Porphyrin derivatives serve as photocatalysts in reversible-deactivation radical polymerization and as photosensitizers in photodynamic therapy (PDT). Herein, a triple function porphyrin, ZnTPPC6Br, was synthesized as photocatalyst and initiator for photoATRP. Oxygen-tolerant photoATRP produced fructose-based star-shaped glycopolymers as targeted photosensitizers for PDT. ZnTPPC6Br/CuII/PMDETA could synthesize polymer photosensitizers with predictable Mn and low Ð. Mechanistic studies unveiled the transition of ZnTPPC6Br from a singlet excited state (1PC*) to a triplet excited state (3PC*), enabling the activator CuI/L generation and initiates photoATRP. The excess ligands facilitate the active species return to the ground state, while the presence of DMSO assisting in oxygen depletion. Three fructose-based monomers with different polymerizable groups (acrylated, methacrylated, and p-vinylbenzoated) were employed to scale up polymerization, yielding glycopolymeric photosensitizers post-deprotection. In vitro cellular studies showed enhanced PDT efficacy of glycopolymeric photosensitizers against MCF-7 cells, attributed to specific GLUT5 binding for targeted endocytosis, highlighting their potential for precise cancer treatment compared to L929 cells. The multifunctional capabilities of ZnTPPC6Br are anticipated to serve as a strategic avenue for the advancement of polymer photosensitizers with potential PDT applications.

中文翻译：

---

糖聚合物光敏剂中的三功能卟啉：从 PhotoATRP 到靶向 PDT


卟啉衍生物在可逆失活自由基聚合中用作光催化剂，在光动力疗法 （PDT） 中用作光敏剂。在此，合成了三功能卟啉 ZnTPPC6Br 作为光催化剂和光 ATRP 的引发剂。耐氧 photoATRP 产生基于果糖的星形糖聚合物作为 PDT 的靶向光敏剂。ZnTPPC6Br/CuII/PMDETA 可以合成具有可预测的 Mn 和低 Ð 的聚合物光敏剂。机理研究揭示了 ZnTPPC6Br 从单重态激发态 （1PC*） 到三重态激发态 （3PC*） 的转变，使激活剂 CuI/L 产生并启动光 ATRP。过量的配体有助于活性物质返回基态，而 DMSO 的存在有助于氧消耗。采用三种具有不同可聚合基团（丙烯酸化、甲基丙烯酸化和对乙烯基苯并化）的果糖基单体来扩大聚合，产生脱保护后的糖聚合物光敏剂。体外细胞研究表明，糖聚合物光敏剂对 MCF-7 细胞的 PDT 疗效增强，这归因于靶向内吞作用的特异性 GLUT5 结合，突出了与 L929 细胞相比，它们具有精确癌症治疗的潜力。ZnTPPC6Br 的多功能能力有望成为具有潜在 PDT 应用的聚合物光敏剂发展的战略途径。