Effect of cooking on non-starch polysaccharides of hard-to-cook beans

Experiments carried out to study changes induced by hard-to-cook (HTC) phenomenon in the non-starch polysaccharides of beans stored at 30 degrees C and 75% RH for 8 months showed that the development of HTC did not affect the amounts of soluble and insoluble fibre in cooked seeds but changed their carbohydrates physical properties. Aged beans non-starch polysaccharides presented lower water-solubility and underwent lower degradation of galacturonans and arabinose-rich polysaccharides when submitted to cooking. The decrease in non-starch polysaccharides water-solubility produced a shift in the polymers fractionation profile which resulted in an increase of weak and middle-alkali soluble polymers bulk as well as in their arabinose and uronic acid contents. Uronic acid contents were higher in polymers released by 1 M NaOH and in the cellulose-rich residues while the arabinose contents were higher in the mild-alkali soluble polymers of aged seeds. Methylation analysis showed no evident alterations in the xyloglucans and arabinans branching degree with beans ageing. However, both, the molecular mass of water-soluble pectins and CDTA-soluble pectins, increased. Even though changes in the non-starch polysaccharide solubility were not related to the decrease in the arabinan and xyloglucan degree of branching they may be related to the formation of new chemical interactions other than hydrogen bond. There was a correlation between acidic and neutral polysaccharides insolubilisation in beans ageing and probably in beans hardening. After processing, aged seeds present higher amounts of insoluble fibre when compared to normal beans. (C) 2008 Elsevier Ltd. All rights reserved.

Investigation of charged polymer influence on green fluorescent protein thermal stability

Methods of stabilization and formulation of proteins are important in both biopharmaceutical and biocatalysis industries. Polymers are often used as modifiers of characteristics of biological macromolecules to improve the biochemical activity and stability of proteins or drug bioavailability. Green fluorescent protein (GFP) shows remarkable structural stability and high fluorescence; its stability can be directly related to its fluorescence output, among other characteristics. GFP is stable under increasing temperatures, and its thermal denaturation is highly reproducible. Relative thermal stability was undertaken by incubation of GFP at varying temperatures and GFP fluorescence was used as a reporter for unfolding. At 80 degrees C, DEAE-dextran did not have any effect on GFP fluorescence, indicating that it does not confer stability.

Nitric oxide photorelease from hydrogels and from skin containing a nitro-ruthenium complex

Nitric oxide (NO) is a gaseous molecule that has specific functions dictated by its localization and its kinetics of release. As NO-donors have a range of potential uses in the skin, much attention has been paid to the development of topical NO delivery systems. The aim of this work was to study the release rate and the skin penetration of the NO-donor cis[Ru(NO(2))(bpy)(2)(4-pic)](+) from different gel formulations and their potential as topical NO delivery systems under light stimuli. Among the formulations developed, the anionic gel retarded the nitro-ruthenium complex diffusion and also obstructed NO release after light irradiation. On the other hand, NO release before light irradiation was observed when the complex was dispersed in the cationic chitosan gel, possibly due to oxi-redox reactions between the amino groups of the polymer and the drug molecule. Finally, the non-ionic gel released the NO after light irradiation to the same extent as a drug aqueous solution at the same pH. The drug dispersed in this gel also penetrated into the stratum corneum skin layer, and the nitro-ruthenium complex present in the skin was able to release the NO after light stimuli, suggesting the potential use of this formulation as a topical NO delivery system. (C) 2010 Elsevier B.V. All rights reserved.

The effects of pH and ionic strength on topical delivery of a negatively charged porphyrin (TPPS(4))

Meso-tetra-[4-sulfonatophenyl]-porphyrin (TPPS(4)) is a charged porphyrin derivate used in photodynamic therapy (PDT) by parenteral administration. This study means to investigate potential enhancement for its topical delivery by determining the TPPS(4) dependence on the environmental characteristics and applying iontophoresis. In order to accomplish this task, cathodal and anodal iontophoresis as well as passive delivery of the drug were studied in vitro and in vivo in function of its concentration, pH and ionic strength. A reduction in drug concentration as well as the NaCl elimination from donor formulation at pH 2.0 increased TPPS(4) passive permeation through the skin in vitro. Iontophoresis improved TPPS(4) delivery across the skin when applied in solutions containing NaCl at pH 2.0, regardless electrode polarity. However, at pH 7.4, the amount of TPPS(4) permeated by iontophoresis was not different from that one permeated after passive experiments from a solution containing NaCl. Despite the fact that iontophoresis did not improve TPPS(4) transdermal delivery at this specific condition, in vivo experiments showed that 10 min of iontophoresis quickly and homogeneously delivered TPPS(4) to deeper skin layers when compared to passive administration, which is an important condition for topical treatment of skin tumors with PDT. (C) 2008 Wiley-Liss, Inc. and the American Pharmacists Association.

