Amylopectin Fine Structure and Rice Starch Paste Breakdown

Ten rice starches with a fairly narrow range of amylose content, but wide variation in RVA pasting curves, were selected to study a possible relationship between amylopectin fine structure and RVA paste viscosity parameters. Amylopectin fine structure was found to significantly correlate with paste breakdown. Proportion of long chains of amylopectin (FrI) was negatively correlated (r=0·84, p<0·01) and proportion of short chains of amylopectin (FrIII) was positive correlated (r=0·89, p<0·001) with paste breakdown. The findings imply that amylopectin fine structure relates to the extent of breakdown of swollen granules and the viscosity after gelatinised starch granule structure is disrupted. The results suggest the possibility that lines can be selected with high proportion of amylopectin long chains for reduced paste breakdown.     

Storage retrogradation behavior of sorghum, maize and rice starch pastes related to amylopectin fine structure

Storage retrogradation behavior and properties of sorghum, maize, and rice starches were compared to better understand the relationship of amylopectin fine structure to quality issues. Long-term changes in texture of starch gels were attributed to amylopectin retrogradation. In starch pastes aged 7 days at 4 °C, change in the storage modulus (ΔG^′) during heating (representing intermolecular associations) was highly and positively correlated (r = 0.93, p < 0.01) with the proportion of fraction I (FrI) long chains from debranched amylopectin. One sorghum cultivar, Mota Maradi, showed a dramatic increase in the storage modulus (G′) over the 7 day storage period that was related to its high proportion of FrI. Pastes/gels made from starches with normal (20–30%) amylose content and higher proportions of FrI long chains from debranched amylopectin tended to become firmer with more syneresis during extended storage. Both degree of polymerization measurements and previous models for amylopectin structure indicate that FrI represents long B chains of amylopectin. Cereal cultivars having amylopectin structures with lower proportion of long B chains were speculated to give improved quality products with lower rates of retrogradation and staling. This is particularly an issue in sorghum foods where products generally lack storage stability and tend to stale relatively quickly.     

Molecular Structure of a Low-Amylopectin Starch and Other High-Amylose Maize Starches

The molecular structure of two commercially available high-amylose maize starches, HYLON® V starch and HYLON® VII starch, and of a newly developed low-amylopectin starch (LAPS) was examined. These high-amylose starches give three apparent fractions as determined by gel-permeation chromatography: a high-molecular weight (mol.wt) amylopectin fraction, a low-mol.wt amylose fraction, and an intermediate-mol.wt fraction which contains both linear and branched components. The low-mol.wt amylose fraction increases from 9·4% in HYLON V starch to 17·7% in HYLON VII starch and 26·5% in LAPS, whereas the high-mol.wt amylopectin fraction decreases from 31·1% in HYLON V starch to 13·8% in HYLON VII starch and 2·5% in LAPS. The percentage of linear components in HYLON V starch, HYLON VII starch, and LAPS are 42, 54, and 80%, respectively. High-amylose starches have a large proportion of long chains in their branched fractions compared to waxy-maize and normal-maize starch. Both HYLON VII starch and the LAPS give B plus V-type X-ray diffraction patterns, but the LAPS has even a higher gelatinization temperature, lower swelling power in hot water, and is more resistant to acid digestion. With the lack of amylopectin, amylose accounts for at least part of the double helical structure in the LAPS granules.     

Rheological properties of starches with different amylose/amylopectin ratios

The rheological properties of corn starches with different amylose/amylopectin ratios (80/20, 50/50, 23/77, and 0/100) were systematically studied by Haake rheometry. The starches were initially pre-compounded with water to designated moisture content levels using a twin-screw extruder. A single-screw extruder with a slit capillary die was then used to characterize the shear stress and melt viscosity characteristics of sample pellets, as a function of both moisture content (19–27%) and extrusion temperature (110–140 °C). The melts exhibited shear thinning behavior under all conditions, with the power law index (0 < n < 1) increasing with increasing temperature and moisture content in the majority of cases. The higher the amylose content, the higher is the viscosity (for example, η increases from 277 Pa s to 1254 Pa s when amylose content increases from 0% to 80% under a certain condition), which is opposite to the sequence of molecular weight; amylopectin-rich starches exhibited increased Newtonian behavior. These rheological behaviors are attributed to the higher gelatinization temperature of amylose-rich starches, and in particular the multiphase transitions that occur in these starches at higher temperatures, and the gel-ball structure of gelatinized amylopectin.     

