Linoleic acid peroxidation initiated by Fe(3+)-reducing compounds recovered from Eucalyptus grandis biotreated with Ceriporiopsis subvermispora

This work work evaluates linoleic acid peroxidation reactions initiated by Fe(3+)-reducing compounds recovered from Eucalyptus grandis, biotreated with the biopulping fungus Ceriporiopsis subvermispora. The aqueous extracts from biotreated wood had the ability to reduce Fe(3+) ions from freshly prepared solutions. The compounds responsible for the Fe(3+)-reducing activity corresponded to UV-absorbing substances with apparent molar masses from 3 kDa to 5 kDa. Linoleic acid peroxidation reactions conducted in the presence of Fe(3+) ions and the Fe(3+)-reducing compounds showed that the rate of O(2) consumption during peroxidation was proportional to the Fe(3+)-reducing activity present in each extract obtained from biotreated wood. This peroxidation reaction was coupled with in-vitro treatment of ball-milled E. grandis wood. Ultraviolet data showed that the reaction system released lignin fragments from the milled wood. Size exclusion chromatography data indicated that the solubilized material contained a minor fraction representing high-molar-mass molecules excluded by the column and a main low-molar-mass peak. Overall evaluation of the data suggested that the Fe(3+)-reducing compounds formed during wood biodegradation by C subvermispora can mediate lignin degradation through linoleic acid peroxidation. (C) 2010 Elsevier Ltd. All rights reserved.

The roles of xylan and lignin in oxalic acid pretreated corncob during separate enzymatic hydrolysis and ethanol fermentation

High yields of hemicellulosic and cellulosic sugars are critical in obtaining economical conversion of agricultural residues to ethanol. To optimize pretreatment conditions, we evaluated oxalic acid loading rates, treatment temperatures and times in a 2(3) full factorial design. Response-surface analysis revealed an optimal oxalic acid pretreatment condition to release sugar from the cob of Zea mays L ssp. and for Pichia stipitis CBS 6054. To ferment the residual cellulosic sugars to ethanol following enzymatic hydrolysis, highest saccharification and fermentation yields were obtained following pretreatment at 180 degrees C for 50 min with 0.024 g oxalic acid/g substrate. Under these conditions, only 7.5% hemicellulose remained in the pretreated substrate. The rate of cellulose degradation was significantly less than that of hemicellulose and its hydrolysis was not as extensive. Subsequent enzymatic saccharification of the residual cellulose was strongly affected by the pretreatment condition with cellulose hydrolysis ranging between 26.0% and 76.2%. The residual xylan/lignin ratio ranged from 0.31 to 1.85 depending on the pretreatment condition. Fermentable sugar and ethanol were maximal at the lowest ratio of xylan/lignin and at high glucan contents. The model predicts optimal condition of oxalic acid pretreatment at 168 degrees C, 74 min and 0.027 g/g of oxalic acid. From these findings, we surmised that low residual xylan was critical in obtaining maximal glucose yields from saccharification. Published by Elsevier Ltd.

Linoleic acid peroxidation and lignin degradation by enzymes produced by Ceriporiopsis subvermispora grown on wood or in submerged liquid cultures

Ceriporiopsis subvermispora is a white-rot fungus used in biopulping processes and seems to use the fatty acid peroxidation reactions initiated by manganese-peroxidase (MnP) to start lignin degradation. The present work shows that C. subvermispora was able to peroxidize unsaturated fatty acids during wood biotreatment under biopulping conditions. In vitro assays showed that the extent of linoleic acid peroxidation was positively correlated with the level of MnP recovered from the biotreated wood chips. Milled wood was treated in vitro by partially purified MnP and linoleic acid. UV spectroscopy and size exclusion chromatography (SEC) showed that soluble compounds similar to lignin were released from the milled wood. SEC data showed a broad elution profile compatible with low molar mass lignin fractions. MnP-treated milled wood was analyzed by thioacidolysis. The yield of thioacidolysis monomers recovered from guaiacyl and syringyl units decreased by 33% and 20% in MnP-treated milled wood, respectively. This has suggested that lignin depolymerization reactions have occurred during the MnP/linoleic acid treatment. (C) 2009 Elsevier Inc. All rights reserved.

A study on the pretreatment of a sugarcane bagasse sample with dilute sulfuric acid

Experiments based on a 2(3) central composite full factorial design were carried out in 200-ml stainless-steel containers to study the pretreatment, with dilute sulfuric acid, of a sugarcane bagasse sample obtained from a local sugar-alcohol mill. The independent variables selected for study were temperature, varied from 112.5A degrees C to 157.5A degrees C, residence time, varied from 5.0 to 35.0 min, and sulfuric acid concentration, varied from 0.0% to 3.0% (w/v). Bagasse loading of 15% (w/w) was used in all experiments. Statistical analysis of the experimental results showed that all three independent variables significantly influenced the response variables, namely the bagasse solubilization, efficiency of xylose recovery in the hemicellulosic hydrolysate, efficiency of cellulose enzymatic saccharification, and percentages of cellulose, hemicellulose, and lignin in the pretreated solids. Temperature was the factor that influenced the response variables the most, followed by acid concentration and residence time, in that order. Although harsher pretreatment conditions promoted almost complete removal of the hemicellulosic fraction, the amount of xylose recovered in the hemicellulosic hydrolysate did not exceed 61.8% of the maximum theoretical value. Cellulose enzymatic saccharification was favored by more efficient removal of hemicellulose during the pretreatment. However, detoxification of the hemicellulosic hydrolysate was necessary for better bioconversion of the sugars to ethanol.

