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.     

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.     

Preparation and swelling properties of a pH‐sensitive superabsorbent hydrogel based on psyllium gum

A series of natural polymer‐based superabsorbent hydrogels were prepared by free radical graft copolymerization of partially neutralized acrylic acid (AA) onto psyllium gum (PSY) in aqueous solution, using ammonium persulfate (APS) as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker. Fourier transform infrared spectroscopy (FTIR) confirmed that AA monomers have been grafted onto PSY macromolecular chains. The swelling properties of the hydrogels in various saline and pH solutions were investigated, and the swelling kinetics and reswelling ability of the hydrogels were also evaluated systematically. The hydrogels showed excellent responsive properties and reversible On‐Off switching characteristics in various pH buffer solutions, which render the hydrogels available as a candidate for drug delivery system.     

Synthesis and Characterization of Cross‐linked Carboxymethyl Potato Starch Ether Gels

Hydrogels were synthesized by cross‐linking of potato starch (PS) with dichloroacetic acid (DCA) in the presence of monochloroacetic acid (MCA) to form etherified carboxymethyl starch (CMS) gels, to be used for ultrasonic medical examinations. By etherification cross‐linked CMS‐hydrogels can be produced, that are stable in contrast to the in the long‐term unstable esterified gels, that were presented in the last paper. The rheological benchmarks for the CMS‐hydrogels were set in comparison with synthetic ultrasonic gels. Gels with potato starch contents in the reaction batch ranging from 12.5% to 20% showed the best compliance with the benchmark parameters. The DS values of these CMS‐hydrogels vary from 0.42 to 0.49, increasing with decreasing amount of starch in the reaction mixture. The free swelling capacities (FSC) vary between 77 g/g for the 12.5% PS‐gel and 34 g/g for 20% PS‐gel, the turbidities of the samples being in the range from 14.5 NTU (Nephelometric Turbidity Units) (12.5% PS) up to 20.5 NTU (20% PS). The variation of the PS fraction in the reaction mixture showed that with an increased amount of PS in the reaction batch the number of cross‐links of the CMS‐gels increases, too. At a higher number of cross‐links the swelling capacity is reduced and the concentration needed to form stable hydrogels is greatly increased. Thus a hydrogel of a polymer concentration of 5 mass‐% from a 12.5% PS batch was produced, that showed the best accordance with the rheological benchmark parameters such as gelatinization time, visco‐elastic and pseudoplastic properties and long‐term stability. The ultrasonic pictures taken with this CMS‐gel were not different from those taken with the synthetic gels. This hydrogel was then subjected to long‐term‐stability measurements performed over one year and to rheological temperature cycle tests. The tests showed that the long‐term stability of the gels is sufficient for their use as ultrasonic gel.     

Synthesis and properties of carboxymethyl Pueraria thomsonii Benth. starch

As a source of starch, Pueraria thomsonii Benth. was selected to synthesize carboxymethyl starch (CMS) with monochloroacetic acid (MCA) in the presence of sodium hydroxide for the first time. The influence of the molar ratio of NaOH/AGU and MCA/AGU, reaction time, temperature, and water content of solvent on the degree of substitution and reaction efficiency were studied. IR spectrometry showed bands at 1609, 1420, and 1369 cm⁻¹ due to –COO⁻ symmetric and asymmetric stretching vibration when starch was successfully substituted. The SEM results displayed that the granules were agglomerate, and curly wrinkles appeared upon carboxymethylation. XRD revealed that the crystallinity reduced from 41.45 to 5.91%. Furthermore, the ¹³C NMR spectra of the CMS showed a broad band at d = 178.85 ppm, which was assigned to the –CO carbon (C‐8) of the carboxymethyl group.     

Structure Analysis of Carboxymethyl Starch by Capillary Electrophoresis and Enzymic Degradation

Carboxymethyl starches (CMS) with a degree of substitution (DS) in the range of 1.2 to 1.5 were analysed by capillary electrophoresis (CE) after hydrolysis and reductive amination in a borate buffer. The monomer composition determined was compared to data calculated by the statistical models of Spurlin and Reuben. In addi­tion, the starch derivatives were exhaustively degraded by α‐amylase and amylo­glucosidase and the amount of glucose liberated was determined. Results were discussed with regard to derivatisation conditions and properties of the carboxymethyl starches.     

