Molecular, kinetic, thermodynamic, and structural analyses of Mycobacterium tuberculosis hisD-encoded metal-dependent dimeric histidinol dehydrogenase (EC 1.1.1.23)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interaction between Pluronic F127 and Dioctadecyldimethylammonium Bromide (DODAB) Vesicles Studied by Differential Scanning Calorimetry

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

Kinetic asymmetry in the gel-liquid crystalline state transitions of DDAB vesicles studied by differential scanning calorimetry

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

Thermotropic phase behavior in aqueous mixtures of dioctadecyldimethylammonium bromide and alkyltrimethylammonium bromide surfactant series studied by differential scanning calorimetry

The effect of the micelle-forming surfactant series alkyltrimethylammonium bromide (C(n)TAB, n = 12, 14, 16 and 18) on the thermotropic phase behavior of dioctadecyldimethylammonium bromide (DODAB) vesicles in water was investigated by differential scanning calorimetry at constant 5.0 mM total surfactant concentration and varying individual surfactant concentrations. The pre-, post- and main transition temperatures (T-s, T-p and T-m), melting enthalpy (Delta H) and peak width of the main transition (Delta T-1/2) are reported as a function of the surfactant molar fraction. No clear dependence of these parameters on the C(n)TAB chain length was found. At 5 mM, neat DODAB in water exhibits two transition temperatures, T-s = 32.1 and T-m = 42.7 degrees C, as obtained from the DSC upscans, but not a clear T-p. For every n, except n = 12, T-s vanishes as CnTAB concentration increases and approaches CMC. T-m behaves differently for different n, the longer C(14)TAB and C(16)TAB decrease, while C(18)TAB increases T-m with increasing concentration. The data indicate that changes in T-m, T-s, T-p and Delta H of the transition are related not only to the extent of C(n)TAB affinity to DODAB but also to the surfactant chain length. Accordingly, C18TAB yields a more compact bilayer, thus increasing T-m, while C(14)TAB and C(1G)TAB yield a less organized bilayer and reduce T-m. C(12)TAB does not much affect T-s and T-m, although it yields T-p approximate to 51.6 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

Thermal and Structural Behavior of Dioctadecyldimethylammonium Bromide Dispersions Studied by Differential Scanning Calorimetry and X-Ray Scattering

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

Aging kinetics in the Cu-8 wt.% Al alloy with Ag additions

The influence of additions of 2, 4, 6, 8, 10 and 12 wt.% Ag in the isothermal aging kinetics of the Cu-8 wt.% Al alloy was studied using microhardness measurements, differential scanning calorimetry, optical and scanning electron microscopy and X-ray diffractometry. The results indicate that the presence of silver is responsible for the shift of the equilibrium concentration to higher Al contents, allowing the formation of the gamma(1) phase (Al4Cu9) in this alloy. For Ag additions up to 6% the dominant kinetic process is Ag precipitation and for additions from 8 to 12% Ag the nucleation of the perlitic phase dominates. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Isothermal decomposition kinetics in the Cu-9%Al-4%Ag alloy

The influence of 4 wt.%Ag addition on the isothermal decomposition kinetics of the beta' phase in the Cu-9wt.%Al alloy was studied by microhardness measurements, optical and scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, and X-ray diffractometry. The results showed that the presence of Ag decreases the beta' --> (alpha + gamma(1)) decomposition reaction rate in the Cu-9%Al-4%Ag alloy, an effect that may be associated to the gamma(1) phase which catalyses the Ag precipitation, making it faster than the decomposition reaction, and thus, stabilizing the martensitic phase. (C) 2003 Elsevier B.V. All rights reserved.

Isothermal aging kinetics in the Cu-19 at.%Al alloy

The influence of the disordered (Cu)-alpha phase in the isothermal aging kinetics of the Cu-19 at.%Al alloy was studied using microhardness measurements, optical and scanning electron microscopy and X-ray diffractometry. The results indicate that the beta'-->(alpha+gamma (1)) decomposition reaction rate increases with the increase of the temperature in the range between 150 and 500 degreesC and at 600 degreesC the reaction is delayed by the alpha phase precipitation. The value obtained for the activation energy indicates an interface diffusion controlled reaction. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Influence of Ag additions on the activation energy for the reverse eutectoid reaction in Cu-Al alloys

