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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

SÃntese e caracterizacÃo de novos fotossensibilizadores de complexos polipiridÃnicos de rutÃnio / Synthesis and Characterization of New photosensitizers polipiridÃnicos complexes Rutenio

Felipe DiÃgenes Abreu 28 February 2013 (has links)
CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Nesse trabalho foram sintetizados e caracterizados os sistemas bicromofÃricos do tipo [Ru(dcbpy2)mbpy-L], onde dcbpy = 4,4â- dicarboxi-2,2â-bipiridina, mbpy-OH = 4â-metil-2,2â-bipiridina-4-Ãcido carboxÃlico e L = 2-aminoantraceno (2-ant) ou 2-aminonaftaleno (2-naf), com a finalidade de avaliar a potencial aplicaÃÃo dos mesmos em dispositivos fotovoltaicos (CÃlulas Solares Sensibilizadas por Corantes, DSCs) e em terapia fotodinÃmica (TFD). Os compostos foram caracterizados por UV-vis, emissÃo, IV, RMN 1H e voltametria cÃclica. Os espectros UV-vis destes complexos apresentaram bandas na regiÃo do visÃvel (aproximadamente 460 nm) atribuÃdas a transiÃÃes de transferÃncia de carga metal ligante (MLCT). Os complexos apresentam bandas intensas de luminescÃncia com tempos de vida do estado excitado de 712 e 787 ns para [Ru(dcbpy2)mbpy-naf]2+ e [Ru(dcbpy2)mbpy-ant]2+, respectivamente. O par redox RuIII/II dos complexos sÃo deslocados positivamente (~1.36 V vs Ag/AgCl) em relaÃÃo ao complexo de partida [Ru(dcbpy2)Cl2] (0,50 V vs Ag/AgCl). A performance fotovoltaica das cÃlulas solares sensibilizadas com estes complexos foram obtidas sob condiÃÃes de 1,5 AM. Os valores de eficiÃncia global de conversÃo de energia () sÃo muito inferiores aos obtidos para o corante Ru(dcbpy)2(NCS)2 (N3) nas mesmas condiÃÃes experimentais. Os compostos foram tambÃm investigados em relaÃÃo a geraÃÃo de oxigÃnio singlete (1O2) com irradiaÃÃo em 460 nm, e sua capacidade de fotoclivagem em DNA. Para o complexo [Ru(dcbpy2)mbpy-naf]2+, o estado excitado de menor energia à 3MLCT com rendimento quÃntico de 0,0654 em metanol. Por outro lado, para o complexo [Ru(dcbpy2)mbpy-ant]2+, o estado excitado de menor energia està localizado no 3 do ligante antraceno, e exibe alto rendimento quÃntico de geraÃÃo de 1O2 (0,81). Estudos preliminares da interaÃÃo destes complexos com DNA plasmÃdico investigada por eletroforese em gel (agarose) mostram indÃcios de clivagem, sugerindo a potencialidade dos mesmos em TFD. / In this study were synthesized ruthenium (II) bichromophoric complexes of the type [Ru (dcbpy2) mbpy-L] where dcbpy = 4,4 '- dicarboxy-2, 2'-bipyridine and mbpy-OH (4'- methyl-2, 2'-bipyridine-4-carboxylic acid) and L dyes 2-aminoanthracene (2-ant) or 2- aminonaphthalene (2-naphthyl) for the purpose of evaluating the potential use in photovoltaic devices (dye sensitizer solar cells DSC) and photodynamic therapy (PDT). Each of the complexes were characterized by UV/vis, visible emission, IV, 1H NMR and cyclic voltammetric studies. The UV-vis spectra shows bands in the visible region (approximately 460 nm) assigned to metal to ligand charge transfer transition (MLCT). Both complexes showed strong luminescent bands in the visible region with an excited-state lifetime of 712 and 787 ns for [Ru(dcbpy2)mbpy-naf]2+ and [Ru(dcbpy2)mbpy-ant]2+, respectively. The Ru(II)/(III) couple in the complexes are shifted (1.36 V vs Ag/AgCl) positively with regard to that of the starting complex (0.50 V vs Ag/AgCl). The photovoltaic performance of the solar cells based on these complexes was obtained under AM 1.5 conditions. The overall efficiency of energy conversion (η) are much lower than those achieved for the dye cis- [Ru(dcbpy)2(NCS)2] (N3) under the same experimental conditions. The compounds were also investigated with respect on their 1O2 generation quantum yields, with irradiation at 350, 419 and 575 nm, and photocleavage capabilities on DNA. For the [Ru(dcbpy2)mbpy-ant]2+ complex, the lowest energy excited state is 3MLCT with better quantum yield of 0,0654. On the other hand, for [Ru(dcbpy2)mbpy-ant]2+ complex the lowest energy excited state is localized on 3ππ of the anthracene ligand, and exhibit high 1O2 generation quantum yields (0,86). Preliminary studies of the interaction of these complexes with plasmid DNA conducted by gel electrophoresis showed signs of cleavage, suggesting their promising applications in PDT

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