Effect of heating temperature,pH, concentration and starch/whey protein ratio on the viscoelastic properties of corn starch/whey protein mixed gels

The viscoelastic properties of corn starch (CS) gels were more dependent on heating temperature, while the properties of whey protein isolate (WPI) gels were more dependent on pH. Thus heating temperature (75, 85, 95 °C) and pH (5, 7, 9) were varied to obtain a series of mixed gels with interesting viscoelastic properties. WPI gels showed extensive stress relaxation (SR) indicative of a highly transient network structure, while CS gels relaxed very little in 2000 s. Based on SR results, it appeared that CS/WPI mixed gels with 25 and 50% CS formed compatible network structures at 15% total solids only at pH 9. This supposition was supported by SEM microstructures obtained for dehydrated gels and a synergistic increase in the large‐strain fracture stress for these gels. Some synergy was also found for mixed gels at 30% total solids at pH 9, while at pH 7 the mixed gels seemed to contain separate additive WPI and CS networks unlike the case for pH 7 at 15% total solids. In both cases (15 and 30% total solids) the degree of elasticity of the mixed gels decreased as the WPI content increased. Mixed gels (CS:WPI = 0.5) at pH 9 showed increased fracture stress and fracture strain relative to the same gels at pH 7. This suggests that a unique chemical compatibility exists at pH 9 and results in gels that combine the elasticity of CS and the internal stress dissipation of WPI. © 2001 Society of Chemical Industry     

Rheological,thermal and microstructural properties of whey protein isolate‐modified cassava starch mixed gels at different pH values

The objective of this study was to investigate the rheological, thermal and microstructural properties of whey protein isolate (WPI)‐hydroxypropylated cassava starch (HPCS) gels and WPI‐cross‐linked cassava starch (CLCS) gels at different pH values (5.75, 7.00 and 9.00). The rheological results showed that the WPI‐modified starch gels had greater storage modulus (G?) values than the WPI‐native cassava starch gels at pH 5.75 and 7.00. Differential scanning calorimetry curves suggested that the phase transition order of the WPI and modified starch changed as the pH increased. Scanning electron microscopy images showed that the addition of HPCS and CLCS contributed to the formation of a compact microstructure at pH 5.75 and 7.00. A comprehensive analysis showed that the gelling properties of the WPI‐modified starch were affected by the difference between the WPI denaturation temperature and modified starch gelatinisation temperature and by the granular properties of the modified starch during gelatinisation. These results may contribute to the application of WPI‐modified starch mixtures in food preparation.     

Swelling and Rheological Studies of Some Starch Hydrogels

Hydrogels with moderate water retention capacity and salt stability have been prepared from starch, oxidized starch, and amylopectin all crosslinked with epichlorohydrin. The swelling power was measured in water and in various salt solutions of different concentrations. The swelling capacity decreases with increasing both the crosslinker and the polymer concentration. The plateau modulus (G′_p) of the prepared gels was determined from complex dynamic viscosity measurements. G′_p was measured as a function of the epichlorohydrin and polymer concentrations. The loss modulus (G″) for the prepared gels was also measured and was always found to be almost zero. The molecular weight between two entanglement points (mesh width) was estimated from the G′_p values. The ratio between the number of elastically effective entanglement points, calculated from the G′_p values, and that calculated from complete conversion of the cross-linker was also estimated for various gels. It was found that this ratio is very small (0.2–0.7%) for gels prepared with 10 wt-% starch, it increases however to 13% at higher starch concentration of 25 wt-%.     

