扩展细菌叶绿素能否作为光动力疗法中的光敏剂？来自密度泛函理论计算的好消息。

Can Expanded Bacteriochlorins Act as Photosensitizers in Photodynamic Therapy? Good News from Density Functional Theory Computations.

作者信息

Mazzone Gloria, Alberto Marta E, De Simone Bruna C, Marino Tiziana, Russo Nino

机构信息

Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, I-87036 Arcavacata di Rende, Italy.

Chimie ParisTech, CNRS, Institut de Recherche de Chimie Paris (IRCP), PSL Research University, F-75005 Paris, France.

出版信息

Molecules. 2016 Feb 29;21(3):288. doi: 10.3390/molecules21030288.

The main photophysical properties of a series of expanded bacteriochlorins, recently synthetized, have been investigated by means of DFT and TD-DFT methods. Absorption spectra computed with different exchange-correlation functionals, B3LYP, M06 and ωB97XD, have been compared with the experimental ones. In good agreement, all the considered systems show a maximum absorption wavelength that falls in the therapeutic window (600-800 nm). The obtained singlet-triplet energy gaps are large enough to ensure the production of cytotoxic singlet molecular oxygen. The computed spin-orbit matrix elements suggest a good probability of intersystem spin-crossing between singlet and triplet excited states, since they result to be higher than those computed for 5,10,15,20-tetrakis-(m-hydroxyphenyl)chlorin (Foscan©) already used in the photodynamic therapy (PDT) protocol. Because of the investigated properties, these expanded bacteriochlorins can be proposed as PDT agents.

通过密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）方法，对一系列最近合成的扩展细菌叶绿素的主要光物理性质进行了研究。用不同的交换相关泛函B3LYP、M06和ωB97XD计算得到的吸收光谱已与实验光谱进行了比较。所有考虑的体系都显示出最大吸收波长落在治疗窗口（600 - 800 nm）内，这与实验结果吻合良好。所得到的单重态-三重态能隙足够大，以确保产生具有细胞毒性的单重态分子氧。计算得到的自旋-轨道矩阵元表明，单重态和三重态激发态之间存在体系间自旋交叉的良好可能性，因为它们的值高于已用于光动力疗法（PDT）方案中的5,10,15,20-四（间羟基苯基）卟吩（Foscan©）的计算值。鉴于所研究的性质，这些扩展细菌叶绿素可被提议作为光动力疗法的药物。