitoring shrimp freshness, which aligned with the RGB analysis results obtained via a smartphone application in total volatile base nitrogen (TVB-N) determination. Theoretical analysis revealed that NBSe was more sensitive to pH changes because its acidic type possessed a larger surface distribution in the high electrostatic potential region for promoting H+ ionization. Furthermore, SA/NBSe film contributed superior preservation efficacy for fresh beef cuts (6-day extension) and strong bacteriostatic ability attributed to 1O2 and O2•− generation of photodynamic antimicrobial therapy. Overall, these findings highlight the pH-responsiveness and antibacterial potency of Nile blue–based packaging films, making them promising for the qualitative freshness monitoring and preservation of protein-rich foods.
The advancement of intelligent packaging systems that integrate real-time freshness monitoring with active preservation capabilities is critically important for enhancing food safety. Beyond traditional single-function packaging materials, we synthesized sulfur/selenium-substituted Nile blue (NBS/NBSe) dyes for fabricating multifunctional films (SA/NBS, SA/NBSe) using sodium alginate (SA) via an extended-flow casting method. The obtained films exhibited dual functionality of freshness monitoring and antibacterial preservation, with excellent mechanical properties and stability. Compared with SA/NBS, SA/NBSe films demonstrated high sensitivity in monitoring shrimp freshness, which aligned with the RGB analysis results obtained via a smartphone application in total volatile base nitrogen (TVB-N) determination. Theoretical analysis revealed that NBSe was more sensitive to pH changes because its acidic type possessed a larger surface distribution in the high electrostatic potential region for promoting H+ ionization. Furthermore, SA/NBSe film contributed superior preservation efficacy for fresh beef cuts (6-day extension) and strong bacteriostatic ability attributed to 1O2 and O2•− generation of photodynamic antimicrobial therapy. Overall, these findings highlight the pH-responsiveness and antibacterial potency of Nile blue–based packaging films, making them promising for the qualitative freshness monitoring and preservation of protein-rich foods.
2026, 37(12): 112320
doi: 10.1016/j.cclet.2025.112320
Abstract:
Natural products have long served as invaluable resources for drug discovery, providing unique scaffolds to investigate disease-related targets. Here, we report a novel mechanism by which tanshinone IIA (TIIA), a bioactive constituent of Salvia miltiorrhiza Bge., exerts vascular protective effects through covalent modification of Annexin A2 (ANXA2). By employing an alkynylated TIIA probe (A-TIIA) in combination with chemical proteomics, we identified ANXA2 as a direct binding target of TIIA, wherein the 11,12-ortho-phenanthrenequinone moiety of TIIA forms an amine-quinone adduct with the guanidinium group of Arg145 in ANXA2. This interaction inhibits protein tyrosine phosphatase 1B (PTP1B)-mediated dephosphorylation of ANXA2 at Tyr24, locking the protein in an inactive conformation and disrupting the ANXA2-integrin α5-focal adhesion kinase (FAK)/intercellular adhesion molecule 1 (ICAM-1) signaling axis. This study not only uncovers a previously unknown mechanism underlying the therapeutic action of TIIA but also underscores the potential of natural product-inspired covalent modifiers in modulating protein-protein interactions. The evolutionarily conserved Arg145 residue in ANXA2 emerges as a promising target site for future drug development.
Natural products have long served as invaluable resources for drug discovery, providing unique scaffolds to investigate disease-related targets. Here, we report a novel mechanism by which tanshinone IIA (TIIA), a bioactive constituent of Salvia miltiorrhiza Bge., exerts vascular protective effects through covalent modification of Annexin A2 (ANXA2). By employing an alkynylated TIIA probe (A-TIIA) in combination with chemical proteomics, we identified ANXA2 as a direct binding target of TIIA, wherein the 11,12-ortho-phenanthrenequinone moiety of TIIA forms an amine-quinone adduct with the guanidinium group of Arg145 in ANXA2. This interaction inhibits protein tyrosine phosphatase 1B (PTP1B)-mediated dephosphorylation of ANXA2 at Tyr24, locking the protein in an inactive conformation and disrupting the ANXA2-integrin α5-focal adhesion kinase (FAK)/intercellular adhesion molecule 1 (ICAM-1) signaling axis. This study not only uncovers a previously unknown mechanism underlying the therapeutic action of TIIA but also underscores the potential of natural product-inspired covalent modifiers in modulating protein-protein interactions. The evolutionarily conserved Arg145 residue in ANXA2 emerges as a promising target site for future drug development.
2026, 37(12): 112323
doi: 10.1016/j.cclet.2025.112323
Abstract:
This study highlights the universality of 172 nm excimer vacuum ultraviolet (EVUL) etching for high-resolution patterning of polymer materials, achieving a resolution of ∼350 nm. The technique was successfully used to fabricate polymer thin-film transistor (PTFT) array consisting of 360 PTFTs, based on doped indaceno-dithiophene–benzothiadiazole (IDT-BT) films, achieving a significant reduction in off-state current by four orders of magnitude (from 10−5 A to 10−9 A). Additionally, an active PTFT-organic light-emitting diode (OLED) active-matrix circuit was fabricated, demonstrating the practical applicability of this method in organic optoelectronics. These results underscore the potential of 172 nm EVUL etching in enabling high-performance, polymer-based electronic circuit, with promising applications in flexible integrated circuit and displays.
This study highlights the universality of 172 nm excimer vacuum ultraviolet (EVUL) etching for high-resolution patterning of polymer materials, achieving a resolution of ∼350 nm. The technique was successfully used to fabricate polymer thin-film transistor (PTFT) array consisting of 360 PTFTs, based on doped indaceno-dithiophene–benzothiadiazole (IDT-BT) films, achieving a significant reduction in off-state current by four orders of magnitude (from 10−5 A to 10−9 A). Additionally, an active PTFT-organic light-emitting diode (OLED) active-matrix circuit was fabricated, demonstrating the practical applicability of this method in organic optoelectronics. These results underscore the potential of 172 nm EVUL etching in enabling high-performance, polymer-based electronic circuit, with promising applications in flexible integrated circuit and displays.
2026, 37(12): 112336
doi: 10.1016/j.cclet.2025.112336
Abstract:
Intracerebral hemorrhage (ICH) is a severe condition caused by the rupture of cerebral blood vessels and subsequent blood entry into the brain parenchyma, characterized by high mortality and poor prognosis. The formation of hematoma and the release of erythrocyte lysis products following ICH are critical factors contributing to brain injury. Rosiglitazone (RSG), a thiazolidinedione drug, has demonstrated therapeutic potential in neurological disorders. However, the clinical translation of RSG for ICH is limited by its poor water solubility, low blood-brain barrier (BBB) permeability, and off-target organ toxicity such as hepatotoxicity and nephrotoxicity. In this study, we synthesized an amphiphilic ternary copolymer by covalently conjugating poly(ethylene glycol)-poly(lactic acid) (PEG-PLA) with chitosan (CS). This polymer, designated as PEG-PLA-CS, was utilized to encapsulate RSG, forming positively charged nanoparticles (RSG@CS-NPs) to enhance mucoadhesion and transepithelial permeability. In two distinct mouse models of ICH, intranasal administration of RSG@CS-NPs enhanced erythrocyte phagocytosis by microglia and macrophages, which in turn reduced the release of cytotoxic lysis products and promoted hematoma resolution. Consequently, this treatment attenuated hematoma volume, BBB damage, and neuronal injury, leading to the amelioration of neurological deficits. This study provides a novel perspective for ICH treatment.
Intracerebral hemorrhage (ICH) is a severe condition caused by the rupture of cerebral blood vessels and subsequent blood entry into the brain parenchyma, characterized by high mortality and poor prognosis. The formation of hematoma and the release of erythrocyte lysis products following ICH are critical factors contributing to brain injury. Rosiglitazone (RSG), a thiazolidinedione drug, has demonstrated therapeutic potential in neurological disorders. However, the clinical translation of RSG for ICH is limited by its poor water solubility, low blood-brain barrier (BBB) permeability, and off-target organ toxicity such as hepatotoxicity and nephrotoxicity. In this study, we synthesized an amphiphilic ternary copolymer by covalently conjugating poly(ethylene glycol)-poly(lactic acid) (PEG-PLA) with chitosan (CS). This polymer, designated as PEG-PLA-CS, was utilized to encapsulate RSG, forming positively charged nanoparticles (RSG@CS-NPs) to enhance mucoadhesion and transepithelial permeability. In two distinct mouse models of ICH, intranasal administration of RSG@CS-NPs enhanced erythrocyte phagocytosis by microglia and macrophages, which in turn reduced the release of cytotoxic lysis products and promoted hematoma resolution. Consequently, this treatment attenuated hematoma volume, BBB damage, and neuronal injury, leading to the amelioration of neurological deficits. This study provides a novel perspective for ICH treatment.
2026, 37(12): 112339
doi: 10.1016/j.cclet.2025.112339
Abstract:
Given the critical role of hydrogen persulfide (H2S2) in biological systems, its accurate quantification and visualization within deep tissues are essential for understanding associated pathophysiological processes. However, conventional hydrogen polysulfide probes often suffer from inadequate selectivity among reactive sulfur species, limiting their reliability for quantitative imaging applications. Herein, we developed a novel dual ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescence/photoacoustic probe for deep imaging of H2S2 with unprecedented specificity through electronic tuning of cyanine. Strong electron-donating moieties were responsible for modulating the specific responsiveness to H2S2 over H2S. Such a designed probe (H2S2–4) exhibited robust dual-ratiometric NIR-Ⅱ fluorescence (I890/I1020, 42-fold) and photoacoustic (PA840/PA960, 4.49-fold) responses towards Na2S2 species with high specificity and sensitivity. By use of dual ratiometric NIR-Ⅱ fluorescence/photoacoustic imaging, we successfully mapped endogenous H2S2 fluctuations in bacterial infection-induced inflammation models in vivo with enhanced accuracy and reliability. Thus, this study not only provides a versatile tool for dissecting H2S2-related biological events but also establishes an electronic-tuning strategy to guide the design of advanced H2S2-specific probes.
Given the critical role of hydrogen persulfide (H2S2) in biological systems, its accurate quantification and visualization within deep tissues are essential for understanding associated pathophysiological processes. However, conventional hydrogen polysulfide probes often suffer from inadequate selectivity among reactive sulfur species, limiting their reliability for quantitative imaging applications. Herein, we developed a novel dual ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescence/photoacoustic probe for deep imaging of H2S2 with unprecedented specificity through electronic tuning of cyanine. Strong electron-donating moieties were responsible for modulating the specific responsiveness to H2S2 over H2S. Such a designed probe (H2S2–4) exhibited robust dual-ratiometric NIR-Ⅱ fluorescence (I890/I1020, 42-fold) and photoacoustic (PA840/PA960, 4.49-fold) responses towards Na2S2 species with high specificity and sensitivity. By use of dual ratiometric NIR-Ⅱ fluorescence/photoacoustic imaging, we successfully mapped endogenous H2S2 fluctuations in bacterial infection-induced inflammation models in vivo with enhanced accuracy and reliability. Thus, this study not only provides a versatile tool for dissecting H2S2-related biological events but also establishes an electronic-tuning strategy to guide the design of advanced H2S2-specific probes.
2026, 37(12): 112359
doi: 10.1016/j.cclet.2026.112359
Abstract:
The sensitive and specific identification of lymph node (LN) metastasis is critical for cancer staging and guiding intraoperative decisions. However, the inability to accurately distinguish metastatic from healthy LNs represents a critical gap in oncologic imaging. Here, we transform the conventional near-infrared (NIR) dye indocyanine green (ICG) into a pH-activatable probe (denoted as ICCPs) for the precise detection of lymphatic metastasis. The probe design utilizes a pH-sensitive calcium phosphate nanocarrier to induce a fluorescent “OFF” state via aggregation-caused quenching (ACQ). Upon exposure to the acidic microenvironment characteristic of metastatic lesions, the nanocarrier rapidly disassembles, triggering a robust fluorescent “ON” signal. Through comprehensive in vitro and in vivo validation in a metastatic LNs model, we demonstrate that ICCPs achieve superior specificity compared to free ICG and Evans blue. The probe accurately identified primary tumors and, crucially, allowed for the precise differentiation between metastatic and normal LNs. This work establishes ICCPs as a highly promising tool for clinical translation, offering a solution for high-precision, real-time intraoperative guidance in cancer surgery.
The sensitive and specific identification of lymph node (LN) metastasis is critical for cancer staging and guiding intraoperative decisions. However, the inability to accurately distinguish metastatic from healthy LNs represents a critical gap in oncologic imaging. Here, we transform the conventional near-infrared (NIR) dye indocyanine green (ICG) into a pH-activatable probe (denoted as ICCPs) for the precise detection of lymphatic metastasis. The probe design utilizes a pH-sensitive calcium phosphate nanocarrier to induce a fluorescent “OFF” state via aggregation-caused quenching (ACQ). Upon exposure to the acidic microenvironment characteristic of metastatic lesions, the nanocarrier rapidly disassembles, triggering a robust fluorescent “ON” signal. Through comprehensive in vitro and in vivo validation in a metastatic LNs model, we demonstrate that ICCPs achieve superior specificity compared to free ICG and Evans blue. The probe accurately identified primary tumors and, crucially, allowed for the precise differentiation between metastatic and normal LNs. This work establishes ICCPs as a highly promising tool for clinical translation, offering a solution for high-precision, real-time intraoperative guidance in cancer surgery.
2026, 37(12): 112360
doi: 10.1016/j.cclet.2026.112360
Abstract:
Mitochondrial gene delivery for functional compensation of defective proteins represents a promising therapeutic strategy for currently untreatable mitochondrial disorders. However, the double-membrane structure of mitochondrial poses a fundamental barrier for the transport of genetic therapeutics into the organelle. Here, we report a novel mitochondria-targeted fluorinated lipid nanoparticle (F6 mtLNP) for efficient mitochondrial gene delivery. F6 mtLNP successfully overcame mitochondrial barriers and delivered the therapeutic NDI1 gene into the mitochondrial matrix leveraging the mitochondrial targeting capacity of the mitochondrial targeting signal (MTS) peptide combined with the superior membrane affinity and penetration capability of F6 lipid. In a rotenone-induced Leber's hereditary optic neuropathy (LHON) model characterized by complex Ⅰ deficiency, F6 mtLNP mediated superior functional protein expression, leading to significant restoration of complex Ⅰ activity and consequent amelioration of disease symptoms. Collectively, our findings established F6 mtLNP as a promising platform to overcome the mitochondrial membrane barrier for effective functional gene delivery, offering a potential therapeutic strategy for LHON and other mitochondrial complex Ⅰ deficiency-related mitochondrial disorders.
