22 research outputs found

    Photophysics and reductive quenching reactivity of gadusol in solution

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    The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10-2 and 1 × 10-4 at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π → π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 108 M-1 s-1 has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments. © The Royal Society of Chemistry and Owner Societies 2011.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de QuĂ­mica; Argentina. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados. - Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; ArgentinaFil: Churio, Maria Sandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones FĂ­sicas de Mar del Plata. Grupo de InvestigaciĂłn del Departamento de QuĂ­mica de la Unmdp | Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones FĂ­sicas de Mar del Plata. Grupo de InvestigaciĂłn del Departamento de QuĂ­mica de la Unmdp; Argentin

    A photophysical and spectroelectrochemical study on N-phenyl-carbazoles and their oxidized species

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    A series of N-phenyl-carbazole derivatives namely TCz (N-tolyl-carbazol), TCz-TCz (a 3,3ÂŽ-linked dimer), and CzPh-CH2-PhCz (a methylene-bridged N-phenyl-carbazole), have been synthesized and studied by means of absorption and fluorescence spectra, DFT calculations, cyclic voltammetry and spectroelectrochemistry. It is concluded that the methylene bridge in CzPh-CH2-PhCz isolates the two TCz units, whereas TCz-TCz allows extending the electronic coupling along both carbazoles. Moreover, the phosphorescence spectrum of TCz-TCz showed a high energy triplet state (2.76 eV). It was observed that oxidation of CzPh-CH2-PhCz generates an electrochromic polymer containing TCz-TCz dimer units separated by methylene bridges. Oxidized TCz-TCz subunit was analyzed by EPR spectroscopy, and found to be a Class III mixed valence ion in Robin and Day classification. All results suggest that these molecules might be suitable as selective probes in fluorescence sensing or as host materials in electroluminescent devices.Fil: Ramirez, Cristina Lujan. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones en Biodiversidad y BiotecnologĂ­a; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Mangione, Maria Ines. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Rosario. Instituto de QuĂ­mica Rosario. Universidad Nacional de Rosario. Facultad de Ciencias BioquĂ­micas y FarmacĂ©uticas. Instituto de QuĂ­mica Rosario; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; ArgentinaFil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; ArgentinaFil: Parise, Alejandro Ruben. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones en Biodiversidad y BiotecnologĂ­a; Argentin

    Sensitized photo-oxidation of gadusol species mediated by singlet oxygen

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    Gadusols are efficient nature UV sunscreens with antioxidant capacity. The kinetics of the quenching reactionsof singlet oxygen O2(1Δg) by gadusol species was evaluated in aqueous solution as well as in the presenceof direct charged micelles. Time-resolved phosphorescence detection of O2(1Δg) indicated that gadusolate, themain species under biological pH, is a more efficient quencher than the enol form with a rate constant of ca.1.3 × 108 L mol−1 s−1. The deactivation proceeds via a collisional mechanism with clear dominance of chemicalpathways, according to the rates of gadusol and oxygen consumptions, and typical photooxidation quantumyields of ca. 7%. The relative contributions of the chemical and physical quenching steps were not affected bythe presence of anionic or cationic micelles emulating simple pseudo-biological environments. The products ofthe photo-oxidative quenching support a type II mechanism initiated by the addition of O2(1Δg) to the C-C doublebond of gadusolate. These results point to the relevance of considering the role of sacrifice antioxidant along withthe UV-screening function for gadusol, particularly in the context of potential biotechnological applications ofthis natural molecule.Fil: Orallo, Dalila Elisabet. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones FĂ­sicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones FĂ­sicas de Mar del Plata; Argentina. Departamento de QuĂ­mica y BioquĂ­mica; ArgentinaFil: Lores, Nayla Jimena. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y TecnologĂ­a de Materiales. Universidad Nacional de Mar del Plata. Facultad de IngenierĂ­a. Instituto de Investigaciones en Ciencia y TecnologĂ­a de Materiales; ArgentinaFil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados. - Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados; Argentina. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados. - Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados; Argentina. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Churio, MarĂ­a Sandra. Departamento de QuĂ­mica y BioquĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - Mar del Plata. Instituto de Investigaciones FĂ­sicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones FĂ­sicas de Mar del Plata; Argentin

