A micelle nucleation model for the interaction of dodecyl sulphate with Lys49-phospholipases A(2)

Bothropstoxin-I (BthTx-I) is a Lys49-PLA(2) from the venom of Bothrops jararacussu that lacks detectable catalytic activity, yet causes rapid Ca2+-independent membrane damage. With the aim of understanding the interaction between BthTx-I and amphiphilic molecules, we have studied the interaction of sodium dodecyl sulphate (SDS) with the protein. Circular dichroism and attenuated total reflection Fourier-transform infrared spectra of BthTx-I reveal changes in the alpha-helical organization of the protein at an SDS/BthTx-I molar ratio of 20-25. At SDS/BthTx-I ratios of 40-45 the alpha-helices return to a native-like conformation, although fluorescence emission anisotropy measurements of 2-amino-N-hexadecyl-benzamide (AHBA) demonstrate that the total SDS is below the critical micelle concentration when this transition occurs. These results may be interpreted as the result of SDS accumulation by the BthTx-I homodimer and the formation of a pre-micelle SDS/BthTx-I complex, which may subsequently be released from the protein surface as a free micelle. Similar changes in the alpha-helical organization of BthTx-I were observed in the presence of dipalmitoylphosphatidylcholine liposomes, suggesting that protein structure transitions coupled to organization changes of bound amphiphiles may play a role in the Ca2+-independent membrane damage by Lys49-PLA(2)s. (c) 2006 Elsevier B.V. All rights reserved.

Selectivity in the mechanism of action of antimicrobial mastoparan peptide Polybia-MP1

Many potent antimicrobial peptides also present hemolytic activity, an undesired collateral effect for the therapeutic application. Unlike other mastoparan peptides, Polybia-MP1 (IDWKKLLDAAKQIL), obtained from the venom of the social wasp Polybia paulista, is highly selective of bacterial cells. The study of its mechanism of action demonstrated that it permeates vesicles at a greater rate of leakage on the anionic over the zwitterionic, impaired by the presence of cholesterol or cardiolipin; its lytic activity is characterized by a threshold peptide to lipid molar ratio that depends on the phospholipid composition of the vesicles. At these particular threshold concentrations, the apparent average pore number is distinctive between anionic and zwitterionic vesicles, suggesting that pores are similarly formed depending on the ionic character of the bilayer. To prospect the molecular reasons for the strengthened selectivity in Polybia-MP1 and its absence in Mastoparan-X, MD simulations were carried out. Both peptides presented amphipathic alpha-helical structures, as previously observed in Circular Dichroism spectra, with important differences in the extension and stability of the helix; their backbone solvation analysis also indicate a different profile, suggesting that the selectivity of Polybia-MP1 is a consequence of the distribution of the charged and polar residues along the peptide helix, and on how the solvent molecules orient themselves according to these electrostatic interactions. We suggest that the lack of hemolytic activity of Polybia-MP1 is due to the presence and position of Asp residues that enable the equilibrium of electrostatic interactions and favor the preference for the more hydrophilic environment.

Characterization of mineral contents on androgen deficient and chronic ethanol consuming rats by biochemistry and non-destructive techniques

Ethanol can compromise the body mineral composition and affect bone, and when associated to hypogonadism is considered an important risk factor for osteoporosis in man. The aim of this study was to investigate the effect of androgen deficient and chronic ethanol consuming on mineral contents by biochemistry and non-destructive techniques. Wistar rat (n=54) were divided in orchiectomy (ORQ) or SHAM-operated and subdivided by diet. They were daily fed with a Lieber DeCarli diet model for 8 weeks long. The controls groups were free-diet and pair-fed. Ca and P were analyzed by biochemistry test in the blood and by nX-ray fluorescence and FT-Raman on the femur area. Serum analysis revealed hypocalcaemia and hypeiphosphataemia in ethanol groups more than pair-fed and free-diet. In similarity, spectroscopy indicated a decrease in bone Ca content in ORQ groups, mainly for ethanol groups. Phosphorus content and Ca/P molar ratio, otherwise, doesn't diverge in all 6 groups. Ethanol consumption impaired Ca and P homeostasis in ORQ rat more than SHAM. The relationships among ethanol consume and androgen deficit support the hypothesis that ethanol affects the mineral-regulating hormones and may mediate some effects on bone. These findings demonstrate that ethanol seemed to interfere with the normal compensatory response to these Ca and P levels and is more significant M androgen deficiency rats.

