Thermoplastic starch modified during melt processing with organic acids: The effect of molar mass on thermal and mechanical properties

Thermoplastic starch (TPS) was modified with ascorbic acid and citric acid by melt processing of native starch with glycerol as plasticizer in an intensive batch mixer at 160 degrees C. It was found that the molar mass decreases with acid content and processing time causing the reduction in melting temperature (T(m)). As observed by the results of X-ray diffraction and DSC measurements, crystallinity was not changed by the reaction with organic acids. T(m) depression with falling molar mass was interpreted on the basis of the effect of concentration of end-chain units, which act as diluents. FTIR did not show any appreciable change in starch chemical compositions, leading to the conclusion that the main changes observed were produced by the variation in molar mass of the material. We demonstrated that it is possible to decrease melt viscosity without the need for more plasticizer thus avoiding side-effects such as an increase in water affinity or relevant changes in the dynamic mechanical properties. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization, and bactericidal properties of composites based on crosslinked resins containing silver

Two different commercial crosslinked resins (Amberlite GT73 and Amberlite IRC748) were employed for anchoring silver. The -SH and -N(CH2COOH)2 groups, respectively, present on these resins were used for Ag+ chelation from an aqueous solution. The Ag+ ions were reduced with three different reductants: hydrazine, hydroxylamine, and formaldehyde (under an alkaline pH). The produced composites were characterized with thermogravimetry/differential thermogravimetry and scanning electron microscopy combined with a backscattered scanning electron detector. Energy-dispersive X-ray spectroscopy coupled to scanning electron microscopy allowed the observation of submicrometer particles of silver, and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites was determined toward 10(3)-10(7) cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain; the networks containing anchored submicrometer silver particles were completely bactericidal within a few minutes because of the combined action of silver and functional groups of the resins. (c) 2007 Wiley Periodicals, Inc.

Chemical interaction between EVA and Portland cement hydration at early-age

Ethylene/vinyl acetate (EVA) copolymer. as latex or redispersable powder, is added to mortars and concrete to improve the fracture toughness, impermeability and bond strength to various substrates. The physical and chemical interactions were already proved after one day of hydration but during the first hour just the physical interaction was identified and some evidences of a chemical interaction. The aim of this paper was to evaluate the chemical interaction between EVA and Portland cement during the first hours of hydration in the thermogravimetric analysis. The results confirmed that the EVA hydrolyses in pH alkaline and consumes calcium ions from the solution, forming an organic salt (calcium acetate). reducing the calcium hydroxide content. And, its interaction occurred in the first 15 min of hydration. (C) 2009 Elsevier Ltd. All rights reserved.

Material properties and nondestructive evaluation of laminated veneer lumber (LVL) made from Pinus oocarpa and P. kesiya

This study aimed at evaluating the mechanical, physical and biological properties of laminated veneer lumber (LVL) made from Pinus oocarpa Schiede ex Schltdl (PO) and Pinus kesiya Royle ex Gordon (PK) and at providing a nondestructive characterization thereof. Four PO and four PK LVL boards from 22 randomly selected 2-mm thickness veneers were produced according to the following characteristics: phenol-formaldehyde (190 g/m(2)), hot-pressing at 150A degrees C for 45 min and 2.8 N/mm(2) of specific pressure. After board production, nondestructive evaluation was conducted, and stress wave velocity (v (0)) and dynamic modulus of elasticity (E (Md) ) were determined. The following mechanical and physical properties were then evaluated: static bending modulus of elasticity (E (M) ), modulus of rupture (f (M) ), compression strength parallel to grain (f (c,0)), shear strength parallel to glue-line (f (v,0)), shear strength perpendicular to glue-line (f (v,90)), thickness swelling (TS), water absorption (WA), and permanent thickness swelling (PTS) for 2, 24, and 96-hour of water immersion. Biological property was also evaluated by measuring the weight loss by Trametes versicolor (Linnaeus ex Fries) Pilat (white-rot) and Gloeophyllum trabeum (Persoon ex Fries.) Murrill (brown-rot). After hot-pressing, no bubbles, delamination nor warping were observed for both species. In general, PK boards presented higher mechanical properties: E (M) , E (Md) , f (M) , f (c,0) whereas PO boards were dimensionally more stable, with lower values of WA, TS and PTS in the 2, 24, and 96-hour immersion periods. Board density, f (v,0), f (v,90) and rot weight loss were statistically equal for PO and PK LVL. The prediction of flexural properties of consolidated LVL by the nondestructive method used was not very efficient, and the fitted models presented lower predictability.

