| 张 喜,王柳,赵建章,赵伟杰.化学通报,2022,85(12):1505-1509,1482. |
| 新型二氢卟吩类光敏剂的设计及理论计算研究 |
| Design and Theoretical Calculation of Novel Chlorin-Based Photosensitizers |
| 投稿时间：2022-04-22 修订日期：2022-05-24 |
| DOI： |
| 中文关键词: 密度泛函理论 二氢卟吩 光动力治疗 吸收光谱 电荷分布 |
| 英文关键词:Density Functional Theory Chlorin Photodynamic therapy Absorption spectrum Charge distribution |
| 基金项目:国家科技支撑计划重点项目(2015BAD17B05)资助 |
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| 中文摘要: |
| 本文采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）方法对一系列具有π共轭结构的二氢卟吩类光敏剂进行了理论模拟研究，计算了此类衍生物的吸收光谱特征、分子内电荷分布特点以及三重激发态特性。结果显示，在二氢卟吩大环结构中共轭引入给电子芳香基团（对甲氧基苯基），可使化合物（B2）的Q带吸收发生红移，分子内负电荷聚集增强，减小单重态-三重态能级差（ΔEST），有利于发生系间窜越，使单线态氧产量增加，导致强效的肿瘤生长抑制。并且在B2分子大环中心配合Pd原子会进一步减小ΔEST。因此，对于二氢卟吩类光敏剂，引入给电子共轭基团并配合金属原子是提高其PDT治疗效果的有效改进策略。 |
| 英文摘要: |
| A series of chlorin-based photosensitizers with π-conjugated structures were studied through theoretical simulation in this article. The absorption spectrum characteristics, intramolecular charge distribution characteristics and triplet excited state properties of these derivatives were calculated by Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods. The calculation results indicated that the introduction of electron-donating aromatic substituents (p-methoxyphenyl) in the chlorin macrocyclic structure could show a red-shift of the Q-band within the absorbance spectra and enhance the accumulation of intramolecular negative charges. Besides, this strategy could also reduce the energy difference between singlet and triplet states (ΔEST) of B2 after irradiation, which could increase the production of singlet oxygen via boosting intersystem crossing (ISC), and lead to a strong inhibition of tumor growth. In addition, coordinating Pd atoms in the macrocycle of B2 could further decrease ΔEST. Therefore, it is an effective strategy to enhance PDT therapeutic effect of chlorin-based photosensitizers by introducing electron-donating conjugated substituents and coordinating metal atoms. |
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