Mitochondrial gene delivery for functional compensation of defective proteins represents a promising therapeutic strategy for currently untreatable mitochondrial disorders. However, the double-membrane structure of mitochondrial poses a fundamental barrier for the transport of genetic therapeutics into the organelle. Here, we report a novel mitochondria-targeted fluorinated lipid nanoparticle (F6 mtLNP) for efficient mitochondrial gene delivery. F6 mtLNP successfully overcame mitochondrial barriers and delivered the therapeutic NDI1 gene into the mitochondrial matrix leveraging the mitochondrial targeting capacity of the mitochondrial targeting signal (MTS) peptide combined with the superior membrane affinity and penetration capability of F6 lipid. In a rotenone-induced Leber's hereditary optic neuropathy (LHON) model characterized by complex Ⅰ deficiency, F6 mtLNP mediated superior functional protein expression, leading to significant restoration of complex Ⅰ activity and consequent amelioration of disease symptoms. Collectively, our findings established F6 mtLNP as a promising platform to overcome the mitochondrial membrane barrier for effective functional gene delivery, offering a potential therapeutic strategy for LHON and other mitochondrial complex Ⅰ deficiency-related mitochondrial disorders.
2026, 37(12): 112361
doi: 10.1016/j.cclet.2026.112361
Abstract:
Melanin is the characteristic product of the vast majority of melanomas which is the most lethal and invasive type of skin cancer. We synthesized a new probe that target melanin, H-3, and its variant that connected to the Evans blue, H-3-EB, were radiolabeled with [68Ga]Ga and [177Lu]Lu, respectively. Both [68Ga]Ga-H-3 and [68Ga]Ga-H-3-EB have favorable affinity and specificity for melanin, and good diagnostic efficacy for melanoma. [177Lu]Lu-H-3-EB showed a more pronounced therapeutic effect than [177Lu]Lu-H-3 in B16 tumors since its extended effective half life in vivo by its ability binding to albumin. [68Ga]Ga-H-3-EB was well tolerated by malignant melanoma (MM) patients, and detected all primary melanoma lesions and lymph node metastases. This suggests that [177Lu]Lu-H-3-EB could become a highly promising therapeutic option for patients with advanced melanoma.
Melanin is the characteristic product of the vast majority of melanomas which is the most lethal and invasive type of skin cancer. We synthesized a new probe that target melanin, H-3, and its variant that connected to the Evans blue, H-3-EB, were radiolabeled with [68Ga]Ga and [177Lu]Lu, respectively. Both [68Ga]Ga-H-3 and [68Ga]Ga-H-3-EB have favorable affinity and specificity for melanin, and good diagnostic efficacy for melanoma. [177Lu]Lu-H-3-EB showed a more pronounced therapeutic effect than [177Lu]Lu-H-3 in B16 tumors since its extended effective half life in vivo by its ability binding to albumin. [68Ga]Ga-H-3-EB was well tolerated by malignant melanoma (MM) patients, and detected all primary melanoma lesions and lymph node metastases. This suggests that [177Lu]Lu-H-3-EB could become a highly promising therapeutic option for patients with advanced melanoma.
2026, 37(12): 112422
doi: 10.1016/j.cclet.2026.112422
Abstract:
The translocation of a functional group (FG) within a molecule has perceived as a powerful strategy in synthetic chemistry, providing a unique and economic approach to molecular structure modification. Despite substantial advances, the translocation of such functional groups, such as cyano group, still heavily relies on radical-involved pathways. In contrast, the mechanically complementary polar FGs translocation remains far less underdeveloped. Herein, we report an unprecedented copper-catalyzed borylcyanation of unactivated alkenes via polar cyano group translocation. This reaction proceeds under exceptionally mild conditions with high regioselectivity and excellent functional group tolerance, affording valuable borylcyanation products containing 1,n-dinitrile motifs from readily available starting materials. The transformation is proposed to initiate through borocupration of the unactivated alkene, followed by an intramolecular addition of the resulting alkyl-copper intermediate to C≡N bond and sub-sequent β-carbon elimination. The success of this methodology is attributed to the discovery of a bidentate phosphine-ligated copper catalyst, exerting precise regioselectivity and effectively suppressing the competing rapid protonation of in-situ formed alkyl- and iminocopper intermediates by an alcohol.
The translocation of a functional group (FG) within a molecule has perceived as a powerful strategy in synthetic chemistry, providing a unique and economic approach to molecular structure modification. Despite substantial advances, the translocation of such functional groups, such as cyano group, still heavily relies on radical-involved pathways. In contrast, the mechanically complementary polar FGs translocation remains far less underdeveloped. Herein, we report an unprecedented copper-catalyzed borylcyanation of unactivated alkenes via polar cyano group translocation. This reaction proceeds under exceptionally mild conditions with high regioselectivity and excellent functional group tolerance, affording valuable borylcyanation products containing 1,n-dinitrile motifs from readily available starting materials. The transformation is proposed to initiate through borocupration of the unactivated alkene, followed by an intramolecular addition of the resulting alkyl-copper intermediate to C≡N bond and sub-sequent β-carbon elimination. The success of this methodology is attributed to the discovery of a bidentate phosphine-ligated copper catalyst, exerting precise regioselectivity and effectively suppressing the competing rapid protonation of in-situ formed alkyl- and iminocopper intermediates by an alcohol.
2026, 37(12): 112431
doi: 10.1016/j.cclet.2026.112431
Abstract:
Physicochemical properties of amino acids are fundamental to understanding the structure and biological function of peptides, inversely guiding us to control their conformation and function. The construction of conformationally constrained peptides enabled by modification cannot only precisely lock the specific folding structure, but also introduce an additional functional group to enhance their properties and diversify their structures for functional studies. While macrocyclization via various cyclic linkers for the α-helix/cyclic peptides formation has been well established, constructing functionalized β-sheet peptides through modification remains a synthetic challenge. To address this issue, herein we developed a dehydroalanine (Dha)-proline turn template to stabilize β-sheet peptides, in which the Dha-containing turn moiety undergoes a designed double-bond-retained coupling reaction to generate diverse functionalized peptides while maintaining β-sheet integrity. Mechanistic study reveals the unique deprotonation property of Dha under basic conditions and subsequent single-electron transfer (SET) from the enamine moiety of Dha to the diaryliodonium salt.
Physicochemical properties of amino acids are fundamental to understanding the structure and biological function of peptides, inversely guiding us to control their conformation and function. The construction of conformationally constrained peptides enabled by modification cannot only precisely lock the specific folding structure, but also introduce an additional functional group to enhance their properties and diversify their structures for functional studies. While macrocyclization via various cyclic linkers for the α-helix/cyclic peptides formation has been well established, constructing functionalized β-sheet peptides through modification remains a synthetic challenge. To address this issue, herein we developed a dehydroalanine (Dha)-proline turn template to stabilize β-sheet peptides, in which the Dha-containing turn moiety undergoes a designed double-bond-retained coupling reaction to generate diverse functionalized peptides while maintaining β-sheet integrity. Mechanistic study reveals the unique deprotonation property of Dha under basic conditions and subsequent single-electron transfer (SET) from the enamine moiety of Dha to the diaryliodonium salt.
2026, 37(12): 112432
doi: 10.1016/j.cclet.2026.112432
Abstract:
Asymmetric catalytic hydrophosphination of alkenes provides an atom-economical approach for accessing enantioenriched chiral organophosphorus compounds. However, unactivated alkenes remain challenging substrates. By merging borrowing catalysis and metal-catalyzed hydrophosphination, we have achieved the enantioconvergent hydrophosphination of racemic allylic alcohols, a class of readily available unactivated alkenes. This reaction is enabled by a trimetallic cooperative catalytic system, affording enantioenriched functionalized phosphines, γ-hydroxyphosphine derivatives, with two remote chiral centers. Excellent stereoselectivities (up to 20:1 dr and 99% ee) and broad substrate scope (44 examples) are demonstrated. The hydroxy group in the products could be transformed into various functional groups, allowing for the synthesis of a range of functionalized phosphorus compounds. Mechanistic studies suggest that a single chiral ruthenium catalyst controls the absolute configuration of two remote chiral centers via dynamic kinetic asymmetric transformation, which is enabled by achiral copper-catalyzed intermediate racemization through retro-conjugate addition.
Asymmetric catalytic hydrophosphination of alkenes provides an atom-economical approach for accessing enantioenriched chiral organophosphorus compounds. However, unactivated alkenes remain challenging substrates. By merging borrowing catalysis and metal-catalyzed hydrophosphination, we have achieved the enantioconvergent hydrophosphination of racemic allylic alcohols, a class of readily available unactivated alkenes. This reaction is enabled by a trimetallic cooperative catalytic system, affording enantioenriched functionalized phosphines, γ-hydroxyphosphine derivatives, with two remote chiral centers. Excellent stereoselectivities (up to 20:1 dr and 99% ee) and broad substrate scope (44 examples) are demonstrated. The hydroxy group in the products could be transformed into various functional groups, allowing for the synthesis of a range of functionalized phosphorus compounds. Mechanistic studies suggest that a single chiral ruthenium catalyst controls the absolute configuration of two remote chiral centers via dynamic kinetic asymmetric transformation, which is enabled by achiral copper-catalyzed intermediate racemization through retro-conjugate addition.
2026, 37(12): 112436
doi: 10.1016/j.cclet.2026.112436
Abstract:
The construction of molecules with multiple stereogenic axes has garnered growing attention due to their wide potential applications in natural products, pharmaceuticals, functional materials, and asymmetric catalysis. However, the enantioselective synthesis of such skeletons remains underdeveloped, as simultaneous control over diastereo- and enantioselectivity in assembling multiple stereogenic axes poses significant challenges. Reported methodologies mainly focuse on the atropisomeric synthesis of biaxial molecules, while the asymmetric construction of multiaxial systems with more than two stereogenic axes remains in its fancy. Herein, we report an enantioselective one-step synthesis of atropisomeric calix[4]arenes bearing four chiral C–N or N–N axes through an efficient cobalt-catalyzed asymmetric multisite C–H activation/annulation strategy. This method accommodates diverse benzamides and calix[4]arenes, efficiently constructing four C–N or N–N axes on the calix[4]arene scaffold in high yields and excellent stereoselectivities. The absolute stereochemistry was precisely controlled by employing different ligand enantiomers, enabling access to both product enantiomers. The resulting multiaxial atropisomers exhibit a well-defined bowl-shaped architecture and outstanding optical properties, as demonstrated by fluorescence emission, circular dichroism, circularly polarized luminescence studies, and chiral recognition. This work not only demonstrates the robustness of cobalt catalysis in synthesizing complex stereogenic frameworks but also highlights the applications of atropisomeric multiaxes compounds in optical materials.
The construction of molecules with multiple stereogenic axes has garnered growing attention due to their wide potential applications in natural products, pharmaceuticals, functional materials, and asymmetric catalysis. However, the enantioselective synthesis of such skeletons remains underdeveloped, as simultaneous control over diastereo- and enantioselectivity in assembling multiple stereogenic axes poses significant challenges. Reported methodologies mainly focuse on the atropisomeric synthesis of biaxial molecules, while the asymmetric construction of multiaxial systems with more than two stereogenic axes remains in its fancy. Herein, we report an enantioselective one-step synthesis of atropisomeric calix[4]arenes bearing four chiral C–N or N–N axes through an efficient cobalt-catalyzed asymmetric multisite C–H activation/annulation strategy. This method accommodates diverse benzamides and calix[4]arenes, efficiently constructing four C–N or N–N axes on the calix[4]arene scaffold in high yields and excellent stereoselectivities. The absolute stereochemistry was precisely controlled by employing different ligand enantiomers, enabling access to both product enantiomers. The resulting multiaxial atropisomers exhibit a well-defined bowl-shaped architecture and outstanding optical properties, as demonstrated by fluorescence emission, circular dichroism, circularly polarized luminescence studies, and chiral recognition. This work not only demonstrates the robustness of cobalt catalysis in synthesizing complex stereogenic frameworks but also highlights the applications of atropisomeric multiaxes compounds in optical materials.
2026, 37(12): 112446
doi: 10.1016/j.cclet.2026.112446
Abstract:
Donor-acceptor (D-A) cyclopropanes have been widely used in asymmetric (3+2) dipolar cyclizations with various acceptors. However, the enantioselective construction of ring systems bearing heteroatom stereocenters using 2π-components with two different heteroatoms remains a challenge due to their low reactivity and the difficulty in controlling heteroatom chirality. Here, we report a Pd-catalyzed asymmetric (3+2) cyclization of oxindole-derived vinylcyclopropanes, a subclass of D-A cyclopropanes, with sulfinylamines, providing a versatile platform for synthesizing oxindole scaffolds bearing adjacent S(Ⅳ) and spiro stereocenters. The resulting products demonstrate excellent stability and are promising precursors for cyclic sulfinamides through stereospecific transformations. In addition, control experiments and NMR analysis reveal the crucial role of hydrogen bonding in substrate activation and stereoinduction.
Donor-acceptor (D-A) cyclopropanes have been widely used in asymmetric (3+2) dipolar cyclizations with various acceptors. However, the enantioselective construction of ring systems bearing heteroatom stereocenters using 2π-components with two different heteroatoms remains a challenge due to their low reactivity and the difficulty in controlling heteroatom chirality. Here, we report a Pd-catalyzed asymmetric (3+2) cyclization of oxindole-derived vinylcyclopropanes, a subclass of D-A cyclopropanes, with sulfinylamines, providing a versatile platform for synthesizing oxindole scaffolds bearing adjacent S(Ⅳ) and spiro stereocenters. The resulting products demonstrate excellent stability and are promising precursors for cyclic sulfinamides through stereospecific transformations. In addition, control experiments and NMR analysis reveal the crucial role of hydrogen bonding in substrate activation and stereoinduction.
