金（I）-巯基丙酸纳米片层的组装动力学调控 Controlling the assembly kinetics of Au(I)-MPA nanosheets
作者姓名：代楚盈
专业名称：高分子化学与物理
指导教师：李敏杰副教授
学位类别：理学硕士
答辩日期：年月日
2018528
金（I）-巯基丙酸纳米片层的组装动力学调控
摘要
超分子组装体是组装基元通过非共价键形成的有序结构，由于非共价键具有较低的能量，赋予了组装体动态-可逆性。因此，超分子组装体普遍具有刺激响应性和环境适应性。超分子组装体常按组装驱动力（
非共价键，例如，氢键、配位键、静电相互作用、范德华力、π-π相互作用、疏水相互作用等）的类型进行分类，其中金（I）-硫醇配位聚合物是超分子组装体中较为独特的一类，它的组装驱动力不仅有其它超分子体系中常见的几种弱相互作用（例如，范德华力、氢键、静电相互作用、配位键等），还存在独特的“亲金”相互作用，这就使其具有复杂的多级组装过程和多样化的组装结构。调控金（I）-硫醇配位聚合物模型体系的结构可以为研究其他复杂的多级组装体（例如，蛋白质、DNA等）结构带来重要的借鉴作用。目前，对于超分子组装体结构的调控手段主要是改变组装体系的温度、浓度、反应物料的配比、溶剂等，这些参数通常会同时带来热力学和动力学两方面的影响；同时，一些开创性的研究表明，在反应过程中，施加外界刺激（例如，超声、光等）能保持体系的热力学不变，发现动力学过程对调节组装体的尺寸、尺寸分布等具有非常明显的效果。
在本文中，我们维持所有反应物种类、用量及溶剂环境不变，确保不改变组装体系的热力学参数，仅通过改变反应物混合顺序及改变前躯体的预组装方式两种方法，探究了组装动力学过程对组装结构的影响。研究表明：反应物不同的混合顺序能够得到不同尺寸的前驱体，进而生成不同尺寸的组装体；并且，通过将反应物预组装能够使组装过程中的聚集过程和结晶过程分开，从而影响组装的速度和产率，基于此，我们开发了使用预组装的金（I）-巯基丙酸和银（I）-巯基丙酸制备金（I）/银（I）-巯基丙酸杂化共组装纳米片层的方法。本论文是基于不改变热力学参数的前提，单独考察组装动力学对组装体结构的影响，研究结果向人们展示了组装动力学过程对复杂组装体系的强大的调控作用。
react to 结构
关键词：
金（I）-硫醇配位聚合物，组装过程，反应物顺序，预组装，金银纳米合金粒子
Controlling the assembly kinetics of Au(I)-MPA nanosheets
Abstract
Supramolecular assemblies have dynamic reversibility due to the weak noncovalent driving forces, and they have properties of stimuli-responsiveness and environmental accumulation. Supramolecular assemblies are usually classified by the assembly driving force, such as, hydrogen bond, coordination bond, host-guest interaction, electrostatic interaction, π-π interaction, hydrophobic interaction, and so on. Au(I)-thiolate coordination polymers, as a special kind of supramolecular building block, not only have the traditional weak interactions (such as, hydrogen bond, coordination interaction, and Van der Waals' force) as the driving forces, but also have the unique aurophilic interaction, which makes the assembly pathway and the structures more complicated, therefore, Au(I)-thiolate can be used as a model system to understand the hierarchical assembly process of biomacromolecules, such as protein and DNA. At present, most of the methods to control the assembly pathway are changing the temperature, concentration, recipee, solvent, and so on. These methods can both change the thermod
ynamics and the kinetics. And some poinner researches have investigated the role of kinetic parameters, such as ultrasound and light on the assembly process, and it reveals the kinetic parameters have played important role in control of the assembly sizes and size distributions.
Here, all the thermodynamic parameters are kept invariable by keeping reactants and solvent unchanged, the reactants mixing sequence and preassembly of reactants was used to tune the assembly kinetics. Results show that the mixing sequence at the very first several seconds can greatly change the size of the product because of the change of the size of the precusor; pre-assemble of the reactants to different sized precursors can separate aggregation and crystallization and change the conversion rates and yields, based on the above results, we exploit a method of synthesizing Au(I)/Ag(I)-MPA hybrid assemblies by mixing pre-assemblied Au(I)-MPA and Ag(I)-MPA. The study aims to study the role of kinetic parameters on the assembly of

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