卟啉半遥爪聚合物的制备及其在光动力疗法中的应用探讨  

Synthesis of Porphyrin Semitelechelic Polymers and Application in Photodynamic Therapy

作　　者：陈帅 庞瑞淇 刘思奕 洪晨雨 马绍花 杲云[1] 田佳 CHEN Shuai;PANG Ruiqi;LIU Siyi;HONG Chenyu;MA Shaohua;GAO Yun;TIAN Jia(School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,上海200237

出　　处：《华东理工大学学报（自然科学版）》2020年第3期349-359,共11页Journal of East China University of Science and Technology

基　　金：国家自然科学基金(51803058)。

摘　　要：通过"点击化学"偶联反应将不同分子量(Mn=1 000,2 000,5 000)的亲水性高分子聚乙二醇(PEG)与卟啉光敏剂(TPP)键合在一起,成功合成了一系列水溶性很好的卟啉半遥爪聚合物光敏剂(TPP-PEG),并探讨了高分子链长对TPP-PEG的单线态氧(1O2)产率和细胞毒性的影响。相比于自由的卟啉小分子,这类亲水高分子光敏剂在水溶液中以单个分子存在,有效地减少了卟啉分子之间的π-π堆积,提高了光敏剂的1O2产率,同时改善了生物相容性。以1,3-二苯基异苯并呋喃(DPBF)为捕获剂检测1O2,结果表明,接枝分子量分别为1 000、2 000、5 000的TPP-PEG光敏剂的1O2产率比卟啉小分子如四苯基卟啉的1O2产率有显著提高,而且1O2产率随着PEG链长的增加而降低。HeLa细胞的毒性实验证明TPP-PEG几乎没有暗毒性,并且在655 nm光照下表现出很好的光毒性,证明TPP-PEG可以作为潜在的大分子光敏剂用于光动力疗法。Porphyrin and its derivatives,which are widely existed in organisms and participate in essential physiological processes,are well-known and promising photosensitizers.However,many drawbacks,such as strong hydrophobicity and self-quenching induced by aggregation,have greatly limited their applications in photodynamic therapy(PDT).Herein,a series of water-soluble porphyrin semitelechelic polymers(TPP-PEG)were successfully synthesized via click reaction between hydrophilic polyethylene glycol chains with various molecular weight(PEG,Mn=1000,2000,5000)and tetraphenyl porphyrin unit(TPP).Compared with small porphyrin molecules,these PEGlated porphyrin semitelechelic polymers exhibit excellent solubility in aqueous solution,greatly reducing the intermolecularπ-πstacking and thereby enhancing the singlet oxygen generation.In addition,the introduction of PEG chains also improves the biocompatibility of the porphyrin photosensitizer.Using 1,3-diphenylisobenzofuran(DPBF)as the 1O2 detecting probe,the UV-vis absorption intensity results show that the 1O2 generation of TPP-PEG are faster and more extensive than the free TPP molecules.Additionally,the results indicate that the 1O2 generation capability of TPP-PEG decreases with the increase of the lergth of PEG chain.The Thiazolyl Blue Tetrazolium Bromide method(MTT)assay results of dark cytotoxicity and phototoxicity in HeLa cells also confirmed that TPP-PEG possesses good biocompatibility and high cytotoxicity under light irradiation.

关 键 词：卟啉 光敏剂 聚乙二醇 单线态氧 高分子链长 

分 类 号：O632.3[理学—高分子化学]