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I. <種々の複素環窒素配位子による銀 (I) および金 (I) 錯体の合成と生理活性>
http://hdl.handle.net/10487/1258
http://hdl.handle.net/10487/12580a7856a7-2422-4c58-9d44-c5b742063222
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
kana-1-5-0030.pdf (527.4 kB)
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| Item type | 紀要論文 / Departmental Bulletin Paper(1) | |||||
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| 公開日 | 2009-02-23 | |||||
| タイトル | ||||||
| タイトル | I. <種々の複素環窒素配位子による銀 (I) および金 (I) 錯体の合成と生理活性> | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
| 資源タイプ | departmental bulletin paper | |||||
| 著者 |
野宮, 健司
× 野宮, 健司× 小田, 宗宏× Nomiya, Kenji× Oda, Munehiro |
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| 抄録 | ||||||
| 内容記述タイプ | Abstract | |||||
| 内容記述 | (1) Two novel polymeric silver (I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Ag (1,2,3-triz) (PPh_3)_2]_n 3 and [Ag (1,2,4-triz) (PPh_3)_2]_n 4 (Htriz=triazole) were synthesized from reactions of polymeric precursors [Ag (1,2,3-triz)]_n 1 and [Ag (1,2,4-triz)]_n 2 with 3 equiv of PPh_3 in CH_2Cl_2,respectively. The polymeric precursors 1 and 2 have been obtained as a non-crystalline, colorless powder-solid : 2 showed a wide spectrum of excellent antibacterial activities, but 1 did not. The antimicrobial activities of the complexes 1-4,evaluated by MIC (minimum inhibitory concentration), were compared and key factors affecting them were discussed. The crystal structures of the complexes 3 and 4 were determined by single-crystal X-ray diffraction. The complexes 3 and 4 in the solid-state were helical polymers consisting of AgN_2P_2 cores formed by bridging triazolate anions and two PPh_3 ligands. The complexes 3 and 4 were also fully characterized by elemental analyses, TG/DTA and FT-IR in the solid-state and by various solution NMR (^<31>P, ^<109>Ag, ^1H and ^<13>C) spectroscopies and molecular weight measurements in solution. (2) Two novel gold (I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Au (1,2,3-L) (PPh_3)] 1 and [Au (1,2,4-L) (PPh_3)]_2・xH_2O (x=0.5-1.0) 2 (HL=triazole) were synthesized from stoichiometric reactions of a precursor complex [AuCl (PPh_3)] with HL in acetone in the presence of aqueous NaOH, and isolated as colorless needles and cubic crystals, respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. 1 and 2 were also fully characterized by complete elemental analyses, TG/DTA and FT-IR in the solid-state and by solution NMR (^<31>P, ^1H and ^<13>C) spectroscopies and solution molecular-weight measurements. 1 consisted of a monomeric 2-coordinate AuNP core both in the solid-state and in solution, while, in contrast, 2 comprised a dimeric (AuNP)_2 core through an Au-Au bond in the solid-state, but a monomeric AuNP core in solution. Within the two gold (I) complexes composed of very closely related nitrogen-containing heterocycles and a common bulky PPh_3,ligand, it was found that the aggregation through the Au…Au interaction in 2 was overruled in 1. The molecular structures of 1 and 2 were also compared with those of the corresponding silver (I) analogs, [Ag (1,2,3-L) (PPh_3)_2]_n 3 and [Ag (1,2,4-L) (PPh_3)_2]_n 4,the molecular structures of both of which have been recently determined as helical polymers in the solid-state. (3) Polymeric silver (I) imidazolate [Ag (imd)]_n (1; Himd=imidazole, C_3H_4N_2) showing a wide spectrum of excellent antimicrobial activities against bacteria, yeast and mold, which has been obtained as non-crystalline, colorless powder, was successfully converted to molecular, crystalline complex [Ag (imd) (PPh_3)_3] 2 by a reaction of 1 with 3 equivalents of PPh_3 in CH_2Cl_2. This novel complex 2 was not obtained from reactions in solutions of the precursors [AgCl (PPh_3)_3] and/or [AgCl(PPh_3)_2]_2 with Himd in the presence of NaOH or with sodium salt of imd. On the contrary, the corresponding gold (I) complex [Au (imd) (PPh_3)] 3 was formed by a reaction of the precursor [AuCl (PPh_3)] and Himd in the presence of NaOH. From a synthetic viewpoint, these facts show the ordering of ligand replacement in these complexes to be Ag-P>>Ag-Cl>Ag-N, while Au-P>>Au-N>Au-Cl. This ordering also exhibits the different reactivity of silver (I) and gold (I) complexes with biological ligands such as proteins, enzymes, nucleic acids and amino acids. The complex 2 was fully characterized by complete elemental analyses, TG/DTA, FT-IR, solution molecular weight measurement and various solution NMR (^1H, ^<13>C, ^<31>P and ^<109>Ag) spectroscopies. The complex 2 in solution was present in a rapid equilibrium with the dissociated species of two PPh_3 ligands, i. e., [Ag (imd) (PPh_3)]. The ^<31>P NMR measurements at low temperature showed that (i) all PPh_3 ligands in 2 in CHCl_3 solution migrated at room temperature between the two isotopes ^<109>Ag and ^<107>Ag, in addition to the dissociation of two PPh_3 ligands, and (ii) there were present the 4-coordinate tetrahedral complex 2 and the dissociated complex [Ag (imd) (PPh_3)] in solution. | |||||
| 書誌情報 |
年報 巻 '98, p. 161-162, 発行日 1999-03 |
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| 書誌レコードID | ||||||
| 収録物識別子タイプ | NCID | |||||
| 収録物識別子 | AA11822302 | |||||
| 著者版フラグ | ||||||
| 出版タイプ | VoR | |||||
| 出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||
| 出版者 | ||||||
| 出版者 | 神奈川大学 | |||||
