Design of Photoactivatable Metallodrugs: Selective and Rapid Light-induced Ligand Dissociation from Half-Sandwich [Ru([9]aneS3)(N\u2013N')(py)]2+ Complexes
| Autor: | Giulio Ragazzon, Ioannis Bratsos, Luca Salassa, Abraha Habtemariam, Ruth J. McQuitty, Guy J. Clarkson, Peter J. Sadler, RAGAZZON, GIULIO, ALESSIO, ENZO |
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| Přispěvatelé: | Giulio Ragazzon, Ioannis Bratso, Enzo Alessio, Luca Salassa, Abraha Habtemariam, Ruth J. McQuitty, Guy J. Clarkson, Peter J. Sadler, Giulio, Ragazzon, Ioannis, Bratso, Alessio, Enzo, Luca, Salassa, Abraha, Habtemariam, Ruth J., Mcquitty, Guy J., Clarkson, Peter J., Sadler, Ragazzon, Giulio |
| Jazyk: | angličtina |
| Rok vydání: | 2012 |
| Předmět: |
Photochemistry
Ruthenium Macrocycle Coordination complex Pyridine ligand Bioinorganic Aquation chemistry.chemical_element coordination complex 010402 general chemistry 01 natural sciences Medicinal chemistry Dissociation (chemistry) Nucleobase Adduct Inorganic Chemistry chemistry.chemical_compound Pyridine Materials Chemistry macrocyle QD Physical and Theoretical Chemistry chemistry.chemical_classification 010405 organic chemistry RUTHENIUM PHOTOCHEMISTRY bioinorganic QP 0104 chemical sciences Intersystem crossing chemistry pyridine ligand |
| Zdroj: | Inorg. Chim. Acta 2012, 393, 230-238.. |
| ISSN: | 0020-1693 |
| Popis: | The synthesis of the inert Ru(II) half-sandwich coordination compounds, [Ru([9]aneS 3 )(bpy)(py)][PF 6 ] 2 (1, [9]aneS 3 = 1,4,7-trithiacyclononane, bpy = 2,2 0 -bipyridine, py = pyridine), [Ru([9]aneS 3 )(en)(py)][PF 6 ] 2 (2, en = 1,2-diaminoethane), and [Ru([9]aneN 3 )(en)(dmso-S)][PF 6 ] 2 (3, [9]aneN 3 = 1,4,7-triazacyclo- nonane), is reported along with the X-ray crystal structure of 1. We investigated whether these com- plexes 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 (k = 420 or 467 nm). The photode- composition 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]aneS 3 )(bpy)} 2+ . Density functional theory (DFT) calcula- tions and time-dependent DFT reproduced the major features of the absorption spectra and suggested that the lowest-lying triplet state with 3 MLCT character, which is readily accessible via intersystem cross- ing, might be responsible for the observed dissociative behavior of the excited states. These complexes are promising for further study as potential photochemotherapeutic agents. |
| Databáze: | OpenAIRE |
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