Freeze-Thaw Stability of Amaranth Starch and the Effects of Salt and Sugars

Freeze-thaw stability of amaranth, corn, wheat, and rice starches was determined measuring the percent of syneresis by centrifugation. Thermal properties were calculated by differential scanning calorimetry (DSC). The effects of salt (NaCl at 2 and 5%) and sugars (sucrose, glucose, and fructose at 10, 20, and 30%) on the freeze-thaw stability of amaranth starch were also studied. Based on DSC and centrifugation methods, amaranth starch had better stability after freezing and thawing through four cycles than did corn, wheat, and rice starches. Amaranth starch with added salt showed similar stability as compared with a control when measured by centrifugation and showed increased stability when measured by DSC. Adding sugars to amaranth starch gels had varying results, but for the most part, they showed similar or increased stability when compared with a control.     

Cross‐Linked Resistant Starch: Preparation and Properties

Resistant starches (RS) were prepared by phosphorylation of wheat, waxy wheat, corn, waxy corn, high‐amylose corn, oat, rice, tapioca, mung bean, banana, and potato starches in aqueous slurry (≈33% starch solids, w/w) with 1–19% (starch basis) of a 99:1 (w/w) mixture of sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) at pH 10.5–12.3 and 25–70°C for 0.5–24 hr with sodium sulfate or sodium chloride at 0–20% (starch basis). The RS₄ products contain ≤100% dietary fiber when assayed with the total dietary fiber method of the Association of Official Analytical Chemists (AOAC). In vitro digestion of four RS₄ wheat starches showed they contained 13–22% slowly digestible starch (SDS) and 36–66% RS. However after gelatinization, RS levels fell by 7–25% of ungelatinized levels, while SDS levels remained nearly the same. The cross‐linked RS₄ starches were distinguished from native starches by elevated phosphorus levels, low swelling powers (≈3g/g) at 95°C, insolubilities (<1%) in 1M potassium hydroxide or 95% dimethyl sulfoxide, and increased temperatures and decreased enthalpies of gelatinization measured by differential scanning calorimetry.     

Physical properties of octenyl succinic anhydride modified rice,wheat, and potato starches

The physical properties of octenyl succinic anhydride (OSA) starches prepared from rice, wheat, and potato starches were studied. Rice and wheat OSA starches had significantly higher peak viscosity (PV), hot paste viscosity (HPV), and cool paste viscosity (CPV), but potato OSA starch had only significantly higher CPV, relative to the native starch. The gel hardness was higher with lower degree of substitution (DS) but lower with higher DS OSA compared to native starch. The swelling volumes (SV) of rice and wheat OSA starches were significantly higher compared to native starch, but the SV of potato OSA starch was slightly lower at high DS. The gelatinization temperature (GT) of rice OSA starches was sharply lower at low DS; for wheat OSA starch it was slightly lower even at high DS, but potato OSA starches had higher GT than the native starch. The enthalpy of all the OSA starches decreased gradually with increased DS. This study showed that the magnitude of changes in physical properties of OSA-modified starches depends not only on their DS but also on the botanical origin of the native starches.     

Volatile Compounds in Five Starches

Volatile compounds in commercial wheat, corn, potato, waxy corn, and tapioca starches and in laboratory‐prepared wheat, corn, and potato starches were collected, separated, and identified by a purge and trap concentrator (P&T) interfaced to a gas chromatograph (GC) equipped with a Fourier transform infrared detector (FTIRD) and a mass selective detector (MSD). Hexanal was the most abundant compound in the corn and potato starches and in the laboratory‐prepared wheat starch as determined by total ion chromatogram (TIC) peak areas. Hexanal was the third most abundant compound in commercial wheat starch after 2‐ethyl‐1‐hexanol and benzaldehyde. Among the volatile organics, the level of aldehydes was the highest, followed by alcohols, ketones, benzenes, esters, and terpenes. Specific compounds identified, the majority of which appear to be degradation products of lipid peroxidation, include hexanal, heptanal, octanal, nonanal, decanal, benzaldehyde, 2‐propanone, 2‐propanol, 1‐butanol, 2‐ethyl‐1‐hexanol, methylbenzene, and tetradecane. Waxy corn starch, which released a substantially higher level of total volatiles than all other starches, contained large amounts of pentyl, 2‐methyl‐1‐butyl, benzyl, and isobornyl acetates; and citronella and 1,8‐cineole. Tapioca starch contained few volatiles but did contain an increased level of 2‐propanol. No alcohols occurred in the commercial corn starch. Terpene compounds were detected only in commercial potato, waxy corn, and tapioca starches. Many volatiles detected in wheat and corn starches also were detected in the kernels of their commercial samples.     

Retrogradation of Starches from Different Botanical Sources

Retrogradation in 2% pastes prepared from unmodified commercial starches by cooking at 98–100°C under low shear, then held at 4°C for 56 days, was examined by turbidometric analysis and light microscopy. Turbidometric analysis revealed that retrogradation rates followed the order of wheat, common corn > rice, tapioca, potato ≫ waxy maize. Microstructures of stored pastes were examined both before and after centrifugation. Granule remnant morphologies and fresh and stored paste microstructures were unique to each starch examined. Fresh pastes from amylose-containing starches were dominated by networked amylose that condensed into higher density aggregates upon storage. Unique phenomena seen in some stored pastes included interactions of granular remnants with aggregated amylose, composite networks of co-associated amylopectin and amylose, and slight birefringence regained by granule remnants. Microstructural changes in stored pastes could be related to changes in turbidity and to the results of other methods used to quantitate retrogradation.     

Utilization of Hydroxypropylated Waxy Rice and Corn Starches in Korean Waxy Rice Cake to Retard Retrogradation

A traditional waxy rice gel cake in Korea, Injulmi, was prepared with hydroxypropylated waxy rice and corn starches (molar substitutions 0.13 and 0.11, respectively), and the textural and retrogradation characteristics of the cake were compared with a conventional cake made of waxy rice flour. In the pasting viscogram, hydroxypropylated starches exhibited reduced pasting temperatures, but increased peak viscosities compared with the unmodified starches. Under differential scanning calorimetry, the T_g′ and ice melting enthalpy of the starch gel cakes were reduced by hydroxypropylation, which indicated that the modified starches had higher water‐holding capacity than the unmodified starches. The degree of retrogradation, as measured by the hardness of the gel cake and the melting enthalpy, was significantly reduced by hydroxypropylation and hydroxypropylated waxy rice starch was more effective in retarding the retrogradation than hydroxypropylated waxy corn starch     

Effects of Granular Structures on the Pasting Behaviors of Starches

Japonica (Tainung 67 [TNu67]) and waxy (Taichung 70 [TCW70]) rice, normal and waxy corn, and cross-linked waxy rice and corn starches were used in an investigation of the influence of the granular structure on the pasting behavior of starch, using small amplitude oscillatory rheometry. Both normal corn and normal rice (TNu67) starches had the highest storage moduli (G′), followed by their cross-linked versions; native waxy corn and rice starches had the lowest. Native waxy starches showed paste characteristics (G′ < 500 Pa; tan δ > 0.2) at concentrations of up to 35%. However, cross-linked waxy starches exhibited gel behavior at 10% concentration (cross-linked TCW70) or higher (cross-linked waxy corn starch). The degrees of swelling power were in the order: TCW70 > native waxy corn > TNu67 ≅ cross-linked TCW70 ≅ normal corn ≅ cross-linked waxy corn starches. Solubilities were in the order: normal corn > TNu67 > native waxy > cross-linked waxy starches. The addition of 2% purified amylose from indica rice (Kaohsiung Sen 7) did not induce gelation of waxy corn starch. Swelling powers of normal corn, TNu67, and crosslinked waxy starches were similar, but normal corn and TNu67 had much higher G′ value. Such results implied that the formation of gel structure was governed by the rigidity of swollen granules and that the hot-water soluble component could strengthen the elasticity of the starch gel or paste.     

Morphological Changes of Granules of Different Starches by Surface Gelatinization with Calcium Chloride

Native starch granules of 11 selected cultivars (potato, waxy potato, sweet potato, normal maize, high‐amylose maize, waxy maize, wheat, normal barley, high‐amylose barley, waxy barley, and rice) were treated with a calcium chloride solution (4M) for surface gelatinization. The surface‐gelatinized starch granules were investigated using light microscopy and scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). In general, those starches with larger granule sizes required longer treatment time to complete the gelatinization. The salt solution treatment of starch was monitored by light microscopy and stopped when the outer layer of the granule was gelatinized. The surface gelatinized starch granules were studied using scanning electron microscopy. On the basis of the gelatinization pattern from calcium chloride treatments, the starches could be divided into three groups: 1) starches with evenly gelatinized granule surface, such as normal potato, waxy potato, sweet potato, maize, and high‐amylose maize; 2) starches with salt gelatinization concentrated on specific sites of the granule (i.e., equatorial groove), such as wheat, barley, and high‐amylose barley; and 3) starches that, after surface gelatinization, can no longer be separated to individual granules for SEM studies, such as waxy barley, waxy maize, and normal rice. The morphology of the surface gelatinized starch resembled that of enzyme‐hydrolyzed starch granules.     

