有序二氧化硅纳米通道薄膜的分子选择透过性研究及其分析应用

Analysis and separation based on nanochannels is one of hot topics in the fundamental and applied analytical chemistry field, in which the preparation of nanochannel film remains to be a big challenging. On the basis of our previous work, this project aims at preparing the highly ordered and vertically aligned silica nanochannels on the solid electrode surface by the co-operative assembly of surfactant templates and hydrolysis/polycondensation of organosilanes. First, we plan to study the selective extraction, preconcentration and electrochemical detection of trace lipophilic yet redox-active organic compounds by the binary assembly of surfactant micelles and silica nanochannels. Then we shall focus on the preparation of free-standing silica nanochannel film and the modification of nanochannels with desired size, surface charge and lipophilicity. The primary goal is to investigate the molecule recognition and separation at the molecular level, as well as the surface/interface effect, the nanoconfinement effect, the thermodynamic and kinetics of molecule transport process. We also plan to combine the free-standing silica nanochannel film with the microfluidic device.

基于纳米通道的分析和分离是分析化学基础和应用研究的热点领域之一，而纳米通道薄膜的制备仍有很大的挑战。本项目拟在我们前期的工作基础之上，利用表面活性剂分子自组装和有机硅烷分子水解/缩聚反应的协同作用，生长孔道高度有序排列且垂直于电极表面的二氧化硅(SiO2)纳米通道薄膜。首先，以得到的SiO2纳米通道/表面活性剂胶束的二元自组装薄膜为对象，研究有机胶束对疏水有机小分子（与生命健康、公共安全和环境污染等相关）的选择性萃取、预富集和痕量电化学分析方法。重点研究从电极表面剥离制备双通的SiO2纳米通道薄膜及其表界面化学修饰，调控纳米通道孔径、表面电荷和亲疏水性质，实现分子水平的识别和高效分离，剖析纳米通道的表界面效应和离子跨膜过程的界面结构、热力学和动力学问题，并探索与微流控芯片的集成。

基于纳米通道的分析和分离是分析化学基础和应用研究的热点领域之一。本项目利用表面活性剂分子自组装和有机硅烷分子水解/缩聚反应的协同作用，生长孔道高度有序排列且垂直于电极表面的二氧化硅(SiO2)纳米通道薄膜。利用SiO2纳米通道/表面活性剂胶束的二元自组装薄膜对疏水有机小分子的选择性萃取、预富集，实现了一系列复杂样品中免预处理的直接电化学分析；基于薄膜的表面抗污染效应，制备薄膜修饰的碳纤维微电极，实现了长程稳定地活体脑氧电化学的检测；以薄膜修饰电极孵育细胞，利用薄膜对电化学发光的显著增强作用，实现了细胞-基质黏着的选择性、动态电化学发光成像，揭示了黏着的空间分布和细胞群体迁移的基质；基于双通的SiO2纳米通道薄膜的尺寸选择性、高渗透性和表面电荷、亲疏水效应，实现了分子水平的识别、高效分离和仿生电化学温度测量。项目执行期内共发表论文40篇，包括1篇Angew. Chem., 2篇JACS和14篇Anal. Chem., 获得授权中国发明专利3项。