Distribution and Molecular Characterization of β-Glucans from Hull-Less Barley Bran, Shorts and Flour

Six hull-less barley cultivars widely grown in China were roller-milled to produce bran, shorts and flour fractions. The distribution and molecular characteristics of β-glucans from the three roller-milled fractions were investigated. The β-glucan contents in the six hull-less barley cultivars varied from 4.96% to 7.62%. For all the six cultivars, the shorts fraction contained the highest concentration of β-glucan (8.12-13.01%), followed by bran (6.15-7.58%) and flour (2.48-2.95%). Crude β-glucans were prepared from the three roller-milled fractions using aqueous sodium carbonate (pH 10). These preparations contained 45.38-71.41% β-glucan, 10.81-17.26% arabinoxylan, 2.6-9.6% protein, 2.7-9.0% starch, and 5.23-9.68% ash. Purification using α-amylase and β-xylanase in combination with pH adjustment and dialysis produced high purity β-glucan preparations (91-95%). The molecular weight (Mw) of β-glucan preparations from roller-milled fractions ranged from 117,600 to 852,400 g/mol. β-Glucan from flour had higher Mw than those from shorts and bran within the same cultivar, and β-glucan preparations from bran had the lowest Mw.     

Simulation of α- and β-PVDF melting mechanisms

Molecular dynamics (MD) simulations have been used to study the melting of α- and β-poly (vinylidene fluoride) (α- and β-PVDF). It is seen that melting at the ends of the polymer chains precedes melting of the bulk crystal structure. Melting of α-PVDF initially occurs via transitions between the two gauche dihedral angles (G ? G′) followed by transitions between trans and gauche dihedral angles (T ? G/G′). Melting of β-PVDF initially occurs via T → G/G′ transitions and via transitions of complete β- (TTTT) to α- (TGTG') quartets. The melting point of β-PVDF is higher than that of α-PVDF, and the simulated melting points of both phases depend on the length of the polymer chains used in the simulations. Since melting starts at the chain ends, it is important to include these in the simulations, and simulations of infinitely long chains yield melting points far larger than the experimental values (at least for periodic cells of the size used in this work), especially for β-PVDF. The simulated heats of fusion are in agreement with available experimental data.     

A comparison of the tape casting of α- and β-alumina

This work concerns the manufacture of planar cell configurations for molten sodium batteries in energy storage devices such as vehicle batteries and stationary storage cells. Tape casting of beta-alumina electrolyte could provide a low-cost mass production route but intriguingly there are only a few reports of tape casting using beta-alumina directly as the raw powder. We first compared tape casting of α-alumina and beta-alumina using polyvinyl butyral (PVB) in conventional formulations. While it is relatively easy to obtain homogeneous α-alumina tape cast sheet, beta-alumina resulted in adhesion to the substrate and cracking. These problems were shown to be attributable to particle characteristics. When the binder was changed to polymethylmethacrylate (PMMA), tape casting of beta-alumina and three different α-alumina powders was facilitated, producing a formulation that was more tolerant to different powder types. Screening of several commercial dispersants provided two which were effective with PMMA and a conventional MEK/ethanol dual solvent.     

Enzymatic Properties of Populus α- and β-NAD-ME Recombinant Proteins

Plant mitochondrial NAD-malic enzyme (NAD-ME), which is composed of α- and β-subunits in many species, participates in many plant biosynthetic pathways and in plant respiratory metabolism. However, little is known about the properties of woody plant NAD-MEs. In this study, we analyzed four NAD-ME genes (PtNAD-ME1 through PtNAD-ME4) in the genome of Populus trichocarpa. PtNAD-ME1 and -2 encode putative α-subunits, while PtNAD-ME3 and -4 encode putative β-subunits. The Populus NAD-MEs were expressed in Escherichia coli cells as GST-tagged fusion proteins. Each recombinant GST-PtNAD-ME protein was purified to near homogeneity by glutathione-Sepharose 4B affinity chromatography. Milligram quantities of each native protein were obtained from 1 L bacterial cultures after cleavage of the GST tag. Analysis of the enzymatic properties of these proteins in vitro indicated that α-NAD-MEs are more active than β-NAD-MEs and that α- and β-NAD-MEs presented different kinetic properties (V_max, k_cat and k_cat/K_m). The effect of different amounts of metabolites on the activities of Populus α- and β-NAD-MEs was assessed in vitro. While none of the metabolites evaluated in our assays activated Populus NAD-ME, oxalacetate and citrate inhibited all α- and β-NAD-MEs and glucose-6-P and fructose inhibited only the α-NAD-MEs.     

