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)

Scaling and branching in wet sonogels as a function of the volume fraction of the liquid phase

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

Dynamic Scaling and Growth Kinetics of 3-Glycidoxypropyltrimethoxysilane-Derived Organic/Silica Hybrids

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

Synthesis, characterization and photophysical properties of Eu3+ doped in BaMoO4

In this work Ba0.99Eu0.01MoO4 (BEMO) powders were prepared by the first time by the Complex Polymerization Method. The structural and optical properties of the BEMO powders were characterized by Fourier Transform Infra-Red (FTIR), X-ray Diffraction (XRD), Raman Spectra, High-Resolution Scanning Electron Microscopy (HR-SEM) and Photoluminescent Measurements. XRD show a crystalline scheelite-type phase after the heat treatment at temperatures greater than 400 degrees C. The ionic radius of Eu3+ (0.109 nm) is lower than the Ba2+ (0.149 nm) one. This difference is responsible for the decrease in the lattice parameters of the BEMO compared to the pure BaMoO4 matrix. This little difference in the lattice parameters show that Eu3+ is expected to occupy the Ba2+ site at different temperatures, stayed the tetragonal (S-4) symmetry characteristic of scheelite-type crystalline structures of BaMoO4. The emission spectra of the samples, when excited at 394 nm, presented the D-5(1)-> F-7(0, 1 and 2) and D-5(0)-> F-7(0, 1, 2, 3 and 4) Eu3+ transitions at 523, 533, 554, 578, 589, 614, 652 and 699 nm, respectively. The emission spectra of the powders heat-treated at 800 and 900 degrees C showed a marked increase in its intensities compared to the materials heat-treated from 400 to 700 C. The decay times for the sample were evaluated and all of them presented the average value of 0.61 ms. Eu3+ luminescence decay time follows one exponential curve indicating the presence of only one type of Eu3+ symmetry site.

Preparation and Characterization of Graphite-Epoxy Composite Modified with Zinc Hexacyanoferrate and Their Electrochemical Behaviour in Presence of Substituted Anilines

The growth of zinc hexacyanoferrate (ZnHCF) hybrid film on the surface of graphite-epoxy composite (GEC) electrodes was demonstrated by cyclic voltammetry. Surface morphology of the hybrid film was investigated by using scanning electron microscopy. The effect of the type of monovalent cations on the redox behaviour of hybrid film was also studied. This effect indicated that the radius of the hydrated cation mainly determines the ion permeability of the film.The electrochemical behavior of the substituted anilines (procaine and sulfamerazine) in 1 M KCl of the modified GEC electrode showed a decrease of the cathodic currents while increasing the concentration of these analytes. The developed sensor also showed excellent stability for long time usage, higher sensitivity and cost-effective fabrication.

Arrays of gold microelectrodes made from split integrated circuit chips

A simple and inexpensive way to fabricate arrays of gold microelectrodes is proposed. Integrated circuit chips are sawed through their middle, normal to the longest axis, leading to destruction of the silicon circuit and rupture of the gold wires that interconnect it with the external terminals. Polishing the resulting rough surface converts the tips of the wires embedded in the chip halves into arrays of gold microdisks of about 25 mu m diameter. The number of active microelectrodes (MEs), of an array depends on the number of pins in the chip, n, being typically (n/2)-4. These MEs can be used individually or externally interconnected in any combination. X-ray images of the chips and micrographs of the resulting surface of the polished arrays have revealed variable distances between neighbor MEs, which are, however, larger than 10 times the radius of the disks. This feature of the MEs prevents diffusional cross-talk between electrodes. The use of these microdisk electrodes for analytical purposes exhibits sigmoidal voltammograms, and chronoamperometric experiments confirm the nonlinear i vs. t(1/2) plots, typical for processes where radial diffusion prevails. Satisfactory uniformity was observed for the response of each electrode of an array, indicating similarity of geometry and disk areas. The potentialities of these MEs were demonstrated by the determination of cadmium at ppb levels using square wave voltammetry with preconcentration. Due to the relative ease with which these MEs can be manufactured and their good performance in (chemical) analysis, wide applications in electrochemistry and electroanalysis is envisioned.