2026, 37(12): 112447
doi: 10.1016/j.cclet.2026.112447
Abstract:
Photocatalytic hydrogen evolution from water is considered a promising route for solar energy utilization. However, the efficiency of plasmonic photocatalysts under broad-spectrum sunlight remains hampered by inefficient charge management. Systems such as TiO2/Au suffer from electron counterflow under simultaneous UV and visible excitation: UV-excited electrons in TiO2 migrate toward Au, while visible-light-induced hot electrons from Au inject into TiO2, resulting in severe recombination losses. Here, we construct a ternary TiO2/Au-Pt heterostructure with a deliberately aligned Fermi-level gradient (TiO2 → Au → Pt), establishing a unidirectional, downhill electron-transfer pathway. This stepwise energy alignment channels both UV- and visible-light-excited electrons sequentially to Pt catalytic sites, effectively suppressing charge counterflow and maximizing electron utilization. Consequently, TiO2/Au-Pt achieves a remarkable H2 evolution rate of 16.67 mmol g-1 h-1 under broad-spectrum irradiation, surpassing those of TiO2/Au and TiO2/Pt by factors of 3.18 and 2.32, respectively, while maintaining excellent stability over 20 h. This Fermi-level-guided strategy provides a general paradigm for engineering multicomponent photocatalysts with optimized interfacial energetics toward efficient broad-spectrum solar-to-hydrogen conversion.
Photocatalytic hydrogen evolution from water is considered a promising route for solar energy utilization. However, the efficiency of plasmonic photocatalysts under broad-spectrum sunlight remains hampered by inefficient charge management. Systems such as TiO2/Au suffer from electron counterflow under simultaneous UV and visible excitation: UV-excited electrons in TiO2 migrate toward Au, while visible-light-induced hot electrons from Au inject into TiO2, resulting in severe recombination losses. Here, we construct a ternary TiO2/Au-Pt heterostructure with a deliberately aligned Fermi-level gradient (TiO2 → Au → Pt), establishing a unidirectional, downhill electron-transfer pathway. This stepwise energy alignment channels both UV- and visible-light-excited electrons sequentially to Pt catalytic sites, effectively suppressing charge counterflow and maximizing electron utilization. Consequently, TiO2/Au-Pt achieves a remarkable H2 evolution rate of 16.67 mmol g-1 h-1 under broad-spectrum irradiation, surpassing those of TiO2/Au and TiO2/Pt by factors of 3.18 and 2.32, respectively, while maintaining excellent stability over 20 h. This Fermi-level-guided strategy provides a general paradigm for engineering multicomponent photocatalysts with optimized interfacial energetics toward efficient broad-spectrum solar-to-hydrogen conversion.
2026, 37(12): 112468
doi: 10.1016/j.cclet.2026.112468
Abstract:
A facile route to 2,2-difluoro-4-sulfonylthiochromanes through a reaction of {difluoro(phenylthio)methyl}triphenylphosphonium iodides with vinyl sulfones under visible light irradiation is reported. This transformation is highly efficient through radical difluoro(phenylthio)methylation/cyclization in the absence of catalyst and additives under mild conditions. The structure of 2,2-difluoro-4-(phenylsulfonyl)thiochromanes is found to be a novel structure for anti-influenza, and further structure-activity relationship (SAR) studies show that cyano and fluoro substitution on phenyl and thiochromanes, respectively, can improve the activity significantly. The supposed mechanism of hemagglutinin inhibition is also investigated by molecular docking analysis.
A facile route to 2,2-difluoro-4-sulfonylthiochromanes through a reaction of {difluoro(phenylthio)methyl}triphenylphosphonium iodides with vinyl sulfones under visible light irradiation is reported. This transformation is highly efficient through radical difluoro(phenylthio)methylation/cyclization in the absence of catalyst and additives under mild conditions. The structure of 2,2-difluoro-4-(phenylsulfonyl)thiochromanes is found to be a novel structure for anti-influenza, and further structure-activity relationship (SAR) studies show that cyano and fluoro substitution on phenyl and thiochromanes, respectively, can improve the activity significantly. The supposed mechanism of hemagglutinin inhibition is also investigated by molecular docking analysis.
2026, 37(12): 112469
doi: 10.1016/j.cclet.2026.112469
Abstract:
The direct three-component reactions of carboxylic/amino acids, secondary amines and α-trichloromethyl ketone for the direct synthesis of β-acyloxyl alkenyl amides (AAAs) has been realized simply with the promotion of Cs2CO3 under mild conditions. As activated form of carboxylic and amino acids, the AAAs have been verified with excellent performance in the synthesis of di- to tetra peptides under mild and catalyst-/promoter-free conditions without confronting evident racemization or epimerization. The three-component protocol breaks the previous method relying on multi-step linear synthesis involving highly sensitive intermediate, showing amazingly high step efficiency by offering one-step access to these activated acid esters in fashion of target-oriented synthesis, delivering the discovery of simple α-trichloromethyl ketone—secondary amine combination as new coupling reagent for peptide synthesis
The direct three-component reactions of carboxylic/amino acids, secondary amines and α-trichloromethyl ketone for the direct synthesis of β-acyloxyl alkenyl amides (AAAs) has been realized simply with the promotion of Cs2CO3 under mild conditions. As activated form of carboxylic and amino acids, the AAAs have been verified with excellent performance in the synthesis of di- to tetra peptides under mild and catalyst-/promoter-free conditions without confronting evident racemization or epimerization. The three-component protocol breaks the previous method relying on multi-step linear synthesis involving highly sensitive intermediate, showing amazingly high step efficiency by offering one-step access to these activated acid esters in fashion of target-oriented synthesis, delivering the discovery of simple α-trichloromethyl ketone—secondary amine combination as new coupling reagent for peptide synthesis
2026, 37(12): 112483
doi: 10.1016/j.cclet.2026.112483
Abstract:
Guest substituent electronic effects and chemical fuel selection govern the kinetics of anion-responsive dissipative molecular switches. Using Texas-sized macrocycles (Na-TxSB/An-TxSB) and 17 para-phthalic acid dianion guests, time-resolved UV–vis spectroscopy reveals substituent-dependent the half reaction time (t1/2) and fuel-driven rate modulation ((2-cyano-2-(p-tolyl)propanoic acid (ACA2) accelerated switching up to 6-fold vs. trichloroacetic acid (ACA1)). DFT calculations established a proportional relationship between guest Mulliken charge and t1/2, rationalizing kinetic trends confirmed with both hosts. This provides design principles for tailoring dissipative switches via host-guest and fuel engineering.
Guest substituent electronic effects and chemical fuel selection govern the kinetics of anion-responsive dissipative molecular switches. Using Texas-sized macrocycles (Na-TxSB/An-TxSB) and 17 para-phthalic acid dianion guests, time-resolved UV–vis spectroscopy reveals substituent-dependent the half reaction time (t1/2) and fuel-driven rate modulation ((2-cyano-2-(p-tolyl)propanoic acid (ACA2) accelerated switching up to 6-fold vs. trichloroacetic acid (ACA1)). DFT calculations established a proportional relationship between guest Mulliken charge and t1/2, rationalizing kinetic trends confirmed with both hosts. This provides design principles for tailoring dissipative switches via host-guest and fuel engineering.
2026, 37(12): 112505
doi: 10.1016/j.cclet.2026.112505
Abstract:
We have established a glycosyl radical-based synthesis of C-alkyl glycosides, utilizing a deoxygenative Giese reaction between alkenes and phosphitylated 1-hydroxycarbohydrates. This approach introduces a novel strategy to generate glycosyl radicals through SET reduction enabled by 2–iodophenethyl methyl phosphite. It operates under mild conditions, avoids the use of toxic hydrogen-atom donors while utilizing readily available precursors. The protocol is also amenable to late-stage functionalization of drug molecules and scale-up using continuous-flow. Mechanistic studies confirm the formation of glycosyl radicals and indicate that the hydrogen atoms originate from TMS3SiH.
We have established a glycosyl radical-based synthesis of C-alkyl glycosides, utilizing a deoxygenative Giese reaction between alkenes and phosphitylated 1-hydroxycarbohydrates. This approach introduces a novel strategy to generate glycosyl radicals through SET reduction enabled by 2–iodophenethyl methyl phosphite. It operates under mild conditions, avoids the use of toxic hydrogen-atom donors while utilizing readily available precursors. The protocol is also amenable to late-stage functionalization of drug molecules and scale-up using continuous-flow. Mechanistic studies confirm the formation of glycosyl radicals and indicate that the hydrogen atoms originate from TMS3SiH.
2026, 37(12): 112507
doi: 10.1016/j.cclet.2026.112507
Abstract:
The disproportionation reaction of selenium powder with aqueous NaOH affords a facile route to Se(-Ⅱ), a key selenium species for synthesizing low-valence selenium carbohydrates, which are the compounds widely used in agriculture and medicine. However, Se(Ⅳ) is inevitably generated as a by-product, accounting for a 33% molar ratio of the reaction products. To address the material surplus of Se(Ⅳ) and achieve industrial chain material balance, this study converted Se(Ⅳ) into value-added nano-Se pesticide. The nano-Se showed uniform size, good stability, strong antioxidant activity, and favorable leaf wettability. It exhibited potent antifungal activity against Magnaporthe oryzae with a low EC50 value of 15.21 mg/L and effective rice blast control in vivo, while enhancing rice antioxidant enzyme activities and showing high safety to non-target organisms. This work realizes Se(Ⅳ) recycling and provides a green rice blast control strategy.
The disproportionation reaction of selenium powder with aqueous NaOH affords a facile route to Se(-Ⅱ), a key selenium species for synthesizing low-valence selenium carbohydrates, which are the compounds widely used in agriculture and medicine. However, Se(Ⅳ) is inevitably generated as a by-product, accounting for a 33% molar ratio of the reaction products. To address the material surplus of Se(Ⅳ) and achieve industrial chain material balance, this study converted Se(Ⅳ) into value-added nano-Se pesticide. The nano-Se showed uniform size, good stability, strong antioxidant activity, and favorable leaf wettability. It exhibited potent antifungal activity against Magnaporthe oryzae with a low EC50 value of 15.21 mg/L and effective rice blast control in vivo, while enhancing rice antioxidant enzyme activities and showing high safety to non-target organisms. This work realizes Se(Ⅳ) recycling and provides a green rice blast control strategy.
2026, 37(12): 112511
doi: 10.1016/j.cclet.2026.112511
Abstract:
Developing highly efficient and stable photocatalysts is of utmost significance for realizing solar-driven CO2 reduction. In this research, a palladium (Pd) nanocluster-decorated nitrogen-doped molybdenum dioxide (MoO2-N-Pd) composite was successfully synthesized. Systematic characterizations demonstrated that Pd nanoclusters were evenly anchored onto MoO3-N nanosheets, triggering a crystalline phase reconstruction from MoO3 to MoO2. Meanwhile, a substantial number of oxygen defects and nitrogen active sites were introduced. The fabricated MoO2-N-Pd composite exhibited excellent charge separation and transport capabilities. Density functional theory (DFT) calculations unveiled the incorporation of Pd significantly reduces the work function and band gap width of the material, effectively broadening its visible light absorption range. More crucially, a strong Pd-N bond was formed between Pd and N atoms, which not only optimizes the interface electronic structure of the material but also significantly lowers the energy barrier for the formation of key intermediate (*COOH). Additionally, the introduction of Pd elongates the C—O bond length of *COOH from 1.34 Å to 1.35 Å, creating favorable thermodynamic conditions for the dissociation of CO. As a result, MoO2-N-Pd displayed superior CO generation performance and stability compared to the initial material. This study comprehensively expounded on the synergistic mechanism of Pd nanocluster-induced phase transition and interface engineering in enhancing the CO2 photoreduction performance.
Developing highly efficient and stable photocatalysts is of utmost significance for realizing solar-driven CO2 reduction. In this research, a palladium (Pd) nanocluster-decorated nitrogen-doped molybdenum dioxide (MoO2-N-Pd) composite was successfully synthesized. Systematic characterizations demonstrated that Pd nanoclusters were evenly anchored onto MoO3-N nanosheets, triggering a crystalline phase reconstruction from MoO3 to MoO2. Meanwhile, a substantial number of oxygen defects and nitrogen active sites were introduced. The fabricated MoO2-N-Pd composite exhibited excellent charge separation and transport capabilities. Density functional theory (DFT) calculations unveiled the incorporation of Pd significantly reduces the work function and band gap width of the material, effectively broadening its visible light absorption range. More crucially, a strong Pd-N bond was formed between Pd and N atoms, which not only optimizes the interface electronic structure of the material but also significantly lowers the energy barrier for the formation of key intermediate (*COOH). Additionally, the introduction of Pd elongates the C—O bond length of *COOH from 1.34 Å to 1.35 Å, creating favorable thermodynamic conditions for the dissociation of CO. As a result, MoO2-N-Pd displayed superior CO generation performance and stability compared to the initial material. This study comprehensively expounded on the synergistic mechanism of Pd nanocluster-induced phase transition and interface engineering in enhancing the CO2 photoreduction performance.
2026, 37(12): 112515
doi: 10.1016/j.cclet.2026.112515
Abstract:
Inherently chiral octagon-containing polycyclic arenes have attracted significant attention due to their broad applications in asymmetric catalysis and material science. However, the catalytic enantioselective construction of all-carbon-based eight-membered ring scaffolds with inherent chirality remains elusive. Herein, we report the efficient kinetic resolution of racemic tribenzocyclooctanones via chiral phosphoric acid-catalyzed condensation with phenylhydrazines. Through this approach, a variety of hydrazones were obtained with high enantioselectivities, which could be converted into tribenzocyclooctaindoles without loss of enantiopurity via Fischer indolization under acidic conditions. The synthetic utility of this method was further demonstrated by the facile preparation of inherently chiral tribenzocyclooctatetraenes and tetraphenylenes from recovered tribenzocyclooctanones in high enantiopurity. DFT calculations were performed to elucidate the notable thermodynamic stability associated with the inherent chirality of these tribenzo-fused eight-membered carbocycles.
