Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

Carbon supported Pt-Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 degrees C and 90 degrees C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt3Sn1/C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Natural rubber latex LbL films: Characterization and growth of fibroblasts

The recent biomedical applications of natural rubber (NR) latex, mostly in dry membranes, have motivated research into novel, more noble uses of this low-cost biomaterial. In this article, we provide the first report on the fabrication of layer-by-layer (LbL) films of NR alternated with the polyelectrolytes polyethylenimine (PEI) and polyallylamine hydrochloride (PAH). Stable (PAH/NR)n and (PEI/NR)n LbL films displayed similar physicochemical properties, but differed in terms of film morphology according to atomic force microscopy (AFM) and scanning electron microscopy (SEM) data. Most significantly, (PEI/NR)5 LbL films were made of smaller and flattened particles, which were not efficient for the growth and proliferation of normal human fibroblasts (NHF). In contrast, efficient NHF proliferation could be obtained with (PAH/NR)n LbL films, with the fibroblasts exhibiting the expected elongated morphology. Furthermore, cell growth did not occur for cast films of NR, thus demonstrating the suitability of the LbL method for this biologically related application. The differences between the two polyelectrolytes illustrate the importance of the film architecture and morphology, which open the way for exploiting the molecular control inherent in the LbL technique for further applications of NR-containing films. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Morphology and topography analysis of mesoporous titania templated by micrometric latex sphere arrays

In this work, mesoporous titania is prepared by templating latex sphere arrays with four different sphere diameters at the micrometric scale (phi > 1 mu m). The mesoporous titania homogeneously covers the latex spheres and substrate, forming a thin coating characterized by N-2 adsorption isotherm, small angle X-rays scattering, atomic force, field emission and transmission electronic microscopies. Mesoporous titania has been templated into different shapes such as hollow particles and monoliths according to the amount of sol used to fill the voids of the close packed latex spheres. Titania topography strongly depends on the adsorption of polymeric segments over latex spheres surface, which could be decreased by changing the dimensions of latex spheres (phi = 9.5 mu m) generating a lamellar architecture. Thus, micrometric latex sphere arrays can be used to achieve new surface patterns for mesoporous materials via a fast and inexpensive chemical route for construction of functional devices in different technological fields such as energy conversion, inclusion chemistry and biomaterials. (C) 2011 Elsevier Inc. All rights reserved.

Structural aspects of polyanion and hydrophobically modified polycation multilayers on hydrophilic or hydrophobic surfaces

Multilayer films of carboxymethylcellulose (CMC), a polyanion, and bromide salts of poly(4-vinylpyridine) quaternized with linear aliphatic chains of 2 (ethyl) and 5 (pentyl) carbon atoms, coded as QPVP-C2 and QPVP-C5, respectively, were fabricated by layer-by-layer (LbL) self-assembly onto Si/SiO2 wafers (hydrophilic substrate) or polystyrene, PS, films (hydrophobic substrate). The films were characterized by means of ex situ and in situ ellipsometry, atomic force microscopy (AFM), contact angle measurements and sum frequency generation vibrational spectroscopy (SFG). Antimicrobial tests were used to assess the exposure of pyridinium moieties to the aqueous medium. In situ ellipsometry indicated that for Si/SiO2 the chains were more expanded than the PS films and both substrates systems composed of QPVP-C5 were thicker than those with QPVP-C2. For dried layers, the alkyl side group size had a small effect on the thickness evolution, regardless of the substrate. At pH 2 the multilayers showed high resistance, evidencing that the build-up is driven not only by cooperative polymer-polymer ion pairing, but also by hydrophobic interactions between the alkyl side chains. The LbL films became irregular as the number of depositions increased. After the last deposition, the wettability of QPVP-C2 or QPVP-C5 terminated systems on the Si/SiO2 wafers and PS films were similar, except for QPVP-C2 on Si/SiO2 wafers. Unlike the morphology observed for LbL films on Si/SiO2 wafers, PS induced the formation of porous structures. SFG showed that in air the molecular orientation of pyridinium groups in multilayers with QPVP-C5 was stronger than in those containing QPVP-C2. The exposure of pyridinium moieties to the aqueous medium was more pronounced when the LbL were assembled on Si/SiO2 wafers.

