富勒烯光敏剂的合成及单线态氧量子产率的性能

Singlet oxygen is an important class of active species, which has been widely used in photodynamic therapy, light induced reaction and polymer science. Fullerene as the photosensitizer produces singlet oxygen species as high as 95% yield induced by light，which has been named as singlet oxygen generator. However, the weak absorption of fullerene in Vis-NIR region limits its application. The attachment of visible light-harvesting antenna onto fullerene core has been proved to be an effective strategy to improve its absorption. In comparison to the studies of different visible light-harvesting antennas, researches on the linker between light-harvesting antenna and fullerene are rare. Herein, chemical modification of fullerene would be explored by employing diketopyrrolopyrrole (DPP) derivatives, which have high molar absorption coefficient in visible region, through different linkers such as amino and methylene groups. The relationship among linker, molecular structure, triplet distribution and singlet oxygen quantum yield will also be investigated in details, employing spin density distribution calculation. It would offer some theoretical guidance for rational design of the fullerene-based photosensitizers.

单线态氧是广泛应用在光动力治疗癌症、光催化反应和聚合物科学等诸多领域的一类重要活性物种。富勒烯作为光敏剂，通过光诱导产生单线态氧的效率高达95%，被喻为“单线态氧的发生器”。但富勒烯在可见光以及红外区的吸光能力差，通过连接基团将吸光范围宽、吸光能力强的荧光分子接到富勒烯上面是改善其吸光性的最直接方法。目前所报道的工作多集中在对不同荧光分子的考察，对于荧光分子与富勒烯连接方式的研究地较少。本项目以富勒烯的化学修饰为切入点，将在可见光区域具有较高摩尔吸光系数的DPP衍生物（吡咯并吡咯二酮）作为吸光基团，拟采用亚甲基、胺基等不同的键连基团将DPP与富勒烯直接相连；系统考察键连方式、分子结构、三重态分布、单线态氧量子产率之间的相互影响；结合自旋密度分布理论计算，为富勒烯类光敏剂的设计提供理论指导。

癌症是威胁人类健康与生命的重大疾病之一，创伤小、毒性低、非入侵性的光动力、光热、气体等肿瘤治疗方法越来越引起研究者的关注。申请人基本按照申请书中的研究计划开展了富勒烯、吡咯并吡咯二酮类有机光敏剂的合成及其在肿瘤光治疗中的应用。结合荧光光声、成像对肿瘤精确定位与治疗过程的动态监测，考察富勒烯、吡咯并吡咯二酮类光敏剂纳米颗粒的气体治疗、光动力、光热多模式治疗肿瘤性能，阐明细胞凋亡机理。在本项目的资助下，培养硕士生4人，在Biomaterials, Chem. Sci., ACS Appl. Mater. Interfaces, Adv. Funct. Mater., Sci. China Chem.等期刊上发表标注本项目基金号(No.21704043) SCI 论文8篇。