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.     

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.     

Production of Boiling‐Stable Granular Resistant Starch by Partial Acid Hydrolysis and Hydrothermal Treatments of High‐Amylose Maize Starch

The purpose of the present work was to examine whether partial acid hydrolysis (PAH) of a high‐amylose maize starch (ae‐VII) would enhance the effects of hydrothermal treatments to produce granular resistant starch (RS) that is stable to further heat treatment at atmospheric pressure. PAH ae‐VII starches were prepared by heating 35% (w/v) suspensions with 1% (w/w) HCl at 25°C for 6, 30, and 78 hr. Native and PAH starches were then treated by annealing (ANN) or heat‐moisture treatment (HMT). ANN was done at 70% moisture at 50, 60, or 70°C for 24 hr, and HMT was done at 30% moisture at 100, 120, or 140°C for 80 min. RS that survives boiling during analysis was determined by a modification of the AOAC method for determining total dietary fiber. RS was also determined by the Englyst method. Little change in the gelatinization enthalpy was found for ae‐VII starch after PAH, ANN, or HMT as individual treatments. After PAH, either ANN or HMT led to decreased gelatinization enthalpy. HMT and ANN alone increased boiling‐stable RS but decreased total RS. After PAH of ae‐VII, either ANN or HMT tended to increase the yield of boiling‐stable granular RS, with the greatest yield (≤63.2%) observed for HMT.     

Physicochemical Properties of Rice Starch Modified by Hydrothermal Treatments

Rice starches of long grain and waxy cultivars were annealed (ANN) in excess water at 50°C for 4 hr. They were also modified under heat-moisture treatment (HMT) conditions at 110°C with various moisture contents (20, 30, and 40%) for 8 hr. The modified products were analyzed by rapid-viscosity analysis (RVA), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). Generally, these hydrothermal treatments altered the pasting and gelling properties of rice starch, resulting in lower viscosity peak heights, lower setbacks, and greater swelling consistency. The modified starch showed increased gelatinization temperatures and narrower gelatinization temperature ranges on ANN or broader ones on HMT. The effects were more pronounced for HMT than for ANN. Also, the typical A-type XRD pattern for rice starch remained unchanged after ANN or HMT at low moisture contents, and the amorphous content increased after HMT at 40% moisture content.     

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.     

Association of Starch Granule Proteins with Starch Ghosts and Remnants Revealed by Confocal Laser Scanning Microscopy

Starch suspensions (0.25%) were gelatinized to 70 and 100°C, and starch ghosts (defined as gelatinized starch granule envelopes after the majority of internal starch polymers have been released) and remnants were collected by centrifugation and washed with water. Protein was revealed in isolated gelatinized normal starch ghosts using confocal laser scanning microscopy and a protein‐specific dye that fluoresces only after reaction with primary amines in protein. This technique eliminates background interference from residual dye. Observation of fluorescent‐labeled protein in the starch ghosts at different optical depths of field revealed that protein was concentrated in the envelopes of swollen, gelatinized potato, maize, and wheat starch ghosts. Only traces of protein were found in gelatinized starch granule remnants of waxy maize and amylose‐free potato starches after they were heated to 100°C, indicating that the proteins observed in gelatinized normal maize starch were largely granule‐bound starch synthase (GBSS). Moreover, fragility of the gelatinized waxy and amylose‐free starch granule remnants might be caused in part by the lack of GBSS. Gel electrophoresis of proteins in starch ghosts confirmed that GBSS in potato and maize was tightly associated with the starch ghosts. The study provides a structural explanation for a role of granule‐associated proteins in maintaining the integrity of starch ghosts and remnant structures, and their consequent effect on paste rheology.     

Effect of Partial Acid Hydrolysis and Heat‐Moisture Treatment on Formation of Resistant Tuber Starch

Structural characteristics of resistant starch (RS) were investigated. Tuber starches, hydrolyzed with 1N HCl at 35°C for 8 hr followed by autoclaving‐cooling treatment, were heated at 100°C for 16 hr after adjusting the moisture content to 20 or 30%. RS content of the tuber starches ranged from 5.4 to 22.7% depending on the source and type of treatment. Gelatinization parameters of RS isolated from partially acid‐hydrolyzed starch with autoclaving‐cooling followed by heat‐moisture treatment (HMT) showed higher enthalpy (ΔH) values and lower peak temperature (T_p) compared with non‐acid‐hydrolyzed RS. R values, the difference between completion and initial temperatures, and ΔH of RS increased by HMT. The X‐ray diffraction patterns of potato and sweet potato RS isolated from partially acid‐hydrolyzed starch with autoclaving‐cooling showed distinct sharp peaks at 15, 25, 27, and 28°, which decreased by HMT.     

