Amino Acid Transformation Mediated upon Metal Complex as a Apoenzyme-Coenzyme-Substrate Model

作为脱辅基酶-辅酶-底物模型的金属配合物介导的氨基酸转化

• 批准号: 09640707
• 负责人: JITSUKAWA Koichiro
• 金额: $ 2.11万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640707/
• 关键词: Amino Acids; Transition Metal Complexes; Polypyridine Ligand; Mixed Ligand Complexes; Molecular Recognition; Enzyme Model; 水酸化反応

Amino acid transformations catalyzed by pyridoxal coenzyme were mimicked non- enzymatically on ternary metal complexes. New type oxidative transformation of amino acids were carried out using by the Co(II) or Co(III) complexes with 2,2' : 6', 2"-terpyridine (terpy) and salicylidene-amino acid (SAS). Here, terpy in the ternary complex, [Co(sas)(terpy)], is considered as a apoenzyme model, salicylaldehyde is as a coenzyme one, and amino acid is as a substrate one. In weakly alkaline media under aerobic condition, the alpha-position of amino acid was oxidized to give a salicylidene-alpha-hydroxyamino acid (SEAS) complex, [Co(shas)(terpy)]. Oxygen atom of the hydroxyl group substituted at alpha-position of SHAS was derived from molecular oxygen, which was determined on the basis of mass spectra and ESR study. Interligand interactions between sas and terpy ligands play an important role for the reaction control. This alpha-hydroxylation is inhibited by the CH-pi interaction, which is caused by the proximity of & and gamma-methyl groups of amino acid sidechain and terpy plane. CH-pi interaction mediated upon the other ternary complexes is also discussed in this report.

以吡哆醛辅酶为催化剂，在三元金属配合物上非酶催化氨基酸转化反应.以2，2 '：6'，2”-三联吡啶（terpy）和水杨醛缩氨基酸（SAS）为配体的Co（II）或Co（III）配合物为催化剂，进行了氨基酸的新型氧化转化反应。本文以三元配合物[Co（sas）（terpy）]中的三联吡啶为脱辅基模型，水杨醛为辅酶模型，氨基酸为底物模型。在弱碱性介质中，在有氧条件下，氨基酸的α位被氧化，得到水杨醛-α-羟基氨基酸（SEAS）配合物[Co（shas）（terpy）]。质谱和ESR研究表明，SHAS α位羟基上的氧原子来自分子氧。sas和三联吡啶配体之间的相互作用对反应控制起着重要作用。这种α-羟基化被CH-pi相互作用抑制，这是由氨基酸侧链和三联平面的α和γ-甲基基团的接近引起的。CH-π相互作用介导的其他三元复合物也讨论了本报告。

项目成果

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T.Irisa、K.Jitsukawa 等人：“三元介导的氨基酸衍生物的 α-羟基化……”J.Inorg.Biochem.67 (1997)。

H.Kumita, K.Jitsukawa, et al.: "Structures and Electrochemical Properties of the Co(III) Ternary Complexes Containing -" Inorg.Chim.Acta. 283. 160-166 (1998)

H.Kumita、K.Jitsukawa 等人：“含有 - 的 Co(III) 三元配合物的结构和电化学性质”Inorg.Chim.Acta。

M.Mizutani, K.Jitsukawa, et al.: "An Infinite Chiral Single-helical Structure formed in Cu(II)-L-/D-glutamic Acid System" Inorg.Chim.Acta. 283. 105-110 (1998)

M.Mizutani、K.Jitsukawa 等人：“Cu(II)-L-/D-谷氨酸系统中形成的无限手性单螺旋结构”Inorg.Chim.Acta。

H.Kumita, K.Jitsukawa, H.Masuda, and H.Einaga: "Structure and Electrochemical Properties of the Co (III) Ternary Complexes Containing NO3-type Tripodal Tetradentate Ligands and Amino Acids : Effect of the Outer Coordination Sphere on the Electrochemical P

H.Kumita、K.Jitsukawa、H.Masuda 和 H.Einaga：“含有 NO3 型三齿四齿配体和氨基酸的 Co (III) 三元配合物的结构和电化学性质：外配位球对电化学的影响

M.Mizutani,K.Jitsukawa,et al.: "Nucleobase Stacking Evidenced on Ternary Metal(Pd(II),Cu(II))Complexes with…" Inorg.Chem.38. 420-421 (1999)

M. Mizutani、K. Jitsukawa 等人：“三元金属 (Pd(II),Cu(II)) 配合物上的核碱基堆积证据……”Inorg.Chem.38 (1999)。