基于铀的人工金属蛋白的分子组装及不对称催化性能研究

项目名称： 基于铀的人工金属蛋白的分子组装及不对称催化性能研究

项目编号： No.11275090

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 聂长明

作者单位： 南华大学

项目金额： 80万元

中文摘要： 铀化合物催化剂由于其优异性能已成为近年的研究热点。用人工金属配合物作辅基与脱辅基金属蛋白组装而成的人工金属蛋白在分子识别和分子催化方面有着巨大的应用前景。α,β-不饱和醛酮的不对称催化加成和1-炔化物选择性催化加成一直是研究的难点。本项目拟以铀为金属中心，以Salophen修饰物为配体，设计及合成与血红素分子结构类似的配合物，将该配合物作为人工金属蛋白辅基，与脱辅基肌红蛋白Apo-Mb进行人工组装,构建以铀配合物为辅基的人工金属蛋白U-S-Apo-Mb。同时利用基因工程和蛋白质工程技术，调节蛋白质活性中心结构，研制出温和反应条件下对α,β-不饱和醛酮的不对称Michael加成和对1-炔化物选择性硅氢化加成具有高催化活性的新型人工金属蛋白催化剂，取得以铀配合物为辅基的人工金属蛋白的构建方法和理论。为人工金属蛋白的催化应用研究提供新线索，拓展铀的应用研究领域，并为不对称催化研究提供新的切入点。

中文关键词： 铀；人工金属蛋白；分子设计；分子组装；不对称催化

英文摘要： The catalysis of uranium compounds has been a research hotspot recently due to its excellent properties. Artificial metalloproteins, as assembled by artificial metal complexes with apo-metalloproteins, have great potential applications in molecular recognition and molecular catalysis. The asymmetric catalytic addition for α，β-unsaturated aldehydes and ketones and the selective catalytic addition for 1-acetylides have been the difficulties in catalysis research. The project intends to design and synthesize some complexes with uranium as a metal center and salophen derivatives as ligands, which are structurally similar to heme molecule. The complexes are then used as artificial prosthetic groups of metalloproteins and assembled with apo-myoglobin (Apo-Mb) to construct artificial metalloproteins based on uranium complexes, U-S-Apo-Mb. At the same time, the protein active site structure and catalytic properties are adjusted by using genetic engineering and protein engineering techniques, and the new artificial metalloproteins are developed with high asymmetric Michael catalytic addition activity for α, β-unsaturated aldehydes and ketones and highly selective catalytic hydrosilylation addition for 1-cetylides under temperate conditions. The methodology and theory of construction of artificial metalloproteins are the

英文关键词： uranium；artificial metalloprotein；molecular design；molecular assembly；asymmetric catalysis