摘要：
The accurate and sensitive quantification of hydroxyl radical (·OH) and glucose is necessary for disease diagnosis and health guidance, but still challenging owing to the low concentration of ·OH and poor water solubility of fluorescent probes. In addition, fluorescent probes may cause secondary pollution to the environment. Here an organic cage was reported as a sensitive fluorescent probe for ·OH and glucose in aqueous solution without serious secondary pollution. The prepared organic cage with good water solubility showed specific redox affinity to ·OH in acidic condition, resulting in two oxidation stages of mild oxidation and subsequent oxidative degradation. Fluorescence around 485 nm enhanced remarkably in the first stage, and benzene ring in organic cage was degraded in the second stage. Based on the significant fluorescence enhancement, a sensitive fluorescence turn-on sensing method for ·OH was established within 90 s with the limit of detection (3 s/k , where s and k are the standard deviation for 10 replicate detections of blank and the slope of calibration function) of 5 nM. The recoveries of spiked ·OH in human serum and water samples ranged from 95.2 % to 102.7 %. After the glucose oxidase enzyme-Fenton reaction was involved, the ·OH detection was also applied to sensitive sensing of glucose with the limit of detection (3 s/k ) of 6 nM. The recoveries of spiked glucose in sugary drinks ranged from 96.2 % to 102.6 %. Furthermore, the proposed method would also be suitable for other hazardous substances and biomarkers which can produce hydrogen peroxide and further form ·OH via Fenton reaction.
The accurate and sensitive quantification of hydroxyl radical (·OH) and glucose is necessary for disease diagnosis and health guidance, but still challenging owing to the low concentration of ·OH and poor water solubility of fluorescent probes. In addition, fluorescent probes may cause secondary pollution to the environment. Here an organic cage was reported as a sensitive fluorescent probe for ·OH and glucose in aqueous solution without serious secondary pollution. The prepared organic cage with good water solubility showed specific redox affinity to ·OH in acidic condition, resulting in two oxidation stages of mild oxidation and subsequent oxidative degradation. Fluorescence around 485 nm enhanced remarkably in the first stage, and benzene ring in organic cage was degraded in the second stage. Based on the significant fluorescence enhancement, a sensitive fluorescence turn-on sensing method for ·OH was established within 90 s with the limit of detection (3 s/k , where s and k are the standard deviation for 10 replicate detections of blank and the slope of calibration function) of 5 nM. The recoveries of spiked ·OH in human serum and water samples ranged from 95.2 % to 102.7 %. After the glucose oxidase enzyme-Fenton reaction was involved, the ·OH detection was also applied to sensitive sensing of glucose with the limit of detection (3 s/k ) of 6 nM. The recoveries of spiked glucose in sugary drinks ranged from 96.2 % to 102.6 %. Furthermore, the proposed method would also be suitable for other hazardous substances and biomarkers which can produce hydrogen peroxide and further form ·OH via Fenton reaction.
期刊：
FRONTIERS IN ONCOLOGY,2025年15:1509810 ISSN：2234-943X
作者机构：
[Zhang, Shu-Ping; Zhao, Jing-Jun; Gu, Biao; Tang, Si-Ping; Fu, Da; Zhai, Peng-Lei] Key Laboratory of Functional Organometallic Materials of College of Hunan Province, College of Chemistry and Materials Science, Hengyang Normal University, Hengyang, China;[Tang, Xiao-Mei; Lu, Cui-Ni; Chen, Meng-Min; Yang, Qin-Xin; Fu, Da; Zhai, Peng-Lei; Liu, Jia] Department of General Surgery, Pancreatic Disease Center, Ruijin Hospital, Shanghai Jiao Tong University School of Medicine, Shanghai, China;[Chen, Meng-Min] Research Institute of Pancreatic Diseases, Shanghai Key Laboratory of Translational Research for Pancreatic Neoplasms, Shanghai Jiao Tong University School of Medicine, Shanghai, China;[Chen, Meng-Min] State Key Laboratory of Oncogenes and Related Genes, Institute of Translational Medicine, Shanghai Jiao Tong University, Shanghai, China;[Wang, Qi] Department of Urology, Ruijin Hospital, Shanghai Jiao Tong University School of Medicine, Shanghai, China
关键词：
drug prediction;genomic alterations;immunotherapy;liquid-liquid phase separation;tumor immune microenvironment
摘要：
BACKGROUND: Growing evidence indicates that abnormal liquid-liquid phase separation (LLPS) can disrupt biomolecular condensates, contributing to cancer development and progression. However, the influence of LLPS on the prognosis of head and neck squamous cell carcinoma (HNSCC) patients and its effects on the tumor immune microenvironment (TIME) are not yet fully understood. Therefore, we aimed to categorize patients with HNSCC based on LLPS-related genes and explored their multidimensional heterogeneity. METHODS: We integrated the transcriptomic data of 3,541 LLPS-related genes to assess the LLPS patterns in 501 patients with HNSCC within The Cancer Genome Atlas cohort. Subsequently, we explored the differences among the three LLPS subtypes using multi-omics analysis. We also developed an LLPS-related prognostic risk signature (LPRS) to facilitate personalized and integrative assessments and then screened and validated potential therapeutic small molecule compounds targeting HNSCC via experimental analyses. RESULT: By analyzing the expression profiles of 85 scaffolds, 355 regulators, and 3,101 clients of LLPS in HNSCC, we identified three distinct LLPS subtypes: LS1, LS2, and LS3. We confirmed notable differences among these subtypes in terms of prognosis, functional enrichment, genomic alterations, TIME patterns, and responses to immunotherapy. Additionally, we developed the LPRS, a prognostic signature for personalized integrative assessments, which demonstrated strong predictive capability for HNSCC prognosis across multiple cohorts. The LPRS also showed significant correlations with the clinicopathological features and TIME patterns in HNSCC patients. Furthermore, the LPRS effectively predicted responses to immune checkpoint inhibitor therapy and facilitated the screening of potential small-molecule compounds for treating HNSCC patients. CONCLUSION: This study presents a new classification system for HNSCC patients grounded in LLPS. The LPRS developed in this research offers improved personalized prognosis and could optimize immunotherapy strategies for HNSCC.
