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.     

Behaviour of Oxidized Starches Towards Cyanoethylation

Starch of different molecular sizes brought about by oxidation of maize and rice starches were cyanoethylated under identical conditions. The degree of cyanoethylation, expressed as % N, was found to depend mainly on the molecular size of starch irrespective of its kind. As the molecular size decreases the degree of cyanoethylation increases. Cyanoethyl starches are water soluble and can be precipitated by ethanol. It was also found that the rheological properties are determined by the nitrogen content of cyanoethyl starch. When the latter acquires low nitrogen content, it exhibits non-Newtonian pseudoplastic behaviour. On the other hand, cyanoethyl starches with higher nitrogen content are characterized by non-Newtonian thixotropic. At constant rate of shear, the apparent viscosity of cyanoethyl starches is directly related to its molecular size. Storing of pastes prepared from these cyanoethyl starches for 7 d exerts considerable influence on rheological properties and apparent viscosity of these derivatives.     

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.     

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.     

Cationized Starch Derived From Pre‐Oxidized Starch For Textile Sizing and Printing

Maize starch was subjected first to oxidation using H₂O₂ in presence and absence of ferrous sulfate as catalyst and then to cationization using 3‐chloro‐2‐hydroxypropyl trimethyl ammonium chloride. A thorough investigation of the chemical and rheological characteristics of the oxidized starch and oxidized‐cationized starch samples was made. It was found that these modified starches display characteristics, which qualify them to function as excellent sizing agent and to less extent as thickeners for printing polyester fabric with disperse dyes. The differences among the oxidized samples prepared in acidic and alkaline media in presence and absence of ferrous sulfate with respect to carboxyl and carbonyl group content were explained on the basis of the different mechanisms involved in the oxidation reaction of starch. The amenability of the different oxidized starch samples to cationization and variation in the apparent viscosity after cationization of the oxidized starches were also reported.     

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.     

Gelatinization of Starch in Aqueous Alkaline Solutions

The effect of kind and concentration of alkali on the gelatinization of maize, rice and wheat starches were thoroughly investigated. No gelatinization could be observed on using the carbonate and/or bicarbonate of sodium and potassium even on using their saturated solutions, while both sodium and potassium hydroxides undergo gelatinization. Gelatinization of starch occurs immediately at a concentration of sodium hydroxide of 1.2%, while clear gelatinized pastes could be obtained at 4% or more. Infra-red spectra of maize and rice starches before and after alkali treatment reveal that treatment of starch with sodium hydroxide is accompanied by some physicochemical changes in the structure of starch. The rheological properties as well as the apparent viscosity of the gelatinized starch pastes depend on the kind of starch as well as the nature and concentration of alkali used.     

韧化处理对不同玉米淀粉理化特性的影响

以不同直/支链比例的普通玉米淀粉和蜡质玉米淀粉为材料,在40、50、60℃进行韧化处理,研究韧化处理对玉米淀粉理化特性的影响。结果表明：韧化处理的两种玉米淀粉颗粒形貌有较小变化。韧化处理后,两种淀粉的溶解度和膨胀度随着处理温度的升高而降低;所有韧化处理过的玉米淀粉黏度低于原淀粉,起糊温度高于原淀粉;韧化处理后淀粉的糊化温度升高,热焓变化不大。     

Properties of jackfruit seed starch oxidized with different levels of sodium hypochlorite

The effect of active chlorine concentrations (1–5%) on the properties of jackfruit seed starch was investigated. Both the carbonyl and carboxyl contents of the oxidized starches generally increased with progressive increases in the active chlorine concentration. No evidences of alteration in the morphology and X-ray diffraction pattern were observed after oxidation, while the decrease in relative crystallinity was found. The swelling power of the oxidized starch tended to decrease with the active chlorine levels, particularly at a low level of active chlorine (1–3%). No significant differences in the peak temperature (Tp) and the end temperature (Te) were found between the native and the oxidized starches, while the oxidized starches had lower onset temperatures (To). Parameters, such as pasting temperature, peak viscosity, and setback, decreased with the concentration of active chlorine. In addition, lower syneresis and turbidity were found in all oxidized starches during refrigerated storage compared to the native starch.     