Evaluating responses of maize (Zea mays L.) to soil physical conditions using a boundary line approach

The functional relation between the decline in the rate of a physiological process and the magnitude of a stress related to soil physical conditions is an important tool for uses as diverse as assessment of the stress-related sensitivity of different plant cultivars and characterization of soil structure. Two of the most pervasive sources of stress are soil resistance to root penetration (SR) and matric potential (psi). However, the assessment of these sources of stress on physiological processes in different soils can be complicated by other sources of stress and by the strong relation between SR and psi in a soil. A multivariate boundary line approach was assessed as a means of reducing these cornplications. The effects of SR and psi stress conditions on plant responses were examined under growth chamber conditions. Maize plants (Zea mays L.) were grown in soils at different water contents and having different structures arising from variation in texture, organic carbon content and soil compaction. Measurements of carbon exchange (CE), leaf transpiration (ILT), plant transpiration (PT), leaf area (LA), leaf + shoot dry weight (LSDW), root total length (RTL), root surface area (RSA) and root dry weight (RDW) were determined after plants reached the 12-leaf stage. The LT, PT and LA were described as a function of SR and psi with a double S-shaped function using the multivariate boundary line approach. The CE and LSDW were described by the combination of an S-shaped function for SR and a linear function for psi. The root parameters were described by a single S-shaped function for SR. The sensitivity to SR and psi depended on the plant parameter. Values of PT, LA and LSDW were most sensitive to SR. Among those parameters exhibiting a significant response to psi, PT was most sensitive. The boundary line approach was found to be a useful tool to describe the functional relation between the decline in the rate of a physiological process and the magnitude of a stress related to soil physical conditions. (C) 2009 Elsevier B.V. All rights reserved.

Physical and sensory characterization of coffee produced in the topoclimatic conditions at Jesuitas, Parana State (Brazil)

Climatic variations influence formation and maturation of coffee grains by altering their intrinsic characteristics, which call allow for several types of coffee qualities, including the potential for production of special coffee. This study was carried out to verify the effect of environmental conditions and crop cultivation on chemical composition and their consequences in cup quality of coffees from region of Jesuitas, Parana State. During the same crop season this study was accomplished (2002-2003), cup quality was evaluated among the producers in several coffee-growing municipalities in Parana State. It was observed that 86% of samples were classified simply as ""soft"" (smooth flavor) or ""hard"" (bolder flavor), and 14% were classified as rioysh/rio (strong unpleasant taste). The results concluded that the practices adopted by producers, who have collaborated with the study, reflected positively oil the final cup quality, when compared to the overall quality results in the State. The climatic conditions and practices of crop management and harvest ill the Jesuitas region made for bolder coffee with low acidity, comparable to high quality coffees produced in Brazil and abroad.

Synergism between lipoxygenase-active soybean flour and ascorbic acid on rheological and sensory properties of wheat bread

BACKGROUND: The interaction between lipoxygenase-active soybean flour (LOX) and ascorbic acid (AA), on colour, rheological and sensory properties of wheat bread was studied with the aim of reducing the applied quantity of additives in bread formulations. RESULTS: The ascorbic acid (0-500 ppm) and active soybean flour (0-1%) mixture improved bread-crumb colour by lowering the yellow hue in a higher proportion than those expressed by the components alone, characterising a synergistic mechanism ((y) over cap (b) = 15.1- (1.7 x LOX) - (0.5 x AA) - (5.8 x LOX x AA), where : (y) over cap (b) represent the estimated value for the yellow hue parameter). No differences in flavour and porosity were seen between the samples. As supported by the instrumental methods, breads made with active soybean flour and ascorbic acid (LOX + AA) had whiter crumbs and were softer and springier than controls as assessed by a trained sensory panel. In summary, the combination of both active soybean flour and ascorbic acid showed synergism, promoting a greater bleaching effect than when used alone. CONCLUSION: These results suggest the potential use of active soybean flour as a synergistic ingredient in the substitution of artificial additives in bread making. Since the interaction on the bleaching response was not linear and active soybean flour showed a higher iron concentration (66.40 +/- 4.23 mu g g(-1)) than non-active soybean flour (52.30 +/- 0.40 mu g g(-1)), more studies are warranted to establish the biochemical mechanisms involved in this interaction. (c) 2007 Society of Chemical Industry.

