Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 24, Pages 3899-3908Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201200344
Keywords
Vanadium; Polypyridyl ligands; Phenanthroline bases; Crystal structure; DNA damage; Photocytotoxicity; Photochemistry; Photodynamic therapy
Categories
Funding
- Department of Science and Technology (DST)
- Government of India [SR/S5/MBD-02/2007]
- University Grants Commission (UGC), New Delhi
- DST
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Oxidovanadium(IV) complexes [VO(pyphen)(L)]Cl2 (1, 2) and [VO(pydppz)(L)]Cl2 (3, 4), where L is 1,10-phenanthroline (phen in 1 and 3) and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 2 and 4) are prepared and characterized. The crystal structure of [VO(pyphen)(phen)](ClO4)2 (1a) shows a six-coordinate VN5O geometry with a VO2+ moiety in which the polypyridyl ligand binds in a meridional fashion and the phen ligand displays a chelating binding mode with an N-donor site trans to the oxidovanadyl group. The complexes show a dd band within 720-750 nm in DMF. The one-electron paramagnetic complexes are 1:2 electrolytes in DMF. The complexes exhibit an irreversible VIV/VIII redox response near -0.85 V vs. SCE in DMF/0.1 M TBAP. The complexes bind to calf thymus (ct) DNA giving Kb values within 7.5 x 104 to 1.1 x 106 M1. The complexes show poor chemical nuclease activity in the dark and exhibit significant DNA-photocleaving activity in near-IR light of 705 and 785 nm forming .OH radicals. Complexes 2-4 show remarkable photocytotoxicity in HeLa cancer cells. FACS analysis of the HeLa cells treated with complex 4 shows cell death as highlighted by the sub G1 peak. Propidium iodide staining data indicate apoptosis as the primary mode of cell death.
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