微波湿法氧化淀粉的制备及其性质研究

在微波辐射条件下,以玉米淀粉、双氧水为主要原料制备氧化淀粉,研究不同处理时间淀粉结构和性能的变化。结果表明:微波辐射加快了氧化反应的进行,其作用时间对淀粉的结构有很大的影响。随着微波处理时间的增加,淀粉羧基含量逐渐增大,淀粉糊化液的黏度显著下降,淀粉糊化各阶段的温度逐渐升高,但糊化温度范围变窄。此外,经微波处理的氧化淀粉具有高溶解度、低膨胀度的特点。     

Preparation and Characterization of Carboxymethyl Starch (CMS) Products and Their Utilization in Textile Printing

Starch and oxidized starches of different molecular sises were carboxymethylated under identical conditions. The degree of substitution (DS) of the so obtained. CMS samples increases by decreasing the molecular sise of starch which, indeed, is a manifestation of higher extents of oxidation. The latter was effected using different sodium hypochlorite concentrations and the extent of oxidation was expressed as chlorine consumption. Pastes of these CMS samples exhibit pseudoplastic behaviour and their apparent viscosity decreases as the extent of oxidation increases, when used as thickeners in printing polyester fabric with disperse dyes, these pastes bring about prints the colour strength (K/S) of which are comparable with these for conventional thickeners, namely commercial CMS and sodium alginate. Mixing of sodium alginate with the prepared CMS samples increases the efficiency of the latter to act as the thickening agent. The highest K/S is obtained with CMS derived from starch oxidized using 1.25g active chlorine/1. Mean while, the colour fastness properties of the prints towards rubbing, washing and perspiration are nearly equal to those fabrics printed using the conventional thickeners such as sodium alginate or commercial CMS.     

Characterization of Different Starches Oxidized by Hypochlorite

The effects of starch origin (potato, corn, and rice starches) and hypochlorite level (NaOCl, 0.8% and 2% w/w) on the structures and physicochemical properties of oxidized starches were investigated. Carboxyl and carbonyl group contents of oxidized starches increased with increasing NaOCl level, with potato starch having the highest and corn starch having the lowest carboxyl groups content at both NaOCl levels. Oxidation generally reduced the pasting temperature and viscosity of native starches as demonstrated by using a Rapid Visco Analyser. The peak viscosities of oxidized rice and corn starches were higher than those of their native counterparts at 0.8% NaOCl. The morphology of starches was not altered and X‐ray diffraction patterns of all the starches remained unchanged after oxidation. Oxidized starch batters exhibited greater adhesions than did native starch batters, with rice starch batter exhibiting the greatest adhesion. Carbohydrate profiles by high‐performance size‐exclusion chromatography indicated that both amylopectin and amylose were degraded during oxidation. The level of oxidation was largely dependent on the degree of crystallinity of starch and the degree of polymerization of amylose, whereas the adhesion property of oxidized starch was mainly attributed to its granular size and shape.     

Comparative Studies on Some Physico-chemical, Thermal, Morphological, and Pasting Properties of Acid-thinned Jicama and Maize Starches

Comparative studies on acid hydrolysis of jicama and maize starch were carried out using concentrations of hydrochloric acid of 1.5%, 3.0%, and 4.5% (w/v), for 3 and 6 h, at 40°C. Native maize and jicama starches showed important morphological, thermal, and structural differences from those of tubers and cereals which potentially offer diverse industrial applications. Jicama starch showed low amylose content (12%) and small size of starch granules. Due to these characteristics, jicama starch was more susceptible to degradation during hydrolysis process than maize starch. Under the experimental conditions employed, the acid degradation was not particularly severe, as shown by scanning electronic microscopy analysis which showed small degraded zones and similar X-ray patterns in both starches. However, jicama starch was more susceptible to acid hydrolysis than maize starch, as revealed by the considerable increase in water solubility index, damaged starch, and crystallinity values. Also, the higher susceptibility of jicama starch than maize starch to the hydrolysis conditions was reflected in the sugar content release during hydrolysis. The relative crystallinity of hydrolyzed maize starches decreased during hydrolysis, while those of hydrolyzed jicama starches increased attributable to the lower amylose content of jicama starch in relation to maize starch. Maize and jicama hydrolyzed starches showed low viscosity values with relation to their native starch counterparts. However, native jicama starch showed lower viscosity values than maize starch, suggesting a lower internal stability of the starch granules during hydrolysis. Both native and hydrolyzed maize starches showed higher enthalpy, T _o, T _p, and T _c values than jicama starch and the broadening of the endotherms decreased during the hydrolysis of both starches.     

Rheological Properties of Rice Starch Dispersions in Dimethyl Sulfoxide

The steady and dynamic shear rheological properties of rice starches dispersed in dimethyl sulfoxide (DMSO) solution (90% DMSO‐10% water) were evaluated at various concentrations (7, 8, 9 and 10%, w/w). Rice starch dispersions in DMSO solution at 25°C showed a shear‐thinning flow behavior (n=0.44–0.60) and their consistency index (K) and apparent viscosity (η_a,100) increased with the increase in concentration. The apparent viscosity over the temperature range of 25–70°C obeyed the Arrhenius temperature relationship, indicating that the magnitudes of activation energy (E_a) were in the range of 11.7–12.7 kJ/mol. The Carreau model provided better fit on the shear rate‐apparent viscosity data than the Cross model. Dynamic frequency sweep test showed that both storage modulus (G′) and loss modulus (G′′) of rice starch dispersions increased with the increase in concentration. G′′ showed a higher dependence on frequency (ω) compared to G′ due to the higher G′′ slopes. All rice starch dispersions showed the plateau of G′ at high frequencies. Intrinsic viscosity of rice starch dispersions in DMSO was 104.1 mL/g.     

Partial Characterization of Tamarind (Tamarindus indica L.) Kernel Starch Oxidized at Different Levels of Sodium Hypochlorite

The effects of different levels of sodium hypochlorite (1–4 g/100 g dry solids active chlorine) on the physicochemical, pasting, and structural properties of tamarind kernel starches were investigated. The isolated starch had low traces of non-starch components, such as protein, fat, and ash, indicating its purity. Both the carboxyl and carbonyl contents in the oxidized starches increased significantly with the increase in chlorine concentration. The introduction of carboxyl and carbonyl groups resulted in significantly lower amylose content. The swelling power of oxidized starches was significantly lower than native starch and the solubility values increased when the chlorine concentration increased at all the measured temperatures. The percentage of light transmittance increased progressively after oxidation. Pasting properties showed that in treatments at high active chlorine concentrations, the peak viscosity decreased more drastically than in treatments at low chlorine concentration, indicating a greater degradation of starch. The morphology of the starches was not altered after oxidation. After oxidative treatment no change in the X-ray diffraction pattern was observed but intensity of the peaks increased. Therefore, tamarind kernel being underutilized raw material, has a great potential as a non-conventional source of starch and desirable properties of this starch can be enhanced by oxidation for applications in food industry.     

