Mechanism of the formation and properties of antimony polyphosphate

Formation of antimony polyphosphate using Sb2O3 and/or (NH4)2HPO4 and NH4H 2PO4 as starting materials has been simulated by thermal analysis technique. The elimination of water and ammonia molecules induced by heating leads to the formation of intermediate ammonium polyphosphate, which subsequently reacts with Sb2O3. Morphologically, vitreous Sb(PO3)3 is composed of plaques having irregular shapes. Infrared spectra and NMR study is consistent with tetrametaphosphate anion arrangement. The compound is thermally unstable and may be recommended as a donor of -O-P-O- linkers in the preparation of special phosphate glasses. © 2005 Akadémiai Kiadó, Budapest.

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Conductive nanocomposites based on cellulose nanofibrils coated with polyaniline-DBSA via in situ polymerization

Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI-DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet-visible-near infrared (UV-Vis - NIR) and Fourier-transform infrared (FTIR) spectroscopies and X-ray diffraction (XRD). FTIR and UV-Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10 -1 S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X-ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of polypropylene surface modification by air dielectric barrier discharge operated at two different frequencies

In this work, air dielectric barrier discharge (DBD) operating at the line frequency (60 Hz) or at frequency of 17 kHz was used to improve the wetting properties of polypropylene (PP). The changes in the surface hydrophilicity were investigated by contact angle measurements. The plasma-induced chemical modifications of PP surface were studied by X-ray photoelectron spectroscopy (XPS) and Fourier-transformed infrared spectroscopy (FTIR). The polymer surface morphology and roughness before and after the DBD treatment were analyzed by atomic force microscopy (AFM). To compare the plasma treatment effect at different frequencies the variation of the contact angle is presented as a function of the deposited energy density. The results show that both DBD treatments leaded to formation of water-soluble low molecular weight oxidized material (LMWOM), which agglomerated into small mounts on the surface producing a complex globular structure. However, the 60 Hz DBD process produced higher amount of LMWOM on the PP surface comparing to the 17 kHz plasma treatment with the same energy dose. The hydrophilic LMWOM is weakly bounded to the surface and can be easily removed by polar solvents. After washing the DBD-treated samples in de-ionized water their surface roughness and oxygen content were reduced and the PP partially recovered its original wetting characteristics. This suggested that oxidation also occurred at deeper and more permanent levels of the PP samples. Comparing both DBD processes the 17 kHz treatment was found to be more efficient in introducing oxygen moieties on the surface and also in improving the PP wetting properties. © 2012 Elsevier B.V. All rights reserved.

A new palladium chelate compound for determination of sulfide

A new palladium chelate compound is described for the determination of sulfide in aqueous samples. The reagent, bis(2-aminobenzoate)palladium(II) (PdA 2), was prepared by reaction of tetrachloropalladate (PdCl 4 -) with 2-aminobenzoic acid. The compound was characterized by infrared spectroscopy and CHN elemental analysis. The measurement was based on the selective reaction of PdA 2 with sulfide in an aqueous medium, which quantitatively produced fluorescent 2-aminobenzoate (λ ex=245nm, λ em=410nm). The analytical response was linear in the range 0.10-20.0μmol (S 2-) L -1 (r>0.99), with a limit of detection of 0.075μmolL -1 and repeatability (RSD) of 3.4%. There was no interference from CO 3 2-, NO 3 -, Cl -, SO 4 2-, Br -, NO 2 -, K +, NH 4 +, Na +, citrate or S 2O 8 2-. The fluorescence intensity decreased in the presence of H 3CCOO -, PO 4 3- and SCN -, while OH - caused a positive interference. The new fluorescent compound was successfully applied for the determination of sulfide in synthetic wastewater and natural water sample. The advantages of the proposed palladium chelate are absence of toxic by-products, simple synthesis procedure of reagent and yield reaction of about 85%, easy handling and fast acquirement of analytical signal. © 2012 Elsevier B.V.

