壹:結合?酚衍生的四級胺鹽六足歧狀混成體在光激發DNA交聯鏈結作用之研究;貳:具嵌合基團之掌性氧釩錯合物於DNA光激斷序之研究

陳皓瑋(Hao-Wei Chen)

指導教授 ： 陳建添

國立臺灣師範大學/理學院/化學系/碩士(2006年)

摘要

在第一部份中，我們利用以三羥基苯甲?胺為核心的三足歧狀結構雙聚合體經由Click chemistry，接上三甲基胺的?酚，其上的三甲基胺的?酚在完成甲基化反應後，生成四級胺鹽?酚的三足歧狀雙聚合物，其經光激發後，產生o-quinone methid的中間產物，經分子?的共振效應和DNA的鹼基對作用交聯鍊結。使用瓊膠電泳、凝膠滲和原子力顯微鏡(AFM)去觀測六足歧狀混成體和DNA鹼基對交聯鍊結的狀況，由於六足歧狀混成體和DNA的交聯效果太好，導致有聚集(aggregation)的現象；第二部份中，利用我們實驗室在2005年發表的掌性氧釩錯合物對DNA光激斷序的結果作衍生；改變配位子，接上發光基團增加了π-π共振效應。在光激發後，分子內電子共振產生過渡產物，氧釩鍵會釋放出單重態的氧或產生氫氧自由基與DNA作用進而使其斷鍵。我們由瓊膠電泳分析得知，我們所改良的IMS-complex和Q-IMS complex對於DNA光激斷序有更好的效果。

關鍵字

DNA光激交聯鏈結 ； 速配組合化學 ； DNA光激DNA斷序

並列摘要

In one part, we investigated a new tripodal, trimethyl-2-naphthol-capped gallamide dendritic dimer are synthesized via click chemistry. After methylation with the dendritic dimmer, it possessed six side of quaternary ammonium groups which increased solublility. When photoinduced, it transferred to o-quinone methide (o-QM) intermediate. Meanwhile, photo-cross-links of DNA by irradiation with light under mild conditions and without any additives., and reducing agents will offer considerable potential in clinical. We use agarose gel electrophoresis and AFM to observe the result of cross-links. It aggregated because that beta-naphthol ammonium-capped dendritic dimmer worked efficiently. In part two, we derivated vanadyl(V) complexes that we have reported in 2005 to investigate two new complexes , iminostilbene and quinoxaline. After they were photoduced, the transient indicate the involvement of LMCT with concomitant tautomerization, leading to a distinctive, o-quinone methide-type V-bound hydroxyl species that is responsible for the observed photocleavage profiles. The resonace of π-π bonding of flat template legand chelated to DNA efficiently. We can demonstrate the good results from agarose gel electrophoresis.

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