Síntesis y caracterización de fotocatalizadores de TiO2 nanomodificados con Ag para descontaminación de aguas en Santiago del Estero.

Capítulo de libroEn este trabajo se exponen algunos de los avances logrados en la etapa inicial del desarrollo de un nuevo material fotocatalítico, relacionados con su síntesis y modificación de la actividad fotocatalítica.Fil: Monasterio, Fernanda E.. Instituto de Bionanotecnología del NOA, INBIONATEC-CONICET/Universidad Nacional de Santiago del Estero (UNSE), Santiago del Estero, Argentina. Email: [email protected]: Borsarelli, Claudio D.. Instituto de Bionanotecnología del NOA, INBIONATEC-CONICET/Universidad Nacional de Santiago del Estero (UNSE), Santiago del Estero, Argentina.Fil: Morán Vieyra, Faustino E.. Instituto de Bionanotecnología del NOA, INBIONATEC-CONICET/Universidad Nacional de Santiago del Estero (UNSE), Santiago del Estero, Argentina

Photosensitizing properties of hollow microcapsules built by multilayer self-assembly of poly(allylamine hydrochloride) modified with rose Bengal

A polymeric photosensitizer based on poly(allylamine hydrochloride) (PAH) and rose Bengal (RB) was synthesized. The modified polycation PAH-RB was demonstrated to be suitable for construction of microcapsules via a layer-by-layer (LbL) assembly technique, using sodium poly(styrene sulfonate) (PSS) as counter-polyelectrolyte and CaCO3 microcrystals as templates. After CaCO3 core removal, a stable suspension of hollow microcapsules with shells incorporating RB (HM-RB) was obtained. The spectroscopic and photophysical behavior of both PAH-RB and HM-RB in aqueous environments were studied and described in terms of dye–dye interactions and dye hydrophobicity. Only HM-RB was able to generate singlet molecular oxygen with similar efficiency to free RB in air-saturated solutions upon green light irradiation. In order to explore possible practical applications as a supramolecular photosensitizer, experiments of HM-RB irradiation in the presence of chemically and biologically relevant target molecules were carried out. It was observed that is possible to use visible light to initiate the photooxidation of biological compounds in water, with many interesting advantages compared to low-molecular-weight photosensitizers such as an enhancement of the photosensitizing effect, due to a significant reduction of dye–dye interaction, or improved reuse given the straightforward size-based separation from the reaction mixture without loss of efficiency.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Mono- and Dinuclear Complexes of Tricarbonylrhenium(I) with 4-Methyl-2,2'-bipyridine-4'-carbonitrile

Novel mono- and dinuclear tricarbonylrhenium(I) complexes of formula [Re(Mebpy-CN)(CO)3Cl] (1), [Re(Mebpy-CN)-(CO)3(CH3CN)](PF6) (2), and [(CH3CN)(CO)3Re(Mebpy-CN)Ru(NH3)5](PF6)3 (3), in which Mebpy-CN = 4-methyl-2,2-bipyridine-4-carbonitrile, were prepared and characterized by spectroscopic, photophysical, and computational techniques. The complete structure of complex 2 was determined by X-ray diffraction. The increased conjugation in the bipyridyl ring owing to the nitrile substituent increases the emission quantum yields of the 3MLCT (metal-to-ligand charge-transfer) lowest-lying excited states of 1 and 2 with respect to the corresponding bpy complexes (bpy = 2,2-bipyridine). The mixed-valent species of formula [(CH3CN)(CO)3Re(Mebpy-CN)Ru(NH3)5]4+ (4) was prepared in situ and as a mixed salt; the charge recombination from its metal-to-metal charge-transfer(MMCT) excited state is predicted to lie in the Marcus inverted region. The electronic structures and optical properties of all the reported complexes calculated by DFT and TD-DFT methods agree reasonably well with experimental results.Fil: Mecchia Ortiz, Juan Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; ArgentinaFil: Moran Vieyra, Faustino Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro de Investigaciones y Transferencia de Santiago del Estero; Argentina. Universidad Nacional de Santiago del Estero; ArgentinaFil: Borsarelli, Claudio Darío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro de Investigaciones y Transferencia de Santiago del Estero; Argentina. Universidad Nacional de Santiago del Estero; ArgentinaFil: Romero, Isabel. Universidad de Girona; EspañaFil: Fontrodona, Xavier. Universidad de Girona; EspañaFil: Parella, Teodor. Universitat Autonoma de Barcelona; EspañaFil: Lis de Katz, Noemí D.. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; ArgentinaFil: Fagalde, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; ArgentinaFil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; Argentin

Thermal Degradation Kinetics Of Bixin In An Aqueous Model System.

The kinetics of the thermal degradation of the natural cis carotenoid bixin in a water/ethanol (8:2) solution was studied as a function of temperature (70-125 degrees C), using high-performance liquid chromatography. The curves for the decay of bixin and formation of products (e.g., di-cis and all-trans isomers and a C17 degradation compound) did not adjust well to a first-order rate law, but very good fits were obtained using a biexponential model. This mathematical modeling gave the rate constant values for the formation of the primary products from bixin, and the energy barrier for each step was obtained. The di-cis isomers were formed immediately (15 kcal/mol) together with the decay of bixin, followed by a slow consumption, indicating their role as reaction intermediates. In fact, the di-cis isomers could easily revert to bixin (Ea approximately 3 kcal/mol) or yield the primary C17 degradation product, with an energy barrier of 6.5 kcal/mol. In turn, 24 kcal/mol was necessary for the Bix --> all-trans step, explaining its slower formation.532307-1

Singlet Molecular Oxygen Quenching Ability of Carotenoids in a Reverse-micelle Membrane Mimetic System

ABSTRACT The influence of the medium heterogeneity upon the bimolecular rate constants for the physical quenching, k q , and chemical quenching, k r , of singlet molecular oxygen O 2 ( 1 ⌬ g ) by seven natural and three synthetic carotenoids (CAR) with different substituent patterns was studied in a reverse micelle system of sodium bis(2-ethylhexyl)sulfosuccinate, hexane and water. Because O 2 ( 1 ⌬ g ) was generated inside the water pools of the reverse micelles by photosensitization of the water-soluble dye rose bengal and the CAR are mainly located in the external hexane pseudophase, the quenching process was interpreted using a pseudophase model for the partition of O 2 ( 1 ⌬ g ) between the water pools and the organic pseudophases. The k q values were mainly dependent on the extent of the double-bond conjugation of the CAR, as demonstrated by a good empirical relationship between log(k q ) and the energy E(S) of the longest wavelength transition →* of the CAR. In contrast, the k r values were almost independent of the extent of the double-bond-conjugated system and about four orders of magnitude lower than k q . However, in all cases, CAR photobleaching was observed with the formation of various oxidation products, depending on the photosensitization time. Chromatographic and spectroscopic product analysis for the reaction products of ␤-carotene with O 2 ( 1 ⌬ g ) indicated the Dedicated to Professor Silvia E. Braslavsky on the occasion of her 60th birthday