Sensor arrays to detect humic substances and Cu(II) in waters

The interaction between poly(o-ethoxyaniline) (POEA) adsorbed onto solid substrates and humic substances (HS) and Cu(2+) ions has been investigated using UV-vis spectroscopy and atomic force microscopy (AFM). Both HS and Cu(2+) are able to dope POEA and change film morphology. This interaction was exploited in a sensor array made with nanostructured films of POEA, sulfonated lignin and HS, which could detect small concentrations of HS and Cu(2+) in water. (C) 2009 Elsevier B.V. All rights reserved.

Influence of carbon source and inoculum type on anaerobic biomass adhesion on polyurethane foam in reactors fed with acid mine drainage

This paper analyzes the influence of carbon source and inoculum origin on the dynamics of biomass adhesion to an inert support in anaerobic reactors fed with acid mine drainage. Formic acid, lactic acid and ethanol were used as carbon sources. Two different inocula were evaluated: one taken from an UASB reactor and other from the sediment of a uranium mine. The values of average colonization rates and the maximum biomass concentration (C(max)) were inversely proportional to the number of carbon atoms in each substrate. The highest C(max) value (0.35 g TVS g(-1) foam) was observed with formic acid and anaerobic sludge as inoculum. Maximum colonization rates (v(max)) were strongly influenced by the type of inoculum when ethanol and lactic acid were used. For both carbon sources, the use of mine sediment as inoculum resulted in a v(max) of 0.013 g TVS g(-1) foam day(-1), whereas 0.024 g TVS g(-1) foam day(-1) was achieved with anaerobic sludge. (C) 2011 Elsevier Ltd. All rights reserved.

Citric acid as anti-hydration additive for magnesia containing refractory castables

Magnesia hydration is a key concern in refractory castable processing. The volumetric expansion that follows this reaction can result in cracks or even explosion during the first heating-up. Citric acid (CA) and other chelants can significantly reduce MgO hydration rate in aqueous suspensions by forming an insoluble magnesium citrate protective coating on the magnesia particles` surface. In the present work, the performance of CA as an anti-hydration additive in refractory castables was evaluated by hydration tests, mechanical strength and apparent volumetric expansion (AVE) measurements and thermogravimetry. The results attained have shown that CA effectiveness depends strongly on the amount added and by the interaction with other raw materials in the composition, in particular calcium aluminate cement. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

Influence of the rubbery phase on the crystallinity and thermomechanical properties of poly(3-hydroxybutyrate)/elastomer blends

Poly(3-hydroxybutyrate) (PHB) is a very promising biopolymer. In order to improve its processability and decrease its brittleness, PHB/elastomer blends can be prepared. In the work reported, the effect of the addition of a rubbery phase, i.e. ethylene - propylene-diene terpolymer (EPDM) or poly(vinyl butyral) (PVB), on the properties of PHB was studied. The effects of rubber type and of changing the PHB/elastomer blend processing method on the crystallinity and physical properties of the blends were also investigated. For blends based on PHB, the main role of EPDM is its nucleating effect evidenced by a decrease of crystallization temperature and an increase of crystallinity with increasing EPDM content regardless of the processing route. While EPDM has a weak effect on PHB glass transition temperature, PVB induces a marked decrease of this temperature thank to its plasticizer that swells the PHB amorphous phase. A promising solution to improve the mechanical properties of PHB seems to be the melt-processing of PHB with both plasticizer and EPDM. In fact, the plasticizer is more efficient than the elastomer in decreasing the PHB glass transition temperature and, because of the nucleating effect of EPDM, the decrease of the PHB modulus due to the plasticizer can be counterbalanced. (C) 2010 Society of Chemical Industry

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

This work investigates the influence of the addition of cerium (IV) ions on the anticorrosion properties of organic-inorganic hybrid coatings applied to passivated tin coated steel. In order to evaluate the specific effect of cerium (IV) addition on nanostructural features of the organic and inorganic phases of the hybrid coating, the hydrolytic polycondensation of silicon alkoxide and the radical polymerization of the methyl methacrylate (MMA) function were induced separately. The corrosion resistance of the coatings was evaluated by means of linear polarization, Tafel type curves and electrochemical impedance measurements. The impedance results obtained for the hybrid coatings were discussed based on an electrical equivalent circuit used to fit the experimental data. The electrochemical results clearly showed the improvement of the protective properties of the organic-inorganic hybrid coating mainly when the cerium (IV) was added to the organic phase solution precursor, which seemed to be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. (C) 2010 Elsevier Ltd. All rights reserved.