Molecular dynamics simulations of α- to β-poly(vinylidene fluoride) phase change by stretching and poling

The mechanism of inducing a phase change from α-poly(vinylidene fluoride) (α-PVDF) to β-PVDF is addressed using molecular dynamics simulations based on a molecular mechanics force field. The effect of applying a strain to the α-PVDF crystal along the axis of the molecules is investigated, as well as poling the crystal before or after stretching. Rather large (at least 10¹⁰ V/m) electric fields that are perpendicular to the axis of the PVDF molecules are required to induce α- to β-PVDF phase change when no strain is applied to the α-PVDF crystal. However, at a strain of 1.0475 (i.e., when the crystal is stretched by 4.75%) α-PVDF changes to a β-PVDF like structure, where the β-PVDF molecules orientate anti-parallel relative to each other. Transformation of the anti-parallel β-PVDF to β-PVDF can be induced by poling (even at the lowest electric field of 10⁵ V/m studied here) or by thermal annealing.     

Synthesis and Characterization of the Inclusion Complex of β-cyclodextrin and Azomethine

A β-cyclodextrin (β-Cyd) inclusion complex containing azomethine as a guest was prepared by kneading method with aliquot addition of ethanol. The product was characterized by Fourier Transform Infrared (FTIR) spectrometer, ¹H Nuclear Magnetic Resonance (¹H NMR) and Thermogravimetric Analyzer (TGA), which proves the formation of the inclusion complex where the benzyl part of azomethine has been encapsulated by the hydrophobic cavity of β-Cyd. The interaction of β-Cyd and azomethine was also analyzed by means of spectrometry by UV-Vis spectrophotometer to determine the formation constant. The formation constant was calculated by using a modified Benesi-Hildebrand equation at 25 °C. The apparent formation constant obtained was 1.29 × 10⁴ L/mol. Besides that, the stoichiometry ratio was also determined to be 1:1 for the inclusion complex of β-Cyd with azomethine.     

Synthesis and Characterization of the Inclusion Complex of Dicationic Ionic Liquid and β-Cyclodextrin

The supramolecular structure of the inclusion complex of β-cyclodextrin (β-CD) with 1,1',2,2'-tetramethyl-3,3'-(p-phenylenedimethylene) diimidazolium dibromide (TetraPhimBr), a dicationic ionic liquid, has been investigated. The inclusion complex with 1:1 molar ratio was prepared by a kneading method. Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD) analysis, (1)H NMR and thermogravimetric analysis (TGA) confirmed the formation of the inclusion complex. The results showed that the host-guest system is a fine crystalline powder. The decomposition temperature of the inclusion complex is lower than that of its parent molecules, TetraPhimBr and β-CD individually.     

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.     

Cross-influence of membrane polyunsaturated fatty acids and hypoxia-reoxygenation on α- and β-adrenergic function of rat cardiomyocytes

The purpose of the present investigation was to determine whether the beneficial effects of polyunsaturated fatty acids (PUFA) may influence ischemia-reperfusion-induced alterations of myocardial α- and β-adrenoceptor (α-AR, β-AR) responsiveness. This study was carried out using monolayer cultures of neonatal rat ventricular myocytes in a substrate-free, hypoxia-reoxygenation model of ischemia. The cardiomyocytes (CM) were incubated during 4 days in media enriched either with n−6 PUFA (arachidonic acid, AA) or with n−3 PUFA (eicosapentaenoic acid, EPA, and docosahexaenoic acid, DHA). The n−6/n−3 ratio in n−3 CM was close to 1.2, compared to 20.1 in n−6 CM. The contractile parameters of n−6 CM and n−3 CM were similar in basal conditions as well as during hypoxia and reoxygenation. In basal conditions, the phospholipid (PL) enrichment with long chain n−3 PUFA resulted in an increased chronotropic response to isoproterenol (ISO) and to phenylephrine (PHE). After posthypoxic reoxygenation, the chronotropic response to β-AR activation in n−6 CM was significantly enhanced as compared with the control response in normoxia. In opposition, the ISO-induced rise in frequency in n−3 CM in control normoxia and after reoxygenation was similar. In these n−3 CM, the changes in contractile parameters, which accompanied the chronotropic response, were also similar in reoxygenation and in normoxic periods, although the rise in shortening velocity was slightly increased after reoxygenation. In response to PHE addition, only the chronotropic effect of n−6 CM appeared significantly enhanced after hypoxic treatment. These results suggested that increasing n−3 PUFA in PL reduced the increase in α- and β-AR functional responses observed after hypoxia-reoxygenation. This effect may partly account for the assumed cardiac protective effect of n−3 PUFA, through the attenuation of the functional response to catecholamines in the ischemic myocardium.     