Nanocomposite Polymer Electrolyte Membranes: Methanol Crossover and Conductivity

Commercial Nafion® 117 membranes were successfully modified by in-situ reactions (sol-gel of TEOS and/or polymerization of aniline) within Nafion structures. Water-methanol permeability and proton conductivity were investigated in order to determine the potential performance of these membranes for DMFC systems. Silica-polyaniline modification resulted in 84% methanol crossover reduction, from 2.45x10^-5 cm2.s^-1 for conventional Nafion membranes to 3.71x10^-6 cm2.s^-1 for the modified silica-polyaniline composite membrane at 75 degrees C. In addition, conductivity was not hindered, as the polyaniline-Nafion membrane increased from 12.2 to 15 mS.cm^-1 as compared to Nafion, while a reduction of 11% was observed for silica-polyaniline-Nafion composite membrane. The results in this work strongly suggest the potential of polyaniline nanocomposites to enhance the performance of DMFCs.

Effect of ionic strength and clay mineralogy on Na-Ca exchange and the SAR-ESP relationship

The relationship between sodium adsorption ratio (SAR) and exchangeable sodium percentage (ESP) for all soils has traditionally been assumed to be similar to that developed by the United States Salinity Laboratory (USSL) in 1954. However, under certain conditions, this relationship has been shown not to be constant, but to vary with both ionic strength and clay mineralogy. We conducted a detailed experiment to determine the effect of ionic strength on the Na+-Ca2+ exchange of four clay minerals (kaolinite, illite, pyrophyllite, and montmorillonite), with results related to the diffuse double-layer (DDL) model. Clays in which external exchange sites dominated (kaolinite and pyrophyllite) tended to show an overall preference for Na+, with the magnitude of this preference increasing with decreasing ESP. For these external surfaces, increases in ionic strength were found to increase preference for Na+. Although illite (2:1 non-expanding mineral) was expected to be dominated by external surfaces, this clay displayed an overall preference for Ca2+, possibly indicating the opening of quasicrystals and the formation of internal exchange surfaces. For the expanding 2:1 clay, montmorillonite, Na+-Ca2+ exchange varied due to the formation of quasicrystals (and internal exchange surfaces) from individual clay platelets. At small ionic strength and large ESP, the clay platelets dispersed and were dominated by external exchange surfaces (displaying preference for Na+). However, as ionic strength increased and ESP decreased, quasicrystals (and internal exchange surfaces) formed, and preference for Ca2+ increased. Therefore, the relationship between SAR and ESP is not constant and should be determined directly for the soil of interest.

Volatile products and new polymer structures formed on Co-60 gamma-radiolysis of poly(lactic acid) and poly(glycolic acid)

A gas product analysis has been conducted on gamma-irradiated samples of poly(lactic acid) (PLA) and poly(glycolic acid) (PGA) by means of gas chromatography. The major volatile products have been identified to be CO, CO2, CH4 and C2H6 for PLA, and CO and CO2 for PGA. In addition, the yield of evolved gases for PLA has been found to be 1.81 for CO2, 0.98 for CO, 0.026 for CH4 and 0.012 for C2H6; and that for PGA to be 1.70 for CO2 and 0.42 for CO. The new chain ends formed due to gamma-induced bond cleavage in PLA have been assigned to CH3-CH2-CO-O- and CH3-CH2-O-CO-, and the G values for formation of these chain ends were found to be 1.9 and 0.6, respectively. The G value for chain scission reported previously of 2.3 is comparable with that for the formation of the propanoic acid end group. (C) 1997 Elsevier Science Limited.

