Qu Chulin, Zhao Chengyan, Hu Yingzhe, Liu Shaohai, Xu Haodong, Wen Xidan, Li Pengfei, Zhu Xinhua, Wu Fan, Shen Zhen
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Chemistry and Biomedicine Innovation Center (ChemBIC), Nanjing University, Nanjing, 210023, China.
Department of General Surgery, Nanjing Drum Tower Hospital Clinical College of Nanjing University of Chinese Medicine, Nanjing, 210008, China.
Adv Healthc Mater. 2025 Jun;14(16):e2500789. doi: 10.1002/adhm.202500789. Epub 2025 May 13.
Constructing near-infrared (NIR) phototherapy agents with good biosafety is highly desirable for cancer therapy. Herein, the combined "β-meso-core" engineering of porphyrin produces excellent photothermal/photoacoustic agents that exhibit locally excited NIR bands with high molar extinction coefficients reaching 10 scale. The β-anthracene fusion of porphyrins via retro-Diels-Alder reactions extends the π-systems, generating red-shifted and intensified Q bands with narrow half-widths. The change of meso-substituents leads to distorted, non-aggregated molecules with improved solubility and fine-tunes the photophysical characteristics. The core coordination of copper ions promotes non-radioactive decay in the energy-releasing process and enhances photobleaching resistance. The biocompatible nanoparticles encapsulating the designed porphyrin exhibit a high photothermal conversion efficiency of 68% and promising photoacoustic responses, enabling effective photoacoustic imaging-guided photothermal therapy in vivo at a safe laser intensity (808 nm, 0.3 W cm ). This study provides a novel strategy in the molecular engineering of porphyrin for designing highly efficient photothermal agents.
构建具有良好生物安全性的近红外（NIR）光疗剂对于癌症治疗非常有必要。在此，卟啉的组合“β-中位核心”工程产生了优异的光热/光声剂，其表现出具有高摩尔消光系数达到10量级的局域激发近红外波段。通过逆狄尔斯-阿尔德反应进行的卟啉与蒽的β-融合扩展了π-体系，产生了红移且增强的Q带，半高宽变窄。中位取代基的变化导致分子扭曲、不聚集，溶解度提高，并微调光物理特性。铜离子的核心配位促进了能量释放过程中的非放射性衰变，并增强了抗光漂白能力。封装设计的卟啉的生物相容性纳米颗粒表现出68%的高光热转换效率和良好的光声响应，能够在安全的激光强度（808 nm，0.3 W/cm）下在体内实现有效的光声成像引导光热治疗。这项研究为卟啉的分子工程设计高效光热剂提供了一种新策略。
