离子液体包水微乳液中脂肪酶催化C-C形成反应

Compared to the traditional organic method,enzymatic synthesis works in a high stereo and regio selective or specific manner has been extensively used. In recent years, research finds catalytic promiscuity of enzyme.howover solvents physical properties such as dielectric constant, dipole moment and hydrophobicity are related to various effects on enzyme activity, specificity,promiscuity and enantioselectivity.. The physical-chemical properties of ionic liquids (ILs) can be adjusted for specific applications by varying the structures of their cations and/or anions.The technological utility of enzymes can be enhanced greatly by their use in ILs rather than in conventional organic solvents or in their natural aqueous reaction media due to their unique physicochemical properties.The use of ILs has manifested many advantages, such as high conversion rates, high enantioselectivity,better enzyme stability, as well as better recoverability and recyclability. However one important drawback regarding the use of enzymes in ILs is the fact that they are not soluble in most ILs. To improve enzyme solubility as well as activity in ILs,various attempts have been in vestigated. Many approaches are often laborious and timeconsuming as well tedious,and they also suffer from high costs. one of the most promising approaches to solve this problem is to form nano/micrometer-sized water domain in an ILs continuous phase (noted as w/IL microemulsions). So the project will be studied the reaction of carbon-carbon bond formation catalyzed by lipases in water in ionic liquids microemulsions.. Application of biocatalysis and green organic synthesis will be promoted in the project resaerchs.

酶被认为是一种快速、专一的生物催化剂，许多具有催化选择性的酶广泛应用于有机合成中。研究新发现：酶能够在活性位点催化其它反应，即催化多功能性。本项目将利用离子液体的可设计性，设计合成离子液体，以离子液体包水微乳液（即W/IL微乳液）为反应介质，脂肪酶为多功能生物催化剂，催化多种类型的C-C键形成反应；建立脂肪酶催化C-C形成的反应规律。"离子液体包水"微乳液克服了水、有机介质和离子液体的不足，提高了酶的溶解性、稳定性和活性，增加反应底物的溶解度，提高反应产率和选择性。本项目的研究将推动脂肪酶在生物催化中应用，加快绿色合成技术和方法的发展，具有重要的学术意义和社会效益。

酶作为生物催化剂应用于有机合成是目前最吸引人的研究领域之一，酶的催化多功能性（Catalytic promiscuity）进一步拓展了酶在有机合成领域的应用。“离子液体包水”微乳液是兼顾酶活性、溶解性和稳定性的有效介质。C-C键形成反应是最重要有机合成反应之一，Aldol反应、Henry反应、Michael加成反应等都是建立C-C键的有效途径。本项目以脂肪酶、蛋白酶等水解酶为多功能催化剂，以W/IL微乳液为反应介质，实现了C-C键的高效合成。先后研究了W/IL微乳液中脂肪酶、蛋白酶、酰化酶催化的Henry反应、aldol反应、Michael加成反应及关环反应等C-C键形成反应，并对W/IL微乳液中水解酶催化C-C键形成反应的机理和规律进行了探索。建立了W/IL微乳液中脂肪酶、蛋白酶、酰化酶催化Henry反应、aldol反应、Michael加成反应等形成C-C键的方法；提高了水解酶催化C-C键形成反应的效率，实现了不对称合成；明确了W/IL微乳液中影响脂肪酶活性、溶解性和稳定性的因素，但W/IL微乳液中脂肪酶催化C-C键形成反应的规律还不太明确，相关研究仍在继续进行中。本项目共培养研究生9人，公开发表SCI研究论文9篇。该项目研究结果进一步拓展了离子液体在有机合成领域的应用，对推动绿色化学和酶促反应方法学的发展也将具有重要意义。