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.     

Comparison of Laboratory and Pilot-Plant Corn Wet-Milling Procedures

One waxy and three regular yellow dent corn hybrids were wet milled by using two scales of laboratory procedures (modified 100-g and 1-kg) and a pilot-plant procedure (10-kg). The modified 100-g and 1-kg laboratory procedures gave similar yields of wet-milling fractions. Starch yields and recoveries were significantly lower for the pilot-plant procedure, whereas gluten and fiber yields were greater because of their high contents of unrecovered starch. Protein contents of the starches obtained by all three procedures were within commercially acceptable limits (<0.50% db for normal dent corn and <0.30% for waxy corn). Rankings for starch yields and starch recoveries for the four hybrids, having very different physical and compositional properties, were the same for all three procedures. The harder the grain, the lower the yield and recovery of starch. Least significant differences (P < 0.05) for starch yield were 0.8% for the modified 100-g procedure, 1.2% for the 1-kg procedure, and 2.0% for the pilot-plant procedure.     

Properties of Cross‐Linked Starch from Waxy Mutant Wheat Tanikei A6599‐4

Native starch from waxy mutant wheat Tanikei A6599‐4 is known to exhibit more stable hot paste viscosity than a typical waxy wheat (Tanikei H1881) and waxy corn. The objective of this study was to investigate the starch paste properties of Tanikei A6599‐4 after cross‐linking and compare with Tanikei H1881 and waxy corn. As an example of cross‐linking, the reaction (at 30, 60, 120, and 360 min) with sodium trimetaphosphate was used. In Rapid Visco Analyser (RVA) measurement, the unique characteristic was maintained in Tanikei A6599‐4 starch cross‐linked at low reaction time (<120 min) levels. Cross‐linking at a high reaction time (360 min) level suppressed the swelling of both Tanikei A6599‐4 and Tanikei H1881 starches but not waxy corn starch. Although unmodified Tanikei A6599‐4 starch showed the lowest paste clarity among unmodified waxy starches, this defect became unremarkable when starch was cross‐linked for ≥120 min. In gel‐dispersed dynamic viscoelasticity measurement, the order of G′ and G″ values was always Tanikei A6599‐4 > Tanikei H1881 > waxy corn. This indicates that cross‐linked Tanikei A6599‐4 and Tanikei H1881 starches have different starch properties and that swollen Tanikei A6599‐4 starch granules are more rigid than swollen Tanikei H1881 starch granules.     

Functional Properties of Cross-Linked and Hydroxypropylated Waxy Hull-less Barley Starches

Waxy hull-less barley (HB) starches containing 0 or 5% amylose were cross-linked with phosphorus oxychloride and the cross-linked starches were hydroxypropylated with propylene oxide. For comparison, waxy corn and potato starches were similarly modified. For all starches, cross-linking inhibited granule swelling and prevented swollen granules from disintegration, resulting in dramatic improvement in pasting properties and tolerance to cooking shear and autoclaving. Cross-linked waxy HB starches were more tolerant to cold storage and cooking shear than cross-linked waxy corn starch. Hydroxypropylation of the cross-linked starches reduced granule crystallinity and gelatinization temperature, and improved granule swelling, paste clarity, and freeze-thaw stability. The double-modified waxy HB starches showed higher cold tolerance than similarly modified waxy corn and potato starches, as judged by freeze-thaw stability and clarity after cold storage. These results indicated that the cross-linked and double-modified waxy HB starches together may have a wide range of food applications. This study indicated that the behavior of granule swelling and disintegration of swollen granules played an important role in governing paste viscosity, clarity, and freeze-thaw stability of waxy HB starches.     

Composition and Reactivity of A‐ and B‐type Starch Granules of Normal,Partial Waxy,and Waxy Wheat

Wheat has great potential to make inroads into starch markets with the advent of partial waxy and waxy starches of diverse composition and properties. The majority of isolated starch utilized in food applications is chemically modified to improve starch properties according to the intended use. Therefore, it is critical to understand factors that affect wheat starch reactivity. This work investigated the relative reactivities of normal, partial waxy, and waxy wheat starches and their respective A‐ and B‐type starch granule fractions. Native starch isolated from four closely related soft wheat lines (normal, partial waxy, and full waxy) was modified through 1) substitution (propylene oxide analog) and 2) cross‐linking (phosphorus oxychloride) reactions to generate both types of modified starch products for each wheat line. Characterization of the unmodified starch fractions confirmed compositional differences among the cultivars and their respective granule types. In cross‐linking reactions, B‐type granules were slightly more reacted than A‐type granules for all cultivars, while the waxy starch generally exhibited higher reactivity compared with normal and partial waxy starches. For the substituted starches, no differences in reactivity were observed among the cultivars or between the two granule types.     

