含氟高分子界面调控金纳米粒子单层膜的构建及其在超灵敏表面增强拉曼检测中的应用

纳米金二维单层膜因集成等离子耦合和光电效应广泛应用于传感检测、柔性可穿戴器件、防伪变色等领域。目前制备该膜的界面自组装法存在膜面积小、稳定性差、工艺复杂等缺点。从组装机理出发，无法最大程度地克服动力学吸附势垒是该技术瓶颈的主要诱因。基于粒子表面疏水性对克服吸附势垒的决定性作用，本项目拟设计一系列全氟高分子配体，以调控粒子表面疏水性，实现快速大面积组装，并赋予该膜检测功能性。主要内容包括三个方面：1.拟通过线性全氟分子赋予纳米金超高接触角，构建宏观大面积二维单层膜；2.设计合成嵌段共聚全氟高分子以调控组装形貌，获得热点耦合增强的囊泡组装二维结构，用于超灵敏拉曼检测；3.设计合成多臂全氟高分子，赋予二维膜功能性，应用于自清洁拉曼检测中。本项目为快速制备大面积纳米金单层膜提供了有效的方法，解决传统功能性二维膜在光学拉曼检测中灵敏度低、稳定性差及基底循环利用率低的问题。

Two-dimensional (2D) monolayer films of gold nanoparticles (Au NPs) are widely applied in sensing and detection, flexible wearable devices, anti-counterfeiting and discoloration due to the integration of plasma coupling and photoelectric effect. There are some defects in the preparation of them including limited assembling scale, poor stability, and complex manufacturing process. Ultimately, it is the main inducement that the dynamic adsorption potential barrier cannot be overcome to the greatest extent. Based on the decisive role of hydrophobicity of particle surface in overcoming dynamic adsorption potential barrier, in this project, a series of perfluorinated polymer ligands is designed to control the hydrophobicity of particle surface, realize rapid scale-up assembly, and endow the films with detection functionality. The main contents include three aspects: 1) It is proposed to build a macroscopic large-area 2D monolayer films by giving Au NPs ultra-high contact angle by linear perfluoromolecules; 2) To design and synthesis block perfluoropolymer to control the assembly morphology, and obtain two-dimensional vesicle assembly structures with enhanced hot spot coupling for ultra-sensitive Raman detection; 3) To design and synthesis multi-arm perfluoropolymer to endow Au NPs monolayer films superhydrophobicity and apply to self-cleaning SERS detection. This project provides an effective approach for fast and large-area preparation of dense monolayer films, and to solve the problems of low sensitivity, poor stability, and low substrate recycling rate of traditional Au NPs monolayer films in SERS detection.