基于分子印迹复合量子点纳米材料的(电)化学发光传感器及其环境药物分析应用

As a group of emerging organic contaminants, namely pharmaceuticals and personal care products (PPCPs), various pharmaceuticals that existed in environments have gained growing attention in recent years. Consequently, it becomes a hotspot to develop novel analytical methods for fast analysis of these pharmaceuticals at micro and even trace level. Recently, quantum dots-based chemiluminescence (QDs-CL) and electrochemiluminescence (QDs-ECL) have been rapidly developed due to rapidity and high-sensitivity. But their application in the field of environmental analysis is seriously restricted by the low selectivity of CL/ECL methods. Thus, it would be more significance to introduce molecularly imprinted polymers (MIPs) in a CL/ECL sensor in order to improve the selectivity and sensitivity of sensors due to their unique characteristics for specifically recognition of the imprinted molecules. However, as far as we know, study on MIP-capped QDs nanocomposite as novel CL and ECL sensors seems to be still in its infancy with only several reports. Given this, the present work would focus on synthesis and application of a series of PPCPs-imprinted QDs nanocomposite in CL/ECL sensors; The proposed strategies would be applied to the rapid and on-line determination of some kinds of typical pharmaceuticals (antibiotics, analgesics and estrogens) in real environmental samples; The possible emission mechanisms would be explored in detail via spectroscopic methods, electrochemical methods, surface analysis, and so on. The present research would not only help to broaden the application of QDs-based CL/ECL methods in environmental analysis, but also provide new promising strategies for the accurate and rapid detection of environmental pollutants.

存在于环境中的药物等新型有机污染物（PPCPs）已引起科学家广泛的关注，开发环境中微量及痕量药物的快速分析方法是研究的热点之一。基于量子点的化学发光（CL）法和电致化学发光法（ECL）因快速、高灵敏等特点发展迅速，但其选择性较差的缺陷严重制约了该类方法在环境分析中的应用。分子印迹聚合物对模板分子具有专一的识别性，可用来提高发光传感器的选择性和灵敏度。但目前基于分子印迹复合量子点纳米材料的CL/ECL研究及应用正处于起步阶段，报道很少。鉴于此，本项目拟重点以量子点为核心制备分子印迹复合量子点纳米材料，并以此为基础构建新型高效的分子印迹-量子点CL/ECL传感器，实现自然环境系统中几种典型药物污染物的在线、快速分离和检测，并深度阐释发光机理，为量子点发光技术在环境领域的进一步应用提供重要的理论指导，同时也为环境污染物的快速、准确检测提供新的途径和方法。

发展环境中微量及痕量药物的快速分析方法是环境分析研究的热点之一。基于量子点（QDs）的化学发光（CL）法和电致化学发光法（ECL）快速、灵敏，但选择性较差，结合分子印迹技术的特异性识别能力，是提高发光传感器在环境药物分析中的选择性和灵敏度的一条有效途径。但基于分子印迹复合量子点纳米材料的CL/ECL研究及应用研究报道不多。因此，本项目以基于量子点的化学发光及电化学发光研究为基础，以目标环境药物分子为模板分子制备分子印迹聚合物和分子印迹复合量子点纳米材料，构建了一系列新型高效的分子印迹-量子点CL/ECL传感器并用于几种典型环境药物的快速检测及去除。分别制备了氯霉素和黄芩苷分子印迹聚合物及镉系量子点（CdTe QDs, CdSe QDs, CdTe/CdSe QDs等）表面分子印迹聚合物（CdX QDs-MIPs），建立了石墨烯类量子点（CQDs, N-CQDs, S,N-CQDs等）增敏的高锰酸钾-高良姜素化学发光体系和镉系量子点增敏的鲁米诺-高碘酸钾化学发光体系、以及CdSe量子点-过硫酸钾阴极ECL传感器和PDA-PBA NPs-K2S2O8 阴极ECL传感器，并分别用于对乙酰氨基酚、非那西丁、四环素等环境药物的流动注射化学发光分析及3-硝基丙酸、L-茶氨酸、常见11种氨基酸、氯霉素、黄芩苷等的ECL分析中，研究了相关的发光反应机理；同时，制备了纳米MoS2及CdSe QDs @ MoS2、Ag3PO4 @ MoS2纳米复合材料，分别研究了其对抗生素环丙沙星、头孢噻呋钠和头孢曲松钠的光催化降解性能及降解机理。该课题的研究成果为量子点发光技术在环境领域的进一步应用提供了有益的理论指导和实验依据，同时也为环境药物的快速、准确检测和去除提供了新的途径和方法。