Inherently chiral octagon-containing polycyclic arenes have attracted significant attention due to their broad applications in asymmetric catalysis and material science. However, the catalytic enantioselective construction of all-carbon-based eight-membered ring scaffolds with inherent chirality remains elusive. Herein, we report the efficient kinetic resolution of racemic tribenzocyclooctanones via chiral phosphoric acid-catalyzed condensation with phenylhydrazines. Through this approach, a variety of hydrazones were obtained with high enantioselectivities, which could be converted into tribenzocyclooctaindoles without loss of enantiopurity via Fischer indolization under acidic conditions. The synthetic utility of this method was further demonstrated by the facile preparation of inherently chiral tribenzocyclooctatetraenes and tetraphenylenes from recovered tribenzocyclooctanones in high enantiopurity. DFT calculations were performed to elucidate the notable thermodynamic stability associated with the inherent chirality of these tribenzo-fused eight-membered carbocycles.
2026, 37(12): 112535
doi: 10.1016/j.cclet.2026.112535
Abstract:
Fluorinated ethylene carbonate, e.g., the fluoroethylene carbonate (FEC) and di-fluoroethylene carbonate (DFEC), are widely used as electrolyte additives to regulate the SEI on lithium (Li) anodes, yet the superiority or inferiority of their performance, particularly under different temperatures, remains a subject of debate. Herein, we systematically examine the effects of FEC and DFEC on Li anode performance across the temperature range from -40 ℃ to 60 ℃. By evaluating Li plating/stripping CE, cycling stability, Li nucleation overpotential, and polarization voltage, we observe that FEC and DFEC exhibit temperature-dependent performance variations. Overall, the performance of DFEC is better under low temperatures, while FEC and DFEC each have their own advantages and disadvantages under normal temperatures (30 ℃), and both will experience performance degradation at high temperatures. Mechanistic studies reveal that this temperature dependence primarily stems from differences in the additives’ reaction kinetics on the surface of the Li anode, rather than the changes in Li+ solvation structure or diffusion behavior. The divergent performance originates from temperature-dependent decomposition pathways and distinct reduction products of FEC and DFEC. This study provides theoretical guidance for the optimization of electrolyte additives under varied operating temperatures and the design of wide-temperature-range electrolytes for Li metal batteries.
Fluorinated ethylene carbonate, e.g., the fluoroethylene carbonate (FEC) and di-fluoroethylene carbonate (DFEC), are widely used as electrolyte additives to regulate the SEI on lithium (Li) anodes, yet the superiority or inferiority of their performance, particularly under different temperatures, remains a subject of debate. Herein, we systematically examine the effects of FEC and DFEC on Li anode performance across the temperature range from -40 ℃ to 60 ℃. By evaluating Li plating/stripping CE, cycling stability, Li nucleation overpotential, and polarization voltage, we observe that FEC and DFEC exhibit temperature-dependent performance variations. Overall, the performance of DFEC is better under low temperatures, while FEC and DFEC each have their own advantages and disadvantages under normal temperatures (30 ℃), and both will experience performance degradation at high temperatures. Mechanistic studies reveal that this temperature dependence primarily stems from differences in the additives’ reaction kinetics on the surface of the Li anode, rather than the changes in Li+ solvation structure or diffusion behavior. The divergent performance originates from temperature-dependent decomposition pathways and distinct reduction products of FEC and DFEC. This study provides theoretical guidance for the optimization of electrolyte additives under varied operating temperatures and the design of wide-temperature-range electrolytes for Li metal batteries.
2026, 37(12): 112543
doi: 10.1016/j.cclet.2026.112543
Abstract:
Diradicals serve as efficient electron intermediaries and stabilizers, significantly retarding charge recombination to achieve a long-lived charge-separated state. The inherent instability and complicated relaxation dynamics of diradicals introduce considerable difficulties to the precise prediction and manipulation of their resultant molecular states. Herein, a novel coordination molecular rotor complex 1 adopts a rigid, dumbbell-shaped donor-acceptor (D–A) arrangement with minimized reorganization energy. Steady-state spectroscopy and nanosecond transient absorption spectroscopy reveal the photoinduced energy-transfer process and electron-transfer dynamics of complex 1 from zinc(Ⅱ) tetraphenylporphyrin (ZnTTP) to a perylenediimide derivative (BPPDI). Electron paramagnetic resonance spectroscopy under xenon lamp irradiation, together with theoretical calculations, demonstrates the formation of diradicals (ZnTTP•+ and BPPDI•−) during photo-induced charge separation, resulting in a long-lived charge-separated state with a lifetime exceeding 912 ns.
Diradicals serve as efficient electron intermediaries and stabilizers, significantly retarding charge recombination to achieve a long-lived charge-separated state. The inherent instability and complicated relaxation dynamics of diradicals introduce considerable difficulties to the precise prediction and manipulation of their resultant molecular states. Herein, a novel coordination molecular rotor complex 1 adopts a rigid, dumbbell-shaped donor-acceptor (D–A) arrangement with minimized reorganization energy. Steady-state spectroscopy and nanosecond transient absorption spectroscopy reveal the photoinduced energy-transfer process and electron-transfer dynamics of complex 1 from zinc(Ⅱ) tetraphenylporphyrin (ZnTTP) to a perylenediimide derivative (BPPDI). Electron paramagnetic resonance spectroscopy under xenon lamp irradiation, together with theoretical calculations, demonstrates the formation of diradicals (ZnTTP•+ and BPPDI•−) during photo-induced charge separation, resulting in a long-lived charge-separated state with a lifetime exceeding 912 ns.
2026, 37(12): 112595
doi: 10.1016/j.cclet.2026.112595
Abstract:
Photoelectrochemical cell (PEC) represents a sustainable technology that could convert solar energy into solar fuels. Synthesis of porous carbon nitride (CN) photoanode with large active surface is crucial for efficient PEC water splitting, however, remains challenging. This work reported a porous CN photoanode with large active surface enabled by melamine-urea comonomer film assembly followed with in-situ thermal condensation. It imparts large surface area, broadened light harvesting, facilitated charge separation, and significantly enhanced electrochemically active surface area. The as-synthesized CN photoanode delivered impressive PEC water splitting performance with photocurrent (at 1.23 V) up to 190 µA/cm2 in KOH solution, 2.2 times higher as that of compact CN photoanode. After addition of sacrificial agent in electrolyte, the photocurrent is boosted to 420 µA/cm2. Their IPCEs at 400 nm are 13% and 32%, respectively. The improved PEC activity was also visually evidenced by scanning electrochemical microscope measurement. The concept of comonomer film assembly-initiated porous CN film synthesis in this work provides a reliable approach to tailor the photophysical properties of in-situ synthesized CN film, which paves a pathway to enhance/broaden the applications of CN in electronic devices, not just limited to photoelectrochemical water splitting.
Photoelectrochemical cell (PEC) represents a sustainable technology that could convert solar energy into solar fuels. Synthesis of porous carbon nitride (CN) photoanode with large active surface is crucial for efficient PEC water splitting, however, remains challenging. This work reported a porous CN photoanode with large active surface enabled by melamine-urea comonomer film assembly followed with in-situ thermal condensation. It imparts large surface area, broadened light harvesting, facilitated charge separation, and significantly enhanced electrochemically active surface area. The as-synthesized CN photoanode delivered impressive PEC water splitting performance with photocurrent (at 1.23 V) up to 190 µA/cm2 in KOH solution, 2.2 times higher as that of compact CN photoanode. After addition of sacrificial agent in electrolyte, the photocurrent is boosted to 420 µA/cm2. Their IPCEs at 400 nm are 13% and 32%, respectively. The improved PEC activity was also visually evidenced by scanning electrochemical microscope measurement. The concept of comonomer film assembly-initiated porous CN film synthesis in this work provides a reliable approach to tailor the photophysical properties of in-situ synthesized CN film, which paves a pathway to enhance/broaden the applications of CN in electronic devices, not just limited to photoelectrochemical water splitting.
2026, 37(12): 112613
doi: 10.1016/j.cclet.2026.112613
Abstract:
Zeolites are microporous materials whose adsorption and catalytic performance are governed by their pore structures. Here, we present a topology-based pore matching method that simplifies complex pore channels into "node-link" networks, capturing both connectivity and global topological characteristics of accessible pores. This method enables efficient pore matching and rapid screening of candidate zeolites from massive structures for the first time. Using industrially relevant zeolite CHA as a representative example, our method identifies viable MTO catalyst candidates from both known and hypothetical zeolite databases (ABC-6 and Deem's PCOD). A representative candidate, AABABBCCAABBCC, was validated by DFT calculations to exhibit excellent MTO performance. Comparable success was achieved for six other industrial zeolites (FAU, LTA, etc.). This method offers intuitive characterization, exceptional efficiency, and strong interpretability for functional materials discovery.
Zeolites are microporous materials whose adsorption and catalytic performance are governed by their pore structures. Here, we present a topology-based pore matching method that simplifies complex pore channels into "node-link" networks, capturing both connectivity and global topological characteristics of accessible pores. This method enables efficient pore matching and rapid screening of candidate zeolites from massive structures for the first time. Using industrially relevant zeolite CHA as a representative example, our method identifies viable MTO catalyst candidates from both known and hypothetical zeolite databases (ABC-6 and Deem's PCOD). A representative candidate, AABABBCCAABBCC, was validated by DFT calculations to exhibit excellent MTO performance. Comparable success was achieved for six other industrial zeolites (FAU, LTA, etc.). This method offers intuitive characterization, exceptional efficiency, and strong interpretability for functional materials discovery.
2026, 37(12): 112647
doi: 10.1016/j.cclet.2026.112647
Abstract:
Control of surfactant self-assembly under multiple physical and chemical stimuli is critical in many applications. Although stimuli-responsive surfactants are no longer uncommon, surfactants with mechanical-responsive property are still in the nascent stage. Here, we report a triply responsive bowl-shaped nano-assembly of spiropyran surfactant capable of on-demand deformation to achieve controllable formation and reconfiguration. Under alternating ultrasonic/UV or pH/UV stimuli, the nano-bowl switching relies on the reversible conversion of the spiropyran moiety, from closed-ring isomer (SP-COOH) to mixed spiropyran isomers (SP/MC—COOH), and then to opened-ring isomer (MC—COOH). Accompanied with the change of the SP/MC—COOH ratio, various structures are captured, including irregular molecular nano-assemblies, spheroids, buckled inward spheroids, nano-bowls, and agglomerated nanoparticles. As far as we know, the reversible evolution process of nano-structures under multiple stimuli, particularly ultrasonic co-stimulation, is seldom to be seen. Such a triple-stimuli-responsive surfactant enriches the family of smart surfactants and provides new choices for constructing smart soft materials.
Control of surfactant self-assembly under multiple physical and chemical stimuli is critical in many applications. Although stimuli-responsive surfactants are no longer uncommon, surfactants with mechanical-responsive property are still in the nascent stage. Here, we report a triply responsive bowl-shaped nano-assembly of spiropyran surfactant capable of on-demand deformation to achieve controllable formation and reconfiguration. Under alternating ultrasonic/UV or pH/UV stimuli, the nano-bowl switching relies on the reversible conversion of the spiropyran moiety, from closed-ring isomer (SP-COOH) to mixed spiropyran isomers (SP/MC—COOH), and then to opened-ring isomer (MC—COOH). Accompanied with the change of the SP/MC—COOH ratio, various structures are captured, including irregular molecular nano-assemblies, spheroids, buckled inward spheroids, nano-bowls, and agglomerated nanoparticles. As far as we know, the reversible evolution process of nano-structures under multiple stimuli, particularly ultrasonic co-stimulation, is seldom to be seen. Such a triple-stimuli-responsive surfactant enriches the family of smart surfactants and provides new choices for constructing smart soft materials.
2026, 37(12): 112693
doi: 10.1016/j.cclet.2026.112693
Abstract:
Large π-conjugated systems are promising near-infrared (NIR) fluorophores but are often limited by synthetic complexity and compromised luminescence efficiency. Herein, we report the first synthesis of benzofuran-fused oligo-boron-dipyrromethene (BODIPY) dyes via a synergistic combination of SNAr and C–H coupling strategy. This modular strategy enables efficient construction of mono-, bis-, and fully fused oligomeric architectures. Progressive benzofuran and BODIPY fusion induces pronounced bathochromic shifts and markedly enhanced molar extinction coefficients. The fully fused trimer BFB-tri exhibits strong NIR absorption (716 nm in toluene, ε = 4.0 × 105 L mol−1 cm−1) and bright NIR emission (733/808 nm) with a fluorescence quantum yield up to 65.4%. Experimental and theoretical studies reveal that benzofuran fusion raises the highest occupied molecular orbital (HOMO) level, while increasing BODIPY units lowers the lowest unoccupied molecular orbital (LUMO), allowing precise frontier orbital modulation for rational design of π-extended NIR fluorophores.
Large π-conjugated systems are promising near-infrared (NIR) fluorophores but are often limited by synthetic complexity and compromised luminescence efficiency. Herein, we report the first synthesis of benzofuran-fused oligo-boron-dipyrromethene (BODIPY) dyes via a synergistic combination of SNAr and C–H coupling strategy. This modular strategy enables efficient construction of mono-, bis-, and fully fused oligomeric architectures. Progressive benzofuran and BODIPY fusion induces pronounced bathochromic shifts and markedly enhanced molar extinction coefficients. The fully fused trimer BFB-tri exhibits strong NIR absorption (716 nm in toluene, ε = 4.0 × 105 L mol−1 cm−1) and bright NIR emission (733/808 nm) with a fluorescence quantum yield up to 65.4%. Experimental and theoretical studies reveal that benzofuran fusion raises the highest occupied molecular orbital (HOMO) level, while increasing BODIPY units lowers the lowest unoccupied molecular orbital (LUMO), allowing precise frontier orbital modulation for rational design of π-extended NIR fluorophores.
