Synthesis and Adduct Formation of Metal Complexes with a Repetitive Structure

具有重复结构的金属配合物的合成和加合物形成

基本信息

批准号：
13440202
负责人：
YAMAUCHI Osamu
金额：
$ 8.51万
依托单位：
Kansai University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

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

合成了含有聚吡啶配体和氨基酸或肽的金属配合物，并通过X射线衍射法确定了铂(II)配合物与核苷酸和辅因子等生物分子之间通过非共价相互作用形成的加合物。铜(II)等配合物的自组装导致超分子结构的形成。(1)Pt(II)配合物作为功能单元， [Pt(A)(DA)]，其中A指氨基酸，DA指芳香族二亚胺，例如1,10-菲咯啉(phen)，合成了具有甲硫氨酰甘氨酸或精氨酰甘氨酸的新Pt(II)-肽复合物。还合成了 A 和吡嗪桥双核 Pt-甘氨酰甘氨酸络合物，但发现它们在水和其他溶剂中的溶解度较低(2)通过光谱法和X-r ay分析测定了[Pt(A)(DA)]-核苷酸加合物(DA=phen；核苷酸=AMP或GMP)的稳定性常数。 [Pt(arg)(phen)]-GMP (arg=精氨酸) 的分析表明 GMP 通过堆积和氢键结合到复合物上。 FMN (=黄素) 的氧化还原电位。 (3)含有合成芳香配体和甘氨酰酪氨酸的三元Cu(II)配合物的结构和稳定常数揭示了分子内CH-π相互作用的存在(4)多种Os(II)-聚吡啶配合物被确定为GOx-葡萄糖氧化还原反应的有效介体(GOx=葡萄糖)氧化酶），因此可用于测定血糖水平，发现含有氨基酸的 Ru(II)-聚吡啶复合物在 H_2O_2 存在下会发生光诱导 DNA 裂解。(5)含有 Cu( 的水溶液。 II)、M(=Fe(II)、Co(II) 或 Ru(II))，具有较长亚甲基链的 EDTA 衍生物 L，和 phen 得到[M(phen)_3]_2[Cu_2L_2]，被认为是由复杂分子通过π-π和CH-π相互作用自组装而成。