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.     

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     

Comparison of Physicochemical Properties and Structures of Sugary‐2 Cornstarch with Normal and Waxy Cultivars

Starches from normal, waxy, and sugary‐2 (su2) corn kernels were isolated, and their structures and properties determined. The total lipid contents of normal, waxy, and su2 corn starches were 0.84, 0.00, and 1.61%, respectively. Scanning electron micrographs showed that normal and waxy corn starch granules were spherical or angular in shape with smooth surfaces. The su2 starch granules consisted of lobes that resembled starch mutants deficient in soluble starch synthases. Normal and waxy corn starches displayed A‐type X‐ray patterns. The su2 starch showed a weak A‐type pattern. The chain‐length distributions of normal, waxy, and su2 debranched amylopectins showed the first peak chain length at DP (degree of polymerization) 13, 14, and 13, respectively; second peak chain length at DP 45, 49, and 49, respectively; and highest detectable DP of 80, 72, and 76, respectively. The su2 amylopectin showed a higher percentage of chains with DP 6–12 (22.2%) than normal (15.0%) and waxy (14.6%) amylopectins. The absolute amylose content of normal, waxy, and su2 starches was 18.8, 0.0, and 27.3%, respectively. Gel‐permeation profiles of su2 corn starch displayed a considerable amount of intermediate components. The su2 corn starch displayed lower gelatinization temperature, enthalpy change, and viscosity; a significantly higher enthalpy change for melting of amylose‐lipid complex; and lower melting temperature and enthalpy change for retrograded starch than did normal and waxy corn starches. The initial rate of hydrolysis (3 hr) of the corn starches followed the order su2 > waxy > normal corn. Waxy and su2 starches were hydrolyzed to the same extent, which was higher than normal starch after a 72‐hr hydrolysis period.     

Whole Grain Amylose Analysis in Maize Using Near-Infrared Transmittance Spectroscopy

The development of genetically modified starches has relied on the use of maize (Zea mays L.) endosperm mutant alleles that alter starch structural and physical properties. A rapid method for predicting amylose content would benefit breeders and commercial handlers of specialty starch corn. For this reason, a study was conducted to investigate the use of near-infrared transmittance spectroscopy (NITS) as a rapid and nondestructive technique for predicting grain amylose content (GAC) in maize. Many single- and double-mutant inbreds and hybrids were used to create a calibration set for the development of a predictive model using partial least squares analysis. A validation set composed of similar genetic material was used to test the prediction model. A coefficient of correlation (r) of 0.94 was observed between GAC values determined colorimetrically and those predicted by NITS; however, the predicted values were associated with a large standard error of prediction (SEP = 3.5). Overall, NITS discriminated well among high amylose and waxy genotypes. The NITS calibration was used to determine levels of contamination by normal kernels in waxy and high-amylose (Amy VII) grain samples intended for wet milling. In both cases, a 5% contaminated sample could be detected from pure samples according to predicted NITS values.     

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.     

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.     

Physicochemical and Structural Characteristics of Flours and Starches from Waxy and Nonwaxy Wheats

A waxy spring wheat (Triticum aestivum L.) genotype was fractionated into flour and starch by roller and wet‐milling, respectively. The resultant flour and starch were evaluated for end‐use properties and compared with their counterparts from hard and soft wheats and with commercial waxy and nonwaxy corn (Zea mays L.) starches. The waxy wheat flour had exceptionally high levels of water absorption and peak viscosity compared with hard or soft wheat flour. The flour formed an intermediate‐strength dough that developed rapidly and was relatively susceptible to mixing. Analysis by differential scanning calorimetry and X‐ray diffractometry showed waxy wheat starch had higher gelatinization temperatures, a greater degree of crystallization, and an absence of an amylose‐lipid complex compared with nonwaxy wheat. Waxy wheat and corn starches showed greater refrigeration and freeze‐thaw stabilities than did nonwaxy starches as demonstrated by syneresis tests. They were also similar in pasting properties, but waxy wheat starch required lower temperature and enthalpy to gelatinize. The results show analogies between waxy wheat and waxy corn starches, but waxy wheat flour was distinct from hard or soft wheat flour in pasting and mixing properties.     

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.     

