金属纳米晶簇@多形态蛋白孔道：调控、机理与应用

It is a low-pollution, size-controllable, versatile and highly stable green synthesize method for the assembly of metal nanocrystals and nanoclusters with unique optical, electronic and magnetic properties and high chemical activity within various protein pores. The purpose of this proposal is to control the assembly of metal nanocrystal and nanoclusters within multiple pores of protein molecular chains, crystals and films (i.e. nanocluster@chain, nanocrystal@crystal and nanocrystal@film), and to carry out the mechanism analysis and practical application of protein-nanocrystal/nanocluster assembly. (1) Regulation: investigating the effects of assembly conditionson the nanocrystal/nanocluster formation by using pore control, chemical modification and nanocrystal growth control, as well as determining the key factors for their assembly behavior; (2) Characterization: systematically analyzing the structures and properties of metal nanocrystal/nanocluster within protein pores using a combination of electron microscopy and spectroscopic techniques, together with discussing the relationship between microstructure and performance of the assembly; (3) Mechanism: analyzing the interaction between protein and metal nanosurfaces for understanding the assembly forces of nanocrystal/nanocluster within the protein pores using surface force apparatus, combined with discussing the adsorption energy and assembly mechanism using molecular dynamic simulation of the formation of nanocrystals and nanoclusters; (4) Applications: building the sensing system of enzyme activity and small hazard molecules using "nanocluster@chain", together with the recyclable catalysis system of environmental pollutants using "nanocrystal@crystal" and "nanocrystal@film", for exploring the potential applications of protein-nanocrystal/nanocluster composites in biosensing and environmental catalysis metal nanoclusters. This research will promote the rational desigh, process regulation and application of nanocrystals and nanoclusters within protein pores.

基于蛋白孔道组装具有化学活性高和光电磁性能独特的金属纳米晶簇，是一种污染小、尺寸可控、功能多样、稳定性高的绿色合成新方法。本项目旨在蛋白质分子链、晶体、膜等多形态内部孔道中可控组装金属纳米晶簇（即链中簇、晶中晶、膜中晶），明确孔道调控晶簇形成规律，开展组装机理及其应用研究。①调控：以孔道调控、化学修饰及晶簇生长为调控手段，考察晶簇在蛋白孔道中形成过程的影响规律，确定组装关键因素；②表征：组合光谱、电镜、波谱等多尺度分析技术表征蛋白孔道中金属纳米晶簇的结构和性能，探讨组装体构效关系；③机理：采用表面力分析仪定量考察蛋白与金属纳米表面的结合力及其影响规律，基于分子动力学模拟剖析纳米晶簇在蛋白孔道中的组装机理；④应用：构建"链中簇"检测酶活力和小分子危害物传感体系，"晶中晶"和"膜中晶"对环境污染物的循环催化系统。研究成果将促进金属纳米晶簇@蛋白孔道复合材料的理性设计、有效调控并推进其开发应用。

利用天然生物大分子及其超分子结构的多形态孔道表面作为分子框架，组装调控出不同形貌、尺寸、组成的无机纳米材料，是一种高效且环境友好的新型功能材料合成策略，可应用于环境污染物的高效检测与催化降解。本项目以“链中簇”、“晶中晶”、“膜中晶”为设计主线，探讨在多形态蛋白孔道结构内金属纳米晶簇的生长和组装行为规律及其应用，系统分析金属纳米晶簇@蛋白孔道复合材料的结构、性能、组装过程，计算蛋白与金属纳米表面的作用力，探讨不同形态蛋白孔道中金属纳米晶簇组装过程的影响因素，深入理解纳米晶簇之间及其与蛋白孔道的相互作用规律；采用乳球蛋白聚集成膜，制备合金纳米晶，或者在天然鸡蛋膜表面引入多酚官能团，使其与前体离子具有很强的结合力，构建多种金属纳米晶，制备基于天然膜、蛋白聚集组装膜的循环催化膜，可用于多种污染物的高效降解；提出了“多巴胺仿生镀金膜”研究思路，揭示多巴胺聚合层加速金纳米晶在光纤表面的吸附规律，建立了圆柱形光纤表面纳米金膜快速化学成型法，并基于金银纳米膜/晶与蛋白质相互作用构建超低蛋白吸附表面，可用于多种污染物的高效且特异性检测分析。研究结果在Angew Chem、Biosens Bioelectron、Environ Sci Technol、Chem Eng J、ACS Appl Mater Interfaces、J Mater Chem C、Langmuir、IECR等发表20篇SCI论文，其中一区9篇、二区10篇，获得2017年教育部自然科学二等奖。申请中国发明专利5项，授权3项。积极开展国内外学术交流活动，培养博士生6名、硕士生5名。