"Weak gel"-type rheological properties of aqueous dispersions of nonaggregated kappa-carrageenan helices

The rheological properties of kappa-carrageenan helices dispersed in an aqueous medium, which prevents aggregation of helices, were investigated. A dispersion of 1.5% w/w nonaggregated kappa-carrageenan helices exhibited gel-like dynamic mechanical spectra at 20 degrees C; that is, the storage modulus G' predominated over the loss modulus G' ' in the entire frequency range examined (0.5-100 rad/s). However, the observed slight frequency dependence of the moduli and the relatively large value of tan delta (= G' '/G' > 0.1) were typical of so-called weak gels. The magnitude of G' of the kappa-carrageenan weak gels was less than that of conventional gels formed by 0.15% w/w kappa-carrageenan in an aggregating condition at 20 degrees C. Under large deformation, enough for the conventional gels to rupture, the weak gel systems flowed but never ruptured, suggesting that the weak gel-type rheological properties of the kappa-carrageenan dispersions were due to a sufficiently long relaxation time of topological entanglements among double-helical conformers but not due to the formation of a three-dimensionally percolated permanent network.     

Effect of galactomannans on the thermal and rheological properties of sago starch

The thermal and rheological properties of sago starch have been studied in the presence of various concentrations of locust bean gum and guar gum of various molecular masses. At the concentrations studied (<1%) the galactomannans gave rise to only a very slight increase in the gelatinization temperature (up to 0.6 degrees C), and the gelatinization enthalpy remained constant within experimental error. For the low molecular mass galactomannans, depending on the concentration, the storage modulus, G', of the mixtures remained constant or actually decreased, and tan delta remained very low (0.01-0.03 at 0.1 Hz), indicating strong elastic gels. For the higher molecular mass samples G' increased significantly; however, the loss modulus, G' ', increased proportionally to a greater extent, and at 1% galactomannan tan delta was approximately 0.20 at 0.1 Hz, indicating a reduction in elastic character. The systems were shown to undergo phase separation, and the variations in rheological properties have been discussed in the context of their phase behavior and the relative rates of the phase separation and gelation processes. The presence of galactomannans significantly improved the freeze-thaw stability.     

Gelation of iota-carrageenan and micellar casein mixtures under high hydrostatic pressure

Effects of high-pressure treatment (HPT) on the rheological parameters and gelation of iota-carrageenan (iota-Car) and mixtures of micellar casein (MC) and iota-Car have been investigated under neutral pH conditions. It was established that HPT showed no significant effect, in the presence or absence of ionic calcium, with or without initial thermal processing, on the rheology or gelation/melting temperatures of the pure iota-Car solution. However, in mixed systems containing varying concentrations of iota-Car (up to 1 wt %) and MC (up to 8 wt %), considerable changes were detected. At the higher molar ratios of MC to iota-Car, and especially at the higher pressures, the dispersions were not thermoreversible in gelation, presumably due to the strong interactions of disrupted casein micelles with iota-Car molecules, as well as due to the formation of a dominant proteinaceous network at higher concentrations of MC. The associative protein-polysaccharide interactions in these systems are highly dependent on the ionic calcium content.     

State diagram of temperature vs date solids obtained from the mature fruit

Mature dates were dried achieving an increase in the level of solids from 70.8% to 92.4% (wet basis). Small deformation dynamic oscillation was employed to identify changes in the viscoelastic properties of dates as a function of solids. Samples were cooled or heated at a constant scan rate of 1 degrees C/min. At high temperatures, e.g., 70 degrees C, the storage and loss modulus (G' and G' ', respectively) remained relatively independent of the time or frequency of observation, thus delineating the plateau zone. Cooling resulted in rapid development of both moduli with G' ' overtaking G'. This is known as the glass transition region and was used to define the rheological T(g). Eventually, the glassy state is reached where the storage modulus becomes dominant once more and approaches values of 10(9.5) Pa. The values of T(g) were used to determine the metastable glass transition curve of mature dates. At lower levels of solids, i.e., between 11.7% and 64%, freezing experiments were employed to identify the equilibrium melting curve of ice. The state diagram yielded a maximally freeze-concentrated solute at 70% solids with the characteristic temperature of glass formation being -50 degrees C. Data on equilibrium and kinetic events were modeled using the Chen and Gordon-Taylor equations yielding the rheological T(g) for date solids at their effective molecular weight.     

Effect of sucrose on the thermomechanical behavior of concentrated wheat and waxy corn starch-water preparations

The rheological behavior of concentrated starch preparations from two different origins (wheat and waxy corn) was studied in the presence of sucrose by dynamic mechanical thermal analysis (DMTA). Moisture contents ranged from 30 to 60% (w/w wsb), and samples contained 0, 10, or 20 g of sucrose for 100 g of the starch-water mixture. The storage modulus (G') changes during heating depended strongly on water content (in the moisture range studied), and the importance of these variations was dependent upon the starch type. Sucrose addition resulted in a shift to higher temperatures of the increase in G' during heating. Differential scanning calorimetry (DSC) and electron-spin resonance (ESR) analyses were performed in parallel in order to relate the viscoelastic changes to water migrations and to structural disorganization of starch. Sucrose was found to increase the gelatinization temperature and enthalpy of both starches, implying a stabilization of the granular structure during heating. The sugar-water interactions do not appear to be the only way by which sucrose delays starch gelatinization. The obtained results suggest that sugar-starch interactions in the amorphous and/or the crystalline regions of the starch granules should be envisaged.     

Effects of thermal and high hydrostatic pressure processing and storage on the content of polyphenols and some quality attributes of fruit smoothies

The aim of the present study was the evaluation of high hydrostatic pressure (HHP) processing on the levels of polyphenolic compounds and selected quality attributes of fruit smoothies compared to fresh and mild conventional pasteurization processing. Fruit smoothie samples were thermally (P(70) > 10 min) or HHP processed (450 MPa/1, 3, or 5 min/20 °C) (HHP1, HHP3, and HHP5, respectively). The polyphenolic content, color difference (ΔE), sensory acceptability, and rheological (G'; G'; G*) properties of the smoothies were assessed over a storage period of 30 days at 4 °C. Processing had a significant effect (p < 0.001) on the levels of polyphenolic compounds in smoothies. However, this effect was not consistent for all compound types. HHP processed samples (HHP1 and HHP3) had higher (p < 0.001) levels of phenolic compounds, for example, procyanidin B1 and hesperidin, than HHP5 samples. Levels of flavanones and hydroxycinnamic acid compounds decreased (p < 0.001) after 30 days of storage at 2-4 °C). Decreases were particularly notable between days 10 and 20 (hesperidin) and days 20 and 30 (chlorogenic acid) (p < 0.001). There was a wide variation in ΔE values recorded over the 30 day storage period (p < 0.001), with fresh and thermally processed smoothies exhibiting lower color change than their HHP counterparts (p < 0.001). No effect was observed for the type of process on complex modulus (G*) data, but all smoothies became less rigid during the storage period (p < 0.001). Despite minor product deterioration during storage (p < 0.001), sensory acceptability scores showed no preference for either fresh or processed (thermal/HHP) smoothies, which were deemed acceptable (>3) by panelists.     

Compositional analysis and rheological properties of gum kondagogu (Cochlospermum gossypium): a tree gum from India

Gum kondagogu ( Cochlospermum gossypium) is a tree exudate gum that belongs to the family Bixaceae. Compositional analysis of the gum by HPLC and LC-MS revealed uronic acids to be the major component of the polymer ( approximately 26 mol %). Furthermore, analysis of the gum by GC-MS indicated the presence of sugars such as arabinose (2.52 mol %), mannose (8.30 mol %), alpha- d-glucose (2.48 mol %), beta- d-glucose (2.52 mol %), rhamnose (12.85 mol %), galactose (18.95 mol %), d-glucuronic acid (19.26 mol %), beta- d-galactouronic acid (13.22 mol %), and alpha- d-galacturonic acid (11.22 mol %). Gum kondagogu, being rich in rhamnose, galactose, and uronic acids, can be categorized on the basis of its sugar composition as a rhamnogalacturonan type of gum. The rheological measurements performed on the gum suggest that above 0.6% (w/v) it shows a Newtonian behavior and shear rate thinning behavior as a function of gum concentration. The viscoelastic behavior of gum kondagogu solutions (1 and 2%) in aqueous as well as in 100 mM NaCl solution exhibits a typical gel-like system. The G' (viscous modulus)/ G' (elastic modulus) ratios of native gum kondagogu (1 and 2%) in aqueous solution were found to be 1.89 and 1.85 and those in 100 mM NaCl to be 1.54 and 2.2, respectively, suggesting a weak gel-like property of the polymer. Crossover values of G' and G' were observed to be at frequencies of 0.432 Hz for 1% and 1.2 Hz for 2% for native gum in aqueous condition, indicating a predominantly liquid- to solid-like behavior, whereas crossover values of 2.1 Hz for 1% and 1.68 Hz for 2% gum in 100 mM NaCl solution suggest a larger elastic contribution.     

Rheological properties of fast skeletal myosin rod and light meromyosin from walleye pollack and white croaker: contribution of myosin fragments to thermal gel formation

Myosin rod and light meromyosin (LMM) of walleye pollack and white croaker were examined for their rheological properties by measuring dynamic viscoelastic parameters. Rods from walleye pollack and white croaker increased their storage moduli (G') in the ranges of 29-43 degrees C and 31-38 degrees C, respectively, in temperature sweep analysis. Walleye pollack LMM showed no peak of G' upon heating, whereas the white croaker counterpart exhibited a single sharp peak of G' at 35 degrees C. Loss modulus (G") showed similar temperature-dependent changes for the two fish species as the case of G', irrespective of rod and LMM, although G" values were lower than those of G'. Thus, rheological properties of rod and LMM were different between walleye pollack and white croaker. Taken together with data previously reported for myosin, it was considered that both myosin rods from walleye pollack and white croaker are attributed to thermal gel formation of myosin in a low-temperature range, though in a species-specific manner.     

Effect of annealing temperature on gelatinization of rice starch suspension as studied by rheological and thermal measurements

The effect of annealing temperature (Ta) on the rheological behavior of 10 wt % rice starch suspension was investigated by the dynamic viscoelasticity, the differential scanning calorimetry (DSC), and the amount of leached out amylose and the swelling ratio of starch suspension. The rheological behaviors of the annealed samples are classified into three types in terms of Ta: Ta1, 48 and 55 degrees C, which are much lower than the gelatinization temperature, Tgel (=62 degrees C); Ta2, 58, 60, and 62 degrees C, which are almost the same as Tgel; and Ta3, 65, 68, 70, and 73 degrees C, which are much higher than Tgel. For the samples annealed at Ta2, the onset temperature of the storage and the loss moduli, G' and G', increased with increasing T(a), and G' and G" in the temperature range from 65 to 90 degrees C gradually increased though smaller than those for the nonannealed sample, the control. This can be understood by the partial gelatinization; i.e., the leached out amylose prevents further amylose from leaching out. The rheological property of the samples annealed at Ta1 is not so different from that of the control, and the samples annealed at Ta3 are almost gelatinized. The rheological behavior of starch suspension can be controlled by Ta.     

Gelation of chicken pectoralis major myosin and heat-denatured beta-lactoglobulin

Thermal, rheological, and microstructural properties of myosin (1 and 2% protein) were compared to mixtures of 1% myosin and 1% heat-denatured beta-lactoglobulin aggregates (myosin/HDLG) and 1% myosin and 1% native beta-lactoglobulin (myosin/beta-LG) in 0.6 M NaCl and 0.05 M sodium phosphate buffer, pH 6.0, 6.5, and 7.0 during heating to 71 degrees C. Thermal denaturation patterns of myosin and myosin/HDLG were similar except for the appearance of an endothermic peak at 54-56 degrees C in the mixed system. At pH 7.0, 2% myosin began to gel at 48 degrees C and had a storage modulus (G') of 500 Pa upon cooling. Myosin/HDLG (2% total protein) had a gel point of 48 degrees C and a G' of 650 Pa, whereas myosin/beta-LG had a gel point of 49 degrees C but the G' was lower (180 Pa). As the pH was decreased, the gel points of myosin and myosin/HDLG decreased and the G' after cooling increased. The HDLG was incorporated within the myosin gel network, whereas beta-LG remained soluble.     

Effects of endogenous flour lipids on the quality of semisweet biscuits

Fractionation and reconstitution techniques were used to study the contribution of endogenous flour lipids to the quality of semisweet (Rich Tea-type) biscuits. Biscuit flour was defatted with chloroform and baked with bakery fat but without endogenous lipid addition. Semisweet biscuits baked from defatted flour were flatter, denser, and harder and showed collapse of gas cells during baking when compared with control biscuits. Defatted flour semisweet doughs exhibited a different rheological behavior from the control samples showing higher storage and loss moduli (G' and G' ' values), that is, high viscoelasticity. Functionality was restored when total nonstarch flour lipids were added back to defatted flour. Both the polar and nonpolar lipid fractions had positive effects in restoring flour quality, but the polar lipid fraction was of greatest benefit. Both fractions were needed for complete restoration of both biscuit quality and dough rheological characteristics.     

Effect of salts on the gelatinization and rheological properties of sago starch.

The effects of various salts on the gelatinization and rheological properties of sago starch have been studied using differential scanning calorimetry, small deformation oscillation, and large deformation techniques. The presence of salts affected the gelatinization peak temperature, T(p), gelatinization enthalpy, DeltaH, swelling properties, storage modulus, G', gel strength, GS, and gelation rate constants, k, depending on the type of salt and the concentration. Their influence followed the Hofmeister series, and the effect of anions was more pronounced than that of cations. Sulfate ions increased T(p), G', GS, and k and reduced the swelling properties, whereas iodide and thiocyanate ions reduced T(p), G', GS, and k but increased the swelling properties. For all of the salts studied except for Na(2)SO(4), T(p) increased to a maximum and then decreased again at higher salt concentrations while DeltaH reduced with concentration. In the presence of MgCl(2), CaCl(2), and LiCl complex behavior was observed such that at approximately 3.5 M MgCl(2) and CaCl(2) and 8 M LiCl the starch samples were gelatinized at room temperature, whereas at much higher concentration T(p) increased again and the transition became exothermic.     

Heat-induced gelation of chicken Pectoralis major myosin and beta-lactoglobulin

The denaturation, aggregation, and rheological properties of chicken breast muscle myosin, beta-lactoglobulin (beta-LG), and mixed myosin/beta-LG solutions were studied in 0.6 M NaCl, 0.05 mM sodium phosphate buffer, pH 7.0, during heating. The endotherm of a mixture of myosin and beta-LG was identical to that expected if the endotherm of each protein was overlaid on the same axis. The maximum aggregation rate (AR(max)) increased, and the temperature at the AR(max) (T(max)) and initial aggregation temperature (T(o)) decreased as the concentration of both proteins was increased. The aggregation profile of <0.5% myosin was altered by the presence of 0.25% beta-LG. Addition of 0.5-3.0% beta-LG decreased storage moduli of 1% myosin between 55 and 75 degrees C, but increased storage moduli (G') when heated to 90 degrees C and after cooling. beta-LG had no effect on the gel point of > or =1.0% myosin, but enhanced gel strength when heated to 90 degrees C and after cooling. After cooling, the G' of 1% myosin/2%beta-LG gels was about 1.7 times greater than that of gels prepared from 2% myosin/1% beta-LG.     

Toward the recognition of structure-function relationships in galactomannans

In this paper the determination of the physical/rheological characteristics is described for a series of commercial galactomannans of which the structural details have been reported previously. Both solubility of the galactomannans and rheological properties of galactomannan solutions and galactomannan/xanthan mixtures were determined. Using a statistical analysis approach an attempt was undertaken to recognize correlations between structural and rheological data. The best correlation found was between the abundance of galactose substituents at a regular distance (type of galactomannan) and the storage modulus (G') of mixed galactomannan/xanthan gels, underscoring the hypothesis that branching hinders the formation of a network with xanthan gum. Also, the G' for the group of locust bean gums correlated with the degree of blockiness, that is, the size and occurrence of nonsubstituted regions on the mannose backbone. In addition, galactomannans displayed an apparent decrease in gelling ability with increasing average molecular weight. That G' also relates to the type of galactomannan can therefore partly be attributed to differences in average molecular weight for the various galactomannan types. However, within the series of locust bean gums tested, also an increase of G' with molecular weight was observed. This can be explained by the decreasing number of loose ends of the polymers and the concomitant increasing efficiency in network participation with increasing molecular weight.     

Morphological, structural, thermal, and rheological characteristics of starches separated from apples of different cultivars

The starches were separated from unripe apples of five cultivars (Criterion, Ruspippum, Red Spur, Skyline Supreme, and Granny Smith) and evaluated using scanning electron microscopy (SEM), gel permeation chromatography (GPC), X-ray diffraction, differential scanning calorimetry (DSC), and dynamic viscoelasticity. SEM showed the presence of round granules as well as granules that had been partially degraded, probably by amylases. The starch granules in different apple starches ranged between 4.1 and 12.0 mum. Debranching of starch with isoamylase and subsequent fractionation of debranched materials by GPC revealed the presence of an apparent amylose, an intermediate fraction (mixture of amylose and amylopectin), long side chains of amylopectin, and short side chains of amylopectin in the range of 28-35.2, 3.6-4.4, 20-21.3, and 39.9-47.1%, respectively. The swelling power of starches ranged between 14.4 and 21.3 g/g. X-ray diffraction of apple starches showed a mixture of A- and B-type patterns. All apple starches showed peak intensities lower than that observed for normal corn and potato starch, indicating the lower crystallinity. The transition temperatures (onset temperature, T(o); peak temperature, T(p); and conclusion temperature, T(c)) and enthalpy of gelatinization (deltaH(gel)) determined using DSC ranged between 54.7 and 56.2 degrees C, between 57.1 and 59.1 degrees C, between 60.2 and 63.5 degrees C, and between 3.3 and 4.2 J/g, respectively. The viscoelastic properties of starch from different cultivars measured during heating and cooling using a rheometer differed significantly. Red Spur and Criterion starches with larger granule size showed higher G' and G' ' values, whereas those containing smaller size and amylolytically degraded granules showed lower G' and G' '.     

Heat-induced soy-whey proteins interactions: formation of soluble and insoluble protein complexes

The aggregation behavior during heating of a solution containing soy protein and whey protein isolate (WPI) was studied using rheology, confocal microscopy, gel filtration, and electrophoresis. Soy/WPI mixtures formed gels at 6% total protein concentration with a high elastic modulus (G') and no apparent phase separation. The ratio of soy to WPI was fundamental in determining the type of network formed. Systems containing a high soy to WPI ratio (>70% soy protein) showed a different evolution of the elastic modulus during heat treatment, with two apparent stages of network development. Whey proteins formed disulfide bridges with soy proteins during heating, and at low ratios of soy/WPI, the aggregates seemed to be predominantly formed by 7S, the basic subunits of 11S and beta-lactoglobulin. Size exclusion chromatography indicated the presence of high molecular weight soluble complexes in mixtures containing high soy/WPI ratios. Results presented are the first evidence of interactions between soy proteins and whey proteins and show the potential for the creation of a new group of functional ingredients.     

Dynamic Viscoelastic Behavior of High-Pressure-Treated Wheat Gluten

The effects on the viscoelastic behavior of hydrated wheat gluten after treatment at different pressures (200–800 MPa), temperatures (20, 40, and 60°C), and holding times (20 and 50 min) were investigated by controlled stress rheometry. Because of the wide range of properties, four different torque amplitudes were used (0.5, 1.00, 3.00, and 6.00 mNm). Significant effects on rheological properties were observed, except when samples were analyzed at 0.5 mNm (limited heat and pressure treatments). Both storage modulus (G′) and loss modulus (G″) were more affected by temperature than pressure. The holding time had substantial effect on the slopes of both moduli at mild treatments; for the more severe treatments, the intercepts of the storage moduli in particular were extensively affected.     

Conformational and rheological changes in catfish myosin as affected by different acids during acid-induced unfolding and refolding

Changes in the conformation of catfish (Ictalurus punctatus) myosin due to (i) anions, (ii) acid pH, and (iii) salt addition were determined using tryptophan fluorescence, hydrophobicity measurements, differential scanning calorimetry, and circular dichroism. The relationship between conformation and storage modulus (G') of acid-treated myosin was studied. Three acids, HCl, H2SO4, and H3PO4, were used for unfolding myosin at three acidic pH conditions, 1.5, 2.0, and 2.5. Unfolded myosin was refolded to pH 7.3. Denaturation and unfolding of myosin was significantly (p < 0.05) lower when salt (0.6 M NaCl) was present during acid unfolding than in the absence of salt. When salt was added before unfolding, the alpha-helix content of myosin treated at pH 1.5 was significantly lower than that treated at pH 2.5. When salt was added after refolding, the alpha-helix content of myosin was unaffected by different pH treatments. The G' of myosin increased with an increase in myosin denaturation. The G' of myosin was significantly (p < 0.05) higher when salt was added to myosin after refolding than before acid unfolding. Among the different anion treatments, the G' of acid-treated myosin decreased in the order Cl- approximately SO42- > PO43-. Among the different pH treatments, the G' of myosin treated at pH 1.5 was significantly (p < 0.05) higher than myosin treated at pH 2.5. The conditions that would result in maximum myosin denaturation and maximum G' were unfolding of myosin at pH 1.5 using Cl- (from HCl) followed by refolding at pH 7.3 and subsequent addition of 0.6 M NaCl.     

Stopped-flow kinetic study of the aroxyl radical-scavenging action of catechins and vitamin C in ethanol and micellar solutions

Kinetic study of the aroxyl radical-scavenging action of catechins (epicatechin (EC), epicatechin gallate (ECG), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) and related compounds (methyl gallate (MG), 4-methylcatechol (MC), and 5-methoxyresorcinol (MR)) has been performed. The second-order rate constant ( k s) for the reaction of these antioxidants with aroxyl radical has been measured in ethanol and aqueous Triton X-100 micellar solution (5.0 wt %). The k s values decreased in the order of EGCG > EGC > MC > ECG > EC > MG > MR in ethanol, indicating that the reactivity of the OH groups in catechins decreased in the order of pyrogallol B-ring > catechol B-ring > gallate G-ring > resorcinol A-ring. The structure-activity relationship in the free radical-scavenging reaction by catechins has been clarified by the detailed analyses of the pH dependence of k s values. From the results, the p K a values have been determined for catechins. The monoanion form at catechol B- and resorcinol A-rings and dianion form at pyrogallol B- and gallate G-rings show the highest activity for free radical scavenging. It was found that the free radical-scavenging activities of catechins are 3.2-13 times larger than that of vitamin C at pH 7.0.     

Gelling properties of heat-denatured beta-lactoglobulin aggregates in a high-salt buffer

Thermal denaturation, rheological, and microstructural properties of gels prepared from native beta-lactoglobulin (beta-LG) and preheated or heat-denatured beta-LG (HDLG) aggregates were compared. The HDLG was prepared by heating solutions of 4% beta-LG in deionized water, pH 7.0, at 80 degrees C for 30 min and then diluted to the desired concentration in 0.6 M NaCl and 0.05 M phosphate buffer at pH 6.0, 6.5, and 7.0. When reheated to 71 degrees C, HDLG formed a gel at a concentration of 2% protein. At pH 7.0, 3% HDLG gelled at 52.5 degrees C and had a storage modulus (G') of 2200 Pa after cooling. beta-LG (3%) in 0.6 M NaCl and 0.05 M phosphate buffer, pH 7.0, did not gel when heated to 71 degrees C. The gel point of 3% HDLG decreased by 10.5 degrees C and the G' did not change when the pH was decreased to 6.0. The HDLG gel microstructure was composed of strands and clumps of small globular aggregates in contrast to beta-LG gels, which contained a particulate network of compacted globules. The HDLG formed a gel at a lower concentration and lower temperature than beta-LG in the high-salt buffer, suggesting an application in meat systems or other food products prepared with salt and processed at temperatures of < or =71 degrees C.