皂荚糖胶对玉米淀粉老化性质的影响及体系的水分分布

以玉米淀粉为原料,用流变分析、食品物性分析、差示扫描量热分析、低场核磁共振成像分析等研究冷藏过程中不同含量（相对玉米淀粉干基质量的1%、3%、5%和7%）皂荚糖胶对玉米淀粉老化特性的影响。动态流变时间扫描结果表明：随着老化时间的延长,玉米淀粉的弹性模量增加,皂荚糖胶的加入使复配体系弹性模量的变化率减小,一定程度上抑制玉米淀粉的短期老化;凝胶强度实验表明：随着冷藏时间的延长,玉米淀粉凝胶体系的硬度值增加,皂荚糖胶的加入使玉米淀粉形成质地更柔软的凝胶,硬度值明显降低;差示扫描量热测定结果表明：随着皂荚糖胶含量的增加,复配体系的老化率逐渐减小。用低场核磁水分运动性实验方法,通过5%皂荚糖胶加入前后淀粉凝胶中自由水、结合水和不易流动水含量的对比证实该胶对凝胶的水分分布有较大的影响;该研究能进一步丰富植物胶体对淀粉老化性能影响的理论。     

Effects of cornstarch on the gel properties of black bean protein isolate

The effects of common starch (CS) and high amylopectin starch (HAS) from corn on the properties of heat induced black bean protein isolate (BBPI) gels prepared by heating at 95°C for 30 min were investigated by using dynamic oscillatory rheometer, texture analyzer, and scanning electron microscopy (SEM). Compared with BBPI alone, the presence of cornstarch (1–4%, wt/vol) could improve storage modulus (G′) and textural properties of BBPI (10%, wt/vol) gels. The mixed system of BBPI and 4% (wt/vol) HAS exhibited the highest G′ and formed the gel faster and more easily, which resulted in firmer and more elastic gel than BBPI‐CS at all starch concentrations. It was possible that HAS had lower pasting temperature and higher viscosity than CS, which was beneficial to the formation of BBPI gel network and strengthened the stability of network structure. Moreover, it might also be related to the synergistic effect between protein and starch. The CS and HAS existed in the BBPI gel network could bind water, leading to the increase in the water‐holding capacity (WHC) of mixed gels, especially 4% (wt/vol) HAS, which was related to homogeneous and compact microstructure with small pores.     

Rheological Properties of Mixed Gels using Waxy and Non‐waxy Wheat Starch

Mixed starches with an amylose content of 5, 10, 18, 20, 23, and 25% were prepared by blending starches isolated from waxy and non‐waxy wheat at different ratios. The dynamic viscoelasticity of mixed 30% and 40% starch gels was measured using a rheometer with parallel plate geometry. The change in storage shear modulus (G′) over time at 5 °C was measured, and the rate constant of G′ development was estimated. As the proportion of waxy starch in the mixture increased, starch gels showed lower G′ and higher frequency dependence during 48 h storage at 5 °C. Since the amylopectin of waxy starch granules was solubilized more easily in hot water than that of non‐waxy starch granules, mixed starch containing more waxy starch was more highly solubilized and formed weaker gels. G′ of 30% and 40% starch gels increased steadily during 48 h. 30% starch gel of waxy, non‐waxy and mixed starches showed a slow increase in G′. For 40% starch gels, mixed starch containing more waxy starch showed rapidly developed G′ and had a higher rate constant of starch retrogradation. Waxy starch greatly influenced the rheological properties of mixed starch gels and its proportion in the mixture played a major role in starch gel properties.     

Comparison of Thermal and Viscoelastic Properties of Four Waxy Starches and the Effect of Added Surfactant

The waxy starches used in this investigation (maize (WM), barley (WB) and two rice starches RD4 and IR29) showed different gelatinization temperatures (GT) and enthalpies (ΔH_G) measured with differential scanning calorimetry (DSC). The differences in GT and ΔH_G could only partially be related to X-ray crystallinity. The high GT waxy starches WM and RD4 retrograded to a greater extent measured with DSC and the order of increased retrogradation agreed well with the order of X-ray crystallinity of the retrograded waxy starches. The melting temperature (T_C) of the retrograded waxy starches in contrast to GT was very similar for all starches. This indicates that the temperature of the glass transition (T_g) of the amorphous regions in the starch granules controlled the onset GT and perhaps also the extent of retrogradation. Addition of cetyl trimethyl ammonium bromide (CTAB) decreased the extent of retrogradation more than 45% compared to the melting enthalpy (ΔH_C) of the waxy starches without CTAB addition. The rice starch RD4 was most affected by the CTAB addition, and the WM starch the least. The viscoelastic behaviour in the temperature interval 25–90°C of 12%(w/w) gels differed between the waxy starches. The WB starch gels showed the highest storage modulus (G′) value and the lowest phase angle (δ), i. e. strongest and least viscous gels. The WM starch gels showed the lowest G′ value and the highest δ. The rice starches were in between with the RC4 starch (high GT) showing higher G′ value and lower δ than the IR29 (low GT). The viscoelastic parameters changed only slightly with increased temperature. The addition of CTAB to the waxy starch gels changed the viscoelastic behaviour of the stronger and less viscous starch gels of the WB and RD4 as their G′ value decreased and δ increased with increased temperature. The effect on WM and IR29 was only small.     