    Mycosporine-like amino acid content in the sea anemones Aulactinia marplatensis, Oulactis muscosa and Anthothoe chilensis

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    The occurrence of mycosporine-like amino acids (MAAs) in the sea anemones Aulactinia marplatensis (Zamponi, 1977), Oulactis muscosa (Drayton in Dana, 1846) and Anthothoe chilensis (Lesson, 1830), from the rocky intertidal habitats on the coast of Mar del Plata, Argentina, was assessed by HPLC. The pattern of MAAs in the mussel Brachidontes rodriguezi, main component of the diet for A. marplatensis and O. muscosa, was as well determined. The results were comparatively analyzed together and with previously reported MAA content in species mainly of the genus Anthopleura. The correlation between the MAA concentration and light availability of their habitats is in line with the photoprotective role assigned to the compounds. The high proportion of mycosporine-taurine in the three species and the results for the evaluation of MAAs in the mussels point to a non-dietary origin or a regulated biotransformation metabolism of dietary MAAs and/or their precursors that is common to sea anemones.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Carignan, Mario Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Subsede Instituto Nacional de Investigación y Desarrollo Pesquero; ArgentinaFil: Acuña, Fabian Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Churio, Maria Sandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp | Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp; ArgentinaFil: Carreto Iraurgui, Jose Ignacio. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Ciencias Marinas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Subsede Instituto Nacional de Investigación y Desarrollo Pesquero; Argentin

    Photophysics and photochemistry of porphyrin core PAMAM dendrimers. Excited states interaction with quinones

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    Quenching of excited states of the meso-substituted tetraphenyl porphyrins with PAMAM branches, and one with PAMAM generation 1 peripherally-modified with thiazole groups by p-benzoquinones, were studied in DMF solution. Fluorescence lifetime measurements evidence a static component in the quenching process. The dynamic quenching rate constants were close to the diffusional limit except for the case of duroquinone. Apparent association constants of the porphyrin compounds with the quinones were determined by comparison of static and dynamic measurements of fluorescence quenching. The ground state interaction is very weak with the exception of tetrachlorobenzoquinone. The triplet state decay kinetics and the transient absorption spectra in the presence of the quinones were determined by laser flash photolysis. Triplet quenching rate constants were lower than those of singlet quenching. An electron transfer mechanism was proposed to explain the results. The long-time transient absorption spectra were assigned to the radical cation of the dyes. Relative radical yields were determined and a dependence on the side chains and the quencher was observed.Fil: Militello, María Paula. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Hernåndez Ramírez, Raquel E.. Tecnológico de Estudios Superiores de Coacalco; MéxicoFil: Lijanova, Irina Victorovna. Instituto Politécnico Nacional; MéxicoFil: Montejano, Hernan Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Previtali, Carlos Mario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentin

    Photochemical study of Eosin-Y with PAMAM dendrimers in aqueous solution

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    A steady-state and time-resolved study of the xanthene dye Eosin-Y (Eos) in the presence of amino-terminated polyamidoamine (PAMAM) dendrimers in alkaline aqueous solution is presented. Stationary photolysis experiments in deaerated and air equilibrated solutions were carried out. The absorption spectra of the photolyzed solutions in the absence of oxygen showed the formation of several intermediate species. With the aid of laser flash photolysis technique (LFP) those transients could be ascribed to semireduced and partially debrominated species of Eos. The triplet quenching rate-constant (3kq) and radical quantum yields (ΊR) were determined by LFP. In the presence of PAMAM, the triplet lifetime of Eos is greatly decreased and the data fitted to a Stern–Volmer treatment. These experiments indicated that the electron transfer from dendrimers to Eos is a highly favored process. Based on the results found in this work, we concluded that Eos/PAMAM couple might act as a promising photoinitiator of vinyl polymerization with low ecological impact.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba; ArgentinaFil: Previtali, Carlos Mario. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba; Argentina. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Bertolotti, Sonia Graciela. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba; Argentina. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; Argentin

    Photosensitizer-dendrimer systems in anticancer treatments: From photophysics to PDT applications

