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.     

Effect of potato starch addition on the acid gelation of milk

Potato starch was added to skim milk at levels of 0–1.5%. The milks were heated and then acidified to form acid milk gels. The properties of the milks during acidification and the final properties of the acid gels were studied. The addition of starch resulted in a higher storage modulus, G′, in the final acid gels, and increasing the level of starch caused a linear increase in the final G′. Compared with acid gels prepared with no starch, the gelation time was reduced and the gelation pH was increased. However, the temperature and frequency dependences of the acid gels were not affected by the addition of starch. Furthermore, the breaking strain of the acid gels was not markedly affected by the addition of starch, whereas the breaking stress was dependent on the level of starch added. Confocal microscopy showed that the acid gels contained swollen starch granules embedded in a protein network, and that the protein network increased in density as the level of starch added increased.     

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.     

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.     

Preparation,Characterisation, and Rheological Behaviour of Starch-Sodium Trimetaphosphate Hydrogels

Ionic biopolymer hydrogels were prepared by the cross-linking of starches with sodium trimetaphosphate in alkaline medium at 40°C for 2 hours. The swelling capacity is relatively high — up to 310 g H₂0/g polymer. Salt solutions have a marked influence, and result in shrinkage but not in a total collapse. The effect of both the cross-linker and substrate concentrations on the swelling and rheological properties was investigated. The influence of temperature and NaOH concentration on the rheological behaviour suggests that they are both significant in determining the gel properties because of the readiness of the diester phosphate bonds to undergo hydrolysis. The molecular weight between two entanglement points (M_e) and the effectiveness of cross-linking [n_e(r)/n_e(t)] were estimated from the observed G_p′ values, and those calculated from complete conversion of the cross-linker. The effectiveness of cross-linking lay between 0.2 and 2.74% for 10% wlw gels, and reached a maximum of 48.1% at the higher substrate concentration of 20% wlw. ¹³C-NMR signals from the anhydroglucose units became broader and decreased in intensity with rising cross-linker concentration due to the restricted motion arising from the additional bonding.     

Hydrocolloids and Rheology: Regulation of Visco-elastic Characteristics of Waxy Rice Starch in Mixtures with Galactomannans

Texture and sensory properties of starch solutions or gels, resp., can be influenced by regulating the visco-elastic properties that cannot be adjusted by simply varying the waxy rice starch concentration. Therefore, the hydrocolloid galactomannans guar gum and locust bean gum were used for addition. A total polymer concentration of c = 5% was maintained through all tests, the hydrocolloid fractions varied (c_HK = 0.5%, 1%, 2%). The mixtures were entirely decomposed in an autoclave at 130°C resulting in an almost complete destruction of the granular starch structure. With rheomechanical oscillation measurements in the linear-visco-elastic range the influence of the galactomannans onto viscosity yield and visco-elasticity was determined quantitatively. It was found that the influence on the viscosity is depending on the deformation rate. At low frequencies and with increasing galactomannan fraction the viscosity decreases, while above a critical frequency ω_kr an increase in viscosity could be detected compared to pure starch. The mixtures also displayed an increase in viscous fractions versus elastic fractions compared to pure starch. With increasing galactomannan fraction, the ratio storage modulus/loss modulus is reduced continuously from G′:G″ > 10 (definitely mainly elastic) to G′:G″ = 1 with simultaneously decreasing influence of the frequency. Based on the presented data and knowledge on solution structure of the individual components, a model for describing network structures in mixtures was developed. Changes in viscous-elastic properties are based on a thermodynamic incompatibility between starch and galactomannan fractions. The mixtures contain mixed network structures, with waxy rice starch (permanent network points) and galactomannans (temporary network points) contributing individually and characteristically to the resulting flow behaviour.     

Chemical Modification,Cross-Linking and Characterization of Some Starch Hydrogels

Modified starch hydrogels were prepared via the reaction of starch with acrylamide (AAm), under certain conditions and cross-linking with N,N'-methylenebisacrylamide (MBA Am). Rheological measurements of different ratios gels shows that both increasing of cross-linker or substrate concentration, lead to increase the elasticity of the gels. The molecular weight between two entangelement points (M_e), was calculated from plateau modulus (G_p) values. The effectiveness of the cross-linker was calculated by comparison between the number of elastically effective points rheologically [n_e(r)] and that obtained from theoretical values [n_e(t)]. The effectiveness has a maximum value 5.76% at the higher substrate concentration of 25% (w/w) gels. Swelling of different gels were studied in pure water and in different salt solution. The curves show shrinking of the gels, however no collapsing occurs with increasing the concentration of salts. The maximum water absorption capacity were 140 g/g for 15/3 gels. the structure of the gels were interpreted with the guide of 13 C NMR spectrometry.     

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.     

Effect of the extent of pasting on the dynamic rheological properties of acidified skim milk gels containing normal rice starch

The dynamic rheological behaviour of skim milk gels containing 2% normal rice starch granules pasted to different temperatures was investigated. The extent of swelling of the starch granules was also measured. It was found that the complex modulus G* was maximal when the starch granules were pasted to the temperature of maximum swelling and not to the temperature of maximum viscosity. It is suggested that, in these systems, the starch granules behave as inactive fillers and that their main effect is to increase the milk protein concentration during swelling by absorbing water from the continuous phase. A simple empirical model that agrees qualitatively well with the experimental results is proposed.     

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).     

Physicochemical,rheological, morphological,and in vitro digestibility properties of cross-linked starch from pearl millet cultivars

The effect of epichlorohydrin (0.5%) as a cross-linking agent on physicochemical, rheological, morphological, and in vitro digestion properties of pearl millet starches from different cultivars was studied. Degree of cross-linking (DC) ranged between 40.61% and 89.75%, lower values of DC were observed for cv.HC-10 and cv.HHB-67 whereas higher values were observed for cv.HHB-223 and cv.GHB-732. Cross-linked starch from cv.GHB-732 showed the lowest amylose content, swelling power, and solubility as compared to other cultivars. Rheological properties of starches during heating showed their elastic behaviour. G′ value was much higher than the G′′ value at all frequency values for starch pastes. Plots of shear stress (σ) versus shear rate (γ?) data for cross-linked starch pastes were fitted to Herschel-Bulkley model and yield stress (σ_o), flow behaviour index (n), and consistency index (K) were evaluated. Scanning electron micrographs (SEM) investigations revealed that cross-linked starch granules had slightly rough surfaceand grooves with slight fragmentations. Readily digestible starch (RDS) of cross-linked starches varied from 46.1% to 50.6%, cv.GHB-732 had the lowest value. Slowly digestible starch (SDS) and resistant starch (RS) content of cross-linked starches ranged from 34.5% to 36.4% and 13.6% to 19.4%, respectively. cv.HC-10 had the highest value for SDS content while the highest RS content was observed for cv.GHB-732. In comparison to native starches, cross-linked modification decreased SDS and RDS content whereas RS content was increased.     

Rheological, Thermal and Microstructural Properties of Whey Protein-Cassava Starch Gels

Mixed gels of cassava starch (CS) and a whey protein isolate (WPI), obtained by heating solutions of 10% total solids, pH 5.75 to 85°C, were characterized as a function of the starch fraction, θ_s, by axial compression, small-amplitude oscillatory rheometry, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Gelation did not occur for θ_s > 0.7. In the range 0<θ_s < 0.4 mixed gels showed higher mechanical (E, elastic modulus) and rheological (G′, storage modulus) properties than pure gels, with maximum values for θ_s= 0.2–0.3. Viscoelastic measurements as a function of time showed that gels containing higher levels of WPI developed a larger G. Blends of both biopolymers showed independent thermal transitions in DSC measurements, related to gelatinization and denaturation. Microstructure of a mixed gel formed at θ_s= 0.2 showed a continuous matrix formed by strands of WPI particle aggregates and an independent CS phase.     

BRAZILIAN HULL-LESS AND MALTING BARLEY GENOTYPES: II. THERMAL AND RHEOLOGICAL PROPERTIES OF STARCH

Thermal and rheological properties of starch isolated from two Brazilian barley experimental lines, malting and hull‐less, are reported. Gelatinization's thermal properties were T_o 53.3 and 58C, T_p 59.4 and 62.7C, and ΔH 6 and 6.8 J/g for the malting and hull‐less starch, respectively. A trend to slightly higher retrogradation rates were obtained for the malting (73.3%) compared with the hull‐less (72.1%) starch, while lower hot‐paste peak and final viscosity were observed in the former (125 and 114 RVU versus 169 and 179 RVU, respectively). Changes in storage (G′) and loss (G″) moduli during heating and cooling showed higher values for the starch from the hull‐less line. During heating, G′was higher than G″and developed at higher temperatures. A trimodal distribution pattern of G″was observed in the starch from the hull‐less barley line. Two G′peaks at 75 and 87.5C were 6.2 and 2.4 times higher, respectively, in the starch from the hull‐less line than that from the malting line.     

Characteristics of Novel Starch‐based Hydrogels Prepared by UV Photopolymerization of Acryloylated Starch and A Zwitterionic Monomer

New starch‐based hydrogels were prepared by the UV‐induced polymerization of acryloylated starch with the zwitterionic monomer 3‐dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (DMAPS). The swelling kinetics of the resultant hydrogels in distilled water and their equilibrium swelling ratios in aqueous NaCl and CaCl₂ solutions were investigated. With increasing amount of incorporated DMAPS, the formed hydrogel had an enhanced swelling ability in distilled water and in aqueous salt solutions. In particular, antipolyelectrolyte swelling behavior of the hydrogel was observed in aqueous salt solutions.     

Effect of cross‐linking on some properties of potato (Solanum tuberosum L.) starches

Starches separated from different potato cultivars were modified using two different cross‐linking agents: epichlorohydrin (EPI) and phosphoryl chloride (POCl₃) at different concentrations (1.0 and 2.0 g kg^?1 POCl₃; 2.5, 5.0 and 10 g kg^?1 EPI). Differential scanning calorimetry, rheological and retrogradation measurements were performed to characterise the influence of cross‐linking on the properties of potato starches. Cross‐linking considerably reduced swelling power, solubility, water‐binding capacity and paste clarity. The decrease became greater as the reagent concentration increased. The starches treated with 1.0 g kg^?1 POCl₃ exhibited exceptionally higher swelling power than their counterpart native starches. Neither cross‐linking agent caused any change in morphology of the starch granules. Studies on the phase transitions associated with the gelatinisation showed significantly higher values for the onset temperature (T_o), peak temperature (T_p), conclusion temperature (T_c) and enthalpy of gelatinisation (ΔH_gel) for the cross‐linked starches than the native starches. Starches treated with both the reagents showed lower peak storage modulus (G′) and loss modulus (G″) than their native counterparts. The tendency of the starch pastes towards retrogradation increased considerably with increases in storage duration. However, the starches treated with 1 g kg^?1 POCl₃ exhibited much lower syneresis than the other cross‐linked starches. Copyright © 2006 Society of Chemical Industry     

OSCILLATORY PROBE RHEOMETRY AS A TOOL FOR DETERMINING THE RHEOLOGICAL PROPERTIES OF STARCH-WATER SYSTEMS 1

An oscillatory probe rheometer was effective at measuring the viscosity of starch pastes and the viscoelastic properties of starch gels. Because low shear strains were applied, the integrity of the gel was not disrupted during the testing. As the starch concentration of the systems increased, the complex modulus (G*) and storage modulus (G′) increased. At 20°C, the strength of the resulting gels, as measured by log G′, was a linear function of starch concentration. Loss tangent values (G″/G′) could be used to determine the approximate temperature at which the sol became a gel. As the starch concentration of the systems increased, the temperature of the sol to gel transformation increased from approximately 35°C (5% starch) to 60°C (10% starch).     

Sol gel transitions during acid gelation of milk containing modified waxy maize starch. Differences between chemical and bacterial acidification measured using rheological and spectroscopic techniques

Modified waxy maize starch (1%, w/v) was added to skim milk and the mixtures were heated and homogenized. Acidification was conducted at 40 °C, using either glucono-δ-lactone (GDL) or a commercial starter culture. The physico-chemical changes occurring during acidification were monitored using small oscillatory rheology, diffusing wave spectroscopy and ultrasound spectroscopy. A similar gelling behaviour was noted for GDL and bacterial-induced gels; however, a difference was noted in the values of storage modulus (G′). The presence of starch did not seem to affect the development of the gel structure, nor the mobility and positional correlations of the casein micelles during acidification. On the other hand, starch increased the final storage modulus, G′ of the acid milk gels. These results indicate the absence of direct interactions between micelles and the modified starch granules.     

Influence of Soluble Polymer Residues in Crosslinked Carboxymethyl Starch on some Physical Properties of its Hydrogels

Crosslinked carboxymethyl starch (CMS) was synthesized from potato starch in a single‐step procedure with mono‐ (MCA) and dichloroacetic acid (DCA), using the well‐known Williamson reaction. The products varied in their degree of substitution DS (average number of carboxymethyl groups per monomer unit) and crosslinker ratio F_z (number of crosslinker molecules offered per monomer unit). After neutralizing and removal of the formed salt, one part of the synthesized CMS networks was pre‐swollen in water in an additional purification step in order to wash out unlinked, soluble polymer chains. The rest of the product remained unwashed. Different swelling experiments were performed with the two samples, before being dried and ground. Both, the Free Swelling Capacity (FSC) and the Absorption Capacity Under Mechanical Load (AUL) of the hydrogels were strongly influenced by chemically unlinked CMS chains that were only physically entangled in the network structure. These mobile polymer segments were responsible for a significant weight loss of the swollen, unwashed hydrogels over the course of time. Rheological oscillatory experiments showed that, in order to achieve comparable values for the storage and loss moduli (G′ and G′′), the polymer content of an unwashed hydrogel had to be more than twice as high as that of the corresponding purified product. By using a special rheological test procedure with a cyclic temperature program, the long‐term stability of CMS gels could be measured and verified.     

Modification of Starch-Based Hydrogels Through Grafting by a New Chelating Monomer

Native maize starch was grafted by N-acryloyl-N′-cyanoaceto-hydrazide (ACAH) using potassium persulfate as a free radical initiator in aqueous medium. Spectral (FT-IR) and elemental analyses were used in combination to elucidate both the structure and composition of the thoroughly washed grafted samples. Gelation of the produced grafted samples has been carried out in alkaline medium using sodium trimetaphosphate (Na₃P₃O₉) as a cross linker. The effects of temperature and sodium hydroxide, substrate and crosslinker concentrations were found to be significant in determination of the rheological properties of the prepared modified gels. The influence of grafting ratio and cross-linker concentration on the gel swelling ability was investigated in deionized water as well as in sodium and potassium chloride 10⁻² molar solutions. The produced gels showed a great tendency towards complexation with many metal cations. Chelation with Cu(II), Ni(II) and Cr(III) chloride solutions has been spectrophotometrically investigated. Stability constants of the formed complexes were found to be of the order of 10⁷.     

Studies on the morphological,thermal and rheological properties of starch separated from some Indian potato cultivars

The starches separated from five different Indian potato cultivars (Kufri Chandermukhi, Kufri Badshah, Kufri Jyoti, Kufri Sindhuri and S1) were investigated for morphological, thermal, rheological, turbidity and water-binding properties. The starch separated from all the five potato cultivars had a granule size ranging between 15–20 μm and 20–45 μm. The shape of starch granules varied from oval to irregular or cuboidal. Starch isolated from cv. Kufri Badshah had largest irregular or cubiodal granules while starch from cv. Kufri Chandermukhi had small and oval granules. The transition temperatures and enthalpy of gelatinization (ΔH_gel) were determined using differential scanning calorimetry (DSC). The enthalpy of retrogradation (ΔH_ret) of gelatinized starch was also determined after 14 days of storage at 4°C using DSC. Kufri Chandermukhi starch showed the lowest ΔH_gel and ΔH_ret while Kufri Badshah starch showed the highest values. ΔH_gel and ΔH_ret values of 12.55 J/g and 6.42J/g, respectively, for Kufri Chandermukhi starch against 13.85 J/g and 8.61 J/g, respectively, for Kufri Bhadshah starch were observed. Rheological properties of starches from different potato cultivars, measured using the Dynamic Rheometer during heating and cooling, also differed significantly. The starch from cv. Kufri Badshah showed the highest peak G′ and G″ and lowest tan δ. The starches having higher peak G′(G′ at gelatinization temperature) showed higher breakdown in G′ and vice versa. The turbidity of gelatinized aqueous starch suspensions from all potato cultivars increased with increase in storage period. Starches with low water binding capacity had higher G′ and G″ and lower tan δ values.