2026, 37(12): 112694
doi: 10.1016/j.cclet.2026.112694
Abstract:
Biochar-activated peroxydisulfate (PDS) is an effective method for remediating contaminated groundwater via adsorption and electron transfer oxidation. Yet, PDS has traditionally been regarded primarily as an oxidant rather than a competitive adsorbent. Competitive adsorption might both enhance the overall catalytic degradation efficiency and induce a redistribution of pollutants at the biochar interface. This uncertainty results in the regulation of pollutant adsorption and degradation behavior remaining unclear. This study employed an adsorption-desorption approach to quantify the critical role of competitive co-adsorption in regulating the electron-transfer oxidation process of atrazine (ATZ) in biochar/PDS systems. Biochar was synthesized at pyrolysis temperatures of 500, 700, and 900 ℃ (denoted as SS500, SS700, and SS900, respectively). The SS900 showed superior removal efficiency for ATZ (Qm = 86.93 mg/g), driven by electrostatic attraction, hydrogen bonding, and pore-filling. Following the addition of PDS, competitive adsorption on the biochar interface first redistributed ATZ, causing 20.49% of it to desorb into the aqueous phase. Subsequently, the co-adsorption of PDS and ATZ on the biochar surface enabled the degradation of ATZ. The process shifted the removal pathway of ATZ from being adsorption-dominated (~45% adsorption and 0% degradation) to degradation-dominated (~76.42% degradation and ~15.41% adsorption). Based on electron paramagnetic resonance (EPR), galvanic cell experiments, and LC-MS analysis results, the electron transfer oxidation (ETO) involving C=O groups and graphitic structures was the dominant pathway for ATZ degradation. Density functional theory (DFT) calculation and a quantitative structure-activity relationship (QSAR) analysis revealed that the co-adsorption process of ATZ and PDS on biochar is a critical step driving ETO of ATZ. The results proposed a new promising methodology for precisely unraveling interfacial reaction mechanisms in situ chemical oxidation (ISCO) processes.
Biochar-activated peroxydisulfate (PDS) is an effective method for remediating contaminated groundwater via adsorption and electron transfer oxidation. Yet, PDS has traditionally been regarded primarily as an oxidant rather than a competitive adsorbent. Competitive adsorption might both enhance the overall catalytic degradation efficiency and induce a redistribution of pollutants at the biochar interface. This uncertainty results in the regulation of pollutant adsorption and degradation behavior remaining unclear. This study employed an adsorption-desorption approach to quantify the critical role of competitive co-adsorption in regulating the electron-transfer oxidation process of atrazine (ATZ) in biochar/PDS systems. Biochar was synthesized at pyrolysis temperatures of 500, 700, and 900 ℃ (denoted as SS500, SS700, and SS900, respectively). The SS900 showed superior removal efficiency for ATZ (Qm = 86.93 mg/g), driven by electrostatic attraction, hydrogen bonding, and pore-filling. Following the addition of PDS, competitive adsorption on the biochar interface first redistributed ATZ, causing 20.49% of it to desorb into the aqueous phase. Subsequently, the co-adsorption of PDS and ATZ on the biochar surface enabled the degradation of ATZ. The process shifted the removal pathway of ATZ from being adsorption-dominated (~45% adsorption and 0% degradation) to degradation-dominated (~76.42% degradation and ~15.41% adsorption). Based on electron paramagnetic resonance (EPR), galvanic cell experiments, and LC-MS analysis results, the electron transfer oxidation (ETO) involving C=O groups and graphitic structures was the dominant pathway for ATZ degradation. Density functional theory (DFT) calculation and a quantitative structure-activity relationship (QSAR) analysis revealed that the co-adsorption process of ATZ and PDS on biochar is a critical step driving ETO of ATZ. The results proposed a new promising methodology for precisely unraveling interfacial reaction mechanisms in situ chemical oxidation (ISCO) processes.
2026, 37(12): 112703
doi: 10.1016/j.cclet.2026.112703
Abstract:
Green hydrogen energy is highly desired but is constrained by sluggish reaction kinetics and the low efficiency of active sites. This study presented a synergistic enhancement of efficient electron transportation and push-pull charge modulation in the electrocatalytic water splitting system Ru-Ni2P/FeCo2O4 (Ni2P/FCO) by rationally optimizing the charge environment of active sites. Experimental findings exhibited satisfactory overpotentials of 16 mV and 41 mV for the hydrogen evolution reaction (HER) in 1 mol/L KOH and seawater environments, respectively, to reach a current density of 10 mA/cm2. Exceptional oxygen evolution reaction (OER) and overall water splitting performance (with an overpotential of 1.74 V at 100 mA/cm2) were also demonstrated. In addition, the Ru-Ni2P/FCO system showed comparable durability during 50 h. Density functional theory (DFT) simulations explained the reason for the improved activity: The metallic alteration of Ni2P/FCO, along with the established steady built-in electric field at the interface, accelerated charge transportation and improved the adsorption-desorption dynamics during HER/OER procedures. The push-electron activity of Ni2P and the pull-charge capability of Ru promoted the charge accumulation at reactive sites, thereby decreasing the energy barriers for both HER and OER intermediates. This study provides novel insights into the development of effective electron-transfer routes and the enhancement of catalysts’ intrinsic activity.
Green hydrogen energy is highly desired but is constrained by sluggish reaction kinetics and the low efficiency of active sites. This study presented a synergistic enhancement of efficient electron transportation and push-pull charge modulation in the electrocatalytic water splitting system Ru-Ni2P/FeCo2O4 (Ni2P/FCO) by rationally optimizing the charge environment of active sites. Experimental findings exhibited satisfactory overpotentials of 16 mV and 41 mV for the hydrogen evolution reaction (HER) in 1 mol/L KOH and seawater environments, respectively, to reach a current density of 10 mA/cm2. Exceptional oxygen evolution reaction (OER) and overall water splitting performance (with an overpotential of 1.74 V at 100 mA/cm2) were also demonstrated. In addition, the Ru-Ni2P/FCO system showed comparable durability during 50 h. Density functional theory (DFT) simulations explained the reason for the improved activity: The metallic alteration of Ni2P/FCO, along with the established steady built-in electric field at the interface, accelerated charge transportation and improved the adsorption-desorption dynamics during HER/OER procedures. The push-electron activity of Ni2P and the pull-charge capability of Ru promoted the charge accumulation at reactive sites, thereby decreasing the energy barriers for both HER and OER intermediates. This study provides novel insights into the development of effective electron-transfer routes and the enhancement of catalysts’ intrinsic activity.
2026, 37(12): 112723
doi: 10.1016/j.cclet.2026.112723
Abstract:
A critical challenge of porous metal-organic framework (MOF) such as zirconium-based PCN-224 lies in its constrained separation selectivity due to single-metal active sites. To address this limitation, incorporating transition metal ions into porphyrinic ligands enables the creation of bimetallic MOF (BMOF) with multiple interaction mechanisms. Nevertheless, the utility of BMOF in chromatographic separation is often hindered by inherent mass transfer resistance within its microporous structures. In contrast, layered double hydroxide (LDH) enables superior mass transfer by virtue of hierarchical channels, while offering high hydrophilicity and significant ion-exchange capacity. In this study, a novel multimodal PCN-224(Co)/LDH@SiO2 stationary phase was developed through the synergistic integration of BMOF with LDH. The etching-induced partial conversion of PCN-224(Co) into LDH produced a composite that preserved the high surface area of BMOF and suppressed the self-aggregation of LDH. The resulting composite combined the hydrophobic character of BMOF ligands with the hydrophilic and ion-exchange properties of LDH to yield synergistic multimodal functionality. The PCN-224(Co)/LDH@SiO2 stationary phase demonstrated the ability to efficiently separate nucleosides under challenging high-water-content conditions. A systematic mechanistic study utilizing a diverse set of compounds uncovered multiple coexisting retention mechanisms. Furthermore, the PCN-224(Co)/LDH@SiO2 exhibited robust performance across complex sample matrices, as evidenced by the sensitive detection of polycyclic aromatic hydrocarbons in ophthalmic solutions and vitamin B1 in tablets. This work pioneers a BMOF-LDH hybrid stationary phase, thereby establishing a versatile platform for efficient multi-component separations.
A critical challenge of porous metal-organic framework (MOF) such as zirconium-based PCN-224 lies in its constrained separation selectivity due to single-metal active sites. To address this limitation, incorporating transition metal ions into porphyrinic ligands enables the creation of bimetallic MOF (BMOF) with multiple interaction mechanisms. Nevertheless, the utility of BMOF in chromatographic separation is often hindered by inherent mass transfer resistance within its microporous structures. In contrast, layered double hydroxide (LDH) enables superior mass transfer by virtue of hierarchical channels, while offering high hydrophilicity and significant ion-exchange capacity. In this study, a novel multimodal PCN-224(Co)/LDH@SiO2 stationary phase was developed through the synergistic integration of BMOF with LDH. The etching-induced partial conversion of PCN-224(Co) into LDH produced a composite that preserved the high surface area of BMOF and suppressed the self-aggregation of LDH. The resulting composite combined the hydrophobic character of BMOF ligands with the hydrophilic and ion-exchange properties of LDH to yield synergistic multimodal functionality. The PCN-224(Co)/LDH@SiO2 stationary phase demonstrated the ability to efficiently separate nucleosides under challenging high-water-content conditions. A systematic mechanistic study utilizing a diverse set of compounds uncovered multiple coexisting retention mechanisms. Furthermore, the PCN-224(Co)/LDH@SiO2 exhibited robust performance across complex sample matrices, as evidenced by the sensitive detection of polycyclic aromatic hydrocarbons in ophthalmic solutions and vitamin B1 in tablets. This work pioneers a BMOF-LDH hybrid stationary phase, thereby establishing a versatile platform for efficient multi-component separations.
2026, 37(12): 112725
doi: 10.1016/j.cclet.2026.112725
Abstract:
S-scheme heterojunctions effectively reconcile the limited light-harvesting efficiency and redox capability of single photocatalysts. However, the interfacial migration pathways of photogenerated charges remain difficult to elucidate. Here, we fabricate TiO2/CuWO4 S-scheme photocatalysts via electrostatic self-assembly, where TiO2 nanoparticles are tightly coupled to the CuWO4 surface. In suit X-ray photoelectron spectroscopy, together with surface photovoltage measurements, reveals a pronounced internal electric field at the TiO2/CuWO4 interface that drives S-scheme charge transfer. Femtosecond transient absorption spectroscopy further resolves the interfacial charge-transfer mechanism. Density functional theory calculations show that constructing a prototypical S-scheme heterojunction lowers the formation barrier of the key intermediate *COOH. Consequently, under sacrificial-agent-free conditions, the CO production rate of TiO2/CuWO4 reaches 9.53 μmol g-1 h-1, 3.47-folds higher than that of pristine TiO2 (2.13 μmol g-1 h-1). This work underscores the pivotal role of interfacial carrier-transfer kinetics in photocatalytic CO2 reduction.
S-scheme heterojunctions effectively reconcile the limited light-harvesting efficiency and redox capability of single photocatalysts. However, the interfacial migration pathways of photogenerated charges remain difficult to elucidate. Here, we fabricate TiO2/CuWO4 S-scheme photocatalysts via electrostatic self-assembly, where TiO2 nanoparticles are tightly coupled to the CuWO4 surface. In suit X-ray photoelectron spectroscopy, together with surface photovoltage measurements, reveals a pronounced internal electric field at the TiO2/CuWO4 interface that drives S-scheme charge transfer. Femtosecond transient absorption spectroscopy further resolves the interfacial charge-transfer mechanism. Density functional theory calculations show that constructing a prototypical S-scheme heterojunction lowers the formation barrier of the key intermediate *COOH. Consequently, under sacrificial-agent-free conditions, the CO production rate of TiO2/CuWO4 reaches 9.53 μmol g-1 h-1, 3.47-folds higher than that of pristine TiO2 (2.13 μmol g-1 h-1). This work underscores the pivotal role of interfacial carrier-transfer kinetics in photocatalytic CO2 reduction.
2026, 37(12): 112750
doi: 10.1016/j.cclet.2026.112750
Abstract:
Iron-based catalysts-activated peracetic acid (PAA) for water treatment has been seriously limited by the difficulties in Fe(Ⅱ) regeneration and catalyst recovery. Herein, we employed the hydroxylamine (HA) to regulate a facilely prepared iron-carbon composite to activate PAA for organics degradation. Compared with the FONC@BC/PAA system, the incorporation of HA could accomplish about 100% removal of atrazine (ATZ) within only 4 min, which exhibited a high reaction rate constant of 0.524 min−1, representing a remarkable 4.63-fold increase. Notably, in contrast to prior research focusing on the function of HA supplementation in iron cycling, HA in this study played a triple role by activating PAA to generateHO • Fe Ⅳ O 2 + R − O • HO •
Iron-based catalysts-activated peracetic acid (PAA) for water treatment has been seriously limited by the difficulties in Fe(Ⅱ) regeneration and catalyst recovery. Herein, we employed the hydroxylamine (HA) to regulate a facilely prepared iron-carbon composite to activate PAA for organics degradation. Compared with the FONC@BC/PAA system, the incorporation of HA could accomplish about 100% removal of atrazine (ATZ) within only 4 min, which exhibited a high reaction rate constant of 0.524 min−1, representing a remarkable 4.63-fold increase. Notably, in contrast to prior research focusing on the function of HA supplementation in iron cycling, HA in this study played a triple role by activating PAA to generate
2026, 37(12): 112752
doi: 10.1016/j.cclet.2026.112752
Abstract:
Photocatalytic production of hydrogen peroxide (H2O2) offers a sustainable alternative to the traditional anthraquinone process. Herein, a 0D/2D heterojunction photocatalyst was constructed by coupling AgInS2 quantum dots with Mg-doped poly (triazine imide), exhibiting excellent photocatalytic performance under visible light and ambient air. Glycerol was employed as a hole scavenger and proton donor, the optimally proportioned catalyst AIS@M0.1PTI-2 enabling an H2O2 production rate of 4002.81 μmol g-1 h-1 in 40 vol% glycerol solution-nearly 9.9 times higher than that in pure water. Meanwhile, selective oxidation of glycerol yielded 3398.47 μmol g-1 h-1 dihydroxyacetone (DHA) with 60.01% selectivity. Mg doping improved PTI crystallinity, enhanced charge mobility. AgInS2 quantum dots further boosted visible-light absorption and interfacial electron transfer. Mechanistic investigations, including LSV, EPR, XPS, 13C NMR, DFT, and radical trapping, confirmed selective promotion of the two-electron oxygen reduction pathway and clarified the electron flow across the heterojunction. The mutual enhancement between oxidation and reduction processes enables efficient solar-to-chemical energy conversion, highlighting the potential of this system for green chemical manufacturing.