The Penicillium chrysogenum aclA gene encodes a broad-substrate-specificity acyl-coenzyme A ligase involved in activation of adipic acid, a side-chain precursor for cephem antibiotics

Activation of the cephalosporin side-chain precursor to the corresponding CoA-thioester is an essential step for its incorporation into the P-lactam backbone. To identify an acyl-CoA ligase involved in activation of adipate, we searched in the genome database of Penicillium chrysogenum for putative structural genes encoding acyl-CoA ligases. Chemostat-based transcriptome analysis was used to identify the one presenting the highest expression level when cells were grown in the presence of adipate. Deletion of the gene renamed aclA, led to a 32% decreased specific rate of adipate consumption and a threefold reduction of adipoyl-6-aminopenicillanic acid levels, but did not affect penicillin V production. After overexpression in Escherichia coli, the purified protein was shown to have a broad substrate range including adipate. Finally, protein-fusion with cyan-fluorescent protein showed co-localization with microbody-borne acyl-transferase. Identification and functional characterization of aclA may aid in developing future metabolic engineering strategies for improving the production of different cephalosporins. (C) 2009 Elsevier Inc. All rights reserved.

Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

Novel magnetic nanocomposite films with controlled morphology were produced via the electrostatic layer-by-layer assembly of cationic CoFe(2)O(4) nanoparticles and anionic poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonic acid) (PEDOT:PSS) complex. The electrostatic interaction between nanoparticle and the polyelectrolyte complex ensured a stepwise growth of the nanocomposite film with virtually identical amounts of materials being adsorbed at each deposition cycle as observed by UV-vis spectroscopy. AFM images acquired under the tapping mode revealed a globular morphology with dense and continuous layers of nanoparticles with voids being filled with polymeric material. (C) 2010 Elsevier B.V. All rights reserved.

Long-term aging of fiber-cement corrugated sheets - The effect of carbonation, leaching and acid rain

This paper studies the performance of fiber-cement corrugated sheets exposed to long-term weathering, exploring the effect of different environments on fiber-cement degradation. Fiber-cement corrugated sheets that had been exposed to weathering, and in place for more than 30-years, were collected from two different Brazilian cities (Sao Paulo and Criciuma). Mechanical properties (MOR, MOE and fracture toughness) were tested on samples removed from the corrugated sheets. Microstructure was evaluated by X-ray diffraction, SEM with EDS analysis, MIP and TG. The results show that the 37-year-old asbestos-cement corrugated sheets from Sao Paulo presented similar characteristics to those of the non-aged asbestos-cement readily available on the market place. Conversely, deterioration of the asbestos-cement from the industrial area of Criciuma is related to acidic attack, along with carbonation and leaching as a consequence of continued exposition to acid rain during several decades. This process resulted in higher porosity and lower mechanical strength, revealing that leaching mechanisms can have important effect on the performance of thin fiber-cement sheets. (c) 2007 Elsevier Ltd. All rights reserved.

Study of copper electrodeposition mechanism from a strike alkaline bath prepared with 1-hydroxyethane-1,1-diphosphonic acid through cyclic voltammetry technique

Copper strike baths are extensively used in metal plating industry as they present the ability to plate adherent copper layers on less-noble metal substrates such as steel and zinc die castings. However, in the last few years, due to environmental controls and safety policies for operators, the plating industry has been interested in replacing the toxic cyanide copper strike baths with environmentally friendly baths. A broad bibliographic review showed that the published papers, referring to the new nontoxic copper strike baths, are patents, having little or no emphasis focused on electrodeposition mechanisms. Therefore, it was decided to study the copper electrodeposition mechanism from a strike alkaline bath prepared with one of the most nontoxic chelating agents cited in many patents which is the 1-hydroxyethane-1,1-diphosphonic acid, known as HEDP. This acid forms very stable water soluble complexes with Cu(2+) ions, thus cupric sulfate was used for preparing the plating bath. The results obtained through a cyclic voltammetry technique showed that Cu(2+) ion reduction to Cu from an HEDP electrodeposition bath occurs via a direct reduction reaction without a formation of Cu(+) intermediates. (C) 2010 Elsevier Ltd. All rights reserved.