Effect of spring dextrin on retrogradation of wheat and corn starch gels

The influence of spring dextrin (SD) on the gelatinized starch retrogradation was investigated by wide X-ray diffraction (WXRD), differential scanning calorimetry (DSC) and molecular dynamic (MD) simulation. Different wheat and corn starch gels were prepared with the addition of SD₃, SD₅, SD₇ or SD₉. WXRD results showed that recrystallinity of wheat and corn starch gels was reduced with the addition of SD₇ or SD₉. Alternatively, SD₃ or SD₅ accelerated recrystallinity. Enthalpies of retrograde wheat and corn starch gels were analyzed using the Avrami equation and confirmed the WXRD results. Finally, MD simulation was adapted to predict the interaction of SD and starch fraction in water, and the results showed that the SD disturbed starch retrogradation by altering starch fraction–starch fraction interaction. Based on the obtained results of WXRD, DSC and MD, it was concluded that the addition of SDs significantly influences starch long-term retrogradation.     

Synergistic interaction of <Emphasis Type="Italic">Auricularia auricula</Emphasis>-<Emphasis Type="Italic">judae</Emphasis> polysaccharide with yam starch: effects on physicochemical properties and in vitro starch digestibility

Thermal stable polysaccharides from Auricularia auricula-judae (AP) have unique molecularstructures and multiple bioactivities. The effects of AP on the physicochemical properties and in vitro starch digestibility of yam starch (YS) were studied. The addition of AP induced a significant increase in the swelling power, solubility, mean volume diameter and adhesiveness as well as a dramatic decrease in the hardness and gumminess (p?<?0.05). AP showed a strong suppressive effect on in vitro starch digestibility. Higher modulus (G′, G″) and stiffness parameters (A_α), and lower order of relaxation function (α), were observed in oscillatory rheological measurements, indicating that the gels were more elastic-like and had higher pseudoplasticity in the presence of AP. Furthermore, AP remarkably decreased the syneresis and storage modulus (G′), and also retarded the retrogradation process of YS gel at 4°C, revealing a synergistic interaction between AP and YS, which could also be demonstrated by scanning electron microscopy.     

Predicting the Dynamic Elastic Modulus of Mixed Gelatin-Egg White Gels

The storage shear modulus (G′) of mixed gelatin-egg white protein gels was modeled using a modified Takayanagi approach. Ternary phase diagrams for two gelatin-egg white protein-aqueous solvent systems are presented. The composite modulus, G′_c, of mixed gels was found to be determined by the elastic properties of the individual gellants, their thermodynamic compatibility in a common solvent and their mutual reactivity. Rheological data suggested the occurrence of an interpenetrating network morphology, in single phase gels. Gelatin and egg white proteins were more compatible in water than in 0.6M NaCl-0.2 M NaH₂PO₄ buffer (pH 6.0).     

Structure-Mechanical Properties of Heat-Induced Whey Protein/Cassava Starch Gels

Structure-mechanical properties of heat-induced whey protein isolate/cassava starch (WPI/CS) gels were studied by hot-stage video microscopy (HSVM) and axial compression testing (ACT). Elastic moduli (or compression stress) of pure WPI and CS gels followed a power dependence with concentration. ACT confirmed that reinforcement occurred when CS was added at 10–25% of total solids. HSVM revealed that CS granules swelled first, removed water from the system and concentrated the WPI solution that gelled later. Reinforced gels had a continuous WPI phase filled with swollen CS granules. A modified Takayanagi model accounting for water redistribution during gelatinization accurately fitted the mechanical properties of these gels.     