Broadband NIR emission in novel sol-gel Er3+-doped SiO 2-Nb2O5 glass ceramic planar waveguides for photonic applications

This paper reports on the sol-gel preparation and structural and optical characterization of new Er3+-doped SiO2-Nb 2O5 nanocomposite planar waveguides. Erbium-doped (100-x)SiO2-xNb2O5 waveguides were deposited on silica-on-silicon substrates and Si(1 0 0) by the dip-coating technique. The waveguides exhibited uniform refractive index distribution across the thickness, efficient light injection at 1538 nm, and low losses at 632 and 1538 nm. The band-gap values lied between 4.12 eV and 3.55 eV for W1-W5, respectively, showing an excellent transparency in the visible and near infrared region for the waveguides. Fourier Transform Infrared (FTIR) Spectroscopy analysis evidenced SiO2-Nb2O5 nanocomposite formation with controlled phase separation in the films. The HRTEM and XRD analyses revealed Nb2O5 orthorhombic T-phase nanocrystals dispersed in a silica-based host. Photoluminescence (PL) analysis showed a broad band emission at 1531 nm, assigned to the 4I13/2 → 4I15/2 transition of the Er3+ ions present in the nanocomposite, with a full-width at half medium of 48-68 nm, depending on the niobium content and annealing. Hence, these waveguides are excellent candidates for application in integrated optics, especially in EDWA and WDM devices. © 2012 Elsevier B.V. All rights reserved.

Signal classification of submerged aquatic vegetation based on the hemispherical-conical reflectance factor spectrum shape in the yellow and red regions

The water column overlying the submerged aquatic vegetation (SAV) canopy presents difficulties when using remote sensing images for mapping such vegetation. Inherent and apparent water optical properties and its optically active components, which are commonly present in natural waters, in addition to the water column height over the canopy, and plant characteristics are some of the factors that affect the signal from SAV mainly due to its strong energy absorption in the near-infrared. By considering these interferences, a hypothesis was developed that the vegetation signal is better conserved and less absorbed by the water column in certain intervals of the visible region of the spectrum; as a consequence, it is possible to distinguish the SAV signal. To distinguish the signal from SAV, two types of classification approaches were selected. Both of these methods consider the hemispherical-conical reflectance factor (HCRF) spectrum shape, although one type was supervised and the other one was not. The first method adopts cluster analysis and uses the parameters of the band (absorption, asymmetry, height and width) obtained by continuum removal as the input of the classification. The spectral angle mapper (SAM) was adopted as the supervised classification approach. Both approaches tested different wavelength intervals in the visible and near-infrared spectra. It was demonstrated that the 585 to 685-nm interval, corresponding to the green, yellow and red wavelength bands, offered the best results in both classification approaches. However, SAM classification showed better results relative to cluster analysis and correctly separated all spectral curves with or without SAV. Based on this research, it can be concluded that it is possible to discriminate areas with and without SAV using remote sensing. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Development and evaluation of praziquantel solid dispersions in sodium starch glycolate

Purpose: To develop and characterize solid dispersions of praziquantel (PZQ) with sodium starch glycolate (SSG) for enhanced drug solubility. Methods: PZQ solid dispersion (SD) was prepared using co-precipitation method by solvent evaporation. The ratios of PZQ to SSG were 2:1, 1:1, 1:2, 1:3 (w/w). PZQ solubility was evaluated in purified water, and PZQ dissolution test was carried out in 0.1N HCl. Structural characterization of the dispersions was accomplished by x-ray diffraction (XRD) and infrared spectroscopy (FTIR) while the external morphology of the SDs, SSG and PZQ were studied by scanning electron microscopy (SEM). Mucoadhesion properties of the SD (1:3) and SSG, on mucin disks were examined using texture profile analysis. Results: The highest solubility was obtained with 1:3 solid dispersion, with PZQ solubility of 97.31 %, which is 3.65-fold greater than the solubility of pure PZQ and physical misture (PM, 1:3). XRD results indicate a reduction in PZQ crystallinity while infrared spectra showed that the functional groups of PZQ and SSG were preserved. SEM showed that the physical structure of PZQ was modified from crystalline to amorphous. The amount of PZQ in PM and SD (1:3) that dissolved in 60 min was 70 and 88 %, respectively, and these values increased to 76 and 96 %, respectively. The solid dispersion reduced the mucoadhesive property of the glycolate. Conclusion: Solid dispersion formulation using SSG is a good alternative approach for increasing the dissolution rate of PZQ. © Pharmacotherapy Group, Faculty of Pharmacy, University of Benin, Benin City, 300001 Nigeria. All rights reserved.

