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在用于肝细胞癌的水溶性GalNAc功能化四聚乙烯光敏感剂中的分子内 π-π叠加调节的ROS放大

Yin-Ju Li¹, Han-Che Hung¹, Yu-Sheng Tsai Yuan¹

¹Department of Chemistry, National Taiwan University, Taipei, 10617, Taiwan, Republic of China. chenct@ntu.edu.tw.

Journal of materials chemistry. B

|March 10, 2026

概括

这项研究引入了一个新的光敏化平台,通过分子内堆叠来增强反应性氧物种 (ROS) 的产生. 这种设计通过模仿分子层面的聚合效应来提高光动力学治疗的疗效.

科学领域:

超分子化学超分子化学
摄影化学的使用.
生物医学工程生物医学工程

背景情况:

开发用于光动力学治疗 (PDT) 的高效光敏剂至关重要.
针对特定的有机体和控制光物理性质是光敏剂设计的关键挑战.

研究的目的:

设计和研究一个模块化的 geminal-tetraphenylethylene (gem-TPE) 光敏化平台.
探索分子内 π-π 堆叠在调节光物理行为和反应性氧物种 (ROS) 生成中的作用.
为了评估ASGPR介导的细胞吸收和光依赖性细胞毒性.

主要方法:

合成gem-TPE衍生物与ASGPR向的GalNAc单元和有机体指导的图案.
ROS探针测定和电子磁共振 (EPR) 谱学以确定光反活性通路 (I/II型).
理论计算以阐明分子内 π-π 堆叠的机制及其对光物理学的影响.
对焦显微镜用于细胞吸收和分布研究.
在光和黑暗条件下进行体外细胞毒性测定.

主要成果:

经有机细胞修饰的gem-TPE衍生品表现出双重的I型/II型光反应性,性能优于非堆叠控制.
衍生品gem-TPEVP-TsG显示显著更高的I型ROS生成 (∼3.6倍).
理论计算证实,分子内 π-π 堆叠会诱导结构刚性,并增强系统间交叉.
观察到有效的ASGPR介导的细胞吸收和溶酶体分布.
所有衍生品都表现出依赖光的细胞毒性,在黑暗中毒性可忽略不计.

结论:

分子内部的π-π相互作用可以有效地模拟聚合诱导的分子层面的系统间交叉.
这提供了一个一般的设计策略,用于增强光敏剂中的ROS生成,同时保持水溶性.
开发的平台对有针对性的光动力学治疗应用有前途.

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