Development and Evaluation of a Novel pH Indicator Biodegradable Film Based on Cassava Starch

A pH indicator film based on cassava starch plasticized with sucrose and inverted sugar and incorporated with grape and spinach extracts as pH indicator sources (anthocyanin and chlorophyll) has been developed, and its packaging properties have been assessed. A second-order central composite design (2(2)) with three central points and four star points was used to evaluate the mechanical properties (tensile strength, tensile strength at break, and elongation at break percentage), moisture barrier, and microstructure of the films, and its potential as a pH indicator packaging. The films were prepared by the casting technique and conditioned under controlled conditions (75% relative humidity and 23 degrees C), at least 4 days before the analyses. The materials were exposed to different pH solutions (0, 2, 7, 10, and 14) and their color parameters (L*, a*, b*, and haze) were measured by transmittance. Grape and spinach extracts have affected the material characterization. Film properties (mechanical properties and moisture barrier) were strongly influenced by extract concentration presenting lower results than for the control. Films containing a higher concentration of grape extract presented a greater color change at different pH`s suggesting that anthocyanins are more effective as pH indicators than chlorophyll or the mixture of both extracts. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 1069-1079,2011

Genetic Algorithm for the Determination of Linear Viscoelastic Relaxation Spectrum from Experimental Data

Conventional procedures employed in the modeling of viscoelastic properties of polymer rely on the determination of the polymer`s discrete relaxation spectrum from experimentally obtained data. In the past decades, several analytical regression techniques have been proposed to determine an explicit equation which describes the measured spectra. With a diverse approach, the procedure herein introduced constitutes a simulation-based computational optimization technique based on non-deterministic search method arisen from the field of evolutionary computation. Instead of comparing numerical results, this purpose of this paper is to highlight some Subtle differences between both strategies and focus on what properties of the exploited technique emerge as new possibilities for the field, In oder to illustrate this, essayed cases show how the employed technique can outperform conventional approaches in terms of fitting quality. Moreover, in some instances, it produces equivalent results With much fewer fitting parameters, which is convenient for computational simulation applications. I-lie problem formulation and the rationale of the highlighted method are herein discussed and constitute the main intended contribution. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 122-135, 2009

Surface spin disorder in nickel ferrite nanomagnets studied by in-field Mossbauer spectroscopy

The magnetic structure of NiFe(2)O(4) nanoparticles has been investigated by means of Mossbauer spectra at T=4.2 K in applied fields up to 12 T. Four samples were studied, with mean particle diameters ranging from 4.3 to 8.9 nm. All spectra could be decomposed into three sextets, two corresponding to the ferrimagnetic sublattices of Fe ions in the spinel structure (core) and the third one to randomly frozen spins near the particle surface (shell). The shell thickness, calculated from the fraction of disordered spins, was found to be about one-third of the particle radius at H (app)=e0 and to decrease with the applied field toward a common limit of similar to 0.4 nm. The mean canting angle relative to the field was also found to decrease for increasing fields, at a rate inversely correlated to the particle size.

Enzyme immobilization on Ag nanoparticles/polyaniline nanocomposites

We show a simple strategy to obtain all efficient enzymatic broelectrochemical device, in which urease was immobilized oil electroactive nanostructured membranes (ENMs) made with polyaniline and silver nanoparticles (AgNP) stabilized in polyvinyl alcohol (PAni/PVA-AgNP). Fabrication of the modified electrodes comprised the chemical deposition of polyaniline followed by drop-coating of PVA-AgNP and urease, resulting in a final ITO/PAni/PVA-AgNP/urease electrode Configuration. For comparison. the electrochemical performance of ITO/PAni/urease electrodes (without Ag nanoparticles) was also studied. The performance of the modified electrodes toward Urea hydrolysis was investigated via amperometric measurements, revealing a fast increase in cathodic current with a well-defined peak upon addition of urea to the electrolytic solution. The cathodic currents for the ITO/PAni/PVA-AgNP urease electrodes were significantly higher than for the ITO/PAni/urease electrodes. The friendly environment provided by the ITO/PAni/PVA-AgNP electrode to the immobilized enzyme promoted efficient catalytic conversion of urea into ammonium and bicarbonate tons. Using the Michaelis-Menten kinetics equation, a K(M)(aPP) of 2.7 mmol L(-1) was obtained. indicating that the electrode architecture employed may be advantageous for fabrication of enzymatic devices with improved biocatalytic properties. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

