Department of Immunobiology, College of Life Science and Technology, Jinan University, 601 Huangpu West Avenue, Guangzhou, 510632, China.
Research School of Chemistry, The Australian National University, Canberra, ACT, 2601, Australia.
Angew Chem Int Ed Engl. 2020 Jun 22;59(26):10431-10435. doi: 10.1002/anie.202002446. Epub 2020 Apr 8.
A covalent organic polymer (COP) is prepared by crosslinking the photosensitizer 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetraaniline (TAPP) with 4,4'-(anthracene-9,10-diyl)dibenzoic acid (ADDA) via 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/4-dimethylaminopyridine coupling. The COP is further modified with a hydrophilic polymer, poly(poly(ethylene glycol) methyl ether methacrylate) by grafting-from reversible-addition-fragmentation chain transfer (RAFT) polymerization to enhance its solubility in various solvents. The modified COP can bind singlet oxygen through the formation of endoperoxide by ADDA upon the exposure to red light irradiation. Singlet oxygen can be then released via the photodynamic mechanism or the cycloreversion by endoperoxide when heated at 110 °C. These results open new possibilities for simultaneous generation of singlet oxygen by the photodynamic route and singlet oxygen carriers, demonstrating promise for treating hypoxic tumors.
通过 1-乙基-3-(3-二甲基氨基丙基)碳二亚胺/4-二甲基氨基吡啶偶联，将光敏剂 4,4',4'',4'''-(卟啉-5,10,15,20-四基)四苯胺 (TAPP) 与 4,4'-(蒽-9,10-二基)二苯甲酸 (ADDA) 交联制备共价有机聚合物 (COP)。通过接枝聚合，将 COP 进一步用亲水性聚合物聚(聚(乙二醇)甲基醚甲基丙烯酸酯)修饰，通过可逆加成-断裂链转移 (RAFT) 聚合来提高其在各种溶剂中的溶解度。在红光照射下，ADDA 通过形成内过氧化物，改性的 COP 可以通过形成过氧化物键合单线态氧。然后，当在 110°C 加热时，单线态氧可以通过光动力机制或内过氧化物的环化重排释放。这些结果为通过光动力途径和单线态氧载体同时产生单线态氧开辟了新的可能性，为治疗缺氧肿瘤提供了希望。
