-
-
Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
期刊内检索
期刊内热点文章
-
1
Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
-
2
Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
-
3
Development of electron and hole selective contact materials for perovskite solar cells
-
4
Superiority of poly(L-lactic acid) microspheres as dermal fillers
- 5
期刊内下载排行
-
1
Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
- 2
-
3
Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
-
4
Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
-
5
Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(12): 110978
doi: 10.1016/j.cclet.2025.110978
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
2026, 37(12): 113015
doi: 10.1016/j.cclet.2026.113015
摘要:
2026, 37(12): 113114
doi: 10.1016/j.cclet.2026.113114
摘要:
2026, 37(12): 113128
doi: 10.1016/j.cclet.2026.113128
摘要:
2026, 37(12): 113186
doi: 10.1016/j.cclet.2026.113186
摘要:
2026, 37(12): 113229
doi: 10.1016/j.cclet.2026.113229
摘要:
2026, 37(12): 113238
doi: 10.1016/j.cclet.2026.113238
摘要:
2026, 37(12): 113196
doi: 10.1016/j.cclet.2026.113196
摘要:
2026, 37(5): 110827
doi: 10.1016/j.cclet.2025.110827
摘要:
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
2026, 37(5): 110829
doi: 10.1016/j.cclet.2025.110829
摘要:
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
2026, 37(5): 110851
doi: 10.1016/j.cclet.2025.110851
摘要:
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
2026, 37(5): 110852
doi: 10.1016/j.cclet.2025.110852
摘要:
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
2026, 37(5): 110858
doi: 10.1016/j.cclet.2025.110858
摘要:
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
2026, 37(5): 110859
doi: 10.1016/j.cclet.2025.110859
摘要:
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
2026, 37(5): 110862
doi: 10.1016/j.cclet.2025.110862
摘要:
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
2026, 37(5): 110863
doi: 10.1016/j.cclet.2025.110863
摘要:
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
2026, 37(5): 110864
doi: 10.1016/j.cclet.2025.110864
摘要:
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
2026, 37(5): 110889
doi: 10.1016/j.cclet.2025.110889
摘要:
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
2026, 37(5): 110891
doi: 10.1016/j.cclet.2025.110891
摘要:
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
2026, 37(5): 110892
doi: 10.1016/j.cclet.2025.110892
摘要:
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
2026, 37(5): 110893
doi: 10.1016/j.cclet.2025.110893
摘要:
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
2026, 37(5): 110952
doi: 10.1016/j.cclet.2025.110952
摘要:
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
2026, 37(5): 110953
doi: 10.1016/j.cclet.2025.110953
摘要:
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
2026, 37(5): 110954
doi: 10.1016/j.cclet.2025.110954
摘要:
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
2026, 37(5): 110974
doi: 10.1016/j.cclet.2025.110974
摘要:
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
2026, 37(5): 111158
doi: 10.1016/j.cclet.2025.111158
摘要:
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
2026, 37(5): 111236
doi: 10.1016/j.cclet.2025.111236
摘要:
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
2026, 37(5): 111248
doi: 10.1016/j.cclet.2025.111248
摘要:
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
2026, 37(5): 111257
doi: 10.1016/j.cclet.2025.111257
摘要:
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
2026, 37(5): 111274
doi: 10.1016/j.cclet.2025.111274
摘要:
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
2026, 37(5): 111282
doi: 10.1016/j.cclet.2025.111282
摘要:
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
2026, 37(5): 111284
doi: 10.1016/j.cclet.2025.111284
摘要:
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
PROTAC degraders of FSP1 act as potent GPX4 sensitizers to induce ferroptosis for hepatoma treatment
2026, 37(5): 111285
doi: 10.1016/j.cclet.2025.111285
摘要:
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
2026, 37(5): 111291
doi: 10.1016/j.cclet.2025.111291
摘要:
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
2026, 37(5): 111292
doi: 10.1016/j.cclet.2025.111292
摘要:
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
2026, 37(5): 111318
doi: 10.1016/j.cclet.2025.111318
摘要:
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
2026, 37(5): 111324
doi: 10.1016/j.cclet.2025.111324
摘要:
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
2026, 37(5): 111334
doi: 10.1016/j.cclet.2025.111334
摘要:
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