Cold-set whey protein–flaxseed gum gels induced by mono or divalent salt addition

Mixed cold-set whey protein isolate (WPI)–flaxseed gum (FG) gels, induced by the addition of CaCl₂ or NaCl at fixed ionic strength (150 mM), were evaluated with respect to their mechanical properties, water-holding capacity (WHC) and SEM microscopy. They were prepared by mixing FG and thermally denatured (90 °C/30 min) WPI solutions at room temperature, but the gels were formed at 10 °C using two methods of salt incorporation: diffusion through dialysis membranes and direct addition. The mixed systems formed using dialysis membranes showed phase separation with the development of two (axial) layers, and the CaCl₂-induced gels presented radial phase separation. In general the CaCl₂-induced gels were less discontinuous, stronger, and showing lower WHC and deformability than the NaCl-induced gels. An increase in the FG concentration reduced the gel strength and WHC for both systems, which was associated with a prevailing phase separation between the biopolymers over the gelation process. Using direct salt addition, apparently none of the mixed gels showed macroscopic phase separation, but the NaCl-induced gels showed much higher hardness and elasticity than the CaCl₂-induced gels. Since the gelation process occurred more quickly by direct salt addition, and more effectively for the divalent salts, the more fragile structure of the CaCl₂-induced gels was a consequence of disruption of the cross-link interactions of the aggregates during the agitation used to homogenize the salt added.     

Formation of starch spherulites: Role of amylose content and thermal events

Commercial maize starches and potato starches of two cultivars differing in physicochemical composition (granule size distribution; amylose to amylopectin ratio) and crystallinity were heated to 180 °C and then cooled by fast quench using a differential scanning calorimeter (DSC), in order to produce spherulitic starch morphologies. Among the raw maize starches, waxy maize starch had highest relative crystallinity (49%) whereas a lowest crystallinity of 33–39% was calculated for high-amylose maize starches. Potato starches showed a relative crystallinity of 50%. The temperatures and enthalpies of gelatinisation and melting varied among all the starches. High-amylose maize starches showed higher transition temperatures of gelatinisation (T_gel), whereas waxy maize starch had lowest T_gel and enthalpy of gelatinisation (ΔH_gel). Similarly, a considerable variation in parameters related with crystalline melting (T_m1, T_m2 and ΔH_m1, ΔH_m2) was observed for different starches. The superheated gels of different starches treated using DSC were subjected to polarised microscopy, to confirm the formation of spherulites. Both the high-amylose starch gels showed the presence of spherulites exhibiting birefringence and a weak crystalline pattern. No birefringence was observed for waxy maize starch gel, while potato starch gels had some birefringence. The particle size distribution of high-amylose maize starch gels analysed through Zetasizer showed the sizes of spherulitic particles fall in the range of 300 nm–900 nm. The scanning electron micrographs of the dried high-amylose maize starch gels showed the presence of round spherulites consisting of several aggregated spherulitic particles. Amylose content and melting of crystallites during heating play an important role during recrystallisation of amylose (spherulite morphologies).     

Starch–methylcellulose–whey protein film properties

Four % (wt/wt) aqueous solutions were prepared at corn starch:methylcellulose:whey protein isolate (CS:MC:WPI) ratios of 2:2:2, 1:2:3, 2:1:3, 2:2:0, 1:2:0 and 2:1:0. Glycerol (gly) was used as a plasticiser at CS–MC–WPI:gly ratios of 2:1, 2.5:1 and 3:1. CS–MC–WPI blend films were stronger than CS–WPI films and had lower oxygen permeability (OP) than MC–WPI films. The highest tensile strength (TS) of blend films was 8.01 ± 3.41 MPa, at CS:MC:WPI ratio of 2:2:0 and CS–MC–WPI:gly ratio of 3:1. Lowest OP value was 45.05 ± 7.24 cm³ μm m^?2 per day kPa^?1, at CS:MC:WPI ratio of 2:2:2 and CS–MC–WPI:gly ratio of 3:1. OP values were predictable based on relative amounts of components. However, TS and elastic modulus properties of the CS–MC–WPI blend films did not reflect the relative amounts of the components. All of CS–MC–WPI films were translucent indicating some degree of immiscibility among the CS, MC and WPI. These results indicate the influence of complex molecular interactions among the components.     

