The Combined Effect of Oxidation and Carbamoylethylation on the Rheological Properties of Maize and Rice Starches

The combined effect of oxidation and etherification on the molecular structure of starch was investigated. Maize and rice starches were used. Oxidation was effected using sodium hypochlorite while etherification was performed by reacting starch with acrylamide in presence of sodium hydroxide; this reaction is known as carbamoylethylation. The extent of the latter, expressed as % N, was found to increase by decreasing the molecular size of starch through oxidation. The carbamoylethyl starches so obtained could be precipitated by ethanol and they are soluble in water irrespective of the kind of starch. On the other hand, results of rheological properties indicated that they are governed mainly by the molecular size of starch. Oxidized starches with relatively high molecular size exhibit thixotropic behaviour. The degree of thixotropy decreases and changes into pseudoplasticity as the molecular size of starch decreases. The results also indicated that at constant rate of shear the apparent viscosity of carbamoylethyl starches decreases as the molecular size decreases. Furthermore, the rheological properties of carbamoylethyl starch pastes undergo considerable changes and so does the apparent viscosity when these pastes were stored for 3 days.     

Preparation and Characterization of Cationexchange Starches Containing Carboxyl Groups

Rice starch was first crosslinked using epichlorohydrin. The crosslinked starch was then subjected independently, to graft polymerization with acrylonitrile (AN) and cyanoethylation reactions. The poly (AN)-starch graft copolymer and the cyanoethyl starch so obtained were treated with sodium hydroxide to effect conversion of the cyanide groups of the modified starches into carboxyl groups via alkaline hydrolysis. It was found that the alkaline treatment results in decrement in the nitrogen content and increment in the carboxyl content. The magnitude of both contents is determined by sodium hydroxide concentration as well as duration and temperature of the treatment. It was also found that beside conversion of the cyanide groups to carboxyl groups, alkaline hydrolysis brings about cleavage of ether linkage of the copolymer and the cyanoethyl starch. This was evidenced by large difference observed between the sum of the substituents before and after hydrolysis. In this regard, cleavage of the ether linkage is greater with cyanoethyl starch than the poly (AN)-starch graft copolymer. The potential value of the hydrolyzed modified starches to serve as cation exchanger was assessed through measurements of critical properties such as durability, swellability, pK_a values and ion exchange capacity.     

Factors Affecting the Technological Properties of Starch Carbamate

Starches having different molecular sizes were obtained by subjecting rice starch and maize starch, independently, to oxidation with aqueous sodium hypochlorite solutions of different concentrations. These starches were then reacted with urea in a dry state to yield mainly starch carbamate. The latter was isolated from the reaction products by treatment of the latter with either water or 4% aqueous NaOH solution. It was observed that regardless of the kind and molecular size of starch, treatment with water brings about starch carbamate which swells but does not dissolve completely in water. Against this was water soluble starch carbamate isolated by ethyl alcohol precipitation from NaOH solution (after neutralization). Studies of the rheological properties of the water soluble starch carbamates revealed that starch carbamates derived from rice starches are characterized by either thixotropic or pseudoplastic character depending on the molecular structure of starch. On the other hand, starch carbamates derived from maize starch exhibit pseudoplastic behaviour by virtue of their relatively lower molecular weight and higher carboxyl content. It was also found that the apparent viscosity of starch carbamates is determined by the kind of starch, the degree of oxidation and the storing time.     

Technological Evaluation of Nitrogen Containing Starch Derivatives as Sizing Agents

The structural changes brought about by introducing different nitrogen containing groups via cyanoethylation, carbamoylethylation and carbamation in the molecules of rice and maize starches and oxidized starches derived thereof and the onset of these changes on the technical properties of yarns sized with such starch products were investigated. It was found that the apparent viscosity of pastes prepared from those products depends on the nature of starch, the degree of oxidation prior to chemical modification, the nature of modification as well as the measuring conditions, i. e. the rate of shear and temperature. Cotton yarns sized using these starch derivatives were measured for yarn number, tensile strength, C.V.%, elongation at break and C.V.% in elongation. Besides, the weavability test expressed as the minimum number of cycles due to abrasion (St₁) and average number of cycles due to abrasion (St₆) were investigated. A comparison among modified starches prepared from rice starch would reveral that the highest value of St₁ is obtained with yarns sized using carbamoylethylated sample derived from unoxidized starch. With maize starch, on the other hand, the highest value of St₁ is obtained with cotton yarns sized using carbamoylethylated starch derived from starch oxidized by 1 g/l active chlorine.     

