Viscoelastic properties of xanthan gum hydrogels annealed in the sol state

Viscoelastic properties of xanthan gum aqueous solutions and hydrogels were investigated using a cone-plate type rheometer. The change of viscoelasticity during annealing the solution and cooling to gelation temperature was examined as functions of annealing time, temperature and frequencies. In the annealing process, the storage modulus G′ increases with increasing annealing time. In the subsequent cooling process, G′ of the annealed solution increased, whereas the G′ of non-annealed solution remained almost constant. G′ of hydrogels increased with the increase of annealing temperature and concentration. Based on the experimental results obtained, the structural change of the solution in the annealing process and the structure of gels were investigated.     

Characterization of gelation time and texture of gelatin and gelatin–polysaccharide mixed gels

The effects of cooling rate, holding temperature, pH and polysaccharide concentration on gelation characteristics of gelatin and gelatin–polysaccharide mixtures were investigated using a mechanical rheometer which monitored the evolution of G′ and G″. At low holding temperatures of 0 and 4 °C, elastic gelatin gels were formed whereas a higher holding temperature of 10 °C produced less elastic gels. At slow cooling rates of 1 and 2 °C/min, gelling was observed during the cooling phase in which the temperature was decreased from room temperature to the holding temperature. On the other hand, at higher cooling rates of 4 and 8 °C/min, no gelation was observed during the cooling phase. Good gelling behavior similar to that of commercial Strawberry Jell-O^® Gelatin Dessert was observed for mixtures of 1.5 and 15 g sucrose in 100 ml 0.01 M citrate buffer containing 0.0029–0.0066 g low-acyl gellan. Also, these mixed gels were stronger than Strawberry Jell-O^® Gelatin Desserts as evidenced by higher G′ and gel strength values. At a very low gellan content of 0.0029 g, increasing pH from 4.2 to 4.4 led to a decrease in the temperature at the onset of gelation, G′ at the end of cooling, holding and melting as well as an increase in gel strength. The gelation time was found to decrease to about 40 min for gelatin/sucrose dispersions in the presence of 0.0029 g gellan at pH 4.2 whereas the corresponding time at pH 4.4 was higher (79 min). In general, the gelation time of gelatin/sucrose dispersions decreased by a factor of 2 to 3 in the presence of low-acyl gellan. The addition of low-acyl gellan resulted in an increase in the gelation rate constant from 157.4 to 291 Pa. There was an optimum low-acyl gellan content for minimum gelation time, this optimum being pH dependent. Addition of guar gum also led to a decrease in gelation time to 73 min with a corresponding increase in the gelation rate constant to 211 Pa/min though these values were not sensitive to guar gum content in the range of 0.008–0.05 g. The melting temperature of gelatin/sucrose/gellan as well as gelatin/sucrose/guar mixtures did not differ significantly from that of pure gelatin or Strawberry Jell-O^® Gelatin Desserts. At pH 4.2, the melting rate constant was highest at a low-acyl gellan content of 0.0029 g whereas the rate constant was insensitive to low-acyl gellan content at pH 4.4. Addition of guar did not seem to affect the melting temperature or the melting rate constant.     

Characterization of cold-set gels produced from heated emulsions stabilized by whey protein

This paper reports the cold gelation of preheated emulsions stabilized by whey protein, in contrast to, in previous reports, the cold gelation of emulsions formed with preheated whey protein polymers. Emulsions formed with different concentrations of whey protein isolate (WPI) and milk fat were heated at 90 °C for 30 min at low ionic strength and neutral pH. The stable preheated emulsions formed gels through acidification or the addition of CaCl₂ at room temperature. The storage modulus (G′) of the acid-induced gels increased with increasing preheat temperature, decreasing size of the emulsion droplets and increasing fat content. The adsorbed protein denatures and aggregates at the surface of the emulsion droplets during heat treatment, providing the initial step for subsequent formation of the cold-set emulsion gels, suggesting that these preheated emulsion droplets coated by whey protein constitute the structural units responsible for the three-dimensional gel network.     

