基于表面印迹技术的电位型传感器检测海水中多环芳烃

The study on sensor technology for on-site and rapid monitoring of polycyclic aromatic hydrocarbons (PAHs) in seawater will provide important technical support for efficient environmental monitoring and evaluation of marine and coastal zone. Also, it can satisfy the urgent need of our country in environmental water monitoring. In this study, potentiometric sensors based on surface molecular imprinting for detection of PAHs in seawater will be systematically investigated. The mechanism of the proposed senor in the fabrication of the highly selective surface imprinted membrane and enrichment of the trace PAHs will be discussed. The general strategy for potentiometric detection of neutral PAHs using common ions as indicators will further be studied. By choosing suitable polymerization monomers, the highly selective imprinted membrane is synthesized on the surface of ion-selective electrode membrane. In order to achieve the optimal separation and enrichment of PAHs, polymerization conditions are optimized. The specific recognition interactions between the PAHs and surface imprinted membrane are indicated by the common ions. Matrix interferences arising from seawater are eliminated by applying the method of medium exchange which is usually employed in the electrochemistry to overcome the matrix effects. Thus, the neutral PAHs in seawater can be indirectly detected by the potentiometric sensor based on surface molecular imprinting. Combining with the flow analysis system which can be used to improve the sensor efficiency, general potentiometric sensors for rapid determination of PAHs in seawater will be developed. This study will make great contributions on the enhancement of the generality of the proposed sensors and the improvement of sensor sensitivity and selectivity for the detection of trace PAHs in seawater, which will significantly promote the development of sensor technology in the field of marine monitoring.

海水多环芳烃污染物快速检测传感器技术的研究可为及时高效地开展海洋和海岸带环境监测及评价提供重要的技术手段，为满足国家在水环境监测领域的重大需求提供科技支撑。本项目将对基于表面印迹技术的电位型传感器检测海水中多环芳烃进行系统研究，深入探讨电极表面高选择性印迹膜的构建与分离富集机理以及采用常见离子作为指示离子实现电中性多环芳烃的通用性电位检测机制。通过选择合适的单体，优化聚合反应条件，在离子选择性电极表面合成出高选择性多环芳烃印迹膜，实现最佳分离富集效果；选择常见离子指示多环芳烃与印迹膜键合作用，实现多环芳烃的间接电位测定；采用介质变换法消除海水基体效应及复杂成分的干扰；结合流动分析技术提高传感器分析效率，开发出一类能够快速检测海水中多环芳烃的通用型电位型传感器。本项目在提高传感器对海水中多环芳烃检测通用性和响应灵敏度和选择性等方面具有重要的创新，为推动传感器技术在海洋监测领域的发展做出贡献。

本项目对基于表面印迹技术的电位型传感器检测海水中多环芳烃进行了系统研究，在以下方面取得进展：通过引入亲水性的辅助单体，优化聚合反应条件，合成出了亲水性的多环芳烃分子印迹聚合物，成功实现了多环芳烃的高选择性分离富集；在离子选择性电极表面原位合成了多环芳烃的分子印迹聚合物，构建了基于表面印迹技术的多环芳烃电位型传感器，采用常见无机离子作为指示离子，实现了对多环芳烃萘的高灵敏、高选择性间接电位检测，极大地提高了电位检测电中性有机分子的通用性；为了验证表面印迹电位型传感器的普适性，采用无离子交换性质的表面分子印迹膜修饰的聚合物敏感膜同时结合计时电位检测法，利用常见离子作为指示离子，通过优化计时电位检测条件，建立了电极的电位响应与有机物分子的定量关系实现了多种有机分子的计时电位检测；为了拓宽电中性有机分子的检测范围，通过将分子印迹聚合物的高选择性与离子选择性电极的高灵敏度进行有机结合，同时利用与电中性分子具有相似结构的有机离子作为指示离子，实现了气相中单环芳烃分子的高选择性、高灵敏度间接电位检测；为了验证方法在实际海水检测中的实用性，以分子印迹聚合物为高选择性吸附剂，采用固相萃取技术，实现了对海水中多种有机污染物高效分离富集，并分别以分子印迹聚合物膜离子选择性电极和液相色谱串联质谱（LC-MS/MS）作为检测元件，成功实现了海水样品中多种有机污染物的高灵敏检测，并在此基础上发展了基于流动分析的电位检测体系，实现了海水中有机污染物分子的快速检测；为进一步提高电位型传感器在海水高干扰背景条件下检测的选择性和灵敏度，开发了非对称聚合物离子选择性膜，即将亲脂性的离子交换剂直接涂于聚合物膜表面而不是均匀溶于聚合物膜内部，实现了海水基体中离子超灵敏电位检测。在此基础上,发展了非对称性纳米分子印迹聚合物膜离子选择性电极，合成出了具有高键合容量的纳米印迹颗粒，并首次将其应用到离子选择性电极上，实现了有机污染物的高灵敏、高选择性电位检测。已在《美国分析化学》（Anal Chem）、《科学报告》（Sci Rep）等SCI期刊发表论文(含已录用)10篇，中文论文1篇，待发表SCI论文2篇，申请发明专利5项；培养3名硕士生；项目负责人参加国际会议3次、国内会议3次，并做口头报告1次，展报报告4次。