Enhanced Photosensitizer-Embedded Glycopolymers through Self-Catalytic PET-RAFT Polymerization for Targeted PDT

IF 5.4 2区化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Biomacromolecules Pub Date : 2025-04-14 Epub Date: 2025-03-24 DOI:10.1021/acs.biomac.5c00090

Jiaoyang Zhu, Jiahui Lin, Ruili Wang, Zhiyuan Ma, Weiwei Zuo, Meifang Zhu

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Abstract

PET-RAFT polymerization enables precise polymer synthesis, yet conventional systems require an excess chain transfer agent (CTA) over unbound photocatalysts (PCs). Herein, a self-catalyzed strategy employing polymerizable porphyrin MTPPZnH as a dual-functional PC effectively embeds high photosensitizer content into glycopolymers for photodynamic therapy (PDT). Three galactose-bearing monomers (acrylate, methacrylate, 4-vinylbenzoate) were polymerized via PET-RAFT under optimized light conditions, achieving satisfactory M _n and relatively narrow Đ. Mechanistic studies revealed that photoexcited MTPPZnH transfers electrons/energy to CTA via a PET process, initiating polymerization, with DMSO enhancing oxygen depletion. Water-soluble glycopolymeric photosensitizers exhibited high fluorescence and singlet oxygen quantum yield. In vitro, galactose-bearing photosensitizers showed superior ASGPR-mediated endocytosis in HepG2 cells over Huh-7 and MCF-7 cells, enabling targeted PDT. The incorporation of MTPPZnH contributes to an effective multifunctional strategy, offering a promising approach for the development of high photosensitizer-embedded polymeric photosensitizers for potential PDT applications.

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通过自催化PET-RAFT聚合增强光敏剂包埋糖共聚物用于靶向PDT。

PET-RAFT聚合可以实现精确的聚合物合成，而传统的体系需要在未结合的光催化剂（pc）上添加过量的链转移剂（CTA）。本文采用自催化策略，采用可聚合卟啉MTPPZnH作为双功能PC，有效地将高光敏剂含量嵌入到光动力治疗（PDT）的糖共聚物中。在优化的光照条件下，通过PET-RAFT聚合了三种含半乳糖的单体（丙烯酸酯、甲基丙烯酸酯、4-乙烯基苯甲酸酯），获得了满意的Mn和相对狭窄的Đ。机理研究表明，光激发的MTPPZnH通过PET过程将电子/能量转移到CTA，引发聚合，DMSO增强氧消耗。水溶性糖共聚物光敏剂具有较高的荧光和单线态氧量子产率。在体外，含半乳糖光敏剂在HepG2细胞中表现出优于Huh-7和MCF-7细胞的asgpr介导的内吞作用，从而实现靶向PDT。MTPPZnH的加入有助于有效的多功能策略，为开发用于潜在PDT应用的高光敏剂嵌入聚合物光敏剂提供了一条有前途的途径。

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来源期刊

Biomacromolecules 化学-高分子科学

CiteScore

10.60

自引率

4.80%

发文量

417

审稿时长

1.6 months

期刊介绍： Biomacromolecules is a leading forum for the dissemination of cutting-edge research at the interface of polymer science and biology. Submissions to Biomacromolecules should contain strong elements of innovation in terms of macromolecular design, synthesis and characterization, or in the application of polymer materials to biology and medicine. Topics covered by Biomacromolecules include, but are not exclusively limited to: sustainable polymers, polymers based on natural and renewable resources, degradable polymers, polymer conjugates, polymeric drugs, polymers in biocatalysis, biomacromolecular assembly, biomimetic polymers, polymer-biomineral hybrids, biomimetic-polymer processing, polymer recycling, bioactive polymer surfaces, original polymer design for biomedical applications such as immunotherapy, drug delivery, gene delivery, antimicrobial applications, diagnostic imaging and biosensing, polymers in tissue engineering and regenerative medicine, polymeric scaffolds and hydrogels for cell culture and delivery.