Dynamic rheology of structural development in starch/decolourised hsian‐tsao leaf gum composite systems

The gelling process of decolourised hsian‐tsao leaf gum (dHG)/starch mixtures was monitored as a function of starch/gum ratio and starch type using a dynamic rheometer. It was found that the gelling process followed first‐order kinetics. At starch/gum ratios of 5:1, 4:2 and 3:3, dHG interacted with starch synergistically, resulting in a marked increase in storage modulus (G′). Both the gelling reaction rate constant and plateau G′ value as a function of starch/dHG ratio showed a maximum at a certain starch/gum ratio. These results indicated that a suitable starch/dHG ratio could facilitate the formation of a three‐dimensional network structure and the conversion of chains in the sol fraction into a gel. The maximum G′ value reached depended on the unique chemistry of each starch. Mixed systems with tapioca starch generally showed lower plateau G′ values than mixed systems with wheat or corn starch, possibly owing to the lower amylose content of tapioca starch. © 2002 Society of Chemical Industry     

A Comparison of Some Methods for the Determination of the Degree of Substitution of Carboxymethyl Starch

The degree of substitution (DS) markedly affects the properties of sodium carboxymethyl starch (Na‐CMS). In this work Na‐CMS samples with different DS starting from both potato and corn starch were synthesized in an ethanol/water mixture and their DS was determined using three methods: direct titration of the acid form of the carboxymethyl starch (H‐CMS), Cu salt precipitation and back titration. It was found that direct titration gave smaller DS values, while the Cu salt precipitation method gave higher DS values than the back titration method, which was found to be the most accurate. The values of the DS obtained by these methods were similar for lower DS while for higher values the discrepancy was more pronounced. Under the same experimental conditions the CMS obtained from corn starch had a higher DS than the one obtained from potato starch and on average, the discrepancies between the DS values obtained by the employed analytical methods were smaller for the CMS samples synthesized from corn starch.     

Carboxymethyl Starch Octenylsuccinate: Microwave‐ and Ultrasound‐assisted Synthesis and Properties

The synthesis of water‐soluble octenylsuccinates of carboxymethyl starch (OS‐CMS) was performed with octenylsuccinic anhydride by assistance of microwave and ultrasound irradiation using the dimethyl sulphoxide/p‐toluenesulphonic acid system and DMSO as solvents for activation of CMS as well as reaction medium of the following esterification. The prepared OS‐CMS derivatives were characterized with regard to their structural, surface‐active and performance properties. The application of both microwave and ultrasound irradiation as energy sources permitted to shorten the esterification time to several minutes from 24 h of the previously reported conventional heating [33], whereby the reaction efficiencies were high and the water‐soluble derivatives exhibited excellent emulsifying efficiency as well as surfactant performance properties tested by washing power and antiredeposition efficiency. The results indicate also the high potential of both microwave and ultrasound energy sources to innovate and increase the efficiency of technological polysaccharide esterification processes.     

Dynamic rheological properties of rice flour‐starch blends

The dynamic rheological properties of blends of rice flour (RF) with six different commercial starches (sweet potato starch, potato starch, tapioca starch, waxy corn starch, hydroxypropylated potato starch, and hydroxypropylated tapioca starch) were evaluated. The magnitudes of storage modulus (G′) of all blend samples were higher than those of loss modulus (G′′) over most of the frequency range (0.63–62.8 rad · s⁻¹). In general, the dynamic moduli results of all blend samples showed that changes in G′ values were relatively greater than changes in G″ values after adding the starches when compared to RF. tan δ (ratio of G′′/G′) values (0.21–0.22) of the RF‐potato starch and RF‐hydroxypropylated potato starch blends were much lower than those (0.25–0.33) of other blends and RF, indicating that there is a more pronounced synergistic effect on the elastic properties of RF‐starch blend systems in the presence of potato starches.     

Effect of enzyme‐modified carboxymethyl starch as a fat replacer on the functional properties of sausages

Enzyme‐modified carboxymethyl starch (ECMS), carboxymethyl starch (CMS), and enzyme‐modified starch (ES) were prepared and used as fat replacers in low‐fat sausages. The effects of fat level (5, 10, and 20%) and three modified starches (ECMS, CMS, and ES) on energy, color, texture, and sensory characteristics of sausages were investigated. The addition of three modified starches in reduced‐fat sausages reduced total energy and redness, and increased the lightness of the products. Except adhesiveness, ECMS had no effect on any of the textural parameters of sausages, but CMS or ES lowered any of the textural parameters at their respective target fat levels. The 10% fat sausage with added ECMS was similar to the 20% fat sausage control for overall acceptability. The results indicated that the new multiplex modified starch‐ECMS could be used as a suitable fat replacer since it offset some of the changes caused by fat reduction.     