Genetic and Environmental Variation in Sorghum Starch Properties

Starch was isolated from eight local Zimbabwean landrace varieties, an improved cultivar (SV2) and a hybrid (DC-75) of sorghum grown in four environments. Amylose content, pasting (peak (PV), hot-paste (HPV), cool-paste (CPV) viscosity), textural and thermal (gelatinisation peak temperature (T_p) and gelatinisation energy (ΔH)) properties of the starches were determined. The F -tests from analyses of variance detected significant (p<0·001) differences among genotypes and growing environments for the starch properties measured. The results indicate that a range of genetic and environmental variability exists for these traits in sorghum genotypes although the latter could be greater than varietal effects. Hybrid DC-75 largely differed in starch amylose content, pasting PV, and gel hardness from the local landrace varieties. Environments used for local landrace varieties caused significant differences in starch properties, hence selection and monitoring of growing conditions is essential if a particular genotype is to maintain minimum variation in the desired pasting, textural or thermal properties. Genotype×environment interactions indicate that in breeding programmes, selection for starch properties at a single location would be misleading.     

Texture determinants in cooked, parboiled rice. I: Rice starch amylose and the fine stucture of amylopectin

The constituent starches from eleven cultivars of non-waxy rice with different degrees of cooking hardness were subjected to detailed analysis. No significant differences were observed in the granule morphology, crystallinity and size distribution of the starch granules that could be correlated with the textures of the cooked, parboiled rices. Differences in the contents of amylose and the fine structures of amylopectin were detected, however, which did correlate with texture. It appeared that the texture of the rices was critically controlled by the proportion of the longest (DP 92–98) and shortest (DP&lE25) amylopectin chains but not the intermediate (DP 43–68) chains. Hard cooking rice tended to have a higher amylose content (or amylose:amylopectin ratio) and more longer chain amylopectin than soft cooking rice, which feature is thought to encourage more extensive intra and/or inter molecular interactions with other components in rice grain, such as protein, lipid and non-starch polysaccharides and results in a firmer texture. The different amylopectin structures may explain why rices that possess similar amylose contents can have different textural properties. Such a correlation suggests that the structure of the starches determined from the SE–HPLC profile of the debranched amylopectin could be useful as a sensitive screening method in the classification of cooked rice texture.     

Determination of the Average Molecular Weight of Barley β-Glucan within the Range 30-100k by the Calcoflour-FIA Method

A new methodology for the determination of β-glucan average molecular weights within the range 30-100k has been developed. It was found that, when the amount of β-glucan was determined by the Calcoflour flow-injection analysis (Calcoflour-FIA) method with two eluants, one of high ionic strength (0·02 g/l Calcoflour in aqueous 0·1 M Tris, pH 11, 0·17 M NaCl), which fully detects β-glucan of molecular weight (MW) higher than approximately 10k, and the other of very low ionic strength (0·02 g/l Calcoflour in aqueous 0·1 M Tris, pH 11), which fully detects only high MW (> 150k) β-glucan, the ratio of the amounts detected by the two eluants was correlated with the average molecular weight of β-glucan. When compared with the high-performance size-exclusion chromatography with post-column detection by Calcoflour-FIA (HPSEC-FIA) method, both methods gave similar results within the range of applicability of the new method.     

Influence of amylopectin structure on rheological and retrogradation properties of waxy rice starches

A set of 13 waxy rice genotypes prepared by chemical-induced mutation of rice variety TNG67 and 7 waxy rice varieties widely grown in Taiwan were compared for structural, rheological and retrogradation characteristics of starches. Wide differences in retrogradation enthalpy (ΔH_ret), gel firmness and storage modulus (G’_ret) were observed for 2-week stored gels of 20 starches. Ratio of short-to-long amylopectin chains was significantly higher (p < 0.05) in starches from mutant genotypes than in commercial varieties. ΔH_ret and G’_ret of starch pastes stored over 4 weeks showed stronger correlation with amylopectin chain-profile compared to those stored for 2 weeks. Amount of long amylopectin chains was correlated positively (p < 0.05) with ΔH_ret and gel firmness. Overall, ratio of short-to-long amylopectin chains affected almost all the rheological and retrogradation parameters. Results of this study can be useful to plant breeders and food industry for quality improvement and selection of waxy rice mutants for various applications.     