Epidermal iontophoresis: I. Development of the ionic mobility-pore model

Purpose, An integrated ionic mobility-pore model for epidermal iontophoresis is developed from theoretical considerations using both the free volume and pore restriction forms of the model for a range of solute radii (r(j)) approaching the pore radii (r(p)) as well as approximation of the pore restriction form for r(j)/r(p) < 0.4. In this model, we defined the determinants for iontophoresis as solute size (defined by MV, MW or radius), solute mobility, solute shape, solute charge, the Debye layer thickness, total current applied, solute concentration, fraction ionized, presence of extraneous ions (defined by solvent conductivity), epidermal permselectivity, partitioning rates to account for interaction of unionized and ionized lipophilic solutes with the wall of the pore and electroosmosis. Methods, The ionic mobility-pore model was developed from theoretical considerations to include each of the determinants of iontophoretic transport. The model was then used to reexamine iontophoretic flux conductivity and iontophoretic flux-fraction ionized literature data on the determinants of iontophoretic flux. Results. The ionic mobility-pore model was found to be consistent with existing experimental data and determinants defining iontophoretic transport. However, the predicted effects of solute size on iontophoresis are more consistent with the pore-restriction than free volume form of the model. A reanalysis of iontophoretic flux-conductivity data confirmed the model's prediction that, in the absence of significant electroosmosis, the reciprocal of flux is linearly related to either donor or receptor solution conductivity. Significant interaction with the pore walls, as described by the model, accounted for the reported pH dependence of the iontophoretic transport for a range of ionizable solutes. Conclusions. The ionic mobility-pore iontophoretic model developed enables a range of determinants of iontophoresis to be described in a single unifying equation which recognises a range of determinants of iontophoretic flux.

Epidermal iontophoresis: II. Application of the ionic mobility-pore model to the transport of local anesthetics

Purpose, An in vitro study was carried out to determine the iontophoretic permeability of local anesthetics through human epidermis. The relationship between physicochemical structure and the permeability of these solutes was then examined using an ionic mobility-pore model developed to define quantitative relationships. Methods. The iontophoretic permeability of both ester-type anesthetics (procaine, butacaine, tetracaine) and amide-type anesthetics (prilocaine, mepivacaine, lidocaine, bupivacaine, etidocaine, cinchocaine) were determined through excised human epidermis over 2 hrs using a constant d.c. current and Ag/AgCl electrodes. Individual ion mobilities were determined from conductivity measurements in aqueous solutions. Multiple stepwise regression was applied to interrelate the iontophoretic permeability of the solutes with their physical properties to examine the appropriateness of the ionic mobility-pore model and to determine the best predictor of iontophoretic permeability of the local anesthetics. Results. The logarithm of the iontophoretic permeability coefficient (log PCj,iont) for local anesthetics was directly related to the log ionic mobility and MW for the free volume form of the model when other conditions are held constant. Multiple linear regressions confirmed that log PCj,iont was best defined by ionic mobility (and its determinants: conductivity, pK(a) and MW) and MW. Conclusions. Our results suggest that of the properties studied, the best predictors of iontophoretic transport of local anesthetics are ionic mobility (or pK(a)) and molecular size. These predictions are consistent with the ionic mobility pore model determined by the mobility of ions in the aqueous solution, the total current, epidermal permselectivity and other factors as defined by the model.

A comparative study of the fluidized-bed coating of cylindrical metal surfaces with various thermoplastic polymer powders

This paper reports the results of an experimental investigation into the fluidized-bed coating of cylindrical metal specimens using two types of thermoplastic powders, Rilsan(R) PA11, a nylon-11 powder produced by Elf Atochem, France and Cotene(TM) 4612, a linear low density polyethylene powder produced by J.R Courtenay (New Zealand). The effects of dipping time, preheat temperature and particle size distribution on coating thickness and surface finish were investigated. Consistent trends in coating thickness growth with dipping time were obtained for both nylon-11 and polyethylene powders with increases in coating thickness with preheat temperature. For the same preheat temperature, the lower melting point of polyethylene results in thicker coatings compared to those of nylon-11. There is a negligible change in the coating thickness for sieved powders compared to that for unsieved powders. A pre-heat temperatures of between 240 degrees C and 300 degrees C is necessary to achieve an acceptable surface finish with both nylon-11 and polyethylene powders. To minimize errors in achieving the desired coating thickness, dipping times shorter than 2 s are not recommended. The use of graphs of coating thickness versus dipping time in combination with the coating surface roughness plots presented in this paper enable the optimal choice of pre-heat temperature and dipping time to achieve acceptable surface finish. (C) 1999 Elsevier Science S.A. All rights reserved.

