COORDINATION CHEMISTRY OF VANADIUM IN BIOLOGY SYSTEM

钒在生物系统中的配位化学

• 批准号: 2185126
• 负责人: CARL J CARRANO
• 金额: $ 6.53万
• 依托单位: TEXAS STATE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-06-01 至 1995-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2185126
• 关键词: Raman spectrometry; Tunicata; X ray crystallography; active sites; chemical models; chemical structure function; chemical synthesis; electrochemistry; electron spin resonance spectroscopy; magnetic field; metal complex; metalloenzyme; nuclear magnetic resonance spectroscopy; peroxidases; pigments; ultraviolet spectrometry; vanadium

DESCRIPTION (Adapted from the Investigator's Abstract): The presence of vanadium in biological systems is well established. Amavadine from the mushroom a.muscaria, the V(III)-tunichrome system in the blood cells of tunicates, bromoperoxidases from several species of marine algae and a vanadium containing nitrogenase from azotobacter vinelandii are salient examples. It is also now clear that vanadium has a number of important environmental, toxicological and physiological effects. Despite its presence, virtually nothing whatever is known about the structure, function or chemistry of vanadium in any of these systems. Experiments in this proposal are designed to help outline possible structures, oxidation states and ligation of vanadium that give rise to the physicochemical properties of these biomolecules. Accurate structural information is of paramount importance to an understanding of the role of vanadium in biology. A comparison between well-defined small molecule models and the biomolecules themselves represents one viable means of achieving this goal. The investigators propose to use model compounds to help investigate two particular areas of interest: 1) the structure and mechanism of action of first true vanadoenzyme, "bromoperoxidase" and 2) the mechanism of accumulation, and biological function of, vanadium in tunicates. Specific questions/goals to be addressed include: 1) For Bromoperoxidase: The production of accurate small molecule mimics for the active site which will give information about its structure and function along with investigations into the mechanism of action of the enzyme. These investigations will involve the synthesis of new vanadium complexes and their complete characterization. Such characterization will include UV-vis spectro-photometry, NMR (1H, 13C and 51V as appropriate), EPR, magnetic measurements, electrochemistry and, when appropriate, single crystal X-ray diffraction. 2) For Tunicates: To understand the interaction between vanadium and the tunichromes and to determine the mechanism of the reduction/accumulation process involved in its uptake. From these studies the investigators also hope to be able to understand the biological function of the vanadium in these organisms. These studies will involve resonance Raman and magnetic susceptibility studies on both model compounds and actual tunicate blood. The successful conclusion of this research project will provide a sound basis to increase the investigators understanding of the role of vanadium in many biological systems.

描述（改编自研究者的摘要）：存在 钒在生物系统中的作用已得到充分证实。 阿玛瓦定来自 蘑菇 a.muscaria，血细胞中的 V(III)-tunichrome 系统 被囊动物、来自几种海藻的溴过氧化物酶和 来自 azotobacter vinelandii 的含钒固氮酶是显着的 例子。 现在还清楚的是，钒具有许多重要的作用 环境、毒理学和生理影响。 尽管其 存在，实际上对结构、功能一无所知 或任何这些系统中钒的化学性质。 这方面的实验 提案旨在帮助概述可能的结构、氧化态 和钒的连接，产生物理化学特性 这些生物分子。 准确的结构信息至关重要 对于理解钒在生物学中的作用的重要性。 一个 明确的小分子模型和生物分子之间的比较 它们本身就是实现这一目标的一种可行手段。 这 研究人员建议使用模型化合物来帮助研究两个 特别感兴趣的领域：1）结构和作用机制 第一个真正的钒酶，“溴过氧化物酶”和 2) 的机制 被囊动物中钒的积累及其生物学功能。 具体的 要解决的问题/目标包括： 1) 对于溴过氧化物酶：精确小分子模拟物的生产 对于活性位点，它将提供有关其结构的信息和 功能以及作用机制的研究 酶。 这些研究将涉及新钒的合成 配合物及其完整表征。 这样的表征将 包括紫外可见分光光度法、NMR（1H、13C 和 51V，视情况而定）， EPR、磁测量、电化学，以及在适当的情况下，单一 晶体X射线衍射。 2) 对于被囊类动物：了解钒与元素之间的相互作用 tunichromes 并确定减少/积累的机制 其吸收过程。 从这些研究中，研究人员还 希望能够了解钒的生物学功能 这些生物体。 这些研究将涉及共振拉曼和磁 对模型化合物和实际被囊动物血液的敏感性研究。 该研究项目的成功完成将为 增加研究者对钒作用的了解的基础 在许多生物系统中。