A Morphological View of the Sodium 4,4 `-Distyrylbiphenyl Sulfonate Fluorescent Brightness Distribution on Regenerated Cellulose Fibers

Evidence of the sorption of the whitening agent sodium 4,4`-distyrylbiphenyl sulfonate in the presence of the anionic surfactant sodium dodecylsulfate or the cationic surfactant dodecyl trimethyl ammonium chloride on regenerated cellulose fibers is given by several microscopy techniques. Scanning electron microscopy provided images of the cylindrical fibers with dimensions of 3.5 cm (length) and 13.3 mu m (thickness), with empty cores of 1 mu m diameter and a smooth surface. Atomic force microscopy showed a fiber surface with disoriented nanometric domains using both tapping-mode height and phase image modes. Atomic force microscopy also showed that the whitening agent and surfactant molecules were sorbed onto the fiber surface, in agreement with the adsolubilization sorption model. Transmission electron microscopy showed fibers with nanometric parallel cylinders, surrounded by holes where the fluorescent whitening molecules accumulated. On the basis of these techniques, we conclude that the sorption process occurs preferentially on the fiber surface in contact with the water solution, and under saturated conditions, the whitening agent penetrates into the pores and are simultaneously sorbed on the pore walls bulk, forming molecular aggregates. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 2321-2327, 2010

Acetyl Radical Production by the Methylglyoxal-Peroxynitrite System: A Possible Route for L-Lysine Acetylation

Methylglyoxal is an a-oxoaldehyde putatively produced in excess from triose phosphates, aminoacetone, and acetone in some disorders, particularly in diabetes. Here, we investigate the nucleophilic addition of ONOO(-), known as a potent oxidant and nucleophile, to methylglyoxal, yielding an acetyl radical intermediate and ultimately formate and acetate ions. The rate of ONOO(-) decay in the presence of methylglyoxal [k(2,app) = (1.0 +/- 0.1) x 10(3) M(-1) s(-1); k(2) approximate to 1.0 x 10(5) M(-1) s(-1)] at pH 7.2 and 25 degrees C was found to be faster than that reported with monocarbonyl substrates (k(2) < 10(3) M(-1) diacetyl (k(2) = 1.0 x 10(4) M(-1) s(-1)), or CO(2) (k(2) = 3-6 x 10(4) M(-1) s(-1)). The pH profile of the methylglyoxal peroxynitrite reaction describes an ascendant curve with an inflection around pH 7.2, which roughly coincides with the pK(a) values of both ONOOH and H(2)PO(4)(-) ion. Electron paramagnetic resonance spin trapping experiments with 2-methyl-2-nitrosopropane revealed concentration-dependent formation of an adduct that can be attributed to 2-methyl-2-nitrosopropane-CH(3)CO(center dot) (a(N) = 0.83 mT). Spin trapping with 3,5-dibromo-4-nitrosobenzene sulfonate gave a signal that could be assigned to a methyl radical adduct [a(N) = 1.41 mT; a(H) = 1.35 mT; a(H(m)) = 0.08 mT]. The 2-methyl-2-nitrosopropane-CH(3)CO(center dot) adduct could also be observed by replacement of ONOO(-) with H(2)O(2), although at much lower yields. Acetyl radicals could be also trapped by added L-lysine as indicated by the presence of W-acetyl-L-lysine in the spent reaction mixture. This raises the hypothesis that ONOO(-)/H(2)O(2) in the presence of methylglyoxal is endowed with the potential to acetylate proteins in post-translational processes.