Surface modification of bovine bone ash prepared by milling and acid washing process

Bovine bone ash is the main raw material for fabrication of bone china, a special kind of porcelain that has visual and mechanical advantages when compared to usual porcelains. The properties of bone china are highly dependent on the characteristics of the bone ash. However, despite a relatively common product, the science behind formulations and accepted fabrication procedures for bone china is not completely understood and deserves attention for future processing optimizations. In this paper, the influence of the preparation steps (firing, milling, and washing of the bones) on the physicochemical properties of bone ash particles was investigated. Bone powders heat-treated at temperatures varying from 700 to 1000 degrees C were washed and milled. The obtained materials were analyzed in terms of particle size distribution, chemical composition, density, specific surface area, FTIR spectroscopy, dynamic electrophoretic mobility, crystalline phases and scanning electron microscopy. The results indicated that bone ash does not significantly change in terms of chemistry and physical features at calcination temperatures above 700 degrees C. After washing in special conditions, one could only observe hydroxyapatite in the diffraction pattern. By FTIR it was observed that carbonate seems to be mainly concentrated on the surface of the powders. Since this compound can influence in the dispersion stability, and consequently in the quality of the final bone china product, and considering optimal washing parameters based on the dynamic electrophoretic mobility results, we describe a procedure for surface cleaning. (c) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Viroid species associated with the bark-cracking phenotype of `Tahiti` acid lime in the State of Sao Paulo, Brazil

Viroids have been used as ""graft transmissible dwarfing agents"" (GTDA) in several countries, mainly to reduce growth of citrus trees, thus increasing their density in orchards. In the State of Sao Paulo, Brazil, plants of the acid lime `Tahiti` are usually grafted with a complex of GTDA, presumably viroids. The aim of the present work was the identification and molecular characterization of the viroids infecting trees of acid lime `Tahiti` displaying ""Quebra galho"" (bark-cracking). Viroids were identified and characterized by biological indexing in `Etrog` citron, Northern-blot hybridization, RT-PCR, cloning and complete sequencing of the RNA genomes. Citrus exocortis viroid (CEVd), Hop stunt viroid (HSVd) and Citrus dwarfing viroid (CDVd) were found in different combinations. Although we have not been able to infer a direct relationship between the agronomical performance and symptom severity with the presence of a specific viroid or viroid combination, the differences in the severity of ""Quebra-galho"" symptoms among different trees is probably associated with the presence (or absence) of CEVd, with its interaction with other viroids perhaps determining the different phenotypes observed in the field.

Particle size and concentration of poly(epsilon-caprolactone) and adipate modified starch blend on mineralization in soils with differing textures

The objective of this study was to evaluate the effect of particle size and concentration of poly(F.-caprolactone) and adipate modified starch blend on mineralization in soils with differing textures, comparing it with polyethylene under the same experimental conditions. Two soil types were used: a Kandiudalfic Eutrudox with a clayey texture and an Arenic Hapludult with a sandy texture. The two different plastic specimens were incorporated in the form of plastic films with three increasing particle sizes and six doses, from 0 to 2.5 mg C g(-1) soil. Each plastic dose was incorporated into 200 g of soil placed in a hermetically closed jar at 28 degrees C, and incubated for a 120-day period to determine CO(2) evolution. Once again it was confirmed that polyethylene is almost non-biodegradable, in contrast to PCL/S, which can be defined as a biodegradable material. Soil texture affected the mineralization kinetics of the plastic specimens, with higher values for the clayey soil. No changes in soil microbial biomass-C or -N were observed by adding polyethylene and PCL/S to the soil. Also, no significant differences were observed on seed emergence and development of rice seedlings (Oryza sativa L.) in plastic modified soil. (C) 2009 Elsevier Ltd. All rights reserved.