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Partially Solvated Dinuclear Ruthenium Compounds Bridged by Quinoxaline-Functionalized Ligands as Ru(II) Photocage Architectures for Low-Energy Light Absorption
摘要： Ruthenium compounds with coordinated photo-labile molecules that can be selectively released by irradiation with a visible light source are finding increasing applications in photoactivated chemotherapy (PCT) as photocages. Earlier photocages based on mononuclear Ru(II) compounds lack absorption in the therapeutic window (λ > 600 nm). In previous work, we synthesized the first partially solvated tppz bridged (tppz= 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine) dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers. To further explore the effect of the bridging ligand on Ru(II) photocage design, we used quinoxaline-functionalized bridging ligand platforms to prepare [{RuII(NCCH3)4}2(μ-BL)](PF6)4[BL = dpq, 2,3-di(pyridin-2-yl)quinoxaline (1); BL = dpb, 2,3-di(pyridin-2-yl)benzo[g]quinoxaline (2)]. The compounds are capable of absorbing green light with tails extending beyond 650 nm which can be exploited for applications as PCT agents. Experimental results were additionally verified by DFT calculations. The use of two Ru(II) centers equipped with quinoxaline-based bridging ligands is a promising design strategy for the synthesis of a new family of dinuclear Ru(II) photocage prototypes with the ability to absorb low-energy visible light.
关键词： photoactivated chemotherapy,Ruthenium compounds,photocages,low-energy light absorption,dinuclear Ru(II) complexes
更新于2025-09-23 15:19:57
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Photoactivatable Prodrug-Backboned Polymeric Nanoparticles for Efficient Light-Controlled Gene Delivery and Synergistic Treatment of Platinum-Resistant Ovarian Cancer
摘要： Combination of chemotherapy and gene therapy provides an effective strategy for cancer treatment. However, lacking of suitable co-delivery systems with efficient endo/lysosomal escape and controllable drug release/gene unpacking is the major bottleneck for maximizing the combinational therapeutic efficacy. Herein, we developed a photoactivatable Pt(IV) prodrug-backboned polymeric nanoparticles system (CNPPtCP/si(c-fos)) for light-controlled si(c-fos) delivery and synergistic photoactivated chemotherapy (PACT) and RNAi on platinum-resistant ovarian cancer (PROC). Upon blue light irradiation (430 nm), CNPPtCP/si(c-fos) could generate oxygen-independent N3? with mild oxidation energy for efficient endo/lysosomal escape through N3?-assisted photochemical internalization with less gene deactivation. Thereafter, along with Pt(IV) prodrug activation, CNPPtCP/si(c-fos) would be disassociated to release active Pt(II) and unpack si(c-fos) simultaneously. Both in vitro and in vivo results demonstrated that CNPPtCP/si(c-fos) displayed excellent synergistic therapeutic efficacy on PROC with low toxicity. This PACT prodrug-backboned polymeric nanoplatform may provide a promising gene/drug co-delivery tactics for treatment of various hard-to-tackle cancers.
关键词： N3?-assisted photochemical internalization,photoactivatable polymeric nanoparticles,gene delivery,platinum-resistant ovarian cancer,photoactivated chemotherapy
更新于2025-09-19 17:13:59