Dielectric Relaxations of Frozen Wheat Doughs Containing Sucrose, NaCl, Ascorbic Acid and Their Mixtures

The effects of sucrose, NaCl, and ascorbic acid on dielectric relaxations of frozen wheat doughs were investigated using dielectric analysis (DEA). All ingredients were dissolved in distilled water used to prepare wheat flour doughs to optimum consistency using a 10 g bowl Micro-Mixer. DEA measurements were made at a heating rate of 1 °C/min from −150 to 10 °C. Before the measurements, samples were equilibrated at −30 °C for 15 min to allow maximum ice formation, and then cooled at 1 °C/min to −150 °C. The frequencies used were 0·1, 0·5, 1, 5, 10, 20, 50, 100 and 1000 Hz. The dissipation factor (tan δ) of DEA showed an α-relaxation (glass transition), two low temperature relaxations (β and γ) and ice dissolution. Added NaCl had a markedly depressed the glass transition temperature (T_g′) and onset of melting of ice temperature (T_m′), probably because of the higher conductivity of the frozen material, and the decreased transition temperatures of the unfrozen solute phase. At the higher frequencies, the α-relaxation coincided with melting of ice, and all relaxation temperatures (α, β and γ) increased with increasing frequencies.     

Pasting Profiles and Solubility of Native and Cross-Linked Corn Starch inDimethylsulfoxide-Water Mixtures

The pasting profiles of native and cross-linked corn starch in dimethylsulfoxide (DMSO)–water mixtures were investigated with a Rapid Visco Analyser. The temperature profile included an isothermal step of 1 min at 30 °C, followed by a linear gradient to 75 °C in 3 min and finally an isothermal step of 20 min at 75 °C. The profiles were characterised by an initial peak (at 75 °C) followed by a trough, much as is the case with profiles of such starch in water. Increasing the DMSO concentration in the DMSO–water mixture from 70–97·5% (by weight), without changing the starch concentration, resulted in lower end-viscosities. The RVA pasting profiles of a series of sodium trimetaphosphate (STMP) and epichlorohydrin (ECH) cross-linked corn starches were investigated in 92·5% DMSO at different dry matter (d.m.) contents. At high starch concentrations (>60% d.m.), the end viscosity increased with the degree of cross-linking. At lower starch concentrations (<6% d.m.), the more highly cross-linked starches yielded lower peak- and end-viscosities than starches with lower degrees of cross-linking. The solubilisation of the starches in 92·5% DMSO was complete for the native starch and decreased considerably for the highly cross-linked starches. Light microscopy showed that the cross-linked starches, upon heating in DMSO–water, were converted to a biphasic system consisting of insoluble granule remnants and a starch solution.     

Physicochemical properties and amylopectin fine structures of A- and B-type granules of waxy and normal soft wheat starch

This work fractionated waxy and normal wheat starches into highly purified A- and B-type granule fractions, which were representative of native granule populations within parent native wheat starches, to accurately assess starch characteristics and properties of the two granule types. Wheat starch A- and B-type granules possessed different morphologies, granule specific surface area measurements, compositions, relative crystallinities, amylopectin branch chain distributions, and physical properties (swelling, gelatinization, and pasting behaviors). Within a genotype, total and apparent amylose contents were greater for A-type granules, while lipid-complexed amylose and phospholipid contents were greater for B-type granules. B-type (relative to A-type) granules within a given genotype possessed a greater abundance of short amylopectin branch chains (DP_n < 13) and a lesser proportion of intermediate (DP_n 13–33) and long (DP_n > 33) branch chains, contributing to their lower relative crystallinities. Variation in amylose and phospholipid characteristics appeared to account for observed differences in swelling, gelatinization, and pasting properties between waxy and normal wheat starch fractions of a common granule type. However, starch granule swelling and gelatinization property differences between A- and B-type granules within a given genotype were most consistently explained by their differential amylopectin chain-length distributions.     

Macromolecular Features of Starches Determined by Aqueous High-performance Size Exclusion Chromatography

Starches from various botanical sources, having different amylose–amylopectin levels, were treated with 95% (v/v) dimethylsulphoxide and then dissolved by microwave heating in a high pressure vessel (MWHPV). This procedure led to an almost complete dissolution of the starch sample when it was subsequently taken up in water. Various treatment times were tested, and optimal conditions corresponded to 35 s heating time in MWHPV (maximum temperature 143 °C). Under these conditions, degradation of the polymers was not noticeable and the degree of solubilisation of starch in the samples was in the range 87 to 100%. High-performance size exclusion chromatography (HPSEC) in tandem with multi-angle laser light scattering and refractive index detection was used to investigate apparent weight-average molar mass ( _w) and z-average gyration radius ( _G) of the starch components. Apparent _wand _Gvalues for samples with different amylose contents (between ≈0 and 65·8%) were between 2·2±0·2×10⁸and 2·4±0·2×10⁷g/mol and between 250±10 and 163±5 nm, respectively. These values were higher than those reported previously^1,2probably due to our more complete but less severe solubilisation procedure. When the heating time was increased from 35 to 90 s (maximum temperature 211°C), the _wand _Gdecreased, demonstrating possible polymer degradation due to temperature. Partial precipitation of high amylose samples after 24 h storage was detected by modifications in chromatograms, compared with freshly prepared samples.     

