The effect of the degree of hydrolysis of the PVA and the plasticizer concentration on the color, opacity, and thermal and mechanical properties of films based on PVA and gelatin blends

The objective of this work was to study the color, opacity, crystallinity, and the thermal and mechanical properties of films based on blends of gelatin and five different types of PVA [poly(vinyl alcohol)], with and without a plasticizer. The effect of the degree of hydrolysis of the PVA and the glycerol concentration on these properties was studied using colorimetry, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile mechanical tests. All films were essentially colorless (Delta E* < 5) and with low opacity ( Y <= 2.1). The DSC results were typical of partially crystalline materials, showing some phase separation characterized by a glass transition (T(g) = 40-55 degrees C), related to the amorphous part of the material, followed by two endothermic peaks related to the melting (T(m) = 100-160 and 170-210 degrees C) of the crystallites. The XRD results confirmed the crystallinity of the films. The film produced with PVA Celvol((R)) 418 (DH = 91.8%) showed the highest tensile resistance (tensile strength = 38 MPa), for films without plasticizer. However, with glycerol, the above-mentioned PVA and the PVA Celvol((R)) 504 produced the least resistant films of all the PVA types. But, although the mechanical properties of the blended films depended on the type of PVA used, there was no direct relationship between these properties and the degree of hydrolysis of the PVA. The properties studied were more closely dependent on the glycerol concentration. Finally, the mechanical resistance of the films presented a linear relationship with the glass transition temperature of the films. (c) 2007 Elsevier Ltd. All rights reserved.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Oral health in transition: the case of Indigenous peoples from Brazil

The objective of this paper is to summarise epidemiological information about the distribution of dental caries among Indigenous peoples in Brazil. The authors also present a case study of a specific group of Xavante Indians, one of the most numerous of Brazil`s Indigenous peoples, describing how their oral health has deteriorated over recent decades, and showing how an oral health programme is attempting to reverse the present trend of increase in caries. The programme at Etenheritipa Xavante village incorporated three principal components: educational, preventive, and clinical. From the beginning, the programme included epidemiological record keeping for monitoring the level of caries in the population. Transversal studies of the condition of oral health among the Xavante of Etenheritipa were undertaken in 1999, 2004, and 2007. In the period from 2004 to 2007 the DMFS values in the 11-15 age cohort had a significant reduction in caries experience. The mean DMFS score fell from 4.95 in 2004 to 2.39 in 2007 (p<0.01). An increase in the percent of individuals who were free from caries was also noted: in 1999, 20% of adolescents 11-15 had no caries; in 2007, the proportion had risen to 47%. The Xavante case is a prime example of the transition in oral health that is taking place among the Indigenous peoples of the Americas, and it highlights the importance of oral health promotion through preventive measures such as access to fluoridation and basic care in reducing the inequality between Indians and non-Indians.

Microcapsules of a Casein Hydrolysate: Production, Characterization, and Application in Protein Bars

The aim of this work was to encapsulate a casein hydrolysate by spray drying using maltodextrins (DE 10 and 20) as wall materials and to evaluate the efficiency of the microencapsulation in attenuating the bitter taste of the hydrolysate using protein bars as the model system. Microcapsules were evaluated for morphology (SEM), particle size, hygroscopicity, solubility, thermal behavior (DSC), and bitter taste with a trained sensory panel by a paired comparison test (nonencapsulated samples vs. encapsulated samples). Bars were prepared with the addition of 3% casein hydrolysate at free or both encapsulated forms, and were then evaluated for their moisture, water activity (a(w)) and for their bitter taste by a ranking test. Microcapsules were of the matrix type, having continuous surfaces with no apparent porosity for both coatings. Both encapsulated casein hydrolysates had similar hygroscopicity, and lower values than free encapsulated hydrolysates. The degree of hydrolysis of the maltodextrin influenced only the particle size and T(g). The sensory panel considered the protein bars produced with both encapsulated materials less bitter (p < 0.05) than those produced with the free casein hydrolysates. Microencapsulation by spray drying with maltodextrin DE 10 and 20 was successful to attenuate the bitter taste and the hygroscopicity of casein hydrolysates.

Biodegradable Films Based on Blends of Gelatin and Poly (Vinyl Alcohol): Effect of PVA Type or Concentration on Some Physical Properties of Films

The aim of this work was to develop biodegradable films based on blends of gelatin and poly (vinyl alcohol) (PVA), without a plasticizer. Firstly, the effect of five types of PVA with different degree of hydrolysis (DH) on the physical properties of films elaborated with blends containing 23.1% PVA was studied. One PVA type was then chosen for the study of the effect of the PVA concentration on the mechanical properties, color, opacity, gloss, and water solubility of the films. The five types of PVA studied allowed for films with different characteristics, but with no direct relationship with the DH of the PVA. Therefore, the PVA Celvol (R) 418 with a DH = 91.8% was chosen for the second part, because they produced films with greater tensile strength. The PVA concentration affected all studied properties of films. These results could be explained by the results of the DSC and FTIR analyses, which showed that some interactions between the gelatin and the PVA occurred depending on the PVA concentration, affecting the crystallinity of the films.