Coating of Cotton Yarn with Poly(vinyl alcohol) and Poly(N-vinyl-2-pyrrolidone) Crosslinked via Ultraviolet Radiation

The coating of cotton fiber is used in the textile industry to increase the mechanical resistance of the yarn and their resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study was to investigate the use of synthetic hydrophilic polymers, poly(vinyl alcohol) (PVA), and poly(N-vinyl-2-pyrrolidone) (PVP) to coat 100% cotton textile fiber, with the aim of giving the fiber temporary mechanical resistance. For the fixation of the polymer on the fiber, UV-C radiation was used as the crosslinking process. The influence of the crosslinking process was determined through tensile testing of the coated fibers. The results indicated that UV-C radiation increased the mechanical resistance of the yarn coated with PVP by up to 44% and the yarn coated with PVA by up to 67% compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. This study is of great relevance, and it is important to consider that UV-C radiation dispenses with the use of chemical substances and prevents the generation of toxic waste at the end of the process. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 2560-2567, 2011

Phenol-furfural resins to elaborate composites, reinforced with sisal fibers - Molecular analysis of resin and properties of composites

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by H-1, C-13, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI-Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural-phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high-diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. (c) 2008 Wiley Periodicals, Inc.

Derivatives of Biomacromolecules as Stabilizers of Aqueous Alumina Suspensions

The stabilization of alumina suspensions is key to the development of high-performance materials for the ceramic industry, which has motivated extensive research into synthetic polymers used as stabilizers. In this study, mimosa tannin extract and a chitosan derivative, that is, macromolecules obtained from renewable resources, are shown to be promising to replace synthetic polymers, yielding less viscous suspensions with smaller particles and greater fluidity, that is, more homogeneous suspensions that may lead to better-quality products. The functional groups of tannin present in mimosa extract and N,N,N-trimethylchitosan (TMC) are capable of establishing interactions with the alumina surface, thus leading to repulsion between the particles mainly due to steric and electrosteric mechanisms, respectively. The stabilization of the suspension induced by either TMC or mimosa tannin was confirmed by a considerable decrease in viscosity and average particle size, in comparison with alumina suspensions without stabilizing agents. The viscosity/average particle size decreased by 49/84% and 52/87% for suspensions with TMC and mimosa tannin, respectively. In addition, the increase in the absolute zeta potential upon addition of either TMC or mimosa tannin extract, especially at high pHs, points to an increased stability of the suspension. The feasibility of using derivatives of macromolecules from renewable sources to stabilize aqueous alumina suspensions was therefore demonstrated. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 58-66, 2010

Sisal Fibers Treated with NaOH and Benzophenonetetracarboxylic Dianhydride as Reinforcement of Phenolic Matrix

In this work, composites based on a phenolic matrix and untreated- and treated sisal fibers were prepared. The treated sisal fibers used were those reacted with NaOH 2% solution and esterified using benzophenonetetracarboxylic dianhydride (BTDA). These treated fibers were modified with the objective of improving the adhesion of the fiber-matrix interface, which in turn influences the properties of the composites. BTDA was chosen as the esterifying agent to take advantage of the possibility of introducing; the polar and aromatic groups that are also present in the matrix structure into the surface of the fiber, which could then intensify the interactions occurring in the fiber-matrix interface. The fibers were then analyzed by SEM and FTIR to ascertain their chemical composition. The results showed that the fibers had been successfully modified. The composites (reinforced with 15%, w/w of 3.0 cm length sisal fiber randomly distributed) were characterized by SEM, impact strength, and water absorption capacity. In the tests conducted, the response of the composites was affected both by properties of the matrix and the fibers, besides the interfacial properties of the fiber-matrix. Overall, the results showed that the fiber treatment resulted in a composite that was less hygroscopic although with somewhat lower impact strength, when compared with the composite reinforced with untreated sisal fibers. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 269-276, 2010

Evaluation of the light polymerization efficiency of copolymers used in dental formulations by differential scanning calorimetry

Different compositions of visible-light-curable triethylene glycol dimethacrylate/bisglycidyl methacrylate copolymers used in dental resin formulations were prepared through copolymerization photoinitiated by a camphorquinone/ethyl 4-dimethylaminobenzoate system irradiated with an Ultrablue IS light-emitting diode. The obtained copolymers were evaluated with differential scanning calorimetry. From the data for the heat of polymerization, before and after light exposure, obtained from exothermic differential scanning calorimetry curves, the light polymerization efficiency or degree of conversion of double bonds was calculated. The glass-transition temperature also was determined before and after photopolymerization. After the photopolymerization, the glass-transi-tion temperature was not well defined because of the breadth of the transition region associated with the properties of the photocured dimethacrylate. The glass-transition temperature after photopolymerization was determined experimentally and compared with the values determined with the Fox equation. In all mixtures, the experimental value was lower than the calculated value. Scanning electron microscopy was used to analyze the morphological differences in the prepared copolymer structures. (C) 2007 Wiley Periodicals, Inc.