Preparation and Characterization of Carboxymethyl Chitosan and β-Cyclodextrin Microspheres by Spray Drying

Three kinds of carboxymethyl chitosan/β-cyclodextrin microspheres loaded with theophylline were prepared by spray drying intended for pulmonary delivery. Mucociliotoxicity, permeation rate, and drug release characteristics of the product were investigated. The microspheres obtained by spray drying were found to be spherical with smooth or wrinkled surfaces. The mean particle size was between 3.39 and 6.06 µm. The microspheres demonstrated high product yield (43.7–50.2%), high drug loading (13.7–38.1%), and high encapsulation efficiency (86.9–92.8%). FT-IR indicated that there were interactions of theophylline with carboxymethyl chitosan matrix. Further studies on mucociliotoxicity and permeation confirmed that microspheres had better adaptability and high permeation rate. In vitro drug release from the microspheres was not related to the drug/polymer ratios.     

Hydrolysis of methyl α- and β-D-glucopyranosides in the presence of a dealuminated H-Y faujasite

Hydrolysis of methyl α- and β-D-glucopyranosides was performed in the presence of protonic-form zeolites such as a dealuminated Y-faujasite with a Si/Al ratio of 15, at temperatures ranging between 100 and 150°C, and in water as the solvent. The β/α ratio for the hydrolysis reaction rates was found to be equal to 5–6, whereas a ratio of 2–3 was reported in the literature for the homogeneous reaction. The observed higher β/α ratio is proposed to result from the reinforcement of stereoelectronic effects which were shown to apply in reactions taking place on the surface of a solid. Those effects operate in a classical manner on a molecular standpoint, but they are reinforced due to the favorable interaction of oxygen electron lone pairs with the electron-deficient species present on the surface of the solid, protonic species in the case of zeolites. This revised version was published online in August 2006 with corrections to the Cover Date.     

Modeling of the α-lactalbumin and β-lactoglobulin protein separation

This work used the General Rate Model (GRM) to evaluate the experimental data of α-lactalbumin (α-la) and β-lactoglobulin (β-lg) mass transfer using size exclusion chromatography (SEC). The chromatographic simulation has become necessary in large scale production processes. Mathematical models have been used for the optimization and control of different operating conditions of the process, as well as providing calculations for the process scale-up. For the SEC experiments, the aqueous biphasic system was composed of polyethylene glycol 1500 g/mol, potassium phosphate and whey protein isolate. The polymeric phase was enriched with α-la and the saline phase with β-lg. The experiments were conducted using a glass column packed with the Sephadex G-25^® gel. Both proteins were quantified by reverse phase liquid chromatography. The experimental data were fitted by non-linear regression, using the successive quadratic programming algorithm. The mass transfer model utilized represented adequately the SEC experimental results.     

Effect of α-, β-, γ-, and δ-Tocotrienol on the Oxidative Stability of Lard

Despite the structural similarity of tocopherols, the antioxidative activities of tocotrienol homologues have not been studied often. In this study, the antioxidant activities of α-, β-, γ-, and δ-tocotrienols at various concentrations from 100 to 1,000 ppm in lard were evaluated. Headspace oxygen content of the lard without tocotrienol decreased from 21.1 to 10.7 % and the peroxide value increased from 0.4 to 33.4 mequiv/kg after 7 days of storage at 55 °C in the dark. α-Tocotrienol at 100 ppm and β-tocotrienol at 100 and 200 ppm effectively improved the oxidative stability of lard; however, the antioxidative activities of α- and β-tocotrienol reduced as the concentration increased to 1,000 ppm. The γ- and δ-tocotrienols improved the oxidation stability of lard and the effectiveness was essentially same at all concentrations (p > 0.05). The antioxidative activities of tocotrienols in the autoxidation of lard increased in the order of α-, β-, γ-, and δ-tocotrienols. The activities of tocotrienols in lard were different depending on the type of homologues and concentrations.     