2026, 37(5): 111336
doi: 10.1016/j.cclet.2025.111336
摘要:
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
2026, 37(5): 111337
doi: 10.1016/j.cclet.2025.111337
摘要:
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
2026, 37(5): 111338
doi: 10.1016/j.cclet.2025.111338
摘要:
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
2026, 37(5): 111343
doi: 10.1016/j.cclet.2025.111343
摘要:
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
2026, 37(5): 111347
doi: 10.1016/j.cclet.2025.111347
摘要:
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
2026, 37(5): 111350
doi: 10.1016/j.cclet.2025.111350
摘要:
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
2026, 37(5): 111356
doi: 10.1016/j.cclet.2025.111356
摘要:
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
2026, 37(5): 111381
doi: 10.1016/j.cclet.2025.111381
摘要:
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
2026, 37(5): 111399
doi: 10.1016/j.cclet.2025.111399
摘要:
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
2026, 37(5): 111401
doi: 10.1016/j.cclet.2025.111401
摘要:
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
2026, 37(5): 111403
doi: 10.1016/j.cclet.2025.111403
摘要:
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
2026, 37(5): 111405
doi: 10.1016/j.cclet.2025.111405
摘要:
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
2026, 37(5): 111407
doi: 10.1016/j.cclet.2025.111407
摘要:
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
2026, 37(5): 111419
doi: 10.1016/j.cclet.2025.111419
摘要:
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
2026, 37(5): 111426
doi: 10.1016/j.cclet.2025.111426
摘要:
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
2026, 37(5): 111429
doi: 10.1016/j.cclet.2025.111429
摘要:
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
2026, 37(5): 111430
doi: 10.1016/j.cclet.2025.111430
摘要:
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
2026, 37(5): 111442
doi: 10.1016/j.cclet.2025.111442
摘要:
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
2026, 37(5): 111443
doi: 10.1016/j.cclet.2025.111443
摘要:
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
2026, 37(5): 111454
doi: 10.1016/j.cclet.2025.111454
摘要:
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
2026, 37(5): 111461
doi: 10.1016/j.cclet.2025.111461
摘要:
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
2026, 37(5): 111484
doi: 10.1016/j.cclet.2025.111484
摘要:
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
2026, 37(5): 111499
doi: 10.1016/j.cclet.2025.111499
摘要:
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
2026, 37(5): 111501
doi: 10.1016/j.cclet.2025.111501
摘要:
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
2026, 37(5): 111544
doi: 10.1016/j.cclet.2025.111544
摘要:
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
2026, 37(5): 111555
doi: 10.1016/j.cclet.2025.111555
摘要:
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
2026, 37(5): 111614
doi: 10.1016/j.cclet.2025.111614
摘要:
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
2026, 37(5): 111615
doi: 10.1016/j.cclet.2025.111615
摘要:
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
2026, 37(5): 111616
doi: 10.1016/j.cclet.2025.111616
摘要:
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
2026, 37(5): 111617
doi: 10.1016/j.cclet.2025.111617
摘要:
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
2026, 37(5): 111649
doi: 10.1016/j.cclet.2025.111649
摘要:
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
2026, 37(5): 111706
doi: 10.1016/j.cclet.2025.111706
摘要:
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
2026, 37(5): 111717
doi: 10.1016/j.cclet.2025.111717
摘要:
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
2026, 37(5): 111720
doi: 10.1016/j.cclet.2025.111720
摘要:
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
2026, 37(5): 111789
doi: 10.1016/j.cclet.2025.111789
摘要:
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
2026, 37(5): 111790
doi: 10.1016/j.cclet.2025.111790
摘要:
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
2026, 37(5): 111791
doi: 10.1016/j.cclet.2025.111791
摘要:
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
2026, 37(5): 111811
doi: 10.1016/j.cclet.2025.111811
摘要:
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
2026, 37(5): 111825
doi: 10.1016/j.cclet.2025.111825
摘要:
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
2026, 37(5): 111838
doi: 10.1016/j.cclet.2025.111838
摘要:
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
2026, 37(5): 111839
doi: 10.1016/j.cclet.2025.111839