Physical properties of egg albumen and cassava starch composite network formed by a salt-induced gelation method

Effect of cassava starch (CS) filler on the physical properties of egg albumen (EA) and cassava starch composite (EA–CS) gels and films was investigated using EA as the continuous matrix embedded with CS granules. The composite network was formed at 55 °C; below the thermal gelation temperature of both EA and CS, using the salt-induced gelation method. Increasing the pH from 8 to 11 and NaCl from 50 to 200 mM resulted in a softer but more cohesive EA gel (p ⩽ 0.05). Raising CS content increased Young’s modulus, stress and opacity but reduced the cohesiveness of the mixed gel network (p ⩽ 0.05). The release of paprika oleoresin (O/R) from the dried EA–CS composite film into the oil phase was determined as the effective diffusion coefficient (D_eff) based on Fick’s second law of diffusion. D_eff of O/R decreased with increases in the strength and elasticity of the composite film and relative humidity (RH) during film aging. Overall, the study showed that the salt-induced gelation method could be used to form an EA–CS composite film at room temperature. In addition to the strength and elasticity of the protein network, RH during aging could also provide a mean to regulate the controlled-release properties of such a composite film.     

Rheological properties of cereal starch gels and Mesona Blumes gum mixtures

The effect of Mesona Blumes gum (MBG) was examined on steady and dynamic shear of MBG/rice starch and MBG/wheat starch gels. In addition, stress relaxation and creep tests were performed for two types of cereal starch gels. The flow curves of both MBG/starch gels exhibited pseudoplastic behavior at shear rates between 0.01 and 10 s⁻¹, and the data were fitted into the power law model (R² = 0.91–0.98). Dynamic mechanical spectrum showed that all gels were strong gels in frequency between 0.1 and 10 Hz. Stress relaxation data at different strains indicated a strain‐softening phenomenon for both gels. Data were fitted into Maxwell model (R² = 0.91–0.98). Creep curves were conducted at the shear stress 6.4 Pa within linear viscoelastic region of both MBG/starch gels. Data were fitted into Burgers model (R² = 0.91–0.98). Apparent viscosity η, storage moduli G′, equilibrium stress relaxation modulus G_e and zero apparent viscosity η₀ of MBG/rice starch gels decreased in the following order: 6/0>6/0.5>6/0.35>6/0.1 (starch/gum w/w). Whereas η, G′, G_e, and η₀ of MBG/wheat starch gels increased gradually along side the increase of MBG contents. The stress relaxation time λ of MBG/rice starch gels increased in the following order: 6/0<6/0.5<6/0.35<6/0.1 (starch/gum w/w) while λ of MBG/wheat starch gels decreased gradually with the increase of MBG level. The influence of MBG on two examined cereal starch is totally opposite.     

Cold‐set whey protein gels induced by calcium or sodium salt addition

Cold‐set whey protein isolate (WPI) gels formed by sodium or calcium chloride diffusion through dialysis membranes were evaluated by mechanical properties, water‐holding capacity and microscopy. The increase of WPI concentration led to a decrease of porosity of the gels and to an increase of hardness, elasticity and water‐holding capacity for both systems (CaCl₂ and NaCl). WPI gels formed by calcium chloride addition were harder, more elastic and opaque, but less deformable and with decreased ability to hold water in relation to sodium gels. The non linear part of stress–strain data was evaluated by the Blatz, Sharda, and Tschoegl equation and cold‐set gels induced by calcium and sodium chloride addition showed strain‐weakening and strain‐hardening behaviour, respectively. The fractal structure of the gels indicated a weak‐link behaviour. For WPI gels results suggest intrafloc links, formed at heating step, which were more rigid than the interfloc links, promoted by salt addition.     