Photocatalytic production of hydrogen peroxide (H2O2) offers a sustainable alternative to the traditional anthraquinone process. Herein, a 0D/2D heterojunction photocatalyst was constructed by coupling AgInS2 quantum dots with Mg-doped poly (triazine imide), exhibiting excellent photocatalytic performance under visible light and ambient air. Glycerol was employed as a hole scavenger and proton donor, the optimally proportioned catalyst AIS@M0.1PTI-2 enabling an H2O2 production rate of 4002.81 μmol g-1 h-1 in 40 vol% glycerol solution-nearly 9.9 times higher than that in pure water. Meanwhile, selective oxidation of glycerol yielded 3398.47 μmol g-1 h-1 dihydroxyacetone (DHA) with 60.01% selectivity. Mg doping improved PTI crystallinity, enhanced charge mobility. AgInS2 quantum dots further boosted visible-light absorption and interfacial electron transfer. Mechanistic investigations, including LSV, EPR, XPS, 13C NMR, DFT, and radical trapping, confirmed selective promotion of the two-electron oxygen reduction pathway and clarified the electron flow across the heterojunction. The mutual enhancement between oxidation and reduction processes enables efficient solar-to-chemical energy conversion, highlighting the potential of this system for green chemical manufacturing.
2026, 37(12): 112765
doi: 10.1016/j.cclet.2026.112765
Abstract:
With the rapid advancement of artificial intelligence, smart diagnosis is emerging as a transformative force in modern medicine. Herein, we developed a hydrophilic molecular trap to combine with machine learning to collect and analyze hydrophilic peptide patterns fully from human serum samples, enabling effective smart peptidomic diagnostics. Utilizing a hydrophilic molecular trap combined with high-throughput mass spectrometry, high-quality hydrophilic peptide profiles were extracted from serum samples of gastric cancer (GC) patients, pancreatic ductal adenocarcinoma (PDAC) patients, and healthy controls (HC). Machine learning clearly distinguished GC, PDAC, and HC, with the area under the receiver operating characteristic curve exceeding 0.949 for all paired group comparisons. Furthermore, 4 (HC vs. PDAC), 5 (HC vs. GC) and 3 (GC vs. PDAC) key peptides features were selected out, which could be used to achieve precise diagnosis in paired groups. This work demonstrates the strong clinical potential of our smart peptidomic diagnostic approach for accurate disease diagnosis and real-time monitoring.
With the rapid advancement of artificial intelligence, smart diagnosis is emerging as a transformative force in modern medicine. Herein, we developed a hydrophilic molecular trap to combine with machine learning to collect and analyze hydrophilic peptide patterns fully from human serum samples, enabling effective smart peptidomic diagnostics. Utilizing a hydrophilic molecular trap combined with high-throughput mass spectrometry, high-quality hydrophilic peptide profiles were extracted from serum samples of gastric cancer (GC) patients, pancreatic ductal adenocarcinoma (PDAC) patients, and healthy controls (HC). Machine learning clearly distinguished GC, PDAC, and HC, with the area under the receiver operating characteristic curve exceeding 0.949 for all paired group comparisons. Furthermore, 4 (HC vs. PDAC), 5 (HC vs. GC) and 3 (GC vs. PDAC) key peptides features were selected out, which could be used to achieve precise diagnosis in paired groups. This work demonstrates the strong clinical potential of our smart peptidomic diagnostic approach for accurate disease diagnosis and real-time monitoring.
2026, 37(12): 112768
doi: 10.1016/j.cclet.2026.112768
Abstract:
The development of novel materials beyond traditional candidates is critically important for advancing NO reduction reaction (NORR) applications. Inspired by the recent advance in topological catalysis and carbon biphenylene synthesis, we report the catalytic mechanism and selectivity of NORR on a two-dimensional boron-carbon-nitride (BCN) biphenylene network, an isoelectronic analogue of carbon biphenylene with nontrivial topological properties. This structure comprises boron, carbon, and nitrogen atoms in a 1:1:1 stoichiometric ratio. Using density functional theory (DFT) and the constant-potential method (CPM), we systematically investigated the thermodynamic and kinetic processes of the electrocatalytic conversion of nitric oxide (NO) to ammonia (NH3) on this BCN material. Electron-deficient boron sites and robust edge states are responsible for the enhanced NO capture capabilities. Notably, the BCN nanoribbons with a zigzag edge exhibit superior NORR activity and selectivity. These results demonstrate that the topological BCN biphenylene network holds significant potential as a non-precious catalyst for NORR. Its distinctive zigzag-type nanoribbon structure offers crucial insights, guiding the advancement of vertically oriented materials for NORR catalysis.
The development of novel materials beyond traditional candidates is critically important for advancing NO reduction reaction (NORR) applications. Inspired by the recent advance in topological catalysis and carbon biphenylene synthesis, we report the catalytic mechanism and selectivity of NORR on a two-dimensional boron-carbon-nitride (BCN) biphenylene network, an isoelectronic analogue of carbon biphenylene with nontrivial topological properties. This structure comprises boron, carbon, and nitrogen atoms in a 1:1:1 stoichiometric ratio. Using density functional theory (DFT) and the constant-potential method (CPM), we systematically investigated the thermodynamic and kinetic processes of the electrocatalytic conversion of nitric oxide (NO) to ammonia (NH3) on this BCN material. Electron-deficient boron sites and robust edge states are responsible for the enhanced NO capture capabilities. Notably, the BCN nanoribbons with a zigzag edge exhibit superior NORR activity and selectivity. These results demonstrate that the topological BCN biphenylene network holds significant potential as a non-precious catalyst for NORR. Its distinctive zigzag-type nanoribbon structure offers crucial insights, guiding the advancement of vertically oriented materials for NORR catalysis.
2026, 37(12): 112769
doi: 10.1016/j.cclet.2026.112769
Abstract:
Metal-organic frameworks (MOFs) are promising candidates for radio-photoluminescence (RPL) dosimeters due to their structural tunability, radiation stability, and efficient X-ray attenuation capabilities mediated by heavy metal nodes (e.g., Pb2+). However, strategies for fine-tuning their band structures to enhance RPL performance remain elusive. To explore the effect of ligand engineering on the RPL properties of MOFs, we synthesized a series of Pb-based MOFs (Pb-1, Pb-2, and Pb-4) with terephthalic acid ligands functionalized by varying methyl groups. The incorporation of methyl groups modulates the band structure and introduces significant steric hindrance into the framework. This effect reduces the singlet–triplet energy gap, thereby facilitating the formation of RPL centers. Additionally, it enhances the stability of X-ray-induced radicals by suppressing non-radiative recombination and quenching processes. Compared to Pb-1, the detection threshold of Pb-2 and Pb-4 is improved by an order of magnitude, the response rate is increased by 4.51–4.77 times, and the decay process is prolonged by 1.58–3.49 times. This work provides a promising approach for designing high-performance MOFs-based RPL dosimeters through a simple yet effective ligand engineering strategy.
Metal-organic frameworks (MOFs) are promising candidates for radio-photoluminescence (RPL) dosimeters due to their structural tunability, radiation stability, and efficient X-ray attenuation capabilities mediated by heavy metal nodes (e.g., Pb2+). However, strategies for fine-tuning their band structures to enhance RPL performance remain elusive. To explore the effect of ligand engineering on the RPL properties of MOFs, we synthesized a series of Pb-based MOFs (Pb-1, Pb-2, and Pb-4) with terephthalic acid ligands functionalized by varying methyl groups. The incorporation of methyl groups modulates the band structure and introduces significant steric hindrance into the framework. This effect reduces the singlet–triplet energy gap, thereby facilitating the formation of RPL centers. Additionally, it enhances the stability of X-ray-induced radicals by suppressing non-radiative recombination and quenching processes. Compared to Pb-1, the detection threshold of Pb-2 and Pb-4 is improved by an order of magnitude, the response rate is increased by 4.51–4.77 times, and the decay process is prolonged by 1.58–3.49 times. This work provides a promising approach for designing high-performance MOFs-based RPL dosimeters through a simple yet effective ligand engineering strategy.
2026, 37(12): 112770
doi: 10.1016/j.cclet.2026.112770
Abstract:
The blood-brain barrier (BBB) is a dynamic and selective barrier that maintains cerebral homeostasis but severely restricts drug delivery to the central nervous system, hampering the diagnosis and treatment of neurological disorders. Understanding how nanocarriers cross the BBB is thus essential for designing safe and efficient brain-targeted delivery systems. Here, we established an in vitro BBB model with enhanced barrier integrity using a three-cell-type co-culture in a Transwell system. Angiopep-2-functionalized nanoparticles (ANG NPs) were developed to investigate nanoparticle transport mechanisms. Integrated multi-omics analysis revealed that unmodified nanoparticles lack a defined transport pathway, whereas ANG-functionalized nanoparticles cross the BBB through receptor-mediated transcytosis involving lysosomal and phagosomal pathways. Both nanoparticles activated the ABC transporter pathway, leading to the efflux of nonspecific substrates back into the bloodstream. This multi-omics approach systematically elucidated distinct transport mechanisms, holding promise for informing the rational design of safer and more efficient brain-targeted nanocarriers.
The blood-brain barrier (BBB) is a dynamic and selective barrier that maintains cerebral homeostasis but severely restricts drug delivery to the central nervous system, hampering the diagnosis and treatment of neurological disorders. Understanding how nanocarriers cross the BBB is thus essential for designing safe and efficient brain-targeted delivery systems. Here, we established an in vitro BBB model with enhanced barrier integrity using a three-cell-type co-culture in a Transwell system. Angiopep-2-functionalized nanoparticles (ANG NPs) were developed to investigate nanoparticle transport mechanisms. Integrated multi-omics analysis revealed that unmodified nanoparticles lack a defined transport pathway, whereas ANG-functionalized nanoparticles cross the BBB through receptor-mediated transcytosis involving lysosomal and phagosomal pathways. Both nanoparticles activated the ABC transporter pathway, leading to the efflux of nonspecific substrates back into the bloodstream. This multi-omics approach systematically elucidated distinct transport mechanisms, holding promise for informing the rational design of safer and more efficient brain-targeted nanocarriers.
2026, 37(12): 112774
doi: 10.1016/j.cclet.2026.112774
Abstract:
The development of efficient and sustainable synthesis methods for hydrogen peroxide (H2O2) is crucial, given its broad utility as a green oxidant in chemical manufacturing and environmental remediation. Herein, we report a catalyst-free strategy for the abundant production of H2O2 directly from water under ambient conditions via a plasma-microdroplet platform. This approach achieves a high H2O2 yield of 42.7 mg/h and >96% selectivity, substantially surpassing those of other water-activation methods. Mechanistic studies reveal that the reaction proceeds through the in-situ generation of water dimer radical cations ((H2O)2+•), which then follow two possible pathways: (1) Dissociation into hydroxyl radicals (•OH) that recombine to form H2O2, or (2) directly conversion to H2O2+• and H2. Theoretical calculations support these pathways and underscore the ubiquity of (H2O)2+• in various aqueous activation systems (e.g., microdroplets, pneumatic atomization, and ultrasonic β-cyclodextrin cavitation). With its operational simplicity, scalability, and avoidance of complex purification, this method offers a promising and industrially viable route to H2O2 production.
The development of efficient and sustainable synthesis methods for hydrogen peroxide (H2O2) is crucial, given its broad utility as a green oxidant in chemical manufacturing and environmental remediation. Herein, we report a catalyst-free strategy for the abundant production of H2O2 directly from water under ambient conditions via a plasma-microdroplet platform. This approach achieves a high H2O2 yield of 42.7 mg/h and >96% selectivity, substantially surpassing those of other water-activation methods. Mechanistic studies reveal that the reaction proceeds through the in-situ generation of water dimer radical cations ((H2O)2+•), which then follow two possible pathways: (1) Dissociation into hydroxyl radicals (•OH) that recombine to form H2O2, or (2) directly conversion to H2O2+• and H2. Theoretical calculations support these pathways and underscore the ubiquity of (H2O)2+• in various aqueous activation systems (e.g., microdroplets, pneumatic atomization, and ultrasonic β-cyclodextrin cavitation). With its operational simplicity, scalability, and avoidance of complex purification, this method offers a promising and industrially viable route to H2O2 production.
2026, 37(12): 112775
doi: 10.1016/j.cclet.2026.112775
Abstract:
The electrochemical reduction of nitrate to ammonia offers a sustainable route for simultaneous wastewater remediation and decentralized NH3 production, yet it requires advanced catalysts capable of precisely managing the complex multi-step reaction pathway. Herein, we report the rational design of a high-entropy intermetallic (HEI), (FeCoNiCu)6Sn5, which serves as a highly efficient and exceptionally stable electrocatalyst for nitrate-to-ammonia conversion. The HEI catalyst achieves a remarkable NH3 Faradaic efficiency of 97.4% and a high yield rate of 23.3 mg h−1 mgcat−1, maintaining robust stability over 150 h of continuous operation. Mechanistic investigations reveal that this outstanding performance stems from an ingenious synergistic division of site-specific functions: The Cu component promotes nitrate adsorption and initial reduction to nitrite, the Fe/Co/Ni components enhance subsequent hydrogenation kinetics, and the Sn component effectively suppresses the competing hydrogen evolution reaction (HER). When integrated into a practical Zn–NO3− battery system, the (FeCoNiCu)6Sn5 cathode simultaneously delivers a peak power density of 4.32 mW/cm2 alongside continuous ammonia production. This work establishes a versatile and powerful platform based on HEI for the precise construction of multicomponent catalysts, offering a new frontier for sustainable electrochemical synthesis.