摘要:
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
2026, 37(5): 111840
doi: 10.1016/j.cclet.2025.111840
摘要:
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
2026, 37(5): 111844
doi: 10.1016/j.cclet.2025.111844
摘要:
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
2026, 37(5): 111851
doi: 10.1016/j.cclet.2025.111851
摘要:
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
2026, 37(5): 111853
doi: 10.1016/j.cclet.2025.111853
摘要:
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
2026, 37(5): 111857
doi: 10.1016/j.cclet.2025.111857
摘要:
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
2026, 37(5): 111858
doi: 10.1016/j.cclet.2025.111858
摘要:
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
2026, 37(5): 111860
doi: 10.1016/j.cclet.2025.111860
摘要:
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
2026, 37(5): 111862
doi: 10.1016/j.cclet.2025.111862
摘要:
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
2026, 37(5): 111864
doi: 10.1016/j.cclet.2025.111864
摘要:
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
2026, 37(5): 111874
doi: 10.1016/j.cclet.2025.111874
摘要:
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
2026, 37(5): 111903
doi: 10.1016/j.cclet.2025.111903
摘要:
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
2026, 37(5): 111914
doi: 10.1016/j.cclet.2025.111914
摘要:
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
2026, 37(5): 111923
doi: 10.1016/j.cclet.2025.111923
摘要:
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
2026, 37(5): 111927
doi: 10.1016/j.cclet.2025.111927
摘要:
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
2026, 37(5): 111931
doi: 10.1016/j.cclet.2025.111931
摘要:
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
2026, 37(5): 111935
doi: 10.1016/j.cclet.2025.111935
摘要:
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
2026, 37(5): 111975
doi: 10.1016/j.cclet.2025.111975
摘要:
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
2026, 37(5): 112064
doi: 10.1016/j.cclet.2025.112064
摘要:
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
2026, 37(5): 112202
doi: 10.1016/j.cclet.2025.112202
摘要:
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
2026, 37(5): 112348
doi: 10.1016/j.cclet.2025.112348
摘要:
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
2026, 37(5): 112373
doi: 10.1016/j.cclet.2026.112373
摘要:
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
2026, 37(5): 112417
doi: 10.1016/j.cclet.2026.112417
摘要:
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
2026, 37(5): 110860
doi: 10.1016/j.cclet.2025.110860
摘要:
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
2026, 37(5): 110973
doi: 10.1016/j.cclet.2025.110973
摘要:
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
2026, 37(5): 111262
doi: 10.1016/j.cclet.2025.111262
摘要:
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
2026, 37(5): 111319
doi: 10.1016/j.cclet.2025.111319
摘要:
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
2026, 37(5): 111390
doi: 10.1016/j.cclet.2025.111390
摘要:
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
2026, 37(5): 111392
doi: 10.1016/j.cclet.2025.111392
摘要:
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
2026, 37(5): 111396
doi: 10.1016/j.cclet.2025.111396
摘要:
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
2026, 37(5): 111707
doi: 10.1016/j.cclet.2025.111707
摘要:
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
2026, 37(5): 111843
doi: 10.1016/j.cclet.2025.111843
摘要:
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
2026, 37(5): 111861
doi: 10.1016/j.cclet.2025.111861
摘要:
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
2026, 37(5): 111902
doi: 10.1016/j.cclet.2025.111902
摘要:
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
2026, 37(5): 111904
doi: 10.1016/j.cclet.2025.111904
摘要:
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
2026, 37(5): 111915
doi: 10.1016/j.cclet.2025.111915
摘要:
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
2026, 37(5): 111929
doi: 10.1016/j.cclet.2025.111929
摘要:
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
2026, 37(5): 111960
doi: 10.1016/j.cclet.2025.111960
摘要:
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
2026, 37(5): 112142
doi: 10.1016/j.cclet.2025.112142
摘要:
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
2026, 37(5): 112235
doi: 10.1016/j.cclet.2025.112235
摘要:
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
2026, 37(5): 111876
doi: 10.1016/j.cclet.2025.111876
摘要:
2026, 37(5): 112260
doi: 10.1016/j.cclet.2025.112260
摘要:
