Gelatinization and Solubility Properties of Commercial Oat Starch

Gelatinization and solubility characteristics of starch contribute to unique functionality in foods. Corn and oat starch viscoamylographs (35g db) showed peak viscosities of 400 and 390B.U., respectively. Oat starch had a more rapid (89.7 vs 85.6°C) and higher set back (790 vs. 740B.U.) than corn. Data on soluble components of cooled (85°C) starch pastes, as collected and analyzed by high-performance size exclusion chromatography (HPSEC), suggest that amylopectin plays a significant (P<0.05) role in oat paste set back; for corn starch, amylose is the dominant factor. Solubilities and apparent molecular weights (MW) of oat starch heated (65-120°C) under shear and subsequent sonication (0-40s) in water or 90% methyl sulfoxide (DMSO) were also determined by HPSEC. An intermediate MW fraction was eluted on the HPSEC chromatograms only when oat starch was heated in water (100-120°C/30min) or DMSO and sonicated, suggesting that this fraction may not be inherent in the native granule. in water, polymer solubility and peak MW increased with temperature (65-120°C), whereas in DMSO, solubility decreased with heating (65-100°C), while peak MW remained basically constant. Aqueous (aq) leaching at 75°C solubilized more corn amylose than amylopectin, but amylopectin and amylose co-leached from oat starch granules. Aq leaching, at 20°C above their DSC peak ends (85 and 95°C for oat and corn, resepctively), showed more amylopectin leached from oat starch granules whereas more amylose was leached from corn starch granules.     

Solubility Behavior of Granular Corn Starches in Methyl Sulfoxide (DMSO) as Measured by High Performance Size Exclusion Chromatography

The extent of corn starch dispersibility and the relative molecular solubility of amylose and amylopectin in methyl sulfoxide (DMSO) were determined. Granular corn starches with <l, 25, 53, and 70% amylose were dispersed in 0–100% DMSO (in water) solutions at 30°C for 30 min. Maximum dispersibility for all starches (98%) was obtained when 90% DMSO/10% water was used; regular (normal) dent corn starch was equally dispersed in solutions with 88–94% DMSO. Molecular solubility, the presence of individual molecules of amylose and amylopectin, of starches was also measured (after centrifugation and filtration) by high performance size-exclusion chromatography (HPSEC). Starches were dispersed in 90% DMSO and heated for 10 min at temperatures of 35–120ºC. At low temperatures, high coefficients of variation resulted from additional DMSO solubilization after treatment. At 120ºC, 70% amylose starch was >90% solubilized, while waxy starch was only 47% solubilized. When starches were treated for 18–89 h in 90ºC DMSO, solubility stopped increasing after 67 h. High amylose starch (70%) was mostly solubilized, but 53% amylose, waxy and regular starches could only be fully solubilized after exposure to shear. Amylopectin molecules appeared more susceptible to shear induced depolymerization than amylose. The percent amylopectin in the high amylose starches reflected that as determined by iodine binding analysis and the manufacturer; while the percent amylopectin in regular starch was too low (manufacturers: 75%, HPSEC: 65%). Undispersed components were mostly amylopectin. Since amylose is fully solubilized, however, the HPSEC can be used to quickly determine percent amylose in 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.     

Stufenweise Elutionsanalyse der Fraktionen von thermisch dispergierter Amylose-, Kartoffel- und Wachsmaisstärke

Stepwise Elution Analysis of Fractions of Thermically Dispersed High Amylose, Potato and Waxy Corn Starch. Changes in the starch constituents - the amylose and the amylopectin — from dispersions of high amylose, potato- and waxy corn starch were studied by stepwise elution analysis and determination of molecular weight. The dispersions were prepared by dispersing the pastes 1 and 3 h at 120 °C and the amyloses and amylopectins separated by means of n-butanol and methanol, resp. With the exeption of a partial separation in waxy corn starch no separation of pastes into amylose and amylopectin could be observed, probably due to the mild pasting conditions in the Brabender Viscograph. By stepwise elution analysis it could be stated that after prolonged thermic dispersing of the pastes of high amylose starch the amylose and amylopectin do no longer change, which is in good agreement with the values of molecular weight. By analogous treatment of the pastes of potato starch, however, a decomposition of amylose and amylopectin could be stated. In the dispersions of waxy corn starch the amylose molecules decompose to a degree whereafter thermic dispersing of 3 h practically no complex with n-butanol could be observed. Relatively great losses were stated at the isolation of the precipitated constituents. It was stated that the isolated amyloses of potato starch are suitable substrates for activity measurements of α-amylase in human serum and urine as well as in other biologic materials.     

Effects of Cationization on Functional Properties of Pea and Corn Starches

Amylography, scanning electron microscopy and storage tests demonstrated that native pea starches were highly resistant to granule disintegration during heating in dilute slurries, resulting in low hot paste viscosity, high retrogradation and syneresis. Cationization at degrees of substitution of 0.02 to 0.05 reduced the pasting and gelatinization temperatures, increased peak viscosities and set-back on cooling but eliminated syneresis after storage at 4°C and − 15°C. The principal effects of cationization were to promote rapid granule dispersion at low pasting temperatures, yielding a molecular dispersion of amylose and amylopectin on heating to 95°C. On cooling, the gel structures were firm and the cationic groups controlled the realignment of starch chains during low temperature storage.     

Structure‐Functionality Changes in Starch Following Rough Rice Storage

The molecular‐level features of starch in relation to the changes in rice functionality during storage are not yet fully elucidated. This work investigated the effects of rough rice storage conditions on starch fine structures and physicochemical properties. Dried rough rice samples (medium‐grain Bengal and long‐grain Cypress) were stored at 4, 21, and 38°C in temperature‐controlled chambers and then periodically removed and evaluated after 1, 3, 5, 7, and 9 months. Flour (powdered head rice) and starch (extracted from head rice by alkali steeping) samples were evaluated for pasting and thermal properties. High‐performance size‐exclusion chromatography and high‐performance anion exchange chromatography were used to characterize starch molecular size and amylopectin chain‐length distribution, respectively. Significant changes in starch fine structure were observed primarily on the 38°C lots, and to some extent on the 21°C lots. The decreased amylose: amylopectin ratio, shortened amylopectin average chain length, and the shift in chain‐length distribution to shorter branch chains were implicative of molecular‐level starch degradation. The flour and starch samples showed inconsistent trends in pasting and thermal properties, thus suggesting the role of not only starch but also its interaction with non‐starch components in rice aging.     

Effect of cooking time and ingredients on the performance of different starches in white sauces

The effect of white sauce ingredients and increased cooking time at 90 °C on the degree of gelatinization of corn, waxy corn, rice, potato and modified waxy corn starches was studied. The changes in pasting properties, linear viscoelastic properties, and microstructure were determined. In all the native starches in water, a longer cooking time at 90 °C caused greater starch granule swelling and more leaching of solubilized starch polymers into the intergranular space. These effects were more noticeable in the waxy corn and potato starches. The potato starch was the most affected, with complete disruption of the starch granules after 300 s at 90 °C. The microstructural changes which transformed a system characterized by starch granules dispersed in a continuous phase (amylose/amylopectin matrix) into a system with an increase in the continuous phase and a decrease in starch granules were associated with a decrease in system viscoelasticity. The elastic moduli were higher in the sauce than in the starch in water system. However, with the exception of potato starch, the white sauce showed lower viscoelasticity than the starch in water system. The white sauce ingredients decreased the effect of cooking time on the starch gelatinization process, particularly in potato starch.     

Zur genaueren Kenntnis durch Temperatureinfluß modifizierter Wachsmais- und Amylosestärke

Contribution on Waxy Maize Starch and High Amylose Starch Modified under the Influence of Temperature. The starches of the two genetic varieties of the corn grain, waxy maize starch and high amylose starch, were subjected to the influence of different temperatures. Subsequently, the physico-chemical properties of the modified starches were examined. Waxy maize starch which mainly consists of amylopectin, and high amylose starch which contains a high portion of linear chains of polymerized glucose units are interesting test materials because of their properties which are different by nature. Waxy maize starch with its high viscosity values, great swelling power and good solubility in hot water shows no tendency to settle or retrograde. While the process of freezing the starch granules hardly changes the properties mentioned, the influence of a temperature of 100°C causes morphological changes of a small proportion of grains, including the loss of birefringence. These changes are particularly pronounced after treatment of native starch at 120°C. The properties of the starch pastes were also strongly changed. The native high amylose starch characterized by unusual, oblong starch granules without birefringence, a low viscosity, low swelling power and low solubility showed only minor changes after freezing, whereas a temperature of 100°C resulted in reduced values of solubility and aggregation of the starch granules. A temperature treatment at 120°C and at 125°C brought about changes in the swelling properties, the viscosity and limiting viscosity, settling, swelling power, and solubility of the starch pastes. Attempts were made to conform the changes in the different properties observed with the expected influence of temperature treatment on the intermolecular forces (hydrogen bonds, crossbonding).     