Structural and mechanical characterization of κ/ι-hybrid carrageenan gels in potassium salt using Fourier Transform rheology

The mechanical and structural properties of κ/ι-hybrid carrageenan gels obtained at various concentrations in the presence of 0.1 m KCl were studied with Fourier Transform rheology (FTR) and cryoSEM imaging. FTR data show that gels formed at concentration below 1.25 wt% exhibit a strain hardening behavior. The strain hardening is characterized by a quadratic increase of the scaled third harmonic with the strain and a third harmonic phase angle of zero degree. Both features are weakly depending on the concentration and conform to predictions from a strain hardening model devised for fractal colloidal gels. However, the phase angle of the third harmonic reveals that κ/ι-hybrid carrageenan gels obtained at higher concentrations show shear thinning behavior. Colloidal gel models used to extract structural information from the concentration scaling of gel equilibrium shear modulus G₀ and the strain dependence of FTR parameters suggest that κ/ι-hybrid carrageenan gels are built from aggregating rod-like strands (with fractal dimension x = 1.13) which essentially stretch under increasing strain. The mechanically relevant structural parameters fairly match the gel fractal dimension (d = 1.66) obtained from the cryoSEM analysis.     

Effect of oxidised starch on calcium pectinate gels

Small-deformation oscillatory measurements have been used to study the effect of low-viscosity oxidised starch on the rheology of calcium pectinate gels formed by controlled cooling from the sol state at high temperature. Large reductions in modulus (G′; 0.5% strain; 10°C) were observed at starch concentrations below the minimum critical concentration for gelation of oxidised starch alone under the same conditions (32 wt%). This behaviour is tentatively ascribed to thermodynamic incompatibility between the two polymers causing incipient precipitation of calcium pectinate within the gel network.     

Whey protein concentrate/λ-carrageenan systems: Effect of processing parameters on the dynamics of gelation and gel properties

The thermal characteristics, dynamics of gelation and gel properties of commercial whey protein concentrate (WPC), WPC/λ-carrageenan (λ-C) mixtures (M) and WPC/λ-C spray-dried mixtures (DM) have been characterized. In a second stage, the effect of the gelling variables (T, pH, total solid content) on gelation and textural properties of DM was evaluated through a Doehlert uniform shell design.The presence of λ-C either in mixtures (M) or in DM promoted the WPC gelation at lower concentration (8%). M showed higher rates of formation and better gel properties (higher hardness, adhesiveness, springiness and cohesiveness) than DM.Nevertheless, when the effects of pH (6.0–7.0), heating temperature (75–90 °C) and total solid content (12–20 wt%) on gelation dynamics and gel properties of DM were studied, gels with a wide range of rheological and textural properties were obtained. While pH did not affect the gelation dynamics, it had some effect on rheological and textural properties. Total solid content and heating temperature were the most important variables for the dynamics of gelation (gelation rate (1/t_gel), gelation temperature (T_gel), rate constant of gel structure development (k_G), elastic modulus after cooling (G′_c) and textural parameters (hardness, springiness and cohesiveness).     

On solid-like rheological behaviors of globular protein solutions

Dynamic viscoelastic and steady flow properties of β-lactoglobulin, bovine serum albumin, ovalbumin, and α-lactalbumin aqueous solutions were investigated at 20°C. When a sinusoidal strain in the linear viscoelastic region was applied, the solutions of the globular proteins except for α-lactalbumin showed typical solid-like rheological behavior: the storage modulus G′ was always larger than the loss modulus G″ in the entire frequency range examined (0.1–100 rad/s). Under a steady shear flow, strong shear thinning behavior was observed with increasing shear rate from 0.001 to 800 s⁻¹, for the globular proteins except for α-lactalbumin. The values of the steady shear viscosity η were lower than those of the dynamic shear viscosity η* at a comparable time scale of observation, violating the Cox–Merz rule, and thus suggesting that a solid-like structure in a globular protein solution was susceptible to a steady shear strain. During isothermal gelation of the protein colloids at 70°C, no crossover between G′ and G″ was observed so that the gelation point was judged by an abrupt increase in the modulus or a sudden decrease in tanδ.     