Fractal character of the SAXS correlation volume in poly(ethylene glycol)/silica hybrid wet gels

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

Structural characteristics of silica sonogels prepared with different proportions of TEOS and TMOS

Sonohydrolysis of mixtures of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) with different TMOS/(TMOS + TEOS) molar ratio R was carried out to obtain similar to 2.0 x 10(-3) mol SiO2/cm(3) and similar to 86%-volume liquid phase wet gels. Aerogels were obtained by supercritical CO2 extraction in autoclave. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The structure of the wet gels can be described as a mass fractal structure with fractal dimension D similar to 2.2 and characteristic length increasing from similar to 4.6 nm for pure TEOS to similar to 6.4 nm for pure TMOS. A fraction of the porosity is eliminated with the supercritical process. The fundamental role of the TMOS/(TMOS + TEOS) molar ratio on the structure of the aerogels is to increase the porosity and the pore mean size as R changes from pure TEOS to pure TMOS. The supercritical process increases the mass fractal dimension and shortens the fractality domain in the mesopore region. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure with correlated mass fractal dimension D-m similar to 2.6 and surface fractal dimension D-s similar to 2.3. (C) 2007 Elsevier B.V. All rights reserved.

Small-angle X-ray scattering from wet gels prepared from co-hydrolysis of tetraethoxysilane and vinyltriethoxysilane

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

Production of biodiesel by esterification of palmitic acid over mesoporous aluminosilicate Al-MCM-41

Biodiesel has been obtained by esterification of palmitic acid with methanol, ethanol and isopropanol in the presence of Al-MCM-41 mesoporous molecular sieves with Si/Al ratios of 8.16 and 32. The catalytic acids were synthesized at room temperature and characterized by atomic absorption spectrometry (AAS), thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen absorption (BET/BJH), infrared spectroscopy (IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The reaction was carried out at 130 degrees C whilst stirring at 500 rpm, with an alcohol/acid molar ratio of 60 and 0.6 wt% catalyst for 2 h. The alcohol reactivity follows the order methanol > ethanol > isopropanol. The catalyst Al-MCM-41 with ratio Si/Al = 8 produced the largest conversion values for the alcohols studied. The data followed a rather satisfactory approximation to first-order kinetics. (C) 2008 Elsevier Ltd. All rights reserved.

Influence of particle size on the properties of Pt-Ru/C catalysts prepared by a microemulsion method

Pt-Ru/C nanocatalysts were prepared by a microemulsion method using different values of water/surfactant molar ratio in order to get different particle sizes. Crystallite sizes and structural properties were determined by X-ray diffraction. Particle size and distribution were characterized by transmission electron microscopy and average composition was determined by energy-dispersive X-ray analysis. Thermogravimetric analysis was used to estimate the amount of supported metals. Differential scanning calorimetry measurements indicated the presence of hydrous ruthenium oxides in the as-prepared catalysts. Results for the oxidation of adsorbed CO as well as for methanol oxidation revealed significant differences in the behavior of the prepared catalysts. All together, the results demonstrate that the variation of particle size produces changes in other properties of the Pt-Ru/C catalysts and that to establish direct correlations between electrocatalytic activity and particle size is not possible because the effects of the different parameters cannot be separated. (c) 2007 the Electrochemical Society.

Synthesis and characterization of a novel series of meso (nitrophenyl) and meso (carboxyphenyl) substituted porphyrins

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

Binuclear cyclopalladated compounds with antitubercular activity: synthesis and characterization of [{Pd(C-2,N-dmba)(X)}(2)(mu-bpp)] (X = Cl, Br, NCO, N-3; bpp=1,3-bis(4-pyridyl)propane)

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

Atributos químicos do solo e produção do feijoeiro com a aplicação de calcário e manganês

