Síntese e caracterização de híbridos orgânico-inorgânicos luminescentes para aplicação em ensaios biológicos

Pós-graduação em Química - IBILCE

Espécies moleculares e supramoleculares de 'PD'(II)' com ligantes mono, bi e polidentados : caracterização estrutural e atividades biológicas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Propriedades espectroscópicas de sílica contendo crômio

Pós-graduação em Química - IQ

Effect of pressure-assisted heat treatment on photoluminescence emission of α-Bi2O3 needles

Materials with high photoluminescence (PL) intensity can potentially be used in optical and electronic devices. Although the PL properties of bismuth(III) oxide with a monoclinic crystal structure (α-Bi2O3) have been explored in the past few years, methods of increasing PL emission intensity and information relating PL emission to structural defects are scarce. This research evaluated the effect of a pressure-assisted heat treatment (PAHT) on the PL properties of α-Bi2O3 with a needlelike morphology, which was synthesized via a microwave-assisted hydrothermal (MAH) method. PAHT caused an angular increase between the [BiO6]-[BiO6] clusters of α-Bi2O3, resulting in a significant increase in the PL emission intensity. The Raman and XPS spectra also showed that the α-Bi2O3 PL emissions in the low-energy region (below ∼2.1 eV) are attributed to oxygen vacancies that form defect donor states. The experimental results are in good agreement with first-principles total-energy calculations that were carried out within periodic density functional theory (DFT).

Avaliação da atividade mutagênica de complexos heterolépticos de Rutênio(II) com atividade anti - Mycobacterium tuberculosis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Fabrication of coaxial TiO2/Sb2S3 nanowire hybrids for efficient nanostructured organic- inorganic thin film photovoltaics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Planar and UV written channel optical waveguides prepared with siloxane poly(oxyethylene)-zirconia organic-inorganic hybrids. Structure and optical properties

Organic-inorganic hybrids were prepared using ureapropyltriethoxysilane, methacryloxypropyltrimethoxysilane and acrylic acid modified zirconium(IV) n-propoxide precursors and were characterized by small angle X-ray scattering, X-ray diffraction and photoluminescence spectroscopy. The results indicate an effective interaction between the zirconium-based nanoparticles and the siliceous nanodomains that induces changes in the hybrids' emission features. Planar waveguides were obtained by spin-coating of the prepared sols on sodalime and silica substrates. Refractive index, thickness, number of propagating modes, and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm by the prism coupling technique. The synergism between the two hybrid precursors resulted in monomode planar waveguides with low losses in the infrared ( from 0.6-1.1 dB cm(-1)) which also support a number of propagating modes in the visible ( losses from 0.4-1.5 dB cm(-1)). Channel waveguides were also obtained by UV photopatterning using amplitude or phase masks and propagating modes were observed at 1550 nm.

Precipitation chemistry in semi-arid areas of Southern Africa: A case study of a rural and an industrial site

Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO(4)(2-) and a large proportion of the precipitation is acidic, with 98% of samples at Amersfoort and 94% at Louis Trichardt having a pH below 5.6 ( average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.

Precipitation chemistry and wet deposition in Kruger National Park, South Africa

The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H2SO4) and organic acids (18%). Most of the H2SO4 component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS.ha(-1).yr(-1) and 2.8 kgN.ha(-1).yr(-1), respectively. The N deposition was mainly in the form of NH4+. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.

Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids

Nd3+-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly (oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF3SO3)(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), Si-29 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Er(3+)-Based Diureasil Organic-Inorganic Hybrids

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Determination of labile inorganic and organic species of Al and Cu in river waters using the diffusive gradients in thin films technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.