Segregation effects according to the evolutionary stage of galaxy groups

We study segregation phenomena in 57 groups selected from the 2dF Percolation-Inferred Galaxy Groups (2PIGG) catalogue of galaxy groups. The sample corresponds to those systems located in areas of at least 80 per cent redshift coverage out to 10 times the radius of the groups. The dynamical state of the galaxy systems was determined after studying their velocity distributions. We have used the Anderson-Darling test to distinguish relaxed and non-relaxed systems. This analysis indicates that 84 per cent of groups have galaxy velocities consistent with the normal distribution, while 16 per cent of them have more complex underlying distributions. Properties of the member galaxies are investigated taking into account this classification. Our results indicate that galaxies in Gaussian groups are significantly more evolved than galaxies in non-relaxed systems out to distances of similar to 4R(200), presenting significantly redder (B - R) colours. We also find evidence that galaxies with M(R) <= -21.5 in Gaussian groups are closer to the condition of energy equipartition.

Foliar cuticular alkanes of Camarea (Malpighiaceae) and their taxonomic significance

Camarea is a South-American endemic genus comprising eight species. In the present work n-alkanes from foliar cuticular waxes of 23 specimens, representing seven species of Camarea were analyzed, aiming at establishing interspecific affinities and evaluating the usefulness of n-alkane distribution as species characteristic. The sampling included also specimens of Peixotoa rericulata and Janusia guaronitica (both Malpighiaceae). The results were used to obtain a phenogram indicating chemical affinities between species. The results are in agreement with morphological similarities among some Camarea species. Intraspecific variability was small, suggesting that n-alkane distribution may be useful for species characterization and establishment of links among Camarea species. The results support the recognition of Camarea triphylla as a synonym of Camarea axillaris and are not coherent with a hybrid condition of a population exhibiting morphological characteristics combining Camarea affinis and Camarea hirsuta, suggesting instead that the individuals analyzed belong either to Camarea hirsuta or a close species. Distribution of n-alkanes is inadequate to distinguish among Malpighiaceae genera: P reticulata has n-alkane distribution similar to several Cumarea species. (C) 2008 Elsevier Ltd. All rights reserved.

Evidence that L-glutamine is better than L-alanine as gluconeogenic substrate in perfused liver of weaned fasted rats submitted to short-term insulin-induced hypoglycaemia

Gluconeogenesis in livers from overnight fasted weaned rats submitted to short-term insulin-induced hypoglycaemia (IIH) was investigated. For this purpose, a condition of hyperinsulinemia/hypoglycaemia was obtained with an intraperitoneal (ip) injection of regular insulin (1.0 U kg(-1)). Control group (COG group) received ip saline. The studies were performed 30 min after insulin (IIH group) or saline (COG group) injection. The livers from IIH and COG rats were perfused with L-alanine (5 mM), L-lactate (2 mM)), L-glutamine (10 mM) or glycerol (2 mM). Hepatic glucose, L-lactate and pyruvate production from L-alanine was not affected by IIH. In agreement with this result, the hepatic ability in producing glucose from L-lactate or glycerol remained unchanged (IIH group vs. COG group). However, livers from IIH rats showed higher glucose production from L-glutamine than livers front COG rats and, in the IIH rats, the production of glucose from L-glutamine was higher than that front L-alanine. The higher glucose production in livers from the IIH group. when compared with the COG group was due to its entrance further on gluconeogenic pathway. Taken together. the results suggest that L-glutamine is better than L-alanine, as gluconeogenic substrate in livers of hypoglyceaemic weaned rats. Copyright (C) 2008 John Wiley & Sons. Ltd.

Direct Observation of Tetragonal Distortion in Epitaxial Structures through Secondary Peak Split in a Synchrotron Radiation Renninger Scan

This paper reports a direct observation of an interesting split of the (022)(022) four-beam secondary peak into two (022) and (022) three-beam peaks, in a synchrotron radiation Renninger scan (phi-scan), as an evidence of the layer tetragonal distortion in two InGaP/GaAs (001) epitaxial structures with different thicknesses. The thickness, composition, (a perpendicular to) perpendicular lattice parameter, and (01) in-plane lattice parameter of the two epitaxial ternary layers were obtained from rocking curves (omega-scan) as well as from the simulation of the (022)(022) split, and then, it allowed for the determination of the perpendicular and parallel (in-plane) strains. Furthermore, (022)(022) omega:phi mappings were measured in order to exhibit the multiple diffraction condition of this four-beam case with their split measurement.

