Characterization of Dextrins obtained by Enzymatic Treatment of Cationic Potato Starch

The substitution pattern of cationic potato starches was studied using starch hydrolyzing enzymes and a characterization of the hydrolysis products. Native and cationic starch samples were hydrolyzed with pullulanase, isoamylase, and α‐amylase and the molecular‐weight distributions of the resulting dextrins were studied using gel permeation chromatography. Isoamylase hydrolyzed the native potato starch sample readily, whereas hydrolysis with pullulanase was incomplete. Pullulanase hydrolyzed, however, cationic starch with higher DS (degree of substitution) more efficiently than isoamylase. The hydrolysis products obtained with pullulanase were separated according to charge using cation‐exchange chromatography into one unbound and two bound fractions. The unbound fraction possessed an increasing number of short chains from amylopectin with increasing DS of the starch sample. The bound material contained amylose and dextrins with sizes corresponding to the long B‐chains. The high portion of uncharged dextrins after α‐amylolysis suggested that the substitution pattern, on the molecular level, was non‐random. The composition of the unbound and bound material, obtained by ion‐exchange chromatography of α‐amylase treated starches, suggested a more intense fragmentation with increasing DS of the sample. Possibly, the substituents influence substrate conformation and thereby alter the hydrolysis patterns. It is concluded that a thorough understanding of the enzymatic hydrolysis patterns is of ultimate importance in structural studies of modified starch.     

Development and Physicochemical Characterization of New Resistant Citrate Starch from Different Corn Starches

Resistant starch has drawn broad interest for both potential health benefits and functional properties. In this study, a technology was developed to increase resistant starch content of corn starch using esterification with citric acid at elevated temperature. Waxy corn, normal corn and high‐amylose corn starches were used as model starches. Citric acid (40% of starch dry weight) was reacted with corn starch at different temperatures (120–150°C) for different reaction times (3–9 h). The effect of reaction conditions on resistant starch content in the citrate corn starch was investigated. When conducting the reaction at 140°C for 7 h, the highest resistant starch content was found in waxy corn citrate starch (87.5%) with the highest degree of substitution (DS, 0.16) of all starches. High‐amylose corn starch had 86.4% resistant starch content and 0.14 DS, and normal corn starch had 78.8% resistant starch and 0.12 DS. The physicochemical properties of these citrate starches were characterized using various analytical techniques. In the presence of excess water upon heating, citrate starch made from waxy corn starch had no peak in the DSC thermogram, and small peaks were found for normal corn starch (0.4 J/g) and Hylon VII starch (3.0 J/g) in the thermograms. This indicates that citrate substitution changes granule properties. There are no retrogradation peaks in the thermograms when starch was reheated after 2 weeks storage at 5°C. All the citrate starches showed no peaks in RVA pasting curves, indicating citrate substitution changes the pasting properties of corn starch as well. Moreover, citrate starch from waxy corn is more thermally stable than the other citrate starches.     

Influence of Selected Parameters of Starch Gelatinization and Hydrolysis on Stability of Amylose‐Lipid Complexes

Dissociation of amylose – lipid complexes (AMLs) upon gelatinization and enzymatic hydrolysis of wheat starch has been examined using differential scanning calorimetry (DSC). Digestion of starch by the thermostable α‐amylase THERMAMYL 120L was carried out under conditions applied for enzymatic hydrolysis of wheat starch in industry, i.e. 5 min incubation at 105°C, followed by 60–90 min hydrolysis at 95°C. For comparison reasons, samples of wheat starch slurries were incubated under the same conditions but in the absence of enzyme. The enthalpy and temperature of AMLs dissociation and the shapes of peaks in the DSC endo‐ and exotherms depended on conditions of starch processing prior to DSC measurements. Wheat starch gelatinization coupled with its digestion by α‐amylase resulted in more pronounced AML degradation as compared to gelatinization in the absence of enzyme. Different shapes of peaks in thermograms and different temperatures of AMLs dissociation and reassociation indicate that different AML polymorphs were generated in the examined samples. Their concentrations depended on conditions (temperature, time and the presence or absence of α‐amylase) of wheat starch treatment.     

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.     

