基于金纳米团簇增强分离的POPs毛细管电泳分析方法及应用研究

In this proposal,a kind of water-soluble monolayer-protected gold nanoclusters (AuNCs) by the chemical reduction method in ice-bath condition. The polydispersive products with different size from about 1 to 5nm, which will be purified and pre-size fractionated by sequential size-selective precipitation (SSSP) in aqueous medium just proposed by the proposer. The seperation of the typical persistent organic pollutants (POPs), such as polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and organic chlorine pesticides (OCPs) with capillary electrophoresis (CE) will be studied. The prepared uniform AuNCs with different size will be added in the CE running buffer or immobilized on the wall of the capillary, respectively.The interaction of between the AuNCs and POPs in CE procedure and the effects of the AuNCs on the seperation of the typical POPs molecules will be investegated in detail. The influence of Au clusters on the electrophoresis behavior and mechanism will be discussed in the two modes respectively.We shall abtain the optimized conditions for water-soluble monolayer-protected AuNCs in enhancing the electrophoretic separation of POPs, thus construct a typical high performance capillary electrophoresis method to apply the separation and determination of POPs. Coupling with the in-column fiber optic-induced fluorescence detection CE system proposed by the proposer, we shall realize the determination of the trace POPs in environment samples by CE based on the AUNCs enhancement of the separation. The analysis method will be applied to study the pollution characteristics, distribution,migration and transformation of typical POPs soil water and other environmental samples in Jialing River Basin. The successful implementation of this proposal will ascertain the mechanism why the AuNCs can enhance the the POPs separation in capillary electrophoresis. We will provide a new approach for the determination of trace POPs in complex environmental samples in the field of environmental science.

本项目以冰浴化学还原法制备出水溶性单层保护的金纳米团簇(1-5nm)，用连续尺寸分级沉淀法(SSSP)对其进行纯化和分离。将得到的均匀金纳米团簇添加到缓冲溶液或涂固定毛细管内壁，分别考察金纳米团簇与POPs分子在毛细管电泳和毛细管电色谱中的相互作用，探讨两种模式下金纳米团簇对POPs的毛细管电泳行为的影响规律及作用机理，寻求金纳米团簇增强POPs毛细管电泳分离的优化条件，建立典型POPs的高效毛细管电泳分离测定方法。结合申请者提出的用于毛细管电泳的柱内光纤激光诱导荧光检测技术，实现基于金纳米团簇增强分离的环境样品中痕量典型POPs的毛细管电泳测定方法。最后将该方法应用于嘉陵江流域水体、土壤等环境样品中典型POPs的污染特征、分布及迁移转化分析等研究。本项目的成功实施，将探明金纳米团簇对POPs的毛细管电泳分离改善的机制，为环境科学领域复杂样品中典型的痕量POPs测定提供一种新的技术手段。

纳米材料在增强高效液相色谱和毛细管电泳分离及样品分析前处理中得到一定程度的应用。本课题合成了不同含巯基配体保护的单层保护水溶性金纳米团簇的制备，提出了连续尺寸分级法(SSSP)对合成出的金纳米团簇进行尺寸分级，得到了分散性好、尺寸均一的金纳米团簇；将制得的水溶性金纳米团簇分别作为添加剂加入到 毛细管电泳（CE）分离用的缓冲溶液中，探讨了多环芳烃（PAHs）、多溴联苯醚（PBDEs）等POPs分子在区带毛细管电泳中与不同大小及不同配体保护的金纳米团簇的相互作用，并尝试了将制得的金纳米团簇固定到毛细管内壁, 利用界面化学及毛细管电泳分离理论, 完成了部分POPs分子在毛细管电色谱(CEC)中与不同大小及不同配体保护的金纳米团簇的相互作用研究，初步考察了修饰金纳米团簇对样品中PAHs、PBDEs等POPs分子分离效果的影响；结合自主搭建的柱内光纤激光诱导荧光检测毛细管电泳、商用毛细管电泳、高效液相色谱、光化学传感与固相萃取、浊点萃取等样品前处理技术，建立了一系列POPs和其他污染物分子的分析检测方法；用以上建立测试方法，研究了PAHs在南充市多个不同功能区表层和深度垂直剖面土壤中的分布特征,并对PAHs可能的来源进行了分析。综合上述结果，本项目不仅为探讨金纳米团簇应用于色谱及毛细管电泳分离机制奠定了一定的工作基础，涉及的研究方法，可以进行环境含多环芳烃或其他POPs的样品分析，研究其污染分布及其控制对策，评价区域环境POPs的污染现状，查明区域表层土壤中相关POPs的分布特征和迁移转化规律，分析POPs的主要来源、扩散范围及迁移途径等，从而为区域的生态环境的改良和综合调控提供参考依据。项目资助发表学术论文17篇，待发表4篇。培养硕士生9名。项目投入经费78万元，支出59.8195万元，各项支出基本与预算相符。剩余经费18.1805万元，剩余经费计划用于本项目研究后续支出。