The electrochemical reduction of nitrate to ammonia offers a sustainable route for simultaneous wastewater remediation and decentralized NH3 production, yet it requires advanced catalysts capable of precisely managing the complex multi-step reaction pathway. Herein, we report the rational design of a high-entropy intermetallic (HEI), (FeCoNiCu)6Sn5, which serves as a highly efficient and exceptionally stable electrocatalyst for nitrate-to-ammonia conversion. The HEI catalyst achieves a remarkable NH3 Faradaic efficiency of 97.4% and a high yield rate of 23.3 mg h−1 mgcat−1, maintaining robust stability over 150 h of continuous operation. Mechanistic investigations reveal that this outstanding performance stems from an ingenious synergistic division of site-specific functions: The Cu component promotes nitrate adsorption and initial reduction to nitrite, the Fe/Co/Ni components enhance subsequent hydrogenation kinetics, and the Sn component effectively suppresses the competing hydrogen evolution reaction (HER). When integrated into a practical Zn–NO3− battery system, the (FeCoNiCu)6Sn5 cathode simultaneously delivers a peak power density of 4.32 mW/cm2 alongside continuous ammonia production. This work establishes a versatile and powerful platform based on HEI for the precise construction of multicomponent catalysts, offering a new frontier for sustainable electrochemical synthesis.
2026, 37(12): 112802
doi: 10.1016/j.cclet.2026.112802
Abstract:
The pursuit of higher driving ranges for electric vehicles has driven continuous improvement in the energy density of lithium-ion batteries. High-voltage lithium metal batteries have emerged as promising next-generation energy storage devices due to their potential to achieve energy densities exceeding 400 Wh/kg. However, as the charging cut-off voltage increases, the interface between the NCM811 cathode and electrolyte deteriorates severely, resulting in degraded cycling performance and raising safety concerns. In this study, a fluorinated electrolyte was employed to construct a LiF-rich cathode electrolyte interphase (CEI), which effectively suppressed interfacial degradation and significantly enhanced the cycle life and safety of Li||NCM811 cells. The Li||NCM811 cell retained 83.2% of its capacity after 500 cycles even at 4.8 V, far exceeding the 41.0% capacity retention achieved with a commercial electrolyte. The modified electrolyte also demonstrates superior compatibility with the lithium-metal anode compared to conventional commercial electrolytes. Moreover, the designed electrolyte exhibits flame-retardant properties, thereby preserving safety performance. This work contributes to achieving stable operation of lithium metal batteries under high voltages and promotes their further commercialization.
The pursuit of higher driving ranges for electric vehicles has driven continuous improvement in the energy density of lithium-ion batteries. High-voltage lithium metal batteries have emerged as promising next-generation energy storage devices due to their potential to achieve energy densities exceeding 400 Wh/kg. However, as the charging cut-off voltage increases, the interface between the NCM811 cathode and electrolyte deteriorates severely, resulting in degraded cycling performance and raising safety concerns. In this study, a fluorinated electrolyte was employed to construct a LiF-rich cathode electrolyte interphase (CEI), which effectively suppressed interfacial degradation and significantly enhanced the cycle life and safety of Li||NCM811 cells. The Li||NCM811 cell retained 83.2% of its capacity after 500 cycles even at 4.8 V, far exceeding the 41.0% capacity retention achieved with a commercial electrolyte. The modified electrolyte also demonstrates superior compatibility with the lithium-metal anode compared to conventional commercial electrolytes. Moreover, the designed electrolyte exhibits flame-retardant properties, thereby preserving safety performance. This work contributes to achieving stable operation of lithium metal batteries under high voltages and promotes their further commercialization.
2026, 37(12): 112806
doi: 10.1016/j.cclet.2026.112806
Abstract:
The development of efficient hydrogen evolution reaction (HER) electrocatalysts that operate across various pH levels is of paramount importance for advancing the green hydrogen economy. In this work, we report a sequential pre-immobilization and selective nitridation strategy to fabricate ultrasmall Co/VN Mott-Schottky heterojunctions confined in dual-dimensional carbon shells (Co/VN@DDC) for pH-universal HER catalysis. Theoretical calculations show that the work function difference-induced d-orbital electron transfer from metal Co to semiconductor VN at the Mott-Schottky heterointerface creates a built-in electric field, resulting in optimal energy barriers with accelerated water dissociation and H2 evolution kinetics. Besides, the in situ generated carbon protective layers, consisting of two-dimensional (2D) nanosheets modified three-dimensional (3D) nanospheres, can protect the internal Co/VN cores from dissolution and aggregation. Therefore, the well-designed Co/VN@DDC exhibits low overpotentials and high catalytic durability in acidic, neutral, and alkaline electrolytes, respectively. This work provides an innovative approach to fabricating ultrasmall Co/VN Mott-Schottky heterojunctions confined in dual-dimensional carbon shells to advance electrocatalytic applications.
The development of efficient hydrogen evolution reaction (HER) electrocatalysts that operate across various pH levels is of paramount importance for advancing the green hydrogen economy. In this work, we report a sequential pre-immobilization and selective nitridation strategy to fabricate ultrasmall Co/VN Mott-Schottky heterojunctions confined in dual-dimensional carbon shells (Co/VN@DDC) for pH-universal HER catalysis. Theoretical calculations show that the work function difference-induced d-orbital electron transfer from metal Co to semiconductor VN at the Mott-Schottky heterointerface creates a built-in electric field, resulting in optimal energy barriers with accelerated water dissociation and H2 evolution kinetics. Besides, the in situ generated carbon protective layers, consisting of two-dimensional (2D) nanosheets modified three-dimensional (3D) nanospheres, can protect the internal Co/VN cores from dissolution and aggregation. Therefore, the well-designed Co/VN@DDC exhibits low overpotentials and high catalytic durability in acidic, neutral, and alkaline electrolytes, respectively. This work provides an innovative approach to fabricating ultrasmall Co/VN Mott-Schottky heterojunctions confined in dual-dimensional carbon shells to advance electrocatalytic applications.
2026, 37(12): 112892
doi: 10.1016/j.cclet.2026.112892
Abstract:
Electrochemical uranium extraction from seawater is a green mining strategy for the sustainable development of the nuclear industry, while designing advanced electrode materials with high adsorption capacity and efficient electron transfer capability remains a significant challenge. Herein, a novel MOF-based material (Ti-MOFOv-AO) is developed through defect engineering, which integrates multiple sites including oxygen vacancies, amidoxime functional groups, porous architectures and redox-active Ti3+/Ti4+ pairs for U(Ⅵ) adsorption, and catalytic conversion to accelerate the electroextraction kinetics. The synergistic interaction among these active sites facilitates the rapid enrichment of UO22+ on cathode, leading to the formation of Na2O(UO3H2O)x deposits and rapid regeneration of active sites for continuous extraction. Consequently, Ti-MOFOv-AO achieves an exceptionally high extraction capacity of 14.80 mg g-1 d-1 in 30 L of natural seawater under alternating voltages ranging from 0 to -3.5 V. This work presents valuable insights into designing an efficient electrode material for uranium extraction from seawater.
Electrochemical uranium extraction from seawater is a green mining strategy for the sustainable development of the nuclear industry, while designing advanced electrode materials with high adsorption capacity and efficient electron transfer capability remains a significant challenge. Herein, a novel MOF-based material (Ti-MOFOv-AO) is developed through defect engineering, which integrates multiple sites including oxygen vacancies, amidoxime functional groups, porous architectures and redox-active Ti3+/Ti4+ pairs for U(Ⅵ) adsorption, and catalytic conversion to accelerate the electroextraction kinetics. The synergistic interaction among these active sites facilitates the rapid enrichment of UO22+ on cathode, leading to the formation of Na2O(UO3H2O)x deposits and rapid regeneration of active sites for continuous extraction. Consequently, Ti-MOFOv-AO achieves an exceptionally high extraction capacity of 14.80 mg g-1 d-1 in 30 L of natural seawater under alternating voltages ranging from 0 to -3.5 V. This work presents valuable insights into designing an efficient electrode material for uranium extraction from seawater.
2026, 37(12): 112942
doi: 10.1016/j.cclet.2026.112942
Abstract:
Herein, we report an efficient fragment co-cyclization strategy for the synthesis of an orthogonally functionalized copillar[3 + 2]arene bearing propargyl and bromoethyl groups, achieving a yield of up to 50%. Its programmable architecture was unambiguously confirmed by single-crystal X-ray diffraction. This versatile scaffold enabled the precise construction of the water-soluble glycopeptide mimic GM10 via sequential orthogonal click reactions. GM10, featuring rationally integrated lectin-targeting and cationic modules, exhibits a dual inhibitory mechanism: It competitively binds to the Pseudomonas aeruginosa (P. aeruginosa) lectin LecB to block lectin-mediated adhesion, while simultaneously sequestering the key quorum-sensing (QS) signal molecule 3-oxo-C12-HSL through host–guest complexation, thereby suppressing QS and attenuating virulence factor expression. This mimic demonstrates potent, non-bactericidal anti-biofilm activity in vitro and accelerates wound healing in a murine infection model. Our work not only presents a novel synthetic route to functionalized pillar[5]arenes but also underscores the potential of programmable copillar[3 + 2]arene scaffolds for developing next-generation anti-virulence agents against biofilm-associated resistance.
Herein, we report an efficient fragment co-cyclization strategy for the synthesis of an orthogonally functionalized copillar[3 + 2]arene bearing propargyl and bromoethyl groups, achieving a yield of up to 50%. Its programmable architecture was unambiguously confirmed by single-crystal X-ray diffraction. This versatile scaffold enabled the precise construction of the water-soluble glycopeptide mimic GM10 via sequential orthogonal click reactions. GM10, featuring rationally integrated lectin-targeting and cationic modules, exhibits a dual inhibitory mechanism: It competitively binds to the Pseudomonas aeruginosa (P. aeruginosa) lectin LecB to block lectin-mediated adhesion, while simultaneously sequestering the key quorum-sensing (QS) signal molecule 3-oxo-C12-HSL through host–guest complexation, thereby suppressing QS and attenuating virulence factor expression. This mimic demonstrates potent, non-bactericidal anti-biofilm activity in vitro and accelerates wound healing in a murine infection model. Our work not only presents a novel synthetic route to functionalized pillar[5]arenes but also underscores the potential of programmable copillar[3 + 2]arene scaffolds for developing next-generation anti-virulence agents against biofilm-associated resistance.
2026, 37(12): 113084
doi: 10.1016/j.cclet.2026.113084
Abstract:
Plasma-catalytic ammonia (NH3) synthesis has recently emerged as a promising complementary approach to the Haber–Bosch process for mild and electro-driven NH3 production. However, its efficiency is severely limited by the incomplete utilization of plasma-generated reactive species and the lack of tailored catalysts capable of integrating both surface and gas-phase N2 activation pathways within plasma-catalyst coupled systems. In this study, we present Ca2NH, a metal imide catalyst that enables ultra-efficient NH3 synthesis via a dual-mechanism strategy. Owing to its integrated nitride-hydride structure, Ca2NH simultaneously facilitates a surface Mars–van Krevelen pathway for lattice-nitrogen hydrogenation and a gas-phase radical pathway driven by hydrogen radicals released from lattice hydrogen. This coupled mechanism ensures comprehensive N2 activation throughout the reaction space and achieves a remarkable NH3 synthesis rate of 371.8 mg h–1 g–1 under room temperature and atmospheric pressure, outperforming most reported electro–driven catalytic systems. These findings provide an effective strategy for integrating heterogeneous surface reactions with homogeneous radical–mediated pathways to achieve ultra-efficient activation of N2 molecules.
Plasma-catalytic ammonia (NH3) synthesis has recently emerged as a promising complementary approach to the Haber–Bosch process for mild and electro-driven NH3 production. However, its efficiency is severely limited by the incomplete utilization of plasma-generated reactive species and the lack of tailored catalysts capable of integrating both surface and gas-phase N2 activation pathways within plasma-catalyst coupled systems. In this study, we present Ca2NH, a metal imide catalyst that enables ultra-efficient NH3 synthesis via a dual-mechanism strategy. Owing to its integrated nitride-hydride structure, Ca2NH simultaneously facilitates a surface Mars–van Krevelen pathway for lattice-nitrogen hydrogenation and a gas-phase radical pathway driven by hydrogen radicals released from lattice hydrogen. This coupled mechanism ensures comprehensive N2 activation throughout the reaction space and achieves a remarkable NH3 synthesis rate of 371.8 mg h–1 g–1 under room temperature and atmospheric pressure, outperforming most reported electro–driven catalytic systems. These findings provide an effective strategy for integrating heterogeneous surface reactions with homogeneous radical–mediated pathways to achieve ultra-efficient activation of N2 molecules.
2026, 37(12): 113094
doi: 10.1016/j.cclet.2026.113094
Abstract:
Covalent organic frameworks (COFs), with tunable electronic structures, are versatile photocatalysts for sustainable environment and renewable energy. A key challenge remains in the screening of photocatalysts from a vast design space of COFs. Herein, a data-driven strategy that integrates high-throughput density functional theory (DFT)/time-dependent DFT (TD-DFT) calculations with machine learning (ML) accelerates the development of COFs as photocatalysts. Amongst 22 quantum chemical descriptors, the crucial ones, including EHOMO, ELUMO, IP, EA, and λmax, are accurately predicted. Among the eight ML models evaluated, the AdaBoost model achieves the highest predictive accuracy, with an R2 value up to 0.99 for λmax. SHAP analysis further pinpoints Egap is critical to linking the electronic structure to multiple descriptors. A framework is formulated for high-performance COF photocatalysts: A narrow Egap for broad light absorption, appropriately aligned energy levels to drive redox reactions, and efficient charge separation and transfer facilitated by asymmetric donor-π-acceptor architecture and extended π-conjugation. This work establishes a strategy for the accelerated discovery of COF photocatalysts through rational molecular design, high-throughput screening, and data-driven analysis.
