METALLO-BIOCHEMISTRY

金属生物化学

• 批准号: 6107272
• 负责人: HERBERT Bruce SILBER
• 金额: $ 11.75万
• 依托单位: SAN JOSE STATE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-09-01 至 1999-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6107272
• 关键词: actinides; atomic absorption spectrometry; biochemistry; chemical structure; chemical substitution; conformation; electrochemistry; heavy metals; infrared spectrometry; lanthanum; metal complex; nonwater solvent; nuclear magnetic resonance spectroscopy; physical chemical interaction; solvents; stop flow technique; temperature jump; ultraviolet spectrometry; water solution

Because of their spectroscopic and chemical properties, the lanthanide(III) ions have been important spectroscopic probes for calcium and magnesium binding studies in biological systems. For example, Eu(III) luminescence studies have become an important measure of the number of interacting atoms and water molecules between a biochemical material and the metal ion domain. However, despite over twenty years of their applications in biological systems, much fundamental information about the interactions of these lanthanide ions with their surroundings is still unknown. We propose using spectroscopic techniques, including ultrasonic absorption, FT-NMR, FT-IR and UV-vis methods, to develop information about the composition of the inner coordination shell of these cations. A second aspect of this proposal is the study of d-transition ions, cobalt, nickel, copper and zinc, in water and mixed solvents to learn about the domains surrounding the metal ion centers. Specific studies include: (1) Ultrasonic absorption of Yb(III) with sulfate, La(III) with 18-crown-6, and Zn(II) with glycine and possibly carbonic anhydrase or carboxypeptidase A. (2) Equilibrium constant determinations of Co(II) with Cl- and with glycine, Ni(II) and Cu(II) with SCN-, and Cu(II) with sulfate. (3) Structural studies of solvated LaCl/3 in aqueous organic solvents using FT-NMR and FT-IR at low temperatures to determine the composition of the inner coordination shell. (4) FT-NMR studies of zinc complexes in mixed solvents to detect geometry changes in solution. (5) We intend to initiate comparisons between the lanthanides and the actinide elements towards future work on biological and environmental concerns about actinide contamination. (6) We will investigate complex formation between the buckminsterfullerenes and organic donor/acceptor molecules.

由于其光谱和化学特性， 镧系（III）离子是钙的重要光谱探针 和生物系统中的镁结合研究。 例如，Eu(III) 发光研究已成为衡量发光数量的重要指标 生化材料与原子和水分子之间的相互作用 金属离子域。 然而，尽管他们已经工作了二十多年 在生物系统中的应用，有关的许多基本信息 这些镧系元素离子与其周围环境的相互作用仍然存在 未知。 我们建议使用光谱技术，包括超声波 吸收、FT-NMR、FT-IR 和 UV-vis 方法，以开发有关 这些阳离子的内部配位层的组成。 一个 该提案的第二个方面是研究 d-过渡离子、钴、 镍、铜和锌在水和混合溶剂中的含量，以了解 金属离子中心周围的区域。 具体研究包括：（1） 用硫酸盐超声吸收 Yb(III)、用 18-crown-6 超声吸收 La(III)、 和 Zn(II) 与甘氨酸和可能的碳酸酐酶或 羧肽酶A. (2) Co(II)平衡常数测定 与 Cl- 和与甘氨酸、Ni(II) 和 Cu(II) 与 SCN-、以及 Cu(II) 与 SCN- 硫酸盐。 (3) 溶剂化LaCl/3在有机水溶液中的结构研究 在低温下使用 FT-NMR 和 FT-IR 测定溶剂 内配位壳的组成。 (4) 锌的 FT-NMR 研究 混合溶剂中的配合物以检测溶液中的几何变化。 (5) 我们打算开始对镧系元素和锕系元素进行比较 生物和环境问题未来工作的要素 关于锕系元素污染。 (6) 研究复杂的形成 巴克敏斯特富勒烯和有机供体/受体分子之间。