竹红菌甲素光敏活性的量子化学研究

化学学报 ›› 2004, Vol. 62 ›› Issue (8): 762-768. 上一篇下一篇

研究论文

竹红菌甲素光敏活性的量子化学研究

张晓, 陈德展

山东师范大学化学化工与材料科学学院, 济南, 250014

投稿日期:2003-09-04 修回日期:2003-12-23 发布日期:2014-02-18
通讯作者: 陈德展,E-mail:dchen@sdnu.edu.cn;Fax:0531-2615258. E-mail:dchen@sdnu.edu.cn
基金资助:
国家自然科学基金(No.20273042)和山东省自然科学基金重大项目(No.Z2002B01)资助项目.

Quantum Chemical Study on Photo-induced Activity of Hypocrellin A

ZHANG Xiao, CHEN De-Zhan

College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014

Received:2003-09-04 Revised:2003-12-23 Published:2014-02-18

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摘要/Abstract

利用密度泛函B3LYP/6-31G^*方法对茈醌类光敏剂竹红菌甲素hypocrellin A(HA)及其模型化合物的结构性质和分子内氢传递(IHT)过程进行了系统的计算研究,比较了各侧链对分子结构和IHT过程的影响.利用CIS/6-31G^*方法对HA的活性中心苝醌(PQ)及与其结构类似的一系列化合物激发态的IHT过程进行了研究.得到的主要结论包括:(1)常温下,处于基态的HA分子能够进行快速的分子内氢传递.(2)HA的几种模型化合物在基态时的IHT势垒、分子内电荷分布与HA差别很小,这说明侧链对IHT过程的影响不大.(3)HA模型化合物的IHT势垒与氧氢键键长变化和氢键键长变化呈良好的线性关系.(4)IHT反应中伴随着一个电荷分离过程,在氢传递过程中占主导地位的是静电相互作用,这说明此IHT过程本质上是质子转移过程.(5)共轭结构对该类分子的激发态IHT过程具有重要影响,总的趋势是对小共轭体系,单重激发态和三重激发态IHT反应的势能曲线分离,随着分子共轭结构的增大,两个激发态势能曲线逐渐接近,发生交叉的可能性以及交叉的程度也随之增大,即从单重态到三重态发生系间窜越的可能性也随之增大.由于分子内氢传递导致单重激发态和三重激发态势能曲线交叉,致使发生系间窜越,使体系三重态量子效率显著提高,从而提高了茈醌类光敏剂的光敏活性.这说明IHT过程对该类分子保持其光敏活性具有重要的意义.

关键词: 竹红菌甲素, 醌类光敏剂, 分子内氢传递, 量化计算

The B3LYP/6-31G^* method has been applied to the intramolecular hydrogen transfer(IHT)reaction of perylenequinonoid photosensitizer hypocrellin A(HA)and its model compounds in order to illuminate the effect of side chains.A series of compounds with similar molecular structure as that of perylenequinonoid(PQ),the active center of HA,were studied with the CIS/6-31G^* method in this article.The most important results are as follows:(1) HA executes a quick IHT reaction in the ground state at room temperature.(2)There is a little difference between IHT barrier and charge distribution ofHA and the model compounds,which indicates that side chain has little effect on IHT reaction of HA.(3)As for HA series compounds,IHT barrier is linear to the change of H-bond length orO-H bond length.(4)There is a charge separation process coupled with the IHT reaction.The Coulombic interaction dominates the IHT process,which indicates that the IHT reaction of HA is a proton transfer process in nature.(5)Conjugated structure has a vital effect on the IHT reaction of PQ and its similar molecules.As for the molecules with smaller conjugated structures,the singlet and triplet excited state potential energy profiles of IHT reaction separate from each other.The bigger the conjugated structure is,the closer the two potential energy profiles are.Considering PQ,there is an intersection part between its S₁ and T₁ profiles.So the intersystem crossing(ISC)is likely to take place during the IHT reaction of PQ leading to high triplet quantum yield eflqciency.It is well known that most photosensitization processes involve reactions in triplet excited state.So the IHT process plays a vital role in retaining the photosensitization of PQP.

Key words: perylenequinonoid photosensitizer(PQP), hypocrellin A(HA), intramolecular hydrogen transfer(IHT), quantum chemical calculation

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张晓, 陈德展. 竹红菌甲素光敏活性的量子化学研究[J]. 化学学报, 2004, 62(8): 762-768.

ZHANG Xiao, CHEN De-Zhan. Quantum Chemical Study on Photo-induced Activity of Hypocrellin A[J]. Acta Chimica Sinica, 2004, 62(8): 762-768.

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竹红菌甲素光敏活性的量子化学研究

Quantum Chemical Study on Photo-induced Activity of Hypocrellin A

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