Effect of temperature on the interaction between the nonionic surfactant C(12)E(5) and poly(ethylene oxide) investigated by dynamic light scattering and fluorescence methods

The interaction between the nonionic surfactant C(12)E(5) and a high molar mass (M = 5.94 x 10(5)) poly(ethylene oxide) (PEG) in aqueous solution has been examined as a function of temperature by dynamic light scattering and fluorescence methods over a broad concentration range. Clusters of small surfactant micelles form within the PEO coil, leading to its extension. The hydrodynamic radius of the complex increases strongly with temperature as well as with the concentrations of surfactant and polymer. At high concentrations of the surfactant, the coil/micellar cluster complex coexists with free C(12)E(5) micelles in the solution. Fluorescence quenching measurements show a moderate micellar growth from 155 to 203 monomers in PEO-free solutions of C(12)E(5) over a wide concentration range (0.02-2.5%) at 8 degrees C. Below 0.25% C(12)E(5), the average aggregation number (N) of the micelles is smaller in the presence of PEO than in its absence. However, N increases with increasing surfactant concentration up to a plateau value of about 270 at about 1.2% (ca. 30 mM) C(12)E(5). At high surfactant concentrations, N is larger in the presence of polymer than in its absence, a finding which is connected to a significant lowering of the clouding temperature due to the PEO at these compositions. Similar results of increasing aggregation number followed by a plateau were also found at a fixed concentration of surfactant (2.5%) and varied PEO.

Structural organization of cetyltrimethylammonium sulfate in aqueous solution: the effect of Na2SO4

We used dynamic light scattering (DLS), a steady-state fluorescence, time resolved fluorescence quenching (TRFQ), tensiometry, conductimetry, and isothermal titration calorimetry (ITC) to investigate the self-assembly of the cationic surfactant cetyltrimethylammonium sulfate (CTAS) in aqueous solution, which has SO42- as divalent counterion. We obtained the critical micelled concentration (cmc), aggregation number (N-agg), area per monomer (a(0)), hydrodynamic radius (R-H), and degree of counterion dissociation (alpha) of CTAS micelles in the absence and presence of up to 1 M Na2SO4 and at temperatures of 25 and 40 degrees C. Between 0.01 and 0.3 M salt the hydrodynamic radius of CTAS micelle R-H approximate to 16 angstrom is roughly independent on Na2SO4 concentration; below and above this concentration range R-H increases steeply with the salt concentration, indicating micelle structure transition, from spherical to rod-like structures. R-H increases only slightly as temperature increases from 25 to 40 degrees C, and the cmc decreases initially very steeply with Na2SO4 concentration up to about 10 mM, and thereafter it is constant. The area per surfactant at the water/air interface, a(0), initially increases steeply with Na2SO4 concentration, and then decrases above ca. 10 mM. Conductimetry gives alpha = 0.18 for the degree of counterion dissociation, and N-agg obtained by fluorescence methods increases with surfactant concentration but it is roughly independent of up to 80 mM salt. The ITC data yield cmc of 0.22 mM in water, and the calculated enthalpy change of micelle formation, Delta H-mic = 3.8 kJ mol(-1), Gibbs free energy of micellization of surfactant molecules, Delta G(mic) = -38.0 kJ mol(-1) and entropy T Delta S-mic = 41.7 kJ mol(-1) indicate that the formation of CTAS micelles is entropy-driven. (c) 2006 Elsevier B.V. All rights reserved.

SAXS study of crotapotin at low pH

The structure of crotapotin, a protein extracted from the venom of the Crotalus durissus terrificus, in solution at pH = 1.5, was studied by SAXS. The experimental results yield structural parameter values of the molecular radius of gyration R(g) = 13.6 angstrom, volume v = 16.2 x 10(3) angstrom3 and maximal dimension D(max) = 46 angstrom. The distance distribution function deduced from the scattering measurements is consistent with an overall molecular shape of an oblate ellipsoid of revolution with assymetry parameter nu = 0.45.

SAXS study of the kinetics of formation of ZnO colloidal suspensions

We have investigated, by in situ small-angle X-ray scattering (SAXS), the kinetics of formation of zinc oxide colloidal suspensions obtained after refluxing alcoholic solution of zinc acetate and catalysed by lithium hydroxide. The experimental results demonstrate that the suspensions are composed of colloidal spheroidal particles with a multimodal size distribution. The average radius of the main mode, approximately 2 nm, is invariant but the number of these basic particles continuously increases for increasing hydrolysis reaction time. The other two modes correspond to particles with average radii close to 6 and 10 nm, respectively. The larger particles are formed by coagulation of the smaller ones. (C) 1999 Elsevier B.V. B.V. All rights reserved.

