Yang Mingwang, Ou Xinwen, Li Jianwei, Sun Jianwei, Zhao Zheng, Lam Jacky W Y, Fan Jiangli, Tang Ben Zhong
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Division of Life Science, State Key Laboratory of Molecular Neuroscience, and Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, 999077, China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024, China.
Angew Chem Int Ed Engl. 2024 Aug 19;63(34):e202407307. doi: 10.1002/anie.202407307. Epub 2024 Jul 24.
Small organic photothermal agents (PTAs) with absorption bands located in the second near-infrared (NIR-II, 1000-1700 nm) window are highly desirable for effectively combating deep-seated tumors. However, the rarely reported NIR-II absorbing PTAs still suffer from a low molar extinction coefficient (MEC, ϵ), inadequate chemostability and photostability, as well as the high light power density required during the therapeutic process. Herein, we developed a series of boron difluoride bridged azafulvene dimer acceptor-integrated small organic PTAs. The B-N coordination bonds in the π-conjugated azafulvene dimer backbone endow it the strong electron-withdrawing ability, facilitating the vigorous donor-acceptor-donor (D-A-D) structure PTAs with NIR-II absorption. Notably, the PTA namely OTTBF shows high MEC (7.21×10 M cm), ultrahigh chemo- and photo-stability. After encapsulated into water-dispersible nanoparticles, OTTBF NPs can achieve remarkable photothermal conversion effect under 1064 nm irradiation with a light density as low as 0.7 W cm, which is the lowest reported NIR-II light power used in PTT process as we know. Furthermore, OTTBF NPs have been successfully applied for in vitro and in vivo deep-seated cancer treatments under 1064 nm laser. This study provides an insight into the future exploration of versatile D-A-D structured NIR-II absorption organic PTAs for biomedical applications.
吸收带位于第二近红外(NIR-II,1000 - 1700 nm)窗口的小型有机光热剂(PTA)对于有效对抗深部肿瘤非常理想。然而,鲜有报道的NIR-II吸收型PTA仍然存在摩尔消光系数(MEC,ϵ)低、化学稳定性和光稳定性不足以及治疗过程中所需光功率密度高的问题。在此,我们开发了一系列二氟化硼桥连氮杂富烯二聚体受体集成的小型有机PTA。π共轭氮杂富烯二聚体主链中的B-N配位键赋予其强吸电子能力,有利于形成具有NIR-II吸收的强供体-受体-供体(D-A-D)结构PTA。值得注意的是,名为OTTBF的PTA显示出高MEC(7.21×10 M cm)、超高的化学和光稳定性。封装到水分散性纳米颗粒中后,OTTBF NPs在1064 nm照射下,光密度低至0.7 W cm时就能实现显著的光热转换效果,据我们所知,这是PTT过程中报道的用于NIR-II光功率最低的情况。此外,OTTBF NPs已成功应用于1064 nm激光下的体外和体内深部癌症治疗。这项研究为未来探索用于生物医学应用的多功能D-A-D结构NIR-II吸收有机PTA提供了思路。