通讯机构：
[Xiang, Jia-Chen] S;[Ma, Jin-Tian] K;School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
摘要：
We herein report an efficient synthesis of 2-aroyl-3-arylquinolines from phenylalanines and anilines. The mechanism involves I(2)-mediated Strecker degradation enabled catabolism and reconstruction of amino acids and a cascade aniline-assisted annulation. Both DMSO and water act as oxygen sources in this convenient protocol.
摘要：
Circularly polarized luminescence (CPL) materials have attracted considerable attention for their promising applications in encryption, chiral sensing, and three-dimensional (3D) displays. However, the preparation of high-efficiency, pure blue CPL materials remains challenging. In this study, we reported an enantiomeric pair of triangle copper(I) clusters (R/S-Cu(3)) rigidified by employing chiral N-heterocyclic carbene (NHC) ligands with two pyridine-functionalized wingtips. These chiral clusters emitted pure blue phosphorescence that overlapped with that of the commercial blue phosphor having Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.14, 0.10), and the films exhibited an unprecedented photoluminescence quantum yield (PLQY) of ∼70.0%. Additionally, the solutions showed very bright circularly polarized phosphorescence (CPP) with a dissymmetry factor of ±2.1 × 10(-3). The excellent solubility and photostability endowed these pure-blue-emitting chiral clusters with promising applications as pure blue CPP inks for 3D printing white objects, such as precise-atomic-enlarged models of metal clusters and a lovely white stereoscopic "rabbit". The intricate mechanism underlying blue phosphorescence in this small cluster and across various states is elucidated through a comprehensive approach that integrates thorough analysis of luminescence properties, controlled experiments, and theoretical calculations. For the first time, we propose that the dominant high-energy emission center is constituted by delocalized hybrid orbitals over multiple atomic centers, encompassing both the metal and the coordinated atoms. This challenges stereotypical assumptions that the cluster center solely supports low-energy emissions. This work expands the currently limited range of CPP functional materials and provides a new direction for CPP applications involving NHC-stabilized metal clusters.
摘要：
The synthesis of chiral endocyclic allenes, especially the medium-sized ones, remains a challenge in allene chemistry due to unfavorable tension and difficult stereocontrol. Herein, an efficient protocol for the construction of chiral nine-membered endocyclic allenes via palladium-catalyzed asymmetric cycloaddition/Cope rearrangement relay of vinyl carbonates with activated enynes is highlighted. This process provides rapid access to a variety of chiral nine-membered endocyclic allenes in good yields with excellent enantioselectivities. In particular, a chiral P,S-ligand shows good performance on stereoinduction, generating central and axial chirality in a single transformation, which is rationalized by DFT calculations and by a proposed transition state.
1 Introduction
2 Pd-Catalyzed Asymmetric Cycloaddition/Cope Rearrangement Relay
3 Plausible Mechanism and Stereochemical Outcome
4 Conclusion and Outlook
作者机构：
[Lu, Liang-Qiu; Rao, Li; Wang, Bao-Cheng; Qu, Bao-Le; Xiao, Wen-Jing; Xiong, Fen-Ya] Cent China Normal Univ, Minist Educ, CCNU Ottawa Joint Res Ctr, Coll Chem,Key Lab Pesticide & Chem Biol, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Tan, Ying; Fang, Kai-Xin; Feng, Ying] Tsinghua Univ, Tsinghua Shenzhen Int Grad Sch, State Key Lab Chem Oncogen, Key Lab Chem Biol, Shenzhen, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
通讯机构：
[Prof. Ying Tan] S;[Prof. Liang-Qiu Lu] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, 430079 Wuhan, Hubei, P. R. China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, 730000 Lanzhou, P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, 453007 Xinxiang, Henan, China<&wdkj&>State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Biology, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, P. R. China
关键词：
Antitumor Activity;Aza-Ortho-Quinone Methide;Aza-Sulfur Ylide;Azaheterocycle;Transition Metal Catalysis
摘要：
Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially the new reaction modes. Herein, we disclosed an unprecedented dearomatization process of metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, we accomplished three sequential dearomatization-rearomatization reactions of benzimidazolines with aza-sulfur ylides, enabling the divergent synthesis of bis-nitrogen heterocycles with high efficiency and flexibility. Moreover, experimental and theoretical studies were performed to explain the proposed mechanisms and observed selectivity. Further cellular evaluation of the dibenzodiazepine products identified a hit compound for new antitumor drugs.