作者机构：
College of Chemistry and Materials Science, Hengyang Normal University, Hunan 421008, PR China;[Ye-Tang Pan; Rongjie Yang] National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, PR China;[Lubin Liu] Key Lab of Bio-based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, People’s Republic of China;Centre for Future Materials, University of Southern Queensland, Springfield 4300, Australia;School of Agriculture and Environmental Science, University of Southern Queensland, Springfield 4300, Australia
通讯机构：
[Ye-Tang Pan] N;[Lubin Liu] K;Key Lab of Bio-based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, People’s Republic of China<&wdkj&>National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, PR China
摘要：
Biomass resources are natural polymeric materials that are abundant, affordable, non-toxic and renewable. Although they find diverse applications in both everyday life and high-tech materials, their use is often constrained by the associated fire hazards. To address this issue, there is a growing interest in the development of flame-retardant biomass polymeric materials. Metal-organic frameworks (MOFs) consist of transition metal species, flame-retardant elements and potential carbon sources, allowing for easy adjustment of their structure and properties. This versatility makes MOFs and their derivatives and hybrids highly attractive for flame retardancy studies. Despite their distinctive properties, MOFs alone may not fully satisfy the demands of commercial flame-retardant applications. The combination of MOFs with biomass materials has been identified as a promising strategy for developing efficient flame-retardant biomass nanocomposites. This innovative approach aims to address the limitations of MOFs by capitalizing on synergistic effects. This review highlights recent advancements and strategies in MOF-based flame retardants incorporating biomass materials, and it elucidates the flame-retardant mechanisms of MOF/biomass nanocomposites to inform future design efforts in the field. Furthermore, the review discusses the current challenges and prospects in this field, aiming to provide a succinct yet comprehensive overview for researchers to quickly grasp the latest developments.
Biomass resources are natural polymeric materials that are abundant, affordable, non-toxic and renewable. Although they find diverse applications in both everyday life and high-tech materials, their use is often constrained by the associated fire hazards. To address this issue, there is a growing interest in the development of flame-retardant biomass polymeric materials. Metal-organic frameworks (MOFs) consist of transition metal species, flame-retardant elements and potential carbon sources, allowing for easy adjustment of their structure and properties. This versatility makes MOFs and their derivatives and hybrids highly attractive for flame retardancy studies. Despite their distinctive properties, MOFs alone may not fully satisfy the demands of commercial flame-retardant applications. The combination of MOFs with biomass materials has been identified as a promising strategy for developing efficient flame-retardant biomass nanocomposites. This innovative approach aims to address the limitations of MOFs by capitalizing on synergistic effects. This review highlights recent advancements and strategies in MOF-based flame retardants incorporating biomass materials, and it elucidates the flame-retardant mechanisms of MOF/biomass nanocomposites to inform future design efforts in the field. Furthermore, the review discusses the current challenges and prospects in this field, aiming to provide a succinct yet comprehensive overview for researchers to quickly grasp the latest developments.
作者机构：
[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin] Hengyang Normal Univ, Coll Hunan Prov, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin] Hengyang Normal Univ, Coll Hunan Prov, Key Lab Organometall New Mat, Hengyang 421008, Peoples R China.;[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin; Liu, X] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
通讯机构：
[Liu, X ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
关键词：
Cd 0.5 Zn 0.5 S;CoS;S2 adsorption;Photocatalytic H2 evolution
摘要：
Designing surface phase is an efficient strategy to facilitate charge separation and photocatalytic H 2 -evolution performance. In this work, CoS cocatalysts were intimately anchored on Cd 0.5 Zn 0.5 S (denoted as CZS) photocatalyst via in-situ precipitate transformation in S 2− /SO 3 2− solution with cobaltous phosphate (CoPi) as a precursor, meanwhile, S 2− ions were adsorbed on the CZS to form a sulfur-rich surface (denoted as CZS-S). The photocatalytic H 2 -evolution rate of CoS/CZS-S is 2.02 mmol·g −1 ·h −1 in 0.1 M Na 2 S/Na 2 SO 3 sacrificial agent system. In addition, CoS/CZS-S exhibits excellent stability in both Na 2 S/Na 2 SO 3 and lactic acid system. The theoretical calculations (DFT) and experimental results reveal that amorphous CoS can work as a highly effective cocatalyst for H 2 evolution reaction and the intimate contact between CZS and CoS facilitates the photoelectrons transfer from CZS to CoS. The adsorbed S 2− ions mainly work as effective hole acceptors. As a result of the synergism of CoS and adsorbed S 2− ions, the boosted separation and immigration of photoelectrons and photoholes and high photocatalytic H 2 -evolution performance of CoS/CZS-S are realized. The present work highlights simultaneous reinforcing reduction and oxidation half-reaction dynamics via a facile and economic surface strategy to achieve efficient solar H 2 -evolution from H 2 O splitting.