Biochemical and biopharmaceutical properties of PEGylated uricase

PEGylation is a successful strategy for improving the biochemical and biopharmaceutical properties of proteins and peptides through the covalent attachment of polyethylene glycol chains. In this work, purified recombinant uricase from Candida sp. (UC-r) was modified by PEGylation with metoxypolyethilenoglycol-p-nitrophenyl-carbonate (mPEG-pNP) and metoxypolyethyleneglycol-4,6-dichloro-s-triazine (mPEG-CN). The UC-r-mPEG-pNP and UC-r-mPEG-CN conjugates retained 87% and 75% enzyme activity respectively. The K(M) values obtained 2.7 x 10(-5) M (mPEG-pNP) or 3.0 x 10(-5) M (mPEG-CN) lot the conjugates as compared to 5.4 x 10(-5) M for the native UC-r, suggesting enhancement in the substrate affinity of the enzyme attached. The effects of pH and temperature on PEGylated UC-r indicated that the conjugates were more active at close physiological pH and were stable up to 70 degrees C. Spectroscopic study performed by circular dichroism at 20 degrees C and 50 degrees C did not show any relevant difference in protein structure between native and PEGylated UC-r. In rabbit and Balb/c mice, the native UC-r elicited an intense immune response being highly immunogenic. On the other hand, the PEGylated UC-r when injected chronically in mice did not induce any detectable antibody response. This indicates sufficient reduction of the immunogenicity this enzyme by mPEG-pNP or mPEG-CN conjugation, making it suitable for a possible therapeutical use. (C) 2009 Elsevier B.V. All rights reserved.

Thermal Behavior, Microstructure, Polymorphism, and Crystallization Properties of Zero Trans Fats from Soybean Oil and Fully Hydrogenated Soybean Oil

Blends of soybean oil (SO) and fully hydrogenated soybean oil (FHSBO), with 10, 20, 30, 40, and 50% (w/w) FHSBO content were interesterified under the following conditions: 20 min reaction time, 0.4% sodium methoxide catalyst, and 500 rpm stirring speed, at 100 A degrees C. The original and interesterified blends were examined for triacylglycerol composition, thermal behavior, microstructure, crystallization kinetics, and polymorphism. Interesterification produced substantial rearrangement of the triacylglycerol species in all the blends, reduction of trisaturated triacylglycerol content and increase in monounsaturated-disaturated and diunsaturated-monosaturated triacylglycerols. Evaluation of thermal behavior parameters showed linear relations with FHSBO content in the original blends. Blend melting and crystallization thermograms were significantly modified by the randomization. Interesterification caused significant reductions in maximum crystal diameter in all blends, in addition to modifying crystal morphology. Characterization of crystallization kinetics revealed that crystal formation induction period (tau (SFC)) and maximum solid fat content (SFC(max)) were altered according to FHSBO content in the original blends and as a result of the random rearrangement. Changes in Avrami constant (k) and exponent (n) indicated, respectively, that-as compared with the original blends-interesterification decreased crystallization velocities and modified crystallization processes, altering crystalline morphology and nucleation mechanism. X-ray diffraction analyses revealed that interesterification altered crystalline polymorphism. The interesterified blends showed a predominance of the beta` polymorph, which is of more interest for food applications.

Retention of the Enzymatic Activity and Product Properties During Spray Drying of Pineapple Stem Extract in Presence of Maltodextrin

The aim of this work was to investigate the effects of drying parameters on the retention of the enzymatic activity and on the physical properties of spray-dried pineapple stem extract. A Box and Behnken experimental design was used to investigate the effects of the processing parameters on the product properties. The parameters studied were the inlet temperature of drying gas (Tgi), the feed flow rate of the pineapple extract relative to evaporative capacity of the system (Ws /Wmax), and the concentration of maltodextrin added to the extract (MD). Significant effects of the processing parameters on the retention of the proteolytic activity of the powdered extract were observed. High processing temperatures lead to a product with a smaller moisture content, particle size, and lower agglomerating tendency. A product with insignificant losses of the proteolytic activity ( 10%) and low moisture content (less than 6.5%) is obtained at selected conditions.

Dibucaine effects on structural and elastic properties of lipid bilayers

In this work we report the interaction effects of the local anesthetic dibucaine (DBC) with lipid patches in model membranes by Atomic Force Microscopy (AFM). Supported lipid bilayers (egg phosphatidylcholine, EPC and dimyristoylphosphatidylcholine, DMPQ were prepared by fusion of unilamellar vesicles on mica and imaged in aqueous media. The AFM images show irregularly distributed and sized EPC patches on mica. On the other hand DMPC formation presents extensive bilayer regions on top of which multibilayer patches are formed. In the presence of DBC we observed a progressive disruption of these patches, but for DMPC bilayers this process occurred more slowly than for EPC. In both cases, phase images show the formation of small structures on the bilayer surface suggesting an effect on the elastic properties of the bilayers when DBC is present. Dynamic surface tension and dilatational surface elasticity measurements of EPC and DMPC monolayers in the presence of DBC by the pendant drop technique were also performed, in order to elucidate these results. The curve of lipid monolayer elasticity versus DBC concentration, for both EPC and DMPC cases, shows a maximum for the surface elasticity modulus at the same concentration where we observed the disruption of the bilayer by AFM. Our results suggest that changes in the local curvature of the bilayer induced by DBC could explain the anesthetic action in membranes. (C) 2008 Elsevier B.V. All rights reserved.