Maturation effects in fish gelatin and HPMC composite gels

This study assessed the effectiveness of using hydroxylpropylmethylcellulose (HPMC) to enhance mechanical strength and thermal stability in fish skin gelatin (FG). The significant increase in absorbance (A₄₀₀) observed after HPMC had been added to FG and then matured indicated successful formation of a composite gel. Increased gel strength and storage modulus (G′) indicated the enhanced gelation ability of the matured composite gel, while increased melting temperature (T_m) and enthalpy (ΔH) indicated its improved thermal stability. Maturation-related rheological property improvements were more noticeable at 4 °C than 10 °C, but no apparent differences in T_m improvement were observed between 4 °C and 10 °C maturation. Nevertheless, the composite gel exhibited reversible cold and thermal gelation properties.     

Associative and segregative interactions between gelatin and low-methoxy pectin: Part 2—co-gelation in the presence of Ca

The effect of segregative interactions with gelatin (type B; pI=4.9; 0–10 wt%) on the networks formed by low-methoxy pectin on cooling in the presence of stoichiometric Ca²⁺ at pH 3.9 has been investigated by rheological measurements under low-amplitude oscillatory shear. Samples were prepared and loaded at 85 °C, cooled (1 °C/min) to 5 °C, held for 100 min, and re-heated (1 °C/min) to 85 °C, with measurement of storage and loss moduli (G′ and G″) at 10 rad s⁻¹ and 2% strain. The final values of G′ at 5 °C for mixtures prepared at the same pH without Ca²⁺ were virtually identical to those observed for the same concentrations (0.5–10.0 wt%) of gelatin alone, consistent with the conclusion from the preceding paper that electrostatic (associative) interactions between the two polymers become significant only at pH values below 3.9. Increases in moduli on cooling in the presence of Ca²⁺ occurred in two discrete steps, the first coincident with gelation of calcium pectinate alone and the second with gelation of gelatin. Both processes were fully reversible on heating, but displaced to higher temperature (by 10 °C), as was also observed for the individual components. The magnitude of the changes occurring over the temperature range of the gelatin sol–gel and gel–sol transitions demonstrates that the gelatin component forms a continuous network; survival of gel structure after completion of gelatin melting shows that the calcium pectinate network is also continuous (i.e. that the co-gel is bicontinuous). On progressive incorporation of NaCl (to induce phase separation before, or during, pectin gelation) the second melting process, coincident with loss of calcium pectinate gel structure, was progressively abolished, indicating conversion to a gelatin-continuous network with dispersed particles of calcium pectinate. These qualitative conclusions are supported by quantitative analyses reported in the following paper.     

Rheological and thermal properties of milk gels formed with κ-carrageenan. I. Sodium caseinate

Mixed gels, formed by κ-carrageenan, and sodium caseinate were studied by differential scanning calorimetry (DSC) and rheometry. DSC showed that during gelation (i.e. cooling) the thermal behaviour of κ-carrageenan was almost uninfluenced by the presence of sodium caseinate. Thus the interaction of κ-carrageenan with sodium caseinate has little (or no) effect on the carrageenan's coil-to-helix transition. In contrast, during melting, added sodium caseinate strongly modified the thermal behaviour. The DSC peak became progressively broader with addition of sodium caseinate, indicating that the junction zones are highly heterogeneous in the mixed gel. Rheometry showed that sodium caseinate strongly influences the storage modulus (G′). In experiments in which the concentration of sodium caseinate was fixed and that of κ-carrageenan varied, plots of G′ vs. concentration of κ-carrageenan were biphasic, with an abrupt change in slope at a concentration that increased linearly with the concentration of sodium caseinate. When the concentration of κ-carrageenan was constant and that of sodium caseinate varied, G′ as a function of concentration of sodium caseinate passed through a minimum. This behaviour could be modelled quantitatively, by assuming that: (a) the sodium caseinate adsorbs κ-carrageenan, but with a limited adsorptive capacity; (b) sodium caseinate aggregates (sub-micelles) with adsorbed κ-carrageenan can associate via interaction between free ends of adsorbed κ-carrageenan chains and form a gel network; and (c) the contributions to G′ from the sodium caseinate–κ-carrageenan network and the network formed by κ-carrageenan alone are additive. At low κ-carrageenan to sodium caseinate ratios, the sodium caseinate and κ-carrageenan combine to form a mixed gel. As the ratio of κ-carrageenan to sodium caseinate increases, the sodium caseinate becomes saturated and no further association with κ-carrageenan can occur—the increase in G′, as further κ-carrageenan is added, comes from a gel network formed by κ-carrageenan alone.     

