Effect of In concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450 degrees C

Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450 degrees C on glass substrates From solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c-axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn = 10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In = 5 at.%) shows that In substitutes Zn in the wurtzite structure. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Structural and functional characterization of neuwiedase, a nonhemorrhagic fibrin(ogen)olytic metalloprotease from Bothrops neuwiedi snake venom

A fibrino(geno)lytic nonhemorrhagic metalloprotease (neuwiedase) was purified from Bothrops neuwiedi snake venom by a single chromatographic step procedure on a CM-Sepharose column, Neuwiedase represented 4.5% (w/w) of the crude desiccated venom, with an approximate Mr of 20,000 and pI 5.9, As regards the amino acid composition, neuwiedase showed similarities with other metalloproteases, with high proportions of Asx, Glx, Leu, and Ser, Atomic absorption spectroscopy showed that one mole of Zn2+ and one mole of Ca2+ were present per mole olf protein. The cDNA encoding neuwiedase was isolated by RT-PCR from venom gland RNA, using oligonucleotides based on the partially determined amino-acid sequences of this metalloprotease. The fall sequence contained approximately 594 bp, which codified the 198 amino acid residues with an estimated molecular weight of 22,375. Comparison of the nucleotide and amino acid sequences of neuwiedase with those of other snake venom metalloproteases showed a high level of sequential similarity, Neuwiedase has two highly conserved characteristics sequences H(142)E(143)XXH(146)XXG(140)XXH(152) and C164I165M166. The three-dimensional structure of neuwiedase was modeled based on the crystal structure of Crotalus adamanteus Adamalysin II. This model revealed that the zinc binding site region showed a I high structural similarity with other metalloproteases,, the proteolyitc specificity, using the B beta-chain of oxidized insulin as substrate, was shown to be directed to the Ala(14)-Leu(15) and Tyr(16)-Leu(17) peptide bonds which were preferentially hydrolyzed. Neuwiedase is a A alpha,B beta fibrinogenase, Its activity upon the A alpha chain of fibrinogen was detected within 15 min of incubation. The optimal temperature and pH for the degradation of both A alpha and B beta chains were 37 degrees C and 7.4-8.0, respectively. This activity was inhibited by EDTA and 1,10-phenantroline, Neuwiedase also showed proteolytic activity upon fibrin and some components of the extracellular matrix. However, it did not show TAME esterase activity and was not able to inhibit platelet aggregation. (C) 2000 Academic Press.

Hydration effects on the structural properties and haem-haem interaction in haemoglobin

Direct and simultaneous measurements of hydration water content and protein conformation have been performed using quartz crystal microbalance and visible absorption spectroscopy. Equilibrium and kinetics of methaemoglobin/haemichrome transition induced by the alteration of the degree of hydration was investigated in thin films exposed to controlled humidity. The kinetics experiment show that the conversion of species achieve the equilibrium more rapidly that the amount of sorbed water by the protein. The transition shows a sigmoid behaviour and suggest cooperative phenomena manifested by haem-haem interaction. The water hydration network contributing to the haem haem interaction advise that water acts as allosteric effectors for the conversion between species. Irreversible changes produced by complete drying are clearly shown.

Electrochemical oxidation of methanol on Pt nanoparticles dispersed on RuO2

Pt-modified RuO2 was prepared by a sol-gel procedure on titanium substrates in the form of thin films of similar to2-mum thickness. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that these films actually consist of Pt nanoparticles dispersed in RuO2 and that neither metallic Ru nor Pt-Ru alloy are present on the surface. Electrodes with different Pt:Ru nominal compositions were prepared and their electrocatalytic activity for the oxidation of methanol was investigated by potential sweeps and chronoamperometry. The results obtained show an enhancement effect for methanol oxidation that can be interpreted as associated to the formation of hydrous oxides on the RuO2 surface.