Properties of Some Starch Blends

Normal corn, high-amylose corn, waxy corn (waxy maize), wheat, rice, potato, cassava (tapioca), and a modified waxy corn starch were blended in various combinations and ratios. Pasting behavior, paste and thermal properties, and retrogradation tendency were determined. Differential scanning calorimetry (DSC) traces of the mixtures did not resemble those of either of the two components, nor did any DSC trace have two peaks suggestive of a mixture of two distinct starches. Amylograph data suggested that some mixtures behaved like a chemically modified starch. Observations from light microscopy suggested that intermolecular, molecular-supermolecular, and intersupermolecular interactions may be responsible for this behavior.     

Characteristics of Granular Cold‐Water Gelling Starches of Cereal Grains and Legumes Prepared Using Liquid Ammonia and Ethanol

Starches of wheat, corn, smooth and wrinkled peas, and chickpeas were modified to a free‐flowing powder of granular cold‐water gelling (GCWG) starch using liquid ammonia and ethanol at 23°C and atmospheric pressure. Amylose content of starches was 26.3% in wheat, 27.1% in corn, 35.4% in chickpeas, 43.2% in smooth peas, and 79.9% in wrinkled peas. The modified starches remained in granular form with an increased number of grooves and fissures on the surface of the granules compared with native starch, while the crystallinity was mostly lost, as shown by X‐ray diffractograms and DSC endothermic enthalpies. Pasting viscosity of modified starches at 23°C was 171 BU and 305 BU in wheat and corn, respectively, and much higher in legume starches, ranging from 545 BU to 814 BU. Viscosities of modified legume starches at 23°C were at least twice as high as those of native starches determined at 92.5°C. Swelling power of modified starches at 23°C ranged from 8.7 g/g to 15.3 g/g, while swelling power of native starches heated to 92.5°C ranged from 4.8 g/g to 16.0 g/g. GCWG starches exhibited higher dextrose equivalent (DE) values of enzymatic hydrolysis, ranging from 25.2 to 27.0 compared with native starches (1.5–2.9). Modified starches from wheat, corn, smooth peas, and chickpeas formed weak gels without heat treatment and experienced no changes in gel hardness during storage, while native starch gels formed by heat treatment showed an increase in hardness by 1.1–7.5 N during 96 hr of storage at 4°C.     

Release of Bound Lipids in Cereal Starches Upon Hydrolysis by Glucoamylase

The raw starch granules from corn, rice, and wheat were hydrolyzed by practically pure glucoamylase (Rhizopus niveus). The bound lipids remaining in the residual starches were investigated, of which the major components of the lipids, free fatty acids (FFA) in corn starch, FFA and phospholipids (PL) in rice starch, and PL in wheat starch were determined. In each case, the bound FFA and PL were decreased to some extent during the initial stage of hydrolysis. During the later stages, the FFA continued to gradually decrease, while the level of PL stabilized. It was interesting that some of the bound lipids were released from the granules upon glucoamylase hydrolysis, differing from the model amylose-lipid complexes. Furthermore, the structures of the residual starches were investigated. The blue value and λ_max of the starches were increased by partial hydrolysis of the starch granules using practically pure glucoamylase. Two gel-permeation chromatography analyses revealed that the relative amount of amylose fraction was increased by glucoamylase hydrolysis, and also that the increments were reduced by the defatting of bound lipids. The results suggest that the increase in amylose fraction is attributable to the existence of bound lipids in the granules.     

Physical Properties of Poly(Lactic Acid) and Starch Composites with Various Blending Ratios

Two‐phase polymer blends of poly(lactic acid) (PLA) and corn or wheat starches at various ratios were prepared by using a laboratory‐scale twin‐screw extruder and compression molding. The blends were characterized for thermal transitions, mechanical properties, and water absorption. Starch and PLA were immiscible polymers, and the thermal behavior of PLA was not affected by starch. Crystallinity of the blends decreased in some degree as starch content increased 20–40%. Tensile strength and elongation of the blends decreased as starch content increased, but modulus increased as starch content increased up to 70%. As starch content increased to >60%, the PLA phase became discontinuous, and water absorption of the blends increased sharply. Blends made from wheat starch gave slightly better mechanical properties than those made from corn starch, and no differences in other properties were observed.     

