光敏剂光敏活性的溶剂效应及光敏反应机理的理论研究-物理化学专业论文.docxVIP

山东师范大学硕士学位论文(2)竹红菌甲素在溶液中存在三重态与三重态之间的电子转移反应从而产生 山东师范大学硕士学位论文 (2)竹红菌甲素在溶液中存在三重态与三重态之间的电子转移反应从而产生 HA阴离子，产生的HA阴离子又可与氧分子发生电子转移产生超氧阴离子，从而 发生了有氧参与的Ⅱ型反应机制； (3)三重态的竹红菌甲素不能被氧气直接氧化产生超氧阴离子． 我们还根据物质的光敏反应机制，对萘醌及其卤代物在无氧与有氧条件下光 敏反应机制进行了研究．研究发现： (1)在无氧的环境中萘醌及其卤代物对DNA的损伤主要是来自于萘醌及其卤 代物的阳离子； (2)在有氧的条件下萘醌及其卤代物的去激发能可以提供足够的能量与氧气之 间发生能量转移产生单重态的氧；萘醌及其取代物的自动离子化反应只有在水溶 液中两个三重态的分子之间才能进行，并且当萘醌被还原后，只有在水溶液中氧 气的氧化能力才足以从萘醌负离子上夺取电子产生超氧阴离子。然而对于萘醌的 卤代物在两种溶剂中均不会产生超氧阴离子自由基，所以卤素取代对光敏反应作 用不是很大． 关键词：j苣醌类光敏捌花醌萘醌分子内质子传递光敏机理溶剂效应 量子化学计算 Ⅱ 山东师范大学硕士学位论文Abstract 山东师范大学硕士学位论文 Abstract The quality of photosensitizer is a key factor for the efficiency of photodynamic therapy口DD．In recent years，much research att姐tion has been focused on a novel type of photosensitizer,perylencquinonoid derivatives(PQD)．Experimental evidences have suggested that PQD have the potential to replace PhotofrmⅡ嬲the latest photodynamic medicme due to its light-induced antitumor,antifungal and antiviral activities． It haS been proposed that the mechanism ofphotosensitization ofthe compounds is related to the photoinduced矽oton or hydrogen atom transfer．So we have mainly studied the process ofhydrogen atom transfer up to now．It has been found that there is 粗intersection bctwccll Sl and TI potential energy profiles．And the photosensitization ofp(Fmayori#nat量丘omtheintersection．TheIPT删∞ofperylcnequinonoid photosensitizers and the effect of the substitutions in gaseous environment have been studied． As we all known the process ofthe hydrogell atom transfer occur in solution,but we studied the process in gaSeous environment．Considering the pmctice con删on，we perform the hydrogen atom transfer in∞lufiom Employing the ab ini曲methoin the Gaussian 98 package programs．We firstly investigated the mT processes of PQ in different solvents and discussed the IPT mechanisms of diffcreut substituted PQ in aqueous solutiom The results may be invoked to direct the experiment to synthesize new type ofexcellent photosensitizers． The most import聪t results a托8s follow