Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16732
標題: 二價銅Schiff Base與聯吡啶共配位基錯合物 之合成與鑑定及其在DNA裂解之應用
Synthesis and characterization of Cu(II) complexes coordinated with Schiff base and bipyridine coligand and their application in DNA cleavage
作者: 張家誌
Chang, Chia-chih
關鍵字: DNA裂解之應用;Schiff Base
出版社: 化學系所
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摘要: 
製備了一系列NNO-Schiff base的三牙配位基,並且搭配了bipyridine為共配位基合成出一系列銅金屬錯合物[Cu(L)B](ClO4)],藉著改變Schiff bse配位基上之推拉電子基,對銅錯合物的光學及電化學性質做研究與DNA裂解活性之探討。
晶體結構鑑定顯示1b、2b、4b及6b為五配位之金屬錯合物,其τ值介於0.10-0.25之間,可得知其結構為較接近四角錐之構形。
以bipyridine為共配位基的錯合物,最大吸收波長介於300nm到400nm之間,所有錯合物在600nm到700nm間皆可以觀察到微弱的銅金屬d-d band吸收。Schiff base配位基上OH官能基對位若為推電子取代基,其最大吸收波長較拉電子基紅移。在Schiff base配位基中 imine的部分增加共軛之鍊長,可以將配位基及錯合物之最大吸收波長大幅紅移60-80nm。所有的錯合物在0.1-0.2V間皆可以觀察到屬於Cu2+/Cu+的半可逆氧化還原波峰;在EPR光譜上所有的銅錯合物1b-7b、1c及2c在固態的情況下,皆可觀察到d9系統銅金屬錯合物之未成對電子所產生的單一波峰訊號,若在二氯甲烷的溶液中則可以觀察到銅金屬電子和原子核產生偶合而產生分裂的訊號。
所合成出的錯合物1b-7b、1c及2c在有還原劑MPA的條件下皆顯現出不錯的DNA裂解活性,而在365nm的光照條件下則需在錯合物較高濃度(200μM)的條件下才有裂解效果,若將錯合物的共配位基部分由bipyridine置換成1,10-phenanthroline可發現在DNA的裂解效果上有顯著的提升。

A serious of ternary copper(II) complexes of the type [Cu(L)B](ClO4)] (B= a heterocyclic base) supported on NNO-tridentate Schiff base ligands have been synthesized and characterized by different spectroscopy technique.X-ray crystal structural studies of copper(II) complexes 1a-2a, 1b-2b, 4b, 6b and 1c, reveal that all the complexes are mononuclear with tetra-coordinated geometry. The suitability of copper(II) complexes for initiating the DNA-cleavage has been investigated. Experimental results show that, the electron donating and withdrawing group of the Schiff base ligand influence on photo -chemistry of all the complexes. Most of the complexes showing a ligand to metal charge transfer (LMCT) band at 300-400 nm and a very weak d-d transition band for copper at 600-700 nm and with increasing the conjugate chain of imine part of the Schiff base ligand cause noticeable red-shift to the LMCT band. A Quasi-reversible peak is obtained at 0.1V -0.2V which is assigned to the Cu(II)/Cu(I) redox couple. In EPR spectrum, one single peak on solid state at 298K and a quartet splitting in CH2Cl2 solution due to the coupling of copper nuclei and electron was pbserved for all the Copper(II) complexs.
All the complexes with 40μM concentration show excellent DNA cleavage activity in the presence of reducing agent 3-mercapto- propionic (MPA). However, in the photoinduced experiment at 365nm; the cleavage activity was observd only at high concentration of the complexes.The complex 2c with heterocyclic base 1,10-Phenanthroline is more efficient than 1c with bipyridine base, towards DNA cleavage in all the experimental conditions.
URI: http://hdl.handle.net/11455/16732
其他識別: U0005-1806200916095100
Appears in Collections:化學系所

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