Molecular and morphological characterization of bis benzimidazo perylene films and surface-enhanced phenomena

Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication (similar to 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).

Interfacial surface charge and free accessibility to the PLA(2)-active site-like region are essential requirements for the activity of Lys49 PLA(2) homologues

Lys49 phospholipase A(2) homologues are highly myotoxic and cause extensive tissue damage but do not display hydrolytic activity towards natural phospholipids. The binding of heparin, heparin derivatives and polyanionic compounds such as suramin result in partial inhibition (up to 60%) of the myotoxic effects due to a change in the overall charge of the interfacial surface. In vivo experiments demonstrate that polyethylene glycol inhibits more than 90% of the myotoxic effects without exhibiting secondary toxic effects. The crystal structure of bothropstoxin-I complexed with polyethylene glycol reveals that this inhibition is due to steric hindrance of the access to the PLA(2)-active site-like region. These two inhibitory pathways indicate the roles of the overall surface charge and free accessibility to the PLA2-active site-like region in the functioning of Lys49 phospholipases A(2) homologues. Molecular dynamics simulations, small angle X-ray scattering and structural analysis indicate that the oligomeric states both in solution and in the crystalline states of Lys49 phospholipases A2 are principally mediated by hydrophobic contacts formed between the interfacial surfaces. These results provide the framework for the potential application of both clinically approved drugs for the treatment of Viperidae snakebites. (c) 2006 Elsevier Ltd. All rights reserved.

A comparative study of the low energy HD plus o-/p-H-2 rotational excitation/de-excitation collisions and elastic scattering

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

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

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).

Small-angle X-ray scattering and nitrogen adsorption study of the nanoporosity elimination in TEOS sonohydrolysis-derived xerogels

Small-angle X-ray scattering (SAXS) and nitrogen adsorption techniques were used to study the temperature and time structural evolution of the nanoporosity in silica xerogels prepared from acid- and ultrasound-catalyzed hydrolysis of tetraetboxysilane (TEOS). Silica xerogels present a structure of nanopores of fully random shape, size, and distribution, which can be described by an exponential correlation function gamma(r) = exp (-r/a), where a is the correlation distance, as predicted by the Debye, Anderson, and Brumberger (DAB) model. The mean pore size was evaluated as about 1.25 nm from SAXS and about 1.9 nm from nitrogen adsorption. The nanopore elimination in TEOS sonohydrolysis-derived silica xerogels is readily accelerated at temperatures around 900 degrees C probably by the action of a viscous flow mechanism. The nanopore elimination process takes place in such a way that the pore volume fraction and the specific surface are reduced while the mean pore size remains constant. (c) 2005 WILEY-VCH Verlag GmbH S Co. KGaA, Weinheim.

Mass fractal characteristics of wet sonogels as determined by small-angle x-ray scattering and differential scanning calorimetry

Low density silica sonogels were prepared from acid sonohydrolysis of tetraethoxysilane. Wet gels were studied by small-angle x-ray scattering (SAXS) and differential scanning calorimetry (DSC). The DSC tests were carried out under a heating rate of 2 degrees C/min from -120 degrees C up to 30 degrees C. Aerogels were obtained by CO(2) supercritical extraction and characterized by nitrogen adsorption and SAXS. The DSC thermogram displays two distinct endothermic peaks. The first, a broad peak extending from about -80 degrees C up to practically 0 degrees C, was associated to the melting of ice nanocrystals with a crystal size distribution with pore diameter ranging from 1 or 2 nm up to about 60 nm, as estimated from Thomson's equation. The second, a sharp peak with onset temperature close to 0 degrees C, was attributed to the melting of macroscopic crystals. The DSC incremental nanopore volume distribution is in reasonable agreement with the incremental pore volume distribution of the aerogel as determined from nitrogen adsorption. No macroporosity was detected by nitrogen adsorption, probably because the adsorption method applies stress on the sample during measurement, leading to a underestimation of pore volume, or because often positive curvature of the solid surface is in aerogels, making the nitrogen condensation more difficult. According to the SAXS results, the solid network of the wet gels behaves as a mass fractal structure with mass fractal dimension D=2.20 +/- 0.01 in a characteristic length scale below xi=7.9 +/- 0.1 nm. The mass fractal characteristics of the wet gels have also been probed from DSC data by means of an earlier applied modeling for generation of a mass fractal from the incremental pore volume distribution curves. The results are shown to be in interesting agreement with the results from SAXS.

