RESUMO
The efficient conjugation of a ruthenium complex and the peptide hormone somatostatin is presented. The resultant biohybrid offers valuable features for photodynamic therapy such as remarkable cellular selectivity, rapid cell uptake by receptor-mediated endocytosis, efficient generation of (1)O2 upon irradiation, potent phototoxicity as well as low cytotoxicity in the "off"-state.
Assuntos
Complexos de Coordenação/química , Fármacos Fotossensibilizantes/química , Rutênio/química , Somatostatina/química , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/uso terapêutico , Complexos de Coordenação/toxicidade , Endocitose , Humanos , Microscopia Confocal , Neoplasias/tratamento farmacológico , Fotoquimioterapia , Fármacos Fotossensibilizantes/uso terapêutico , Fármacos Fotossensibilizantes/toxicidade , Receptores de Somatostatina/metabolismo , Oxigênio Singlete/metabolismo , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por MatrizRESUMO
The synthesis of a trisheteroleptic ruthenium complex [Ru(tb)(dppz)(tmbiH2 )][PF6 ]2 (tb=4,4'-di-tert-butyl-2,2'-bipyridine, dppz=dipyrido[3,2-a:2',3'-c]phenazin, tmbiH2 =5,6,5',6'-tetramethyl-2,2'-bibenzimidazole) is described. In addition, the structural characterisation by means of 1D, 2D (1) Hâ NMR spectroscopy, and mass spectrometry, along with determination of the solid-state structure of the important precursor Ru(tb)(dppz)Cl2 , supports the proposed octahedral coordination geometry. The capability of tmbiH2 to form hydrogen bonds is corroborated by the solid-state structure. The photochemical characteristics of this complex can be described as a combination of the "light switch" effects, which are either attributed to the dppz or to the tmbiH2 ligand. To illustrate the molecule's double switchable features, steady-state absorption and emission measurements were performed, which include the determination of the quantum yield and the pKa values of the acidic protons of the tmbiH2 ligand. Notably, the emission lifetimes are sensitive to the solvents used. This phenomenon is due to a proton-coupled deactivation of the excited metal-to-ligand charge transfer (MLCT) state of the complex.
RESUMO
The photophysical properties of Ruthenium-bipyridine complexes bearing a bibenzimidazole ligand were investigated. The nitrogens on the bibenzimidazole-ligand were protected, by adding either a phenylene group or a 1,2-ethandiyl group, to remove the photophysical dependence of the complex on the protonation state of the bibenzimidazole ligand. This protection results in the bibenzimidazole ligand contributing to the MLCT transition, which is experimentally evidenced by (resonance) Raman scattering in concert with DFT calculations for a detailed mode assignment in the (resonance) Raman spectra.