Effect of Molar Substitution on Rheological Properties of Hydroxypropylated Rice Starch Pastes

The steady and dynamic shear rheological properties of hydroxypropylated rice starch pastes (5%, w/w) were evaluated at different molar substitution (MS, 0.030‐0.142). The swelling power (35.5‐52.8 g/g) and solubility (8.19‐10.7%) values of the hydroxyproylated rice starches were higher than those of native rice starch (26.6 g/g and 7.78%) and increased with an increase in MS. The hydroxypropylated starch pastes at 25°C showed a pronounced shear‐thinning behavior (n = 0.33‐0.40) with Casson yield stress (σ_oc = 15.9‐31.7 Pa). The consistency index (K) and yield stress (σ_oc) values of the hydroxypropylated starch pastes were lower than those of the native starch, and increased progressively with an increase in MS. The apparent viscosity (η_a,500) obeyed the Arrhenius temperature relationship over the temperature range of 10‐55°C; the activation energies (E_a) of the hydroxypropylated starch pastes were in the range of 14.8‐18.5 kJ/mol, i.e. higher than that (14.1 kJ/mol) of the native starch. Storage (G′) and loss moduli (G′′) of hydroxypropylated starch pastes increased with an increase in MS, while tan δ (G′′/G′) values decreased, indicating that G′ rose more strongly than G′′ with increased MS.     

Steady and Dynamic Shear Rheology of Rice Starch‐Galactomannan Mixtures

Rheological properties of rice starch‐galactomannan mixtures (5%, w/w) at different concentrations (0, 0.2, 0.4, 0.6 and 0.8%, w/w) of guar gum and locust bean gum (LBG) were investigated in steady and dynamic shear. Rice starch‐galactomannan mixtures showed high shear‐thinning flow behaviors with high Casson yield stress. Consistency index (K), apparent viscosity (η_a,100) and yield stress (σ_oc) increased with the increase in gum concentration. Over the temperature range of 20–65°C, the effect of temperature on apparent viscosity (η_a,100) was described by the Arrhenius equation. The activation energy values (E_a = 4.82–9.48 kJ/mol) of rice starch‐galactomannan mixtures (0.2–0.8% gum concentration) were much lower than that (E_a = 12.8 kJ/mol) of rice starch dispersion with no added gum. E_a values of rice starch‐LBG mixtures were lower in comparison to rice starch‐guar gum mixtures. Storage (G′) and loss (G′′) moduli of rice starch‐galactomannan mixtures increased with the increase in frequency (ω), while complex viscosity (η*) decreased. The magnitudes of G′ and G′′ increased with the increase in gum concentration. Dynamic rheological data of ln (G′, G′′) versus ln frequency (ω) of rice starch‐galactomannan mixtures have positive slopes with G′ greater than G′′ over most of the frequency range, indicating that their dynamic rheological behavior seems to be a weak gel‐like behavior.     

Dynamic Rheology of Rice Starch‐Galactomannan Mixtures in the Aging Process

The effect of galactomananns (guar gum and locust bean gum) at different concentrations (0, 0.2, 0.4, 0.6 and 0.8%, w/w) on the dynamic rheological properties of aqueous rice starch dispersions (5%, w/w) was investigated by small‐deformation oscillatory measurements during aging. Magnitudes of storage (G′) and loss (G′′) moduli measured at 4°C before aging increased with the increase in gum concentration in the range of 0.2–0.8%. G′ and G′′ values of rice starch‐locust bean gum (LBG) mixtures, in general, were higher than those of rice starch‐guar gum mixtures. G′ values of rice starch‐guar gum mixtures as a function of aging time (10 h) at 4°C increased rapidly at initial stage and then reached a plateau region at long aging times. However, G′ values of rice starch‐LBG mixtures increased steadily without showing a plateau region. Increasing the guar gum concentration resulted in an increase in plateau values. The rate constant (K) for structure development during aging was described by first‐order kinetics. K values in rice starch‐guar gum mixtures increased with the increase in guar gum concentration. G′ values of rice starch‐galactomannan mixtures after aging were greater than those before aging.     

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.     

Effects of starch alkenylsuccinylation on the grafting efficiency,paste viscosity,and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid)

Commercial cornstarch was alkenylsuccinylated with alkenylsuccinic anhydride to different degrees of substitution (DS) and then the products were graft‐copolymerized with acrylic acid for investigating the effects of starch alkenylsuccinylation on the graft copolymerization with vinyl monomer, as well as on paste viscosity and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid) (ASS‐g‐PAA). The number of carbon atom of alkenyl in alkenylsuccinates considered was 8 and 12, corresponding to octenylsuccinylation and dodecenylsuccinylation of starch, respectively. The graft copolymerization was accessed by grafting efficiency, grafting ratio, and conversion of monomer to polymer, and the film properties of ASS‐g‐PAA considered included tensile strength, breaking elongation, and work‐to‐break. Experimental results demonstrated that the alkenylsuccinylation showed marked effects on the copolymerization, paste viscosity, and film properties. It resulted in increased grafting efficiency, stable paste viscosity, and strong starch film. Carbon‐chain length of the alkenyl and DS value of the alkenylsuccinates also exhibited evident effects on the copolymerization and film properties. Octenylsuccinylation of starch before the copolymerization was superior to dodecenylsuccinylation in improving the efficiency and film properties. Low levels of octenylsuccinylation could be utilized to increase the efficiency of the copolymerization and improve the properties of starch film.     

