SYNTHESIS AND FUCTION OF NOVEL QUINOPROTEIN COENZYME MODEL

1.研究了2-乙基乙酰乙酸甲酯的合成方法，为喹丙氨酸的新型辅酶HO模型的合成提供了一条重要的途径。该方法利用相转移催化体系进行选择性的2-乙基化反应。该方法为TTQ模型体系的合成提供了一条有效的合成路线。在胶束体系中，研究了喹诺蛋白的典型辅酶PQQ对生物有机底物中胺的有效氧化反应。细胞膜的一种成分LECITHIN显著促进了氧化反应，这可能是由于胺分子和辅酶PQQ比胶束更有效地定向到囊泡的反应部位，而在囊泡上的反应似乎类似于生物系统。基于囊泡的概念，考察了几种具有两个疏水基团的表面活性剂对PQQ氧化胺的影响，其中溴化十二烷基二甲基甲烷比卵磷脂更有效，双子型表面活性剂对底物BETHEEN有两个疏水CHAINS固定。阐明了底物、反应部位组分的分子结构与酶模型和辅酶模型的极性之间的密切关系是设计喹诺蛋白模型的重要因素。

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,