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基于金属有机框架功能化的铂纳米粒子和血红素/G-四链体模拟过氧化物酶的葡萄糖氧化酶引发级联催化用于灵敏的基于适配体的阻抗传感器。

Glucose oxidase-initiated cascade catalysis for sensitive impedimetric aptasensor based on metal-organic frameworks functionalized with Pt nanoparticles and hemin/G-quadruplex as mimicking peroxidases.

机构信息

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China.

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China.

出版信息

Biosens Bioelectron. 2017 Dec 15;98:83-90. doi: 10.1016/j.bios.2017.06.039. Epub 2017 Jun 20.

DOI:10.1016/j.bios.2017.06.039
PMID:28654887
Abstract

Based on cascade catalysis amplification driven by glucose oxidase (GOx), a sensitive electrochemical impedimetric aptasensor for protein (carcinoembryonic antigen, CEA as tested model) was proposed by using Cu-based metal-organic frameworks functionalized with Pt nanoparticles, aptamer, hemin and GOx (Pt@CuMOFs-hGq-GOx). CEA aptamer loaded onto Pt@CuMOFs was bound with hemin to form hemin@G-quadruplex (hGq) with mimicking peroxidase activity. Through sandwich-type reaction of target CEA and CEA aptamers (Apt1 and Apt2), the obtained Pt@CuMOFs-hGq-GOx as signal transduction probes (STPs) was captured to the modified electrode interface. When 3,3-diaminobenzidine (DAB) and glucose were introduced, the cascade reaction was initiated by GOx to catalyze the oxidation of glucose, in situ generating HO. Simultaneously, the decomposition of the generated HO was greatly promoted by Pt@CuMOFs and hGq as synergistic peroxide catalysts, accompanying with the significant oxidation process of DAB and the formation of nonconductive insoluble precipitates (IPs). As a result, the electron transfer in the resultant sensing interface was effectively hindered and the electrochemical impedimetric signal (EIS) was efficiently amplified. Thus, the high sensitivity of the proposed CEA aptasensor was successfully improved with 0.023pgmL, which may be promising and potential in assaying certain clinical disease related to CEA.

摘要

基于葡萄糖氧化酶(GOx)驱动的级联催化扩增,通过将负载有 Pt 纳米粒子的铜基金属-有机骨架(Pt@CuMOFs)、适配体、血红素和 GOx(Pt@CuMOFs-hGq-GOx),构建了一种用于检测蛋白质(以癌胚抗原(CEA)为测试模型)的灵敏电化学阻抗适配体传感器。CEA 适配体负载在 Pt@CuMOFs 上,与血红素结合形成具有模拟过氧化物酶活性的血红素@G-四链体(hGq)。通过目标 CEA 和 CEA 适配体(Apt1 和 Apt2)的三明治型反应,将获得的 Pt@CuMOFs-hGq-GOx 作为信号转导探针(STPs)捕获到修饰电极界面。当引入 3,3-二氨基联苯胺(DAB)和葡萄糖时,GOx 启动级联反应,催化葡萄糖的氧化,原位生成 HO。同时,Pt@CuMOFs 和 hGq 作为协同过氧化物催化剂极大地促进了生成的 HO 的分解,伴随着 DAB 的显著氧化过程和不导电的不溶沉淀物(IPs)的形成。因此,有效阻碍了传感界面中的电子转移,从而有效地放大了电化学阻抗信号(EIS)。因此,所提出的 CEA 适配体传感器的高灵敏度得以成功提高,检测限达到 0.023pgmL,这在测定与 CEA 相关的某些临床疾病方面具有很大的应用潜力。

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