Effect of acid‐ethanol treatment followed by ball milling on structural and physicochemical characteristics of cassava starch

Structural and physicochemical characteristics of cassava starch treated with 0.36% HCl in anhydrous ethanol during 1 and 12 h at 30, 40, and 50°C followed by ball milling for 1 h were analyzed. Average yield of acid‐ethanol starches reached 98% independent of the treatment conditions. Solubility of acid‐ethanol starches increased with reaction temperature and time, but it did not change after ball milling. Granule average size reduced with chemical treatment from 25.2 to 20.0 µm after 12 h at 50°C. Ball milling decreased the granule average diameter of the native starch and those chemically treated at 30°C/1 h or 40°C/1 h, but it did not alter the starches treated for 12 h, independent of temperature. From scanning electron microscopy (SEM), starch granules presented round shape and after modification at 50°C/12 h, before and after ball milling, showed a rough and exfoliated surface. Some granules were deformed, suggesting partial gelatinization that was more intense after milling. Starch crystallinity increased as temperature and time of chemical treatment were increased, while amylose content, intrinsic, and pasting viscosities decreased. Gelatinization temperatures increased for all chemical starches. The findings can be related to the preferential destruction of amorphous areas in the granules, which are composed of amylose and amylopectin. After ball milling, the starch crystallinity decreased, amylose content, intrinsic, and pasting viscosities kept unchanged and gelatinization temperatures and enthalpy reduced. Ball milling on native and chemical starches caused the increase of amorphous areas with consequent weakening and decreasing of crystalline areas by breaking of hydrogen bonds within the granules.     

酸解对不同链/支比含量玉米淀粉特性的影响

以4种不同链/支比含量的玉米淀粉为原料,酸解处理不同时间,以酸解玉米淀粉的形貌特性、冻融稳定性、膨胀度、溶解度、晶体性质为指标衡量不同酸解时间对玉米淀粉结构性质的影响。结果表明:4种玉米淀粉酸水解程度的顺序为:蜡质玉米普通玉米淀粉G50G80。酸解后,同品种的4种玉米淀粉的析水率随着酸解天数的增加而增加;溶解度增加,膨胀度降低。酸解并未改变淀粉的晶型,随着酸解时间的延长,蜡质玉米淀粉和普通玉米的相对结晶度先增大后保持不变,G50和G80的相对结晶度随着酸解时间的增加而增大。表明酸解对低直链淀粉(蜡质玉米淀粉和普通玉米淀粉)的结构、性能影响最大。     

Resistant Starch Content and Structural Changes in Maize (Zea mays) Tortillas During Storage

Storage of maize products such as tortillas may cause starch retrogradation and lead to resistant starch (RS) formation. This study was carried out to determine if storage of maize tortillas under refrigerated conditions enhanced RS content and/or modified RS structure. Improved Costeño variety maize grain was nixtamalized and processed into tortillas which were stored for five and ten days at 5°C. Total resistant starch (TRS) and retrograded resistant starch (RRS or RS3) contents were determined on raw and nixtamalized maize grain and tortillas stored for zero, five and ten days. Differential scanning calorimetry (DSC), X‐ray diffraction (XRD) and near‐infrared (NIR) spectroscopy were use to evaluate structural changes in retrograded resistant starch isolated from each sample type. Total starch content was 67 ± 1.5% for all samples, TRS ranged from 3.3% in the raw grain at 7.2% in tortillas stored for ten days, while RRS starch content ranged from 0% in the raw grain to 3.2% in tortillas stored for ten days. DSC showed endothermic transitions corresponding to amylopectin and amylose retrogradation, at 31.9 and 139.7°C in RRS from tortillas stored for five days, and at 47.9 and 146°C in RRS from tortillas stored for ten days. These values agreed with the higher total RS content recorded after prolonged storage. XRD revealed a starch crystallinity of 13.7% in tortillas stored for five days and 15.3% in those stored for ten days. NIR spectroscopy analysis showed evidence of structural changes in polymeric order that were more pronounced in RRS of tortillas stored for ten days, due to increase in crystalline region.     

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

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

板栗淀粉加工特性的研究注

通过对板栗淀粉的纯化和有关成份测试,探索板栗淀粉加工特性指标。包括淀粉颗粒形貌,RVA分析结果,溶解度与膨胀度,糊化温度,直链,支链淀粉的含量等。并与马铃薯淀粉,玉米淀粉进行了比较。     

Corn Starch-Xanthan Gum Interaction and Its Effect on the Stability During Storage of Frozen Gelatinized Suspension

The knowledge of starch pastes behavior during frozen storage becomes necessary to understand more complex systems (e.g. sauces, dressings and desserts) The effect of sub-zero storage on the quality attributes of corn starch pastes (10% w/w) with and without xanthan gum (0.3% w/w) was analyzed. Pastes were frozen at different rates (0.3 to 270cm/h) and stored at −5, −10 and −20°C. Exudate production (syneresis) and rheological behavior were studied by means of capillary suction and rotational viscometry respectively. Ice recrystallization was analyzed by indirect microscopic observations using isothermal freeze fixation and amylopectin retrogradation by differential scanning calorimetry (DSC). Samples stored at −5°C (glass transition temperature) or higher temperatures were under the rubbery state evidenced by starch recrystallization. This state favored molecular mobility leading to deteriorative changes (like spongy structure formation related to amylose retrogradation). At lower storage temperatures (−10 and −20°C) under the glassy state, starch retrogradation was not detected and deteriorative changes can be related to ice recrystallization. The addition of xanthan gum minimized amylose retrogradation, syneresis and rheological changes, however, its presence did not prevent ice recrystallization nor amylopectin retrogradation.     