Oxygen stoichiometry effects in spinel-type NiMn2O4-delta samples

We report the effects of oxygen stoichiometry in the structure and magnetic response of spinel-type NiMn2O4-delta polycrystalline samples controlled by heat-treatments in different atmospheric conditions.The post-annealed samples were analyzed by Scanning Electron Microscopy associated to X-ray Energy Dispersion Spectrometry, X-ray Photoelectron Spectroscopy and AC/DC magnetic measurements.Results indicate that the oxygen stoichiometry highly influences the magnetic interactions between the ferromagnetic, and antiferromagnetic sublattices in these compounds due to the presence of manganese in three possible valence states. (c) 2005 Elsevier Ltd. All rights reserved.

Catalysis and temperature dependence on the formation of ZnO nanoparticles and of zinc acetate derivatives prepared by the sol-gel route

The chemical and structural nature of powders prepared from the zinc acetate-derived precursor using the sol-gel route is discussed. The influence of the synthesis temperature and of the hydrolytic catalyst on the structural features of the powder is focused on the basis of X-ray powder diffraction (XRPD) and extended X-ray absorption fine structure (EXAFS) measurements and complemented with density and thermoanalysis (TG-DTA) results. EXAFS and XRPD results show that no-washed nanoparticulate powders are composed of a mixture of ZnO (wurtzite), zinc acetate, and zinc hydroxyacetate. The latter has a layered structure typical of hydroxy double salts (HDS). The main component of no-washed powders is always unreacted zinc acetate solid but the relative amount of the zinc-based compounds depends on the nature of the hydrolytic catalyst, hydrolysis ratio, and of synthesis temperature. According to the proportion of the three zinc-based compounds, three families of powders could be distinguished. The amount of ZnO nanoparticles (1.6 +/- 0.6 nm) decreases as the synthesis temperature increases, as the hydrolysis ratio decreases, or by changing from basic to acid catalysis. This finding suggests that the formation of zinc compounds is controlled by the equilibrium between hydrolysis-condensation and complexation-reprecipitation reactions.

Structure of redispersible SnO2 nanoparticles

Suspensions of undoped SnO2 nanoparticles and containing Eu3+ ions were prepared by a sol-gel procedure. Using the classical synthesis method ( precipitation), the particles tend to grow by a coarsening process in order to minimize the surface free energy. This effect can strongly be reduced by the addition of an amide and surfactant during the synthesis, which decreases the surface free energy of the colloidal particles. These additives promote the formation of powders composed of very small primary particles formed by a crystallite of 10 Angstrom, and exhibit good redispersion properties. The local and long order structures of the redispersible powder were studied by X-rays absorption spectroscopy at Sn L-I edge and X-rays diffraction, respectively. The structure of the colloidal aggregates in suspension was investigated by small angle X-rays scattering (SAXS). SAXS results indicate the sol are composed by a polidisperse system of hard spheres resulting of agglomeration of the primary particles and their size increasing by agglomeration for progressively higher Eu3+ content.

Study of structural surface modified tin oxide membrane prepared by sol-gel route sintered at 400 degrees C

This work describes the chemical modification by Tiron(R) molecules of the surface of SnO2 nanoparticles used to prepare nanoporous membranes. Samples prepared with Tiron(R) content between 1 and 20 wt% and fired at 400 C were characterised by X-Ray Powder Diffraction (XRPD), Extended X-ray Absorption Fine Structure (EXAFS), N-2 adsorption isotherms analysis and permeation experiments. XRPD and EXAFS results show a continuous reduction of crystallite size by increasing the Tiron(R) contents until 7.5 wt%. The control exercised by Tiron(R) modifying agent in crystallite growth allows the fine tuning of the average pore size that can be screened from 0.4 to 4 nm as the amount of grafted molecules decreases from 10 to 0 wt%. In consequence, the membrane cut-off can be screened from 1500 to 3500 g.mol(-1).