Galactomannan thin films as supports for the immobilization of Concanavalin A and/or dengue viruses

The immobilization of the glucose/mannose-binding lectin from Concanavalia ensiformis seeds (ConA) onto a monolayer made of a galactomannan extracted from Leucaena leucocephala seeds (GML), which was adsorbed onto - amino-terminated surfaces, was investigated by means of ellipsometry and atomic force microscopy. The mean thickness of GML monolayer, which polysaccharide consists of linear 1 -> 4-linked beta-D-mannopyranosil units partially substituted at C-6 by alpha-D-galactopyranosyl units, amounted to (1.5 +/- 0.2) nm. ConA molecules adsorbed onto GML surfaces forming (2.0 +/- 0.5) nm thick layers. However, in the presence of mannose the adsorption failed, indicating that ConA binding sites were blocked by mannose and were no longer available for mannose units present in the GML backbone. The GML film was also used as support for the adsorption of three serotypes of dengue virus particles (DENV-1, DENV-2 and DENV-3), where DENV-2 formed the thickest film (4 +/- 2) nm. The adsorbed layer of DENV-2 onto ConA-covered GML surfaces presented mean thickness values similar to that determined for DENV-2 onto bare GML surfaces. The addition of free mannose units prevented DENV-2 adsorption onto ConA-covered GML films by similar to 50%, suggesting competition between virus and mannose for ConA binding sites. This finding suggests that if ConA is also adsorbed to GML surface and its binding site is blocked by free mannose, virus particles are able to recognized GML mannose unities substituted by galactose. interactions between polysaccharides thin films, proteins, and viruses are of great relevance since they can provide basis for the development of biotechnological devices. These results indicate that GML is a potential polysaccharide for biomaterials development, as those could involve interactions between ConA in immune system and viruses. (C) 2011 Elsevier B.V. All rights reserved.

Photo-induced electron transfer in supramolecular materials of titania nanostructures and cytochrome c

In the present paper, we report on the molecular interaction and photochemistry of TiO2 nanoparticles (NPs) and cytochrome c systems for understanding the effects of supramolecular organization and electron transfer by using two TiO2 structures: P25 TiO2 NPs and titanate nanotubes. The adsorption and reduction of cytochrome c heme iron promoted by photo-excited TiO2, arranged as P25 TiO2 NPs and as nanotubes, were characterized using electronic absorption spectroscopy, thermogravimetric analysis, and atomic force microscopy. In an aqueous buffered suspension (pH 8.0), the mass of cytochrome c adsorbed on the P25 TiO2 NP surface was 2.3 fold lower (0.75 mu g m(-2)) than that adsorbed on the titanate nanotubes (1.75 mu g m(-2)). Probably due to the high coverage of titanate nanotubes by adsorbed cytochrome c, the low amount of soluble remaining protein was not as efficiently photo-reduced by this nanostructure as it was by the P25 TiO2 NPs. Cytochrome c, which desorbed from both titanium materials, did not exhibit changes in its redox properties. In the presence of the TiO2 NPs, the photo-induced electron transfer from water to soluble cytochrome c heme iron was corroborated by the following findings: (i) identification by EPR of the hydroxyl radical production during the irradiation of an aqueous suspension of TiO2 NPs, (ii) impairment of a cytochrome c reduction by photo-excited TiO2 in the presence of dioxane, which affects the dielectric constant of the water, and (iii) change in the rate of TiO2-promoted cytochrome c reduction when water was replaced with D2O. The TiO2-promoted photo-reduction of cytochrome c was reverted by peroxides. Cytochrome c incorporated in the titanate nanotubes was also reversibly reduced under irradiation, as confirmed by EPR and UV-visible spectroscopy.

Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Interface tailoring for adhesion enhancement of diamond-like carbon thin films

We have explored the suitability and characteristics of interface tailoring as a tool for enhancing the adhesion of hydrogen-free diamond-like carbon (DLC) thin films to silicon substrates. DLC films were deposited on silicon with and without application of an initial high energy carbon ion bombardment phase that formed a broad Si-C interface of gradually changing Si:C composition. The interface depth profile was calculated using the TRIDYN simulation program, revealing a gradient of carbon concentration including a region with the stoichiometry of silicon carbide. DLC films on silicon, with and without interface tailoring, were characterized using Raman spectroscopy, scanning electron microscopy, atomic force microscopy and scratch tests. The Raman spectroscopy results indicated sp3-type carbon bonding content of up to 80%. Formation of a broadened Si:C interface as formed here significantly enhances the adhesion of DLC films to the underlying silicon substrate. (C) 2012 Elsevier B.V. All rights reserved.

Color tunability of intense upconversion emission from Er3+-Yb3+ co-doped SiO2-Ta2O5 glass ceramic planar waveguides

This work reports on the infrared-to-visible CW frequency upconversion from planar waveguides based on Er3+-Yb3+-doped 100-xSiO(2)-xTa(2)O(5) obtained by a sol-gel process and deposited onto a SiO2-Si substrate by dip-coating. Surface morphology and optical parameters of the planar waveguides were analyzed by atomic force microscopy and the m-line technique. The influence of the composition on the electronic properties of the glass-ceramic films was followed by the band gap ranging from 4.35 to 4.51 eV upon modification of the Ta2O5 content. Intense green and red emissions were detected from the upconversion process for all the samples after excitation at 980 nm. The relative intensities of the emission bands around 550 nm and 665 nm, assigned to the H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2) transitions, depended on the tantalum oxide content and the power of the laser source at 980 nm. The upconversion dynamics were investigated as a function of the Ta2O5 content and the number of photons involved in each emission process. Based on the upconversion emission spectra and 1931CIE chromaticity diagram, it is shown that color can be tailored by composition and pump power. The glass ceramic films are attractive materials for application in upconversion lasers and near infrared-to-visible upconverters in solar cells.

Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.

Impact of bleaching pine fibre on the fibre/cement interface

The goal of this article was to evaluate the surface characteristics of the pine fibres and its impact on the performance of fibre-cement composites. Lower polar contribution of the surface energy indicates that unbleached fibres have less hydrophilic nature than the bleached fibres. Bleaching the pulp makes the fibres less stronger, more fibrillated and permeable to liquids due to removal the amorphous lignin and its extraction from the fibre surface. Atomic force microscopy reveals these changes occurring on the fibre surface and contributes to understanding the mechanism of adhesion of the resulting fibre to cement interface. Scanning electron microscopy shows that pulp bleaching increased fibre/cement interfacial bonding, whilst unbleached fibres were less susceptible to cement precipitation into the fibre cavities (lumens) in the prepared composites. Consequently, bleached fibre-reinforced composites had lower ductility due to the high interfacial adhesion between the fibre and the cement and elevated rates of fibre mineralization.

Nanostructures on spin-coated polymer films controlled by solvent composition and polymer molecular weight

In this study we systematically investigated how the solvent composition used for polymer dissolution affects the porous structures of spin-coated polymers films. Cellulose acetate butyrate (CAB) and poly(methylmethacrylate) with low(PMMA-L) and high (PMMA-H) molecular weights were dissolved in mixtures of acetone (AC) and ethyl acetate (EA) at constant polymer concentration of 10 g/L The films were spin-coated at a relative air humidity of 55+/-5%, their thickness and index of refraction were determined by means of ellipsometry and their morphology was analyzed by atomic force microscopy. The dimensions and frequency of nanocavities on polymer films increased with the acetone content (phi(AC)) in the solvent mixture and decreased with increasing polymer molecular weight. Consequently, as the void content increased in the films, their apparent thicknesses increased and their indices of refraction decreased, creating low-cost anti-reflection surface. The void depth was larger for PMMA-L than for CAB. This effect was attributed to different activities of EA and AC in CAB or PMMA-L solution, the larger mobility of chains and the lower polarity of PMMA-L in comparison to CAB. (C) 2012 Elsevier B. V. All rights reserved.

Langmuir and Langmuir-Blodgett films of a quinoline-fluorene based copolymer

The fabrication of Langmuir-Blodgett (LB) films of synthetic polymers allows the control of molecular architecture in order to optimize physical properties. In this paper, the surface chemistry of a quinoline-fluorene based copolymer spread on the air-water interface is investigated. Surface pressure-area isotherms as well as Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) were employed to characterize the films, which could be transferred to solid supports by the LB technique. Atomic force microscopy as well as UV-Vis and fluorescence spectroscopies have shown a regular deposition of the polymers, and the luminescence properties could be controlled with the number of layers deposited on the solid support. As a result, the photoluminescence of the LB films was considerably higher than that observed for the spin coated film, and the maximum emission peak was shifted to higher energies, which is attributed to the molecular-level interactions within the layer-ordered structure of the LB film. The luminescence response would possibly be tuned to approach the highest level, which allows the films to be employed in future applications in efficient optical devices such as organic light-emitting diodes (OLEDs). (C) 2011 Elsevier B.V. All rights reserved.

Topography of four different endodontic rotary systems, before and after being used for the 12th time

Root canal preparation may damage NiTi instruments resulting in wear and deformation. The aim of this study was to make a comparative evaluation of the surface topography of the cervical third of four different rotary systems, before and after being used twelve times, in 1.440 resin blocks with simulated root canals with standardized 45 degrees curvatures, and analyzed by atomic force microscopy AFM. The blocks were divided into four groups and prepared according to the manufacturers recommendations: Group 1 - K3 (R); Group 2 - Protaper Universal (R); Group 3 - Twisted Files (R) and Group 4 - Biorace (R). After each preparation, the instruments were washed and autoclaved. A total of 240 instruments were selected, being 30 new instruments and 30 after having been used for the 12th time, from each group. These instruments were analyzed by AFM and for quantitative evaluation, the mean RMS (Root mean square) values of the cervical third of the specimens from the four groups were used. The result showed that all the rotary files used for the 12th time suffered wear with change in the topography of the cervical region of the active portion of the file (ANOVA p < 0.01). Classifying the specimens in increasing order, from the least to the greatest wear suffered, Group 3 (2.8993 nm) presented the least wear, followed by Group 4 (12.2520 nm), Group 1 (36.0043 nm) and lastly, Group 2 (59.8750 nm) with the largest amount of cervical surface wear. Microsc. Res. Tech. 75:97-102, 2012. (c) 2011 Wiley Periodicals, Inc.