Synthesis and Characterization of Hybrid Core–Shell Systems Based on Molecular Silicasols

New hybrid “rigid inorganic core–soft organic shell” systems based on molecular silicasols were synthesized by applying different synthetic schemes. Inorganic core was composed of molecular silicasols, which were synthesized from hyperbranched polyethoxysiloxane and tetraethoxysilane by polymer chemistry methods. Different organic modifiers were used to form soft shell of the hybrid particles. Obtained compounds were characterized by elemental analysis, GPC, IR and NMR spectroscopy. These systems will be designated for use as model objects for investigation of nanoparticles–polymer matrix interactions in polymer nanocomposites.     

Effect of α-, β-, γ-, and δ-Tocotrienol on the Singlet Oxygen Oxidation of Lard

The impacts of four different types of tocotrienol homologues on the singlet oxygen oxidation of lard were evaluated by measuring the headspace oxygen content and the peroxide value. Singlet oxygen oxidation of lard was induced by chlorophyll photosensitization. Samples of 0.100, 0.250, and 0.400 M lard in methylene chloride containing chlorophyll and α‐, β‐, γ‐, or δ‐tocotrienol were prepared and stored under light at 3,000 lux for 4 h. All tocotrienol homologues at 1.20 mM significantly prevented the singlet oxygen oxidation of lard. Chlorophyll under light produced singlet oxygen at 1.09 μmol oxygen/mL headspace/h. A steady state kinetic study showed that tocotrienols reduced the singlet oxygen oxidation of lard by quenching the singlet oxygen. Singlet oxygen reacted with lard at 6.50 × 10⁴M^?1 s^?1. α‐, β‐, γ‐, and δ‐tocotrienol quenched singlet oxygen with the rate of 2.16, 1.99, 2.05, and 0.800 × 10⁷M^?1 s^?1, respectively. Among them, α‐tocotrienol significantly prevented singlet oxygen oxidation of lard.     

Long-chain polyunsaturated fatty acids influence both β- and α-adrenergic function of rat cardiomyocytes

Dietary polyunsaturated fatty acids (PUFA) have been reported to lower the incidence of cardiovascular diseases, but neither the mechanisms that determine these protective effects nor the specific influence of n-3 vs. n-6 PUFA series has been well established. The purpose of this work was to demonstrate the influence of the membrane long-chain fatty acid composition on the spontaneous contractile activity and the adrenergic function of rat cardiomyocytes in culture. Cells were grown for 24 h in a standard culture medium and then for 4 d in media that contained either n-3 (eicosapentaenoic acid and docosahexaenoic acid) or n-6 (arachidonic acid) PUFA. The n-6/n-3 ratio was 1.2 in n-3 cells compared with 20.1 in n-6 cells. The basal contractile properties of these cardiomyocytes were not affected by the PUFA phospholipid composition. However, these modifications influenced the adrenoceptor function because the β-adrenergic stimulation by isoproterenol (10⁻⁷ M) induced a positive chronotropic response that was significantly greater in n-3 cells. Moreover, the chronotropic response to α-adrenoceptor stimulation by phenylephrine (10⁻⁶ M) appeared significantly more pronounced in the n-3 cells than in the n-6 cells. However, the parameters related to the inotropic response induced by these agonists did not differ significantly between the two groups of cells. These results suggested that the membrane long-chain PUFA composition does not influence the basal cardiac contractility and automaticity but is able to modulate the chronotropic function of both α- and β-adrenoceptors.     

An Improved Isolation Method of Soy β-Conglycinin Subunits and Their Characterization

This study aimed at establishing an effective preparative isolation method of soy β-conglycinin constituent subunits and characterizing some of their physicochemical properties and their heat-induced aggregation. These subunits were isolated in relatively large amounts and in high purity by dissociating β-conglycinin in 6 M urea and using a combination of DEAE-Sepharose fast flow column chromatography and immobilized metal ion affinity chromatography (IMAC). At a pH deviating from isoelectric point (pI), zeta potentials of α′ and α subunits were much larger than that of β subunit, while in the latter case, the hydrophobic groups were more buried within the proteins. Dynamic light scattering analysis indicated that the extent of heat-induced aggregation of β subunit was much higher than that of α′ and α subunits, and the aggregation was also more affected by the increase in ionic strength. Atomic force microscopy analysis indicated that more ordered and stranded aggregates were formed for α′ and α subunits. These results confirm a close relationship between physicochemical properties and heat-induced aggregation of β-conglycinin subunits.