Miscibility and specific interactions in blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate)

The properties of the hydrogen-bonded polymer blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate) are presented. Spectroscopic techniques such as C-13 solid-state NMR and FT-IR are used to probe specific interactions of the blends at various compositions. Spectral features from both techniques revealed that site-specific interactions are present, consistent with a significant degree of mixing of the blend components. Changes in chemical shift and line shape of the phenolic carbon and carbonyl resonances in the C-13 CPMAS spectra of the blends as a function of composition are interpreted as resulting from changes in the relative intensities of two closely overlapped signals. A quantitative measure of hydrogen-bonded carbonyl groups using C-13 NMR has been obtained which agreed well with the results from FT-IR analyses. It is also shown that C-13 NMR can be used to measure the fraction of hydroxyl groups associated with carbonyl groups, which was not possible previously using FT-IR due to extensive overlapping of bands in the hydroxyl stretching region. The results of measurements of H-1 T-1 and 1H T-1 rho indicate that PVPh and PEEMA are intimately mixed on a scale less than 2-3 nm.

Synthesis of silica films at the air/water interface: Effect of template chain length and ionic strength

We have grown surfactant-templated silicate films at the air-water interface using n-alkyltrimethylammonium bromide and chloride in an acid synthesis with tetraethyl orthosilicate as the silicate source. The films have been grown with and without added salt (sodium chloride, sodium bromide) and with n-alkyl chain lengths from 12 to 18, the growth process being monitored by X-ray reflectometry. Glassy, hexagonal, and lamellar structures have been produced in ways that are predictable from the pure surfactant-water phase diagrams. The synthesis appears to proceed initially through an induction period characterized by the accumulation of silica-coated spherical micelles near the surface. All syntheses, except those involving C(12)TACl, show a sudden transformation of the spherical micellar phase to a hexagonal phase. This occurs when the gradually increasing ionic strength and/or changing ethanol concentration is sufficient to change the position of boundaries within the phase diagram. A possible mechanism for this to occur may be to induce a sphere to rod transition in the micellar structure. This transformation, as predicted from the surfactant-water phase diagram, can be induced by addition of salts and is slower for chloride than bromide counteranions. The hexagonal materials change in cell dimension as the chain length is changed in a way consistent with theoretical model predictions. All the materials have sufficiently flexible silica frameworks that phase interconversion is observed both from glassy to hexagonal and from hexagonal, to lamellar and vice versa in those surfactant systems where multiple phases are found to exist.

C-13-NMR, H-1-NMR, and FT-Raman study of radiation-induced modifications in radiation dosimetry polymer gels

H-1- and C-13-NMR spectroscopy and FT-Raman spectroscopy are used to investigate the properties of a polymer gel dosimeter post-irradiation. The polymer gel (PACT) is composed of acrylamide, N,N'-methylene-bisacrylamide, gelatin, and water. The formation of a polyacrylamide network within the gelatin matrix follows a dose dependence nonlinearly correlated to the disappearance of the double bonds from the dissolved monomers within the absorbed dose range of 0-50 Gy. The signal from the gelatin remains constant with irradiation. We show that the NMR spin-spin relaxation times (T-2) of PAGs irradiated to up to 50 Gy measured in a NMR spectrometer and a clinical magnetic resonance imaging scanner can be modeled using the spectroscopic intensity of the growing polymer network. More specifically, we show that the nonlinear T-2 dependence against dose can be understood in terms of the fraction of protons in three different proton pools. (C) 2000 John Wiley & Sons, Inc.

The relationship between radiation-induced chemical processes and transverse relaxation times in polymer gel dosimeters

The effects of ionizing radiation in different compositions of polymer gel dosimeters are investigated using FT-Raman spectroscopy and NMR T-2 relaxation times. The dosimeters are manufactured from different concentrations of comonomers (acrylamide and N,N'-methylene-bis-acrylamide) dispersed in different concentrations of an aqueous gelatin matrix. Results are analysed using a model of fast exchange of magnetization between three proton pools. The fraction of protons in each pool is determined using the known chemical composition of the dosimeter and FT-Raman spectroscopy. Based on these results, the physical and chemical processes in interplay in the dosimeters are examined in view of their effect on the changes in T-2 The precipitation of growing macroradicals and the scavenging of free radicals by gelatin are used to explain the rate of polymerization. The model describes the changes in T-2 as a function of the absorbed dose up to 50 Gy for the different compositions. This is expected to aid the theoretical design of new, more efficient dosimeters, since it was demonstrated that the optimum dosimeter (i.e, with the lowest dose resolution) must have a range of relaxation times which match the range of T-2 values which can be determined with the lowest uncertainty using an MRI scanner.