组分可调的PdRh双金属纳米酶用于亚硝酸盐精准高效比色传感  

Component-tunable PdRh Bimetallic Nanozyme for Ultra-sensitive Colorimetric Detection of Nitrite

作　　者：唐玉玺 杨启 直鑫鹏 陈梦媛 刘思源 李嘉昌 刘梓洋 贾会敏[2] 仝玉萍 何伟伟[2] TANG Yuxi;YANG Qi;ZHI Xinpeng;CHEN Mengyuan;LIU Siyuan;LI Jiachang;LIU Ziyang;JIA Huimin;TONG Yuping;HE Weiwei(School of Materials Science and Engineering,North China University of Water Resources and Electric Power,Zhengzhou 450045,China;Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province,Institute of Surface Micro and Nano Materials,College of Chemical and Materials Engineering,Xuchang University,Xuchang 461000,China)

机构地区：[1]华北水利水电大学材料学院,郑州450045 [2]河南省微纳米能量储存与转换材料重点实验室,许昌学院化工与材料学院表面微纳米材料研究所,许昌461000

出　　处：《高等学校化学学报》2025年第1期243-251,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:62274141);河南省科技攻关项目(批准号:242102230074)资助.

摘　　要：采用无模板一锅水热法,通过调控钯(Pd)与铑(Rh)摩尔比,制备了系列PdRh双金属纳米酶(Pd_(3)Rh,PdRh和PdRh_(3)),并研究了其类过氧化物酶(POD-like)及类氧化酶(OXD-like)活性.结果表明,双金属纳米酶的催化活性比单金属纳米酶(Pd和Rh)更高,且表现出明显的组分依赖性.其中,PdRh_(3)和PdRh分别表现出最强的POD-like和OXD-like活性.酶促动力学分析表明,PdRh_(3)纳米酶以3,3',5,5'-四甲基联苯胺(TMB)和H_(2)O_(2)为底物的米氏常数(K_(m))分别为15.65和381.99μmol/L,对应的最大反应速率(v_(max))分别为8.40×10^(-8)和11.01×10^(-8) mol/(L·s).此外,PdRh_(3)纳米酶的POD-like活性表现出pH依赖性,在pH=5时活性最佳.在此条件下,开发了基于PdRh_(3)纳米酶的比色传感体系,根据445和652 nm处吸光度比值(A_(445nm)/A_(652nm))与亚硝酸根离子(NO_(2)^(-))浓度的线性关系,实现了对溶液中亚硝酸盐浓度的快速定量检测.结果表明,在pH=5的缓冲溶液和纯水中,该体系检出限分别为0.467和30.523μmol/L,且在多种盐离子干扰下特异性良好,在生物传感中具有较大应用潜力.A series of bimetallic nanozymes(Pd_(3)Rh,PdRh,PdRh_(3))was prepared using one-pot hydrothermal method by adjusting the ratio of palladium(Pd)to rhodium(Rh).The peroxidase-like(POD-like)and oxidase-like(OXD-like)activities of nanozymes were tested.The results showed that the catalytic activity of bimetallic nanozymes was significantly enhanced compared to that of single metallic nanozymes(Pd,Rh).The POD-like and OXD-like activities exhibited obvious component dependence,and PdRh_(3) and PdRh nanozyme showed the strongest POD-like and OXD-like activity,respectively.The analysis of enzymatic kinetics showed that the Michaelis-Menten constant(K_(m))of PdRh_(3) nanozyme with 3,3',5,5'-tetramethylbenzidine(TMB)and H_(2)O_(2) as substrates are 15.65 and 381.99μmol/L,respectively.The corresponding maximum velocity(v max)reach 8.40×10^(-8) and 11.01×10^(-8) mol/(L·s).In addition,the POD-like activity of PdRh_(3) nanozyme was pH-dependent,and the optimized activity was obtained at pH=5.A colorimetric sensing system was developed based on PdRh 3 nanozyme,which realized the rapid quantitative detection of nitrite concentration in solution according to the fitting relationship between the absorbance ratio(A 445 nm/A 652 nm)and the concentration of nitrite ion(NO_(2)^(-)).The limit of detection(LOD)in pH=5 buffer and pure water are 0.467 and 30.523μmol/L,respectively,and the system has a good specificity under the interference of various salt ions,demonstrating great application potential in biosensing.

关 键 词：纳米酶 组分调控 类酶活性 亚硝酸盐检测 

分 类 号：O614.82[理学—无机化学]