The development and mechanistic understanding of solid-state reactivity for energy- and materials-efficient synthesis

拟议的研究旨在了解和发展固态反应性，以此作为实现清洁、环境友好型化学合成的一种手段，开发用于封存二氧化碳的新材料，并引入在溶液中难以或不可能发生的化学反应。开发更清洁、更安全和更有效的合成方法是现代化学的核心挑战之一。在这方面，无溶剂力化学(即机械研磨或研磨引起的化学转化)显示出可以与传统溶液化学相媲美甚至超过的合成潜力。在实现更清洁、更节能的反应的同时，机械力化学还打开了通往化学反应和产品的途径，而这些反应和产品以前被认为是难以实现的，甚至是不可能实现的。我们的团队一直处于这一发展的前沿，特别是在合成用于气体储存的微孔金属-有机骨架(MOF)方面，开发获得活性药物成分(API)的新途径，并引入第一批机械力化学反应的实时机理研究技术。 然而，尽管有如此快速的发展，机械力化学和相关的固相反应技术仍然知之甚少，缺乏对机理的了解和反应能量学限制了其进一步发展。 我们将以我们在机械化反应的实时、原位反应监测方面的独特专业知识为基础来应对这一挑战，开发新的技术，使我们能够详细了解机械化学在整体反应物结构以及分子结构和环境方面的变化。这些新的衍射、光谱和热技术将与计算模型一起使用，以促进MOF的合成和理解，以及开发新的有机转化。成果将是机械力化学和无溶剂反应方面的进展，不仅为孔隙率而设计的MOF的开发，也为稳定性设计的MOF的开发，以及酰胺和氨基酸的新偶联反应，这些都是制药和化学工业的重要起始原料。我们将在无溶剂化学方面开发新的方向，特别是机械力和光化学的耦合，以及在研磨条件下的酶催化。提供固态作为一种全新的酶活性介质可能会给生物质加工带来革命性的变化，我们将开发这种无溶剂酶催化剂来分解顽固的生物质聚合物甲壳素和木质素。拟议的研究成果将成为开发可持续和清洁化学方法和材料的主要里程碑，并将极大地促进加拿大作为化学创新和制造领域的领导者的地位。

The proposed research is aimed towards understanding and developing solid-state reactivity as a means of achieving clean, environmentally-friendly chemical synthesis, developing new materials for sequestration of carbon dioxide, and introducing chemical reactions that are difficult or not possible in solution. The development of cleaner, safer and more efficient synthetic methodologies is one of the central challenges of modern chemistry. In that context, solvent-free mechanochemistry (i.e. chemical transformations induced by mechanical grinding or milling) has revealed synthetic potential that can match, and even exceed that of conventional solution chemistry. While enabling cleaner, more energy-efficient reactivity, mechanochemistry also opens access to chemical reactions and products that have previously been thought difficult, or even impossible to achieve. Our group has been at the cutting edge of this development, especially in the synthesis of microporous metal-organic frameworks (MOFs) for gas storage, developing new routes to active pharmaceutical ingredients (APIs), and introducing the first techniques for real-time mechanistic studies of mechanochemical reactions. However, despite such rapid growth, mechanochemistry and related solid-state reaction techniques still remain poorly understood, with a lack of mechanistic understanding and reaction energetics limiting its further development. We will address this challenge by building on our unique expertise in real-time, in situ reaction monitoring of mechanochemical reactions, to develop new techniques that will give us a detailed understanding of mechanochemistry in terms of changes in bulk reactant structure, as well as changes in molecular structure and environment. These new diffraction, spectroscopic and thermal techniques will be used along with computational modelling to advance the synthesis and understanding of MOFs, as well as to develop new organic transformations. The deliverables will be advances in mechanochemistry and solvent-free reactivity, development of MOFs designed not only for porosity, but also for stability, as well as new coupling reactions of amides and amino acids, important starting materials in pharmaceuticals and chemical industry. We will develop new directions in solvent-free chemistry, notably the coupling of mechano- and photochemistry, and enzyme catalysis under milling conditions. Offering the solid state as a completely new medium for enzyme activity could revolutionize biomass processing, and we will develop such solvent-free enzyme catalysis for the breakdown of recalcitrant biomass polymers chitin and lignin. The outcomes of proposed research will be major milestones in developing methods and materials for sustainable and clean chemistry, and will greatly contribute to the position of Canada as a leader in chemical innovation and manufacturing.