Brillouin scattering in planar waveguides. II. Experiments

Silica-titania planar waveguides of different thicknesses and compositions have been produced by radio-frequency sputtering and dip coating on silica substrates. Waveguides were also produced by silver exchange on a soda-lime silicate glass substrate. Brillouin scattering of the samples has been studied by coupling the exciting laser beam with a prism to different transverse-electric (TE) modes of the waveguides, and collecting the scattered light from the front surface. In multimode waveguides, the spectra depend on the m mode of excitation. For waveguides with a step index profile, two main peaks due to longitudinal phonons are present, apart from the case of the TE0 excitation, where a single peak is observed. The energy separation between the two peaks increases with the mode index. In graded-index waveguides, m-1 peaks of comparable intensities are observed. The spectra are reproduced very well by a model which considers the space distribution of the exciting field in the mode, a simple space dependence of the elasto-optic coefficients, through the value of the refraction index, and neglects the refraction of phonons. A single-fit parameter, i.e., the longitudinal sound velocity, is used to calculate as many spectra as is the number of modes in the waveguide. (C) 2003 American Institute of Physics.

Interaction between poly(ethylene glycol) and C12E8 investigated by dynamic light scattering, time-resolved fluorescence quenching, and calorimetry

Dynamic light scattering (DLS), time-resolved fluorescence quenching (TRFQ), and isothermal titration microcalorimetry have been used to show that, in dilute solution, low molecular weight poly(ethylene glycol) (PEG, M-w = 12 kDa) interacts with the nonionic surfactant octaethylene glycol n-dodecyl monoether, C12E8, to form a complex. Whereas the relaxation time distributions for the binary C12E8/water and PEG/water systems are unimodal, in the ternary mixtures they may be either uni- or bimodal depending on the relative concentrations of the components. At low concentrations of PEG or surfactant, the components of the relaxation time distribution are unresolvable, but the distribution becomes bimodal at higher concentrations of either polymer or surfactant. For the ternary system in excess surfactant, we ascribe, on the basis of the changes in apparent hydrodynamic radii and the scattered intensities, the fast mode to a single micelle, the surface of which is associated with the polymer and the slow mode to a similar complex but containing two or three micelles per PEG chain. Titration microcalorimetry results show that the interaction between C12E8, and PEG is exothermic and about 1 kJ mol(-1) at concentrations higher than the CMC of C12E8. The aggregation number, obtained by TRFQ, is roughly constant when either the PEG or the C12E8 concentration is increased at a given concentration of the second component, owing to the increasing amount of surfactant micelles inside the complex.

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Role of the surface state and structural feature in the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The sols produced by admixture of ZrOCl2 acidified solutions to hot H2SO4 aqueous solutions were studied to clarify the effects of Cl- and SO42- ions on the kinetic stability of nanoparticles and to obtain some new evidence concerning the mechanism of a thermoreversible sol-gel transition observed in this system. The study of suspensions prepared with different molar ratios R-S = [Zr]/[SO42-] and R-Cl = [Zr]/[Cl-] revealed domains of composition of formation of thermoreversible gels, thermostable sols, and powder precipitation. The effects of R-S and R-Cl on the structural features of nanoparticles and on the particle solution interface were systematically analyzed for samples of thermoreversible and thermostable sol domains. Small-angle X-ray scattering measurements revealed the presence of small fractal aggregates in all samples of thermoreversible domains, while compact packing aggregates of primary particles are present in the thermostable sol. Extended X-ray absorption fine structure and elemental chemical analysis revealed that irrespective of the nominal value of R-S and R-Cl all studied samples of the thermoreversible domain are constituted by a well-defined compound possessing an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded on the surface by complexing sulfate ligands. zeta potentials of powders extracted by freeze-drying from the thermoreversible gel revealed a point of surface charge inversion attributed to the specific adsorption of SO42- ion. Thermoreversible gel formation is rationalized by considering the effect of the specific adsorption on the electrical double-layer repulsion together with the temperature dependency of the physical chemical properties of ions in solution.

