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

拟议的研究旨在理解和发展固态反应性，作为实现清洁，环境友好的化学合成，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的化学反应的手段。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。在这种情况下，无溶剂机械化学（即由机械研磨或碾磨引起的化学转化）已经揭示了可以匹配甚至超过传统溶液化学的合成潜力。在实现更清洁，更节能的反应的同时，机械化学也为以前被认为很难甚至不可能实现的化学反应和产物开辟了途径。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框架（MOFs），开发活性药物成分（API）的新途径，并引入第一种用于机械化学反应实时机理研究的技术。 然而，尽管如此快速的增长，机械化学和相关的固态反应技术仍然知之甚少，缺乏机械理解和反应能量学限制了其进一步发展。 我们将通过建立在我们独特的专业知识，实时，原位反应监测机械化学反应，开发新技术，使我们详细了解机械化学在散装反应物结构的变化，以及分子结构和环境的变化。这些新的衍射、光谱和热技术将与计算建模一起沿着使用，以推进对MOFs的合成和理解，以及开发新的有机转化。交付成果将是机械化学和无溶剂反应性的进步，不仅为孔隙率设计的MOFs的开发，而且还为稳定性设计，以及酰胺和氨基酸的新偶联反应，制药和化学工业中的重要起始材料。我们将在无溶剂化学中发展新的方向，特别是机械和光化学的耦合，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以彻底改变生物质加工，我们将开发这种无溶剂的酶催化剂，用于分解生物质聚合物几丁质和木质素。拟议研究的成果将成为开发可持续和清洁化学方法和材料的重要里程碑，并将大大有助于加拿大作为化学创新和制造业的领导者。

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.