Study of synthesis variables in the nanocrystal growth behavior of tin oxide processed by controlled hydrolysis

Tin dioxide nanoparticle suspensions were synthesized at room temperature by the hydrolysis reaction of tin chloride (II) dissolved in ethanol. The effect of the initial tin (II) ion concentration, in the ethanolic solution, on the mean particle size of the nanoparticles was studied. The Sn2+ concentration was varied from 0.0025 to 0.1 M, and all other synthesis parameters were kept fixed. Moreover, an investigation of the effect of agglomeration on the nanoparticle characteristics (i.e., size and morphology) was also done by modifying the pH of the SnO2 suspensions. The different samples were characterized by transmission electron microscopy, optical absorption spectroscopy in the ultraviolet range, and photoluminescence measurements. The results show that higher initial ion concentrations and agglomeration lead to larger nanoparticles. The concentration effect is explained by enhanced growth due to a higher supersaturation of the liquid medium. However, it was observed that the agglomeration of the nanoparticles in suspension induce coarsening by the oriented-attachment mechanism.

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Electrosprayed superhydrophobic PTFE: a non-contaminating surface

This paper reports on the exposure of superhydrophobic polytetrafluoroethylene ( PTFE) coatings to common aqueous solutions which are used in biology, biotechnology and chemical sensor applications. Advancing contact angles as high as 173 degrees for aqueous solutions were measured on the PTFE surface. Water drop sliding angles at 2 degrees show a very low contact angle hysteresis. X-ray photoelectron spectroscopy measurements confirm that aqueous solutions can move or stay on the superhydrophobic surface without contamination. Owing to the chemical inertness of the polymer, these results indicate that superhydrophobic PTFE can be used in lab-on-a-chip and multi-sensor devices as well as in biological cultures, where aqueous solutions meet solid surfaces, without contaminating the interface.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

Sol-gel prepared Pt-modified oxide layers: Synthesis, characterization, and electrocatalytic activity

Thin films of pure RuO2 and IrO2 and mixed Ru0.5Ir0.5O2 oxide modified with Pt particles were prepared by a sol-gel method in the form of thin films of similar to 2 mu m thickness on Ti substrates. Surface morphology of these Pt- modified oxides was examined by scanning electron microscopy and was found to exhibit a significant influence of the chemical composition of the oxide matrix. Element mapping showed homogeneous distribution of the metals. X- ray diffraction and X- ray photoelectron spectroscopy analyses showed that these films consist of metallic Pt particles dispersed in an oxide matrix. Cyclic voltammetry in acid solutions showed that the sol- gel prepared layers have relatively high Pt surface areas. The electrocatalytic activity of these materials toward the anodic oxidation of formaldehyde and methanol was compared in terms of onset potential and current density and was found to follow the sequence: Pt- Ru0.5Ir0.5O2/ Ti > Pt- RuO2/ Ti > Pt- IrO2/ Ti.

Compact disks, a new source for gold electrodes. Application to the quantification of copper by PSA

In this work we describe a versatile and very sensitive way for copper quantification by potentiometric stripping analysis using gold electrodes obtained from recordable compact disks (CDs). This new source of electrodes (CDtrodes) shown similar performance to the commercial gold electrodes with superior versatility and lower cost. Recordable CDs contains a highly pure gold film with thickness between 50 and 100 nm and superficial area of ca. 100 cm(2). The working electrode developed was used successfully in stationary cell and many experimental parameters have been optimized. For copper, the detection limit attained was 30 ng L-1 (600 s deposition time) with remarkable precision (standard deviation of 1.8 % for 20 repetitive measurements using 25 mu gL(-1) of copper with 60 s of deposition time). The gold electrode developed was used for analysis of copper in sugar cane spirits and tap water samples. The results were compared with those obtained by atomic absorption spectroscopy.

Excitation spectrum for ultrafast photogeneration of charged solitons in polyacetylene

Ultrafast photoinduced absorption by IRAV modes is used to detect charged solitons in oriented polyacetylene. We find that soliton pairs are photogenerated within our time resolution of similar to250 fs with similar to100% quantum efficiency (phi(ch)). The excitation spectrum of phi(ch) shows an onset at 1.0 eV, with a weak photon energy dependence up to 4.7 eV. These results agree with the ultrafast soliton formation predicted by Su and Schrieffer and with the SSH threshold of 2E(g)/pi for soliton pair production.