Functions of Aromatic Rings in the Metal Coordination Sphere.

金属配位层中芳香环的功能。

• 批准号: 09304062
• 负责人: YAMAUCHI Osamu
• 金额: $ 17.92万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09304062/
• 关键词: intermolecular weak interaction; metal-aromatic ring interaction; aromatic-aromatic ring interaction; phenylalaninehydroxylase; galactose oxidase; iodine; plastocyanine; metalloprotein-metalloprotein interaction; ガラストースオキシダーゼ; 酸化還元反応; インドール; フェ

New coordination chemistry of aromatic rings in the proximity of a metal ion was pursued by the studies of the model chemical systems and metalloproteins. Various specific noncovalent interactions such as metal-aromatic, aromatic-aromatic stacking interactions have been established by structural, spectroscopic, and thermodynamic methods. The specific structures revealed the metal-pterin, metal-phenol, metal-indole ring, metal-iodinated phenol, phenol radical, and pterin radical. The present studies focused on the following points :1) weak interactions involving aromatic rings in the proximity of a metal ion, 2) metal-aromatic ring interactions, 3) redox reactions and radical formation in the metal coordination sphece, and 4) construction of functional systems involving specific weak interactions. These points revealed how the chemical reactivity is controlled by the specific structure involving aromatic rings, which serves as a bases for understanding more complex systems containing metalloproteins. Intermolecular interactions between charged groups or aromatic side chains of metalloproteins control the structures and redox properties and thus the function of proteins such as electron transfer.

通过对模型化学系统和金属蛋白的研究，探索了金属离子附近芳环的新配位化学。各种特定的非共价相互作用，例如金属-芳香族、芳香族-芳香族堆积相互作用，已通过结构、光谱和热力学方法建立。具体结构揭示了金属蝶呤、金属苯酚、金属吲哚环、金属碘化苯酚、苯酚自由基和蝶呤自由基。目前的研究主要集中在以下几点：1）涉及金属离子附近芳环的弱相互作用，2）金属-芳环相互作用，3）金属配位空间中的氧化还原反应和自由基形成，以及4）构建涉及特定弱相互作用的功能系统。这些观点揭示了涉及芳环的特定结构如何控制化学反应性，这为理解含有金属蛋白的更复杂系统奠定了基础。金属蛋白的带电基团或芳香侧链之间的分子间相互作用控制结构和氧化还原特性，从而控制蛋白质的功能，例如电子转移。

项目成果

Shun Hirota: "Effects of Charged Peptides on Electron Transfer from [Fe(CN)6]^<4-> to Cyto-chrome c or Plastocyanin" Journal of Biological Inorganic Chemistry. 3. 563-569 (1998)

Shun Hirota：“带电肽对从 [Fe(CN)6]^<4-> 到细胞色素 c 或质体蓝素的电子转移的影响”生物无机化学杂志。

Feng Zhang: "Weak Interactions in Ternary Copper(II) Complexes with Iodotyrosinates. Biological Significance of the Iodines in Thyroid Hormones"Inorg. Chem.. 36. 5777-5784 (1997)

张锋：“三元铜（II）配合物与碘酪氨酸盐的弱相互作用。甲状腺激素中碘的生物学意义”Inorg。

Shun Hirota: "Observation of Cu-N^-_3 Stretching and N^-_3 Asymmetric Stretching Bands for mono-Azide Adduct of Rhus vernicifera Laccase" Biochem.Biophys.Res.Commun.243. 435-437 (1998)

Shun Hirota：“漆树单叠氮加合物的 Cu-N^-_3 拉伸和 N^-_3 不对称拉伸带的观察”Biochem.Biophys.Res.Commun.243。

Feng Zhang: "Electrostativ Ligand-Ligand Interactions in Ternary Copper(II) Complexes with 3, 5-Diiodo-L-tyrosine and Polar Amino Acids"Inorg. Chim. Acta. 278. 136-142 (1998)

张锋：“三元铜（II）与3, 5-二碘-L-酪氨酸和极性氨基酸配合物中的静电配体-配体相互作用”Inorg。

Shun Hirota: "Plastocyanin-Peptide Interactions.Effects of Lysine Peptides on Protein Struc-ture and Electron-Transfer Character" Journal of the American Chemical Society. 120・32. 8177-8183 (1998)

Shun Hirota：“质体蓝素-肽相互作用。赖氨酸肽对蛋白质结构和电子转移特性的影响”美国化学会杂志 120・32（1998）。