A study on X-ray irradiation of composite polyaniline LB films

Composite Langmuir-Blodgett (LB) films from polyaniline and cadmium stearate have been irradiated with ionizing X-rays for various exposure times. In the initial stages of X-ray irradiation the absorption peak at 580 nm of an as-deposited film was seen to decrease with a concomitant increase in the absorption in the long wavelength region (700-1100 nm). Upon prolonging the irradiation, the absorption maximum shifted to 800 nm with the LB film color changing to green, characteristic of acid doped polyaniline. The changes in the Fourier transform infrared (FTIR) spectra upon irradiation are also similar to those observed upon acid doping of polyaniline. When compared with acid doping, two major differences were observed for the LB films exposed to X-rays. First, the packing order of the cadmium stearate domains in the composite LB films - as observed by X-ray diffraction - is not affected by the X-ray irradiation. In addition, no significant increase in the DC conductivity was noted after the X-ray exposure whereas similar LB films have their conductivity increased by an order of magnitude upon acid doping. These differences may be explained by considering that the inter-domain contribution to the conductivity is increased by the acid doping because the insulating cadmium stearate domains are destroyed, which does not occur with the X-ray irradiation. (C) 1998 Elsevier B.V. S.A. All rights reserved.

Effect of presence of an acid catalyst on structure and properties of iron-doped siloxane-polyoxyethylene nanocomposites prepared by sol-gel

In this work we investigate the effect of hydrochloric acid (HC) addition on the structure and thermal and magnetic properties of iron-doped siloxane-polyoxyethylene (POE) hybrids prepared by the sol-gel route. X-ray powder diffraction (XRD) and X-ray absorption near edge structure (XANES) results reveal the dominance of ferrihydrite nanoparticles and a mixture of this phase with FeCl4- species in the hybrid prepared without and with HCl, respectively. Thermal analysis reveals the existence of two crystalline polymeric phases in the hybrid prepared with HCl whereas hybrids prepared without HCl are amorphous. The 105 and 60 Angstrom sized ferrihydrite nanoparticles were detected by SAXS analysis of the composite prepared without and with HCl, respectively. The magnetic results suggest that in both samples antiferromagnetic nanoparticles coexist with small clusters/isolated ions. In the sample without HCl addition, larger particles dominate the magnetic behavior, while the opposite occurs for the sample prepared using HCl catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Enhanced photoelectrocatalytic degradation of an acid dye with boron-doped TiO2 nanotube anodes

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

Raman and photoluminescence of Er3+-doped SnO2 obtained via the sol-gel technique from solutions with distinct pH

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dielectric behavior of PVDF/POMA blends that have a low doped POMA content

The real (epsilon') and imaginary (epsilon) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o-methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA-TSA were determined in the frequency interval between 10(2) and 3 X 10(6) Hz and in the temperature range from -120 up to 120degreesC. It was observed that the values of epsilon' and epsilon had a greater increase with the POMA-TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA-TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell-Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA-TSA in the blends. A strong decrease was observed in POMA-TSA conductivity in the blend, which was bigger the lower the POMA-TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. (C) 2002 Wiley Periodicals, Inc.

Theoretical study of MgO(001) surfaces: Pure, doped with Fe, Ca, and Al, and with and without adsorbed water

Ab initio calculations of large cluster models have been performed in order to study water adsorption at the five-fold coordinated adsorption site on pure Mg(001) and MgO(001) surfaces doped with Fe, Ca, and Al. The geometric parameters of the adsorbed water molecule have been optimized preparatory to analysis of binding energies, charge transfer, preferential sites of interaction, and bonding distances. We have used Mulliken population analysis methods in order to analyze charge distributions and the direction of charge transfer. We have also investigated energy gaps, HOMO energies, and SCF orbital energies as well as the acid-base properties of our cluster model. Numerical results are compared, where possible, with experiment and interpreted in the framework of various analytical models. (C) 2001 John Wiley & Sons, Inc.

