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.     

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.     

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.     

Extrusion of Cross‐Linked Hydroxypropylated Corn Starches I. Pasting Properties

A series of cross‐linked (0, 0.014, 0.018, 0.024, and 0.028% POCl₃, dry starch basis) hydroxypropylated (8%) corn starches were extruded using a Leistritz micro‐18 co‐rotating extruder. Process variables included moisture, barrel temperature, and screw design. Differential scanning calorimetry and X‐ray diffraction studies showed the level of starch crystallinity decreased with increasing severity of extrusion conditions. Pasting properties of the extruded starches were examined using a Rapid Visco Analyser. Pasting profiles of starches extruded at different conditions displayed different hot paste viscosity and final viscosity. Increasing starch moisture content during extrusion and level of cross‐linking increased starch viscosity (P < 0.0001), whereas increasing extrusion temperature and shear decreased starch viscosity (P < 0.0001). Interactions were found between level of cross‐linking and screw design and between extrusion temperature and starch moisture content (P < 0.0001).     

Physicochemical and Pharmaceutical Properties of Cross‐Linked Carboxymethyl Rice Starch Prepared by a Simultaneous Dual Reaction

Cross‐linked carboxymethyl rice starches (CL‐CMRS) were prepared from reactions between a native Klong Luang 1 (KL1) rice starch and varied concentrations (2.5–15% w/w) of sodium trimetaphosphate (STMP) in simultaneous carboxymethylation and cross‐linking reactions set up using methanol as a solvent. Physicochemical as well as pharmaceutical properties of CL‐CMRS were evaluated in relation to the amount of STMP used and the degree of cross‐linking (DCx). At a low DCx, the viscosity of CMRS solution was enhanced through the formation of cross‐linked polymeric network and chain entanglement. At higher concentrations in the preparation reaction, STMP caused proportional decreases in the water solubility and ≤70‐fold of the solution viscosity, but promoted swelling and water uptake of the modified starches. Rheological behavior of the nonsoluble but swellable CL‐CMRS was similar to that of commercial superdisintegrants sodium starch glycolate (SSG), and cross‐carmellose sodium (CCS). The swelling and water uptake of CL‐CMRS were 5–7 and 6–25 times higher, respectively, than that of the native starch. Disintegration test of tablets containing 1 and 3% w/w of native and modified rice starches showed that M‐KL1‐5 and M‐KL1‐10 could be developed as tablet disintegrants.     

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     

Extrusion of Cross‐Linked Hydroxypropylated Corn Starches II. Morphological and Molecular Characterization

A series of cross‐linked hydroxypropylated corn starches were extruded with a Leistritz micro‐18 co‐rotating extruder. Extrusion process variables including moisture (30, 35, and 40%), barrel temperature (60, 80, and 100°C), and screw design (low, medium, and high shear) were investigated. Scanning electron microscopy (SEM) of extruded starches showed a gel phase with distorted granules and granule fragments after extrusion at 60°C. After extrusion at 100°C only a gel phase was observed with no granular structures remaining. High performance size exclusion chromatography (HPSEC) equipped with multiangle laser light‐scattering (MALLS) and refractive index (RI) detectors showed extruded starches degraded to different extents, depending on extrusion conditions. The average molecular weight of the amylopectin of unextruded native corn starch was 7.7 × 10⁸. Extrusion at 30% moisture, 100°C, and high shear reduced the molecular weight of amylopectin to 1.0 × 10⁸. Hydroxypropylated normal corn starch extruded at identical conditions showed greater decreases in amylopectin molecular weight. With the addition of cross‐linking, the amylopectin fractions of the extruded starches were less degraded than those of their native and hydroxypropylated corn starch counterparts. Similarly, increasing moisture content during extrusion lowered amylopectin degradation in the extruded starches. Increasing temperature during extrusion of cross‐linked hydroxypropylated starches at high moisture content (e.g., 40%) lowered amylopectin molecular weights of the extruded starches, whereas increasing extrusion temperature at low moisture content (30%) resulted in less degraded molecules. This difference was attributed to the higher glass transition temperatures of the cross‐linked starches.     

Modification of Starch by Dry Heating with Ionic Gums

Waxy maize (native and hydroxypropylated [HP]) and potato starches were impregnated with ionic gums (sodium alginate, CMC, and xanthan, 1% based on starch solids) and heat‐treated in a dry state for 0, 2, or 4 hr at 130°C. Effects of the dry heating on paste viscosity (RVA) and clarity (light transmittance) were examined. Heat treatment with sodium alginate and CMC raised the paste viscosities of native and HP waxy maize starches, but decreased that of potato starch. Xanthan provided the most substantial changes in paste viscosity among the tested gums. It appeared to heavily restrict granule swelling of the waxy maize starches, but it increased swelling of potato starch granules. Dry heating raised the paste viscosity of all the starch‐gum mixtures tested, except the potato starchalginate mixture. The final viscosity at 50°C of a 7% paste was raised in all other starches by ≈500–1,000 cP by this treatment. The paste of waxy maize starch‐gum products became opaque and shorter textured by the heat treatment, regardless of the gum type, whereas potato starch‐gum products did not show any obvious change in paste clarity. Ionic gums could behave as cross‐linking agents as well as form graft copolymers through heatinduced ester formation. This simple heating process with ionic gums could be used as a modification method for starch.     

Physicochemical Properties of Normal and Waxy Job's Tears (Coix lachryma-jobi L.) Starch

Physicochemical properties of starches from eight coix (Coix lachrymajobi L.) accessions were investigated. There was considerable variation in most measured traits, generally corresponding to the separation into waxy and normal amylose types. The amylose contents of five normal coix ranged from 15.9 to 25.8%, and those of three waxy coix were 0.7–1.1%. Swelling power of waxy coix starches varied between 28.6 and 41.0 g/g, generally higher than waxy maize. Normal coix starches had significantly higher gelatinization peak temperature (T_p) than the normal maize, 71.9–75.5°C. The T_p of waxy coix starches was 71.1–71.4°C, similar to waxy maize. Rapid Visco-Analyser (RVA) pasting profiles of normal coix showed little variation and closely matched the normal maize starch profile. Pasting profiles of waxy coix showed more variation and had lower peak viscosities than waxy maize starch. Waxy coix starches formed very weak gels, while the gel hardness of normal coix starches was 11.4–31.1 g. Amylose content was the main factor controlling differences in starch properties of the coix starches.     

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.     

Starch Characteristics of Waxy and Nonwaxy Tetraploid (Triticum turgidum L. var. durum) Wheats

Manufacture of pasta products is paramount for durum wheat (Triticum turgidum L. var. durum). The recent development of waxy durum wheat containing starch with essentially 100% amylopectin may provide new food processing applications and present opportunities for value‐added crop production. This investigation was conducted to determine differences in some chemical and functional properties of waxy durum starch. Starch was isolated from two waxy endosperm lines and four nonwaxy cultivars of durum wheat. One of the waxy lines (WX‐1) was a full waxy durum wheat whereas the other line (WX‐0) was heterogeneous, producing both waxy and nonwaxy seed. Effects on starch swelling, solubility, pasting, gelatinization, and retrogradation were examined. The full waxy starch had four times more swelling power than the nonwaxy durum starches at 95°C, and was also more soluble at three of the four temperatures used. Starch pasting occurred earlier and peak viscosities were greater for starches from both waxy lines than for the nonwaxy starches, but their slurries were less stable with continued stirring and heating. Greater energy was required to melt gelatinized waxy starch gels, but no differences were found in either refrigerated storage or freeze‐thaw retrogradation, as determined by differential scanning calorimetry. The results of this investigation showed some significant differences in the starch properties of the waxy durum wheat lines compared to the nonwaxy durum wheats.     

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.     

Properties and Structures of Flours and Starches from Whole,Broken, and Yellowed Rice Kernels in a Model Study

The objective of this study was to compare the structure and properties of flours and starches from whole, broken, and yellowed rice kernels that were broken or discolored in the laboratory. Physicochemical properties including pasting, gelling, thermal properties, and X‐ray diffraction patterns were determined. Structure was elucidated using high‐performance size‐exclusion chromatography (HPSEC) and high‐performance anion‐exchange chromatography with pulsed amperometric detection (HPAEC‐PAD). The yellowed rice kernels contained a slightly higher protein content and produced a significantly lower starch yield than did the whole or broken rice kernels. Flour from the yellowed rice kernels had a significantly higher pasting temperature, higher Brabender viscosities, increased damaged starch content, reduced amylose content, and increased gelatinization temperature and enthalpy compared with flours from the whole or the broken rice kernels. However, all starches showed similar pasting, gelling, thermal properties, and X‐ray diffraction patterns, and no structural differences could be detected among different starches by HPSEC and HPAEC‐PAD. α‐Amylase may be responsible for the decreased amylopectin fraction, decreased apparent amylose content, and increased amounts of low molecular weight saccharides in the yellowed rice flour. The increased amount of reducing sugars from starch hydrolysis promoted the interaction between starch and protein. The alkaline‐soluble fraction during starch isolation is presumed to contribute to the difference in pasting, gelling, and thermal properties among whole, broken, and yellowed rice flours.     

Effect of Amylose Content on Gelatinization,Retrogradation, and Pasting Properties of Starches from Waxy and Nonwaxy Wheat and Their F1 Seeds

We studied the effect of amylose content on the gelatinization, retrogradation, and pasting properties of starch using wheat starches differing in amylose content. Starches were isolated from waxy and nonwaxy wheat and reciprocal F1 seeds by crossing waxy and nonwaxy wheat. Mixing waxy and nonwaxy wheat starch produced a mixed starch with the same amylose content as F1 seeds for comparison. The amylose content of F1 seeds ranged between waxy and nonwaxy wheat. Nonwaxy‐waxy wheat had a higher amylose content than waxy‐nonwaxy wheat. Endothermic enthalpy and final gelatinization temperature measured by differential scanning calorimetry correlated negatively with amylose content. Gelatinization onset and peak temperature clearly differed between F1 and mixed starches with the same amylose content as F1 starches. Enthalpy for melting recrystallized starches correlated negatively with amylose content. Rapid Visco Analyser measurement showed that F1 starches had a higher peak viscosity than waxy and nonwaxy wheat starches. Mixed starches showed characteristic profiles with two low peaks. Setback and final viscosity correlated highly with amylose content. Some of gelatinization and pasting properties differed between F1 starches and mixed starches.     

Increasing Slowly Digestible Starch Content of Normal and Waxy Maize Starches and Properties of Starch Products

Changes in the digestibility and the properties of the starch isolated from normal and waxy maize kernels after heat‐moisture treatment (HMT) followed by different temperature cycling (TC) or isothermal holding (IH) conditions were investigated. Moist maize kernels were heated at 80°C for 2 hr. The HMT maize kernels were subjected to various conditions designed to accelerate retrogradation of the starch within endosperm cells. Two methods were used to accelerate crystallization: TC with a low temperature of –24°C for 1 hr and a high temperature of 20, 30, or 50°C for 2, 4, or 24 hr for 1, 2, or 4 cycles, and IH at 4, 20, 30, or 50°C for 24 hr. The starch granules were then isolated from the treated kernels. The starch isolated from HMT normal maize kernels treated by TC using –24°C for 1 hr and 30°C for 2 hr for 2 cycles gave the greatest SDS content (24%) and starch yield (54%). The starch isolated from HMT waxy maize kernels treated by TC using –24°C for 1 hr and 30°C for 24 hr for 1 cycle had an SDS content of 19% and starch yield of 43%. The results suggest that TC after HMT changes the internal structure of maize starch granules in a way that results in the formation of SDS (and RS). They also suggest that thermal treatment of maize kernels is more effective in producing SDS than is the same treatment of isolated starch. All starch samples isolated from treated normal maize kernels exhibited lower peak viscosities, breakdown, and final viscosities and higher pasting temperatures than did the control (untreated normal maize starch). Although peak viscosities and breakdown of the starch isolated from treated waxy maize kernels were similar to those of the control (untreated waxy maize starch), their pasting temperatures were higher. The starch isolated from treated normal and waxy maize kernels with the highest SDS contents (described above) were further examined by DSC, X‐ray diffraction, and polarized light microscopy. Onset and peak temperatures of gelatinization of both samples were higher than those of the controls. Both retained the typical A‐type diffraction pattern of the parent starches. The relative crystallinity of the starch from the treated normal maize kernels was higher than that of the control, while the relative crystallinity of the starch from the treated waxy maize kernels was not significantly different from that of the control. Both treated starches exhibited birefringence, but the granule sizes of both starches, when placed in water, were slightly larger than those of the controls.     

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.     

Starch from Hull‐less Barley: Ultrastructure and Distribution of Granule‐Bound Proteins

Starch granules isolated from waxy, normal, and high‐amylose hullless barley grains were examined by transmission electron microscopy with cytochemical techniques. The micrographs showed two distinct regions of different sizes: 1) densely packed granule growth rings (which varied in size and number depending on the genotype), and 2) a loose filamentous network located in the central region of the granule. The granule ring width decreased with increasing amylose content. In all three genotypes, the growth rings closer to the granule surface were narrower in width than those within the granule interior. The waxy starch had wider intercrystalline amorphous growth rings, semicrystalline growth rings, and more open crystalline lamellae than normal and high‐amylose starches. Granule bound proteins (mainly integral proteins) were located in the central and peripheral (growth ring) regions of the granule.     

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.     

Relationship of Gelatinization and Recrystallization of Cross‐Linked Rice to Glass Transition Temperature

Nonwaxy rice starch was cross‐linked with sodium trimetaphosphate and sodium tripolyphosphate to obtain different degrees of cross‐linking (9.2, 26.2, and 29.2%). The objective was to investigate the influence of cross‐linking on thermal transitions of rice starch. Starch suspensions (67% moisture) were heated at 2°C/min using differential scanning calorimetry (DSC) to follow melting transition of amylopectin. Biphasic transitions were observed at ≈60–95°C in all samples. Melting endotherms of amylopectin shifted to a higher temperature (≤5°C) with an increasing degree of cross‐linking, while there was no dramatic change in enthalpy. Recrystallization during aging for 0–15 days was significantly suppressed by cross‐linking. The delayed gelatinization and retrogradation in crosslinked starch were evident due to restricted swelling and reduced hydration in starch granules. Glass transition temperature (T_g) measured from the derivative curve of heat flow was ‐3 to ‐4°C. No significant change in T_g was observed over the storage time studied.     

Impact of Waxy,Partial Waxy,and Wildtype Wheat Starch Fraction Properties on Hearth Bread Characteristics

Thirteen different wheat cultivars were selected to represent GBSS mutations: three each of wildtype, axnull, and bxnull, and two each of 2xnull and waxy. Starch and A‐ and B‐granules were purified from wheat flour. Hearth bread loaves were produced from the flours using a small‐scale baking method. A‐granules purified from wildtype and partial waxy (axnull, bxnull, and 2xnull) starches have significantly higher gelatinization enthalpy and peak viscosity compared with B‐granules. A‐ and B‐granules from waxy starch do not differ in gelatinization, pasting, and gelation properties. A‐ and B‐granules from waxy starch have the highest enthalpy, peak temperature, peak viscosity, breakdown, and lowest pasting peak time and pasting temperature compared with A‐ and B‐granules from partial waxy and wildtype starch. Waxy wheat flour has much higher water absorption compared with partial waxy and wildtype flour. No significant difference in hearth bread baking performance was observed between wildype and partial waxy wheat flour. Waxy wheat flour produced hearth bread with significantly lower form ratio, weight, a more open pore structure, and a bad overall appearance. Baking with waxy, partial waxy, and wildtype wheat flour had no significant effect on loaf volume.