A dissolution and reaction modeling for hydrolysis of TEOS in heterogeneous TEOS-water-HCl mixtures under ultrasound stimulation

A simplified dissolution and reaction modeling was employed to study the hydrolysis of heterogeneous tetraethoxysilane (TEOS)-water-HCl mixtures under ultrasound stimulation. The nominal pH was changed from 0.8 to 2.0. The acid specific hydrolysis rate constant was determined as k = 6.1 mol(-1) 1 min(-1) [H+](-1) at 39 degreesC, in good agreement with the literature. Along the heterogeneous step of the reaction, the ultrasound maintains an additional quantity of water under a virtual state of dissolution besides the water dissolved due to the homogenizing effect of the alcohol produced in the reaction. The forced virtually dissolved water is probably represented by water at the TEOS-water interface during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TEOS phase, while hydrolysis has not started yet, was evaluated as about 290 A. The HCl concentration accordingly increases the hydrolysis rate constant but its fundamental role on the immiscibility gap of the TEOS-water-ethanol system has not been unequivocally established. (C) 2002 Elsevier B.V. B.V. All rights reserved.

A SAXS study of kinetics of aggregation of TEOS-derived sonogels at different temperatures

The kinetics of aggregation of tetraethoxysilane (TEOS)-derived silica sols, produced by acid-catalyzed and ultrasound-stimulated hydrolysis, were studied by 'in situ' measurements of small-angle X-ray scattering (SAXS) at the temperatures 40 degreesC, 60 degreesC and 70 degreesC. The results were analyzed in terms of the evolution with time (t) of the SAXS intensity probing the mass fractal characteristics of the system, the average radius of gyration (Rc,) of the clusters and the number of primary particles per cluster. The aggregation process yields mass fractal structures which exhibit a scattering exponent (alpha) practically equal to 2, in the probed length scale range (5.3 nm < 1/q < 0.22 nm), beneath and even far beyond the gel point. This suggests that a is a direct measure of the real mass fractal dimension (D) of the structure. The precursor sol (pH = 2) exhibits I nm mean sized clusters with mass fractal dimension D similar to 1.9. Increasing the pH to 4.5, the cluster mean size and the number of primary particles per cluster increase but the system keeps a more opened structure (D similar to 1.4). In the first aggregation stages, D increases up to similar to2 by incorporating primary particles to the clusters without changing their mean size. From this stage, the aggregation progresses following a thermally activated scaling law well described by R-G similar tot(1/D) in all cases. This is indicative of a diffusion-controlled cluster-cluster aggregation process. The activation energy of the process was found to be 91.7 kJ/mol. (C) 2001 Elsevier B.V. B.V. All rights reserved.

A study of the hydrolysis pathway in oxalic acid catalyzed reacting TMOS-water mixtures under ultrasound stimulation

The hydrolysis of TMOS in oxalic acid catalyzed reacting TMOS-water mixtures, under ultrasound stimulation, was studied by fitting a simplified dissolution and reaction modeling for samples, the hydrolysis rate of which had been measured in a previous work. The reaction pathway represented in a ternary diagram shows a heterogeneous step for the reaction which gradually progresses until complete homogenization of the system. Besides the water dissolved due to the homogenizing effect of the alcohol, ultrasound maintains a virtual and additional dissolution of water located at the interface between the TMOS and water during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TMOS was evaluated as around 150 Angstrom. The oxalic acid concentration accordingly increases the hydrolysis rate constant but its fundamental role on the solubility of water in TMOS could not unequivocally be established.

Behavior of plant tissue in osmotic solutions

The effect of the concentration of sucrose solutions on the cellular structure of potato tissue in equilibrium at 27 degreesC was Studied. Two different methods of investigation were used to determine the volume of the different phases composing the cellular tissue of the potato when in equilibrium with the solutions. one based on data of the concentration itself and the overall volume of 2 mm slices after 48 h at equilibrium, and the other on microscopic images of cells in thin slices of fresh tissue stained with neutral red after an hour in equilibrium to show protoplasts, vacuoles and plasmolysis spaces. The results of these methods were compared with those obtained by a predictive thermodynamic approach considering the semipermeability of cell membranes. Phase volume data obtained from microscopic analysis were more similar to what was predicted by the theoretical model than those obtained by means of composition measurement. where the long equilibrium time apparently led to the loss of semi permeability of the cell membranes, since total volumes calculated without consideration of the cell membranes were similar to those measured. This suggests that the length of time of osmotic dehydration brings about a change in cell structure and the consequent involvement of a different mechanism in mass transfer. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.