Scale-up of diluted sulfuric acid hydrolysis for producing sugarcane bagasse hemicellulosic hydrolysate (SBHH)

Sugarcane bagasse was pretreated with diluted sulfuric acid to obtain sugarcane bagasse hemicellulosic hydrolysate (SBHH). Experiments were conducted in laboratory and semi-pilot reactors to optimize the xylose recovery and to reduce the generation of sugar degradation products, as furfural and 5-hydroxy-methylfurfural (HMF). The hydrolysis scale-up procedure was based on the H-Factor, that combines temperature and residence time and employs the Arrhenius equation to model the sulfuric acid concentration (100 mg(acid)/g(dm)) and activation energy (109 kJ/mol). This procedure allowed the mathematical estimation of the results through simulation of the conditions prevailing in the reactors with different designs. The SBHH obtained from different reactors but under the same H-Factor of 5.45 +/- 0.15 reached similar xylose yield (approximately 74%) and low concentration of sugar degradation products, as furfural (0.082 g/L) and HMF (0.0071 g/L). Also, the highest lignin degradation products (phenolic compounds) were rho-coumarilic acid (0.15 g/L) followed by ferulic acid (0.12 g/L) and gallic acid (0.035 g/L). The highest concentration of ions referred to S (3433.6 mg/L), Fe (554.4 mg/L), K (103.9 mg/L), The H-Factor could be used without dramatically altering the xylose and HMF/furfural levels. Therefore, we could assume that H-Factor was directly useful in the scale-up of the hemicellulosic hydrolysate production. (C) 2009 Published by Elsevier Ltd.

Simultaneous saccharification and ethanol fermentation of oxalic acid pretreated corncob assessed with response surface methodology

Response surface methodology was used to evaluate optimal time, temperature and oxalic acid concentration for simultaneous saccharification and fermentation (SSF) of corncob particles by Pichia stipitis CBS 6054. Fifteen different conditions for pretreatment were examined in a 2(3) full factorial design with six axial points. Temperatures ranged from 132 to 180 degrees C, time from 10 to 90 min and oxalic acid loadings from 0.01 to 0.038 g/g solids. Separate maxima were found for enzymatic saccharification and hemicellulose fermentation, respectively, with the condition for maximum saccharification being significantly more severe. Ethanol production was affected by reaction temperature more than by oxalic acid and reaction time over the ranges examined. The effect of reaction temperature was significant at a 95% confidence level in its effect on ethanol production. Oxalic acid and reaction time were statistically significant at the 90% level. The highest ethanol concentration (20 g/l) was obtained after 48 h with an ethanol volumetric production rate of 0.42 g ethanol l(-1) h(-1). The ethanol yield after SSF with P. stipitis was significantly higher than predicted by sequential saccharification and fermentation of substrate pretreated under the same condition. This was attributed to the secretion of beta-glucosidase by P. stipitis. During SSF, free extracellular beta-glucosidase activity was 1.30 pNPG U/g with P. stipitis, while saccharification without the yeast was 0.66 pNPG U/g. Published by Elsevier Ltd.

Effect of pH and oxalic acid on the reduction of Fe(3+) by a biomimetic chelator and on Fe(3+) desorption/adsorption onto wood: Implications for brown-rot decay

Fenton reaction is thought to play an important role in wood degradation by brown-rot fungi. In this context, the effect of oxalic acid and pH on iron reduction by a biomimetic fungal chelator and on the adsorption/desorption of iron to/from wood was investigated. The results presented in this work indicate that at pH 2.0 and 4.5 and in the presence of oxalic acid, the phenolate chelator 2,3-dihydroxybenzoic acid (2,3-DHBA) is capable of reducing ferric iron only when the iron is complexed with oxalate to form Fe mono-oxalate (Fe(C(2)O(4))(+)). Within the pH range tested in this work, this complex formation occurs when the oxalate:Fe(3+) molar ratio is less than 20 (pH 2.0) or less than 10 (pH 4.5). When aqueous ferric iron was passed through a column packed with milled red spruce (Picea rubens) wood equilibrated at pH 2.0 and 4.5. it was observed that ferric iron binds to wood at pH 4.5 but not at pH 2.0, and the bound iron could then be released by application of oxalic acid at pH 4.5. The release of bound iron was dependent on the amount of oxalic acid applied in the column. When the amount of oxalate was at least 20-fold greater than the amount of iron bound to the wood, all bound iron was released. When Fe-oxalate complexes were applied to the milled wood column equilibrated in the pH range of 2-4.5, iron from Fe-oxalate complexes was bound to the wood only when the pH was 3.6 or higher and the oxalate:Fe(3+) molar ratio was less than 10. When 2,3-DHBA was evaluated for its ability to release iron bound to the milled wood, it was found that 2,3-DHBA possessed a greater affinity for ferric iron than the wood as 2,3-DHBA was capable of releasing the ferric iron bound to the wood in the pH range 3.6-5.5. These results further the understanding of the mechanisms employed by brown-rot fungi in wood biodegradation processes. (C) 2009 Elsevier Ltd. All rights reserved.