Endosperm Structure and Physicochemical Properties of Starches from Normal,Waxy, and Super-Sweet Maize

Maize is a main botanical source used for extraction of starch in the world market. New maize cultivars with different amylose contents and special starch metabolism characteristics have been generated. Three types of maize cultivars, namely, normal maize, waxy maize (wxwx homozygous mutant), and super-sweet maize (sh2sh2 homozygous mutant), were investigated to determine differences in endosperm structures, morphologies, and physicochemical properties of starches. Maize kernels exhibited significantly different contents of total starch, soluble sugar, and amylose. Normal maize kernels contained the largest proportion of floury endosperm, followed by waxy maize and then super-sweet maize. Normal maize starch and waxy maize starch were larger in size than super-sweet maize starch. Normal maize starch and waxy maize starch were spherical and polygonal in floury and vitreous endosperms, respectively. Super-sweet maize starch was spherical both in floury and vitreous endosperms. Waxy maize starch showed the strongest birefringence patterns, the highest crystallinity and the largest proportion of ordered structure in external region of granules, and the largest proportion of double helix components, followed by normal maize starch and then super-sweet maize starch. Waxy maize starch showed the highest peak viscosity, trough viscosity, breakdown viscosity, gelatinization temperatures (i.e., gelatinization conclusion temperature, gelatinization onset temperature, gelatinization peak temperature, and gelatinization enthalpy). By contrast, super-sweet maize starch showed the lowest corresponding values for these parameters.     

Effect of acid hydrolysis in the presence of anhydrous alcohols on the structure,thermal and pasting properties of normal,waxy and high‐amylose maize starches

Maize starches with different amylose contents (0%, 23% and 55%) were treated in anhydrous methanol, ethanol, 2‐propanol, 1‐butanol with 0.36% HCl at 25 °C for 5 days. Results showed that the extent of change in physicochemical properties increased from methanol to butanol. Treated waxy maize starch showed higher than 65% solubility at above 75 °C. The diffraction peak at 2θ = 5.3° of amylomaize V starch disappeared after treatment in ethanol, 2‐propanol and 1‐butanol. Acid–alcohol treatment decreased the gelatinisation temperature of normal (from 64.5 to 61.9 °C) and waxy maize (from 68.1 to 61.1 °C) starches, while it increased that of amylomaize V (from 68.7 to 72.3 °C) starch. The extent of the decrease in the pasting viscosity followed the following order: amylomaize V < normal maize < waxy maize. This study indicated that acid–alcohol treatment degraded preferentially the amorphous regions and the different changes depended on the crystal structure and amylose content of starch.     

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。     

几种不同品种淀粉及羟丙基产物糊液性质比较研究

以薯类淀粉(木薯,马铃薯)及禾谷类淀粉(普通玉米、蜡质玉米、高直链玉米及糯米)为原料,以环氧丙烷为醚化剂。制备了羟丙基变性淀粉。反应条件:淀粉乳质量分数40%、反应温度40℃、无水Na_2SO_4添加量12%(以淀粉干基计)、NaOH添加量1.2%、环氧丙烷添加量12%、反应时间18h。分别对原淀粉及在相同的反应条件下制备的羟丙基变性淀粉糊性质做了对比研究。不同品种淀粉糊性质存在很大差别。经过羟丙基改性。淀粉糊液粘度性质、冻融稳定性、透光率、都有不同程度的改善,但凝沉性质不能准确反映羟丙基化对蜡质玉米淀粉和糯米淀粉糊液性质的改善。     

Molecular structure,rheological and thermal characteristics of ozone-oxidized starch

The effects of oxidation by ozone gas on the molecular structure, rheological and thermal properties of starch (corn, sago and tapioca) were investigated. Starch, in dry powder form, was exposed to ozone for 10 min at different ozone generation times (OGTs). Average molecular weight decreased in oxidized corn and sago starches but increased in oxidized tapioca starch. All oxidized starches exhibited non-Newtonian shear-thinning behaviour. Starch viscosity decreased drastically with increasing OGT. Young’s modulus for all oxidized corn and sago starch gels stored for 1 and 7 days at 4 °C increased significantly compared to unmodified starch. No differences were noted in gelatinization temperatures and gelatinization enthalpies of all oxidized starches compared to unmodified starch. Retrogradation enthalpy increased markedly in corn starch after 1 min OGT. These results show that the extent of starch oxidation varies among starches of different botanical origins under similar ozone treatment conditions.