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Design of photoactivatable metallodrugs : selective and rapid light-induced ligand dissociation from half-sandwich [Ru([9]aneS3)(N–N′)(py)]2+ complexes
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Ragazzon, Giulio, Bratsos, Ioannis, Alessio, E. (Enzo), Salassa, Luca, Habtemariam, Abraha, McQuitty, Ruth J., Clarkson, Guy J. and Sadler, P. J. (2012) Design of photoactivatable metallodrugs : selective and rapid light-induced ligand dissociation from half-sandwich [Ru([9]aneS3)(N–N′)(py)]2+ complexes. Inorganica Chimica Acta, Vol.393 . pp. 230-238. doi:10.1016/j.ica.2012.06.031 ISSN 0020-1693.
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WRAP_Habtemariam_494_InorganicaChimicaActa_2012_393_230_R J Mcquitty.pdf - Accepted Version Download (1377Kb) | Preview |
Official URL: http://dx.doi.org/10.1016/j.ica.2012.06.031
Abstract
The synthesis of the inert Ru(II) half-sandwich coordination compounds, [Ru([9]aneS3)(bpy)(py)][PF6]2 (1, [9]aneS3 = 1,4,7-trithiacyclononane, bpy = 2,2′-bipyridine, py = pyridine), [Ru([9]aneS3)(en)(py)][PF6]2 (2, en = 1,2-diaminoethane), and [Ru([9]aneN3)(en)(dmso-S)][PF6]2 (3, [9]aneN3 = 1,4,7-triazacyclononane), is reported along with the X-ray crystal structure of 1. We investigated whether these complexes have photochemical properties which might make them suitable for use as pro-drugs in photochemotherapy. Complexes 1 and 2 underwent rapid (minutes) aquation with dissociation of the pyridine ligand in aqueous solution when irradiated with blue light (λ = 420 or 467 nm). The photodecomposition of 3 was much slower. All complexes readily formed adducts with 9-ethylguanine (9-EtG) when this model nucleobase was present in the photolysis solution. Similarly, complex 1 formed adducts with the tripeptide glutathione (GSH), but only when photoactivated. HPLC and MS studies of 1 showed that irradiation promoted rapid formation of 1:1 (major) and 1:2 (minor) adducts of the oligonucleotide d(ATACATGCTACATA) with the fragment {Ru([9]aneS3)(bpy)}2+. Density functional theory (DFT) calculations and time-dependent DFT reproduced the major features of the absorption spectra and suggested that the lowest-lying triplet state with 3MLCT character, which is readily accessible via intersystem crossing, might be responsible for the observed dissociative behavior of the excited states. These complexes are promising for further study as potential photochemotherapeutic agents.
| Item Type: | Journal Article | ||||
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| Subjects: | Q Science > QD Chemistry Q Science > QP Physiology |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Ruthenium -- Therapeutic use, Photochemistry, Antineoplastic agents, Complex compounds -- Therapeutic use, Metal complexes -- Therapeutic use, Bioinorganic chemistry, Pyridine, Ligands | ||||
| Journal or Publication Title: | Inorganica Chimica Acta | ||||
| Publisher: | Elsevier BV | ||||
| ISSN: | 0020-1693 | ||||
| Official Date: | 2012 | ||||
| Dates: |
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| Volume: | Vol.393 | ||||
| Page Range: | pp. 230-238 | ||||
| DOI: | 10.1016/j.ica.2012.06.031 | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Date of first compliant deposit: | 24 December 2015 | ||||
| Date of first compliant Open Access: | 24 December 2015 | ||||
| Funder: | European Cooperation in the Field of Scientific and Technical Research (Organization) (COST), European Research Council (ERC), Fondazione Beneficentia Stiftung | ||||
| Grant number: | 247450 (ERC) |
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