Laponite RD/polystyrenesulfonate nanocomposites obtained by photopolymerization

The present paper describes the synthesis and characterization by dynamic light scattering, X-ray diffraction, scanning electron microscopy and atomic force microscopy of Laponite RD/Sodium polystyrenesulfonate nanocomposites obtained by radical photopolymerization initiated by the cationic dye safranine. The presence of the clay mineral does not affect the hydrotropic aggregation of the monomers, but allows a better deaggregation of the initiator molecules, decreasing the quenching of the excited states that leads to the radicals that initiate polymerization. Increasing the amount of clay mineral loading in the polymerization mixture promotes higher monomer conversion and faster polymerization. The size of the nanocomposite particles, measured by light scattering decreases from 400 to 80 nm for clay mineral loadings of 1.0 wt.%. The X-ray diffraction patterns indicate that the clay mineral does not present a regular crystalline structure in the nanocomposite. Atomic force microscopy studies show films of sodium polystyrenesulfonate polymer with embedded Laponite platelets in its structure, forming 1-8 nm height and 25-100 nm diameter aggregates. (C) 2011 Elsevier B.V. All rights reserved.

Deactivation of Ferrylmyoglobin by Vanillin as Affected by Vanillin Binding to beta-Lactoglobulin

Vanillin was found to be efficient as a deactivator of ferrylmyoglobin with a second-order rate constant of k(2) = S7 +/- 1 L mol(-1) s(-1) for reduction to metmyoglobin with Delta H(double dagger) = 58.3 +/- 0.3 kJ mol(-1) and Delta S(double dagger) = -14 +/- 1 J mol(-1) K(-1) in aqueous pH 7.4 solution at 25 degrees C. Binding to beta-lactoglobulin (AG) was found to affect the reactivity of vanillin at 25 degrees C only slightly to k(2) = 48 +/- 2 L mol(-1) s(-1) (Delta H(double dagger) = 68.4 +/- 0.4 kJ mol(-1) and Delta S(double dagger) = 17 +/- 1 J mol(-1) K(-1)) for deactivation of ferrylmyoglobin. Binding of vanillin to beta LG was found to have a binding stoichiometry vanillin/beta LG > 10 with K(A) = 6 x 10(2) L mol(-1) and an apparent total Delta H degrees of approximately -38 kJ mol(-1) and Delta S degrees = -S5.4 +/- 4J mol(-1) K(-1) at 25 degrees C and Delta C(p), (obs) = -1.02 kJ mol(-1) K(-1) indicative of increasing ordering in the complex, as determined by isothermal titration microcalorimetry. From tryptophan fluorescence quenching for beta LG by vanillin, approximately one vanillin was found to bind to each beta LG far stronger with K(A) = 5 x 10(4) L, mol(-1) and a Delta H degrees = 10.2 kJ mol(-1) and Delta S degrees = 55J mol(-1) K(-1) at 25 degrees C. The kinetic entropy/enthalpy compensation effect seen for vanillin reactivity by binding to beta LG is concluded to relate to the weakly bound vanillin oriented through hydrogen bonds on the beta LG surface with the phenolic group pointing toward the solvent, in effect making both Delta H(double dagger) and Delta S(double dagger) more positive. The more strongly bound vanillin capable of tryptophan quenching in the fiLG calyx seems less or nonreactive.

Light-Induced Oxidation of Unsaturated Lipids as Sensitized by Flavins

Triplet-excited riboflavin ((3)RF*) was found by laser flash photolysis to be quenched by polyunsaturated fatty acid methyl esters in tert-butanol/water (7:3, v/v) in a second-order reaction with k similar to 3.0 x 10(5) L mol(-1) s(-1) at 25 degrees C for methyl linoleate and 3.1 x 10(6) L mol(-1) s(-1), with Delta H double dagger = 22.6 kJ mol(-1) and Delta S double dagger = -62.3 J K(-1) mol(-1), for methyl linolenate in acetonitrile/water (8:2, v/v). For methyl oleate, k was <10(4) L mol(-1) s(-1). For comparison, beta-casein was found to have a rate constant k similar to 4.9 x 10(8) L mol(-1) s(-1). Singlet-excited flavin was not quenched by the esters as evidenced by insensitivity of steady-state fluorescence to their presence. Density functional theory (DFT) calculations showed that electron transfer from unsaturated fatty acid esters to triplet-excited flavins is endergonic, while a formal hydrogen atom transfer is exergonic (Delta G(HAT)degrees = -114.3, -151.2, and -151.2 kJ mol(-1) for oleate, linoleate, and linolenate, respectively, in acetonitrile). The reaction is driven by acidity of the lipid cation radical for which a pK(a) similar to -0.12 was estimated by DFT calculations. Absence of electrochemical activity in acetonitrile during cyclic voltammetry up to 2.0 V versus NHE confirmed that Delta G(ET)degrees > 0 for electron transfer. Interaction of methyl esters with (3)RF* is considered as initiation of the radical chain, which is subsequently propagated by combination reactions with residual oxygen. In this respect, carbon-centered and alkoxyl radicals were detected using the spin trapping technique in combination with electron paramagnetic resonance spectroscopy. Moreover, quenching of 3RF* yields, directly or indirectly, radical species which are capable of initiating oxidation in unsaturated fatty acid methyl esters. Still, deactivation of triplet-excited flavins by lipid derivatives was slower than by proteins (factor up to 10(4)), which react preferentially by electron transfer. Depending on the reaction environment in biological systems (including food), protein radicals are expected to interfere in the mechanism of light-induced lipid oxidation.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Estudo da viabilidade técnica da utilização de escórias de aciaria do processo LD como adição em cimentos

