Photoactivation Inducing Multifunctional Coupling of Fluorophore for Efficient Tumor Therapy In Situ

Abstract Photoactivatable molecules, with high‐precision spatialtemporal control, have largely promoted bioimaging and phototherapy applications of fluorescent dyes. Here, the first photoactivatable sensor (BI) is described that can be triggered by broad excitation light (405–660 nm), which further undergoes intersystem crossing and H‐atom transfer processes to forming superoxide anion radicals (O₂^−•) and carbon radicals. Particularly, the photoinduced gain of carbon‐centered radicals (BI•) allows for radical‐radical coupling to afford the combined crosslink product (BI─BI), which would be oxidized in the presence of O₂^−• to produce an extended conjugate system with near infrared emission (820 nm). Besides, the photochemically generated product (Cy─BI) possesses ultra‐high photothermal conversion efficiency up to 90.9%, which optimized phototherapy potential. What′s more, Western Blot assay reveals that both BI and the photoproduct Cy─BI can efficiently inhibit the expression of CHK1, and the irradiation of BI and Cy─BI further induces apoptosis and ultimately enhances the phototherapeutic effects. Thus, the combination of cell cycle block inducing apoptosis, photodynamic therapy and photothermal therapy treatments significantly suppress solid tumor in vivo antitumor efficacy explorations. This is a novel finding in developing photoactivatable molecules, as well as the broad applicability of photoimaging and phototherapy in tumor‐related areas.