Bread quality of frozen dough substituted with modified tapioca starches

Rheological properties of dough and bread quality of frozen dough-bread containing 18.4% of hydroxypropylated (HTS), acetylated (ATS), and phosphorylated cross-linked (PTS) tapioca starch with different degrees of modification and 1.6% of dried powdered gluten were compared to the same amount of native tapioca starch (NTS) or wheat flour-bread. Doughs substituted with native or modified tapioca starches had the same mixing tolerance as 100% wheat flour. The dough was frozen and stored for 1 week at −18°C, and thawed (one freeze-cycle). The amount of freezable water in the dough substituted with native or modified tapioca starches was not significantly different from that of wheat flour. Frozen dough-bread substituted with highly modified HTS (degree of substitution; DS 0.09–0.11) retarded bread staling, while lowly modified HTS (DS 0.06–0.07) or ATS (DS 0.02–0.04), and PTS (0.004–0.020% phosphoryl content) substitution fastened bread staling as compared with frozen dough-bread baked from wheat flour. The breadcrumbs containing HTS and ATS felt tacky, whereas the bread containing PTS was dry feel. HTS and ATS swelled and collapsed easily during heating, while PTS was difficult to swell and disperse as compared with NTS, therefore the gelatinization properties seemed to affect the texture of bread. Breadcrumb containing HTS showed small firmness during storage, and highly modified HTS-h (DS 0.1) was the smallest. This means highly hydroxypropylated tapioca starch significantly retards bread staling. Staling properties and texture of frozen dough-bread with various tapioca starches were the same as conventional bread baked with the same amount of tapioca starches. These results suggest that a one freeze–thaw cycle and a 1-week frozen period do not change characteristics of starch, gelatinization and retrogradation properties as compared with the conventional method, and the highly modified HTS-h is prominent anti-staling food-stuff in frozen dough.     

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.     

Gelatinisation Characteristics and Enzyme Susceptibility of Different Types of Barley Starch in the Temperature Range 48–72°C1

The gelatinisation temperatures, pasting characteristics and enzymic susceptibilities in the temperature range 48–72°C of normal, high amylose, low amylose and zero amylose barley starches were determined. Normal starches had the lowest gelatinisation temperatures, but low and zero amylose starches had the lowest pasting temperatures. Normal starches were the most readily soluble in water at 48–60°C in the presence of a mixture of α‐amylase, β‐amylase and limit dextrinase and were most readily broken down to reducing sugars by these enzymes. High amylose starch was the most resistant to enzymic hydrolysis in the temperature range 48–72°C and, hence, produced the lowest level of reducing sugars.     

The Advantages of Using Natural Substrate‐Based Methods in Assessing the Roles and Synergistic and Competitive Interactions of Barley Malt Starch‐Degrading Enzymes

Existing methods of assay of malt starch‐degrading enzymes were critically appraised. New methods based on natural substrates, namely starch and its natural intermediate‐derivative, were developed for all the enzymes, except limit dextrinase for which pullulan was used. Thermostability, optimal temperatures and pHs were established. α‐Amylase and limit dextrinase were the most thermostable and β‐amylase, α‐glucosidase and maltase were the least stable while diastase occupied an intermediate position. The optimal temperatures were congruent with thermostability, β‐ amylase having the lowest (50°C) and α‐amylase the highest (65°C) with the remaining enzymes, including diastase, falling in between. In contrast, α‐amylase has the lowest optimal pH (pH 4.5) and β amylase the highest (pH 5.5) while the others have pHs in between the two values. The roles of the enzymes were evaluated taking into account the level of activity, thermostability, optimum pH, the nature of the product(s), and the relevance to brewing. β‐Amylase production of maltose was synergistically enhanced, mostly by α‐amylase but also limit dextrinase. α‐Glucosidase and maltase are unimportant for brewing, because of their low activity and the negative impact on β‐amylase activity and the negative effect of glucose on maltose uptake by yeast. The starch‐degrading enzymes (diastase) in a gram of malt were able to degrade more than 8 g boiled starch into reducing sugars in 10 min at 65°C. The latter, suggests that it will be possible to gelatinise most of the malt starch at a higher temperature and ensure its hydrolysis to fermentable sugars by mixing with smaller portions of malt and mashing at lower temperatures e.g. 50–60°C.     

