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一种基于 Ni-Co MOF 纳米片修饰的 CNTs/PU 薄膜的可穿戴汗液电化学生物传感器,用于监测应激生物标志物。

A wearable sweat electrochemical aptasensor based on the Ni-Co MOF nanosheet-decorated CNTs/PU film for monitoring of stress biomarker.

机构信息

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, PR China.

Department of Chemical Engineering, Yangzhou Polytechnic Institute, Yangzhou 225127, PR China.

出版信息

Talanta. 2023 Aug 1;260:124620. doi: 10.1016/j.talanta.2023.124620. Epub 2023 May 2.

Abstract

Monitoring cortisol, a hormone released by the adrenal cortex in response to stress, is essential to evaluate the endocrine response to stress stimuli. While the current cortisol sensing methods require large laboratory settings, complex assay, and professional personnel. Herein, a novel flexible and wearable electrochemical aptasensor based on a Ni-Co metal-organic frameworks (MOF) nanosheet-decorated carbon nanotubes (CNTs)/polyurethane (PU) film is developed for rapid and reliable detection of cortisol in sweat. First, the CNTs/PU (CP) film was prepared by a modified wet spinning technology, and the CNTs/polyvinyl alcohol (PVA) solution was thermally deposited on the surface of CP film to form the highly flexible CNTs/PVA/CP (CCP) film with excellent conductivity. Then aminated Ni-Co MOF nanosheet prepared by a facile solvothermal method was conjugated with streptavidin and modified on the CCP film. Biofunctional MOF can effectively capture cortisol aptamer due to its excellent specific surface area. In addition, the MOF with peroxidase activity can catalytic oxidization of hydroquinone (HQ) by hydrogen peroxide (HO), which could amplify the peak current signal. The catalytic activity of Ni-Co MOF was substantially suppressed in the HQ/HO system due to the formation of the aptamer-cortisol complex, which reduced the current signal, thereby realizing highly sensitive and selective detection of cortisol. The sensor has a linear range of 0.1-100 ng/mL and a detection limit of 0.032 ng/mL. Meanwhile, the sensor showed high accuracy for cortisol detection under mechanical deformation conditions. More importantly, the prepared MOF/CCP film based three-electrode was assembled with the polydimethylsiloxane (PDMS) substrate, and the sweat-cloth was used as the sweat collection channel to fabricate a wearable sensor patch for monitoring of cortisol in volunteers' sweat in the morning and evening. This flexible and non-invasive sweat cortisol aptasensor shows great potential for quantitative stress monitoring and management.

摘要

监测皮质醇(一种由肾上腺皮质响应应激而释放的激素)对于评估应激刺激下的内分泌反应至关重要。目前的皮质醇传感方法需要大型实验室设置、复杂的检测和专业人员。在此,开发了一种基于 Ni-Co 金属有机骨架(MOF)纳米片修饰的碳纳米管(CNT)/聚氨酯(PU)薄膜的新型柔性可穿戴电化学适体传感器,用于快速可靠地检测汗液中的皮质醇。首先,通过改进的湿法纺丝技术制备 CNTs/PU(CP)薄膜,然后将 CNTs/聚乙烯醇(PVA)溶液热沉积在 CP 薄膜表面上,形成具有优异导电性的高度柔性 CNTs/PVA/CP(CCP)薄膜。然后,通过简便的溶剂热法制备了氨基化的 Ni-Co MOF 纳米片,并与链霉亲和素偶联,修饰在 CCP 薄膜上。由于具有优异的比表面积,生物功能化的 MOF 可以有效地捕获皮质醇适体。此外,具有过氧化物酶活性的 MOF 可以通过过氧化氢(HO)催化氧化对苯二酚(HQ),从而放大峰电流信号。在 HQ/HO 体系中,由于形成了适体-皮质醇复合物,Ni-Co MOF 的催化活性大大受到抑制,从而减少了电流信号,实现了对皮质醇的高灵敏度和选择性检测。该传感器的线性范围为 0.1-100ng/mL,检测限为 0.032ng/mL。同时,该传感器在机械变形条件下对皮质醇检测表现出较高的准确性。更重要的是,基于 MOF/CCP 薄膜的三电极与聚二甲基硅氧烷(PDMS)基底组装,并将汗布用作汗收集通道,以制造用于监测志愿者早晨和傍晚汗液中皮质醇的可穿戴传感器贴片。这种柔性且非侵入性的汗液皮质醇适体传感器在定量应激监测和管理方面具有很大的潜力。

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