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.     

Effect of the Extent of Conversion and Retrogradation on the Digestibility of Potato Starch

The effect of starch conversion on the susceptibility of potato granules to α‐amylase was studied by direct sampling at different pasting times corresponding to different points on the RVA profile of a 6.4% (w/w) suspension of starch in distilled water. Native granules showed high resistance to α‐amylase with 8.6 ± 0.4% digestibility for a 6 h incubation period with the enzyme. When the suspension was heated to 60 °C, the digestibility increased to 53.5 ± 0.7% although, at this temperature, there was still no noticeable increase in the measured viscosity (≤0.040 Pa · s). The material sampled after a pasting time corresponding to the RVA peak viscosity showed a digestibility of 88.4 ± 0.5%. This suggested, owing to the expected retrogradation of amylose on cooling, the quasi‐total susceptibility of amylopectin to enzymatic digestion at this pasting stage. The effect of ions on the swelling of potato starch was used to assess whether the decrease of the swelling of the granules in the presence of NaCl was paralleled by an increase in resistance to α‐amylase. A small (∼6.1%) but significant decrease in the digestibility of pasted starch was observed in the presence of salt. Finally, the effect of the retrogradation of the amylopectin fraction on its digestibility was assessed in extruded potato starch ribbons containing 35% (w/w) water and stored at different temperatures. After 14 days of storage, the digestibility decreased from 77.0 ± 0.9% in the freshly extruded samples to between 28.0 ± 1.7% and 42.1 ± 0.3%, depending on the storage temperature. This suggested a measurable difference in the α‐amylase susceptibility between the A and B polymorphs of retrograded amylopectin.     

Effects of cross-linking and low molecular amylose on pasting characteristics of waxy corn starch

The action of amylose within the granule of normal corn starch is investigated by changes in pasting characteristics of waxy corn starch in a Rapid Visco Analyzer (RVA), using addition of soluble amylose (DP = 18) and cross-linking with epichlorohydrin. Although waxy corn starch, containing no amylose, did not show an effect of addition of amylose on pasting characteristics, by cross-linking with epichlorohydrin, the pasting peak viscosity and breakdown were greatly enhanced and set-back (viscosity increased in the cooling process after gelatinization) was generated. The cross-linking depressed the disintegration of starch granules in the swelling process, with amylose interaction, resulting in RVA pasting characteristics similar to those seen with normal corn starch containing amylose. Set-back was essentially caused by rearrangement among modified amylopectins. Addition of sodium dodecyl sulfate (SDS) to the RVA more efficiently enhanced the effect. This indicated that amylose in normal corn starch interacts with amylopectin through locally strong linkages.     

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 Retrograded Waxy Corn Starch on Bread Staling

Waxy corn starch pastes (10%) were stored at 5 °C for up to 35 days, and the powder specimens of retrograded starches thus obtained were added to wheat flour for bread baking at a level of 5%. The effect of retrograded starch on the staling of bread was determined. The loaf which contained retrograded waxy corn starch, which was prepared by storing the 10% paste at 5 °C for 7 days, showed an increase in specific volume and the results of the sensory evaluation showed that it was very acceptable. During the storage of bread, the increase in firmness and decrease in degree of gelatinization were suppressed by adding retrograded waxy corn starch. The moisture content of bread crumbs did not relate to firmness. Added retrograded waxy corn starch decreased the final viscosity of flour. The crystalline region of retrograded waxy corn starch used for bread baking included longer chains from amylopectin which in raw starch occurred in the amorphous region.     

热处理对不同直链淀粉含量的玉米淀粉理化性质的影响

采用快速黏度分析法、离心法、差示扫描量热分析法、动态流变仪分析法等,研究了干热与湿热处理对3种不同直链淀粉含量的玉米淀粉糊化性质、膨润性质、热力学性质、流变性质的影响,为淀粉的物理改性研究和加工应用提供理论依据。结果表明,干热处理使淀粉更易糊化,表现为3种玉米淀粉糊化温度降低,溶解度、膨胀度增加。湿热处理加大糊化难度,使3种玉米淀粉的糊化温度升高,膨胀度降低。热处理使玉米淀粉糊稠度、糊化焓值降低。蜡质玉米淀粉经热处理后,溶解度和老化率增加。流变性质测定结果表明,湿热处理不利于高直链玉米淀粉黏弹性凝胶的形成。