作者机构：
[Zhang, Zhi-Han; Lu, Liang-Qiu; Yu, Xu-Hui; Xiao, Wen-Jing; Shi, De-Qing] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China.
通讯机构：
[De-Qing Shi] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
摘要：
The asymmetric Michael addition of phosphorus nucleophiles to electron-deficient alkenes is one of the most direct and atom-economical methods to provide chiral organophosphorus compounds with high efficiency in recent years. Herein, we report a cobalt-catalyzed imidazolyl-directed asymmetric phospha-Michael-type reaction of diarylphosphine oxides with electron-deficient alkenes for synthesizing chiral organophosphorus compounds in moderate to good yields and good to excellent enantioselectivities (25 examples, up to 99% yield, and 99% ee). This protocol features broad substrate scope, good functional group tolerance, and mild conditions as well as avoids the release of massive metal wastes and the use of noble transition metal catalysts. The excellent enantioselectivity of the phospha-Michael reaction can be due to the adoption of a novel chiral N4-ligand. Furthermore, the DFT calculation indicates that the bulky 2,4,6-(i-Pr)3C6H2 group of the ligand induces large steric hindrance which blocks the nucleophilic attack from the Si-face.
作者机构：
[Lu, Liang-Qiu; Rao, Li; Zhou, Zheng-Xin; Xiao, Wen-Jing; Li, Yu-Jie; Liu, Xiao-Peng; Xiao, Yu-Qing] Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol, Minist Educ,Coll Chem, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Li, Miao-Miao] Zhengzhou Univ, Henan Inst Adv Technol, Div Mol Catalysis & Synth, Zhengzhou 45000, Peoples R China.;[Cao, Meng-Yue; Liu, Xiao-Peng] Westlake Univ, Sch Sci, Hangzhou 310024, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
通讯机构：
[Dr. Li Rao; Prof. Liang-Qiu Lu] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000 P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China<&wdkj&>CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China
摘要：
Ring-opening transformations of donor-acceptor (D-A) cyclopropanes enable the rapid assembly of complex molecules. However, the enantioselective formation of chiral quaternary stereocenters using substrates bearing two different acceptors remains a challenge. Herein, we describe the first palladium-catalyzed highly diastereo- and enantioselective (3+2) cycloaddition of vinyl cyclopropanes bearing two different electron-withdrawing groups, a subset of D-A cyclopropanes. The key to the success of this reaction is the remote stereoinduction through hydrogen bond from chiral ligands, which thereby addressed the aforementioned challenge. A variety of chiral five-membered heterocycles were produced in good yields and with high stereoselectivity (up to 99 % yields, 99 : 1 er and >19 : 1 dr). In-depth mechanistic investigations, including control experiments and theoretical calculations, revealed the origin of the stereoselectivity and the importance of H-bonding in stereocontrol.
作者机构：
[Xu, Yuling; Sun, Yao; Li, Chonglu; Yang, Jingfang] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Key Lab Pesticides & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.;[An, Jusung; Kim, Jong Seung] Korea Univ, Dept Chem, Seoul 02841, South Korea.;[Ma, Xin] Hubei Univ, Key Lab Synth & Applicat Organ Funct Mol, Minist Educ, Wuhan 430062, Peoples R China.;[Luo, Lishi] Hunan Univ, State Key Lab Chemo Biosensing & Chemometr, Changsha 410082, Peoples R China.;[Deng, Yun] Jianghan Univ, Key Lab Optoelect Chem Mat & Devices, Minist Educ, Wuhan 430056, Peoples R China.
通讯机构：
[Jong Seung Kim] D;[Yao Sun] K;Department of Chemistry, Korea University, Seoul, Republic of Korea<&wdkj&>Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan, China
摘要：
Although metal-based chemical agents have demonstrated promising bacteriostatic effects in phototherapy, their short excitation/emission wavelengths and inadequate phototherapy efficiencies make their application in vivo difficult. We therefore synthesized a novel Pt(II) metallacycle (Pt1110) that can be activated with a 980 nm laser for photodiagnosis/treatment in deep tissue. We found that Pt1110 significantly improved photothermal conversion (95% improvement) and O-1(2) generation (phi(& UDelta;) 75% increase) compared to the ligand itself 1 and was well capable of light-induced sterilization under safe laser irradiation (0.72 W/cm(2)). In addition, Pt1110 has little to no toxicity to cells. After incorporated into liposome, Pt1110 NPs was effective in wound healing in infection and keratitis models upon laser irradiation, which was accurately observed by NIR-II fluorescence imaging. This novel metal-coordinated supramolecular material has a potential to become a universal platform for phototherapy in deep tissue.
