2003 Fiscal Year Final Research Report Summary
Synthesis and Adduct Formation of Metal Complexes with a Repetitive Structure
| Project/Area Number |
13440202
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Kansai University |
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Principal Investigator |
YAMAUCHI Osamu Kansai Univ., Faculty of Engineering, Professor, 工学部, 教授 (70029643)
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| Co-Investigator(Kenkyū-buntansha) |
ODANI Akira Nagoya Univ., Res.Center for Materials Science, Assoc.Professor, 物質科学国際研究センター, 助教授 (60143913)
NAKABAYASHI Yasuo Kansai Univ., Faculty of Engineering, Assoc.Professor, 工学部, 助教授 (70172385)
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| Project Period (FY) |
2001 – 2003
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| Keywords | Amino acid-and peptide-complexes / Adduct formation / CH-π interaction / Enzyme cofactor / Redox activity / Determination of blood glucose / DNA cleavage / Supramolecule |
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| Research Abstract |
Metal complexes containing a polypyridine ligand and an amino acid or a peptide were synthesized, and their structures were determined by X-ray diffraction method. Adduct formations between platinum(II) complexes and biological molecules such as nucleotides and cofactors by noncovalent interactions were established. Self-assembly of the complexes of copper(II) etc.led to formation of supramolecular structures.
(1)Pt(II) complexes as functional units, [Pt(A)(DA)] where A refers to an amino acid and DA to an aromatic diimine such as 1,10-phenanthroline (phen), were synthesized. New Pt(II)-peptide complexes having methionyiglycine or arginyiglycine in place of A and a pyrazine-bridged dinuclear Pt-glycylglycine complex were also synthesized but were found to be less soluble in water and other solvents than the amino acid complexes.
(2)The stability constants for the [Pt(A)(DA)]-nucleotide adducts (DA=phen ; nucleotide=AMP or GMP) were determined by spectroscopic methods and calorimetry. X-r
… More
ay analysis of [Pt(arg)(phen)]-GMP (arg=arginine) revealed that GMP is bound to the complex by both stacking and hydrogen bonding. The redox potential of FMN (=flavin mononucleotide) was found to be controlled by stacking with the Pt(II) complexes.
(3)The structures and stability constants of the ternary Cu(II) complexes containing a synthetic aromatic ligand and glycyltyrosine revealed the existence of the intramolecular CH-π interaction as a structure-determining factor.
(4)Various Os(II)-polypyridine complexes were established to be effective mediators of the GOx-glucose redox reaction (GOx = glucose oxidase) and thus may be used for determining the blood glucose level. Ru(II)-polypyridine complexes containing an amino acid were found to undergo light-induced cleavage of DNA in the presence of H_2O_2.
(5)An aqueous solution containing Cu(II), M(=Fe(II), Co(II), or Ru(II)), an EDTA derivative L with a longer methylene chain, and phen gave [M(phen)_3]_2[Cu_2L_2], which is considered to be constructed by self-assembly of complex molecules by π-π and CH-π interactions. Less
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