Borel-Leroy summability of a nonpolynomial potential

We investigate the perturbation series for the spectrum of a class of Schrodinger operators with potential V = 1/2 x(2) + g(m-1)x(2m)/(1 + alpha gx(2)) which generalize particular cases investigated in the literature in connection with models in laser theory and quantum field theory of particles and fields. It is proved that the series obey a modified strong asymptotic condition of order (m - 1) and have an order (m - 1) strong asymptotic series in g which are shown to be summable in the sense of Borel-Leroy method.

Surface modification and crystallization of the BaO-B2O3-SiO2 glassy system using CO2 laser irradiation

The surface modification and crystallization process of BaO-B2O3-SiO2 glass compositions when exposed to CO2 laser irradiation was evaluated as a function of the laser power, irradiation time and surface condition. The glass surface was modified by the application of laser power exceeding 0.40 W and an irradiation time of more than 300 s. Micro-Raman and X-ray diffraction measurements revealed at high laser power the formation of beta-BaB2O4 (beta-BBO) crystalline phase. The crystallization of the irradiated region was enhanced when beta-BBO micrometer sized particles were dispersed on the surface of the glass sample. The intensity of the second harmonic generation observed in the crystallized region was found to depend mainly on the condition of the glassy surface prior to glass irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Subsite substrate specificity of midgut insect chymotrypsins

Insect chymotrypsins are distinctively sensitive to plant protein inhibitors, suggesting that they differ in subsite architecture and hence in substrate specificities. Purified digestive chymotrypsins from insects of three different orders were assayed with internally quenched fluorescent oligopeptides with three different amino acids at P1 (Tyr, Phe, and Leu) and 13 amino acid replacements in positions P1`, P2, and P3. The binding energy (Delta G(s), calculated from Km values) and the activation energy (Delta G(T)(double dagger), determined from k(cat)/K-m values) were calculated. The hydrophobicities of each subsite were calculated from the efficiency of hydrolysis of the different amino acid replacements at that subsite. The results showed that except for S1, the other subsites (S2, S3, and S1`) vary among chymotrypsins. This result contrasts with insect trypsin data that revealed a trend along evolution, putatively associated with resistance to plant inhibitors. In spite of those differences, the data suggested that in lepidopteran chymotrypsins S2 and S1` bind the substrate ground state, whereas only S1` binds the transition state, supporting aspects of the present accepted mechanism of catalysis. 2008 Elsevier Ltd. All rights reserved.

Characterization of the products of aniline peroxydisulfate oligo/polymerization in media with different pH by resonance Raman spectroscopy at 413.1 and 1064 nm excitation wavelengths

The pH-structure correlation of the products of aniline peroxydisulfate reaction was mainly investigated by resonance Raman spectroscopy. The reactions of aniline and ammonium peroxydisulfate were carried out in aqueous solutions of initial pH ranging from 4.9 to 13.2 and monomer/oxidant molar ratio of 4/1. For an initial pH of 4.9, the spectroscopic techniques showed that the emeraldine salt form of polyaniline (PANI-ES) is the main product, corroborating that the usual head-to-tail coupling mechanism is taking place. The resonance Raman spectra at 1064 nm exciting wavelength were useful to detect the emeraldine salt as a minor product for reactions at an initial pH of 5.3-11.5. The Raman spectra of the main product of the reaction at initial pH of 13.2 excited at 1064 and 413.1 nm showed new spectral features consistent with 1,4-Michael-type adducts of aniline monomers and 1,4-benzoquinone-monoimine unit. These compounds and their products of hydrolysis/oxidation are the predominant species for the reaction media of initial pH from 5.3 to 13.2. In order to get PANI with different nanoscale morphologies, a pH value of more than 0 or 1 was used in the aniline polymerization. The spectroscopic data obtained in this work reveal that head-to-tail coupling does not occur when aniline reacts at media pH higher than about 5. It is suggested that chemical structures of the products of aniline oxidation by an unusual mechanism are the driving force for the development of assorted morphologies. Copyright (C) 2011 John Wiley & Sons, Ltd.

Formation and decomposition of N-alkyinaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8-N-butyl-naphthalimide (1,8-NBN) to 1,8-N-butyl-naphthalamide (1,8-NBAmide) and of 2,3-N-butyl-naphthalimide (2,3-NBN) to 2,3-N-butyl-naphthalamide (2,3-NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8-NBN equilibrates with 1,8-NBAmide in mild alkali. Under the same conditions 2,3-NBN quantitatively yields 2,3-NBAmide. Over a wide range of acidities the reactions of the 1,8- and 2,3-N-butyl-naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH`s. Anhydride formation in acid was demonstrated for 1,8-NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8- and 2,3-N-butyl-naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six-membered ring intermediates. The rate of carboxylic acid assisted 1,8-N-Butyl-naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright (C) 2010 John Wiley & Sons, Ltd.