Physicochemical properties of Pinhão (Araucaria angustifolia, Bert, O. Ktze) starch phosphates

Physicochemical properties of pinhão (seeds of Paraná pine) starch phosphates were evaluated and compared to corn starch phosphates. The phosphorylation process used yielded starch phosphates with three different degrees of substitution (DS): low (0.015), medium (0.07) and high (?0.12). Medium and high DS starch phosphates had higher cold water binding capacity, swelling power, and paste clarity, but lower paste syneresis (at 5 °C and after freeze-thaw cycles) than native starches (P<0.05). Low, medium, and high DS corn starches had higher solubility than native starches (3.8-, 8-, and 6-fold higher; P<0.05), but the solubility of pinhão starch increased only in medium DS starch phosphates (3-fold higher; P<0.05). Low DS starch phosphates had viscosity curves similar to native starches. In contrast, medium and high DS starch pastes had peak viscosity at room temperature, reached the minimum viscosity when heated to 95 °C, and had low setback.     

Low‐ and Medium‐DE Maltodextrins From Waxy Wheat Starch: Preparation and Properties

The goal of the research was to prepare maltodextrins (MD) from waxy wheat starch and waxy corn starch (control). Waxy wheat starches with 0.2% protein, 0.2% lipid and ∼1% amylose were isolated from two flours by mixing a dough, dispersing the dough in excess water, and separating the starch and gluten from the resultant dispersion. The mean recoveries were 72% for the starches and 76% for the gluten fraction with 80% protein. Maltodextrins having low‐dextrose equivalence (DE) 1—2 and mid‐DE 9—10 were prepared by treatment of 15% slurries of waxy wheat starch and waxy corn starch at 95 °C for 5—10 min and 20—50 min, respectively, with a heat‐stable α‐amylase. Denaturing the enzyme and spray‐drying produced MD's with bulk densities of 0.3 g/cm ³. The powdery MD's were subjected to an accelerated‐rancidity development test at 60 °C, and an off‐odor was detected after 2 days storage for the low‐DE MD's from the two waxy wheat starches (WxWS₁‐MD 1.2 and WxWS₂‐MD 1.5), but not for the low‐DE waxy corn maltodextrin (WxCS‐MD 2.2) or a commercial waxy corn MD with DE 1. None of the mid‐DE 9—10 MD's developed off‐odor after 30 days storage at 60 °C. The experimental products WxWS₁‐MD 9.2, WxWS₂‐MD 9.9 and WxCS‐MD 9.1 showed high water‐solubility and gave 1—10% aqueous solutions of high clarity with no clouding upon cooling.     

不同来源的淀粉制备淀粉磷酸单酯的性能及应用

本文比较了马铃薯淀粉、蜡质玉米淀粉、木薯淀粉、小麦淀粉及经磷酸化后产品的物理性能，着重研究了其粘度及糖、盐对其粘度的影响并比较了磷酸化对糊的透明度、冻融稳定性及其对发泡体系的影响，结果表明不同淀粉制得的淀粉磷酸单酯的性能有很大差别。在蛋糕中的应用试验表明，在蛋糕中添加淀粉磷酸单酯可以增加比容并延长其货架寿命。     

Granule structural,crystalline, and thermal changes in native Chinese yam starch after hydrolysis with two different enzymes–α‐amylase and gluco‐amylase

Starch extracted from Chinese yam was characterized by scanning electron microscope (SEM), X‐ray powder diffractometer (XRD), and differential scanning calorimeter (DSC) in the process of enzymatic hydrolysis. Yam starch was digested by α‐amylase and gluco‐amylase for different lengths of time, respectively, and two different enzymatic hydrolysis results were compared. The most notable phenomenon revealed by SEM after α‐amylase hydrolysis was the formation of the cavum in the center of the starch granules, while after gluco‐amylase hydrolysis, the outer layer of the granules was peeled off and then some granules even broke into pieces. The XRD of the two enzyme hydrolyzed starches revealed the crystal type of the starch changed from typical C‐type XRD pattern to the representative A‐type pattern in the process of enzymatic hydrolysis. The above results also demonstrated that the partially B‐type polymorph was more easily degraded than A‐type. The thermal result showed that the modified yam starches by both enzymes exhibited increased peak gelatinization temperatures (T_p) and decreased gelatinization enthalpy (ΔH).     