Physicochemical Properties of Zero Amylose Hull-less Barley Starch

Zero amylose starch isolated from hull-less barley (HB) showed a typical A-type diffraction pattern. The X-ray analysis suggested that granules of zero amylose (SB94794) and 5% amylose (CDC Candle) HB starches had lower crystallinity than did commercial waxy corn starch. Differential scanning calorimetry showed lower transition temperatures and endothermal enthalpies for the HB starches than for the waxy corn starch. The zero amylose HB starch showed a Brabender pasting curve similar to that of waxy corn starch, but with lower pasting and peak temperatures and a higher peak viscosity. Noteworthy characteristics of zero amylose HB starch were its low pasting temperature and high paste clarity and freezethaw stability, which make this starch useful for many food and industrial applications.     

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.     

Effects of Amylose,Corn Protein,and Corn Fiber Contents on Production of Ethanol from Starch‐Rich Media

The effects of amylose, protein, and fiber contents on ethanol yields were evaluated using artificially formulated media made from commercial corn starches with different contents of amylose, corn protein, and corn fiber, as well as media made from different cereal sources including corn, sorghum, and wheat with different amylose contents. Second‐order response‐surface regression models were used to study the effects and interactions of amylose, protein, and fiber contents on ethanol yield and conversion efficiency. The results showed that the amylose content of starches had a significant (P < 0.001) effect on ethanol conversion efficiency. No significant effect of protein content on ethanol production was observed. Fiber did not show a significant effect on ethanol fermentation either. Conversion efficiencies increased as the amylose content decreased, especially when the amylose content was >35%. The reduced quadratic model fits the conversion efficiency data better than the full quadratic model does. Fermentation tests on mashes made from corn, sorghum, and wheat samples with different amylose contents confirmed the adverse effect of amylose content on fermentation efficiency. High‐temperature cooking with agitation significantly increased the conversion efficiencies on mashes made from high‐amylose (35–70%) ground corn and starches. A cooking temperature of ≥160°C was needed on high‐amylose corn and starches to obtain a conversion efficiency equal to that of normal corn and starch.     

Structural Changes of Debranched Corn Starch by Aqueous Heating and Stirring

Aqueous dispersions (2 mg/mL) of debranched corn starches of different amylose contents (waxy, normal, and high‐amylose) were subjected to extensive autoclaving and boiling‐stirring, and then the changes in starch chain profile were examined using medium‐pressure, aqueous, size‐exclusion column chromatography. As autoclaving time increased from 15 to 60 min, weight‐average chain length (CL_w) of waxy, normal, and high‐amylose corn starches determined using pullulan standards decreased from 46 to 41.2, from 122.1 to 96.3, and from 207.3 to 151.8, respectively. Number‐average chain length (CL_n) measured by the Nelson‐Somogyi method also decreased from 23.0 to 18.4, from 26.4 to 21.8, and from 66.5 to 41.5, respectively, indicating that thermal degradation of starch chains occurred. The CL_w/CL_n ratio for normal corn starch was higher than that for waxy corn starch, indicating an increase in polydispersity of the amylose fraction. Thermal degradation was also observed when the debranched starch was subjected to the boiling‐stirring treatment (0–96 hr). During 96 hr, the CL_w and relative proportion of B≥2 chains of amylopectin released by debranching waxy corn starch increased, whereas those of B1 chains decreased. This change may indicate physical aggregation of B1 chains. But branches from normal and high‐amylose corn starches showed increases in CL_w and the proportion of both B1 and B≥2 chains, along with substantial decreases in those of amylose chains. Therefore, thermal degradation of amylose was greater than that of amylopectin.     

Amylose-Lipid Complex Formation in Acetylated Pea Starch-Lipid Systems

Starch-lipid interactions involving native and acetylated pea starch were studied by differential scanning calorimetry (DSC) and measurements of iodine affinity. Lipids including lauric acid, monopalmitin, and butterfat were added to aqueous starch dispersions after the starch was gelatinized at 85°C. DSC thermal curves of gelatinized modified pea starch systems containing fatty acid or monoglyceride did not show DSC transitions indicative of amylose complexes with external lipids, whereas a DSC endotherm of amylose-lipid complexes was observed for the corresponding native starch-lipid systems. However, iodine binding studies revealed that acetylated pea starch amylose complexed with added fatty acid or monoglyceride in the modified pea starch-lipid composites. The failure of DSC detection of the complexes in these systems was attributed to the absence of crystalline structures of acetylated pea starch amylose complexes. Furthermore, acetylation of starch decreased the complexing ability of the pea starch amylose as revealed by a reduction in iodine affinity. Both DSC and iodine affinity studies showed that neither native nor modified pea starch interacted to a significant extent with butterfat that consisted mainly of triglycerides.     

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.     

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.