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.     

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.     

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.     

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.     

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.     

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.     

Genetic Diversity in Physical Properties of Starch from a World Collection of Amaranthus

Physical and functional properties of starches isolated from 93 noncultivated genotypes of nine Amaranthus species from a world germ plasm collection and an additional 31 cultivated Amaranthus genotypes obtained from China were tested. A wide variation was found in the properties tested among the Amaranthus species and among genotypes within the same species. When comparing starches from cultivated and noncultivated genotypes, it was generally found that amylose was lower; starch pasting profiles were more consistent with higher peak viscosity, lower breakdown, and lower setback; the gelatinization temperature was lower; and energy of enthalpy was higher. Under cool storage, the hardness of cultivated starch pastes was lower and the adhesiveness was higher. As expected, amylose content was a primary factor affecting the physical and functional properties of Amaranthus starch. Compared with reference maize, rice, and wheat starches, Amaranthus starch tended to have lower hot paste viscosity and lower cool paste viscosity; and higher gelatinization temperatures and higher energy of enthalpy. Furthermore, Amaranthus starch pastes showed less change of gel hardness and adhesiveness after cold storage. The environmental effect on the different properties of starch varied among Amaranthus species. It is suggested that Amaranthus starches can be developed for a wide range of food uses.     

Effects of Starch Amylose Content of Wheat on Textural Properties of White Salted Noodles

White salted noodles were prepared through reconstitution of fractionated flour components with blends of waxy and regular wheat starches to determine the effects of amylose content on textural properties of white salted noodles without interference of protein variation. As the proportion of waxy wheat starch increased from 0 to 52% in starch blends, there were increases in peak viscosity from 210 to 640 BU and decreases in peak temperature from 95.5 to 70.0°C. Water retention capacity of waxy wheat starches (80–81%) was much higher than that of regular wheat starch (55–62%). As the waxy wheat starch ratio increased in the starch blends, there were consistent decreases in hardness of cooked noodles prepared from reconstituted flours, no changes in springiness and increases in cohesiveness. White salted noodles produced from blends of regular and waxy wheat flours became softer as the proportion of waxy wheat flour increased, even when protein content of flour blends increased. Amylose content of starch correlated positively with hardness and negatively with cohesiveness of cooked white salted noodles. Protein content of flour blends correlated negatively with hardness of cooked noodles, which were prepared from blends of regular (10.5% protein) and waxy wheat flours (> 16.4% protein).     

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.     

Effect of Ferulic Acid and Catechin on Sorghum and Maize Starch Pasting Properties

The effects of ferulic acid and catechin on starch pasting properties were studied as part of an investigation into the structure and functionality of phenolics in starch‐based products. Commercial maize starch, starches from sorghum cultivars (SV2, Chirimaugute, and DC‐75), and the phenolic compounds ferulic acid and catechin were used in the investigation. Pasting properties were measured using rapid viscosity analysis. Ferulic acid and catechin (up to 100 mg each) were added to maize or sorghum starch (3 g, 14% mb) in suspensions containing 10.32% dry solid content. Addition of catechin resulted in pink‐colored pastes, whereas ferulic acid had no effect on paste color. Ferulic acid and catechin decreased hot paste viscosity (HPV), final viscosity, and setback viscosity of maize and sorghum starch pastes, but had no influence on the peak viscosity (PV) of the former. Both phenolics increased breakdown viscosity. Ferulic acid had greater influence on HPV, final viscosity, breakdown, and setback than catechin. Addition of catechin under acidic conditions (pH 3) decreased HPV, final viscosity, and setback of maize starch, but alkaline conditions (pH 11) slightly increased setback. Both acidic and alkaline conditions resulted in increased breakdown. Investigations on model‐system interactions between ferulic acid or catechin and starch demonstrated that phenolic type and pH level both significantly influence starch pasting properties, with ferulic acid producing a more pronounced effect than catechin. The significance of these interactions is important, especially in food matrices where phenolics are to be added as functional food ingredients.     

Susceptibility of Waxy Starch Granules to Mechanical Damage

Starch samples isolated from wheat flour that represented four possible waxy states (0, 1, 2, and 3‐gene waxy) were subjected to crushing loads under both dry and wet conditions. Calibrated loads of 0.5–20 kg were applied to the starch samples and the percentage of damaged granules was visually determined. Under dry crushing conditions, starches containing amylose (0, 1, and 2‐gene waxy) had between 1% (5‐kg load) to 3% (15‐ and 20‐kg load) damaged granules, whereas waxy starch (3‐ gene waxy; <1% amylose) began rupturing at 0.5‐kg load (3.5% damaged granules) and had 13% damaged granules when ≥10‐kg load was applied. Under wet crushing conditions, normal and partial waxy starch (0, 1, and 2‐gene waxy) showed little difference in percentage of damaged granules when compared to the results of dry crushing. Waxy starch (3‐gene waxy), however, showed substantially increased numbers of damaged granules: 12% damaged granules at 0.5‐kg load, rising to 55% damaged granules at 15‐kg load. The results indicate that waxy starch granules are less resistant to mechanical damage than normal starch granules. Furthermore, blends of normal and waxy wheats or wheat flours intended to have a particular amylose‐amylopectin ratio will be a complex system with unique processing and formulation considerations and opportunities.     