Gelation kinetics of an imitation-mortadella emulsion during heat treatment determined by oscillatory rheometry

The gelation kinetics of an imitation-mortadella emulsion during thermal treatment under both, isothermal and non-isothermal conditions was followed by means of oscillatory rheometry. A first order-kinetic process was found to better describe the variation of the storage modulus G′ (at 1 Hz and strain amplitude of 0.8%) during the two types of thermal treatments. An Arrhenius-type model was able to describe the effect of temperature during gelation of the emulsion under non-isothermal conditions.     

Analysis of cooling curve to determine the end point of freezing

The cooling curve method used for the measurement of freezing point of food is further analyzed to explore whether it can be used to identify the end point of freezing or glass transition. In this method, slope of the cooling curve is determined and plotted as a function of time to identify the end point of freezing (T′_m). Initially, the slope is decreased and then reached a minimum value, which is identified as the nucleation of ice. Then the slope is increased until the end point of freezing. The end point of freezing is identified when the slope starts to decrease from its highest value or plateau. Sucrose solutions and starch gels were used to measure its T′_m in identifying validity of the proposed method. The measured values of T′_m by the proposed method is very close to the literature values.     

Physicochemical properties of pectins from okra (Abelmoschus esculentus (L.) Moench)

Okra pectin obtained by hot buffer extraction (HBSS) consists of an unusual pectic rhamnogalacturonan I structure in which acetyl groups and alpha galactose residues are substituted on rhamnose residues within the backbone. The okra Chelating agent Soluble Solids (CHSS) pectin consists of slightly different structures since relatively more homogalacturonan is present within the macromolecule and the rhamnogalacturonan I segments carry slightly longer side chains. The rheological properties of both okra pectins were examined under various conditions in order to understand the unusual slimy behaviour of okra pectins. The viscosity of the okra HBSS pectin was 5–8 times higher than the viscosity of the okra CHSS pectin. The okra HBSS pectin showed an elastic behaviour (G′ > G″) over a wide range of frequencies (10⁻¹–10 Hz), at a strain of 10%, while okra CHSS and saponified okra HBSS/CHSS pectin showed predominantly viscous responses (G′ < G″) over the same frequency range. The results suggest that the structural variation within the okra pectins greatly affect their rheological behaviour and it is suggested that acetylation of the pectin plays an important role through hydrophobic associations. Dynamic light scattering was used to study the association behaviour of both okra pectins at low concentration (0.001–0.1% w/w). Results showed that the saponified okra pectins did not exhibit a tendency to aggregate in the concentration range studied, whereas both non saponified samples showed a substantial degree of association. These results suggest that the unusual slimy behaviour of the non saponified samples may be related to the tendency of these pectins to associate, driven by hydrophobic interactions.     

Role of cosolutes in gelation of high-methoxy pectin. Part 2. Anomalous behaviour of fructose: calorimetric evidence of site-binding

Gels of high-methoxy pectin (DE 70; 1.0 wt%; pH 3.0) in the presence of fructose at concentrations of 50, 55, 60 and 65 wt% showed an intense endotherm followed immediately by an intense exotherm on heating. These transitions occurred over approximately the same temperature-range as initial gelation on cooling (characterised by low-amplitude oscillatory measurements of G′ and G″) and increased in magnitude with increasing concentration of fructose. The displacement of both transitions, and particularly the exotherm, to progressively higher temperature as the rate of heating was increased was much greater than anticipated from simple thermal lag, indicating that the underlying structural changes are slow. The proposed interpretation is that fructose is capable of site-binding to pectin in both the ordered (threefold helix) and disordered state; the endotherm is attributed to helix melting and displacement of fructose; the subsequent exotherm is attributed to re-attachment of fructose to disordered chains, and the slow kinetics of this process to the conformational mobility of disordered pectin. On cooling over the same temperature range, a single exotherm was observed; the absence of detectable splitting is attributed to rapid re-attachment of fructose to conformationally-rigid helices. The magnitude of this endotherm (ΔH≈20 J/g) is close to the value found for cosolutes that show no evidence of site-binding, and to the net change in enthalpy for the endothermic and exothermic processes observed on heating, suggesting that the values of ΔH for displacement and re-attachment of fructose are essentially equal and opposite, with the net change coming from formation or melting of threefold helices. A smaller thermal process at higher temperature (endothermic on heating and exothermic on cooling) is attributed to hydrophobic association, which was also seen as an increase in G′ and G″ on heating in two consecutive cycles of temperature change.     

