氧自由基型酞菁锌光敏剂的激发态释能机制及光动力治疗研究  

Revealing excited-state dynamics of type Ⅰ zinc phthalocyanine photosensitizer for photodynamic therapy

作　　者：姚卫云 徐曼 李洁 胡文博 黄维 Weiyun Yao;Man Xu;Jie Li;Wenbo Hu;Wei Huang(Frontiers Science Center for Flexible Electronics,Xi’an Institute of Flexible Electronics,Northwestern Polytechnical University,Xi’an 710129,China;Key Laboratory of Flexible Electronics of Zhejiang Province,Ningbo Institute of Northwestern Polytechnical University,Ningbo 315103,China;State Key Laboratory for Organic Electronics and Information Displays&Institute of Advanced Materials(IAM),Nanjing University of Posts&Telecommunications,Nanjing 210023,China)

机构地区：[1]西北工业大学柔性电子研究院,柔性电子前沿科学中心,西安710129 [2]西北工业大学宁波研究院,浙江省柔性电子重点实验室,宁波315103 [3]南京邮电大学信息材料与纳米技术研究院,有机电子与信息显示国家重点实验室,南京210023

出　　处：《中国科学：化学》2022年第8期1384-1392,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:62175201);宁波市自然科学基金重点项目(编号:2021J043)资助。

摘　　要：光动力治疗是一种通过光敏剂在一定波长光照下,产生具有高生物毒性的活性氧来实现癌症治疗的新技术.根据活性氧类型的不同,光敏剂分为Type Ⅰ型(氧自由基)和Type Ⅱ型(单线态氧).与Type Ⅱ型相比,Type Ⅰ型对氧气依赖程度低,在乏氧肿瘤治疗方面具有巨大应用前景.目前Type Ⅰ型光敏剂的种类较少,且机制研究薄弱,阻碍了其进一步发展.本文通过光谱学方法证明了酞菁锌(ZnPc)具有极小的单/三线态能级差、超快的系间窜越速率(3.8×10^(6)s^(-1))以及较长的三线态寿命(327 ns),这些性质促进了三线态光敏化过程,从而产生了活性氧.进一步研究表明,ZnPc产生的单线态氧可以忽略,却产生了高效的超氧阴离子自由基和羟基自由基,证明了其Type Ⅰ的作用机制,并初步研究了其光动力治疗效果.Photodynamic therapy is a clinically approved novel therapeutic technique that employs photosensitizer in the presence of suitable light to produce a cytotoxic reactive oxygen species(ROS).According to the ROS types,photosensitizers are divided into Type Ⅰ(free radical)and TypeⅡ(singlet oxygen).Compared with Type Ⅱ,Type Ⅰ has low dependence on oxygen,presenting excellent prospects in overcoming the limitations of the hypoxic cancer treatment.However,there is a limited scope of Type Ⅰ photosensitizers.Moreover,few studies concentrated on the mechanism research,which hinders the development of Type Ⅰ photodynamic therapy.This study proved that zinc phthalocyanate(ZnPc)has a negligible singlet-triplet energy gap,ultrafast intersystem crossing rate(3.8×10^(6)s^(-1)),and a long triplet excited state lifetime(327 ns),all of these together give rise to facile triplet-photosensitization.Furthermore,ZnPc exhibits efficient generation of superoxide anion radicals and hydroxyl radicals but negligible singlet oxygen production,validating its Type Ⅰ feature.Finally,we demonstrated the preliminary in vitro photodynamic therapy mediated by ZnPc.

关 键 词：酞菁锌 超快光谱 光动力治疗 激发态 自由基 

分 类 号：R454.2[医药卫生—治疗学]