SYNTHESIS AND FUCTION OF NOVEL QUINOPROTEIN COENZYME MODEL

1. 摘要开发了一种新型藜蛋白辅酶HO模型的合成方法——2-乙基乙酰乙酸甲酯的合成方法。采用相转移催化体系进行选择性2-乙基化反应。该方法为TTQ模型系统提供了一种有效的协同路由。作为氧化剂，蚯蚓的盐似乎比在最后的氧化步骤中更有效。研究了一类典型的藜蛋白辅酶PQQ在胶束体系中对胺类生物有机底物的有效氧化反应。卵磷脂是细胞膜的一种成分，它能显著增强氧化反应，而免疫反应通常用于形成酶模型系统。这可能是由于胺分子和辅酶PQQ比胶束更有效地定向进入囊泡的反应位点，并且在囊泡上的反应似乎类似于生物系统。基于囊泡的概念，为了形成更有效的反应位点，研究了几种具有两个疏水性基团的表面活性剂对pqq氧化胺的影响。二十二烷基二甲基溴化铵对该反应的影响大于卵磷脂，而双星型表面活性剂对该反应没有明显的促进作用。双子型表面活性剂似乎将底物固定在两条疏水链之间。阐明了底物、反应部位组分的分子结构与酶和辅酶模型极性之间的密切关系对藜蛋白模型的设计具有重要意义。

1. SYNTHETIC METHOD OF METHYL 2-ETHYLACETOACETATE AS AN IMPORTANT KEY BUILDING BROOK ARE DEVELOPED FOR A SYNThESIS OF HO MODEL WHICH IS ONE OF NOVEL COENZYME OF QUINOPROTEIN.THE SELECTIVE 2-ETHYLATION IS PERFORMED BY USING OF PHASE TRANSFER CATALYTIC SYSTEM.THIS METHOD PROVIDES AN EFFECTIVE SYNIIIEHC ROUT FOR TTQ MODEL SYSTEMS.AS AN OXIDANT, THE FREMY'S SALT SEEMS TO BE AN EFFECTIVE OXIDANT THAN CAN IN THE FINAL OXIDATION STEP.2. EFFECTIVE OXIDATION REACTION OF AMINES AS A BIOORGANIC SUBSTRATE BY PQQ WHICH IA A TYPICAL COENZYME OF QUINOPROTEIN WERE STUDIED IN THE MICELLAR SYSTEMS.LECITHIN, ONE OF THE COMPONENT OF CELL MEMBRANE,ENHANCED SIGNIFICANTLY THE OXIDATION REACTION THAN THE CASE OF JAB WHICH WAS ADAPTED USUALLY TO FORM ENZYME MODEL SYSTEMS.THIS MAY BE DUE TO THE EFFECTIVE ORIENTATION OF AMINE MOLECULE AND COENZYME PQQ INTO THE REACTION SITE OF THE VESICLE THAN THAT OF MICELLE, AND THE REACTION ON THE VESICLE IS SEEMED TO BE RESEMBLE TO THE BIOLOGICAL SYSTEM.3. TO FORM MORE EFFECTIVE REACTION SITE BASED ON THE CONCEPT OF THE VESICLE, EFFECT OF SEVERAL SURFACE ACTIVE AGENTS HAVING TWO HYDROPHOBIC GROUPS ON THE OXIDATION OF AMINE BY PQQ.DIDODECYLDIMETHYLAMMONIUM BROMIDE WAS MOST EFFECTIVE TO THE REACTION THAN LECITHIN, AND GEMINI-TYPE SURFACTANT DID NOT SHOW ANY POSlTIVE EFFECT SURPRISINGLY.IT IS SEEMED THAT GEMINI-TYPE SURFACTANT FIXED THE SUBSTRATE BETHEEN TWO HYDROPHOBIC CHAINS.4. IT IS CLARIFIED THAT THE INTIMATE RELATIONSHIP BETWEEN THE SUBSTRATE, THE MOLECULAR STRUCTURE OF COMPONENT OF THE REACTION SITE AND THE POLARITIES OF ENZYME AND COENZYME MODELS IS IMPORTANT TO DESIGN OF QUINOPROTEIN MODEL,