Designing surface phase is an efficient strategy to facilitate charge separation and photocatalytic H 2 -evolution performance. In this work, CoS cocatalysts were intimately anchored on Cd 0.5 Zn 0.5 S (denoted as CZS) photocatalyst via in-situ precipitate transformation in S 2− /SO 3 2− solution with cobaltous phosphate (CoPi) as a precursor, meanwhile, S 2− ions were adsorbed on the CZS to form a sulfur-rich surface (denoted as CZS-S). The photocatalytic H 2 -evolution rate of CoS/CZS-S is 2.02 mmol·g −1 ·h −1 in 0.1 M Na 2 S/Na 2 SO 3 sacrificial agent system. In addition, CoS/CZS-S exhibits excellent stability in both Na 2 S/Na 2 SO 3 and lactic acid system. The theoretical calculations (DFT) and experimental results reveal that amorphous CoS can work as a highly effective cocatalyst for H 2 evolution reaction and the intimate contact between CZS and CoS facilitates the photoelectrons transfer from CZS to CoS. The adsorbed S 2− ions mainly work as effective hole acceptors. As a result of the synergism of CoS and adsorbed S 2− ions, the boosted separation and immigration of photoelectrons and photoholes and high photocatalytic H 2 -evolution performance of CoS/CZS-S are realized. The present work highlights simultaneous reinforcing reduction and oxidation half-reaction dynamics via a facile and economic surface strategy to achieve efficient solar H 2 -evolution from H 2 O splitting.
作者机构：
[Liu, Xiang; Yang, Qian; Ni, Wenjin; Liu, Jian; Li, Zhongliang; Tan, Liang; Fu, Jinfeng] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Ni, Wenjin; Liu, Jian; Li, Zhongliang; Tan, Liang] Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Zhang, Jiaming] Xiangtan Univ, Sch Chem Engn, Xiangtan 411105, Peoples R China.
通讯机构：
[Ni, WJ; Liu, J ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.
摘要：
In this work, dual active-site Ti-incorporated metal-organic frameworks (MIL-125 and NH2-MIL-125) were synthesized by a simple solvothermal process and applied to prepare cyclohexanone oxime from cyclohexylamine oxidation. A low-temperature thermal calcination strategy was used for the modulation of surface properties while maintaining the crystal structure and morphology. The results demonstrated that novel bifunctional NH2-MIL-125@250 degrees C obtained from thermal calcination possessed a large surface area with both oxygen vacancies and surface hydroxyl-active sites, promoting the adsorption and activation of cyclohexylamine and oxygen molecules, respectively. Under the optimum conditions, the cyclohexylamine conversion was 44.3%, and the selectivity to cyclohexanone oxime was 83.0%. By comparison, the stability of MIL-125 and NH2-MIL-125 was investigated separately in cyclic tests, and the crystal structure and catalytic properties of NH2-MIL-125 have been shown to be more stable than those of MIL-125. Combined with density functional theory, it was further shown that NH2-MIL-125 displayed a higher adsorption and activation ability toward cyclohexylamine and oxygen than MIL-125 and had a more stable metal-organic ligand structure. Finally, a plausible reaction pathway for selective cyclohexylamine oxidation to cyclohexanone oxime was proposed. This work can give new insights into designing novel dual active-site catalysts for the efficient catalytic transformation of organic primary amines to corresponding oximes.
