BIOLOGICALLY IMPORTANT ENOLS

具有重要生物学意义的烯醇

• 批准号: 2181877
• 负责人: ALEXANDER J KRESGE
• 金额: $ 9.47万
• 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 1996-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2181877
• 关键词: carbonyl group; chemical elimination; chemical kinetics; chemical reaction; dihydroxyacetone; diol; divalent cations; enol; enzyme mechanism; flash photolysis; glyoxal; hydroxyl group; ionization constant; isomer; isomerase; phosphoenolpyruvate; phosphorylation; photochemistry; proline; protective chemical group; racemization; solvolysis; thermodynamics; thioester

Enols and enolate ions are essential intermediates in many biological reactions this application describes a program of research designed to investigate the chemistry of biologically important enols for the purpose of providing basic information needed to understand the functions and modes of action of these substances. The investigation would be conducted using techniques which the Principal Investigator has recently developed for studying simple unstable enols in aqueous solution. These include flash photolytic generation of enols by Norrish type II photoelimination, photooxidation-reduction, and photolytic removal of protecting groups, as well as thermal production of enols by hydrolysis of metal enolates and silyl enol ethers. Rates of ketonization of the enols would be measured as well as rates of enolization of their keto isomers; these data would provide keto-enol equilibrium constants and also acidity constants of the enols ionizing as oxygen acids and their keto isomers ionizing as carbon acids. Work would be continued on the enols of thiol esters and mandelic and pyruvic acids, for the purpose of understanding the modes of action of coenzyme A and mandelate racemase as well as the mechanism of the "uncatalyzed" ketonization of pyruvate enol. New research would also be initiated on enediols and the enol of proline, the former to provide information relevant to the enzymatic isomerization of saccharides, especially that catalyzed by triosephosphate isomerase, and the latter in order to furnish a non-enzymatic reaction base against which to assess the efficiency of the process promoted by proline racemase.

烯醇和烯基离子是许多生物学中必不可少的中间体 反应本应用程序描述了一个旨在的研究计划 为此目的研究生物学上重要的烯醇的化学反应 提供理解功能所需的基本信息和 这些物质的作用方式。 调查将进行 使用主要研究者最近开发的技术 用于在水溶液中研究简单的不稳定烯醇。 这些包括 通过Norrish II型光照明的闪光发光生成烯醇， 降低光氧化 - 保护组的光解去除去 以及通过金属烯醇水解烯醇的热产生烯醇和 Silyl Enol Ethers。 将测量烯醇的酮化速率 以及其酮异构体的载体率；这些数据会 提供酮 - 烯醇平衡常数和酸度常数 烯醇电离为氧气及其酮异构体电离为碳 酸。将继续对硫醇酯和mandelic的烯醇进行工作 和丙酮酸，目的是了解 辅酶A和Mandelate Racemase以及机制 丙酮酸烯醇的“未催化”酮化。新研究也将是 以endiols和脯氨酸的烯醇为发，前者提供 与糖的酶异构化有关的信息， 尤其是由三卫二磷酸异构酶催化的，后者在 为了提供非酶反应基础，以评估该反应基础 脯氨酸种族酶促进的过程的效率。