Characterization of potato starch fractions and their interaction with hydrocolloids

Commercial potato starch was separated through sedimentation into three fractions of the size < 25, 25–70 and >70 µm estimated with the laser particle meter method and <21.6, 21.7–30.6 and >30.7 µm according to the Sartorius balance method. Amylose and amylopectin content in particular fractions did not depend on the granule size. Number average and weight average molecular weight slightly decreased and phosphorus content increased with the size of granules in the fractions. Starch fractions and, for comparison, non‐fractionated starch were gelatinized in aqueous solutions of arabic, carob, karaya and xanthan gums and carrageenan. Except for the arabic gum, all tested hydrocolloids decreased onset temperature of gelation, T₀, of all starch fractions. Carob and xanthan gums and carrageenan the most remarkably decreased that parameter for large fraction, whereas other gums most considerably decreased T₀ of starch of the medium fraction. Effect of gums upon such parameters of the characteristics of gelation as η_max, η_min and η_25°C depended irregularly on the size of starch granules. In gels from gums and small granules, the role of G′ and G″ module differed from that in gels from the other starch fractions.     

Rheological behaviour of uncross-linked and cross-linked gelatinised waxy maize starch with pectin gels

Rheological characterisation of uncross-linked (UPS) and cross-linked (CPS) waxy maize starch with pectin was conducted to determine the influence of pectin on the properties of the starch. The viscoelastic behaviour of 5% (w/v) gel systems containing UPS and CPS polysaccharides at 25 °C was evaluated by small angle deformation oscillation rheometry. Viscoelasticity measurements of the cross-linked polysaccharides indicated that the elastic component increased after cross-linking. Among all gels studied, the properties of the CPS mixtures (ratios 2:3 and 3:2) showed quite high storage (G′) and loss (G″) moduli (compared with gels of other ratios), indicating that gels of these two particular ratios had the greatest degree of elasticity and were very well structured. The results suggest that cross-linking between starch and pectin molecules can give rise to novel rheological properties.     

Rheological properties and permeability of soy protein-stabilised emulsion gels made by acidification with glucono-δ-lactone

BACKGROUND: Soy protein, an important efficient emulsifier, is widely used by the food industry for incorporation into milk, yogurts, ice cream, salad dressings, dessert products, etc. The objective of this study was to investigate the rheological and physical properties of soy protein‐stabilised emulsion gels as affected by protein concentration and gelation temperature. RESULTS: The rheological properties and permeability were determined using oscillatory rheometry, permeability and whey separation. The modulus (G′ and G″), fracture stress and fracture strain of acid‐induced emulsion gels after 20 h of glucono‐δ‐lactone addition depended strongly on soy protein concentration and gelation temperature. At increasing soy protein concentrations, acid‐induced emulsion gels had shorter gelation times but higher storage moduli (G′), fracture stresses and strains. Increasing gelation temperature decreased the gelation time, G′, fracture stresses and strains. Permeability and whey separation were significantly affected by the protein concentration and the gelation temperature. A significant positive correlation was observed between whey separation and permeability coefficient in emulsion gels formed at different temperatures. CONCLUSION: The rheological properties and permeability of soy protein‐stabilised emulsion gels were significantly influenced by protein concentration and gelation temperature. Copyright © 2011 Society of Chemical Industry     

Role of cosolutes in gelation of high-methoxy pectin. Part 1. Comparison of sugars and polyols