Viscoelastic Properties of Gelatinized Dispersions of Maize Starch Modified by Solid‐State Milling

Solid‐state milling is an effective physical modification method applied to improve functional properties of starch. In this work the effect of solid‐state milling on the viscoelastic characteristics of maize starch gelatinized dispersions (gels) was investigated by using oscillatory squeeze film rheometry. The relaxation spectrum of the samples under study was calculated from the data obtained. It was found that solid‐state milling resulted in a decrease of the storage (G′) and loss (G″) moduli; meanwhile, loss tangent (tan δ) increased. At a starch milling time more than 10 h, G″ > G′ and the gelatinized starch dispersions behaved as liquid‐like systems. The relaxation maxima shifted to shorter relaxation times, and the heights of the maxima decreased with increasing milling time. The relationship between the complex viscosity η* and steady‐shear viscosity η gradually altered from η* > η to η* < η as the milling time increased. The results can be used to determine the processing conditions of milled starch.     

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.     

Functional properties and enzymatic digestibility of cationic and cross-linked cationic ae, wx, and normal maize starch.

The functional properties and enzymatic digestibility of cationic and cross-linked cationic ae, wx, and normal maize starches were studied. Cationization reduced the endothermic transition temperatures (T(o), T(p), and T(c)), however, it increased peak viscosity, swelling power, solubility, clarity, and digestibility of all the starches compared to the corresponding native starch. After cationization, the enthalpy of waxy and normal starches was little changed but ae starch showed a decrease. For gel texture, cationization increased the hardness, adhesiveness, and springiness of all the starches, except for the hardness and adhesiveness of normal starch which showed a decrease, and the springiness of waxy starch did not show much change compared to the corresponding control starch. Cross-linking of cationic starch increased the endothermic transition temperatures, as well as peak viscosity. However, it reduced the swelling power and solubility, clarity, and enzymatic digestibility of all the cationic starches.     

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.     

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.     

Molecular Size Distribution and Amylase Resistance of Maize Starch Nanoparticles Prepared by Acid Hydrolysis

The molecular size distribution of maize starch nanoparticles (SNP) prepared by acid hydrolysis (3.16M H₂SO₄) and their amylase‐resistant counterparts, before and after debranching, was investigated. The weight average molecular weight (M_w) and linear chain length distribution were determined by high‐performance size‐exclusion chromatography (HPSEC) and high‐performance anion‐exchange chromatography (HPAEC), respectively. The objective was to understand the role of amylose involvement in the formation of SNP showing different crystalline structures (A‐ and B‐types). The HPSEC profiles of SNP before debranching from waxy, normal, and high‐amylose maize starches showed broad monomodal peaks. Debranched SNP from waxy maize eluted in a single narrow peak, whereas those from nonwaxy starches showed a multimodal distribution. Similar trends were also observed for the chain length distribution patterns, for which the longest detectable chains (degree of polymerization [DP] 31) in waxy maize were significantly lower than those of nonwaxy maize starches (DP 55–59). This indicated the potential amylose involvement in the SNP structure of normal and high‐amylose starches. Further evidence of amylose involvement was ascribed to the resistance of SNP toward amylolysis (Hylon VII > Hylon V > normal > waxy). The amylase‐resistant residues of SNP from high‐amylose maize starches were composed of both low M_w linear and branched chains.     

Partial Characterization of Buckwheat (Fagopyrum esculentum) Starch

Laboratory-isolated buckwheat (Fagopyrum esculentum) starch was compared to commercial corn and wheat starches. Buckwheat starch granules (2.9–9.3 μm) were round and polygonal with some holes and pits on the surface. Buckwheat starch had higher amylose content, waterbinding capacity, and peak viscosity, and it had lower intrinsic viscosity when compared with corn and wheat starches. Buckwheat starch also showed restricted swelling power at 85–95°C and lower solubility in water at 55–95°C and was more susceptible to acid and enzymatic attack. Gelatinization temperatures, determined by differential scanning calorimetry, were 61.1–80.1°C for buckwheat starch compared to 64.7–79.2°C and 57.1–73.5°C for corn and wheat starches, respectively. A second endotherm observed at 84.5°C was an amylose-lipid complex attributed to the internal lipids in buckwheat starch, as evidenced by selective extraction. The retrogradation of buckwheat, corn, and wheat starch gels was examined after storage at 25, 4, and -12°C for 1–15 days. In general, buckwheat starch retrogradation was slower than that of corn and wheat starch, but it increased as storage time increased, as did that of the other starch pastes. When the values of the three storage temperatures were averaged for each storage period analyzed, buckwheat starch gels showed a lower percentage of retrogradation than did corn and wheat starch gels. Buckwheat starch also had a lower percentage of water syneresis when stored at 4°C for 3–10 days and had better stability to syneresis after three freeze-thaw cycles at -12 and 25°C.     

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.