A compound model for the origin of Earth's water

One of the most important subjects of debate in the formation of the solar system is the origin of Earth's water. Comets have long been considered as the most likely source of the delivery of water to Earth. However, elemental and isotopic arguments suggest a very small contribution from these objects. Other sources have also been proposed, among which local adsorption of water vapor onto dust grains in the primordial nebula and delivery through planetesimals and planetary embryos have become more prominent. However, no sole source of water provides a satisfactory explanation for Earth's water as a whole. In view of that, using numerical simulations, we have developed a compound model incorporating both the principal endogenous and exogenous theories, and investigating their implications for terrestrial planet formation and water delivery. Comets are also considered in the final analysis, as it is likely that at least some of Earth's water has cometary origin. We analyze our results comparing two different water distribution models, and complement our study using the D/H ratio, finding possible relative contributions from each source and focusing on planets formed in the habitable zone. We find that the compound model plays an important role by showing greater advantage in the amount and time of water delivery in Earth-like planets. © 2013. The American Astronomical Society. All rights reserved.

TiO2-Cu photocatalysts: A study on the long- and short-range chemical environment of the dopant

In this study, the short- and long-range chemical environments of Cu dopant in TiO2 photocatalyst have been investigated. The Cu-doped and undoped TiO2 specimens were prepared by the sol-gel approach employing CuSO4·5H2O and Ti(O-iPr)4 precursors and subjecting the dried gels to thermal treatment at 400 and 500 C. The photocatalytic activity, investigated by methylene blue degradation under sunlight irradiation, showed a significantly higher efficiency of Cu-doped samples than that of pure TiO2. The X-ray diffraction results showed the presence of anatase phase for samples prepared at 400 and 500 C. No crystalline CuSO4 phase was detected below 500 C. It was also found that doping decreases the crystallite size in the (004) and (101) directions. Infrared spectroscopy results indicated that the chemical environment of sulfate changes as a function of thermal treatment, and UV-vis spectra showed that the band gap decreases with thermal treatment and Cu doping, showing the lowest value for the 400 C sample. X-ray absorption fine structure measurements and analysis refinements revealed that even after thermal treatment and photocatalytic assays, the Cu2+ local order is similar to that of CuSO4, containing, however, oxygen vacancies. X-ray photoelectron spectroscopy data, limited to the near surface region of the catalyst, evidenced, besides CuSO4, the presence of Cu1+ and CuO phases, indicating the active role of Cu in the TiO2 lattice. © 2013 Springer Science+Business Media New York.

Photoelectrochemical properties of FTO/m-BiVO4 electrode in different electrolytes solutions under visible light irradiation

Photoelectrochemical properties of FTO/BiVO4 electrode were investigated in different electrolytic solutions, potassium chloride (KCl) and sodium sulphate (Na2SO4), and under visible light irradiation condition. In order to accomplish that, an FTO/BiVO4 electrode was built by combining the solution combustion synthesis technique with the dip-coating deposition process. The morphology and structure of the BiVO4 electrode were investigated through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photoelectrochemical properties were analyzed through chronoamperometry measurements. Results have shown that the FTO/BiVO4 electrode presents higher electroactivity in the electrolyte Na2SO4, leading to better current stabilization, response time, and photoinduced current density, when compared to KCl electrolyte. Besides, this electrode shows excellent performance for methylene blue degradation under visible light irradiation condition. In Na2SO4, the electrode has shown higher degradation rate, 51 %, in contrast to 44 % in KCl, plus higher rate constant, 174 × 10-4 min-1 compared to 150 × 10-4 min-1 in KCl. Results presented in this communication leads to the indication of BiVO4 thin films as alternate materials to use in heterogeneous photoelectrocatalysis, more specifically in decontamination of surface water. © 2013 Springer-Verlag Berlin Heidelberg.