Phenolics and Antioxidant Properties of Fruit Pulp and Cell Wall Fractions of Postharvest Banana (Musa acuminata Juss.) Cultivars

Banana fruits are important foods, but there have been very few studies evaluating the phenolics associated with their cell walls. In the present study, (+) catechin, gallocatechin, and (-) epicatechin, as well as condensed tannins, were detected in the soluble extract of the fruit pulp; neither soluble anthocyanidins nor anthocyanins were present. In the soluble cell wall fraction, two hydroxycinnamic acid derivatives were predominant, whereas in the insoluble cell wall fraction, the anthocyanidin delphinidin, which is reported in banana cell walls for the first time, was predominant. Cell wall fractions showed remarkable antioxidant capacity, especially after acid and enzymatic hydrolysis, which was correlated with the total phenolic content released after the hydrolysis of the water-insoluble polymer, but not for the posthydrolysis water-soluble polymer. The acid hydrolysis released various monosaccharides, whereas enzymatic hydrolysis released one peak of oligosaccharides. These results indicate that banana cell walls could be a suitable source of natural antioxidants and that they could be bioaccessible in the human gut.

Influence of BisGMA, TEGDMA, and BisEMA contents on viscosity, conversion, and flexural strength of experimental resins and composites

Different monomer structures lead to different physical and mechanical properties for both the monomers and the polymers. The objective of this study was to determine the influence of the bisphenylglycidyl dimethacrylate (BisGMA) concentration (33, 50 or 66 mol%) and the co-monomer content [triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol-A dimethacrylate (BisEMA), or both in equal parts] on viscosity (eta), degree of conversion (DC), and flexural strength (FS). eta was measured using a viscometer, DC was obtained by Fourier transfer Raman (FT-Raman) spectroscopy, and FS was determined by three-point bending. At 50 and 66% BisGMA, increases in eta were observed following the partial and total substitution of TEGDMA by BisEMA. For 33% BisGMA, eta increased significantly only when no TEGDMA was present. The DC was influenced by BisGMA content and co-monomer type. Mixtures containing 66% BisGMA showed a lower DC compared with mixtures containing other concentrations of BisGMA. The BisEMA mixtures had a lower DC compared with the TEGDMA mixtures. The FS was influenced by co-monomer content only. BisEMA mixtures presented a statistically lower FS, followed by TEGDMA + BisEMA mixtures, and then by TEGDMA mixtures. Partial or total replacement of TEGDMA by BisEMA increased eta, which was associated with the observed decreases in DC and FS. Although the BisGMA content influenced the DC, it did not affect the FS results.

Effects of Ethanol on the Surface and Bulk Properties of a Microwave-Processed PMMA Denture Base Resin

Purpose: This study evaluated the effect of different concentrations of ethanol on hardness, roughness, flexural strength, and color stability of a denture base material using a microwave-processed acrylic resin as a model system. Materials and Methods: Sixty circular (14 x 4 mm) and 60 rectangular microwave-polymerized acrylic resin specimens (65 x 10 x 3 mm(3)) were employed in this study. The sample was divided into six groups according to the ethanol concentrations used in the immersion solution, as follows: 0% (water), 4.5%, 10%, 19%, 42%, and 100%. The specimens remained immersed for 30 days at 37 degrees C. The hardness test was performed by a hardness tester equipped with a Vickers diamond penetrator, and a surface roughness tester was used to measure the surface roughness of the specimens. Flexural strength testing was carried out on a universal testing machine. Color alterations (Delta E) were measured by a portable spectrophotometer after 12 and 30 days. Variables were analyzed by ANOVA/Tukey`s test (alpha = 0.05). Results: For the range of ethanol-water solutions for immersion (water only, 4.5%, 10%, 19.5%, 42%, and 100%), the following results were obtained for hardness (13.9 +/- 2.0, 12.1 +/- 0.7, 12.9 +/- 0.9, 11.2 +/- 1.5, 5.7 +/- 0.3, 2.7 +/- 0.5 VHN), roughness (0.13 +/- 0.01, 0.15 +/- 0.07, 0.13 +/- 0.05, 0.13 +/- 0.02, 0.23 +/- 0.05, 0.41 +/- 0.19 mu m), flexural strength (90 +/- 12, 103 +/- 18, 107 +/- 16, 90 +/- 25, 86 +/- 22, 8 +/- 2 MPa), and color (0.8 +/- 0.6, 0.8 +/- 0.3, 0.7 +/- 0.4, 0.9 +/- 0.3, 1.3 +/- 0.3, 3.9 +/- 1.5 Delta E) after 30 days. Conclusions: The findings of this study showed that the ethanol concentrations of tested drinks affect the physical properties of the investigated acrylic resin. An obvious plasticizing effect was found, which could lead to a lower in vivo durability associated with alcohol consumption.