作者：
Song, Yongjun;Yu, Renyou;Meng, Xianwen;He, Lei
期刊：
Dyes and Pigments,2023年208:110876 ISSN：0143-7208
通讯作者：
He, Lei(helei@ccnu.edu.cn)
作者机构：
[Song, Yongjun; Meng, Xianwen; He, Lei; Yu, Renyou] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ,Hubei Int Sci & Technol Cooperat Base, Wuhan 430079, Peoples R China.;[He, Lei] South China Univ Technol, State Key Lab Luminescent Mat & Devices, Guangzhou 510640, Peoples R China.
通讯机构：
[Lei He] K;Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, College of Chemistry, Central China Normal University, Wuhan, 430079, PR China<&wdkj&>State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, PR China
作者：
Gao, Yang-Yang;Yang, Wei-Cheng;Ashby Jr, Charles R.;Hao, Ge-Fei
期刊：
Drug Resistance Updates,2023年67:100934 ISSN：1368-7646
通讯作者：
Charles R. Ashby
作者机构：
[Yang, Wei-Cheng; Gao, Yang-Yang; Hao, Ge-Fei] Guizhou Univ, Ctr Res & Dev Fine Chem, Natl Key Lab Green Pesticide, Key Lab Green Pesticide & Agr Bioengn,Minist Educ, Guiyang 550025, Peoples R China.;[Hao, Ge-Fei] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Ashby Jr, Charles R.] St Johns Univ, Dept Pharmaceut Sci, New York, NY 10003 USA.
通讯机构：
[Charles R. Ashby] D;Department of Pharmaceutical Sciences, St. John’s University, New York, NY, USA
关键词：
Drug resistance;Cryptic binding sites;Resistance management
摘要：
The emergence of drug resistance is a primary obstacle for successful chemotherapy. Drugs that target cryptic binding sites (CBSs) represent a novel strategy for overcoming drug resistance. In this short communication, we explain and discuss how the discovery of CBSs and their inhibitors can overcome drug resistance.
期刊：
Drug Discovery Today,2023年:103546 ISSN：1359-6446
通讯作者：
Li, Qing X;Yang, Guang-Fu
作者机构：
[Yang, Jing-Fang; Yang, Guang-Fu; Wang, Meng-Yao; Wang, Di; Wang, Fan; Hao, Ge-Fei] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, PR China;[Yang, Jing-Fang; Yang, Guang-Fu; Wang, Meng-Yao; Wang, Di; Wang, Fan; Hao, Ge-Fei] International Joint Research Center for Intelligent Biosensor Technology and Health, Central China Normal University, Wuhan, 430079, PR China;[Yang, Jing-Fang] State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, PR China;[Zhou, Zhong-Shi] State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, PR China;[Hao, Ge-Fei] State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Research and Development Center for Fine Chemicals, Guizhou University, Guiyang 550025, PR China
通讯机构：
[Li, Qing X] D;[Yang, Guang-Fu] C;Department of Molecular Biosciences and Bioengineering, University of Hawaii at Manoa, Honolulu, HI 96822, USA. Electronic address:;Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, PR China. Electronic address:
摘要：
As major forces for modulating protein folding and molecular recognition, cation-π interactions are extensively identified in protein structures. They are even more competitive than hydrogen bonds in molecular recognition and, thus, are vital in numerous biological processes. In this review, we introduce the methods for the identification and quantification of cation-π interactions, provide insights into the characteristics of cation-π interactions in the natural state, and reveal their biological function together with our developed database (Cation-π Interaction in Protein Data Bank; CIPDB; http://chemyang.ccnu.edu.cn/ccb/database/CIPDB). This review lays the foundation for the in-depth study of cation-π interactions and will guide the use of molecular design for drug discovery. Teaser: We provide an overview of the cation-π interaction from its emergence to measurement and collection, along with a data set developed by us, which guides further research in biology and drug design.