Simple green approach to reinforce natural rubber with bacterial cellulose nanofibers

Natural rubber (NR) is a renewable polymer with a wide range of applications, which is constantly tailored, further increasing its utilizations. The tensile strength is one of its most important properties susceptible of being enhanced by the simple incorporation of nanofibers. The preparation and characterization of natural-rubber based nanocomposites reinforced with bacterial cellulose (BC) and bacterial cellulose coated with polystyrene (BCPS), yielded high performance materials. The nanocomposites were prepared by a simple and green process, and characterized by tensile tests, dynamical mechanical analysis (DMA), scanning electron microscopy (SEM), and swelling experiments. The effect of the nanofiber content on morphology, static, and dynamic mechanical properties was also investigated. The results showed an increase in the mechanical properties, such as Young's modulus and tensile strength, even with modest nanofiber loadings. © 2013 American Chemical Society.

Transdentinal cytotoxicity of experimental adhesive systems of different hydrophilicity applied to ethanol-saturated dentin

The aim of this study was to evaluate the transdentinal cytotoxicity of experimental adhesive systems (EASs) with different hydrophilicity and dentin saturation solutions on odontoblast-like cells. One hundred 0.4-mm-thick dentin discs were mounted in in vitro pulp chambers and assigned to 10 groups. MDPC-23 cells were seeded onto the pulpal side of the discs, incubated for 48 h. The EASs with increasing hydrophilicity (R1, R2, R3 and R4) were applied to the occlusal side after etching and saturation of etched dentin with water or ethanol. R0 (no adhesive) served as controls. R1 is a non-solvated hydrophobic blend, R2 is similar to a simplified etch-and-rinse adhesive system and R3 and R4 are similar to self-etching adhesives. After 24 h, cell metabolism was evaluated by MTT assay (n = 8 discs) and cell morphology was examined by SEM (n = 2 discs). Type of cell death was identified by flow cytometry and the degree of monomer conversion (%DC) was determined by infrared spectroscopy (FTIR) after 10 s or 20 s of photoactivation. Data were analyzed by the Kruskal-Wallis and Mann-Whitney tests (α = 0.05). Dentin saturation with ethanol resulted in higher necrotic cell death ratios for R2, R3 and R4 compared with water saturation, although R2 and R3 induced higher SDH production. Photoactivation for 20 s significantly improved the %DC of all EASs compared with 10 s. A significant positive correlation was observed between the degree of hydrophilicity and %DC. In conclusion, except for R1, dentin saturation with ethanol increased the cytotoxicity of EASs, as expressed by the induction of necrotic cell death. © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Synthesis and characterization of melanin in DMSO

Recently soluble melanin derivatives have been obtained by a synthetic procedure carried out in DMSO (D-melanin). In this work a comparative study of the structural characteristics of synthetic melanin derivatives obtained by oxidation of L-DOPA in H2O and DMSO are presented. To this end, Fourier-transform infrared spectroscopy as well as proton and carbon nuclear magnetic resonance techniques has been employed. In addition, aging effects have been investigated for D-melanin. The results suggest that sulfonate groups (-SO2CH3) from the oxidation of DMSO, are incorporated into melanin, which confers protection to the phenolic hydroxyl group present in its structure. The solubility of D-melanin in DMSO is attributed to the presence of these groups. When D-melanin is left in air for long time periods, the sulfonate groups leave the structure, and an insoluble compound is obtained. NaOH and water have been used, in order to accelerate the release of the sulfonate groups attached to D-melanin, thereby corroborating the proposed structure and the synthesis mechanism. © 2013.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. All rights reserved.