响应性金纳米簇杂化微凝胶的可控制备及性能研究

The responsive nobel metal nanoclusters hybrid microgels have versatile applications such as in sensor, information storage, controllable nano-reactors and the diagnosis and therapy of diseases. However, researches on the controllable preparation and the relationship between the structure and properties of the noble metal nanoclusters hybrid microgels, are still limited, which made them cannot be practically applied. In this project, the controllable preparation and the relationship between the structure and properties of stimuli (pH, temperature, light, ect.) responsive gold nanoclusters hybrided microgels will be investigated in details. The microgels will be prepared by polymerization from the double bonds functionalized gold nanoclusters with uniform sizes and the monomers of responsive polymers, by which to offer the gold nanoclusters hybrid microgels with simple and core-shell structure and single, double or multiple stimuli-responsive (pH, temperature, light, etc.) properties. The structure and properties of the gold nanocluster hybrid microgels will be characterized by using fluorescent spectroscopy, transient fluorescence, HRTEM, DLS, and other methods. The influence of the size and distriburtion of the gold nanoclusters, crosslinking density and the sizes of the hybrid microgels on the fluorescence properties and their responsive properties to the environmental stimuli of the hybrid microgels will be investigated. New approaches for the design, preparation and control the structrue and properties of the stimuli sensitive nobel metal nanoclusters hybrid microgels will be estabilished, by which to provide scientific fundamentals for further developments and applications of the nobel metal nanoclusters hybrid microgels.

响应性贵金属纳米簇杂化微凝胶在传感、信息存储、可控纳米反应器及疾病的诊断与治疗等领域有着广泛的应用前景。但是，响应性贵金属纳米簇杂化微凝胶结构控制及其与性能之间的关系尚不明确，从而限制了其应用。本项目拟以双键化的单尺寸金纳米簇、响应性聚合物单体等为前驱物，采用聚合法可控制备系列单、双与多重环境(pH、温度与光)响应性金纳米簇杂化微凝胶；利用荧光、瞬态荧光、HRTEM、DLS等手段，研究金纳米簇尺寸、金纳米簇的分布密度、交联密度与杂化微凝胶尺寸等对金纳米簇杂化微凝胶荧光与催化性能及其性能随环境响应调控的影响；阐明其结构与荧光性能的关系，揭示其响应调控机理，建立有效的金纳米簇杂化微凝胶的结构和性能调控方法。通过本项目的实施，为响应性贵金属纳米簇杂化微凝胶的结构设计、制备和性能调控提供新思路与方法，为贵金属纳米簇杂化微凝胶的应用提供理论指导和科学依据。

利用小分子巯基乙胺、巯基乙酸为稳定剂，合成了系列荧光金纳米簇，并考察了制备条件对金纳米簇的性能影响。利用双键化的金纳米簇，采用沉淀聚合法，可控制备了单、双环境响应的金纳米簇杂化微凝胶，主要考察了单体用量、交联剂用量、引发剂用量与表面活性剂用量对金纳米簇杂化微凝胶的尺寸与尺寸分布的影响。研究发现杂化微凝胶的尺寸与分布主要与单体与引发剂用量有关，单体浓度越大，杂化微凝胶尺寸越大。利用荧光、DLS等手段研究了制备的杂化微凝胶的荧光性能随环境的响应情况。pH响应的杂化微凝胶在pH为7.5-11.5的范围内，其荧光发射强度随着环境pH增加而弱，反之，增强。其主要的原因是由于pH变化时杂化微凝胶的尺寸发生塌陷或膨胀。温度/光双响应的杂化微凝胶的荧光具有很好的光响应性能，利用紫外/可见光照射，其荧光可以实现蓝绿与红色荧光的转换。