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Issue 33, 2013
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Preliminary anti-cancer photodynamic therapeutic in vitro studies with mixed-metal binuclear ruthenium(ii)–vanadium(iv) complexes

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Abstract

We report the synthesis and characterisation of mixed-metal binuclear ruthenium(II)–vanadium(IV) complexes, which were used as potential photodynamic therapeutic agents for melanoma cell growth inhibition. The novel complexes, [Ru(pbt)2(phen2DTT)](PF6)2·1.5H2O 1 (where phen2DTT = 1,4-bis(1,10-phenanthrolin-5-ylsulfanyl)butane-2,3-diol and pbt = 2-(2′-pyridyl)benzothiazole) and [Ru(pbt)2(tpphz)](PF6)2·3H2O 2 (where tpphz = tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine) were synthesised and characterised. Compound 1 was reacted with [VO(sal-L-tryp)(H2O)] (where sal-L-tryp = N-salicylidene-L-tryptophanate) to produce [Ru(pbt)2(phen2DTT)VO(sal-L-tryp)](PF6)2·5H2O 4; while [VO(sal-L-tryp)(H2O)] was reacted with compound 2 to produce [Ru(pbt)2(tpphz)VO(sal-L-tryp)](PF6)2·6H2O 3. All complexes were characterised by elemental analysis, HRMS, ESI MS, UV-visible absorption, ESR spectroscopy, and cyclic voltammetry, where appropriate. In vitro cell toxicity studies (with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay) via dark and light reaction conditions were carried out with sodium diaqua-4,4′,4′′,4′′′ tetrasulfophthalocyaninecobaltate(II) (Na4[Co(tspc)(H2O)2]), [VO(sal-L-tryp)(phen)]·H2O, and the chloride salts of complexes 3 and 4. Such studies involved A431, human epidermoid carcinoma cells; human amelanotic malignant melanoma cells; and HFF, non-cancerous human skin fibroblast cells. Both chloride salts of complexes 3 and 4 were found to be more toxic to melanoma cells than to non-cancerous fibroblast cells, and preferentially led to apoptosis of the melanoma cells over non-cancerous skin cells. The anti-cancer property of the chloride salts of complexes 3 and 4 was further enhanced when treated cells were exposed to light, while no such effect was observed on non-cancerous skin fibroblast cells. ESR and 51V NMR spectroscopic studies were also used to assess the stability of the chloride salts of complexes 3 and 4 in aqueous media at pH 7.19. This research illustrates the potential for using mixed-metal binuclear ruthenium(II)–vanadium(IV) complexes to fight skin cancer.

Graphical abstract: Preliminary anti-cancer photodynamic therapeutic in vitro studies with mixed-metal binuclear ruthenium(ii)–vanadium(iv) complexes

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Supplementary files

Article information


Submitted
28 Feb 2013
Accepted
03 Jun 2013
First published
03 Jun 2013

Dalton Trans., 2013,42, 11881-11899
Article type
Paper

Preliminary anti-cancer photodynamic therapeutic in vitro studies with mixed-metal binuclear ruthenium(II)–vanadium(IV) complexes

A. A. Holder, P. Taylor, A. R. Magnusen, E. T. Moffett, K. Meyer, Y. Hong, S. E. Ramsdale, M. Gordon, J. Stubbs, L. A. Seymour, D. Acharya, R. T. Weber, P. F. Smith, G. C. Dismukes, P. Ji, L. Menocal, F. Bai, J. L. Williams, D. M. Cropek and W. L. Jarrett, Dalton Trans., 2013, 42, 11881
DOI: 10.1039/C3DT50547B

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