Rheology of Rice Starch‐Sucrose Composites

The effect of sucrose at different concentrations (0, 10, 20 and 30%) on rheological properties of rice starch pastes (5% w/w) was investigated in steady and dynamic shear. The steady shear properties of rice starch‐sucrose composites were determined from rheological parameters for power law and Casson flow models. At 25°C all the starch‐sucrose composites exhibited a shear‐thinning flow behavior (n=0.25–0.44). The presence of sucrose resulted in the decrease in consistency index (K), apparent viscosity (η_a,100) and yield stress (σ_oc). Dynamic frequency sweeps at 25°C indicated that starch‐sucrose composites exhibited weak gel‐like behavior with storage moduli (G′) higher than loss moduli (G′′). G′ and G′′ values decreased with the increase in sucrose concentration. The dynamic (η*) and steady‐shear (η_a) viscosities at various sucrose concentrations did not follow the Cox‐Merz superposition rule. G′ values as a function of aging time (10 h) at 4°C showed a pseudoplateau region at long aging times. In general, the values of G′ and G′′ in rice starch‐sucrose composites were reduced in the presence of sucrose and depended on sucrose concentration.     

Functional and dynamic rheological properties of acetylated starches from two cultivars of cassava

The starches derived from two different cultivars of cassava were modified with acetic anhydride. The increase in swelling power and solubility of the cassava starch (CS) pastes treated with different acetic anhydride concentration could be attributed to easier hydration, resulting from reduction of interaction between starch chains due to the substitution. The transition temperatures (T_o, T_p and T_c) and enthalpy of gelatinisation (ΔH) of acetylated CS, were determined. The values were lower than those of native starches. Rheological properties of CS pastes (5% w/w) as a function of the degree of substitution were evaluated in dynamic shear force measurements. Magnitude of storage modulus (G′), loss modulus (G′′) and complex viscosity (Eta*) of acetylated CS pastes were determined also. Dynamic moduli (G′, G′′ and Eta*) values of acetylated sweet cultivar pastes were generally higher than those of native starch whereas the acetylated samples of the bitter cultivar were lower than those of native starch. The magnitudes of G′ were greater than those of G′′ and Eta* at all frequencies (ω). The fact that all the tan δ (ratio G′′/G′) values (0.7–0.48 and 0.25–0.44) were less than one is an indication that the samples are more elastic than viscous. The acetylated starches could find promising industrial uses in food products like Lemon curd and Mayonnaise and other non‐food applications.     

Starch Phosphate Hydrogels. Part I: Synthesis by Mono‐phosphorylation and Cross‐linking of Starch

Starch‐based hydrogels were synthesized by cross‐linking monostarch monophosphates (MSMP) with different di‐ and tricarboxylic acids such as succinic, adipic or citric acid. Phosphorylation of starch was performed in a semi‐dry process using a mixture of primary and secondary sodium phosphates. The phosphorus content and degree of substitution of phosphate groups (DS_P) of the resulting MSMP were determined using a photometric method. For structural characterization of starch phosphates ³¹P NMR was used. Investigations showed that MSMP hydrogels were strong water absorbing polymer networks with a free swelling capacity (FSC) of up to 185 g water / g dry hydrogel.     

Synthesis,characterisation and in vitro digestibility of carboxymethyl potato starch rapidly prepared with microwave-assistance

Carboxymethyl potato starch was synthesised with the aid of microwave. Optimal degree of substitution (DS) of 0.32 was obtained at 45 °C in 25 min using aqueous ethanol media with water/solvent of 0.15 at 200 W. The molar ratio of sodium hydroxide and monochloroacetic acid to anhydroglucose unit for optimal DS were 2.5 and 1.0, respectively. FT-IR spectrometry revealed the carboxymethyl starch to show new bands at ν = 1614 cm⁻¹ and ν = 1429 cm⁻¹. Wide angle X-ray diffractometry and DSC revealed a remarkable reduction in starch crystallinity after carboxymethylation, which was consistent with destroyed surface observed in SEM. The digestibility of carboxymethyl starch (CMS) was lower than that of native starch. With similar DS, there was no difference in digestibility of carboxymethyl starch prepared with and without microwave. As DS increased from 0.05 to 0.32, the amount of resistant starch in microwave-assisted carboxymethyl starch was elevated from 14.6% to 20.0%, which was much higher than that of native starch (10.8%).