Synthesis of Silver(I) and Gold(I) Complexes Showing a Variety of Spectra of Antimicrobial Activities and Thier Structure-Activity Correlations

本研究获得了以下新的结果：1.以甘氨酸、天冬氨酸、天冬酰胺等氨基酸为配体，合成了水溶性的银配合物，并对它们的固态和溶液结构进行了表征。根据配合物中银中心的成键方式，将配合物分为四类.通过与D-青霉胺、2-巯基丙酸酯等脂肪族硫醇配体的配体交换反应，研究了以AuSP和AuNP为核的2配位金（I）-PPh_3配合物对革兰氏阳性菌的选择性和有效的抗菌活性.合成了2-巯基丙酸根与PPh 3配体形成的“分子金属轮”型Ag 8簇合物和2-巯基烟酸根形成的“环己烷椅”型Ag 6簇合物等几种银（I）配合物，并测定了它们的晶体/分子结构。2-巯基丙酸根与PPh_3配体形成的金（I）配合物以及6-巯基烟酸根与PPh_3配体形成的金（I）配合物均表现出2-配位AuSP核的超分子排列。4.本文研究了几种缩氨基硫脲和扁柏酚金属配合物的抗菌活性的构效关系。金属配合物的抗菌活性强烈依赖于金属中心，而不是它们的分子结构。具有相同金属中心的相似核结构的配合物显示出相似的抗菌谱。

Several novel results in this research were obtained :1. Water-soluble silver(I) complexes with amino-acid ligands such as glycine, aspartic acid and asparagines, showing wide spectra of effective antimicrobial activities, were synthesized and their structures in the solid-state and in solution were characterized. Such complexes were classified into four based on bonding modes of the silver center.2. Selective and effective antimicrobial activities against Gram-positive bacteria found in 2-coordinate gold(I)-PPh_3 complexes with AuSP and AuNP cores were discussed based on ligand-exchange reactions with aliphatic thiol ligands such as D-penicillamine and 2-mercaptopropionate.3. Several silver(I) complexes such as "molecular metal wheel" -type Ag_8 cluster formed by 2-mercaptopropionate and PPh_3 ligands and "cyclohexane-chair" -type Ag_6 cluster formed by 2-mercaptonicotinate were synthesized and their crystal/molecular structures determined. Gold(I) complex formed by 2-mercaptopropionate and PPh_3 ligands, and that formed by 6-mercaptonicotinate and PPh_3 ligands showed supramolecular arrangement of 2-coordinate AuSP cores.4. Structure-activity correlations in the antimicrobial activities by several metal complexes with thiosemicarbazone and hinokitiol ligands have been studied. Antimicrobial activities by metal complexes were strongly dependent on the metal centers rather than their molecular structures. The complexes with similar core-structures of the same metal center showed similar spectra of antimicrobial activities.