A reciclagem de resíduos apresenta-se como uma alternativa adequada com relação à preservação dos recursos naturais e do meio ambiente. As escórias de aciaria são resíduos siderúrgicos originados na fabricação do aço, e são geradas em grandes quantidades. Estes resíduos são estocados nos pátios siderúrgicos, onde permanecem, na sua maioria, sem qualquer destino. Normalmente, as escórias de aciaria são volumetricamente instáveis, apresentando características expansivas, e por esta razão, a aplicação das mesmas em materiais de construção torna-se restrita. Esta pesquisa tem como objetivo estudar a viabilidade técnica do uso das escórias de aciaria LD como adição em cimentos, propondo um método de estabilização por meio de granulação por resfriamento brusco destas escórias, buscando, desta forma, a eliminação do fenômeno da expansão, e visando a melhoria das características destes resíduos. No processo de estabilização, a escória líquida foi granulada em uma usina siderúrgica. Estudos complementares de granulação foram realizados nos laboratórios da UFRGS, empregando-se escórias refundidas. A granulação por resfriamento brusco favoreceu a redução do CaOlivre, a eliminação do MgO na forma de periclásio, e a eliminação do bC2S das escórias, considerados agentes causadores da expansão. No entanto, a elevada basicidade da escória LD dificulta a formação da estrutura vítrea e a separação da fração metálica após o resfriamento brusco. Foram realizados ensaios de expansão das escórias, atividade pozolânica, e resistência mecânica de argamassas com escórias granuladas. O resfriamento brusco proporcionou a eliminação da expansão e o desenvolvimento das propriedades pozolânicas/cimentícias da escória granulada. Como adição em cimentos, do ponto de vista da resistência mecânica, as argamassas compostas com escórias granuladas e clínquer apresentaram níveis de resistência à compressão axial compatíveis com as especificações referentes ao cimento Portland composto, apesar destes resultados serem inferiores aos obtidos para as argamassas de referência.

Propriedade fotoluminescente da ZrO2: Tb+3, Eu+3, Tm+3 obtida pelo método de polimerização de complexos

Recent studies are investigating a new class of inorganic materials which arise as a promising option for high performance applications in the field of photoluminescence. Highlight for rare earth (TR +3 ) doped, which have a high luminous efficiency, long decay time and being able to emit radiation in the visible range, specific to each element. In this study, we synthesized ZrO2: Tb +3 , Eu +3 , Tm +3 nanoparticles complex polymerization method (CPM). We investigated the influences caused by the heat treatment temperature and the content of dopants in zirconia photoluminescent behavior. The particles were calcined at temperature of 400, 500 and 600 ° C for two hours and ranged in concentration of dopants 1, 2, 4 and 8 mol% TR +3 . The samples were characterized by thermal analysis, X-ray diffraction, photoluminescence of measurements and uv-visible of spectroscopies. The results of X-ray diffraction confirmed the formation of the tetragonal and cubic phases in accordance with the content of dopants. The photoluminescence spectra show emission in the region corresponding simultaneous to blue (450 nm), green (550 nm) and red (615 nm). According to the results, ZrO2 particles co-doped with rare earth ions is a promising material white emission with a potential application in the field of photoluminescence

Influência da lubrirrefrigeração na qualidade superficial de metais retificados

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

Synthesis and structural characterization of Eu(III)-doped Zn7Sb2O12

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

Film based on Y2O3: Eu3+ (5 mol% of Eu3+) for flat panel display

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

Europium luminescent polymeric microspheres fabricated by spray drying process

The spray drying method was used to prepare luminescent microspheres. These microspheres were prepared by spraying an aqueous solution of dextrin and an europium(III) complex with subsequent drying in a hot medium. The spray dried powder was characterized by scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). Particle size distribution was estimated from SEM images. The ultrasonic spray drying technique was successfully applied to yield a microparticulated and red luminescent powder composed by the [Eu(dpa)(3)](3-) stop (dpa = dipicolinic acid) complex incorporated in dextrin microspheres.

Morphological and Structural changes of CaxSr1-xTiO3 Powders Obtained by the Microwave-Assisted Hydrothermal Method

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

Optical properties of polydisperse submicrometer aggregates of sulfur-containing zinc oxide consisting of spherical nanocrystallites

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

Structural and Electric-Optical Properties of Zinc Phthalocyanine Evaporated Thin Films: Temperature and Thickness Effects

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

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

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

Sistemas Nanoestruturados: Heteroestruturas Quasi-Periódicas de Nitretos e Cálculos Ab initio em Polimorfos CaCO3

The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di®erent geometry optimizations have been e®ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e®ective masses and optical properties, such as dielectric constant, absorption, re°ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal