Viscoelasticity of oxidized starch/low methoxy pectin mixtures in the presence of glucose syrup

The structural properties of mixtures of pectin, oxidized starch and glucose syrup were investigated using small deformation dynamic oscillation. In the absence of added calcium, preparations of low methoxy pectin with glucose syrup formed viscous solutions, which remained crystal-free at subzero temperatures. Samples of oxidized starch and glucose syrup, on the other hand, exhibited solid-like behaviour because of the crystalline nature of the amylose-like helices. Mixtures of the two polysaccharides with the co-solute clearly showed phase inversion from liquid to solid-like behaviour with increasing amounts of starch in the formulation. The transformation was reflected in the textural properties of samples, which varied from thick solutions to firm gels. The viscoelasticity of the system was modified further by the introduction of high methoxy pectin. Preparations of high methoxy pectin and glucose syrup formed rubbery gels whose amorphous nature underwent a glass transition during cooling.     

Gelation and phase separation in maltodextrin-caseinate systems

A range of rheological techniques, including small deformation isothermal runs following quenching, controlled rate heating profiles, mechanical spectra, and large deformation strain sweeps and creep compliance testing, were employed in the investigation of maltodextrin—sodium caseinate aqueous dispersions. The concentration dependence, viscoelastic ratio and melting profiles of shear moduli for concentrated maltodextrin samples suggest a highly aggregated, enthalpically linked biopolymer gel. By contrast, the caScinate particles form a ‘pasty’ solid at low temperatures with a high viscous component, which upon moderate heating reverts readily into an entropically driven liquid body. Mixing of the polymers results in a composite system whose phase inversion from a maltodextrin continuous network with discontinuous protein inclusions to a caScinate dispersion suspending the polysaccharide particles is determined by the weight ratio of the two components in the blend. The overall strength of the composite has been related to the mechanical functions of the individual components, and the idea of kinetically trapped mixed gels has been put forward to rationalize the solvent partition between the two constituent phases. Results were used to advance the conclusions reached from work on other mixed biopolymer systems carried out in this laboratory.     

Physicochemical and structural characteristics of starches from Chinese hull‐less barley cultivars

Fourteen hull‐less barley cultivars, collected from four major cultivated areas in China, were employed to investigate the structural and physicochemical properties of their starches in this study. Relatively wide variations in physicochemical properties of the starches were observed. Amylose content ranged from 23.1% to 30.0%, swelling power and water solubility index ranged from 12.8 to 19.9 g g^?1 and 12.7% to 23.7% respectively. Peak viscosity was from 170 to 346 Rapid Visco Unit (RVU), peak temperature (T_p) of starch gelatinisation was from 55.6 to 61.8 °C and enthalpy of starch retrogradation ranged from 0.3 to 3.1 J g^?1. Weight‐based chain‐length proportions of fa, fb₁, fb₂ and fb₃ in amylopectins ranged from 21.65% to 24.95%, 44.48% to 49.44%, 15.56% to 17.19% and 9.83% to 16.66% respectively. Correlation analyses showed that amylose content was inversely related to pasting parameters and enthalpy of gelatinisation. Pasting properties and amylopectin structures were the most important parameters to differentiate starch properties among different hull‐less barley cultivars in this study. This work will be useful for exploring applications of Chinese hull‐less barley starches in food and non‐food industries.     

Physical characterization of thermally induced networks of lupin protein isolates prepared by isoelectric precipitation and dialysis

Summary Protein isolates of Lupinus albus were obtained from full fat and defatted lupin flour using isoelectric precipitation or dialysis. Calorimetric tests demonstrated that the main protein fractions of the isolates denature well below 100 °C. Mechanical spectra of isolate dispersions obtained at 80 °C indicated the formation of a 'pseudogel' whose cohesion increased during cooling to 10 °C. Subsequent heating to 90 °C encouraged extensive formation of disulphide bonds as it produced gels that were insoluble in sodium dodecyl sulphate and urea solutions. Dialysis produced isolates of lower gelling concentrations, which also formed networks of a stronger relative elastic character. The presence of NaCl at concentrations up to 0.5 m had a reinforcing effect on networks. Protein over-aggregation caused the opposite effect at higher salt levels. Finally, a comparison with results in the literature on soybean protein gelation suggested similar denaturation temperatures and a common pattern of structure formation for the two legume proteins.     

Thermomechanical study of the phase behaviour of agarose/gelatin mixtures in the presence of glucose syrup as co-solute

In an effort to draw attention to the subject of structure/function relationships in high-solid biopolymer mixtures, this investigation produces binary composites of agarose with gelatin and systematically increases the amount of glucose syrup, which is the co-solute in this system. Experimental work was carried out using small-deformation dynamic oscillation on shear and modulated differential scanning calorimetry. Agarose/gelatin mixtures in an aqueous low-solid environment form non-interactive bicontinuous networks. Addition of glucose syrup to the polymeric blend prevents the formation of stable double helices in the environment. Gelatin, on the other hand, better withstands the co-solute-induced change in solvent quality. At subzero temperatures, materials go through the rubber-to-glass transition whose DSC glass transition temperature (T_g) is governed by the total level of solids in the system. Estimation of the mechanical T_g acquires physical significance by utilising the theory of free volume, as modelled by the Williams, Landel and Ferry (WLF) equation. The single value of T_g estimated by this approach argues in accordance with experimental observations for the predominance of the gelatin network in the high-solid mixture.     

Influence of acid hydrolysis on thermal and rheological properties of amaranth starches varying in amylose content

BACKGROUND: The granules of amaranth starch are very small compared with starches from other sources. In the current work, amaranth starches with different amylose contents were treated with hydrochloric acid as a function of time in order to study the effect of acid treatments on starches. Differential scanning calorimetry and dynamic oscillation in shear were employed to analyse the thermal and rheological properties of acid‐modified amaranth starch. RESULTS: Results showed that gelatinisation temperatures and enthalpy change of gelatinisation (ΔH) decreased steeply initially, and had a slight increase with further treatment up to 12 h then decreased, an outcome that reflected distinct resistance to acid with various amylose contents. Rheological parameters of storage and loss moduli during heating, cooling and frequency sweep of modified starches reflected the differential scanning calorimetry results by decreasing in value as the time of acid hydrolysis increased. CONCLUSION: With amylose content increase, the effects of acid hydrolysis on gelatinisation temperatures became less pronounced. Nevertheless, prolonged acid hydrolysis decreased the storage and loss moduli, with the starch pastes becoming more liquid‐like. Copyright © 2012 Society of Chemical Industry     

Sorption isotherms and the state diagram for evaluating stability criteria of abalone

Water adsorption isotherms and the state diagram of abalone were developed to further investigate the connection between the two distinct criteria of food stability. The isotherms were measured at 23, 40 and 60 °C using an isopiestic method and they were treated with appropriate models available in the literature. The state diagram was developed using freezing points, as derived by the cooling curve method, and glass transition temperatures were measured by dynamic oscillation on shear. The limited glass transition process of the abalone network necessitated derivation of the mechanical glass transition temperature, since the transition could not be detected using MDSC. Results indicate that there is a considerable discrepancy in the temperature-related stability criteria predicted by the concepts of water activity (a_w) and the glass phenomenon (T_g). In contrast to the progressive deviation between a_w and T_g with increasing molecular weight reported earlier for a homologous family of materials, the effect of rising temperature produces a constant index of comparison between the two concepts.     

Hydrostatic pressure effects on the structural properties of condensed whey protein/lactose systems

Hydrostatic pressure effects on whey protein/lactose mixtures were recorded with subsequent analysis of their structural, molecular and glass transition properties in comparison to thermal effects at atmospheric pressure. Experimental techniques used were small deformation dynamic oscillation in shear, modulated differential scanning calorimetry, Fourier transform infrared spectroscopy, and theoretical modelling of glass transition phenomena. Levels of solids ranged from 30 to 80% (w/w) in formulations with a protein/co-solute ratio of four-to-one. Addition of lactose protects the secondary conformation of the protein under application of high hydrostatic pressure. Nevertheless, pressurized protein systems are able to form three-dimensional structures due to the reduction in polymeric free volume and the development of an efficient friction coefficient amongst tightly packed particles. Systems can be seen as developing a “molten globular state”, where the structural knots of pressure-treated networks remain in the native conformation but achieve intermolecular cross-linking owing to frictional contact. Furthermore, pressure treated assemblies of condensed whey protein preparations could match the viscoelasticity of the thermally treated counterparts upon cooling below ambient temperatures. That allowed examination of the physical state and morphology of a condensed preparation at 80% solids by the combined framework of reduced variables and free volume theory thus affording derivation of glass transition temperatures for pressurized and atmospheric samples.     

WATER SORPTION ISOTHERMS AND GLASS TRANSITION PROPERTIES OF GELATIN

The water sorption isotherms of gelatin of different molecular weights (317,700, 228,900, and 197,400) were determined at 50°C using an isopiestic method. The sorption isotherms were modeled using the Brunauer-Emmett-Teller (BET) and Guggenheim-Anderson-deBoer (GAB) equations. The BET and GAB equations were able to predict the equilibrium moisture content (EMC) with a mean relative error of 5.2 and 5.0%, respectively. The BET monolayer moisture content varied from 4.81 to 5.70% (d.b.) while modeling with the GAB equation predicted monolayer moisture content of 6.14-7.58% (d.b.) depending upon molecular weight. The monolayer moisture content increased with increasing molecular weight. Studies on the effect of moisture content on the “rheological glass transition temperature” (T_g) showed a smooth increase in the value of T_g as a function of increasing concentration of gelatin solids. This varied from 7 to 35°C at 75% and 97% solids, respectively for the protein sample with MW = 317,700. Pinpointing of the T_g was implemented with the technique of small deformation dynamic oscillation. It was proposed that the “rheological” T_g is the point between the glass transition region and the glassy state. It acquires physical significance by identifying the transition from free volume phenomena of the polymeric backbone in the glass transition region to an energetic barrier to motions in the glassy state involving stretching and bending of chemical bonds.