Expression, purification and kinetic characterization of His-tagged glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi

Trypanosomes are flagellated protozoa responsible for serious parasitic diseases that have been classified by the World Health Organization as tropical sicknesses of major importance. One important drug target receiving considerable attention is the enzyme glyceraldehyde-3-phosphate dehydrogenase from the protozoan parasite Trypanosoma cruzi, the causative agent of Chagas disease (T. cruzi Glyceraldehyde-3-phosphate dehydrogenase (TcGAPDH); EC 1.2.1.12). TcGAPDH is a key enzyme in the glycolytic pathway of T. cruzi and catalyzes the oxidative phosphorylation of D-glyceraldehyde-3-phosphate (G3P) to 1,3-bisphosphoglycerate (1,3-BPG) coupled to the reduction of oxidized nicotinamide adenine dinucleotide, (NAD(+)) to NADH, the reduced form. Herein, we describe the cloning of the T. cruzi gene for TcGAPDH into the pET-28a(+) vector, its expression as a tagged protein in Escherichia coli, purification and kinetic characterization. The His(6)-tagged TcGAPDH was purified by affinity chromatography. Enzyme activity assays for the recombinant His(6)-TcGAPDH were carried out spectrophotometrically to determine the kinetic parameters. The apparent Michaelis-Menten constant (K(M)(app)) determined for D-glyceraldehyde-3-phosphate and NAD(+) were 352 +/- 21 and 272 +/- 25 mu M, respectively, which were consistent with the values for the untagged enzyme reported in the literature. We have demonstrated by the use of Isothermal Titration Calorimetry (ITC) that this vector modification resulted in activity preserved for a higher period. We also report here the use of response surface methodology (RSM) to determine the region of optimal conditions for enzyme activity. A quadratic model was developed by RSM to describe the enzyme activity in terms of pH and temperature as independent variables. According to the RMS contour plots and variance analysis, the maximum enzyme activity was at 29.1 degrees C and pH 8.6. Above 37 degrees C, the enzyme activity starts to fall, which may be related to previous reports that the quaternary structure begins a process of disassembly. (C) 2010 Elsevier Inc. All rights reserved.

Novel insights for dihydroorotate dehydrogenase class 1A inhibitors discovery

The enzyme dihydroorotate dehydrogenase (DHODH) has been suggested as a promising target for the design of trypanocidal agents. We report here the discovery of novel inhibitors of Trypanosoma cruzi DHODH identified by a combination of virtual screening and ITC methods. Monitoring of the enzymatic reaction in the presence of selected ligands together with structural information obtained from X-ray crystallography analysis have allowed the identification and validation of a novel site of interaction (S2 site). This has provided important structural insights for the rational design of T cruzi and Leishmania major DHODH inhibitors. The most potent compound (1) in the investigated series inhibits TcDHODH enzyme with K(i)(app) value of 19.28 mu M and possesses a ligand efficiency of 0.54 kcal mol(-1) per non-H atom. The compounds described in this work are promising hits for further development. (C) 2010 Elsevier Masson SAS. All rights reserved.

Characterization of Polyurethane Resins by FTIR, TGA, and XRD

Fourier Transformed Infrared Spectroscopy, Thermogravimetric Analysis, and X-ray Diffractometry have been used to investigate the rigid, semi rigid, and soft polyurethane (PU) forms, which were developed by the Group of Analytic Chemistry and Technology of Polymers - USF - Sao Carlos. The -NCO/-OH ratios were 0.6, 0.5, and 0.3% for rigid, semi rigid, and soft PUs, respectively, showing that different ratios cause differences in thermal behaviors and crystalline structures of the synthesized PU resins. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 263-268, 2010

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009