Influence of Amylose Content on Properties of Wheat Starch and Breadmaking Quality of Starch and Gluten Blends

The effects of amylose content on thermal properties of starches, dough rheology, and bread staling were investigated using starch of waxy and regular wheat genotypes. As the amylose content of starch blends decreased from 24 to 0%, the gelatinization enthalpy increased from 10.5 to 15.3 J/g and retrogradation enthalpy after 96 hr of storage at 4°C decreased from 2.2 to 0 J/g. Mixograph water absorption of starch and gluten blends increased as the amylose content decreased. Generally, lower rheofermentometer dough height, higher gas production, and a lower gas retention coefficient were observed in starch and gluten blends with 12 or 18% amylose content compared with the regular starch and gluten blend. Bread baked from starch and gluten blends exhibited a more porous crumb structure with increased loaf volume as amylose content in the starch decreased. Bread from starch and gluten blends with amylose content of 19.2–21.6% exhibited similar crumb structure to that of bread with regular wheat starch which contained 24% amylose. Crumb moisture content was similar at 5 hr after baking but higher in bread with waxy starch than in bread without waxy starch after seven days of storage at 4°C. Bread with 10% waxy wheat starch exhibited lower crumb hardness values compared with bread without waxy wheat starch. Higher retrogradation enthalpy values were observed in breads containing waxy wheat starch (4.56 J/g at 18% amylose and 5.43 J/g at 12% amylose) compared with breads containing regular wheat starch (3.82 J/g at 24% amylose).     

Comparison of Physical Properties of Wheat Starch Gels with Different Amylose Content

The effects of amylose content and other starch properties on concentrated starch gel properties were evaluated using 10 wheat cultivars with different amylose content. Starches were isolated from grains of two waxy and eight nonwaxy wheat lines. The amylose content of waxy wheat lines was 1.4–1.7% and that of nonwaxy lines was 18.5–28.6%. Starch gels were prepared from a concentrated starch suspension (30 and 40%). Gelatinized starch was cooled and stored at 5°C for 1, 8, 16, 24, and 48 hr. The rheological properties of starch gels were studied by measuring dynamic viscoelasticity with parallel plate geometry. The low‐amylose starch showed a significantly lower storage shear modulus (G′) than starches with higher amylose content during storage. Waxy starch gel had a higher frequency dependence of G′ and properties clearly different from nonwaxy starches. In 40% starch gels, the starch with lower amylose showed a faster increase in G′ during 48 hr of storage, and waxy starch showed an extremely steep increase in G′. The amylose content and concentration of starch suspension markedly affected starch gel properties.     

Consequence of Starch Damage on Rheological Properties of Maize Starch Pastes

Waxy and normal maize starches were damaged to different extents by ball milling, with waxy starch notably more susceptible to damage. Starch damage caused substantial decreases in shear stress or apparent viscosity in both waxy and normal maize starch pastes at a wide range of shear rates (5.6 to 400 1/sec). Shear stress or apparent viscosity decreases were more evident in waxy than in normal maize starch pastes at the same ball milling times. Values of storage moduli were much higher than values of loss moduli, and storage moduli decreased with increase in starch damage in both waxy and normal maize starches, indicating decrease in elastic property. The study showed that starch damage causes substantial rheological changes in gelatinized pastes and that waxy starch undergoes more pronounced changes than normal starch. These results can be used to understand the general behavior of damaged normal and waxy starches in processed foods.     

Isolation of Amaranth Starch by Diluted Alkaline-Protease Treatment

Starch was isolated from Amaranthus cruentus seeds by different alkaline treatments and combinations of low alkaline steeping and protease treatments. For low alkaline-protease treatments, amaranth seeds were steeped in a NaOH solution (0.05%, pH 12) for 22 hr to loosen the protein matrix and ground. The pH of the ground slurry was adjusted to 7.5 and subjected to a protease (from Aspergillus sojae) treatment. The slurry was incubated with 1 or 0.5% of the protease (based on total amount of seeds) for 2 hr at 37°C and 50 rpm. The starch was then isolated by screening and centrifugation. This method produced starch with a low protein content (≤0.2%) and a high recovery (≈80%). Amaranth starch isolated by alkaline treatments were also studied by using various concentrations of NaOH steeping solutions and with or without alkaline solution during grinding and washing. The properties of amaranth starch isolated by alkaline and low alkaline-protease treatments were analyzed and compared. The properties of the amaranth starch were also compared with those of normal and waxy maize starches.     

