Development of alternative solvents, catalysts and tools for biomass conversion

这项研究的主要目标是开发和评估替代催化剂、溶剂和流动化学工具，以将木质纤维生物质提升为附加值产品。尽管可切换亲水性溶剂(SHSS)或二氧化碳等替代溶剂领域现在已经很先进，但我建议将SHSS和GASS作为分离系统和催化剂来精制高附加值的生物产品。在所有生物质升级阶段都可以发现新的用途，例如提取(例如用于提取木质素单体的SHSS)或催化(例如使用二氧化碳作为催化剂从纤维素中生产生物喷气燃料)。我的研究计划的长期目标是开发和评估替代催化剂、溶剂和流动化学工具，以将木质纤维生物质提升为附加值产品。在这笔探索补助金的期限内要解决的具体短期目标包括以下两个主题：1)在生产增值产品时使用SHS作为催化剂和溶剂；2)在生产生物质衍生产品时使用气体作为催化剂、反应物和溶剂。主题1和主题2可以被认为是平行的流，其目标是开发替代催化剂、溶剂以及将它们应用于批量和流动的生物质转化的方法。在主题1中，SHSS被评价为催化剂和溶剂；在主题2中，废气被评价为同样的作用。主题1希望扩展我目前的工作，使用SHSS作为羟醛缩合反应的催化剂。展望了四个主要的次级活动：1)在其他反应中用作催化剂以产生高附加值的大分子前体(如伪麻黄碱、安非他明、邻氨基苯甲酸、雷尼替丁、5-(二甲氨甲基)呋喃醇、2-[[(5-dimethylamino-methyl-2-furanyl)methylthio]ethaneamine，等)；2)开发新型手性固体催化剂并评价其作为催化剂的应用；3)在生物质转化和升级中将其作为溶剂和催化剂进行测试；4)开发利用该催化剂的流动系统。主题2旨在将废气的使用扩展到新的反应和生物质转化系统。1)废气将在各种反应中用作催化剂、反应物和溶剂(例如，硫醇类型的Michael加成、Henry反应、Diels-Alder、Nitro Aldol等)。扩大的使用范围将包括评估“肮脏”的废气，而不是清洁的实验室气体。2)第1部分中学到的经验教训将应用于使用气体作为提高木质纤维生物质质量的溶剂和催化剂。3)将利用在以前的子项目中获得的信息来开发流动技术。

This research's primary objective is to develop and assess alternative catalysts, solvents, and flow chemistry tools to upgrade lignocellulosic biomass to value-added products. Although the field of alternative solvents such as switchable hydrophilicity solvents (SHSs) or CO2 is now well advanced, I propose novel uses of SHSs and gasses as separation systems and catalysts for refining of value-added bioproducts. Novel uses can be found in all biomass upgrading stages, such as extraction (e.g. SHSs used to extract lignin monomers) or catalysis (e.g. use of CO2 as a catalyst in producing bio-jet fuel from cellulose). My research program's long-term objective is to develop and assess alternative catalysts, solvents, and flow chemistry tools to upgrade lignocellulosic biomass to value-added products. The specific short-term objectives to be addressed within the tenure of this Discovery Grant fall in the following two themes: 1) Use of SHS as both catalyst and solvent in the production of value-added products; 2) Use of gases as a catalyst, reactant and solvent for the production of biomass-derived products. Themes 1 and 2 can be conceived as parallel streams where the objective is to develop alternative catalysts, solvents, and the methods to apply them to biomass conversion in batch and flow. In Theme 1, SHSs are evaluated as catalysts and solvents; in Theme 2, waste gases are evaluated for the same roles. Theme 1 looks to expand on my current work using SHSs as catalysts in aldol condensation. Four main sub-activities are envisioned: 1) use of SHSs as catalysts in other reactions to produce value-added macromolecule precursor (e.g. pseudoephedrine, acedoben, anthranilic acid, ranitidine, 5-(dimethylamino-methyl)furan alcohol, 2-[[(5-dimethylamino-methyl-2-furanyl)methylthio]ethaneamine, etc.), 2) development of novel chiral SHSs and assessment of their use as catalysts, 3) testing of SHSs as solvents and catalysts in biomass conversion and upgrading, 4) development of flow systems utilizing SHSs. Theme 2 aims at extending the use of waste gasses into novel reactions and biomass conversion systems. Three main sub-activities fall under this theme 1) waste gasses will be used as catalyst, reactant, and solvent in various reactions (e.g. thiol type Michael addition, Henry reaction, Diels-Alder, Nitro aldol etc.). The increased scope of use will include assessing "dirty" waste gasses as opposed to clean laboratory gasses. 2) the lessons learned in part 1 will be applied to using gasses as solvent and catalyst in upgrading lignocellulosic biomass. 3) flow techniques will be developed using the information gained in previous sub-projects.