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.     

Influence of selected hydrocolloids on triticale starch rheological properties

The aim of the study was to define the influence of selected nonstarch polysaccharides (guar gum, xanthan gum and arabic gum) on several rheological properties of triticale starch pastes/gels, at constant polysaccharide concentration (6.5 g/100 g). These included pasting characteristics, flow curves at 50 °C and mechanical spectra at 25 °C. It was found that the presence of a gum in a system modified the rheological properties of triticale starch gels/pastes, depending on the type and concentration of the gums. In the case of guar and xanthan gums, higher pasting viscosity was observed and the shear stress was increased compared with native starch. The presence of guar gum reduced the degree of thixotropy hysteresis, negative values for this being found for systems with xanthan in spite of their shear‐thinning behaviour. Systems containing arabic gum displayed lower values of pasting and flow viscosity. The type and concentration of gums added to the polysaccharide influenced the viscoelastic properties of the gels.     

Water Mobility and Crystallization Action of Lactose-water Systems by Oxygen-17 and Carbon-13 NMR

Systems ranging in concentration from 10-60g lactose/100g water were investigated by fully proton decoupled ¹⁷O and fully proton decoupled ¹³C Nuclear Magnetic Resonance (NMR). The relation between ¹⁷O NMR transverse relaxation rate measurements and lactose concentration showed water mobility decreased linearly with increasing lactose concentration up to 25g lactose/100g water and decreased rapidly and nonlinearly above that level. Water mobility was used to monitor lactose crystallization in supersaturated solutions with time. The 13 C NMR showed no significant differences in chemical shifts of carbon atom peaks in lactose molecules during crystallization. However, depending on the method of sample preparation, mutarotation could be observed.     

Properties of retrograded and acetylated starch preparations Part 2. Dynamics of saccharification with amyloglucosidase and rheological properties of resulting pastes and gels

Various procedures have been used to produce preparations of retrograded starch, by subjecting it to acetylation with methods used in the food industry. The resultant starch preparations were evaluated for their degree of acetylation through titration, swelling power and solubility in water at 80 °C, and saccharification dynamics as affected by amyloglucosidase. Rheological properties of pastes and gels of native starch and modified starch preparations were characterized with the use of a sweep temperature test as a dependency of the storage modulus (G′) and loss modulus (G″) on temperature. In addition, flow curves of pastes were plotted and mechanical spectra of gels of the preparations examined were determined. These modifications had a significant effect on the preparations produced. Retrograded and acetylated starch preparations were characterized by greater solubility in water and greater swelling power, and were less susceptible to amyloglucosidase than the non-acetylated preparations. Rheological properties of the pastes and gels were affected by the methods of their production. Acetylation was found to significantly affect a decrease in the storage modulus value during heating. Pastes of the native starch and modified starch preparations were characterized by the non-Newtonian flow, shear thinning with a tendency to yield stress. In turn, the mechanical spectra demonstrated that - in the concentration applied - both native starch and modified starch preparation were forming weak gels.     

Effects of Na2CO3 and NaOH on Retrogradation of Selected Native Cereal Starches Studied by Differential Scanning Calorimetry and Nuclear Magnetic Resonance

ABSTRACT: Using differential scanning calorimetry and pulsed nuclear magnetic resonance (NMR), it was found that the presence of Na2CO3 and NaOH retarded retrogradation of aged starch (wheat, corn, waxy corn, rice, and waxy rice) gels during storage at 4°C. At the same level of addition (based on a fixed starch/water ratio), the effect of NaOH was observed to be more pronounced than that of Na2CO3. Kinetic studies using pulsed NMR showed a progressive reduction in rate of starch retrogradation with increasing concentration of alkali (up to a level of 1 g/100 starch).     

Steady and dynamic shear rheology of starches from different oat cultivars in relation to their physicochemical and structural properties

Starches isolated from eight oat cultivars were tested for their physicochemical, structural, and rheological properties. The isolated starches had low levels of ash and nitrogen contents with amylose ranging from 21.8 to 32.3 g/100 g. The amount of water released from starch gels decreased significantly (p < 0.05) with increase in freeze thaw cycle. The scanning electron micrographs revealed the presence of polygonal to irregularly shaped starch granules. All the starches exhibited A-type X-Ray diffraction pattern typically characteristic of cereal starches. The rheological properties of pastes were well described by the Herschel-Bulkley model at a shear rate of 0–100 s^?1 (R² > 0.99). The starch pastes behaved like a pseudoplastic fluid and exhibited shear thinning fluid characteristics with values of flow behaviour index considerably less than 1. Both the storage and loss moduli of the pastes increased sharply initially and then dropped after reaching the gelatinization peak. The magnitude of the dynamic rheological parameters varied significantly (p < 0.05) between the cultivars. All the starch pastes were highly elastic than viscous as evidenced by the lower tan δ values. Structure property relationships were established between starches using principal component analysis.     

Rheological and calorimetric properties of corn‐, wheat‐, and cassava‐ starches and soybean protein concentrate composites

The effect of soy protein concentrate (SPC) on the rheological and calorimetric properties of corn, wheat, and cassava starches was assessed. SPC increased T_o values and decreased the ΔH of all tested starches, which could be related to lower availability of water for starch gelatinization and/or to the interactions between SPC and amorphous regions of starch granules. SPC and sugar addition modified the viscosity parameters (obtained through a rapid visco‐analyser) of starch pastes, which was attributed to an increase in solid content and to the interaction of proteins with the starch dispersed phase. Frequency sweeps were carried out with a rheometer on gels containing starch, SPC, and sucrose. SPC raised storage and loss modulus, producing more consistent starch gels. Besides, penetration tests showed that SPC steadily increased starch gel firmness. Scanning electron micrographs showed that protein concentrate produced gels with closer structures. Summarizing, the starch and SPC in the gels obtained were expected to be arranged in a two‐phase system. Results showed that it is possible to achieve different textures for starch dessert formulations.     

Water dynamics in white bread and starch gels as affected by water and gluten content

Three levels of water (180, 220 and 260 g/345 g flour) and three levels of gluten (giving 11.2, 13.0 and 14.2 g protein/100 g flour) were used to study the effects of water and gluten on water mobility in white bread using ¹H nuclear magnetic resonance (NMR) relaxometry. Changes in the transverse relaxation time (T₂) were related to water mobility. The three water levels resulted in three different moisture contents in the finished bread (0.55-0.77 g H₂O/g solids). Distributed exponential analysis showed two distinct regions of T₂ (30-600 μs and 1-60 ms), associated with multiple domains of water in the bread crumb. There was no significant difference in peak T₂ values with different gluten content, but significant differences were observed with different moisture content. The results suggested that the mobility of water associated with starch decreased dramatically because of gelatinization. To further investigate the effect of gluten on starch gelatinization, NMR measurements were made directly on model systems containing starch and various gluten amounts. The starch-gluten gels had higher T₂ values than pure starch gels, indicating less swelling of starch granules and absorption of water. This was attributed to less water available to starch in the presence of gluten.     

Changes in rheological properties of hydroxypropyl potato starch pastes during freeze—thaw treatments. III. Effect of cooking conditions and concentration of the starch paste

The effects of different cooking conditions and concentrations on the freeze-thaw stability of hydroxypropyl potato starch (molar substitution 0·125) paste were investigated by dynamic rheological measurements and syneresis determination. The cooking conditions of the starch were chosen by taking the starch pastes at peak consistency (SP/Peak), at half breakdown consistency (SP/HB), after being held at 95°C for 15 min (SP/95°C) and after the whole pasting cycle (SP/25°C) in the Brabender Amylograph. The concentration effect was studied with the starch pastes after a whole pasting cycle at 35, 50 and 65 g kg^?1. Depending on cooking conditions and concentration, the rheological responses in changes of complex modulus (G*) and phase angle () of the starch pastes, with regard to the number of freeze-thaw cycles, differed considerably. This indicated that the starch pastes had undergone various structural changes during freeze-thaw treatments. With an increased extent of pasting, and with an increased starch concentration, the rheological responses indicative of the destabilisation process of the starch pastes were, in general, delayed. The number of freeze-thaw cycles required for the appearance of a peak in G*, related to the first syneresis, was one, two, five and six for SP/Peak, SP/HB, SP/95°C and SP/25°C, respectively. For the starch pastes at 35, 50 and 65 g kg^?1, it was four, six and seven cycles, respectively. Based on these rheological data, it was suggested that the amount of inter-mingled amylose and amylopectin in the dispersion of hydroxypropyl starch paste is the main controlling factor, which plays a critical role in the rheological response as well as in the syneresis.     

Effect of gluten content on recrystallisation kinetics and water mobility in wheat starch gels

The effect of gluten on starch retrogradation at 5 °C was studied using ¹H NMR relaxometry. Gels were made from gluten and starch at 27.8 and 38.5% total solids and with gluten comprising either 10, 15 or 20% of the solids. Changes in the transverse relaxation time constant (T₂) were related to water mobility. Mono‐exponential analysis of relaxation curves showed that, in general, gluten retarded starch retrogradation. T₂ values in gluten gels also decreased during storage, but to a much lesser extent. Distributed exponential analysis showed that two distinct regions of T₂ were observed in all samples. During aging, the peak values of both regions shifted to lower values for all gels. Starch gel samples showed the most significant shift, and gluten gels showed the least. The three levels of gluten addition in starch/gluten gels produced similar shifts. For all samples the signal intensity of the less mobile region decreased more dramatically than that of the more mobile region during storage. It was suggested that gluten retards water loss in the granule remnants. Copyright © 2004 Society of Chemical Industry     

Effect of the production method on the properties of RS3/RS4 type resistant starch. Part 1: Properties of retrograded starch (RS3) produced under various conditions and its susceptibility to acetylation

The objective of this study was to establish the effect of the concentration of a starch paste subjected to freezing on the properties of the produced retrograded starch, and to determine its susceptibility to acetylation with acetic acid anhydride. A starch paste (1, 4, 10, 18 or 30g/100g) was produced from native potato starch that was frozen, defrosted and dried. Al preparations of retrograded starch had the same chemical structure determined with the technique of nuclear magnetic resonance (NMR) and diversified physical form visible on photos taken with an electron microscope (SEM). An increase in the concentration of paste, used to produce the preparations, resulted in decreased: amylose content (from 25.0 to 20.4/100g), solubility in water (from 41.1 to 20.1/100g), swelling power (from 45.0 to 19.3/g), and susceptibility of the preparations to the action of amyloglucosidase (from 95.4 to 83.6/100g). The heat of phase transition of solubilisation determined with differential scanning calorimetry (DSC) ranged from 3.8 to 7.1J/g, and the initial temperature of transition was increasing from 43.4 to 49.7°C along with an increasing concentration of the paste subjected to retrogradation. The 1-10/100g concentration of the paste used to produce preparations was observed to increase, whereas that between 10 and 30/100g to decrease the susceptibility to acetylation and viscosity of the prepared pastes, determined both with a Brabender viscograph and a Haake oscillating-rotational viscosimeter.     

Effect of the production method on the properties of RS3/RS4 type resistant starch. Part 2. Effect of a degree of substitution on the selected properties of acetylated retrograded starch

Resistant starch displays health-promoting properties. Starch preparations produced through acetylation of retrograded starch may be applied as a food additive. Apart from prebiotic properties, they may as well model the texture of a food product. The objective of this study was to determine the effect of retrogradation and acetylation conditions on properties of the produced RS3/4 type resistant starch. Native potato starch was used to produce starch pastes (1, 4, 10, 18 or 30g/100g), that were frozen, defrosted and dried. The resultant preparations of retrograded starch were acetylated with various doses of an acetic acid anhydride (3.25, 6.5, 13.0, 26.0 or 52.0ml/100g). The acetylated preparations of retrograded starch were characterised by increasing solubility in water and swelling power as well as a lower amylose content along with an increasing degree of their substitution with residues of acetic acid. Dependencies of: pasting temperatures, viscosity of the prepared pastes, and resistance of acetylated starch to the action of amyloglucosidase on the degree of substitution with acetic acid residues were described with a second degree polynomial function. The extent and range of changes were found to depend on the concentration of paste used to produce a retrograded starch preparation. The maximum resistance of RS3/4 preparations to the action of amyloglucosidase ranged from 28.7 to 45.9g/100g.     

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-%.     

Influence of gluten on the viscoelastic properties of starch pastes and gels

Viscoelastic properties of dispersions (60–300 g kg⁻¹) of gluten (G) and wheat starch (S) blends (0 < G/S < 0·20) and wheat flour have been studied during heating and cooling. In both cases, the moduli followed power law relationships with concentration. The temperature at which the transient network development began, caused by granule–granule interactions, decreased as the concentration increased and increased with an increase in the proportion of gluten. Moreover, gluten weakened the strength of both starch pastes and gels, as shown by the lower values of the moduli. The viscoelastic behaviour of flour samples reflected the role played by internal lipids. A structural model is proposed in order to explain the influence of gluten on the rheological behaviour of starch pastes and gels. © 1998 Society of Chemical Industry.     

Studies on the synthesis and properties of hydroxypropyl derivatives of cassava (Manihot esculenta Crantz) starch

Cassava starch was subjected to hydroxypropylation in three different media, which included water, water in the presence of a phase transfer catalyst, and 2‐propanol, all at 30 ± 2 °C for 24 h. Propylene oxide was used in four different concentrations (50, 100, 150 and 200 g kg^?1 of starch dry weight). The products were characterized by determining their molar substitution (MS), structural and functional properties. The analyses were done in triplicate and the data were analyzed using the statistical package 8.01. The MS of the products ranged from 0.26 to 1.41. The MS of the hydroxypropyl derivatives were found to be higher when the reaction was carried out in the aqueous medium in the presence of tetrabutylammonium bromide, a phase transfer catalyst, when compared to the reaction in 2‐propanol, which was found to be not very effective at 30 ± 2 °C. The etherification altered the granular properties of starch, as could be seen from scanning electron micrographs. Hydroxypropylation resulted in starch pastes which were stable and with higher swelling volume, solubility, light transmittance and water binding capacity as compared to native starch. The hydroxypropyl starches showed significantly lower pasting temperatures and setback viscosities. The enzyme digestibility of the derivatives was seen to decrease with increase in MS and there was a significant reduction in the syneresis of the starch pastes of hydroxypropyl derivatives. Texture profile analysis showed that hydroxypropylated starch gels exhibited higher hardness, springiness (elasticity) and gumminess and lower cohesiveness than the native starch. Copyright © 2007 Society of Chemical Industry     

Dielectric properties of Indian Basmati rice flour slurry

Dielectric properties of Indian Basmati rice samples (dry ground flour and wet aqueous slurry) were measured over the frequency range 500–2500 MHz. Temperature dependence of dielectric properties of rice flour slurries (20, 30 and 50 g flour per 100 g water yielding approximately 1:5, 1:3 and 1:2 flour to water ratio) were studied between 30 and 80 °C. Results indicated that dielectric constants (ε′) generally did not vary with frequency while the loss factor (ε″) showed an increasing trend. A sharp change in dielectric parameters were noted above 70 °C attributable to rice starch gelatinization, an observation confirmed later by differential scanning calorimetry. An increase in flour slurry concentration systematically reduced ε′ during the entire frequency range while variations in ε″ values were mixed. Addition of 1% salt markedly increased ε″ of slurries whereas butter resulted in significant reduction in ε′ values. Rice flour slurry containing both salt and butter exhibited intermediate values of dielectric properties. Both ε′ and ε″ data of rice slurries generally fitted a 2nd order polynomial relationship with temperature. These results suggest that dielectric measurements could be used to study frequency, concentration, ingredient and temperature dependent changes in starch–water systems during heating.     

Staling of Starch-based Products: A Comparative Study by Firmness and Pulsed NMR Measurements

A study of the staling of corn starch gel, bread, and rice cup-cake showed that measurements by pulsed NMR (based on the increase in signal from the solid phase of a system on ageing) gave very highly significant correlations (P < 0.001) with firmness measurements using the Instron Food Testing Instrument. Experimental data from the two methods were fitted into the Avrami equation. Values for the Avrami exponent (n) and the rate constant (k) obtained by compression were in good agreement with the corresponding values derived from NMR measurements. The pulsed NMR method thus offers a rapid and non-destructive means of monitoring changes at the molecular level which manifest themselves at the macroscopic level as an increase in firmness during ageing of starch gels and starch-based products.     

Steady and Dynamic Shear Rheology of Fucoidan‐Buckwheat Starch Mixtures

Rheological properties of fucoidan (F) and buckwheat starch (B) mixtures (3% or 6%) at different blending ratios of fucoidans (0, 0.1, 0.2, 0.5 and 1.0%) were investigated in steady and dynamic shear. Steady shear viscosity measurement revealed that aqueous pastes of the BF blends (3%, w/v) had a pseudoplastic and shear‐thinning behavior with flow behavior index (n) values of 0.61–0.68. The substitution of starch with fucoidan polymers significantly lowered the apparent viscosities compared with the pure starch paste and, when mixed with less than 0.5% of fucoidan, the viscosities of the pastes were even lower than those of the starch pastes at the corresponding starch concentrations. According to dynamic viscoelastic measurement performed at 6% total carbohydrate concentration, buckwheat starch mixtures behaved like weak gels and the BF blends containing less than 0.5% fucoidan had considerably lower storage (G') and loss (G') moduli than the starch paste at the corresponding starch concentrations. However, the magnitude of G' increased with fucoidan concentrations over 0.5%, suggesting that a concentration of fucoidans > 0.5% might enhance the formations of three‐dimensional networks and crosslinking of the starch samples, probably because of the mutual exclusion between starch and fucoidan polymers through the phase separation process. This study indicates that it is possible to obtain the BF blends having various rheological properties by changing the concentration of fucoidan polymers.     

Rheological and textural properties of sorghum-based formulations modified with variable amounts of native or pregelatinised cassava starch

Sorghum bread was made from native or pregelatinised cassava starch and sorghum flour in the ratio 10:90, 20:80, 30:70, 40:60 and 50:50. The other ingredients, measured on flour-weight-basis, were water (100%), sugar (6.7%), egg white (6%), fat (2%), salt (1.7%) and yeast (1.5%). The dynamic oscillatory behaviours of the batters were affected by the amount and type of starch. In the amplitude sweep measurements, increasing concentration of native starch decreased storage modulus, whereas increasing concentration of pregelatinised starch increased the linear viscoelastic range of the batters. In the frequency sweep measurements, the loss factor of batters treated with native starch declined with increasing frequency. Batters treated with 10 or 20% pregelatinised starch showed declining loss factors, whereas batters treated with 40 or 50% pregelatinised starch showed increasing loss factors with increasing frequency. Sorghum-based batters containing native starch gave bread with better crumb properties than batters containing pregelatinised starch. Crumb firmness and chewiness declined with increasing native or pregelatinised starch concentration. Crumb adhesiveness of breads containing pregelatinised starch increased with increasing starch content but was not affected by native starch. Cohesiveness, springiness and resilience increased with increasing native starch content, but were minimally affected by increasing pregelatinised starch content.     

Waxy corn starch affecting texture and ultrastructure of sardine surimi gels

 The effect of waxy corn starch (WCS) on the texture, water-holding capacity and microstructure of sardine (Sardina pilchardus) surimi gels in two different systems was studied. In the type A system, increasing amounts of WCS (2, 4, 6 or 8 g/100 g surimi) were added to surimi while maintaining the gel moisture constant at 78%; in the type B system, WCS was added without correcting the gel moisture. Gels were made using two different heat treatments [heat-induced setting (HS) and direct cooking (DC)]. When starch was replaced by surimi (type A) and a heat treatment was applied that favoured formation of a preliminary actomyosin (AM) network (i.e. HS), gel strength (GS) was lower than in the control and decreased as more starch was added, despite an increase in the amount of water held by the gel. Scanning electron microscopy (SEM) showed that the matrix network was fibrillar with a globular surface. Starch appeared to be totally gelatinized and surrounded by a continuous matrix. When the amount of dry matter in gels was increased (type B), in no case did starch have a reinforcing effect, despite an increasing water-holding capacity; SEM showed a denser continuous matrix surrounding the gelatinized starch. Both types of gel made using the heat treatment that allows simultaneous gelling of surimi and gelatinization of starch (i.e. DC) exhibited much poorer GS than did HS gels, while addition of starch made practically no difference to gel texture. The findings suggest that the effect of starch is related to the type of gel matrix that forms upon addition of ingredients. Although such gels contained more water or dry matter, their texture parameters were lower, possibly because of the type of network formed by sardine surimi. Nonetheless, gels of acceptable quality were successfully made with added starch by incorporating less surimi. Received: 18 March 1996