Detection of Proteins in Starch Granule Channels

Proteins were detected in channels of commercial starches of normal maize, waxy maize, sorghum, and wheat through labeling with a protein‐specific dye and examination using confocal laser scanning microscopy (CLSM). The dye, specifically 3‐(4‐carboxybenzoyl)quinoline‐2‐carboxaldehyde (CBQCA), fluoresces only after it reacts with primary amines in proteins, and CLSM detects fluorescence‐labeled protein distribution in an optical section of a starch granule while it is still in an intact state. Starch granules in thin sections of maize kernels also had channel proteins, indicating that proteins are native to the channels and not artifacts of isolation. Incubation of maize starch with protease (thermolysin) removed channel proteins, showing that channels are open to the external environment. SDS‐PAGE analysis of total protein from gelatinized commercial waxy maize starch revealed two major proteins of about M_r 38,000 and 40,000, both of which disappeared after thermolysin digestion of raw starch. Commercial waxy maize starch granule surface and channel proteins were extracted by SDS‐PAGE sample buffer without gelatinization of the granules. The major M_r 40,000 band was identified by MALDI‐TOF‐MS and N‐terminal sequence analysis as brittle‐1 (bt1) protein.     

Contents of Indigestible Fraction,Water Solubility,and Color of Pyrodextrins Made from Waxy Sorghum Starch

To investigate the effect of prethinning of starch by acid before pyrolysis on the formation of indigestible fraction (IF) in pyrodextrins, native and prethinned (50°C for 1, 4, and 24 hr) waxy sorghum starches were heated at 120–160°C with 20–60 μL of 9% HCl/g of starch. Pyrodextrin containing 14.6% IF, measured as total dietary fiber by enzymatic‐gravimetric method, was produced at 120°C with 20 μL of HCl from native waxy sorghum starch. Prethinning before pyrolysis increased IF content by 0–68%, depending on the conditions for pyrolysis, compared with that of the native starch. Reduction in the molecular size of starch by prethinning might cause greater mobility during pyroconversion reaction and thus generate higher IF contents. Increasing temperature and acid concentration during pyroconversion also increased IF content of pyrodextrins. Pyrodextrin of 44.9% IF was produced at 160°C with 60 μL of HCl from prethinned starch (50°C for 24 hr). Solubility of pyrodextrins was inversely proportional to IF content (r = ‐0.87) and had a range of 62.7–98.3%. Color of pyrodextrins became brownish with more severe pyroconversion conditions.     

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.     

Effect of Dry Heating with Ionic Gums at Controlled pH on Starch Paste Viscosity

Waxy maize and potato starches were dispersed in pH 6.0 and 8.0 aqueous solutions (1%) of an ionic gum (sodium alginate, sodium carboxymethylcellulose, and xanthan). The mixture was dried at 45°C overnight and then heat‐treated 2 hr at 130°C. Effects on the paste viscosity of the products in a pH 7.0 buffer were examined. Heating with sodium alginate or sodium carboxymethylcellulose (CMC) increased the paste viscosity of waxy maize starch but reduced that of potato starch. In both starches, xanthan effected greater viscogram changes than did sodium alginate or CMC. Use of xanthan in the treatment produced products with restricted granular swelling and increased shear stability of the pastes. The pH of the starch‐gum mixtures affected the thermally induced viscosity changes. Mild acidity (pH 6.0) effected a viscosity decrease for the heat‐treated starch product, whereas alkalinity (pH 8.0) raised the viscosity regardless of the presence of gum. But pH 6 before heat treatment was favored for viscosity increase by sodium alginate, whereas pH 8 gave a greater increase in viscosity when xanthan was used. By using gum mixtures such as xanthan‐alginate and xanthan‐CMC, both viscosity increase and good shear‐stability were achieved.     

Characterization of Maize Starch Nanoparticles Prepared by Acid Hydrolysis

Starch nanoparticles (SNP) from maize starches of varying amylose content (0–71%) were prepared by acid hydrolysis (3.16M H₂SO_4, at 40°C up to 6 days) followed by repeated water washings. During the washing cycles, nonwaxy starches (normal, Hylon V, and Hylon VII) had suspended particles in the water washings, which were not evident in waxy starch. Microscopic examination revealed the presence of SNP in the “cloudy supernatants” of nonwaxy starches and in the “final washed residue” of waxy maize. The objective of this study was to collect SNP fractions accordingly and determine whether variation in the native starch amylose content would influence the yield, morphology, and crystallinity of the SNP. In nonwaxy starches, the yield of SNP increased up to 26.6% with hydrolysis time and was proportional to the amylose content. Morphology of SNP differed with starch type: flat/elliptical (500 nm) in waxy, oval/irregular (50–200 nm) in normal, oval/round (40–50 nm) in Hylon V, and square/polygonal (50–100 nm) in Hylon VII. X‐ray diffraction confirmed the presence of A‐type crystals in SNP from all starch types and a crystalline transformation from B‐ to A‐type in Hylon starches. The relative crystallinity of SNP was higher than their native starch counterparts.     