Physicochemical Properties of Different Types of Starch Phosphate Monoesters

Different types of starch were phosphorylated to different degrees of substitution using monosodium and disodium hydrogen orthophosphate at 160 °C under vacuum. Generally, phosphation enhanced the physicochemical properties of the modified starches compared to their native counterparts. Solubility and swelling power greatly increase when phosphorylation was carried out to a low degree of substitution, while the solubility and swelling power decreased gradually by increasing the degree of substitution. However, the values of the monoesters were still higher than those of the corresponding native polysaccharides. Viscosities of different starch types except corn amylose showed the highest values at the lowest degree of substitution, when the degree of phosphation increased the viscosity values decreased. Native potato starch formed a clear paste (96% transmittance) due to the presence of phosphate groups while the paste clarity of potato starch decreased gradually by increasing the degree of phosphation. Generally, phosphorylation increased the light transmittance of the other starches investigated at the lowest degree of substitution but the clarity decreased by increasing the degree of substitution.     

Granular Properties of Different Starch Phosphate Monoesters

Different starch types (corn, rice, and potato starch, corn amylose and corn amylopectin) were phosphorylated by reaction with a mixture of mono and disodium phosphate at different molar ratios (mol phosphate/mol anhydrous glucose) under heat and vacuum. The starch granules of the modified and the native starches were microscopically examined for their sizes and morphology. The correlation between the variation in granular size of the modified starches with the extent of phosphorylation and some other physicochemical properties was studied. The granular size was generally increased while the iodine absorption capacity was decreased by phosphorylation. There were strong correlations between the variation in the starch granular size in dependence on phosphorylation and the corresponding changes in some physicochemical parameter of starch, e.g. solubility, swelling and paste clarity. This relationship was most evident in the case of phosphorylated corn amylopectin. Starch granular size can be taken as a quick indicator of the physicochemical properties of the native and modified starches.     

An improved enzymic method for the determination of native and modified starch

An improved method for the determination of starch by sequential hydrolysis with thermostable bacterial α-amylase and fungal amyloglucosidase is described. Glucose was determined colorimetrically by a glucose oxidase-peroxidase-chromogen system at pH 7. Native normal and waxy starches, and distarch phosphate, gave quantitative yields of glucose with a high degree of precision (coefficient of variation less than 1%). Acetylated distarch phosphate, high-amylose starch and retrograded amylose were initially treated with 1M NaOH for 30 min, then neutralised and analysed successfully as normal starch. Oxidised starch did not give a quantitative yield of glucose because of the presence of dicarboxylic groups in the polymer. For samples containing normal and waxy starch the analysis was carried out in about 4 h. The method was applied to a range of starch-containing foodstuffs and the results are reported.     

Effect of Aqueous Ethanol Cationization on Functional Properties of Normal and Waxy Starches

Cationic starch ethers of normal and waxy corn, normal and waxy barley and normal pea starch were prepared by an aqueous alcoholic process for evaluation of their functional properties as compared to the native starch controls. The native starches exhibited a wide range in average granule size (10–21 μm diameter), amylose content (0–34%) and swelling power (13–31). Cationization to degrees of substitution (DS) of 0.030–0.035 with 3-chloro-2-hydroxypropyltrimethylammonium chloride resulted in marked increases in swelling power of all starches, with little corresponding increases in starch solubility. Cationization also decreased the onset of endothermic transitions and pasting temperatures quite substantially, and promoted the development of sharp peak viscosities in the amylographs of all normal and waxy starches, including that of pea starch. Final cold viscosities of the cationic starches exhibited positive setbacks, and the cooked starch gels, after storage for 7 days at 4°C and −15°C, showed no syneresis. All cationic starches except for waxy corn were more susceptible to α-amylase hydrolysis than native control starches. The general improvement in functional properties, especially in the waxy corn, waxy barley and pea starches, due to the aqueous alcoholic-alkaline cationization process would greatly enhance their industrial applications.     