摘要：
In this work, a fascinating nanocomposite based on manganese-cobalt sulfide (MnS/Co3S4) wrapped by electrochemically reduced graphene oxide (ERGO) has been successfully synthesized on the surface of a glassy carbon electrode (GCE) by a facile hydrothermal assisted electrochemical reduction method. The modified electrode was fully characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The morphological results illustrate that MnS/Co3S4 are embedded in the ERGO layers, resulting in a rough surface and three-dimensional (3D) microstructure. The as-synthesized MnS/Co3S4-ERGO/GCE displays distinctly enhanced electrocatalytic activity for vanillin oxidation in comparison with that of the ERGO/GCE and MnS/Co3S4/GCE. Therefore, the MnS/Co3S4-ERGO/GCE can be used as an effective electrochemical sensing platform for the sensitive determination of vanillin, and the fabricated sensor displays a wide linear range of 0.02-1.00 mmol/L and 1.0-40.0 mmol/L, low detection limit of 4.0 nmol/L and satisfactory recoveries between 98.0% and 102.8%. (c) 2025BeijingAcademyofFoodSciences.Publishingservic esbyElsevierb.V.onbehalfofKeAiCommunicationsCo.,Ltd.ThisisanopenaccessarticleundertheCCbY-NC-NDlicense(http://creativecommons.org/licenses/by-nc-nd/4.0/
摘要：
In this study, a preparation of hollow nanoscale tubular polysulfide Co 9 S 8 is reported, along with its use in building an electrochemical sensor that can detect dopamine (DA). Utilizing electrochemically reduced graphene oxide (ErGO) as a substrate, the Co 9 S 8 -ErGO/GCE sensor was made by attaching Co 9 S 8 nanotubes to a glassy carbon electrode (GCE) surface. The use of ErGO in the sensor fabrication process not only improves the conductivity but also effectively prevents the aggregation of Co 9 S 8 . A large number of hollow Co 9 S 8 nanotubes are anchored on ErGO, providing more catalytic active sites for electrode reactions. The constructed sensor shows remarkable DA detection ability, with a notable rise in peak current, thanks to the synergistic action of Co 9 S 8 and ErGO. This sensor has a lower detection limit of 4.0 nM and a wide linear range of 0.01–0.1 µM, 0.1–2.0 µM, and 2.0–10 µM. It is also possible to quantify DA in actual samples using Co 9 S 8 -ErGO/GCE, meeting clinical requirements for reproducibility, selectivity and accuracy.
In this study, a preparation of hollow nanoscale tubular polysulfide Co 9 S 8 is reported, along with its use in building an electrochemical sensor that can detect dopamine (DA). Utilizing electrochemically reduced graphene oxide (ErGO) as a substrate, the Co 9 S 8 -ErGO/GCE sensor was made by attaching Co 9 S 8 nanotubes to a glassy carbon electrode (GCE) surface. The use of ErGO in the sensor fabrication process not only improves the conductivity but also effectively prevents the aggregation of Co 9 S 8 . A large number of hollow Co 9 S 8 nanotubes are anchored on ErGO, providing more catalytic active sites for electrode reactions. The constructed sensor shows remarkable DA detection ability, with a notable rise in peak current, thanks to the synergistic action of Co 9 S 8 and ErGO. This sensor has a lower detection limit of 4.0 nM and a wide linear range of 0.01–0.1 µM, 0.1–2.0 µM, and 2.0–10 µM. It is also possible to quantify DA in actual samples using Co 9 S 8 -ErGO/GCE, meeting clinical requirements for reproducibility, selectivity and accuracy.
作者机构：
[Liu, B; Wang, Cheng-Yong; Zhang, Fu-Xing; Xu, Zhi-Feng; Liu, Bang; Wang, Zhi-Qiang; Yu, Jiang-Xi; Tang, Jie] Hengyang Normal Univ, Coll Hunan Prov, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov,Key Lab Or, Hengyang 421008, Peoples R China.
通讯机构：
[Liu, B ] H;Hengyang Normal Univ, Coll Hunan Prov, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov,Key Lab Or, Hengyang 421008, Peoples R China.
摘要：
Integrating fluorine into heterocyclic structures via cyclization reactions under metal-free conditions is attractive for organic synthesis. Herein, we describe solvent dependent fluorinative cyclizations of o -hydroxyarylenaminones, which were promoted by H 2 O and NFSI under metal-free conditions, to furnish 2,3-substituted chromanones. Di- and monofluorinated 2-hydroxyl chromanones could be achieved selectively in a THF–H 2 O or EtOH–H 2 O system at ambient temperature under an air atmosphere.
Integrating fluorine into heterocyclic structures via cyclization reactions under metal-free conditions is attractive for organic synthesis. Herein, we describe solvent dependent fluorinative cyclizations of o -hydroxyarylenaminones, which were promoted by H 2 O and NFSI under metal-free conditions, to furnish 2,3-substituted chromanones. Di- and monofluorinated 2-hydroxyl chromanones could be achieved selectively in a THF–H 2 O or EtOH–H 2 O system at ambient temperature under an air atmosphere.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2025年90(5):2022-2035 ISSN：0022-3263
通讯作者：
Xu, L;Wang, GW
作者机构：
[Huang, Xiao-Man; Xu, Liang; Liang, Si-Si; Zhou, Qian; Wu, Pei-Xi; Shu, Meng-Ping; Xu, L; Zhu, Xiao-Ming] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat Hunan Prov Coll, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Hunan, Peoples R China.;[Wang, Guan-Wu] Univ Sci & Technol China, Dept Chem, Hefei 230026, Anhui, Peoples R China.;[Wang, Guan-Wu] Anhui Normal Univ, Key Lab Funct Mol Solids, Anhui Lab Mol Based Mat, Minist Educ, Wuhu 241002, Anhui, Peoples R China.;[Wang, Guan-Wu] Anhui Normal Univ, Sch Chem & Mat Sci, Wuhu 241002, Anhui, Peoples R China.
通讯机构：
[Wang, GW ] U;[Xu, L ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat Hunan Prov Coll, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Hunan, Peoples R China.;Univ Sci & Technol China, Dept Chem, Hefei 230026, Anhui, Peoples R China.;Anhui Normal Univ, Key Lab Funct Mol Solids, Anhui Lab Mol Based Mat, Minist Educ, Wuhu 241002, Anhui, Peoples R China.