Influence of Annealing on Gel Properties of Mung Bean Starch

Mung bean starch gels (8% solids) were prepared after annealing at 45–60°C for 1–24 hr, and the relationship between the physical properties of gels and the swelling power (SP) and solubility of starch was investigated. The SP and solubility decreased with increasing annealing temperature and time, mostly in the first 6 hr. The solubles were mainly composed of amylose. Gel hardness at a 5 mm depth of annealed starch was larger than that of native starch, and gel hardness increased as SP decreased (r = ‐0.94). Upon continued compression, the yield force of gel showed a different function. Above SP of ≈12.5, the yield force of annealed starch gels decreased, but at <12.5 the yield force increased with increasing SP. Both granular rigidity and extent of packing appeared to determine the yield force. Although annealing increased the gel hardness, α‐amylase digestibility of gel was not affected. Pasting analysis in the Rapid Visco Analyser (RVA) revealed that annealing increased pasting temperature. A pasting peak was found only in 45 and 50°C annealed starches. Overall paste viscosities of the starches annealed at >55°C were lower than that of the control starch. Final viscosities in RVA were correlated with the yield force of gel (r = 0.99).     

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.     

Structure and Functionality of Barley Starches

Amylose contents of prime starches from nonwaxy and high-amylose barley, determined by colorimetric method, were 24.6 and 48.7%, respectively, whereas waxy starch contained only a trace (0.04%) of amylose. There was little difference in isoamylase-debranched amylopectin between nonwaxy and high-amylose barley, whereas amylopectin from waxy barley had a significantly higher percentage of fraction with degree of polymerization < 15 (45%). The X-ray diffraction pattern of waxy starch differed from nonwaxy and high-amylose starches. Waxy starch had sharper peaks at 0.58, 0.51, 0.49, and 0.38 nm than nonwaxy and high-amylose starches. The d-spacing at 0.44 nm, characterizing the amylose-lipids complex, was most evident for high-amylose starch and was not observed in waxy starch. Differential scanning calorimetry (DSC) thermograms of prime starch from nonwaxy and high-amylose barley exhibited two prominent transition peaks: the first was >60°C and corresponded to starch gelatinization; the second was >100°C and corresponded to the amylose-lipid complex. Starch from waxy barley had only one endothermic gelatinization peak of amylopectin with an enthalpy value of 16.0 J/g. The retrogradation of gelatinized starch of three types of barley stored at 4°C showed that amylopectin recrystallization rates of nonwaxy and high-amylose barley were comparable when recrystallization enthalpy was calculated based on the percentage of amylopectin. No amylopectin recrystallization peak was observed in waxy barley. Storage time had a strong influence on recrystallization of amylopectin. The enthalpy value for nonwaxy barley increased from 1.93 J/g after 24 hr of storage to 3.74 J/g after 120 hr. When gel was rescanned every 24 hr, a significant decrease in enthalpy was recorded. A highly statistically significant correlation (r = 0.991) between DSC values of retrograded starch of nonwaxy barley and gel hardness was obtained. The correlation between starch enthalpy value and gel hardness of starch concentrate indicates that gel texture is due mainly to its starch structure and functionality. The relationship between the properties of starch and starch concentrate may favor the application of barley starch concentrate without the necessity of using the wet fractionation process.     

Method for Determining the Rate and Extent of Accelerated Starch Retrogradation

A method to accelerate and quantitate retrogradation of starch pastes using a freeze-thaw cycle (FTC) process and turbidometric analysis has been developed. Using this method and differential scanning calorimetry (DSC), it was determined that the rate of retrogradation in 2.5% waxy maize pastes was inversely correlated to the rate of freezing, and that the thawing temperature affected perfection of the crystallites in retrograded amylopectin. DSC and X-ray diffraction were used to determine whether the crystallites formed during the FTC process were the same as those formed in starch pastes held isothermally at 4°C. Analysis of retrogradation of pastes of starches from various botanical sources indicated that the method reflects retrogradation in higher concentration pastes. Retrogradation rates were reduced by the addition of sodium dodecyl sulfate. Microstructures of freeze-thaw processed waxy maize and common corn starch pastes were examined.