Effect of processing conditions on the nucleation and growth of indium-tin-oxide nanowires made by pulsed laser ablation

Indium-tin oxide nanowires were deposited by excimer laser ablation onto catalyst-free oxidized silicon substrates at a low temperature of 500 degrees C in a nitrogen atmosphere. The nanowires have branches with spheres at the tips, indicating a vapor-liquid-solid (VLS) growth. The deposition time and pressure have a strong influence on the areal density and length of the nanowires. At the earlier stages of growth, lower pressures promote a larger number of nucleation centers. With the increase in deposition time, both the number and length of the wires increase up to an areal density of about 70 wires/mu m(2). After this point all the material arriving at the substrate is used for lengthening the existing wires and their branches. The nanowires present the single-crystalline cubic bixbyite structure of indium oxide, oriented in the [100] direction. These structures have potential applications in electrical and optical nanoscale devices.

Production and physicochemical properties of resistant starch from hydrolysed wrinkled pea starch

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

Resveratrol toxicity: Effects on risk factors for atherosclerosis and hepatic oxidative stress in standard and high-fat diets

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nanocomposites of Styrene-Butadiene Rubber and Synthetic Anatase Obtained by a Colloidal Route and Their Photooxidation

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

Electrochemistry of organometallic compounds. Part II. Oxidations of alkyl and aryl derivatives of bis(salicylaldehyde)ethylenediimine cobalt(III) in dimethylformamide

The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

Electrochemistry of organometallic compounds. Part III. Oxidations of methyl derivatives of organocobalt(III) complexes with delocalized electronic structure in dimethylformamide

The influence of the equatorial ligand on the electrochemical oxidation of the compounds [H3CCo(chel)B], where chel is bis (dimethylglyoximato), (DH)2; bis(salicylaldehyde)ethylenediimine, salen; bis(salicylaldehyde) o-phenylenediimine, salophen; bis(salicylaldehyde)cyclohexylenediimine, salcn; bis(acetylacetone) ethylenediimine, bae; and where B is pyridine when chel is (DH2), and dimethylformamide (DMF) when chel represents a Schiff base (salen, salcn, salophen and bae), was studied by means of cyclic voltammetry in DMF, 0.2 M in tetraethylammonium perchlorate, between 25 and -25°C, with a platinum disk working electrode. Absorption spectra in the visible and near ultraviolet regions for these compounds in DMF at 25°C were obtained. The complexes exhibit a reversible one-electron oxidation, at -20°C with scan rates >0.5 V s-; chemical reactions following electron transfer are not detected under these conditions. At slower potential or higher temperatures, the oxidized product decomposes chemically in a solvent-assisted (or nucleophile-assisted) reaction, yielding products which are electroactive in the applied potential range. The behavior of the [H3CCo (DH2)py] derivative is better described as a quasi-reversible charge transfer followed by an irreversible chemical reaction. Experimental evidence suggests that in the case of the [H3CCo(bae)] derivative at -20°C, the reactive -species is pentacoordinated and weakly adsorbed at the electrode surface. The value of E 1 2 and the energies of the first two absorption bands in the visible spectra reveal the ability of the studied complexes to donate and to delocalize electronic charge. © 1982.

Electrochemistry of organometallic compounds. Part IV. Oxidations of benzylic derivatives and p-substituted benzylic derivatives of bis(dimethylglyoximato) and bis(salicylaldehyde)o-phenylenediimine cobalt(III) in dimethylformamide

The electrochemical oxidation of some p-substituted benzylic derivatives of Co(III) dimethylglyoximato and Co(III)bis(salicylaldehydc)o-phenylenediimine in dimethylformamide. 0.2 M in tetraethyammonium perchlorate, on a platinum electrode, at several temperatures, is described as an ECE type, the first electrochemical step being a quasi-reversible one-electron charge transfer at room temperature. At temperatures around -20°C, or lower, the influence of the irreversible chemical decomposition of the oxidized species, via a solvent or other nucleophilic-assisted reaction, is negligible. It is suggested that at low temperatures the oxidation to the formally CoIV-R species is followed by an isomerization reaction in which this complex is partially transformed in a CoIII-(R) species or a s π-complex which undergoes an electroreduction at less positive potentials than those corresponding to the reduction of the CoIV-R species. © 1982.

Characterization of the colloidal products of pentacarbonyliron oxidation

Pentacarbonyliron was oxidized with H2O2, in organic solvents, to give colloidal sols. The aqueous-ethanolic sol is highly stable and undergoes thermally-reversible coagulation. Its solid phase was found to be a non-crystalline Fe (III) hydroxoacetate which is transformed to α-Fe2O3 when heated to 300°C. Iron-bound acetate groups are assumed to have a major role in the sol stability, by preserving the amorphous solid phase. Dry hydroxoacetate particles were heated under vacuum; scanning electron microscopy revealed that these particles coalesce and grow, as in a sintering process but at low temperatures (100-250°). © 1987.

The electrochemistry of ferrocene in non-aqueous solvents

the electrochemical oxidation of ferrocene on Pt in dimethylformamide, ethanol, propylene carbonate and their aqueous solutions was studied at 25°C. The concentration of the supporting electrolyte, NaClO4, was varied from 0.1 to 0.5 M. The results show that the electrode process may be described as a quasi-reversible one-electron charge transfer, followed by slow decomposition of the oxidized species. © 1987.

