Single-atom nanozymes with axial ligand-induced self-adaptive conformation in alkaline medium boost chemiluminescence

作     者：Zhen Luo Liliang Tian Hengjia Wang Zhichao Wu Xin Luo Xiaosi Wang Lei Jiao Xiaoqian Wei Ying Qin Lirong Zheng Liuyong Hu Wenling Gu Le Shi Chengzhou Zhu 

作者机构：Key Laboratory of Pesticides and Chemical Biology of Ministry of EducationInternational Joint Research Center for Intelligent Biosensing Technology and HealthCollege of ChemistryCentral China Normal UniversityWuhan 430079China State Key Laboratory of Electrical Insulation and Power EquipmentCentre of Nanomaterials for Renewable EnergySchool of Electrical EngineeringXi’an Jiaotong UniversityXi’an 710049China Beijing Synchrotron Radiation FacilityInstitute of High Energy PhysicsChinese Academy of SciencesBeijing 100049China Hubei Key Laboratory of Plasma Chemistry and Advanced MaterialsHubei Engineering Technology Research Center of Optoelectronic and New Energy MaterialsWuhan Institute of TechnologyWuhan 430205China Fujian Shuikou Power Generation Group Corp.Fuzhou 350000China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2023年第66卷第3期

页      面：904-912页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by the National Natural Science Foundation of China(22074049,22004042) the Natural Science Foundation of Hubei Province(2021CFB518) the Open Funds of the State Key Laboratory of Electroanalytical Chemistry(SKLEAC202102) the Fundamental Research Funds for the Central Universities(CCNU22JC006) the Program of Introducing Talents of Discipline to Universities of China(111 program,B17019) 

主　　题：single-atom nanozymes chemiluminescence hydrogen peroxide activation biosensing 

摘      要：Mimicking the structure of natural enzymes for designing advanced alternatives provides great opportunities to address the bottleneck of enzyme-involved chemiluminescence(CL). Herein, according to theoretical calculations, we found that an endogenous axial ligand of M-N-C single-atom nanozymes(SAzymes), originating from OH-spontaneously bonding to the metal center in an alkaline medium, can self-adaptively change its strength to facilitate intermediate steps. Furthermore, the lowest energy barrier of the rate-determining step and the strongest affinity and fastest electron transfer with luminol anion endow CoN-C with the highest peroxidase-like activity. Guided by the theoretical calculations, a series of M-N-C SAzymes(M=Fe, Co,Ni) were synthesized to boost CL, where Co-N-C SAzymes with superior catalytic activity and high selective generation of O_(2)·- were validated. As a proof-of-concept, Co-N-C SAzymes were employed for sensitive detection of acetylcholinesterase and organophosphorus pesticide.