基于共轭集聚作用的羟基多环芳烃原位富集传感研究

项目名称： 基于共轭集聚作用的羟基多环芳烃原位富集传感研究

项目编号： No.31501397

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 食品科学、农学基础与作物学

项目作者： 庞月红

作者单位： 江南大学

项目金额： 20万元

中文摘要： 多环芳烃(PAHs)是发现最早且数量最多的致癌物，其代谢产物羟基多环芳烃(OH-PAHs）作为生物标志物综合评价人体对PAHs内暴露情况已被广泛接受。然而不论选择哪个或者哪几个OH-PAHs都不能真实反映PAHs的内暴露水平。本项目在充分研究OH-PAHs同系结构、环位异构和羟基取代区域异构(K区和L区)电化学氧化还原特性的基础上，验证我们提出的“轻质PAHs代谢物苯环数量的增加对其电化学氧化还原性质影响显著；重质苯环的数量影响变小；苯环数量越多，影响越小”的假设。采用具有线性离域π电子体系的聚烷基噻吩导电聚合物共轭贯穿二维石墨烯，通过共轭集聚作用选择性富集零维OH-PAHs，采用Freundlich和BET方程进行拟合，计算热力学函数，推测吸附机理；总结氧化电位规律，按照相似统一、相差分类的原则，实现OH-PAHs总量测定，为PAHs人体暴露水平评价提供一种简单、高效且灵敏的分析新方法。

中文关键词： 多环芳烃；生物标志物；富集；传感

英文摘要： Polycyclic aromatic hydrocarbons (PAHs) are compounds widespread in the environment and food, many of them showing carcinogenic effects. Human urinary hydroxylated metabolites (OH-PAHs) are a class of PAH metabolites used as biomarkers for estimating human internal exposure to PAHs. However, using only one or several biomarkers cannot reflect internal exposure level of PAHs. The present project will systematically examine the electrochemical behaviors of typical OH-PAHs such as homologous compounds, isomers by benzene ring, K region and L region hydroxylated OH-PAHs. Statistical analysis is performed based on the above results to verify our proposals, “1) Increasing the number of confused benzene on the light OH-PAHs significantly affect the electrochemical redox properties; 2) The influence on the redox peaks is negligible for heavy OH-PAHs; 3) The effects decrease with the increase of the benzene ring”. Graphene, a two-dimensional atomically thick crystal containing highly delocalized π electrons, is an excellent candidate for preconcentration of OH-PAHs. However, the two-dimensional nature of graphene brings another great challenge: it tends to re-aggregate due to π-π interactions between graphene layers. Thus, conductive conjugated poly(3-alkyl-thiophene)s are electropolymerized with graphene in this project. The composite films will be used to pre-concentrate OH-PAHs via π-π-π compacting interaction. The adsorption isotherms such as using Freundlich and Bruauer, Emmet & Teller (BET) models will be used to fit the pure component experimental data. Combined with the achieved preconcentration, in situ electrochemical sensing will be employed to determinate total OH-PAHs. If successful, the proposed research will provide an in-depth understanding of how these OH-PAHs oxidized at solid electrodes and enable a new methodology for characterizing and classifying of OH-PAHs. The results of this project also provides reference of electrochemical properties of OH-PAHs and develop an inexpensive, sensitive, and reliable method for evaluating the internal exposure level of PAHs.

英文关键词： Polycyclic aromatic hydrocarbons;Biomarker;Preconcentration;Sensor