Mixtures of high-methoxy pectin (DE 70; 1.0 wt%; pH 3.0) with ethan-1,2-diol, glycerol, xylitol, sorbitol, glucose, fructose or sucrose at concentrations of 50, 55, 60 and 65 wt% were prepared at 95 °C and changes in storage modulus (G′) and loss modulus (G″) during cooling to 5 °C, heating to 90 °C and re-cooling to 5 °C (at 1 °C/min) were measured at 1 rad s⁻¹ and 0.5% strain. In all cases, the onset temperature for gelation during cooling and the moduli recorded at 5 °C increased with increasing concentration of cosolute. Both values, however, were substantially lower for the liquid cosolutes (ethan-1,2-diol and glycerol) than for mixtures incorporating the same concentrations of the solid cosolutes. The difference is attributed to inhibition of pectin–pectin interactions by pectin–cosolute interactions, which in turn are inhibited by cosolute–cosolute interactions, these being weaker for the liquid cosolutes than for the solids (as indicated by lower melting points). On heating, there was an initial reduction in modulus, with the same temperature-course as the increase on cooling; for the solid cosolutes, this was followed by an increase attributable to hydrophobic association of methyl ester substituents. No such increase was seen with the liquid cosolutes, but differential scanning calorimetry studies showed two (reversible) thermal transitions in all cases, one over the temperature-range of the initial gelation process on cooling and the other coincident with the increase in modulus on heating in the presence of the solid cosolutes. The absence of any detectable increase in modulus on heating with the liquid cosolutes is attributed to accumulation of cosolute around the polymer chains (i.e. pectin–cosolute interactions) promoting hydrophobic association between methyl ester groups on the same chain, or within small clusters of chains, with, therefore, no contribution to network structure. At high concentrations of the solid cosolutes, the increase in modulus on heating was followed by a decrease at higher temperature; this is attributed to excessive aggregation, and was reflected in lower moduli on subsequent re-cooling to 5 °C, in contrast to the enhancement in gel strength after heating and cooling that was observed at lower concentrations of the same cosolutes.     

Gelling property of soy protein–gum mixtures

Gelling properties of soy protein–gum mixtures were determined by small deformation oscillation measurement and the experimental data were analyzed with blending laws of polymers. Gel strength of soy protein–carrageenan mixture was found to follow either upper or lower bounds depending on the concentration of the constituents, suggesting the occurring of phase shift. G′ of soy protein–xanthan mixed gel always followed the upper bound, indicating that soy protein was the continuous phase regardless variations of the gum concentration. Combination of soy protein with propylene glycol alginate (PGA) produced a mixed gel with high gel strength and stayed above the upper bound at all gum concentrations examined. Covalent bonds between PGA and soy protein was suggested to contribute to the rigidity. Storage modulus of the mixture of soy protein–locust bean gum (LBG) was below the lower bound at low gum concentrations due to the limited demixing process of LBG. G′ values of the mixture of soy protein and LBG–xanthan followed the lower bound but approached upper bound on reducing protein concentration, suggesting that the presence of soy protein might inhibit LBG–xanthan mixture from forming continuous networks.     

Effect of polysaccharides with different ionic charge on the rheological,microstructural and textural properties of acid milk gels

The effects of addition of polysaccharides with different ionic charge on rheology, microstructure, texture and water holding capacity (WHC) of acid milk gels were studied and compared to that of gelatin addition. Similar to gelatin, starch (neutral) and xanthan gum (anionic) did not prevent milk gelation in the first 30 min of the acidification stage, even at high concentrations, and the typical casein network in acid milk gels could still be seen from electron micrographs; gelling and melting of these hydrocolloids were observed during the cooling and heating stages at specific concentrations. On the other hand, two neutral polysaccharides, guar gum (≥ 0.05%) and locust bean gum [LBG] (≥ 0.1%) inhibited milk gelation from the beginning of the acidification stage; the microstructure of the gel was modified greatly and no gelling/melting was observed during the cooling or heating stages. Another anionic polysaccharide, carrageenan, induced earlier milk gelation at low concentration (≤ 0.05%), but inhibited gelation entirely at high concentration (0.2%); inflections at ~ 27 °C and 21 °C were also observed during the cooling and heating stages at 0.05% concentration. The gel microstructure was not changed greatly, but showed smaller particle size at a carrageenan concentration of 0.05% than control sample. None of the polysaccharides showed as much improvement in WHC of the milk gels as gelatin did. Hence, xanthan and starch were found to be closer to gelatin in their effect on acid milk gels compared to guar gum, LBG and carrageenan.