Synthesis and Characterization of Hypochlorite Oxidized Starches

Egyptian rice and maize starches were treated with sodium hypochlorite at different concentrations. The oxidized starches so obtained were monitored for carboxyl content and rheological properties. In addition, the extent and rate of the oxidation reaction was assessed by investigating the chlorine consumption. Results indicated that the extent and rate of oxidation of rice starch, expressed as chlorine consumption, are much higher than those of maize starch. The opposite holds true for the carboxyl content. Pastes of rice and maize starches before and after oxidation exhibit non-Newtonian thixotropic behaviour but their apparent viscosity decreases by increasing the hypochlorite concentration. At any event, however, the apparent viscosity of rice starch is substantially higher than that of maize starch. Storing the pastes for 24 h adversely affect the apparent viscosity particularly with oxidized starches prepared using higher hypochlorite concentrations.     

Physicochemical Properties of Waxy and Normal Maize Starches Irradiated at Various pH and Salt Concentrations

Waxy and normal maize starches of various pH values and salt contents were prepared, irradiated with gamma rays (5–20 kGy) and their molecular structure, pasting viscosity and rheological properties determined. Average molar mass and size of both waxy and normal maize starches decreased considerably by irradiation from >338.0×10⁶ to <39.4×10⁶ g/mol and from >237.5 to <125.2 nm, respectively. Adjustments of pH had little influence on the average molar mass and size of irradiated starch, whereas incorporation of salt greatly reduced the molar mass and size of irradiated waxy and normal maize starches. As the pH increased from 4 to 8, the pasting viscosity of the irradiated starches decreased from 1032 to 279 mPa s in waxy and from 699 to 381 mPa s in normal starches. Pasting viscosity of both irradiated waxy and normal starch decreased from 689 to 358 mPa s and from 327 to 184 mPa s as the salt concentration increased from 1 to 5%. The G′ of gels, determined during cooling from 90 to 10°C or storage for 8 h, decreased in irradiated waxy and normal starches by pre‐conditioning at pH 8 and in irradiated waxy starches by pre‐conditioning at 5% NaCl. With 5% NaCl, G′ of irradiated normal maize starch during cooling increased up to the irradiation level of 10 kGy, and increased during storage for 8 h at all levels of irradiation. Incorporated salt prior to irradiation appears to induce incremental modifications in the molecular structure, rheological and retrogradation properties of starch by boosting the degradation of molecules.     

Rheological Properties of Acidified and UV‐Irradiated Starches

This study evaluated the effect of added lactic acid and/or UV irradiation on the depolymerization and rheological properties of cassava and corn starches. Combination of lactic acid addition and UV irradiation decreased the intrinsic viscosity of corn and cassava starches. Lactic acid addition alone also decreased paste viscosity in both starches. The paste viscosity of cassava (but not corn) starch was also reduced after UV irradiation. Acidification and UV irradiation increased expansion volume during the baking of cassava (but not corn) starch dough. The baking expansion of cassava starch may be due to its high swelling capacity and solubility resulting from molecular degradation after acidification and irradiation. For corn starch, its high gelatinization temperature and internal lipids content could interfere in starch leaching and thus delay the decrease in viscosity and inhibit dough expansion.     

Isolation and characterization of Mexican chayote tuber (Sechium edule Sw.) starch

Starch was isolated from Mexican chayote tubers (Sechium edule Sw.) and the yield, physicochemical, rheological, and molecular characteristics were investigated. Commercial potato was used for comparison. Starch yield was 49% with a purity of 89.1%. AM content of chayote tuber starch was 26.3%. Birefringence was shown in chayote tuber starch and granules had diverse shapes such as spherical, oval, and polygonal, with size between 10 and 25 µm. B‐type XRD pattern was shown by chayote tuber starch. Chayote tuber starch had higher peak viscosity (PV) than potato starch and the maximum PV for chayote tuber starch was obtained at lower temperature. Flow properties of chayote tuber starch showed higher hysteresis than potato at the same concentration. In chayote tuber and potato starches, G′ > G″ at both temperatures. Chayote tuber starch presented slightly lower gelatinization temperatures, but slightly higher enthalpy of gelatinization than potato starch, and similar retrogradation rate (due to the enthalpy value of the phase transition) were found in both tuber starches. Chayote tuber starch presented higher Mw and Rz values than potato starch. Chayote tuber could be an alternative for starch isolation with specific physicochemical and molecular characteristics.     

