Redox Chemistry of 2His-1 Carboxylate Metalloenzymes

2His-1 羧酸金属酶的氧化还原化学

• 批准号: 6837421
• 负责人: JOSEPH P EMERSON
• 金额: $ 4.3万
• 依托单位: UNIVERSITY OF MINNESOTA
• 依托单位国家: 美国
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-08-10 至 2006-08-09
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6837421
• 关键词: Raman spectrometry; SDS polyacrylamide gel electrophoresis; binding sites; carboxylate; catalyst; chemistry; enzyme activity; metalloenzyme; metalloproteins; oxidation reduction reaction; oxygenases; postdoctoral investigator

DESCRIPTION (provided by applicant): A common metal binding motif, namely the 2-His-l-carboxylate (2H-1D/E) facial triad, is emerging in metalloenzymes that catalyze dioxygen activation. These enzymes catalyze a diverse range of "metabolically important transformations. The reduction-oxidation (redox) potentials of these 2H-1D/E dependent metal centers are proposed to play an important role in this dioxygen activation, and it is the goal of this proposal to better understand this role. Specifically, this study aims to characterize the redox potential between the resting M2+ and the oxidized M3+ states of metalloenzymes with the 2H-1D/E metal binding motif. This study will provide a benchmark to compare metal centers within this family of enzymes, thus beginning a collection of physical properties describing the 2H-1D/E metal binding motif. To do this, we propose to characterize the chemically oxidized 2H-1D/E dependent metal centers both spectroscopically and chemically. Probing these centers with a series of dioxygen related species, we will explore the chemistry of these active centers, explicitly searching for intermediates similar to those proposed in their reaction mechanisms.

描述（由申请人提供）：一种常见的金属结合基序，即2-His-1-羧酸酯（2H-1D/E）面部三联体，正在催化双氧活化的金属酶中出现。这些酶催化多种“代谢上重要的转化”。这些 2H-1D/E 依赖性金属中心的还原-氧化 (氧化还原) 电位被认为在这种分子氧活化中发挥重要作用，这就是该提案的目标具体来说，为了更好地理解这一作用，本研究旨在表征金属酶与 2H-1D/E 金属的静止 M2+ 状态和氧化 M3+ 状态之间的氧化还原电位。这项研究将为比较该酶家族中的金属中心提供基准，从而开始收集描述 2H-1D/E 金属结合基序的物理特性。为此，我们建议表征化学氧化的 2H-。通过光谱和化学方法探测这些中心的一维/电子相关物质，我们将探索这些活性中心的化学性质，明确寻找与其反应机制中提出的类似的中间体。