Project/Area Number |
09640707
|
Research Category |
Grant-in-Aid for Scientific Research (C)
|
Allocation Type | Single-year Grants |
Section | 一般 |
Research Field |
物質変換
|
Research Institution | Nagoya Institute of Technology |
Principal Investigator |
JITSUKAWA Koichiro Associate Professor, Nagoya Institute of Technology, Faculty of Engineering, 工学部, 助教授 (50235793)
|
Co-Investigator(Kenkyū-buntansha) |
MASUDA Hideki Nagoya Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (50209441)
EINAGA Hisahiko Nagoya Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (10114042)
|
Project Period (FY) |
1997 – 1998
|
Project Status |
Completed (Fiscal Year 1998)
|
Budget Amount *help |
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,800,000 (Direct Cost: ¥2,800,000)
|
Keywords | Amino Acids / Transition Metal Complexes / Polypyridine Ligand / Mixed Ligand Complexes / Molecular Recognition / Enzyme Model / 水酸化反応 |
Research Abstract |
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.
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