UV-visible absorption characteristics of TEOS-derived and Cr-doped silica sonogels aged in different pH solutions and heat treated up to 600 degrees C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl3.6H(2)O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600degreesC and analyzed by UV-visible absorption spectroscopy. Cr3+ is the preferable oxidation state of the chromium ion in the gels annealed up to 250-300degreesC, in the case of aging in solutions of pH=5 and 11. A high UV absorption below similar to320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below similar to250degreesC, in the case of aging in solutions of pH=1 and 2. These absorption bands have not been assigned. Above 300degreesC up to 600degreesC, Cr5+, and possibly Cr6+, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Nucleation and growth of mullite whiskers from lanthanum-doped aluminosilicate melts

Nucleation and growth of mullite whiskers in the La2O3-Al2O3-SiO2 system were investigated in the 1500degrees-1700degreesC temperature range. A differential thermal analysis (DTA) showed that the mullitization temperature decreases from 1350degreesC to 1240degreesC as a result of lanthania doping. In the temperature range of 1250-1500degreesC, most of the mullite grains have an Al2O3/SiO2 = 1.5 composition throughout the ceramic body; however, from 1400degreesC upward, the number of anisotropic grains with the Al2O3/SiO2 = 1.3 composition begins to increase. The concentration of alumina in the composition of the grain-boundary phase decreases as firing temperatures increase. At temperatures > 1500degreesC, alumina grains and whiskers grow on the internal and external surfaces of the ceramic body with the characteristic Al2O3/SiO2 = 1.3 composition. Removal of the mullite whisker layer by acid attack revealed an alumina-rich, rosace-like patterned microstructure correlated with the process of whisker nucleation and growth. In the early stages, whisker growth rates were found to be near 60 mum/h. Experimental evidence pointed to nucleation inside the thin glass layer on the external surface.

Distributed feedback multipeak laser emission in Rhodamine 6G doped organic-inorganic hybrids

Organic-inorganic hybrid materials were prepared from an ureasil precursor (ureapropyltriethoxysilane designated as UPTES) and acrylic acid modified zirconium (IV) n-propoxide. Thin films containing rhodamine 6G (Rh6G) were prepared by spin-coating on glass substrates with different Zr:Si molar ratios (Zr:Si = 75:25, 50:50 and 25:75). Refractive index, thickness, number of propagating modes and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm wavelengths by the prism coupling technique. Distributed feedback (DFB) laser effect was observed and studied as a function of films thickness and refractive index.

Selective UV-filter detection with sensors based on stainless steel electrodes modified with polyaniline doped with metal tetrasulfonated phthalocyanine films

This work describes the construction and application of two amperometric sensors for sensitive UV-filter determination. The sensors were prepared using stainless steel electrodes in which polyaniline (PANI) was electrochemically polymerized in the presence of nickel (NiPcTS) or iron (FePcTS) tetrasulfonated phthalocyanines. The sensor surface characterizations were carried out using atomic force microscopy (AFM). The PANI/NiPcTS sensor was selective for the chemical UV-filter p-aminobenzoic acid (PABA) and the PANI/FePcTS sensor was selective for octyldimethyl-PABA (ODP), both in a mixture of tetrahydrofuran (THF) and 0.1 mol L(-1) H(2)SO(4) at a volume ratio of 30 : 70, and with an applied potential of 0.0 mV vs. Ag vertical bar AgCl. A detailed investigation of the selectivity was carried out for both sensors, in order to determine their responses for ten different UV filters. Finally, each sensor was successfully applied to PABA or ODP quantification in sunscreen formulations and water from swimming pools.