Physicochemical and Gelatinization Properties of Starches Separated from Various Rice Cultivars

Morphological, viscoelastic, hydration, pasting, and thermal properties of starches separated from 10 different rice cultivars were investigated. Upon gelatinization, the G′ values of the rice starch pastes ranged from 37.4 to 2057 Pa at 25 °C, and remarkably, the magnitude depended on the starch varieties. The rheological behavior during gelatinization upon heating brought out differences in onset in G′ and degree of steepness. The cultivar with high amylose content (Goami) showed the lowest critical strain (γ_c), whereas the cultivars with low amylose content (Boseokchal and Shinseonchal) possessed the highest γ_c. The amylose content in rice starches affected their pasting properties; the sample possessing the highest amylose content showed the highest final viscosity and setback value, whereas waxy starch samples displayed low final viscosity and setback value. The onset gelatinization temperatures of the starches from 10 rice cultivars ranged between 57.9 and 64.4 °C. The amylose content was fairly correlated to hydration and pasting properties of rice starches but did not correlate well with viscoelastic and thermal characteristics. The combined analysis of hydration, pasting, viscoelastic, and thermal data of the rice starches is useful in fully understanding their behavior and in addressing the processability for food applications.     

Einfluß von Sorte und Standort auf die Viskositätseigenschaften von Kartoffelstärke

Influence of Sort and Locality on Viscosity Properties of Potato Starch. Regarding its rheological properties potato starch holds a special position compared with all other starches, which is mainly due to the phosphoric acid, resp. phosphate groups bound ester-like to the amylopectin. The present work was carried out in order to find out, whether rheological properties of potato starch are also affected by outer influences such as year of cultivation, locality and sort. A marked influence of year of cultivation and locality as well as a less marked influence of the sort on phosphate and ash content of the starches became apparent. Locality exerts the strongest influence on viscosity. An influence of the sort can be stated, but it is mostly obliterated by superimposition.     

Morphological,thermal, rheological and noodle‐making properties of potato and corn starch

A comparison between the morphological, thermal, rheological and noodle‐making properties of corn starch and potato starches separated from five different potato cultivars was made. The granule size and shape of all starches differed significantly. Potato starch granules were comparatively larger than corn starch granules, while the transition temperatures were found to be higher for corn starch. Consistency coefficients and flow behaviour indices measured by back extrusion were higher for potato starches than for corn starch. Stickiness of cooked starch pastes was observed to depend upon their consistency coefficient. The gels made from all potato starches showed higher gel strength than those from corn starch. The gel strength of starches from both corn and potato increased during refrigerated storage. The amylose content, swelling power, solubility and light transmittance values of potato starches were significantly higher than those of corn starch. Noodles made from potato starches had higher cooked weight and cooking loss than corn starch noodles. Texture profile analysis revealed that potato starch noodles also had higher hardness and cohesiveness than corn starch noodles. Hardness of cooked noodles from all starches increased and cohesiveness decreased during storage. Noodles made from starches of higher viscosity exhibited higher hardness and cohesiveness. Textural differences among cooked starch noodles appeared to be associated with morphological, thermal and rheological properties of corn starch and potato starches. © 2002 Society of Chemical Industry     

Preparation and Aqueous Properties of Starch‐grafted Polyacrylamide Copolymers

In the present work, starch‐grafted polyacrylamide copolymers were prepared and their rheological properties, either in water or in water‐based muds, were investigated. The advantages in using starches as substrates to prepare additives which are suited for improving stability and the rheological properties of water‐based muds, lie in their low cost, and their lower biodegradability than native starches. Thus, various copolymer series were prepared by free‐radically grafting acrylamide (AM) onto starch using ceric ammonium sulphate (CAS) as initiator. It is shown that the intrinsic viscosity and the molecular weight of the grafted starches are controlled by the initiator and monomer concentrations. Furthermore, to predict the behaviour of the samples under oil‐well conditions, the aqueous solution properties of the copolymers such as water solubility, viscosity, shear rate, were determined as function of temperature, salt concentration and type, and aging time. The knowledge of these properties is a prerequisite for the use of the copolymers in drilling fluids. The data indicate that starch‐grafted polyacrylamide copolymers as compared to the non‐modified starch, behave as shear‐thinning, are salt resistant, and their rheological properties are stable with time. The grafted starches as prepared above were also added to water‐based mud and the rheological properties of the resulting muds were determined under oil‐well conditions. Grafted starches, having high AM contents, are more efficient in decreasing the filtrate volume, and increasing the plastic viscosity of the muds, when compared to PAC‐L, a modified cellulosic polymer used in the filtration control of most water‐based muds. Such improvements in the rheological properties of the muds were found to result from the behaviour and/or properties of the grafted starches in water.     

荞麦淀粉糊化特性研究

本实验采用快速黏度分析仪及流变仪对荞麦(甜荞、苦荞)淀粉糊化过程中的黏度和流变特性进行系统分析,并测定荞麦淀粉膨胀度、凝沉性、冻融稳定性、透光率等糊化特性。结果表明,荞麦淀粉(甜荞、苦荞)的糊化温度高于绿豆淀粉,低于大米淀粉和小麦淀粉。苦荞麦淀粉膨胀过程与绿豆淀粉相似,而甜荞淀粉与小麦淀粉相似;荞麦淀粉(甜荞、苦荞)糊透明性好;荞麦淀粉(甜荞、苦荞)冻融稳定性高于大米淀粉,低于小麦淀粉和绿豆淀粉;荞麦淀粉(甜荞、苦荞)糊具有较好的凝沉稳定性;荞麦淀粉糊属于非牛顿流体中的假塑性流体,其流变曲线符合Sisko 方程。     

颗粒冷水可溶亲脂性玉米淀粉的制备及性质研究

该研究以玉米淀粉为原料,首先利用酒精-碱法对其α-化,在此基础上,以辛烯基琥珀酸酐(octenyl succinic anhydride,OSA)为酯化剂,在干法条件下制备出颗粒冷水可溶亲脂性淀粉,所得产品取代度最高可达0.0192。通过分析试验制备的颗粒冷水可溶玉米淀粉和颗粒冷水可溶亲脂性玉米淀粉的透明度、冻融稳定性、凝沉性、黏度、流变学特性,并进一步探索这些特性与产品取代度之间的关系。结果表明:这两种淀粉的性质比原淀粉有显著的改善,后者又比前者具有良好的性质,随着取代度的增大,颗粒冷水可溶亲脂性玉米淀粉的透明度增强,冻融稳定性提高,凝沉性降低,表观黏度增加;流变学分析显示两种淀粉呈现出假塑性流体的性质,表观黏度随着剪切速率的增加而降低。     

Physicochemical properties of starches obtained from Polish potato cultivars

Selected physicochemical, thermal, and rheological properties of starches isolated from new Polish potato varieties were determined. The starches contained 25.7–30.0 g/100 g d.m. of amylose and 59.5–90.2 mg/100 g d.m. of phosphorus. Gelatinization temperatures were 62.6–64.0, 68.9–69.9, and 73.6–77.0°C for T_O, T_P, and T_E, respectively, whilst enthalpy of gelatinization amounted to 11.1–15.3 J/g. The retrogradation degree of starch was from 52.90 to 78.53%. Pasting curves showed significant differences between the starches. Peak viscosity and final viscosity ranges were 2035–4458 and 1931–2985 mPa · s, respectively. Starch pastes exhibited non‐Newtonian, shear thinning, and thixotropic behavior. After cooling they demonstrated diversified viscoelastic properties, however, all of them were classified as weak gels. Significant linear correlations among selected rheological parameters and amylose and phosphorus content were found. Results of principal component analysis demonstrated an ability to differentiate the starches isolated from different potato varieties.     

流化床气流超微粉碎对马铃薯淀粉结构及性质的影响

为研究流化床气流超微粉碎对淀粉结构及性质的影响,以马铃薯淀粉为原料,采用激光粒度分析仪、扫描电子显微镜、光电子能谱仪、同步热分析仪、流变仪等多种仪器及分析手段,考察气流粉碎对马铃薯淀粉颗粒大小及形貌、表面基团、热稳定性、流变特性、溶解度、膨胀度及透明度等结构及性质的影响。结果表明:马铃薯原淀粉经气流粉碎微细化处理后,平均粒径（D₅₀）减小至13.59±0.04 μm;X射线光电子能谱（XPS）的谱图中没有出现新元素峰位,淀粉颗粒表面没有引入新元素;直链淀粉含量增加,支链淀粉分子链变短,溶解度、膨胀度和淀粉糊透明度增加;粘性阻力减小,表观粘度降低;淀粉分子氢键及分子链均发生断裂,凝沉性下降,该研究为马铃薯淀粉的深度加工与应用提供了理论依据及技术支撑。     