摘要：
Pd/SSZ-13 has been proposed as a passive NOx adsorber (PNA) to effectively alleviate NOx emission during vehicle cold start. However, the chemical poisons which are derived from biodiesel and lubricant oil are challenging for the practical application of PNA technology. In this paper, Pd/SSZ-13 was poisoned by alkali/alkaline earth metals to investigate the effects of chemical poisons on the adsorption performance of Pd/SSZ-13. It was found that the alkali/alkaline earth metals led to the decrease of surface area and Brønsted acid sites of Pd/SSZ-13. Strikingly, the 27Al MAS NMR demonstrated that the alkali/alkaline earth metals could effectively prevent Pd/SSZ-13 from dealumination during hydrothermal aging treatment. The H2-TPR results showed that more than 70% of Pd2+ ions were lost in the Na- and K-impregnated Pd/SSZ-13, while almost complete loss of Pd2+ ions was observed in the Mg- and Ca-impregnated Pd/SSZ-13, which resulted in the deactivation of Pd/SSZ-13. Further, the DRIFTS results showed that Mg2+ and Ca2+ ions exhibited preferential substitution for Pd2+ ions, while Na+ and K+ ions preferentially replaced the H+ ions. This work provides insights into the effects of alkali/alkaline earth metals on Pd/SSZ-13, expecting to attract attention to design PNA materials with resistance to chemical poisons.
作者机构：
[Yuhua Zhu; Leyi Yang; Yarong Fang; Ji Yang; Xiaoping Chen; Juan Zheng; Shuhong Zhang; Wei Chen; Chuanqi Pan; Baojian Zhang; Xiaofeng Qiu; Yuhua Zhu Yuhua Zhu Yuhua Zhu; Leyi Yang Leyi Yang Leyi Yang; Yarong Fang Yarong Fang Yarong Fang; Ji Yang Ji Yang Ji Yang; Xiaoping Chen Xiaoping Chen Xiaoping Chen; Juan Zheng Juan Zheng Juan Zheng; Shuhong Zhang Shuhong Zhang Shuhong Zhang; Wei Chen Wei Chen Wei Chen; Chuanqi Pan Chuanqi Pan Chuanqi Pan; Baojian Zhang Baojian Zhang Baojian Zhang; Xiaofeng Qiu Xiaofeng Qiu Xiaofeng Qiu] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei, 430082 P. R. China;Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430082 P. R. China;[Jiami Ma; Jiami Ma Jiami Ma Jiami Ma] School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan, 430070 P. R. China;[Zhu Luo; Jinlong Wang; Yanbing Guo; Zhu Luo Zhu Luo Zhu Luo; Jinlong Wang Jinlong Wang Jinlong Wang; Yanbing Guo Yanbing Guo Yanbing Guo] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei, 430082 P. R. China<&wdkj&>Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430082 P. R. China
通讯机构：
[Yanbing Guo; Yanbing Guo Yanbing Guo Yanbing Guo] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei, 430082 P. R. China<&wdkj&>Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430082 P. R. China
摘要：
Catalytic ozone (O3) decomposition at high relative humidity (RH) remains a great challenge due to the catalysts poison and deactivation under high humidity. Here, we firstly elaborate the role of water activation and the corresponding mechanism of the promoted O3 decomposition over the three-dimensional monolithic molybdenum oxide/graphdiyne (MoO3/GDY) catalyst. The O3 decomposition over MoO3/GDY reaches up to 100 % under high humid condition (75 % RH) at room temperature, which is 4.0 times as high as that of dry conditions, significantly surpasses other carbon-based MoO3 materials(≤7.1 %). The sp-hybridized carbon in GDY donates electrons to MoO3 along the C−O−Mo bond, facilitating water activation to form hydroxyl species. As a result, hydroxyl species dissociated from water act as new active sites, promoting the adsorption of O3 and the generation of new intermediate species (hydroxyl ⋅OH and superoxo ⋅O2−), which significantly lowers the energy barriers of O3 decomposition (0.57 eV lower than dry conditions).
期刊：
ACS CHEMICAL BIOLOGY,2023年18(4):915-923 ISSN：1554-8929
通讯作者：
Jun Guo
作者机构：
[Zhang, Zhi-Ming; Zhang, Ru-Yan; Feng, Ran-Ran; Ding, Dong; Wen, Yu; Guo, Jun; Zhou, Shi-Hao] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Hubei Int Sci & Technol Cooperat Base Pesticide &, Wuhan 430079, Peoples R China.;[Wei, Hua-Wei] Jiangsu East Mab Biomed Technol Co Ltd, Nantong 226499, Peoples R China.