Pore structure characterization of kaolin, metakaolin, and their acid-treated products using small-angle X-ray scattering

Pore structure of dealuminated kaolin and metakaolin was studied by small-angle X-ray scattering (SAXS). Both parent kaolin and metakaolin have about 10% of the total pore volume provided by globular pores with 105 Å mean pore size. Their surface area is about 14 m2/g. Acid dealumination of kaolin causes an increase of its globular pore volume without an appreciable change in the mean pore size, its surface area increasing up to about 90 m2/g. Acid dealumination of metakaolin enhances the globular pore volume, although there is generation of slit-shaped pores with a narrow thickness distribution whose mean value is 14 Å. This interlayer spacing causes an increase in surface area of about 190 m2/g by SAXS. © 1994.

Comparative study using small-angle x-ray scattering and nitrogen adsorption in the characterization of silica xerogels and aerogels

A comparative study using small-angle x-ray scattering (SAXS) and nitrogen adsorption has been carried out in the structural characterization of silica xerogels and aerogels, obtained from tetraethoxysilane sonohydrolysis. The specific surface and the mean pore size as measured by both the techniques were found to be in notable agreement in all cases for aerogels and xerogels. According to the SAXS data, aerogels at 500 °C exhibit a mass fractal structure with fractal dimension D∼2.4 in the range between the correlation length ξ∼5.3 nm and a∼0.75 nm. An experimental method to probe the mass fractal structure of aerogels from exclusively nitrogen adsorption isotherms has been presented. For aerogels at 500 °C, we have found D∼2.4 in the range between the pore width 2rξ∼33 nm and 2ra∼4.5 nm, which is in notable agreement with the SAXS results (D ∼2.4, ξ∼5.3 nm, a∼0.75 nm) if we assign the pore width 2r probed by the Kelvin equation in the adsorption method to the Bragg distance 2π/q associated to the correlation length 1/q probed by SAXS.

Small-angle x-ray scattering study of the structural evolution of the drying of sonogels with the liquid phase exchanged by acetone

The structural evolution on the drying of wet sonogels of silica with the liquid phase exchanged by acetone, obtained from tetraethoxisilane sonohydrolysis, was studied in situ by small-angle x-ray scattering (SAXS). The periods associated to the structural evolution as determined by SAXS are in agreement with those classical ones established on basis of the features of the evaporation rate of the liquid phase in the obtaining of xerogels. The wet gel can be described as formed by primary particles (microclusters), with characteristic length a ∼ 0.67 nm and surface which is fractal, linking together to form mass fractal structures with mass fractal dimension D=2.24 in a length scale ξ∼6.7 nm. As the network collapses while the liquid/vapor meniscus is kept out of the gel volume, the mass fractal structure becomes more compacted by increasing D and decreasing ξ, with smoothing of the fractal surface of the microclusters. The time evolution of the density of the wet gels was evaluated exclusively from the SAXS parameters ξ, D, and a. The final dried acetone-exchanged gel presents Porod's inhomogeneity length of about 2.8 nm and apparently exhibits an interesting singularity D →3, as determined by the mass fractal modeling used to fit the SAXS intensity data for the obtaining of the parameters ξ and D.

Mass and surface fractal in supercritical dried silica aerogels prepared with additions of sodium dodecyl sulfate

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