Characterization of Residues from Partially Hydrolyzed Potato and High Amylose Corn Starches by Pancreatic α‐Amylase

High amylose corn starch (HACS) and potato starch were hydrolyzed by pancreatic α‐amylase in vitro. Residues after hydrolysis were collected and characterized for their physicochemical properties and molecular structure. Compared with raw starches, residues had lower apparent amylose contents and higher resistant starch contents. The gelatinization enthalpy of residues from HACS increased while enthalpy of residues from potato starch decreased from 15.4 to 11.3 J/g. Peak viscosity and breakdown values of the residues from potato starch were markedly decreased but final viscosity values did not show much change. Chain length distribution of debranched amylopectin from the residues indicated that the relative portion of short chain in the residue decreased for both starches. More molecules with intermediate chain length (DP 16—31) were found in residue after 48‐h hydrolysis of potato starch.     

Physicochemical properties of lotus (Nelumbo nucifera Gaertn.) and kudzu (Pueraria hirsute Matsum.) starches

Lotus and kudzu starches have been used as functional foods in East Asia for thousands of years. The objective of this work is to investigate the starches’ basic physicochemical properties. The amylose content was the highest (30.61%) in lotus starch. The average particle size (diameters) was 50.27, 24.08 and 38.97 μm for lotus, kudzu and corn starches, respectively. Lotus starch exhibited a B‐type X‐ray diffraction pattern and kudzu starch exhibited a C‐type pattern. Kudzu starch was characterised by a maximum viscosity immediately followed by a sharp decrease in viscosity, while the lotus starch was characterised by a plateau when the maximum viscosity was reached.     

A Comparison of mango kernel starch with a novel starch from litchi (Litchi chinensis) kernel: Physicochemical,morphological, pasting,and rheological properties

A novel starch was isolated from litchi kernel and compared with mango kernel starch. The properties studies were physicochemical, morphological, pasting, rheological, X-ray diffraction, and morphological. Litchi kernel starch had significantly (p < 0.05) higher amylose content and solubility, whereas its swelling power and paste clarity were lower than mango kernel starch. Peak viscosity and breakdown viscosity of litchi kernel starch were lower than mango kernel starch; however, it showed higher setback viscosity. The scanning electron microscopy revealed the presence of starch granules varying in size and shape from small to large and oval to elliptical, respectively, in litchi kernel starch. The mean length of small and large litchi starch granules was 9.52 and 50 µm, respectively, while the mean breadth of small and large litchi starch granules was 7.14 and 35.7 µm, respectively. X-ray diffractions of both litchi and mango kernel starches showed typical A-type patterns. During heating, litchi kernel starch showed higher peak G’ (storage modulus), G’’ (loss modulus), and breakdown in G’ in comparison to mango kernel starch. The peak tan δ of litchi and mango kernel starch was <1, which indicated that both litchi and mango kernel starches were more elastic than viscous.     

Morphological,Thermal, Pasting,and Rheological Properties of Barley Starch and Their Blends

Native barley starch, as well as its blends with corn, wheat, and rice starch at different ratios of 75:25, 50:50, 25:75 were examined in terms of morphology, thermal, pasting, rheological, and retrogradation properties. Amylose content varied between 10.9–41.4% in rice, corn, wheat, and barley while it ranged from 18.02–38.40% in blends of barley starch with rice, corn, and wheat. A rapid visco analyzer showed that barley starch and its blends having low amylose content exhibited higher peak viscosity, breakdown, and setback than the high-amylose-containing starches and their blends. Amylose content was found to be negatively correlated with swelling power while it exhibited nonlinear relationship with solubility index. The transmittance of starch suspension stored at 4°C decreased during storage up to 6 days. Barley starch granules were largest (<110 μm) in size followed by wheat (<30 μm), corn (<25μm) and rice (<20μm) starches. Gelatinization temperatures (To, Tp, Tc) and enthalpies of gelatinization (ΔHgel) of starches from different sources also differed significantly. Corn and rice starches showed higher transition temperatures in general than those from wheat and barley; however, they showed higher ΔHgel values. Barley starch showed a higher tendency towards retrogradation than the cereal starches. Barley starch showed highest peak G′, G″ and lower tan Ð than corn, rice and wheat starches during the heating cycle. This study showed that the magnitude of changes in their properties during blending depends on the amylase content and morphological characteristics.