通讯机构：
[Jun Guo] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
Modification of antigens to improve their immunogenicity represents a promising direction for the development of protein vaccine. Here, we designed facilely prepared adjuvant-free vaccines in which the N-glycan of SARS-CoV-2 receptor-binding domain (RBD) glycoprotein was oxidized by sodium periodate. This strategy only minimally modifies the glycans and does not interfere with the epitope peptides. The RBD glycoprotein oxidized by high concentrations of periodate (RBD(HO)) significantly enhanced antigen uptake mediated by scavenger receptors and promoted the activation of antigen-presenting cells. Without any external adjuvant, two doses of RBD(HO) elicited 324- and 27-fold increases in IgG antibody titers and neutralizing antibody titers, respectively, compared to the unmodified RBD antigen. Meanwhile, the RBD(HO) vaccine could cross-neutralize all of the SARS-CoV-2 variants of concern. In addition, RBD(HO) effectively enhanced cellular immune responses. This study provides a new insight for the development of adjuvant-free protein vaccines.
作者机构：
[Chen, Yuanxing; Xu, Wentao; Wen, Jing; Peng, Xiang; Hu, Liuyong; Xiao, Runshi] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Qin, Ying; Zhu, Chengzhou; Chen, Yuanxing; Gu, Wenling; Liu, Mingwang; Gu, WL; Xiao, Runshi; Tan, Rong] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Yu, Han] Hong Kong Univ Sci & Technol, Energy Inst, Guangdong Hong Kong Macao Joint Lab Optoelect & Ma, Dept Chem,Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China.;[Yu, Han] Hong Kong Univ Sci & Technol, Hong Kong Branch, Chinese Natl Engn Res Ctr Tissue Restorat & Recons, Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China.
通讯机构：
[Hu, LY ] W;[Gu, WL ] C;Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
The intelligent molecular design of organic semiconductors allows for the introduction of specific moieties with recognition functions, while the recognition reactions are largely overlooked for constructing an advanced photoelectrochemical sensor. For the first time, a photoelectrochemical sensing platform for urease detection based on organic semiconductor heterojunction (PM6‐Y6) is constructed benefiting from the selective chemical reactivity of its organic building blocks. Abstract Non‐fullerene acceptors (NFAs) are a crucial component of organic photovoltaics, and they have gained significant attention due to their outstanding photoelectric conversion efficiency. However, the recognition reactions of specific building blocks in NFAs are largely overlooked in the construction of photoelectrochemical (PEC) biosensing platforms. In this study, the potential of Y6, a prototype NFA, is explored to construct a sensitive PEC biosensor for monitoring urease activity due to the selective chemical reactivity of its organic building blocks. The resultant biosensor relies on the urease‐mediated enzymatic reaction, which produces OH− anions that act as a nucleophilic reagent for the linkage of C═C in the Y6 moiety. This results in the formation of Y6‐OH, which exhibits a depressive photoelectric response due to the destroyed conjugated structure and intramolecular charge transfer. As expected, a linear relationship is observed between the recession of photoelectric performance and the concentration of urease, with good sensitivity and selectivity. Furthermore, urease activity detection is also successfully realized in human saliva samples, suggesting the promising potential of NFA‐based PEC biosensors for clinical applications even in the absence of common biological recognition units.
通讯作者：
Prof. Liuyong Hu<&wdkj&>Prof. Wenling Gu<&wdkj&>Prof. Chengzhou Zhu<&wdkj&>Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu<&wdkj&>Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu<&wdkj&>Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu
作者机构：
[Mengzhen Xi; Zhichao Wu; Zhen Luo; Ling Ling; Weiqing Xu; Hengjia Wang; Qie Fang; Prof. Wenling Gu; Prof. Chengzhou Zhu; Mengzhen Xi Mengzhen Xi Mengzhen Xi; Zhichao Wu Zhichao Wu Zhichao Wu; Zhen Luo Zhen Luo Zhen Luo; Ling Ling Ling Ling Ling Ling; Weiqing Xu Weiqing Xu Weiqing Xu; Hengjia Wang Hengjia Wang Hengjia Wang; Qie Fang Qie Fang Qie Fang; Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China;[Prof. Liuyong Hu; Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu] Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China;[Runshi Xiao; Runshi Xiao Runshi Xiao Runshi Xiao] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China<&wdkj&>Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China
通讯机构：
[Prof. Liuyong Hu; Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu] H;[Prof. Wenling Gu; Prof. Chengzhou Zhu; Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] N;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China<&wdkj&>Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China
摘要：
In conventional luminol electrochemiluminescence (ECL) systems, hydrogen peroxide and dissolved oxygen are employed as typical co-reactants to produce reactive oxygen species (ROS) for efficient ECL emission. However, the self-decomposition of hydrogen peroxide and limited solubility of oxygen in water inevitably restrict the detection accuracy and luminous efficiency of luminol ECL system. Inspired by ROS-mediated ECL mechanism, for the first time, we used cobalt-iron layered double hydroxide as co-reaction accelerator to efficiently activate water to generate ROS for enhancing luminol emission. Experimental investigations verify the formation of hydroxyl and superoxide radicals in the process of electrochemical water oxidation, which subsequently react with luminol anion radicals to trigger strong ECL signals. Finally, the detection of alkaline phosphatase has been successfully achieved with impressive sensitivity and reproducibility for practical sample analysis.
