Journal
DALTON TRANSACTIONS
Volume 46, Issue 2, Pages 445-454Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6dt04028d
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Funding
- National Natural Science Foundation of China [21231007, 21328101, 21572282, 21401217]
- 973 program [2014CB845604, 2015CB856301]
- Ministry of Education of China [IRT1298]
- Guangdong Provincial Government [207999, 2015A030306023]
- Science and Technology Program of Guangzhou [201504281600481]
- Fundamental Research Funds for the Central Universities
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New TEMPO-functionalized Ru(II) polypyridyl complexes were synthesized as efficient theranostic photo-sensitizers for cancer treatment. Interestingly, due to the presence of a redox sensitive TEMPO moiety, an enhancement in the intracellular fluorescence of TEMPO-functionalized Ru(II) complexes was observed during photodynamic treatment in both confocal microscopy and flow cytometry. This can be explained by the conversion of the TEMPO radical moiety to diamagnetic non-radical species in cells upon PDT-induced oxidative stress. To the best of our knowledge this is the first ruthenium complex capable of simultaneously inducing and monitoring the oxidative stress. The tethered TEMPO moiety decreased the inherent dark-cytotoxicity and increased the photo-toxicity simultaneously, both of which contributed to the greatly improved photodynamic therapy (PDT) efficacy, ultimately resulting in cancer cell apoptosis. The phototoxicity index value for TEMPO-functionalized Ru(II) complexes was selective towards cancer cell lines (280.5 for HeLa cells vs. 30.2 for LO2 cells) and ca. 40-fold higher than that for TEMPO-free Ru(II) analogues (6.7 for HeLa cells). The main contributor for such a greatly enhanced PDT efficacy was the effect of the TEMPO moiety on the cellular uptake and intracellular ROS levels. We therefore demonstrate that the combination of TEMPO with the photosensitizers may be an emerging strategy to develop novel photosensitizer-based theranostic platforms, which can induce and monitor the PDT response simultaneously.
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