Influence of Botanical Source and Processing on Formation of Resistant Starch Type III

Influence of botanical source and gelatinization procedure (autoclaving or boiling) on resistant starch (RS) formation was investigated in starches from wheat, corn, rice, and potato. RS yields did not vary within the same sample but differed among samples with different starch botanical sources. Differences also existed in RS contents in native and retrograded starches. Slight or minor variations in RS values were found after both gelatinization procedures, although no clear pattern was found in the behavior of samples based on gelatinization procedure. The degree of polymerization (DP) of retrograded samples was assigned using high-performance anion exchange chromatography with pulsed amperometric detector (average DP 50–60), with no differences between autoclaved and boiled samples.     

Starch Molecular Mass and Size by Size-Exclusion Chromatography in DMSO-LiBr Coupled with Multiple Angle Laser Light Scattering

The weight average molar mass (M_w) and root mean square radii of starches from waxy maize (Amioca), waxy rice flour, cassava, Hylon V, Hylon VII, and potato amylose were determined by size-exclusion chromatography (SEC) and multiple-angle laser light scattering (MALLS). Dimethylsulfoxide (DMSO) containing 50 mM LiBr was used to dissolve the starches and also served as the mobile phase. SEC with large particle size polystyrene divinylbenzene packing materials and MALLS instrumentation were evaluated for the ability to separate and determine molar mass (MM) of starch polymers, respectively. The determination of M_w by MALLS is necessary because the M_w of many cereal starches exceeds the available molecular standards by one or two orders of magnitude. The M_w depends on the method of calculation. The M_w (Berry method) of starch from waxy corn was 2.27 × 10⁸ Da, waxy rice 8.9 × 10⁷ Da, cassava 5.7 × 10⁷ Da, Hylon V 2.7 × 10⁷ Da, Hylon VII 4.8 × 10⁶ Da, and potato amylose 1.9 × 10⁵ Da. Recovery dropped dramatically for molecules with root mean square radii >200 nm.     

Isolation of Small Starch Granules and Determination of Their Fat Mimic Characteristics

Small starch granules from wheat and amaranth were isolated and examined by light microscopy (wheat), scanning electron microscopy (wheat and amaranth), and rapid viscosity (RVA) analysis. The isolated wheat and amaranth starches were incorporated into reduced‐fat frozen dessert mixes (2%, w/w) and the frozen desserts were characterized by sensory analysis for smoothness, creaminess, and preference. The results of the sensory analysis suggest that up to 50% of the fat in a frozen dessert may be replaced when substituted by these starches at the 2% level (w/w).     

Comparison of Amylose Determination Methods and the Development of a Dual Wavelength Iodine Binding Technique

It has long been recognized that limitations exist in the analytical methodology for amylose determination. This study was conducted to evaluate various amylose determination methods. Purified amylose and amylopectin fractions were obtained from corn, rice, wheat, and potato and then mixed in proportion to make 10, 20, 30, 50, and 80% amylose content starch samples for each source. These samples, considered amylose standards, were analyzed using differential scanning calorimetry (DSC), high-performance size-exclusion chromatography (HPSEC), and iodine binding procedures to generate standard curves for each of the methods. A single DSC standard equation for cereal starches was developed. The standard curve of potato starch was significantly different. Amylose standard curves prepared using the iodine binding method were also similar for the cereal starches, but different for potato starch. An iodine binding procedure using wavelengths at 620 nm and 510 nm increased the precision of the method. When HPSEC was used to determine % amylose, calculations based on dividing the injected starch mass by amylose peak mass, rather than calculations based on the apparent amylose/amylopectin ratio, decreased the inaccuracies associated with sample dispersion and made the generation of a cereal amylose standard curve possible. Amylose contents of pure starch, starch mixtures from different sources with different amylose ranges, and tortillas were measured using DSC, HPSEC, iodine binding, and the Megazyme amylose/amylopectin kit. All the methods were reproducible (±3.0%). Amylose contents measured by these methods were significantly different (P < 0.05). Amylose measurements using iodine binding, DSC, and Megazyme procedures were highly correlated (correlation coefficient >0.95). DSC and traditional iodine binding procedures likely overestimated true amylose contents as residual butanol in the amylose standards caused interference. The modified two-wavelength iodine binding procedure seemed to be the most precise and generally applicable method. Each amylose determination method has its benefits and limitations.     

Utilization of Oxidized and Cross-Linked Corn Starches in Wheat Flour Batter

Starch is often added to batters to improve the texture and appearance of fried food products. However, comparisons of commercially available starches in terms of batter characteristics are rare. In this study, various corn starches, native or modified, were mixed with wheat flour (20% dry solids basis), and the physical properties of the batters after deep-fat frying were examined. Native corn starches of different amylose contents (high-amylose, normal, and waxy) and chemically modified corn starches (oxidized and cross-linked) were tested. The batter was prepared by adding water to the starch-flour mixtures (42% solids) and deep-fat frying at 180°C for 30 sec. The texture of the fried batter was analyzed using a texture analyzer (TA) with a Kramer shear cell. The pasting viscosity profile of the starch-flour mixtures (7% solids in water) was also measured with a Rapid Visco Analyser. When the native corn starches of different amylose contents were compared, the crispness (peak number before breakage) and hardness (maximum peak force) measured using the instrument were positively correlated with the amylose content in starches but negatively correlated with the residual moisture content of the fried batters. The peak viscosity and breakdown in viscosity profiles of the starch-flour mixtures were also negatively correlated with crispness. The use of high-amylose corn starch was effective not only in increasing the crispness, but also in reducing the oil uptake. However, the fried batter containing high-amylose starch was denser and harder than the batter containing normal starch. Among the modified starches tested, oxidized (0.4% active Cl₂) and cross-linked (4% 99:1 mixture of STMP and STPP) starches showed improvements in the overall properties of the fried batters. With excessive oxidizations (>0.4% Cl₂), however, the crispness was reduced.     

General Application of Raman Spectroscopy for the Determination of Level of Acetylation in Modified Starches

A method using Raman spectroscopy was recently developed for the determination of the degree of acetylation in modified wheat starch. In this article, we show that the method can be generalized to a wide range of starches of different botanical origin and amylose content. Calibration sets were used to develop regression equations for 11 types of acetylated starches, including cereal (rice, maize, wheat) and noncereal (potato and sweetpotato) sources. The calibration lines were then used to predict the level of acetylation of starch samples with unknown level of acetylation using their Raman spectra. In each case, R² > 0.98 for linear regression of Raman vs. titrimetric determination of acetylation. The Raman-based calibration curves allow fast and nondestructive determination of the degree of acetylation for different types of starches.     

Suitability of Different Starches for Production of Kuanfen (Chinese Flat Starch Noodles)

Starches from potato, corn, sweet potato, and rice were compared with mung bean starch for their suitability for producing kuanfen, Chinese flat starch noodles. Significant differences were found in the chemical composition and swelling power among starches (P < 0.05). Maximum tensile stress and maximum tensile strain was highest for kuanfen made from mung bean starch and sweet potato starch, respectively. Higher work was needed to break kuanfen made from mung bean and sweet potato starches. Kuanfen made from mung bean starch was most favored by panelists, followed by those from sweet potato starch. General acceptability of kuanfen correlated positively and significantly with chewiness, cohesiveness, and elasticity of the noodles. For predicting sensory acceptability of kuanfen using instrumental methods, correlation was performed between sensory variables and tensile parameters. Results showed that work-to-break correlated significantly with chewiness, elasticity, and general acceptability while maximum tensile strain correlated significantly with sensory cohesiveness. Therefore, both of these two tensile parameters could be useful for predicting the textural properties of kuanfen.     

Effects of Amylopectin Branch Chain Length and Amylose Content on the Gelatinization and Pasting Properties of Starch

Structures and properties of starches isolated from different botanical sources were investigated. Apparent and absolute amylose contents of starches were determined by measuring the iodine affinity of defatted whole starch and of fractionated and purified amylopectin. Branch chain-length distributions of amylopectins were analyzed quantitatively using a high-performance anion-exchange chromatography system equipped with a postcolumn enzyme reactor and a pulsed amperometric detector. Thermal and pasting properties were measured using differential scanning calorimetry and a rapid viscoanalyzer, respectively. Absolute amylose contents of most of the starches studied were lower than their apparent amylose contents. This difference correlated with the number of very long branch chains of amylopectin. Studies of amylopectin structures showed that each starch had a distinct branch chain-length distribution profile. Average degrees of polymerization (dp) of amylopectin branch chain length ranged from 18.8 for waxy rice to 30.7 for high-amylose maize VII. Compared with X-ray A-type starches, B-type starches had longer chains. A shoulder of dp 18–21 (chain length of 6.3–7.4 nm) was found in many starches; the chain length of 6.3–7.4 nm was in the proximity of the length of the amylopectin crystalline region. Starches with short average amylopectin branch chain lengths (e.g., waxy rice and sweet rice starch), with large proportions of short branch chains (dp 11–16) relative to the shoulder of dp 18–21 (e.g., wheat and barley starch), and with high starch phosphate monoester content (e.g., potato starch) displayed low gelatinization temperatures. Amylose contents and amylopectin branch chain-length distributions predominantly affected the pasting properties of starch.