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光控热敏电化学发光水凝胶用于异恶草酮检测。

Photocontrolled Thermosensitive Electrochemiluminescence Hydrogel for Isocarbophos Detection.

机构信息

Key Laboratory of Chem-Biosensing, Anhui Province; Key Laboratory of Functional Molecular Solids, Anhui Province; and College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, P. R. China.

Beijing Key Laboratory for Green Catalysis and Separation, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, P. R. China.

出版信息

Anal Chem. 2020 Apr 21;92(8):6136-6143. doi: 10.1021/acs.analchem.0c00719. Epub 2020 Apr 3.

Abstract

Endowing specificity and controllability with the electrochemiluminescence (ECL) thermosensitive hydrogels is vitally crucial to expanding their sensing applications. Herein, a novel photocontrolled thermosensitive electrochemiluminescence hydrogel (PT-ECL hydrogel) sensing platform with sufficient simplicity, specificity, and precise controllability is proposed, for the first time, by the integration of Ru(bpy) (bpy = 2,2'-bipyridine) derivatives (signal reporter), split aptamers (recognition unites), and Au nanorods (AuNRs) (photothermal energy converter) into the poly(-isopropylacrylamide) (pNIPAM) matrix. In the presence of the model target isocarbophos (ICP), the conjugation of two split aptamers initiated the ECL-resonance energy transfer (ECL-RET) between the Au nanorods and the Ru(bpy) centers. Surprisingly, under the irradiation of near-infrared (NIR) light, the photothermal effect of AuNRs prompted the shrinkage of the hydrogel, resulting in the enhancement of the ECL-RET and further ∼7 times signal amplification. Consequently, the PT-ECL hydrogel sensing platform performed well for ICP detection with a low detection limit of 20 pM (S/N = 3) and a wide linear range from 50 pM to 4 μM, with great stability and repeatability. Obviously, the results showed that AuNRs utilized in this study served the role as not only the ECL-RET acceptor but also the photothermal converter to prompt the phase change of the PT-ECL hydrogel precisely and simply controlled by NIR light. Use of the proposed PT-ECL hydrogel detection scheme is a first step toward enabling a newly upgraded highly sensitive and selective hydrogel-based assay and also paving the way for the application of smart photothermal reagents.

摘要

赋予电化学发光(ECL)热敏水凝胶特异性和可控性对于扩展其传感应用至关重要。在此,首次通过将 Ru(bpy)(bpy = 2,2'-联吡啶)衍生物(信号报告器)、分裂适体(识别单位)和 Au 纳米棒(AuNRs)(光热能量转换器)整合到聚(异丙基丙烯酰胺)(pNIPAM)基质中,提出了一种新颖的光控热敏电化学发光水凝胶(PT-ECL 水凝胶)传感平台。在存在模型靶标异稻瘟净(ICP)的情况下,两个分裂适体的缀合引发了 Au 纳米棒和 Ru(bpy)中心之间的 ECL-共振能量转移(ECL-RET)。令人惊讶的是,在近红外(NIR)光照射下,AuNRs 的光热效应促使水凝胶收缩,导致 ECL-RET 增强,进一步信号放大约 7 倍。因此,PT-ECL 水凝胶传感平台在 ICP 检测中表现良好,检测限低至 20 pM(S/N = 3),线性范围从 50 pM 到 4 μM 很宽,具有很好的稳定性和重复性。显然,结果表明,本研究中使用的 AuNRs 不仅充当 ECL-RET 受体,还充当光热转换器,通过 NIR 光精确且简单地触发 PT-ECL 水凝胶的相变化。该 PT-ECL 水凝胶检测方案的使用是实现新型高灵敏度和选择性水凝胶基分析的第一步,也为智能光热试剂的应用铺平了道路。

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