Supramolecular Dynamics in Solution and in Gels

溶液和凝胶中的超分子动力学

• 批准号: RGPIN-2017-04458
• 负责人: Bohne, Cornelia
• 金额: $ 5.39万
• 依托单位: University of Victoria
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747790
• 关键词: Supramolecular; Dynamics; Solution; Gels

Supramolecular chemistry occupies the space between individual molecules and macroscopic systems in terms of complexity and functionality. Two key features of supramolecular systems are: 1) the reversible assembly of a supermolecule from molecular building blocks and 2) the co-existence of related species that compete with one another. These characteristics are those exhibited in very complex macroscopic living systems. My research aims to understand the dynamic nature of supramolecular systems and will provide the concepts necessary for rational control of these systems from the kinetic point of view. Such kinetic control, which is currently lacking, will open new ways to design functional materials, where the dynamics of the components are essential for function. The research proposed is at the forefront of fundamental studies and does not directly address any particular function, but the outcomes have implications for any supramolecular system where binding and release of building blocks is integral to function, such as membrane transport, drug delivery, catalysis, or stimuli-responsive materials. The proposed research is allied with “systems chemistry”, in which interactions of molecular building blocks produce new properties that the individual components cannot achieve on their own.To develop and exploit inherently complicated systems, we need to develop tools to explore and manipulate the system's outcomes. The proposed work confronts the diversity of supramolecular systems, with a focus on the kinetic control of gel-forming systems.The proposed work with cucurbit[n]urils (CB[n]s) as host systems will provide the tools to manipulate the dynamics of host-guest systems. This knowledge will lay the groundwork for rationally using kinetics to change the behaviour of systems with multiple species, which currently is not possible. The mechanistic diversity we uncovered for guest binding with CB[n]s will be explored to determine how co-adjuvant players can lead to switches in mechanism, how self-sorting systems can be diverted as they evolve, and how the residence time of guests that simultaneously bind to CB[8] can affect the formation of gels.The mobility of small guests in gels will be studied over microscopic to macroscopic length scales to provide information focused on the gel's molecular components. This approach will uncover knowledge that is different from the macroscopic characterization usually reported for gels. This type of experiment, where the focus is on the kinetics of individual components and the relationship to the microscopic structural features of gels, is unprecedented. As a potential practical application, the proposed work will contribute to moving the development of gels away from a trial and error approach.

超分子化学在复杂性和功能性方面占据了单个分子和宏观系统之间的空间。超分子系统的两个关键特征是：1）从分子构建块可逆组装超分子和2）相互竞争的相关物种的共存。这些特征是在非常复杂的宏观生命系统中表现出来的。我的研究旨在了解超分子系统的动态性质，并将提供从动力学角度合理控制这些系统所需的概念。目前缺乏的这种动力学控制将为设计功能材料开辟新的途径，其中组件的动力学对于功能至关重要。这项研究处于基础研究的最前沿，并不直接涉及任何特定的功能，但其结果对任何超分子系统都有影响，其中构建模块的结合和释放是功能不可或缺的，例如膜转运，药物递送，催化或刺激响应材料。这项研究与“系统化学”有关，在系统化学中，分子构件的相互作用产生了单个组分无法单独实现的新特性。为了开发和利用内在复杂的系统，我们需要开发工具来探索和操纵系统的结果。本论文针对超分子体系的多样性，重点研究了凝胶形成体系的动力学控制，并以葫芦型联脲（CB[n]s）为主体体系，为调控主客体体系的动力学提供了工具。这些知识将为合理地使用动力学来改变多物种系统的行为奠定基础，这在目前是不可能的。我们发现的客体与CB[n]结合的机制多样性将被探索，以确定辅助剂参与者如何导致机制的转换，自我分选系统如何随着它们的进化而转移，以及同时与CB绑定的客人的停留时间如何[8]可以影响凝胶的形成。凝胶中小客体的迁移率将在微观到宏观的长度尺度上进行研究，以提供信息专注于凝胶的分子组成。这种方法将揭示不同于凝胶通常报告的宏观表征的知识。这种类型的实验，其中的重点是对单个组件的动力学和凝胶的微观结构特征的关系，是前所未有的。作为一个潜在的实际应用，拟议的工作将有助于移动凝胶的发展远离试错法。