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    Photodynamic therapy (PDT) is a modern form of treatment of cancers and other diseases. It is based on the use of a photosensitizer (PS), a molecule that after absorbing light generates reactive oxygen species with the potential to cause the destruction of the target tumoral cells. A great deal of research in this area has improved the efficiency of the process and eliminated its side effects by properly combining PS with nanomaterials. In this context, dendrimers are excellent candidates because their highly branched 3D architectures allow them to form a wide variety of supramolecular assemblies with PSs (PS-Ds) either covalently or by complexation, which possess a number of advantages for PDT application. This chapter reviews the recent progress in the development of PS-Ds systems, their photophysical characterization and achievements in PDT technology.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Militello, María Paula. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Previtali, Carlos Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentin

    Antioxidant activity of gadusol and occurrence in fish roes from Argentine Sea

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    The occurrence of the natural antioxidant gadusol (3,5,6-trihydroxy-5-hydroxymethyl-2-methoxycyclohex-2-en-1-one) was quantified in fish roes of three species from Argentine Sea: argentine hake (Merluccius hubbsi), brazilian sandperch (Pinguipes brasilianus) and argentinian sandperch (Pseudopercis semifasciata). Significant yields of the compound were found in the sandperchs. The antioxidant activity of the isolated metabolite in aqueous solution was assessed by ORAC and ABTS assays and compared with that of other known natural antioxidants. The results indicate that gadusol is a good breaker of chain reactions carried by peroxyl radicals. Besides, its ability to reduce radicals is comparable to that of ascorbic acid. On this basis, fish roes from brazilian and argentinian sandpearchs are proposed as useful sources of antioxidants for human consumption. © 2009 Elsevier Ltd. All rights reserved.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Uez, María J.. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Churio, Maria Sandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentin

    Synthesis and characterization of latex nanoparticles using a visible-light photoinitiating system in reverse micelles

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    This work shows the feasibility of using the photoinitiating system composed by the xanthene dye Eosin-Y and triethanolamine on the polymerization of acrylamide in benzyl-hexadecyl-dimethylammonium chloride (BHDC) reverse micelles. Molecular weights of polyacrylamide (MWPAA) in the order of 105 and conversions up to 90 % are obtained. The size of the latex particles is in the range of the nanometers (d < 50 nm). The effect of water content and concentrations of surfactant, amine, dye, and monomer on the particle size and MWPAA are examined. Only the amine and monomer concentrations affect the MWPAA. These results are interpreted on the basis of an exchange mechanism between micelles. Practically no effect on hydrodynamic diameters is observed when the value of MWPAA is doubled. This is ascribed to a supercoiled structure of PAA inside of micelles. Our results also suggest that the polymer properties can be modulated by appropriate combination of the dye/surfactant electrical charges.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Porcal, Gabriela Valeria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Previtali, Carlos Mario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

    Photophysics of thionine in AOT and BHDC reverse micelles. Quenching of the triplet state by aliphatic amines studied by transient absorption spectroscopy

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    The photophysics of thionine (3,7-diamino-5-phenothiazinium) (Th+) was investigated in reverse micelles (RMs) of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and benzyldimethylhexadecylammonium chloride (BHDC) with special emphasis on the triplet state processes. In RMs both the absorption and emission spectra of the dye present a red shift with respect to pure water. The absorption maximum wavelength and Stokes shift show a tendency towards the values in water, although do not reach them even with the higher water content examined. The photophysical parameters are more affected by the water content in BHDC than in AOT. The triplet state of Th+ was investigated by the technique of laser flash photolysis. The T-T absorption spectrum presents a strong absorption band in the region between 770 and 800 nm, corresponding to the monoprotonated triplet form of the dye. This spectrum is red shifted with respect to water in the RMs. The triplet quenching by aliphatic amines was investigated. The triplet decay is well fitted by a bi-exponential function in the presence of the hydro-soluble triethanolamine (TEOA) in both RMs. This behavior is interpreted as the result of a very fast intramicellar quenching, followed by slow process that may be ascribed to an intermicellar exchange of amine molecules between RMs. The kinetic analysis showed that intermicellar exchange rate constant is two orders of magnitude more effective in BHDC than in AOT. Meanwhile, in the quenching by the hydrophobic tributylamine (TBA) the decay is mono-exponential. The amine is located preferentially in the bulk organic phase and the quenching mechanism involves the interaction of the amine with the monoprotonated triplet of dye reaching in the micellar interface. It is interesting to note that the apparent quenching rate constant by TBA is one order of magnitude lower than the exchange rate constant by TEOA.Fil: Porcal, Gabriela Valeria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Previtali, Carlos Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentin
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