摘要：
Accelerating the migration of interfacial carriers ina heterojunctionis of paramount importance for driving high-performance photoelectricresponses. However, the inferior contact area and large resistanceat the interface limit the eventual photoelectric performance. Herein,we fabricated an S-scheme heterojunction involving a 2D/2D dual-metalloporphyrinmetal-organic framework with metal-center-regulated CuTCPP-(Cu)/CuTCPP-(Fe)through electrostatic self-assembly. The ultrathin nanosheet-likearchitectures reduce the carrier migration distance, while the similarporphyrin backbones promote reasonable interface matching through pi-pi conjugation, thereby inhibiting the recombinationof photogenerated carriers. Furthermore, the metal-center-regulatedS-scheme band alignments create a giant built-in electric field, whichprovides a huge driving force for efficient carrier separation andmigration. Coupling with the biomimetic catalytic activity of CuTCPP-(Fe),the resultant heterojunction was utilized to construct photoelectrochemicaluric acid biosensors. This work provides a general strategy to enhancephotoelectric responses by engineering the interfacial structure ofheterojunctions.
作者机构：
[Zhang, Yu; Wen, Yating; Gu, Wenling; Xu, Weiqing; Wu, Yu; Su, Rina] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079, P.R. China;[Cai, Xiaoli; Zheng, Qihui; Huang, Yuteng] Department of Nutrition, Hygiene and Toxicology, School of Public Health, Medical College, Wuhan University of Science and Technology, Wuhan, 430065, P.R. China;[Hu, Liuyong] School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, 430205, P.R. China;[Zheng, Lirong; Cui, Xiaowen] Beijing Synchrotron Radiation Facility, Institute of High Energy Physics Department, Chinese Academy of Sciences Institution, Beijing, 100049, P.R. China;[Zhang, Shipeng] School of Materials Science and Engineering, Peking University, Beijing, 100871, P.R. China
通讯机构：
[Zhu, Chengzhou] N;[Guo, Shaojun] S;School of Materials Science and Engineering, Peking University, Beijing, 100871, P.R. China.;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079, P.R. China.
摘要：
Neurotoxicity of organophosphate compounds (OPs) can catastrophically cause nervous system injury by inhibiting acetylcholinesterase (AChE) expression. Although artificial systems have been developed for indirect neuroprotection, they are limited to dissociating P-O bonds for eliminating OPs. However, these systems have failed to overcome the deactivation of AChE. Herein, we report our finding that Al3+ is engineered onto the nodes of metal–organic framework to synthesize MOF-808-Al with enhanced Lewis acidity. The resultant MOF-808-Al efficiently mimics the catalytic behavior of AChE and has a self-defense ability to break the activity inhibition by OPs. Mechanism investigations elucidate that Al3+ Lewis acid sites with a strong polarization effect unite the highly electronegative –OH groups to form the enzyme-like catalytic center, resulting in superior substrate activation and nucleophilic attack ability with a 2.7-fold activity improvement. The multifunctional MOF-808-Al, which has satisfactory biosafety, is efficient in reducing neurotoxic effects and preventing neuronal tissue damage. The neurotoxicity of organophosphate compounds damages nerve system by inhibiting acetylcholinesterase (AChE) expression, but it is difficult to overcome the deactivation of AChE. Here, the authors report the design of Lewis acid sites in metal-organic frameworks as AChE mimics for effective neuroprotection.
