Synthesis and Adduct Formation of Metal Complexes with a Repetitive Structure

合成了含有多吡啶配体和氨基酸或肽的金属配合物，并用x射线衍射法测定了它们的结构。铂（II）配合物与生物分子（如核苷酸和辅因子）之间通过非共价相互作用形成加合物。铜（II）等配合物的自组装导致了超分子结构的形成。(1)合成了以Pt（II）配合物为功能单元的[Pt(A)(DA)]，其中A指氨基酸，DA指芳香二亚胺，如1,10-菲罗啉（phen）。还合成了以甲硫甘氨酸或精氨酸甘氨酸代替A的新型Pt(II)-肽配合物和吡嗪桥接的双核Pt-甘氨酸配合物，但发现与氨基酸配合物相比，它们在水和其他溶剂中的可溶性较低。(2)用光谱法和量热法测定了[Pt(A)(DA)]-核苷酸加合物（DA=phen；核苷酸=AMP或GMP）的稳定性常数。对[Pt(arg)(phen)]-GMP （arg=精氨酸）的进一步分析表明，GMP通过堆叠和氢键结合在配合物上。发现FMN（=黄素单核苷酸）的氧化还原电位通过与Pt（II）配合物的堆叠来控制。(3)含合成芳基配体和glyglyyrosine的三元Cu（II）配合物的结构和稳定性常数表明分子内CH-π相互作用的存在是结构决定因素。(4)多种Os(II)-多吡啶配合物是GOx-葡萄糖氧化还原反应（GOx =葡萄糖氧化酶）的有效介质，可用于测定血糖水平。发现含有氨基酸的Ru(II)-多吡啶配合物在H_2O_2存在下发生光诱导的DNA裂解。(5)水溶液中含有Cu（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 [M(phen)_3]_2[Cu_2L_2]，认为是由π-π和CH-π相互作用形成的络合物分子自组装而成。少

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