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不同修饰的二硫化钼纳米片的过氧化物酶样活性及其在过氧化氢和葡萄糖检测中的应用。

Peroxidase-like activity of MoS nanoflakes with different modifications and their application for HO and glucose detection.

作者信息

Yu Jie, Ma Dongqing, Mei Linqiang, Gao Qin, Yin Wenyan, Zhang Xiao, Yan Liang, Gu Zhanjun, Ma Xiaoyan, Zhao Yuliang

机构信息

Key Laboratory of Polymer Science and Technology, School of Science, Northwestern Polytechnical University, Xi'an, Shaanxi 710129, P. R. China.

出版信息

J Mater Chem B. 2018 Jan 21;6(3):487-498. doi: 10.1039/c7tb02676e. Epub 2018 Jan 5.

Abstract

MoS nanoflakes (MoS NFs) with a diameter of ∼390 nm were obtained by a facile one-pot hydrothermal method and the NFs exhibited intrinsic peroxidase-like activity. After being modified by commonly used biocompatible surfactants including polyethyleneimine (PEI), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP), and cysteine (Cys), the peroxidase-like catalytic activities of MoS NFs were investigated by using 3,3',5,5'-tetramethylbenzidine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) as chromogenic substrates. Compared to the polymer modified MoS NFs, Cys functionalized MoS NFs exhibited a high catalytic activity toward HO in the presence of TMB or ABTS. Zeta potential and Michaelis-Menten analyses implied that the electrostatic force induced affinity or repulsion between the MoS NFs and substrates, as well as surface modifications of the MoS NFs played a key role in the catalytic reactions. Notably, a new peroxidase-like catalytic reaction mechanism was proposed based on the formation of a transient state of Cys-MoS NFs containing HO and ABTS, and the catalytic reaction could occur because the Cys on the surface of the MoS NFs served as an electron transfer bridge between HO and ABTS. Based on this finding, we also established a platform for colorimetric detection of HO and glucose using Cys-MoS NFs as a peroxidase substitution. The limit of detection (LOD) was determined to be 4.103 μmol L for HO, and the linear range (LR) was from 0 to 0.3 mmol L. The LOD for glucose was 33.51 μmol L and the LR was from 0.05 to 1 mmol L, which is suitable for biomedical diagnosis. This work provides a new insight into the catalytic mechanism of peroxidase-like MoS NFs, and paves the way for enzyme-like nanomaterials to be used for medical diagnosis.

摘要

通过简便的一锅水热法制备了直径约为390 nm的二硫化钼纳米片(MoS NFs),这些纳米片表现出固有的过氧化物酶样活性。在用包括聚乙烯亚胺(PEI)、聚丙烯酸(PAA)、聚乙烯吡咯烷酮(PVP)和半胱氨酸(Cys)在内的常用生物相容性表面活性剂修饰后,以3,3',5,5'-四甲基联苯胺(TMB)和2,2'-联氮-双(3-乙基苯并噻唑啉-6-磺酸)二铵盐(ABTS)作为显色底物,研究了MoS NFs的过氧化物酶样催化活性。与聚合物修饰的MoS NFs相比,Cys功能化的MoS NFs在TMB或ABTS存在下对H₂O₂表现出高催化活性。zeta电位和米氏分析表明,MoS NFs与底物之间的静电力诱导的亲和力或排斥力以及MoS NFs的表面修饰在催化反应中起关键作用。值得注意的是,基于含有H₂O₂和ABTS的Cys-MoS NFs瞬态的形成,提出了一种新的过氧化物酶样催化反应机制,并且由于MoS NFs表面的Cys作为H₂O₂和ABTS之间的电子转移桥,催化反应能够发生。基于这一发现,我们还建立了一个以Cys-MoS NFs作为过氧化物酶替代物比色检测H₂O₂和葡萄糖的平台。确定H₂O₂的检测限(LOD)为4.103 μmol L,线性范围(LR)为0至0.3 mmol L。葡萄糖的LOD为33.51 μmol L,LR为0.05至1 mmol L,适用于生物医学诊断。这项工作为过氧化物酶样MoS NFs的催化机制提供了新的见解,并为类酶纳米材料用于医学诊断铺平了道路。

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