Effect of acetylation on the properties of corn starch

Acetylated corn starches with different degrees of substitution (DS 0.85, DS 1.78, DS 2.89) were synthesized by the reaction of corn starch with acetic anhydride in the presence of acetic acid under varying reaction temperatures. The product was characterized by FTIR spectroscopy, ¹H NMR, X-ray diffraction and contact angle measurement. Acid-base titration and ¹H NMR methods were employed to determine the degree of substitution of product. FTIR spectroscopic analysis showed that the characteristic absorption intensities of esterified starch increased with increase in the degree of substitution, and the characterized peak of hydroxyl group almost disappeared in the spectrum of DS 2.89 acetylated starch. The detailed chemical microstructure of native starch and acetylated starch was confirmed by ¹H NMR, ¹³C NMR and ¹³C–¹H COSY spectra. Analysis of ¹H NMR spectra of acetylated starches was assigned accurately. Strong peaks in X-ray diffraction of acetylated starch revealed that new crystalline regions were formed. Compared with native starch, the hydrophobic performance of acetylated starch esters was increased. The contact angle of acetylated starch with DS 2.89 was 68.2°.     

Studies on the properties of citrate derivatives of cassava (Manihot esculenta Crantz) starch synthesized by microwave technique

Cassava starch citrates with degree of substitution (DS) ranging from 0.005 to 0.063 were synthesized by the microwave‐assisted reaction of cassava starch with citric acid. A response surface small composite design was used to study the effect of different reaction conditions, viz. time, temperature and reagent concentration. All these variables significantly affected the substitution level in the modified starches. The DS increased with increase in the time of reaction and temperature. However, reagent concentration had a negative effect on the DS. The modified starches showed higher viscosity with lower breakdown, lower setback and higher final viscosities in comparison to native starch. Differential scanning calorimetry showed that the modified starches exhibited a decrease in gelatinization temperatures, T_o, T_p, T_e, in comparison to native starch. However, the heat of gelatinization was not significantly affected. The citrate derivatives exhibited reduced swelling volume and enhanced water binding capacities. They were found to be less susceptible to enzyme hydrolysis than native starch. Copyright © 2007 Society of Chemical Industry     

两种大米淀粉及其磷酸酯淀粉理化特性的比较研究

对比分析2种大米(籼米和粳米)的全粉、淀粉和取代度均为0.068的磷酸酯淀粉的理化特性.粳米的全粉、淀粉和磷酸酯淀粉的膨胀力分别为7.5,10.7,21.6 g/g,分别高于籼米的全粉、淀粉和磷酸酯淀粉的膨胀力(5.8,8.9,17.4 g/g).2种大米淀粉经磷酸酯化后透光率增高,相应淀粉的透光率次之,全粉的透光率最低,籼米的全粉、淀粉和磷酸酯淀粉的透光率分别低于粳米的全粉、淀粉和磷酸酯淀粉的透光率.经快速黏度分析仪测定的糊化特性结果表明,淀粉或变性淀粉膨胀力高,其峰值黏度和崩解值也高,此外,蛋白质含量和直链淀粉含量也极大的影响了淀粉的糊化特性.使用动态流变仪测定的流变特性表明,在相同的温度下,籼米的全粉、淀粉和变性淀粉的储能模量(G')分别比粳米的全粉、淀粉和变性淀粉的储能模量(G')高,对于相同的大米品种,全粉的储能模量(G')最高,变性淀粉的储能模量(G')最低.     

Response surface optimization and characteristics of Indica rice starch‐based fat substitute prepared by α‐amylase

Response surface methodology (RSM) was used to study the effect of enzyme to substrate ratio (11.8–23.6 U α‐amylase/g rice starch), hydrolysis temperature (90–100°C) and pH value (6.0–6.6) on the gel strength of rice starches‐based fat substitute using α‐amylase hydrolysis. The optimum conditions obtained from response surface analysis was 16.52 U/g enzyme dosage, 92°C hydrolysis temperature while the influence of pH was found insignificant in the range tested. Under these optimum conditions, the gel strength of this fat substitute was 113 g/cm², very close to the gel strength of butter of 114 g/cm², while the solubility of the substitute was 1.33 ± 0.01% and the swelling power 4.85 ± 0.02. There were no observable differences in the granular size distribution between the untreated rice starch and the hydrolyzed rice starch. Rheological properties of this rice starch‐based fat substitute implied that it is easier for the substitute to form three‐dimensional networks under 34°C.