O feijão (Phaseolus vulgaris L.) constitui a base alimentar da população brasileira. Muitos fatores determinam a baixa produtividade do feijoeiro, desde problemas políticos até fatores técnicos, dentre eles a adubação e nutrição. O objetivo foi avaliar os atributos químicos do solo e produção do feijoeiro (cv. Pérola) de acordo com a aplicação de calagem e Mn. O experimento foi realizado em vasos com Latossolo Vermelho-Amarelo distrófico típico fase cerrado, em delineamento inteiramente casualizado com três repetições, em esquema fatorial 2 x 6, envolvendo duas doses de uma mistura de CaCO3 e MgCO3, na relação molar 3:1 (de calcário, calculadas) para elevar a saturação por base para 50 % e para 70 % e seis doses de Mn (0, 20, 40, 60, 80 e 100 mg dm-3). Na análise dos resultados, verificou-se decréscimo no teor foliar de Mn de acordo com o aumento da saturação por base, não sendo observado o mesmo efeito no solo após o cultivo. O teor de Mn no solo para produção máxima de grãos mostrou-se semelhante para saturação por base de 50 e 70 %; no entanto, a dose do micronutriente aplicada para essa produção foi de 28 mg dm-3 e 57 mg dm-3, respectivamente.

Mass fractal characteristics of silica sonogels as determined by small-angle x-ray scattering and nitrogen adsorption

A sample series of silica sonogels was prepared using different water-tetraethoxysilane molar ratio (r(w)) in the gelation step of the process in order to obtain aerogels with different bulk densities after the supercritical drying. The samples were analyzed by means of small-angle x-ray-scattering (SAXS) and nitrogen-adsorption techniques. Wet sonogels exhibit mass fractal structure with fractal dimension D increasing from similar to2.1 to similar to2.4 and mass-fractal correlation length xi diminishing from similar to13 nm to similar to2 nm, as r(w) is changed in the nominal range from 66 to 6. The process of obtaining aerogels from sonogels and heat treatment at 500degreesC, in general, increases the mass-fractal dimension D, diminishes the characteristic length xi of the fractal structure, and shortens the fractal range at the micropore side for the formation of a secondary structured particle, apparently evolved from the original wet structure at a high resolution level. The overall mass-fractal dimension D of aerogels was evaluated as similar to2.4 and similar to2.5, as determined from SAXS and from pore-size distribution by nitrogen adsorption, respectively. The fine structure of the secondary particle developed in the obtaining of aerogels could be described as a surface-mass fractal, with the correlated surface and mass-fractal dimensions decreasing from similar to2.4 to similar to2.0 and from similar to2.7 to similar to2.5, respectively, as the aerogel bulk density increases from 0.25 (r(w)=66) up to 0.91 g/cm(3) (r(w)=6).

Structural modelling of Eu3+-based siloxane-poly( oxyethylene) nanohybrids

The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.

Calorimetric study of the effect of water quantity on tetramethoxysilane hydrolysis under ultrasound stimulation

The ultrasound stimulated and oxalic acid-catalyzed hydrolysis of tetramethoxysilane (TMOS) was studied by means of a heat flux calorimetric method as a function of the initial water/TMOS molar ratio (r) ranging from 2 to 10. The method is based on the time recording of the hydrolysis exothermic heat peak. which takes place in acidulated heterogeneous water-TMOS mixtures under ultrasonic stimulation, accounting for the instantaneous hydrolysis rate. The hydrolysis rate increases from zero up to a maximum value during the heterogeneous step of the process and then diminishes naturally according to the reactant consumption. The total hydrolyzed quantity was found to be slightly increasing with r. The immiscibility gap of the TMOS- water system in the presence of the hydrolysis products has been inferred from the evaluation of the reacted quantity during the heterogeneous step of the reaction and it has been represented in a ternary diagram in the studied r-range.

Functionalized silica synthesized by sol-gel process

This work considers some aspects of the chemistry involved in the preparation and description of silicon oxide functionalized by sol-gel process. In this work we studied the synthesis and measured the properties of silicon oxide functionalized with 3-chloropropyl, through a sol-gel process. Thermogravimetic analysis, infrared spectra, and elemental analyses were measured. The samples were prepared in the following proportions of tetraethylorthosilicate (TEOS): 3-chloropropyl trimethoxisilane molar ratio: 1:0, 1:1, 2:1, 3:1 and 4:1. The thermogravimetric data for the resulting materials established the 'minimum formulae' 2:0, 3:1, 4.1, 7:1 and 11:1, respectively. As expected, the relative amount of water is inversely proportional to the presence of propyl groups. Infrared data show Si-C and -CH2-vibration modes at 1250 to 1280 and 2920 to 2940 cm(-1), respectively. Thermogravimetric data and infrared spectra showed that inorganic polymers contained organic polymers. (C) 1999 Elsevier B.V. B.V. All rights reserved.