The eutectoid transformation may be defined as a solid-state diffusion-controlled decomposition process of a high-temperature phase into a two-phase lamellar aggregate behind a migrating boundary on cooling below the eutectoid temperature. In substitutional solid solutions, the eutectoid reaction involves diffusion of the solute atoms either through the matrix or along the boundaries or ledges. The effect of Ag on the non-isothermal kinetics of the reverse eutectoid reaction in the Cu-9 mass%Al, Cu-10 mass%Al, and Cu-11 mass%Al alloys were studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The activation energy for this reaction was obtained using the Kissinger and Ozawa methods. The results indicated that Ag additions to Cu-Al alloys interfere on the reverse eutectoid reaction, increasing the activation energy values for the Cu-9 mass%Al and Cu-10 mass%Al alloys and decreasing these values for the Cu-11 mass%Al alloy for additions up to 6 mass%Ag. The changes in the activation energy were attributed to changes in the reaction solute and in Ag solubility due to the increase in Al content.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from flunixin-meglumine adducts

Meglumine, (2R,3R,4R,5S)-6-methylaminohexane-1,2,3,4,5-pentol, is a carbohydrate derived from sorbitol in which the hydroxyl group in position one is replaced by a methylamine group. It forms binary adducts with substances having carboxyl groups, which have in common the presence of hydrogen bonding as the main force in the stabilization of these species. During melting, adducts of meglumine with flunixin (2-[[2-methyl-3-(trifluoromethyl)phenyl]amino]pyridine-3-carboxylic acid) polymerize or self-assemble in amorphous supramolecular structures with molecular weights around 2.0 x 10(5) kDa. DSC curves, in a first heating, show isomorphic transitions where the last one at 137 A degrees C for the flunixin-meglumine adduct originated the supramolecular amorphous polymers with glass transition around 49.5 A degrees C. The kinetic parameters for the thermal decomposition step of the polymers were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15, and 20 A degrees C min(-1), the E (alpha) and B (alpha) terms could be determined and, consequently, the pre-exponential factor, A(alpha), as well as the kinetic model, g(alpha).

Decomposition kinetics of iron (III)-diclofenac compound

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetic parameters for thermal decomposition of microcrystalline, vegetal, and bacterial cellulose

Cellulose can be obtained from innumerable sources such as cotton, trees, sugar cane bagasse, wood, bacteria, and others. The bacterial cellulose (BC) produced by the Gram-negative acetic-acid bacterium Acetobacter xylinum has several unique properties. This BC is produced as highly hydrated membranes free of lignin and hemicelluloses and has a higher molecular weight and higher crystallinity. Here, the thermal behavior of BC, was compared with those of microcrystalline (MMC) and vegetal cellulose (VC). The kinetic parameters for the thermal decomposition step of the celluloses were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and at heating rates of 5, 10, and 20 A degrees C/min, the E(alpha) and B(alpha) terms could be determined and consequently the pre-exponential factor A(alpha) as well as the kinetic model g(alpha). The pyrolysis of celluloses followed kinetic model g(alpha) = [-ln(1 - alpha)](1.63) on average, characteristic for Avrami-Erofeev with only small differences in activation energy. The fractional value of n may be related to diffusion-controlled growth, or may arise from the distributions of sizes or shapes of the reactant particles.

Approximations for the generalized temperature integral: a method based on quadrature rules

The generalized temperature integral I(m, x) appears in non-isothermal kinetic analysis when the frequency factor depends on the temperature. A procedure based on Gaussian quadrature to obtain analytical approximations for the integral I(m, x) was proposed. The results showed good agreement between the obtained approximation values and those obtained by numerical integration. Unless other approximations found in literature, the methodology presented in this paper can be easily generalized in order to obtain approximations with the maximum of accurate.

Crystallization study of molybdate phosphate glasses by thermal analysis

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

Application of differential scanning calorimetry in hair samples as a possible tool in Forensic Science

A calorimetria Exploratória Diferencial (DSC) foi utilizada para estudar o comportamento térmico de amostras de cabelo e verificar a possibilidade de identificar um indivíduo com base nas curvas DSC de um banco de dados. Amostras de cabelo de estudantes e funcionários do Instituto de Química de Araraquara UNESP, foram obtidas para construir um banco de dados. Procurou-se assim identificar de um indivíduo sob incógnita, utilizando-se a curva DSC deste banco de dados.