摘要：
The synthesis of perfluoroalkylated fullerenes (PFAFs) holds significant importance due to their enhanced molecular stability, increased lipophilicity, and high electron affinity. Herein, we report a copper-catalyzed multicomponent reaction conducted under aerobic conditions, which enables the production of highly soluble PFAFs with half-wave reduction potentials similar to those of C 60 . Furthermore, the challenges posed by C–F coupling in carbon signal assignment were addressed through fluorine-decoupled carbon spectroscopy, facilitating precise structural characterization of the perfluoroalkyl moieties.
The synthesis of perfluoroalkylated fullerenes (PFAFs) holds significant importance due to their enhanced molecular stability, increased lipophilicity, and high electron affinity. Herein, we report a copper-catalyzed multicomponent reaction conducted under aerobic conditions, which enables the production of highly soluble PFAFs with half-wave reduction potentials similar to those of C 60 . Furthermore, the challenges posed by C–F coupling in carbon signal assignment were addressed through fluorine-decoupled carbon spectroscopy, facilitating precise structural characterization of the perfluoroalkyl moieties.
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作者机构：
[Jia-Min Hu; Wen-Xia Su; Wei-Min Qin; Zhixuan Wu; Hanqin Zou; Zhiqin Ruan] School of Chemistry, South China Normal University, Guangzhou, 510006, People's Republic of China;[Zhongliang Li] Key Laboratory of Functional Metal-Organic Compounds of Hunan Province, College of Chemistry and Material Science, Hengyang Normal University, Hengyang, 421008, People's Republic of China;[Yue-Peng Cai] School of Chemistry, South China Normal University, Guangzhou, 510006, People's Republic of China. caiyp@scnu.edu.cn;[Yue-Peng Cai] Guangzhou Key Laboratory of Energy Conversion and Energy Storage Materials, Guangzhou, 510006, People's Republic of China. caiyp@scnu.edu.cn;[Kang Li] School of Chemistry, South China Normal University, Guangzhou, 510006, People's Republic of China. likang5@m.scnu.edu.cn
通讯机构：
[Cai, Yue-Peng; Zheng, Qifeng; Li, Kang] S;School of Chemistry, South China Normal University, Guangzhou, 510006, People's Republic of China.;Guangzhou Key Laboratory of Energy Conversion and Energy Storage Materials, Guangzhou, 510006, People's Republic of China.;School of Chemistry, South China Normal University, Guangzhou, 510006, People's Republic of China. qifeng.;Guangzhou Key Laboratory of Energy Conversion and Energy Storage Materials, Guangzhou, 510006, People's Republic of China. qifeng.
关键词：
Cavity-induced anion-trapping;Homogeneous Li+ flux;Lithium metal battery;Porous organic cage;Quasi-solid-state electrolyte
摘要：
Porous organic cages (POCs) with permanent porosity and excellent host-guest property hold great potentials in regulating ion transport behavior, yet their feasibility as solid-state electrolytes has never been testified in a practical battery. Herein, we design and fabricate a quasi-solid-state electrolyte (QSSE) based on a POC to enable the stable operation of Li-metal batteries (LMBs). Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC, the resulting POC-based QSSE exhibits a high Li(+) transference number of 0.67 and a high ionic conductivity of 1.25 × 10(-4) S cm(-1) with a low activation energy of 0.17eV. These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000h. As a proof of concept, the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85% capacity retention after 1000 cycles. Therefore, our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems, such as Na and K batteries.
作者机构：
[He, Ting; Xu, Dahai; Zhang, Xinjie; Dai, Haizhong; Ouyang, Xiaoping] Xiangtan Univ, Sch Mat Sci & Engn, Xiangtan 411105, Hunan, Peoples R China.;[Liu, Yang; Zhang, Yi] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Chen, Yang] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Pan, Dingjie; Chen, Shaowei; Chen, SW] Univ Calif Santa Cruz, Dept Chem & Biochem, 1156 High St, Santa Cruz, CA 95064 USA.
通讯机构：
[Chen, SW ] U;[He, T; Ouyang, XP ] X;Xiangtan Univ, Sch Mat Sci & Engn, Xiangtan 411105, Hunan, Peoples R China.;Univ Calif Santa Cruz, Dept Chem & Biochem, 1156 High St, Santa Cruz, CA 95064 USA.
关键词：
Fe single atom;Ru nanocluster;Trifunctional electrocatalyst;Water splitting;Zinc-air battery
摘要：
Design and engineering of high-performance electrocatalysts is of significance for the development of integrated electrochemical energy technologies. Herein, N-doped carbon aerogels doped with Fe single atoms and adjacent Ru nanoclusters are prepared by two-step pyrolysis of a biomass hydrogel precursor. The obtained NCA/FeRu composites show an exceptional trifunctional activity towards the oxygen reduction reaction (ORR, half-wave potential +0.92 V), oxygen evolution reaction (OER, +275 mV overpotential at 10 mA cm −2 ) and hydrogel evolution reaction (HER, −7 mV overpotential at 10 mA cm −2 ), markedly better than those of relevant catalysts reported in the literature. First-principles calculations show that the Ru nanoclusters facilitate the *OH desorption for ORR and the formation of O−O bonds for OER on the FeN 4 sites, and the Ru clusters are primarily responsible for the high HER activity. Such a unique property can be exploited for the development of an integrated device for zinc-air battery-powered water splitting.
Design and engineering of high-performance electrocatalysts is of significance for the development of integrated electrochemical energy technologies. Herein, N-doped carbon aerogels doped with Fe single atoms and adjacent Ru nanoclusters are prepared by two-step pyrolysis of a biomass hydrogel precursor. The obtained NCA/FeRu composites show an exceptional trifunctional activity towards the oxygen reduction reaction (ORR, half-wave potential +0.92 V), oxygen evolution reaction (OER, +275 mV overpotential at 10 mA cm −2 ) and hydrogel evolution reaction (HER, −7 mV overpotential at 10 mA cm −2 ), markedly better than those of relevant catalysts reported in the literature. First-principles calculations show that the Ru nanoclusters facilitate the *OH desorption for ORR and the formation of O−O bonds for OER on the FeN 4 sites, and the Ru clusters are primarily responsible for the high HER activity. Such a unique property can be exploited for the development of an integrated device for zinc-air battery-powered water splitting.
作者机构：
[Ren, Jun; Yang, Sufang; Yang, Chunming; Liang, Yun; Xiang, Qian] Hunan Normal Univ, Natl & Local Joint Engn Lab New Petro Chem Mat & F, Changsha 410081, Peoples R China.;[Ren, Jun; Yang, Sufang; Yang, Chunming; Liang, Yun; Xiang, Qian] Hunan Normal Univ, Coll Chem & Chem Engn, Key Lab Chem Biol & Tradit Chinese Med Res, Minist Educ China, Changsha 410081, Peoples R China.;[Liu, Jinlong; Qian, Dong] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Li, Junhua] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Chem Sensing & Catalysis, Hengyang 421008, Peoples R China.;[Waterhouse, Geoffrey I. N.; Waterhouse, GIN] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构：
[Qian, D ] C;[Yang, CM ] H;[Waterhouse, GIN ] U;Hunan Normal Univ, Natl & Local Joint Engn Lab New Petro Chem Mat & F, Changsha 410081, Peoples R China.;Hunan Normal Univ, Coll Chem & Chem Engn, Key Lab Chem Biol & Tradit Chinese Med Res, Minist Educ China, Changsha 410081, Peoples R China.
摘要：
Advanced electrode materials with simple manufacturing processes and wide voltage windows are needed for the commercialization of high energy density supercapacitors. Herein, a facile method is presented for fabricating self-supporting anodes and cathodes for quasi-solid-state asymmetric supercapacitors (QASCs) by hydrothermally reacting 2-thiobarbituric acid (TBA) with Fe foam (IF) and Co foam (CF), yielding FeTBA 4 /FeOOH/IF and Co 9 S 8 /CF electrodes, respectively. Due to the perfect match between the two electrodes, the redox-active TBA ligands in FeTBA 4 , the 2D ultrathin nanosheet structure of FeTBA 4 /FeOOH/IF, and multiple pairs of reversible redox reactions for suppressing water splitting, the configured Co 9 S 8 /CF//FeTBA 4 /FeOOH/IF QASC device delivers outstanding performance. The device possesses a wide operating voltage window of 1.6 V, leading to a high energy density of 82.64 Wh kg −1 at 486.38 W kg −1 and an equally impressive 35.36 Wh kg −1 at 4595.92 W kg −1 . Furthermore, a 98.5% capacitance retention is realized after 10000 charging–discharging cycles. Impressively, density functional theory (DFT) calculations reveal the unique pseudocapacitive reactions on the surface of Co 9 S 8 /CF and FeTBA 4 /FeOOH/IF electrodes. Importantly, this work guides the development of high-energy-density supercapacitors via the matching of electrodes and the use of redox-active complex electrodes.
摘要：
Esterification reactions are crucial in industries such as chemicals, fragrances, and pharmaceuticals but often face limitations due to high reversibility and low reactivity, leading to restricted yields. In this work, an electrified esterification pathway utilizing a Joule-heated interfacial catalysis (JIC) system is proposed, where a hydrophilic, sulfonic acid-functionalized covalent organic framework grown on carbon felt (COF─SO(3)H@CF) acts as the interfacial catalyst, and the carbon felt serves as the electric heat source. This approach achieves an acetic acid conversion of 80.5% at a heating power density of 0.49Wcm(-3), without additional reagents by vaporizing reaction products, surpassing the theoretical equilibrium limit of 62.5% by 1.29 times. Comprehensive analysis indicates that the intimate contact between the electric heat source and the COF─SO(3)H catalyst enables efficient, localized Joule heating directly at catalytic sites, minimizing thermal losses and allowing precise control over reaction interfaces. This finding demonstrates that this JIC system not only enhances esterification efficiency but may also offer a sustainable, energy-efficient pathway for high-yield chemical processes.
作者机构：
[Wang, Wei; He, Zhenhu; Liao, Yacong; Chen, Juan] Cent South Univ, Xiangya Hosp 3, Dept Radiol, Changsha 410008, Peoples R China.;[Tang, Siping; Lin, Xiaoping; Chen, Wen; Chen, W] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421001, Peoples R China.
通讯机构：
[Wang, W ] C;[Chen, W ] H;Cent South Univ, Xiangya Hosp 3, Dept Radiol, Changsha 410008, Peoples R China.;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421001, Peoples R China.
摘要：
Nucleus is the largest and most important organelle within eukaryotic cells, containing most of the cell’s genetic material, DNA. It serves as the central hub for genetic regulation and metabolism, making it an ideal target for subcellular drug delivery. The development of nucleus-targeted photosensitizers allows for the rapid and effective destruction of critical components such as DNA within the nucleus. This achieves the goal of efficiently eliminating cancer cells. However, most organic molecules, including photosensitizers, cannot penetrate the nuclear membrane, making the design and synthesis of nucleus-targeted photosensitizers both significant and challenging. The authors have designed and synthesized a nucleus-targeted activatable photosensitive probe (CMT-I). In vitro spectral analyses demonstrate that CMT-I is specifically activated by ct-DNA, significantly enhancing fluorescence-a 49-fold increase is observed upon binding. Furthermore, under 590 nm light irradiation, CMT-I effectively generates 1O2. Molecular docking show that CMT-I selectively binds to DNA through hydrogen bonds and ᴨ-ᴨ conjugation. RNA sequencing experiments reveal that photodynamic therapy activates immunity within tumor cells, triggering an adaptive immune response. In vivo therapeutic experiments further verify the enhanced anti-tumor immunity of CMT-I, which is crucial for effectively eliminating immunologically cold tumors and highlights the potential of DNA-targeted photodynamic therapy in precise cancer treatment.
Nucleus is the largest and most important organelle within eukaryotic cells, containing most of the cell’s genetic material, DNA. It serves as the central hub for genetic regulation and metabolism, making it an ideal target for subcellular drug delivery. The development of nucleus-targeted photosensitizers allows for the rapid and effective destruction of critical components such as DNA within the nucleus. This achieves the goal of efficiently eliminating cancer cells. However, most organic molecules, including photosensitizers, cannot penetrate the nuclear membrane, making the design and synthesis of nucleus-targeted photosensitizers both significant and challenging. The authors have designed and synthesized a nucleus-targeted activatable photosensitive probe (CMT-I). In vitro spectral analyses demonstrate that CMT-I is specifically activated by ct-DNA, significantly enhancing fluorescence-a 49-fold increase is observed upon binding. Furthermore, under 590 nm light irradiation, CMT-I effectively generates 1O2. Molecular docking show that CMT-I selectively binds to DNA through hydrogen bonds and ᴨ-ᴨ conjugation. RNA sequencing experiments reveal that photodynamic therapy activates immunity within tumor cells, triggering an adaptive immune response. In vivo therapeutic experiments further verify the enhanced anti-tumor immunity of CMT-I, which is crucial for effectively eliminating immunologically cold tumors and highlights the potential of DNA-targeted photodynamic therapy in precise cancer treatment.
作者机构：
[Zhu, Haihong; Chen, Shoushun; Chen, SS] Lanzhou Univ, Coll Chem & Chem Engn, Lanzhou Magnet Resonance Ctr, Frontiers Sci Ctr Rare Isotopes, Lanzhou 730000, Peoples R China.;[Zhang, Zelin; Lei, Dongsheng; Lei, DS] Lanzhou Univ, Electron Microscopy Ctr, Sch Phys Sci & Technol, Lanzhou 730000, Peoples R China.;[Zheng, Anmin; Chen, Wei] Chinese Acad Sci, Innovat Acad Precis Measurement Sci & Technol, Wuhan 430071, Peoples R China.;[Huang, Yining; Chen, Mansheng; Lucier, Bryan E. G.; Zhang, Wanli] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada.;[Chen, Mansheng] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat, Hengyang 421008, Hunan, Peoples R China.
通讯机构：
[Chen, SS ; Lei, DS ] L;[Huang, YN ] U;Lanzhou Univ, Coll Chem & Chem Engn, Lanzhou Magnet Resonance Ctr, Frontiers Sci Ctr Rare Isotopes, Lanzhou 730000, Peoples R China.;Lanzhou Univ, Electron Microscopy Ctr, Sch Phys Sci & Technol, Lanzhou 730000, Peoples R China.;Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada.
摘要：
Metal-organic frameworks (MOFs) are a class of porous materials that are of topical interest for their utility in water-related applications. Nevertheless, molecular-level insight into water-MOF interactions and MOF hydrolytic reactivity remains understudied. Herein, we report two hydrolytic pathways leading to either structural stability or framework decomposition of a MOF (ZnMOF-1). The two distinct ZnMOF-1 water reaction pathways are linked to the diffusion rate of incorporated guest dimethylformamide (DMF) molecules: slow diffusion of DMF triggers evolution of the initial MOF into a water-stable MOF product exhibiting enhanced water adsorption, while fast exchange of DMF with water leads to decomposition. The starting MOF, three intermediates from the water reaction pathways and the final stable MOF have been characterized. The documentation of two distinct pathways counters the stereotype that water exposure always leads to destruction or degradation of water-sensitive MOFs, and demonstrates that water-stable MOFs with improved adsorption properties can be prepared via controlled solvent-triggered structural rearrangement. Interactions between metal-organic frameworks (MOFs) and water are difficult to predict. Here, the authors report a Zn MOF follows two pathways upon water exposure. Characterization of both routes has revealed insights for future rational design.