Covalent organic frameworks (COFs), with tunable electronic structures, are versatile photocatalysts for sustainable environment and renewable energy. A key challenge remains in the screening of photocatalysts from a vast design space of COFs. Herein, a data-driven strategy that integrates high-throughput density functional theory (DFT)/time-dependent DFT (TD-DFT) calculations with machine learning (ML) accelerates the development of COFs as photocatalysts. Amongst 22 quantum chemical descriptors, the crucial ones, including EHOMO, ELUMO, IP, EA, and λmax, are accurately predicted. Among the eight ML models evaluated, the AdaBoost model achieves the highest predictive accuracy, with an R2 value up to 0.99 for λmax. SHAP analysis further pinpoints Egap is critical to linking the electronic structure to multiple descriptors. A framework is formulated for high-performance COF photocatalysts: A narrow Egap for broad light absorption, appropriately aligned energy levels to drive redox reactions, and efficient charge separation and transfer facilitated by asymmetric donor-π-acceptor architecture and extended π-conjugation. This work establishes a strategy for the accelerated discovery of COF photocatalysts through rational molecular design, high-throughput screening, and data-driven analysis.
2026, 37(12): 113201
doi: 10.1016/j.cclet.2026.113201
Abstract:
Phase change materials (PCMs) exhibit great application potential in solar-thermal energy storage and thermal management. However, pure block-shaped phase change materials have shortcomings such as low thermal conductivity, easy phase change leakage, and poor photothermal conversion efficiency. To address these issues, this work uses the synergistic assembly of intermolecular forces and multi-component hierarchical pore interconnection networks to prepare composite phase change materials (CPCMs) that combines high storage density, high photothermal capacity, and leak-proof performance. One-dimensional (1D) copper nanowires (CuNWs) act as thermally conductive bridges and assemble with reduced graphene oxide (rGO) to form continuous heat transfer networks. Covalent organic frameworks (COFs) interfacial anchoring effect is utilized to achieve synergistic enhancement of photothermal conversion and heat transfer in the multi-component composite matrix. Meanwhile, the hierarchical pore structure strengthens capillary confinement, thereby effectively suppressing PCMs leakage at high temperatures. The optimal sample GCOFCu1.5 achieves a photothermal conversion efficiency of 89% under 1.2 suns illumination, with a thermal conductivity of 0.87 W m-1 K-1 (an increase of 335% compared with pure paraffin). After 100 heating-cooling cycles, the photothermal conversion efficiency remains at 85.44%. The leakage rate is controlled below 3.96% after 20 cold-hot cycles at 75 °C. The phase change enthalpy is stable and the thermal reliability is excellent. This research further uses the finite element method to simulate the temperature field and phase change evolution under the multi-component microstructure, providing a novel insight into the structural design and application of graphene-based high-performance solar thermal energy storage and thermal management materials.
Phase change materials (PCMs) exhibit great application potential in solar-thermal energy storage and thermal management. However, pure block-shaped phase change materials have shortcomings such as low thermal conductivity, easy phase change leakage, and poor photothermal conversion efficiency. To address these issues, this work uses the synergistic assembly of intermolecular forces and multi-component hierarchical pore interconnection networks to prepare composite phase change materials (CPCMs) that combines high storage density, high photothermal capacity, and leak-proof performance. One-dimensional (1D) copper nanowires (CuNWs) act as thermally conductive bridges and assemble with reduced graphene oxide (rGO) to form continuous heat transfer networks. Covalent organic frameworks (COFs) interfacial anchoring effect is utilized to achieve synergistic enhancement of photothermal conversion and heat transfer in the multi-component composite matrix. Meanwhile, the hierarchical pore structure strengthens capillary confinement, thereby effectively suppressing PCMs leakage at high temperatures. The optimal sample GCOFCu1.5 achieves a photothermal conversion efficiency of 89% under 1.2 suns illumination, with a thermal conductivity of 0.87 W m-1 K-1 (an increase of 335% compared with pure paraffin). After 100 heating-cooling cycles, the photothermal conversion efficiency remains at 85.44%. The leakage rate is controlled below 3.96% after 20 cold-hot cycles at 75 °C. The phase change enthalpy is stable and the thermal reliability is excellent. This research further uses the finite element method to simulate the temperature field and phase change evolution under the multi-component microstructure, providing a novel insight into the structural design and application of graphene-based high-performance solar thermal energy storage and thermal management materials.
2026, 37(12): 113206
doi: 10.1016/j.cclet.2026.113206
Abstract:
Cartilage defect (CD) refers to the local loss of cartilage covering the joint surface, often accompanied by the excessive reactive oxygen species (ROS) and inflammation response. Reprogramming cartilage cavity microenvironment is the most effective strategy to treat CD. Herein, the nanosized cerium dioxide (CeO2) was incorporated into 4% methacrylic modified carboxymethyl cellulose to establish nanocomposited hydrogel scaffold (4%CC), applied as a CD therapeutic strategy with the functions of antioxidant, anti-inflammation and tissue repair. The incorporation of CeO2 in 4%CC, ensuring a stable release of Ce ions, had confirmed its excellent abilities of lowering intracellular ROS levels, downregulating inflammatory factors expression, promoting chondrogenic factors expression, inhibiting nuclear factor kappaB (NF-κB) pathway, and inducing macrophage M2 polarization both in lipopolysaccharide induced cells, and CD rat models. It may provide a novel perspective on the design of hydrogel scaffold with multiple functions for future tissue engineering application.
Cartilage defect (CD) refers to the local loss of cartilage covering the joint surface, often accompanied by the excessive reactive oxygen species (ROS) and inflammation response. Reprogramming cartilage cavity microenvironment is the most effective strategy to treat CD. Herein, the nanosized cerium dioxide (CeO2) was incorporated into 4% methacrylic modified carboxymethyl cellulose to establish nanocomposited hydrogel scaffold (4%CC), applied as a CD therapeutic strategy with the functions of antioxidant, anti-inflammation and tissue repair. The incorporation of CeO2 in 4%CC, ensuring a stable release of Ce ions, had confirmed its excellent abilities of lowering intracellular ROS levels, downregulating inflammatory factors expression, promoting chondrogenic factors expression, inhibiting nuclear factor kappaB (NF-κB) pathway, and inducing macrophage M2 polarization both in lipopolysaccharide induced cells, and CD rat models. It may provide a novel perspective on the design of hydrogel scaffold with multiple functions for future tissue engineering application.
2026, 37(12): 113223
doi: 10.1016/j.cclet.2026.113223
Abstract:
Composite solid-polymer electrolytes (SPEs) integrate the merits of polymer electrolytes and inorganic fillers, demonstrating excellent interfacial wetting with lithium metal and competitive ionic conductivity. However, the formidable interfacial impedance and poor compatibility between the polymer matrix and inorganic fillers often hinder the realization of high-rate capability and long-term cycling stability. Herein, we report a PVDF-HFP-based SPE featuring garnet-type Li7La3Zr2O12 (LLZO) as the inorganic filler and fluoroethylene carbonate (FEC) as a functional additive, that enhancing binding energies with LLZO and induces local lithium salts enrichment at the LLZO surface. This FEC absorbs and wet the surface of LLZO, resulting in lithium salts aggregation at the interface between LLZO and PVDF-HFP. This unique local ion rich characteristic provides additional lithium-ion channels and enables high ionic conductivity. In addition, the replacement of N,N-dimethylformamide (DMF) by FEC, inhibits the DMF with the La sites of LLZO, preventing the subsequent dehydrofluorination of the PVDF-HFP chains and fundamentally securing the intrinsic chemical stability throughout the SPE. Furthermore, FEC introduction induces a dense and LiF-rich solid electrolyte interphase (SEI), effectively curtailing dendrite penetration and establishing a stabilized interfacial contact. Consequently, the engineered electrolyte membrane achieves a remarkable ambient ionic conductivity of 7.4 × 10–4 S/cm. The SPE enables exceptionally stable Li plating/stripping for 650 h. The assembled Li//LiFePO4 cells deliver outstanding high-rate (640 cycles at 8C) and high-temperature (400 cycles at 5 C, 50 ℃) lifespans. Furthermore, high-voltage Li//NCM811 cells exhibit superior compatibility with over 250 stable cycles. This work offers a compelling paradigm to overcome the inherent interfacial mismatch among rigid inorganic fillers, polymeric networks, and active electrodes, for next-generation solid-state lithium metal batteries.
Composite solid-polymer electrolytes (SPEs) integrate the merits of polymer electrolytes and inorganic fillers, demonstrating excellent interfacial wetting with lithium metal and competitive ionic conductivity. However, the formidable interfacial impedance and poor compatibility between the polymer matrix and inorganic fillers often hinder the realization of high-rate capability and long-term cycling stability. Herein, we report a PVDF-HFP-based SPE featuring garnet-type Li7La3Zr2O12 (LLZO) as the inorganic filler and fluoroethylene carbonate (FEC) as a functional additive, that enhancing binding energies with LLZO and induces local lithium salts enrichment at the LLZO surface. This FEC absorbs and wet the surface of LLZO, resulting in lithium salts aggregation at the interface between LLZO and PVDF-HFP. This unique local ion rich characteristic provides additional lithium-ion channels and enables high ionic conductivity. In addition, the replacement of N,N-dimethylformamide (DMF) by FEC, inhibits the DMF with the La sites of LLZO, preventing the subsequent dehydrofluorination of the PVDF-HFP chains and fundamentally securing the intrinsic chemical stability throughout the SPE. Furthermore, FEC introduction induces a dense and LiF-rich solid electrolyte interphase (SEI), effectively curtailing dendrite penetration and establishing a stabilized interfacial contact. Consequently, the engineered electrolyte membrane achieves a remarkable ambient ionic conductivity of 7.4 × 10–4 S/cm. The SPE enables exceptionally stable Li plating/stripping for 650 h. The assembled Li//LiFePO4 cells deliver outstanding high-rate (640 cycles at 8C) and high-temperature (400 cycles at 5 C, 50 ℃) lifespans. Furthermore, high-voltage Li//NCM811 cells exhibit superior compatibility with over 250 stable cycles. This work offers a compelling paradigm to overcome the inherent interfacial mismatch among rigid inorganic fillers, polymeric networks, and active electrodes, for next-generation solid-state lithium metal batteries.
2026, 37(12): 113292
doi: 10.1016/j.cclet.2026.113292
Abstract:
Although zinc-air batteries (ZABs) are considered promising energy storage technologies due to their high energy density and low cost, their efficiency and durability are severely limited by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Hence, an atomic-level electronic reconstruction strategy is proposed, in which atomically dispersed Co and Fe bimetallic sites are anchored on α-MnO2 nanorods (Co-Fe@MnO2), thereby enabling highly reversible and durable electrocatalysis. The strong electronic interactions between Co-Fe dual sites and the MnO2 support induce the generation of abundant low-valence Mn species and oxygen vacancies, enriching electronic states near the Fermi level and downshifting the d-band center. This dual-site-induced electronic reconstruction optimizes the adsorption and desorption of oxygen intermediates, effectively accelerating the kinetic processes of ORR and OER. Therefore, the Co-Fe@MnO2 catalyst delivers outstanding bifunctional electrocatalytic activity, with a half-wave potential of 0.85 V for the ORR, and an overpotential of 230 mV for the OER at 10 mA/cm2, yielding a narrow bifunctional potential gap of 0.83 V. Consequently, the self-assembled rechargeable ZAB integrated with the Co-Fe@MnO2 air cathode achieves a peak power density of 249 mW/cm2 at 360 mA/cm2 and exhibits excellent cycling stability. This study reveals the key role of dual-site-induced electronic reconstruction in regulating the catalytic behavior of MnO2 and provides a practical strategy for designing high-performance bifunctional electrocatalysts for metal-air energy storage systems.
Although zinc-air batteries (ZABs) are considered promising energy storage technologies due to their high energy density and low cost, their efficiency and durability are severely limited by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Hence, an atomic-level electronic reconstruction strategy is proposed, in which atomically dispersed Co and Fe bimetallic sites are anchored on α-MnO2 nanorods (Co-Fe@MnO2), thereby enabling highly reversible and durable electrocatalysis. The strong electronic interactions between Co-Fe dual sites and the MnO2 support induce the generation of abundant low-valence Mn species and oxygen vacancies, enriching electronic states near the Fermi level and downshifting the d-band center. This dual-site-induced electronic reconstruction optimizes the adsorption and desorption of oxygen intermediates, effectively accelerating the kinetic processes of ORR and OER. Therefore, the Co-Fe@MnO2 catalyst delivers outstanding bifunctional electrocatalytic activity, with a half-wave potential of 0.85 V for the ORR, and an overpotential of 230 mV for the OER at 10 mA/cm2, yielding a narrow bifunctional potential gap of 0.83 V. Consequently, the self-assembled rechargeable ZAB integrated with the Co-Fe@MnO2 air cathode achieves a peak power density of 249 mW/cm2 at 360 mA/cm2 and exhibits excellent cycling stability. This study reveals the key role of dual-site-induced electronic reconstruction in regulating the catalytic behavior of MnO2 and provides a practical strategy for designing high-performance bifunctional electrocatalysts for metal-air energy storage systems.
2026, 37(12): 113008
doi: 10.1016/j.cclet.2026.113008
Abstract:
2026, 37(12): 113015
doi: 10.1016/j.cclet.2026.113015
Abstract:
2026, 37(12): 113114
doi: 10.1016/j.cclet.2026.113114
Abstract:
2026, 37(12): 113128
doi: 10.1016/j.cclet.2026.113128
Abstract:
2026, 37(12): 113186
doi: 10.1016/j.cclet.2026.113186
Abstract:
2026, 37(12): 113229
doi: 10.1016/j.cclet.2026.113229
Abstract:
2026, 37(12): 113238
doi: 10.1016/j.cclet.2026.113238
Abstract:
2026, 37(12): 113196
doi: 10.1016/j.cclet.2026.113196
Abstract:
