Influence of the Cross‐linking Agent on the Gel Structure of Starch Derivatives

Hydrogels were synthesized through cross‐linking of carboxymethyl starch (CMS; Degree of Substitution DS = 0.45) using polyfunctional carboxylic acids (malic, tartaric, citric, malonic, succinic, glutaric and adipic acid). The syntheses used a cross‐linking agent ratio (ratio of the number of cross‐linking agent molecules to the number of monomer units constituting the polymer) of F_Z = 0.05. After cross‐linking the gels were dried, ground and then hydrogels of a polymer concentration of 4 mass‐% were produced. These CMS‐hydrogels were then rheologically characterized using dynamic oscillatory measurements. From measurements of the plateau region storage modulus G'_P, the network parameters molar mass between two entanglement points M_e (M_e ranging from 9.318 (citric acid) to 281.397 g/mol (tartaric acid)), the cross‐link density ν_e and the distance between two entanglement points ξ were calculated. Using carboxylic acids without other functional groups, a maximum in gel sturdiness is found at a spacer length of two CH₂‐groups. The evaluation of the loss factor tan δ for the CMS‐hydrogels showed that values of tan δ = 0.2 varied only slightly with the frequency ω. Flow curves showed a pseudopIastic flow behavior for all CMS‐hydrogels (the shear viscosity η declining over five decades in the range of the shear rate γ of 10⁻³ to 10³ s⁻¹) The different polyfunctional carboxylic acids have a strong influence on the sturdiness of the synthesized CMS‐hydrogels.     

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.     

Investigation of sweet potato starch as a structural enhancer for three‐dimensional printing of Scomberomorus niphonius surimi

Three‐dimensional printing (3DP) of surimi requires a structural modifier to achieve a stable construct. This work investigated the effect of addition of sweet potato starch (0–10% wt/wt) on the physical properties (rheological properties, gel strength, water‐holding capacity [WHC], and microstructural characteristics) of surimi gels and the 3D printed behavior of these gels. The results showed that as the starch content increased, the viscosity of the starch–surimi mixture decreased facilitating the flow of the surimi out of the printer nozzle. The surimi gel with 8% sweet potato starch concentration showed good gel strength (2,021.70 g mm), WHC (82.39%), microstructural characteristics, and less cooking loss (1.95%). A comparison of the traditional surimi preparation method with 3DP showed that the surimi gel prepared by a 3D printed construct was softer in gel strength (1,398.65 g mm) and lower in hardness (945.17 g) although showing slightly higher cooking loss (6.76%) and lower WHC (72.66 g) than the conventional product. The results suggest that sweet potato starch can be effectively used as a structural enhancer for 3DP complex‐shaped surimi.     

Hydroxypropyl-Distarch Phosphate from Potato Starch Increases Fecal Output, but Does Not Reduce Zinc, Iron, Calcium, and Magnesium Absorption in Rats

The physiological effects of hydroxypropyl‐distarch phosphate (HDP) were examined in rats. Male rats were fed a fiber‐free purified diet containing gelatinized potato starch (PS, 50 g/kg diet) that was not modified chemically or gelatinized, chemically modified potato starch (CMS, 50 g/kg diet) for 21 d. PS was used as the control. Six kinds of gelatinized HDP from potato with 2 different degrees of hydroxypropylation and 3 different degrees of cross‐linking were used as CMS. The wet weight and moisture of the fecal output of the rats fed highly hydroxypropylated HDP was 70% and 30% greater, respectively, than that in the control rats. The weights of the cecal wall and content of the rats fed highly hydroxypropylated HDP were 15% and 30% higher, respectively, than those of the control rats. The apparent absorption of Mg was 15% higher in the rats fed highly hydroxypropylated HDP than in the control rats. On the other hand, the apparent absorptions of Ca, Zn, and Fe were not affected by the diet. Cross‐linking did not influence the above‐mentioned physiological effects of HDP. Fecal excretion of bile acids and the plasma cholesterol concentration were not affected by the diet. These results show that the physiological effects of HDP depend on the hydroxypropylation but not the cross‐linking.     

Thermal and rheological properties of hydrogels prepared with retrograded waxy rice starch powders

Waxy rice starch dispersed in water (50% solids) was gelatinized by heating the dispersion at 121°C for 20 min, and retrograded by storing the paste at 4°C for 2 days. The starch gel was then freeze-dried and ground into powders. The retrograded starch powders were hydrated at 20–30% solid concentration at different temperatures (4 and 23°C), and then thermal and rheological properties were analyzed using the hydrogels. The gel hydrated at 4°C had an onset temperature of melting at 34.9°C, which was approximately 10°C lower than that observed for the gel hydrated at 23°C. The enthalpy value was greater for the gel hydrated at 4°C (14.2 J/g) than the gel hydrated at 23°C (8.8 J/g). The yield stress and consistency of the hydrogels were proportional to the solid concentration. The hydrogel prepared with 30% retrograded starch powders at 4°C displayed a thick creamy texture with retrograded starch crystals that could melt at a temperature range of 35–51°C. The thermal and rheological properties of the hydrogels exhibited the possibility for the retrograded starch powders to be used as fat mimetic in foods.     

Starch enzymatic hydrolysis,structural, thermal and rheological properties of pigeon pea (Cajanus cajan) and dolichos bean (Dolichos lab-lab) legume starches

Cajanus Cajans and Dolichos lab-lab legume starches from Argentine cultivars were investigated under a technological and nutritional point of view. Their physico-chemical, structural, thermal and the rheological properties of their gels were evaluated. Rice (RS) and potato (PS) starches were included as references. In vitro digestibility from Englyst method was also evaluated. Legume starches had the highest amylose content and the most stable chemical structure. Their rapidly digestible starch and starch digestibility rate index were very low, similar to PS, and fivefold lower than RS. They had a much higher slowly digestible starch content than PS. Legume starches showed the highest gel stability versus heating and stirring and an intermedium pasting temperature between RS and PS. They formed viscoelastic gels at 6% concentration with stronger elastic-like behaviour and higher yield stress than references. Our results indicate these legumes represent an efficient starch source to provide tailor-made properties to food/industrial applications.     

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.     

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.     

Rheological/textural properties of starch and crude hsian‐tsao leaf gum mixed systems

The Effects of hsian‐tsao leaf gum (HG) on the rheological/textural properties of non‐waxy starches were studied. Pronounced interactions between starch and HG were observed. The rheological properties, including pseudo‐gel viscosity in the rapid visco‐analyser test, storage and loss moduli in the dynamic rheological test, as well as firmness in the texture analyser test, of the mixed gels generally improved with increasing gum concentration to a certain level, then deteriorated with further increase in gum concentration. The critical gum concentration for the development of optimal rheological properties depended on the starch type and concentration. Within the concentration range studied, mixed systems with wheat starch could generally reach the highest pseudo‐gel viscosity, firmness, and storage modulus if the starch/HG ratio was appropriate, followed by those with corn and tapioca starch. Copyright © 2003 Society of Chemical Industry     

Radiation‐Modified Carboxymethyl Starch Derivative as Metal Scavenger in Aqueous Solutions

Corn starch was chemically modified using sodium chloroacetate to yield carboxymethyl starch (CMS). The aqueous solutions of CMS at 15 and 50% (w/w) concentration were then irradiated by electron beam (EB) at various dosages (1, 2, 3, 5, 10, 20, and 50 kGy), resulting in a cross‐linked carboxymethyl starch (CCMS). The maximum gel fraction, i.e. the highest degree of cross‐linking, was achieved with a 50% (w/w) aqueous CMS solution irradiated at 2 kGy EB dosage. Metal removal efficiency of the CCMS was then evaluated for the extraction of copper (Cu) and cadmium (Cd) ions from aqueous solutions. Our results showed that the metal adsorption is pH dependent and the adsorption increases with increase of the pH of the metal solution from acidic towards neutral. The adsorption efficiency also showed the maximum value at the highest gel content, demonstrating the enhancement of adsorption by the physical entrapment of the ions in the CCMS network in addition to the primary chemical adsorption.     

Physicochemical and structural characteristics of cross‐linked banana starch using three cross‐linking reagents

Banana starch was cross‐linked using different cross‐linking reagents, phosphoryl chloride (POCl₃), sodium trimetaphosphate (STMP), and epichlorohydrin (ECH), under alkaline conditions. The reaction conditions were selected to produce similar pasting profiles. The effects of the different cross‐linking reagents on the physicochemical and structural characteristics of cross‐linked starches were evaluated. The microscopy study did not show difference on the surface of the granules. Slight decrease in the peak temperature and enthalpy were found in the cross‐linked banana starch. The chemical groups introduced in the starch molecules by the diverse reagents promoted the re‐association of starch chains during storage. The rheological analysis of all starch dispersion at 10% (flow curves) showed a non‐Newtonian shear‐thinning; pastes obtained were time‐independent, suggesting an important contribution of the continuous phase. Structural study showed that the cross‐linked STMP‐starch had the lowest level of amylose and the ratio short/long amylopectin chains. The three reagents used for cross‐linking presented different action mode on starch granule and its components.     

冻融循环次数对超声改性玉米淀粉凝胶特性和结构的影响

探讨经超声处理的玉米淀粉在冻融循环过程中其凝胶特性和结构的变化,以期为提升速冻淀粉基食品品质提供理论指导。利用流变仪、物性分析仪、低场强核磁共振仪、傅里叶变换红外光谱仪及X射线衍射仪,分析冻融循环次数对超声改性玉米淀粉凝胶动态流变学和质构特性的影响,并对其结构进行表征。结果表明：不同冻融循环次数下,以天然玉米淀粉作对照,超声改性玉米淀粉凝胶的析水率在第4次冻融时显著下降了5.19%(P<0.05),提高了冻融稳定性;超声改性玉米淀粉凝胶的储能模量和损耗模量降低,凝胶强度变弱;硬度在第4次冻融时显著降低了10.83%(P<0.05),直链淀粉含量下降了0.15%;超声改性玉米淀粉凝胶的碘结合力减弱,横向弛豫时间分布曲线整体左移,短程有序结构减弱,相对结晶度降低。综合凝胶特性和结构表征结果,表明超声处理能够抑制冻融循环过程中玉米淀粉凝胶体系中的水分迁移和双螺旋结构的形成,改善其冻融稳定性。     

Understanding the structural characteristics,pasting and rheological behaviours of pregelatinised cassava starch

The structural characteristics, pasting and rheological behaviours of cassava starch before and after pregelatinisation were determined by various modern analysis techniques. Pregelatinisation, especially in an ultrasonic environment, can disrupt the granule structure, crystalline structure and short‐range ordered molecular structure of cassava starch. Compared with native starch, pregelatinisation had significantly decreased viscosities and weakened gel structures of starch pastes. Not only did native and pregelatinised starch pastes exhibit shear‐thinning behaviours but also the pregelatinised treatment resulted in the formation of weak gel structures. This study enabled us to acquire the desired pasting and rheological properties of pregelatinised starch by modulating its hierarchical structural changes.     

Rheology and Relationship among Rheological Parameters of Cross-Linked Waxy Maize Starch Dispersions Heated in Fructose Solutions

ABSTRACT: Dispersions of 5% cross‐linked waxy maize starch heated in Newtonian aqueous fructose solutions, 0 to 600 g per kg, exhibited either thixotropic or antithixotropic flow behavior, and viscoelastic behavior. The mean starch granule dia in the dispersions changed slightly with fructose content. Values of G' of the dispersions were higher than those of G', reflecting gel‐like behavior of the dispersions. Values of the first normal stress coefficient predicted from dynamic rheological and apparent viscosity data based on the Goddard‐Miller model were in reasonable agreement with experimental values.     

Effects of starches on the textural,rheological, and color properties of surimi–beef gels with microbial tranglutaminase

In order to evaluate effects of starches (corn starch, potato starch, and tapioca starch) on the characteristics of surimi–beef gels with microbial transglutaminase, the cooking loss, gel strength, color and rheological properties of samples were investigated. Results demonstrated that starches gave negative effects on the cooking loss of surimi–beef gels. The gel with corn starch had the highest cooking loss while that with tapioca starch showed the lowest value. The gel with potato starch obtained the highest gel strength. During the sol–gel transitions, surimi–beef complexes with 3% corn starch exhibited the highest storage modulus value, while that with 3% tapioca starch had the lowest one. The addition of starch caused the increase of L* values of surimi–beef gels. Results showed that the excessive amount of starch resulted in the decrease in gel strength of surimi–beef gels.     

Effect of non-starch polysaccharides on the in vitro digestibility and rheological properties of rice starch gel

The starch digestibility and rheological properties of gels were evaluated in the presence of three non-starch polysaccharides (agar, xanthan gum and konjac glucomannan) with rice starch. Each polysaccharide was added to 30% (w/w) rice starch suspension at defined concentrations and starch gels were prepared. The extent of starch gel digestibility was determined by an in vitro method and rheological properties by a dynamic oscillatory test and a compression test. The added polysaccharides suppressed starch hydrolysis in the gels compared with the control, and a concentration dependency of this suppressive effect was observed. Adding agar and xanthan gum increased the storage shear modulus (G′) of starch gels, while adding konjac glucomannan decreased G′ values. The results indicate that the suppressive effect of non-starch polysaccharides on starch digestibility appears to be not only due to the rigidity of the gel, but also the interaction between starch and non-starch polysaccharides.     

The effect of modified starches on the gel properties and protein conformation of Nemipterus virgatus surimi

The study investigated the effect of native cassava starch (NCS), hydroxypropylated starch, acetic acid esterification starch (AAES), acetylated distarch phosphate on gel properties and protein conformation of Nemipterus virgatus surimi. Addition of 10 g kg^?1 NCS or 20 g kg^?1 AAES could significantly promote the gel strength and textural profiles of the surimi gels (p < .05). The water holding ability and whiteness of surimi were remarkably increased when the four types of starch were added at all concentrations (p < .05). In rheological test, the lower G′ was observed in surimi samples added with starch at low temperature, suggesting starch played an inactive filler role in surimi. Along with the increase of starch additive amount, ionic bond and hydrophobic interaction first increased and then decreased, while hydrogen bond first decrease and then increased. According to Raman spectroscopy data, small content of starch promoted the heat‐induced conformational transition of surimi protein from α‐helix to β‐sheet, leading to the change in gel properties of surimi gels. Scanning electron microscopy photographs showed surimi gels added with 20 g kg^?1 starch had the finer and denser network structure. Therefore, 20 g kg^?1 AAES or 10 g kg^?1 NCS or 10 g kg^?1 HS could be proposed to a potential modifier to effectively improve the quality of surimi products.     

Structures and Physicochemical Properties of Acid‐Thinned Corn,Potato and Rice Starches

The structures and physicochemical properties of acid‐thinned corn, potato, and rice starches were investigated. Corn, potato, and rice starches were hydrolyzed with 0.14 N hydrochloric acid at 50 °C until reaching a target pasting peak of 200—300 Brabender Units (BU) at 10% solids in the Brabender Visco Amylograph. After acid modification the amylose content decreased slightly and all starches retained their native crystallinity pattern. Acid primarily attacked the amorphous regions within the starch granule and both amylose and amylopectin were hydrolyzed simultaneously by acid. Acid modification decreased the longer chain fraction and increased the shorter chain fraction of corn and rice starches but increased the longer chain fraction and decreased the shorter chain fraction of potato starch, as measured by high‐performance size‐exclusion chromatography. Acid‐thinned potato starches produced much firmer gels than did acid‐thinned corn and rice starches, possibly due to potato starch's relatively higher percentage of long branch chains (degree of polymerization 13—24) in amylopectin. The short‐term development of gel structure by acid‐thinned starches was dependent on amylose content, whereas the long‐term gel strength appeared dependend on the long branch chains in amylopectin.     

Effects of Soy Protein on Physical and Rheological Properties of Wheat Starch

It is necessary to understand the interaction phenomena between proteins and polysaccharides for the development of starch‐based products with better physical and sensory properties. A simplified model system was chosen to study the influence of soy protein on physical and rheological properties of wheat starch and the possible interactions between them. Thermal and pasting behaviors of the slurries and texture properties, water retention capacity and ultra structure of soy protein‐wheat starch gels were analyzed. While soy protein isolate increased the viscosity of starch suspension during and after heating, gels with soy protein presented a weaker structure than wheat starch gels. Results suggested association between leached out material and swollen granule surface of starch with soy protein. Scanning electron microscopy reflected these changes in the gel ultrastructure.     

Octenylsuccinate Derivatives of Carboxymethyl Starch – Synthesis and Properties

Carboxymethyl starch (CMS, DS_CM 0.1) was modified with octenylsuccinic anhydride in various solvent systems. Using the dimethyl sulphoxide (DMSO)/p‐toluenesulphonic acid (p‐Ts‐OH) system, carboxymethyl starch octenylsuccinates (OS‐CMS) were obtained with degrees of substitution (DS) ranging from 0.03 to 0.53 at high reaction efficiency, and characterized with regard to their molecular structure, their rheological and surface active properties. The water‐soluble OS‐CMS derivatives showed a pseudoplastic behavior dependent on both the DS and polymer concentration (c_p). The thickening power displayed a maximum at DS 0.14 at higher c_p (2.5 and 5.0%). In spite of the only moderate surface‐tension decreasing effect of the OS‐CMS derivatives, most of them exhibited excellent emulsifying, foaming and antiredeposition effects. They represent novel polysaccharide‐based biosurfactants with a broad application potential.