Conformational control of the structure and properties of synthetic porous materials

合成多孔材料结构和性能的构象控制

• 批准号: EP/W036673/1
• 负责人: Matthew Rosseinsky
• 金额: $ 107.49万
• 依托单位: University of Liverpool
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FW036673%2F1
• 关键词: Conformational; control; structure; properties; synthetic

This is a long-range basic research project that targets the synthesis of crystalline porous materials that respond to their chemical environment in the way that biological molecules do. Although the potential analogy between synthetic porous materials and biological molecules has been suggested for many years, we can now address this problem meaningfully for the first time because of the results on which the project is based. This will create immediate opportunities in fundamental science and understanding.Porous materials underpin the separation and catalysis processes of the modern chemical industry by controlling the organisation of guests in their pores. These high-performing materials, such as zeolites and carbons, all have rigid structures that do not change regardless of their chemical environment: dynamics within this single structural minimum can be important, but the size and shape of the pores that control guest response are unchanged. In contrast, the biological molecules involved in sorting, separation and catalysis can respond in a flexible manner to their chemical environment. To do this, they use rotation about single bonds to restructure in the presence of guest molecules, adopting different structures within their conformational energy landscape. The responses are characterised as conformational selection and induced fit according to the nature of the final structure and its relationship to the accessible structural states of the biological molecule. This produces exquisite chemical selectivity by organising the diverse array of spatially ordered chemical functionality that is also characteristic of biological molecules for functional performance.In contrast, we have not previously been able to prepare synthetic porous materials with controllably interconvertible structures accessible via single bond rotation, nor to introduce spatially ordered multiple chemical functions into a synthetic porous material that could restructure by such single bond rotation. The creation of tuneable synthetic porous materials that can controllably respond to guests as biomolecules do would offer pathways for the separation and transformation of small molecules that are distinct from those accessible to current synthetic porous materials.In a recent paper in Nature, we reported a crystalline porous material that responds to guests like a biological molecule. Specifically, it displays both conformational selection and induced fit responses that demonstrate a conformational energy landscape created by different rotations of single bonds in the porous material structure: these responses are then used to controllably trigger guest uptake. This project will establish how to achieve and control such guest response by creating new families of such porous materials with diverse structure and chemistry. It will thus create a new direction in porous materials research.This will be achieved by defining the synthetic chemistry required to introduce diverse chemical functionality that can broadly direct guest response, by ordering multiple functionalities precisely in space and by expanding the size and geometry of the pore systems. The resulting materials will offer new modes of guest response that will be understood through detailed evaluation of the arising structures and associated sorption behaviour. This will allow the design of improved materials based on knowledge of how to determine guest response through single bond rotation by chemistry and sequence. The range of new materials families with distinct conformational energy landscapes spanning pore sizes, geometries and chemical functionalities offer control of function in sorption, separation and catalysis by previously inaccessible mechanisms. This will allow us to evaluate and understand the impact of biomolecule-like conformational response on the capabilities of synthetic porous materials.

这是一个远程基础研究项目，它针对晶体多孔材料的合成，以生物分子的方式响应其化学环境。尽管已经提出了多年的合成多孔材料和生物分子之间的潜在类比，但由于项目的结果，我们现在可以首次有意义地解决这个问题。这将在基本科学和理解中立即创造机遇。孔子材料是通过控制毛孔中客人的组织来支撑现代化学工业的分离和催化过程。这些高性能的材料，例如沸石和碳，都具有不变的刚性结构，无论其化学环境如何：在此单个结构最小值内的动态可能很重要，但是控制来宾响应的孔的大小和形状不变。相比之下，分类，分离和催化涉及的生物分子可以灵活地对其化学环境做出反应。为此，他们使用围绕单个键的旋转在宾客分子的存在下进行重组，并在其构象能量范围内采用不同的结构。这些响应的特征是构象选择，并根据最终结构的性质及其与生物分子的可访问结构状态的关系而诱导拟合。 This produces exquisite chemical selectivity by organising the diverse array of spatially ordered chemical functionality that is also characteristic of biological molecules for functional performance.In contrast, we have not previously been able to prepare synthetic porous materials with controllably interconvertible structures accessible via single bond rotation, nor to introduce spatially ordered multiple chemical functions into a synthetic porous material that could restructure by such single bond rotation.创建可调的合成多孔材料，可以像生物分子一样对客人做出反应，这将为途径提供途径，用于分离和转化小分子，这些分子与目前的合成多孔材料不同。在最近的一篇论文中，我们报告了一种晶体的多孔材料，对客人响应了像生物学分子一样。具体而言，它既显示构象选择，又显示诱导的拟合响应，这些响应证明了由多孔材料结构中单键不同旋转产生的构象能量景观：然后使用这些响应来控制触发客人的吸收。该项目将通过创建具有多种结构和化学的多孔材料的新家庭来建立如何实现和控制此类来宾的反应。因此，它将在多孔材料研究中创建一个新的方向。这将通过定义引入各种化学功能所需的合成化学能力来实现，这些化学功能可以通过精确订购空间中的多个功能，并扩大孔系统的大小和几何形状，从而广泛地指导客人响应。最终的材料将提供新的客人响应方式，这些方式将通过详细评估出现的结构和相关的吸附行为来理解。这将允许根据如何通过化学和序列单键旋转来确定客人响应的知识来设计改进的材料。具有独特构象能景观的新材料家族跨越孔径，几何形状和化学功能的范围可通过以前无法访问的机制控制吸附，分离和催化中的功能。这将使我们能够评估和理解类似于生物分子的构象反应对合成多孔材料能力的影响。