Molecular basis of the gelatinisation and swelling characteristics of waxy barley starches grown in the same location during the same season. Part II. Crystallinity and gelatinisation characteristics

Nine waxy barley samples (grown at the same site during the same season) were investigated to identify those molecular aspects of amylopectin structure and architecture which define the order and gelatinisation characteristics. Using ¹³C CP-MAS/NMR it was confirmed that the number of double helices within the starches were approximately constant although differences in crystallinity were identified by X-ray diffraction. These differences in terms of amount of crystalline order correlated well with gelatinisation temperatures. The onset (T_o), peak (T_p) and conclusion (T_c) gelatinisation temperatures were 53.4, 59.2 and 68.1 °C on average with the associated enthalpy (ΔH) of 11.0 and 13.5 J g⁻¹ on a starch and amylopectin basis. Annealing of the starches below T_o elevated T_o, T_p and T_c by +11.9, +8.2 and +5.1 °C on average and sharpened the gelatinisation range (T_c−T_o). Acid hydrolysis after annealing increased T_o, T_p and T_c (especially T_c) by +2.3, +17.4 and +34.7 °C on average. Annealing in the presence of α-amylase elevated similarly the gelatinisation parameters by +10.2, +7.1 and +2.8 °C for T_o, T_p and T_c, respectively. Crystalline lamellae lengths were found to be 5.2±0.7 and 6.2±0.4 nm using high sensitivity differential scanning micro-calorimetry and differential scanning calorimetry, respectively.     

Cultivar and Environmental Effects on (1→3,1→4)-β-D-Glucan and Protein Content in Malting Barley

A low β-glucan and protein content is desirable for malting barley. In China high β-glucan content has been considered a major factor contributing to the inferior malting quality of local barleys. In this study 10 barley cultivars were planted in multi-location trials in the southern winter-barley zone to determine genotypic and environmental effects on β-glucan and protein content. There were highly significant differences in both β-glucan and protein content between the 10 barleys, the eight locations and the 2 planting years. The average β-glucan content over the 2 years for the 10 cultivars in the eight locations ranged from 3·91% for Gangpi 1 to 4·95% for Xiumei 3, and from 3·76% for Hangzhou to 4·75% for Taian in eight locations. Correspondingly, the protein contents of the 10 cultivars ranged from 11·37% for Yanyin 1 to 12·52% for ZAU, and of the eight locations from 9·5% for Hangzhou to 14·69% for Taian. Environmental factors contributed the largest component of the variation in both β-glucan and protein content. Five climatic factors, namely the total accumulated temperature, accumulated temperature to 25 °C and to 30 °C, precipitation and days with rain during seed development were included in a regression equation relating climatic factors and β-glucan content. In the regression equation relating climatic factors and protein content, two other factors, days from heading to maturity and accumulated temperature to 20 °C were included, in addition to the five climatic factors that significantly affected β-glucan content.     

The Role of Dextrins in the Stickiness of Bread Crumb made from Pre-Harvest Sprouted Wheat or Flour Containing ExogenousAlpha-Amylase

Dextrins were extracted in water from bread made from pre-harvest sprouted wheat or standard flour supplemented with exogenousalpha-amylases. The dextrins were separated by gel permeation chromatography and the dextrin content (% of crumb weight) determined for different degree of polymerisation (DP) size classes; DP 1–2, DP 3–10, DP 11–50, DP 51–200 and DP >200. There were significant correlations between the dextrin content in each size class and crumb stickiness (r=0·84–0·91, 22 df ). The most significant correlation (r=0·96) was between total dextrin content and crumb stickiness. Addition of dextrins of various DP ranges from various sources to standard flour produced bread with sticky crumb. Again, the degree of stickiness was generally related to the amount of total dextrin in the crumb and not to size distribution of dextrins. In this instance, extensive enzymic hydrolysis of starch was not necessary to produce sticky crumb; the dextrins caused crumb stickiness directly. Addition of dextrins to reconstituted gluten–starch flour produced bread with unexpectedly low dextrin levels and correspondingly low stickiness scores. It is concluded that, to produce sticky crumb, high levels of dextrin of any size are necessary in the crumb; a sticky mass is produced when dextrins dissolve in the excess «free» water that is normally «bound» to starch, gluten and other insoluble components of bread crumb.     

