新型类过氧化物纳米酶NC@MIL-100(Fe)的制备及其对生物硫醇的测定

Preparation of a Novel Peroxide-like Nanozyme NC@MIL-100(Fe)and Its Application in Biothiols Analysis

该文利用针状焦(NC)与金属有机框架(MOFs)材料MIL-100(Fe)间的静电相互作用,制备了新型纳米酶NC@MIL-100(Fe),并将其应用于生物硫醇的分析。新材料不仅可充分利用针状焦固有的类酶活性,其片层结构也能够有效改善MIL-100(Fe)的团聚现象,提高材料的整体催化效果。与单独使用针状焦和MIL-100(Fe)作为纳米酶相比,NC@MIL-100(Fe)对底物的亲和力更强,催化反应速度更快,表现出良好的类过氧化物酶催化活性。以3,3′,5,5′-四甲基联苯胺(TMB)和H_(2)O_(2)为底物对其性能进行评价,得到的米氏常数(K_(m))分别为0.27 mmol/L和0.43 mmol/L,比辣根过氧化物酶小1.61倍和8.6倍。将该材料用于生物硫醇的分析,谷胱甘肽和半胱氨酸检测的线性范围分别为3~70μmol/L、1~80μmol/L,检出限分别为0.33μmol/L和0.22μmol/L。该法具有线性范围宽、检出限低且选择性良好的特点,用于人血清中生物硫醇浓度的检测取得了良好的效果。

Enzyme-catalyzed reactions are characteristic of high selectivity and high efficiency.Special⁃ly designed metal-organic frameworks(MOFs)have catalytic activities similar to natural enzymes,and their porous structures also provide a large number of active sites for catalytic reactions.In this paper,a novel nanozyme NC@MIL-100(Fe)was prepared based on the electrostatic interaction between needle coke(NC)and MOF material(MIL-100(Fe)),which was applied to the analytical methods develop⁃ment of biothiols.The inherent enzyme-like activity of NC was made full use for the new material,whose lamellar structure could effectively avoid the agglomeration phenomenon of MIL-100(Fe),improving the overall catalytic effect of the material.Compared with needle coke and MIL-100(Fe),NC@MIL-100(Fe)as nanozyme has a stronger affinity for the substrate and a faster reaction rate,thus showing a better peroxidase-like catalytic activity.Its performance was evaluated with 3,3′,5,5′-tetramethyl⁃benzidine(TMB)and H_(2)O_(2) as substrates,and the Michaelis constants(K_(m))obtained were 0.27 mmol/L and 0.43 mmol/L,respectively,which were 1.61 times and 8.6 times smaller than that of horseradish peroxidase.The material was applied to the development of analytical methods for glutathione and cyste⁃ine,with the linear ranges of 3-70μmol/L and 1-80μmol/L,and the detection limits of 0.33μmol/L and 0.22μmol/L,respectively,showing the advantages of wide linear range,low detec⁃tion limit and good selectivity.Furthermore,this material was successfully applied to the detection of biothiols concentration in human serum with satisfactory results.