Synthesis, characterization and spectroscopy of the europium doped lanthanum trimetaphosphate

Orthorhombic modification of europium doped lanthanum trimetaphosphate has been prepared. The compound was obtained by precipitation of rare earth chloride solution with trimetaphosphoric acid. The characterizations were made using X-ray diffractometry, chemical analysis and infrared spectroscopy. Excitation and emission spectra were recorded at liquid nitrogen and room temperatures. Assignments of the 5D0→7FJ (J=0, 1, 2, 3, 4, 5) transitions were made and an unusual high 5D0→7F4 transition intensity with six split lines has been observed. Structural distortion of the crystal lattice may be caused by the Eu3+ ion inclusion. The simple overlap model was applied for the calculation of the total splitting of the 5D0→7F1 transition, the 5D0→7F0/5D 0→7F2 transition intensity ratio and the Ωλ (λ=2.4) intensity parameters. Theoretical predictions showed to be in good accordance with the experimental data. © 1988 Elsevier Science S.A.

The effect of laminin-1-doped nanoroughened implant surfaces: Gene expression and morphological evaluation

Aim. This study aimed to observe the morphological and molecular effect of laminin-1 doping to nanostructured implant surfaces in a rabbit model. Materials and Methods. Nanostructured implants were coated with laminin-1 (test; dilution, 100 g/mL) and inserted into the rabbit tibiae. Noncoated implants were used as controls. After 2 weeks of healing, the implants were removed and subjected to morphological analysis using scanning electron microscopy (SEM) and gene expression analysis using the real-time reverse transcriptase-polymerase chain reaction (RT-PCR). Results. SEM revealed bony tissue attachment for both control and test implants. Real-time RT-PCR analysis showed that the expression of osteoblast markers RUNX-2, osteocalcin, alkaline phosphatase, and collagen I was higher (1.62-fold, 1.53-fold, 1.97-fold, and 1.04-fold, resp.) for the implants modified by laminin-1 relative to the control. All osteoclast markers investigated in the study presented higher expression on the test implants than controls as follows: tartrate-resistant acid phosphatase (1.67-fold), calcitonin receptor (1.35-fold), and ATPase (1.25-fold). The test implants demonstrated higher expression of inflammatory markers interleukin-10 (1.53-fold) and tumour necrosis factor-α (1.61-fold) relative to controls. Conclusion. The protein-doped surface showed higher gene expression of typical genes involved in the osseointegration cascade than the control surface. © 2012 Humberto Osvaldo Schwartz-Filho et al.

Evidence of weak ferromagnetism in doped plasticized polyaniline (PANI-DDoESSA)0.5 from electron spin resonance measurements

X-band electron spin resonance (ESR) measurements have been performed on a conducting free-standing film of polyaniline plasticized and protonated with di-n-dodecyl ester of sulfosuccinic acid (DDoESSA). The magnetic field was applied parallel and perpendicular to the plane of the film. At around 75 K a transition is observed from Pauli susceptibility to a localized state in which the spin 1/2 polarons behave as spin 1/2 dimers. A rough estimation of the intradimer and interdimer exchange constants is obtained. Below 5 K, ESR data reveal a weak ferromagnetism with the Dzyaloshinskii-Moriya vector mainly oriented in the plane of the film. The existence of a relatively well-defined n-fold axis along the chain direction in the crystalline regions confers a symmetry compatible with such analysis. © 2013 IOP Publishing Ltd.

Nanoparticle characterization of Er-doped SnO2 pellets obtained with different pH of colloidal suspension

SnO2:2 at. %Er xerogel samples were obtained by sol-gel technique from colloidal suspensions with distinct pHs. The evaluation of critical regions inside the nanocrystallite is fundamental for the interpretation of the influence of pH on the emission data. In this way, the nanocrystal depletion layer thickness was obtained with the help of photoluminescence, Raman, X-ray diffraction, and field-emission gun scanning electron microscopy measurements. It was observed that acid suspensions (pH < 7) lead to high surface disorder in which a larger number of cross-linked bonds Sn-O-Sn among nanoparticles are present. For these samples, the nanoparticle depletion layer is larger as compared to samples obtained from other pH. Photoluminescence measurement in the near infrared region indicates that the emission intensity of the transition 4I13/2 → 4I15/2 is also influenced by the pH of the starting colloidal suspension, generating peaks more or less broadened, depending on location of Er3+ ions in the SnO2 lattice (high or low symmetry sites). © 2013 AIP Publishing LLC.