Study on melting and crystallization of short-linear chains from debranched waxy starches by in situ synchrotron wide-angle X-ray diffraction

In situ melting and crystallization of short-linear α-1,4-glucan (short-chain amylose, or SCA) from debranched waxy starches were investigated by synchrotron wide-angle X-ray diffraction. Amorphous SCA was prepared by dissolving completely debranched waxy starches in alkaline solution and neutralized by hydrochloric acid. When hydrated with 50% water at 25 °C, all amorphous SCA crystallized immediately and gave a B-type structure. The SCA from debranched waxy potato starch had a longer average chain length and a higher melting temperature but relatively lower crystallinity upon hydration; it was not completely melted at 100 °C and retained its original B-type structure during rapid cooling. In contrast, the SCA from debranched waxy wheat and waxy maize starches had a large portion of low molecular weight fractions, a higher crystallinity upon hydration, and a lower melting temperature. These differences suggest that amylopectin short chains crystallized more readily but their crystals were weaker than those of long chains. After the B-type crystals of hydrated SCA from waxy wheat and waxy maize starches melted, they reformed into the A-type polymorph upon rapid cooling. The thermal properties showed that the A-type polymorph of debranched waxy wheat and waxy maize starches had a higher melting temperature than their B-type structure.     

Thermal, Dynamic-mechanical, and Dielectric Analysis of Phase and State Transitions ofFrozen Wheat Doughs

The physical state of wheat dough at sub-zero temperatures was investigated using Differential Scanning Calorimetry (DSC), Dynamic-mechanical Analysis (DMA) and Dielectric Analysis (DEA). Also, the water sorption properties of freeze-dried dough were investigated. DMA and DEA measurements were made at a heating rate of 1 °C/min from −150 to 10 °C. Before the measurements, samples were equilibrated at −25 °C for 15–20 min to allow maximum ice formation, and then cooled at 1 °C/min to −150 °C. The frequencies used were 0·1, 0·5, 1, 2·5, 5, 10, and 20 Hz for DMA and 0·1, 0·5, 1, 5, 10, 20, 50, 100 and 1000 Hz for DEA. The DSC thermograms were obtained for annealed samples by scanning from −80 to 20 °C at 5 °C/min, and they showed only ice melting starting at −18 °C. The tan δ of DMA and DEA showed an α-relaxation (glass transition), two low temperature relaxations (β and γ) and melting of ice. At the higher frequencies (>0·5 Hz), the α-relaxation coincided with melting of ice, and all relaxation temperatures (α, β and γ) increased with increasing frequencies as measured by DEA.     

Gelation of Waxy Barley Starch Hydrolysates

Thealpha-amylolysis of gelatinized waxy barley starch and the gelation of the hydrolysates was studied. The progress of the hydrolysis was monitored with gel permeation and ion exchange chromatography. Initial attack occurred mainly between the clusters, without significant hydrolysis of the external chains. The stiffness of 20% gels prepared from the polymeric products decreased with increasing hydrolysis of the amylopectin. A linear relationship between the shear modulus and the original high-molecular weight amylopectin content was observed. Although the branched degradation products of amylopectin (average DP <6×10⁴) were not involved in network formation, they retained their ability to recrystallize as analysed by differential scanning colorimetry. For more extensively hydrolysed products (average DP <5000) no recrystallization or gel formation was observed under the conditions tested. Information on the gel structure was obtained with acid hydrolysis and ion exchange chromatography. The structure of the acid-resistant gel residues was complicated, showing a five-peak distribution when analysed with ion exchange chromatography. No differences between the original and hydrolysate gels was observed. The gel residues were resistant to isoamylase.     

Water Sorption and Dielectric Relaxations of Wheat Dough (Containing Sucrose, NaCl, and their Mixtures)

Dielectric relaxations of wheat doughs with different water contents and effects of sucrose, NaCl, and their mixture on relaxation temperatures were investigated using dielectric analysis (DEA). All ingredients were dissolved in distilled water used to prepare wheat flour doughs to optimum consistency. Before analysis, samples were stored at room temperature in vacuum desiccators over a_w range of 0·225–0·753. Dynamic DEA measurements were made at a heating rate of 2 °C/min from 40 °C below and above the observed relaxation zone. The frequencies used were 0·1, 0·5, 1, and 5 Hz. Steady state water contents varied from 3·21 to 10·89 g H₂O/100 g dm over a_w range used for the plain dough (flour+water). Added ingredients increased sorption of doughs. The tan δ of DEA showed an α-relaxation (glass transition) in all doughs at all frequencies used. The relaxation peak temperature, taken as T_g, increased with increasing frequency. Added sucrose decreased the T_g of doughs, as well as added NaCl. A dramatic depressing effect of NaCl on T_g was probably due to an increase in conductivity of doughs.