Since the discovery of cisplatin, the search for diagnostic or therapeutic agents based on other metals, has expanded intensively owing to the numerous possibilities offered by coordination chemistry. This mini-review focuses on recent advances in the search for Ru(II) polyazaaromatic complexes of potential interest as molecular tools applied to cellular diagnostics or as specific cellular photo-reagents for future biomedical applications. The interaction of Ru(II) polyazaaromatic complexes with living cells is reported, as well as the photo-reaction mechanisms of photo-oxidizing Ru(II) complexes with nucleic acids. The novel strategies currently developed to improve their reactivity and specificity towards DNA, more particularly in the gene-silencing framework, are also discussed.
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Photo-Oxidizing Ruthenium(II) Complexes with Enhanced Visible-Light Absorption and G-quadruplex DNA Binding Abilities.
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Photosensitizers that gather high photo-oxidizing power and strong visible-light absorption are of great interest in the development of new photo-chemotherapeutics. Indeed, such compounds constitute attractive candidates for the design of type I photosensitizers that are not dependent on the presence of oxygen. In this paper, we report on the synthesis and studies of new ruthenium(II) complexes that display strong visible-light absorption and can oxidize guanine residues under visible-light irradiation, as evidenced by nanosecond transient absorption spectroscopy.
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Materials Science & Engineering, University of Sheffield, Mappin St, Sheffield S1 3JD, U.K.
The dinuclear photo-oxidizing Ru complex [{Ru(TAP)}(tpphz)] (TAP = 1,4,5,8- tetraazaphenanthrene, tpphz = tetrapyrido[3,2-:2',3'-:3″,2''-:2‴,3'''-]phenazine), , is readily taken up by live cells localizing in mitochondria and nuclei. In this study, the two-photon absorption cross section of is quantified and its use as a two-photon absorbing phototherapeutic is reported. It was confirmed that the complex is readily photoexcited using near-infrared, NIR, and light through two-photon absorption, TPA.
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Organic Chemistry and Photochemistry, Université Libre de Bruxelles, (U. L. B.), 50 Av. F. D. Roosevelt, CP 160/08, 1050 Bruxelles, Belgium.
Ru polyazaaromatic complexes have been studied with the aim of developing molecular tools for DNA and oligonucleotides. In this context, Ru-TAP (TAP = 1,4,5,8-tetraazaphenanthrene) complexes have been developed as specific photoreagents targeting the genetic material. The advantage of such compounds is due to the formation of photo-addition products between the Ru-TAP complex and the biomolecule, originating from a photo-induced electron transfer process that takes place between the excited Ru-TAP complex and guanine (G) bases of DNA.
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Polyazaaromatic ruthenium(ii) complexes have been largely studied over the last decades, particularly in the scope of the biological applications, for the development of new diagnostic and phototherapeutic agents. In this context, Ru(ii) complexes able to react with biomolecules upon excitation are of great interest. Photo-oxidizing Ru(ii) complexes based on π-deficient ligands, such as bpz (2,2'-bypyrazine) and TAP (1,4,5,8-tetraazaphenathrene), were designed to allow a photo-induced electron transfer (PET) to take place in presence of biomolecules, thanks to their highly photo-oxidizing MLCT state.
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Laboratoire de Chimie Organique et Photochimie CP160/08, Université libre de Bruxelles, 50 Av. Franklin D. Roosevelt, 1050 Brussels, Belgium.
Ruthenium(II) polyazaaromatic complexes have gained interest in recent decades as biomolecular tools, especially in the development of new phototherapeutic agents. These light emissive Ru complexes based on π-deficient ligands were first designed to allow a photo-induced electron transfer (PET) with the guanine base in DNA since their (3)MLCT state is highly photo-oxidizing. Later the field of research was extended to proteins with the highlighting of a PET process with the tryptophan residue.
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