High temperature X-ray diffraction study of the U4O9 formation on UO2 sintered plates

The surface oxidation of UO2 sintered plates at 170-275 ° C was studied in situ by high temperature X-ray diffractometry. At very low oxygen concentration, UO2 is oxidized to U4O9, while at 300°C and argon-20 vol% oxygen it is oxidized up to U3O7. X-ray diffraction profiles of the UO2, U4O9 and U3O7 phases were well characterized during the transformations. The activation energy for the transformation of UO2 to U4O9, obtained from X-ray diffraction data, was found to be 117 ± 9 kJ/mol and 90 ± 14 kJ/mol for the β-(311) and α-(200) reflections, respectively. © 1991.

Gold-bearing iron duricrust in Central Brazil

In the Cuiabá region-State of Mato Grosso, Central Brazil-primary gold mineralization is hosted by two generations of quartz veins in Precambrian metamorphic terrains of the Cuiabá Group. Gold is mined from the veins and mainly from the eluvial horizons that cover the deeply altered basement. In the lodes gold occurs as small particles (less than 1 mm) associated with pyrite and contains up to 5% Ag. Larger particles and nuggets of almost pure gold are found in the iron duricrust which caps the upper levels of the weathering profile. It is difficult to determine the average grade of this kind of deposit but some prospects in the Cuiabá region produce up to 2 g gold per ton of ore. Lateritization is responsible for both the formation of the iron crust and the concentration of gold within the regolith. Under a tropical climate, the supergene alteration of phyllites of the Cuiabá Group has led to the formation of a weathering profile consisting typically of saprolite, mottled clay zone and duricrust, from bottom to top. The duricrust is directly derived form the in situ weathering of phyllites. Geochemical balance calculations indicate that in the transition from the saprolite to the duricrust lateritization has promoted a progressive loss of Si, Al and K, and more than 500% of absolute Fe enrichment. Gold underwent a supergene evolution related to the development of the weathering profile. In the saprolite and mottled clay zone, associated with quartz and oxidized sulfides, gold dissolves as demonstrated by corrosion features at the surface of the particles. The formation of secondary gold in the duricrust is indicated by the larger size of the nuggets, their higher fineness and the close relationship between gold and the neoformed iron oxy-hydroxides. © 1991.

Rapid, quantitative determination of polar compounds in fats and oils by solid-phase extraction and size-exclusion chromatography using monostearin as internal standard

A rapid and simple method was developed for quantitation of polar compounds in fats and oils using monostearin as internal standard. Starting from 50 mg of oil sample, polar compounds were obtained by solid-phase extraction (silica cartridges) and subsequently separated by high-performance size-exclusion chromatography into triglyceride polymers, triglyceride dimers, oxidized triglyceride monomers, diglycerides, internal standard and fatty acids. Quantitation of total polar compounds was achieved through the internal standard method and then amounts of each group of compounds could be calculated. A pool of polar compounds was used to check linearity, precision and accuracy of the method, as well as the solid-phase extraction recovery. The procedure was applied to samples with different content of polar compounds and good quantitative results were obtained, especially for samples of low alteration level.

The structure of waxy corn starch: Effect of granule size

The granules of waxy corn starch were isolated and various samples were separated by size and classified according to their average diameter in: non-separated granules (N), granules with diameter < 15 μm (S) and granules with diameter ≥ 15 μm (L). The samples were hydrolyzed by bacterial α-amylase and fungal amyloglucosidase. The starch granules remaining after enzymatic hydrolysis were analysed by X-ray diffraction and optical and scanning electron microscopy. Sephadex G-50 gel permeation chromatography of the dissolved residues from the hydrolysis of the N and S samples was performed directly and after successive enzymatic digestion with pullulanase and β-amylase. The results showed that the percentage of hydrolysis increased with a decrease in diameter. No apparent differences in waxy corn starch when observed under light and scanning electronic microscope were observed, regardless of diameter and enzyme action, although both large and small granules showed extensive surface corrosion after enzymatic attack. X-ray analysis suggested a decrease in the quantity of crystalline areas in the smaller granules, which would explain the high percentage of hydrolysis evidenced by these granules. The elution patterns of the α-glucans of both starches (N and S) were similar and reveled the presence of two fractions which were not susceptible to a-amylase and amyloglucosidase attack suggesting that these fractions were involved in the waxy corn starch crystalline regions. Debranching with pullulanase followed by gel-permeation chromatography showed that the amylopectins from the starch granules studied contained three groups of unit chains instead of the two reported in the literature.

Oxidative dissolution of covellite by Thiobacillus ferrooxidans

Oxidation of research-grade covellite was investigated in respirometric and growth experiments with Thiobacillus ferrooxidans. Covellite was directly oxidized by T. ferrooxidans in respirometric experiments, but the pH of mineral salts medium increased to prohibitively high values because of high sulfide concentrations. In glycine-H 2SO 4 buffered medium the pH remained steady and the oxygen uptake activity of T. ferrooxidans was not inhibited. In cultures growing with covellite as the sole source of energy, the pH increased to about 4. Redox potential increased to 500-600 mV during bacterial oxidation of covellite in the presence and absence of additional Fe 2+, whereas it remained mostly at about 350 mV in abiotic control. Jarosite was a major solid-phase product in T. ferrooxidans cultures. The solubilization of copper from covellite in inoculated flasks was higher than that obtained in control flasks and was not enhanced in the presence of additional Fe 2+.The sample also contained bornite (Cu 5FeS 4) which released iron in solution under all experimental conditions. Accumulation of S 0 was apparent only in inoculated covellite samples. © 1997 Elsevier B.V. All rights reserved.