BIOLOGICALLY IMPORTANT ENOLS

具有重要生物学意义的烯醇

• 批准号: 3302194
• 负责人: ALEXANDER J KRESGE
• 金额: $ 6.26万
• 依托单位: UNIVERSITY OF TORONTO
• 依托单位国家: 美国
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-09-01 至 1993-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3302194
• 关键词: acetyl coA; chemical elimination; chemical structure function; cyclic ketone; dihydroxyacetone; diol; enol; enzyme mechanism; flash photolysis; glycerophosphates; high energy compound; oxidation reduction reaction; phosphoenolpyruvate; photochemistry; thioester; triose phosphate isomerase; water solution

This application describes a program of research designed to investigate the chemistry of biologically important keto-enol systems using the new methods which we have recently developed for examining simple unstable enols in aqueous solution. Three different enols and related substances would be studied: (1) triosephosphate enediol, (2) enolpyruvate, and (3) the enol of acetyl coenzyme A. These enols would be generated flash photolytically by photooxidation-reduction and Norrish type Ii photoelimination as well as thermally by hydrolysis of silyl enol ethers and potassium enolate salts, and rates of their ketonization reactions as well as rates of enolization of the carbonyl isomers would be measured. This would provide basic information, such as keto-enol equilibrium constants and acidity constants of the enols and their keto isomers, which would be helpful in understanding the functions and modes of action of these biologically important molecules. For example, further insight would gained into the mechanism of conversion of dihydroxyacetone phosphate into gyceraldehyde-3-phosphate through catalysis by triosephosphate isomerase, which is a critical step in the glycolytic pathway. The proposed research would also show just how much of the high energy content of phosphoenolpyruvate resides in its masked enol function, and it would elucidate the advantage that thiol esters such as acetyl coenzyme A have over oxygen esters in promoting biological reactions.

该应用程序描述了一项旨在调查的研究计划 使用新的生物学上重要的酮 - 烯醇系统的化学 我们最近开发了用于检查简单不稳定的方法 烯醇水溶液。 三种不同的烯醇和相关物质 将研究：（1）三塞磷酸烯二醇，（2）烯醇酮，（3） 乙酰辅酶A的烯醇A。这些烯醇将产生闪光灯 通过光氧化降低和Norrish II型光子释放 通过水解水解的光照明和热解 盐和钾的腐蚀及其酮化反应的速率为 将测量羰基异构体的载体。 这将提供基本信息，例如酮 - 烯醇平衡 烯醇及其酮异构体的常数和酸度常数 将有助于理解的功能和行动方式 这些在生物学上重要的分子。 例如，进一步的见识将 进入二羟基丙酮磷酸转化为 三卫二磷酸异构酶催化，酮醛3-磷酸盐， 这是糖酵解途径中的关键步骤。 拟议的研究 还将显示多少高能量含量 磷酸烯醇丙酮酸属于其掩盖烯醇功能，它将 阐明硫醇酯（如乙酰辅酶A）具有的优势 在促进生物反应中的氧酯上。