作者机构：
[Jiang Yifan; He Lifang; Zhang Fuxing; Liu Zhihui; Qing Jingjing; He Fan; Tan Mengting; Zhu Xiaoming; Hou Shuaipeng; Liu Ya] Hengyang Normal Univ, Dept Chem & Mat Sci,Hunan Prov Key Lab Funct Met, Hunan Engn Res Ctr Monitoring & Treatment Heavy M, Coll Hunan Prov,Key Lab Organometall New Mat, Hengyang 421008, Hunan, Peoples R China.
通讯机构：
[Zhang, FX ] H;Hengyang Normal Univ, Dept Chem & Mat Sci,Hunan Prov Key Lab Funct Met, Hunan Engn Res Ctr Monitoring & Treatment Heavy M, Coll Hunan Prov,Key Lab Organometall New Mat, Hengyang 421008, Hunan, Peoples R China.
作者机构：
[Liu, Qin; He, Yingjian; Liu, Jinlong; Qian, Dong; Chen, Xiangxiong; Wang, Bowen; Luo, Ziyu; Liu, JL; Zhang, Xinxin] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Chen, Xiangxiong] Yoening Tianci Min Changsha Technol Ctr, Changsha 410083, Peoples R China.;[V. Kennedy, John] GNS Sci, Natl Isotope Ctr, POB 30368, Lower Hutt 5010, New Zealand.;[Li, Junhua] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Waterhouse, Geoffrey I. N.; Waterhouse, GIN] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构：
[Qian, D; Liu, JL ] C;[Waterhouse, GIN ] U;Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
关键词：
Electrochemical reconstruction;CoMoO4-based catalyst;Phosphorization;Heterojunction;Overall water splitting
摘要：
Phosphorization of molybdates has been shown to promote hydrogen evolution reaction (HER) activity but is usually detrimental to oxygen evolution reaction (OER) activity, frustrating efforts to create bifunctional HER/OER electrocatalysts. Herein, we show that Fe2O3-modulated P-doped CoMoO4 on nickel foam (Fe-P-CMO) is an excellent bifunctional HER/OER electrocatalyst in alkaline media, with the adverse effect of phosphorization on the OER activity of CoMoO4 being countered via Fe2O3 introduction. An alkaline splitting electrolyser assembled directly using the self-supporting Fe-P-CMO electrode possessed outstanding long-term durability with ultralow cell voltages of 1.48 and 1.59 V required to achieve current densities of 10 and 100 mA cm−2, respectively. Detailed experimental investigations showed that during HER, P-doped CoMoO4 in Fe-P-CMO underwent surface reconstruction with the in-situ formation of Co(OH)2 on the P-CoMoO4 (Co(OH)2/P-CoMoO4). During OER, P-doped CoMoO4 was deeply reconstructed to CoOOH with the complete dissolution of Mo, leading to the in-situ formation of Fe2O3/CoOOH heterojunctions.
摘要：
Metal single-atom catalysts offer the dual advantages of high electrochemical activity and near 100 % metal atom utilization, leading to their potential use in low-cost electrochemical sensor development. Herein, a novel electrocatalyst comprising atomically-dispersed Mn on B,N co-doped bamboo-derived carbon (MnSAs-BN-BC) was synthesized via a facile pyrolysis procedure. A high dispersion of Mn single atoms in MnSAs-BN-BC was confirmed by aberration-corrected transmission electron microscopy and elemental mapping. The Mn loading in the MnSAs-BN-BC determined by inductively coupled plasma mass spectrometry was 255 mg kg-1. MnSAs-BNBC displayed outstanding electrocatalytic performance for levodopa (LD) oxidation, allowing a robust electrochemical sensing platform for LD detection to be established. The MnSAs-BN-BC/GCE sensing platform offered a wide LD detection range (concentrations from 2 to 683 mu M) and a very low limit of detection (LOD) of 0.45 mu M, outperforming almost all electrochemical sensors reported to date for LD sensing. The MnSAs-BN-BC/GCE platform also featured outstanding repeatability, reproducibility, selectivity, and stability. The as-developed sensing platform was successfully applied to LD quantification in commercial tablets with satisfactory recoveries (85.2-102.4 %), with the analytical precision of method validated against a traditional UV-vis spectrophotometry method. Density functional theory (DFT) calculations showed that Mn single atom sites lowered the reaction energy barrier for LD oxidation, with the favorable d-band center position of Mn single atom sites in MnSAs-BN-BC contributing to the enhanced LD sensing performance. This work encourages the use of singleatom metal catalysts in design of high-performance electrochemical sensors for the rapid detection of LD.