Characterization of commercial cellulases and their use in the saccharification of a sugarcane bagasse sample pretreated with dilute sulfuric acid

This study aimed to correlate the efficiency of enzymatic hydrolysis of the cellulose contained in a sugarcane bagasse sample pretreated with dilute H(2)SO(4) with the levels of independent variables such as initial content of solids and loadings of enzymes and surfactant (Tween 20), for two cellulolytic commercial preparations. The preparations, designated cellulase I and cellulase II, were characterized regarding the activities of total cellulases, endoglucanase, cellobiohydrolase, cellobiase, beta-glucosidase, xylanase, and phenoloxidases (laccase, manganese and lignin peroxidases), as well as protein contents. Both extracts showed complete cellulolytic complexes and considerable activities of xylanases, without activities of phenoloxidases. For the enzymatic hydrolyses, two 2(3) central composite full factorial designs were employed to evaluate the effects caused by the initial content of solids (1.19-4.81%, w/w) and loadings of enzymes (1.9-38.1 FPU/g bagasse) and Tween 20 (0.0-0.1 g/g bagasse) on the cellulose digestibility. Within 24 h of enzymatic hydrolysis, all three independent variables influenced the conversion of cellulose by cellulase I. Using cellulase II, only enzyme and surfactant loadings showed significant effects on cellulose conversion. An additional experiment demonstrated the possibility of increasing the initial content of solids to values much higher than 4.81% (w/w) without compromising the efficiency of cellulose conversion, consequently improving the glucose concentration in the hydrolysate.

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.

Compatible Ternary Blends of Chitosan/poly(vinyl alcohol)/poly(lactic acid) Produced by Oil-in-Water Emulsion Processing

Ternary compatible blends of chitosan, poly(vinyl alcohol), and poly(lactic acid) were prepared by an oil-in-water (O/W) emulsion process. Solutions of chitosan in aqueous acetic acid, poly(vinyl alcohol) (PVA) in water, and poly(lactic acid) (PLA) in chloroform were blended with a high shear mixer. PVA was used as an emulsifier to stabilize the emulsion and to reduce the interfacial tension between the solid polymers in the blends-produced. It proved to work very well because the emulsions were stable for periods of days or weeks and compatible blends were obtained When PVA was added. This effect was attributed to a synergistic effect of PVA and chitosan because the binary blends PVA/PLA and chitosan/PLA were completely incompatible; The blends were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), stress strain tests, and Fourier transform infrared spectroscopy (FTIR). The results indicated that despite the fact that the system contained distinct phases some degree of molecular miscibility occurred when the three components were present in the blend.

Controlling the luminescence properties of poly(p-phenylene vinylene) entrapped in Langmuir and Langmuir-Blodgett films of stearic acid

Properties of hybrid films can be enhanced if their molecular architecture is controlled. In this paper, poly (p-phenylene vinylene) was mixed with stearic acid in order to form stable hybrid Langmuir monolayers. Surface properties of these films were investigated with measurements of surface pressure, and also with polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The films were transferred from the air-water interface to solid supports through the Langmuir-Blodgett technique, and the viability of the film as optical device was investigated with fluorescence spectroscopy. Comparing the fluorescent spectra for the polymer in solution, as a casting film, and as an LB film, the emission bands for LB films were narrower and appeared at lower wavelengths. The interactions between the film components and the design for the LB film may take advantage of the method to immobilize luminescent polymers in mixed ultrathin films adsorbed in solid matrices. (C) 2011 Elsevier B.V. All rights reserved.

Polyethylene/(organo-montmorillonite) composites modified with ethylene/ methacrylic acid copolymer: Morphology and mechanical properties

Several composites based on high-density polyethylene (PE), organically modified montmorillonite (OMMT) and ethylene/methacrylic acid copolymer (EMAA) were prepared by melt compounding. Three Na(+)-montmorillonites (MMT) of different precedence were modified with hexadecyl trimethyl ammonium chloride in order to change their nature from hydrophilic to organophilic. The composites morphology was examined by XRD, SEM and TEM. Mechanical properties were evaluated under static conditions. A slight reinforcement was achieved only when OMMT was added to PE. When EMAA was added to the composites, it negatively interacted with OMMT, diminishing the interlayer distance of OMMT, changing the composite morphology, as if OMMT was not present in composites, and deteriorating their mechanical properties. (C) 2008 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.

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.