Segregative interactions and competitive binding of Ca in gelling mixtures of whey protein isolate with Naκ-carrageenan

Gelling mixtures of Na⁺κ-carrageenan with whey protein isolate (WPI) at pH 7.0 have been studied rheologically and by differential scanning calorimetry (DSC), with comparative measurements for the individual constituents of the mixtures. The concentration of WPI was held fixed at 10.0 wt% and carrageenan concentration was varied in the range 0.05–3.0 wt%. Ca²⁺ cations, which have been shown previously to be particularly effective in inducing gelation of κ-carrageenan, were introduced as CaCl₂. The concentration of CaCl₂ used in most of the experiments was 8 mM, but other concentrations were also studied. Mixtures were prepared in the solution state at 45 °C, and showed no evidence of either phase separation or complex formation. Rheological changes were monitored by low-amplitude oscillatory measurements of storage modulus, G′, during (i) cooling (1 °C/min) and holding at 5 °C, to induce gelation of the carrageenan in the presence of non-gelled WPI; (ii) heating and holding at 80 °C to dissociate the carrageenan network and induce gelation of WPI; (iii) cooling and holding again at 5 °C, to give composite networks with both components gelled; and (iv) re-heating to 80 °C to dissociate the carrageenan network. Gel structure was characterised further by creep–recovery measurements at the end of each holding period, and by torsion measurements at 5 °C, before and after thermal gelation of WPI.     

Ca2+-Induced Gelation of Pre-heated Whey Protein Isolate

Addition of CaCl₂ to pre-heated whey protein isolate (WPI) suspensions caused an increase in turbidity when pre-heating temperatures were ≥ 64°C. Pre-heating to ≥ 70°C was required for gelation. WPI suspensions which contained CaCl₂ became turbid at 45°C and formed thermally induced gels at 66°C. Thermally and Ca²⁺-induced gels showed significant time/temperature effects but the penetration force values in the Ca²⁺-induced gels were always lower. However, Ca²⁺-induced gels were higher in shear stress at fracture. The Ca²⁺-induced gels had a fine-stranded protein matrix that was more transparent than the thermally induced gels, which showed a particulate microstructure.     

Effects of fluid shear and temperature on whey protein gels, pure or mixed with xanthan

The effects of shear on whey protein isolate (WPI) gels, pure or mixed with xanthan, have been investigated at pH 5.4 by dynamic oscillatory measurements and light microscopy (LM). The shear was performed on the suspensions under a constant stress of between 0.04 and 2.1 Pa. Various temperature conditions were chosen in order to describe the effects of shear at the different states of aggregation of the WPI. Shear-sensitive aggregation phenomena were already found around 40°C for the pure WPI samples. Continuous shearing during heating from 20 to 40°C, prior to heat treatment at 90°C, resulted in a gel with a storage modulus (G′) half that of the unsheared gel, independent of the shear stress. Continuous shearing during heating from 20 to 76°C resulted in a further decrease in G′. Inhomogeneities arose in networks formed from continuously sheared suspensions during heating from 20 to 50°C and above. Depending on the shear stress and on the heating range of the shear, the networks showed areas of varied compactness and different classes of pores, ranging from 10 to 200 μm. A higher G′, compared to that for the unsheared gel, was found for gels subjected to shear for short periods in the vicinity of the gel point. The presence of xanthan inhibited the aggregation and demixing of the WPI, described as a sterical phenomenon. Under static conditions, the presence of xanthan resulted in a more homogeneous WPI network. Exposing the mixed suspensions to shear generally increased the inhomogeneity of the network structure. Short periods of shearing in the vicinity of the gel point affected the kinetics of the gel formation and resulted in gels with higher G′ values than the unsheared gel. Continuous shearing under stresses below 0.09 Pa, during heating from 20 to 60°C and above, also resulted in gels with an increased G′. Continuous shear under stresses above 0.9 Pa resulted in gels with a decreased G′