BIOLOGICAL VANADIUM--MODELS OF STRUCTURE AND FUNCTION

生物钒——结构和功能模型

• 批准号: 2181603
• 负责人: VINCENT L PECORARO
• 金额: $ 14.45万
• 依托单位: UNIVERSITY OF MICHIGAN AT ANN ARBOR
• 依托单位国家: 美国
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-06-01 至 1997-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2181603
• 关键词: chelating agents; chemical structure function; cofactor; enzyme complex; enzyme mechanism; halogenation; metalloenzyme; metalloproteins; organometallic compounds; oxidation; peroxidases; photoactivation; plant physiology; siderophores; vanadium; chelating agents; chemical structure function; cofactor; enzyme complex; enzyme mechanism; halogenation; metalloenzyme; metalloproteins; organometallic compounds; oxidation; peroxidases; photoactivation; plant physiology; siderophores; vanadium

The chemistry of vanadium in biological systems has been enigmatic both in terms of the terms of the forms in which it is found and in its biological functions. Natural products containing vanadium are documented, but no functional activities for these compounds are known. The potential importance of vanadium in mammalian metabolism as an inhibitor of phosphoryl transfer enzymes and Na+-K+ ATPases, as ouabain/insulin mimics and in the production of thyroid hormone is known. The first documented vanadium enzyme was isolated from red and brown algae and lichens and shown to catalyze a haloperoxidase reaction. By producing volatileatmosphere. Vanadium is also an important regulator of the natural ozone balance in the atmosphere. Vanadium is also an important cofactor in plant metabolism by acting as a key component in chlorophyll biosynthesis and a regulator of the carbon fixation cycle in the dark reactions of photosynthesis. The proposed experiments for the next project period focus on broadly elucidating the biochemistry of vanadium in four main areas: Probe the mechanism of vanadium haloperoxidase by designing new vanadium complexes that increases the stability of peroxovanadate species, reduce the hydrolytic susceptibility of the ligands and activate peroxide to react with halides and organic substrates. In particular, we will focus on the reactivity of diperoxo and peroxo/hydroxylamine containing compounds. Examine the mechanism of vanadate catalyzed peptide photodegradation by evaluating the photochemical degradation of vanadium chelates that we have shown are photooxidizable. Test the hypothesis that the true function of amavadin in fungi is as a rudimentary haloperoxidation reagent. Define the spatulation, structure and solution chemistry of vanadium phytosiderophore complexes that are probably involved in the sequestration and transport of trace metals into plants. Taken together, successful completion of these studies will provide a broad, yet detailed, description of the biological chemistry of vanadium. This work provides a foundation to study and to understand the more complex and poorly defined processes in which vanadium participates endogenously (as in thyroid function) or exogenously (as an insulin mimic) in mammalian metabolism.

生物系统中钒的化学既是神秘的 就发现形式的术语而言 生物功能。 含钒的天然产品是 已记录，但没有针对这些化合物的功能活动。 钒在哺乳动物代谢中的潜在重要性 磷酸转移酶和Na+ -K+ ATPases的抑制剂，AS 乌巴因/胰岛素模拟物和甲状腺激素的产生是已知的。 从红色和棕色中分离出第一个记录的钒酶 藻类和地衣可催化卤代氧化酶反应。 经过 产生挥发性。 钒也是重要的调节器 天然臭氧在大气中的平衡。 钒也是 通过充当植物代谢中重要的辅助因子 叶绿素生物合成和碳固定周期的调节剂 光合作用的黑暗反应。 提出的实验 下一个项目时期的重点是广泛阐明的生物化学 在四个主要领域的钒： 通过设计新的钒，探测钒卤代氧化酶的机制 提高过氧烷物种稳定性的复合物，减少 配体的水解敏感性并激活过氧化 与卤化物和有机底物反应。 特别是，我们将集中精力 关于二氧毒和过氧/羟胺的反应性 化合物。 检查通过通过 评估钒螯合物的光化学降解我们 显示的是光氧化。 检验假设真菌中amavadin的真实功能是一种 基本的卤氧化试剂。 定义钒的径流，结构和溶液化学 可能与 痕量金属进入植物。 综上所述，这些研究的成功完成将提供 广泛但详细的描述了钒的生物化学。 这项工作为学习和了解更多的基础 钒参与的复杂且定义较差的过程 内源性（如甲状腺功能）或外源（作为胰岛素 模仿哺乳动物代谢。