Effects of Heat-Moisture Treatment and Lipids on Gelatinization and Retrogradation of Maize and Potato Starches

Effects of heat-moisture treatment (HMT) and lipids on the structure and gelatinization of maize and potato starches were studied, and the retrogradation process of 20% HMT starch gels was also investigated. Maize starch was physically modified by HMT or by defatting. Potato starch was physically modified by HMT or by adding monoglycerides. The X-ray pattern of the HMT maize starch was assigned to a combination of A and V patterns, which indicated that HMT formed crystallized amylose complexes and recrystallized amylose in maize starch granules. However, the X-ray pattern of defatted maize starch did not change for HMT, so the lipids originally existing in starch granules were important to the formation of new crystallites during this treatment. Differential scanning calorimetry (DSC) results suggested that weaker structures in amylopectin crystallites were more susceptible to degradation after HMT, while crystallized amylose complexes developed thermal stability after treatment. The amylose contents increased with increasing degree of HMT, which suggested that the newly created amylose arose from exterior linear chains of amylopectin degraded by the treatment. Investigation of retrogradation process showed that HMT significantly promoted retrogradation of starch gels, especially the initiation of recrystallization.     

Effect of Partial Gelatinization and Lipid Addition on α‐Amylolysis of Barley Starch Granules

The effect of partial gelatinization with and without lipid addition on the granular structure and on α‐amylolysis of large barley starch granules was studied. The extent of hydrolysis was monitored by measuring the amount of soluble carbohydrates and the amount of total and free amylose and lipids in the insoluble residue. Similarly to the α‐amylolysis of native large barley starch granules, lipid‐complexed amylose (LAM) appeared to be more resistant than free amylose and amylopectin. Partial gelatinization changed the hydrolysis pattern of large barley starch granules; the pinholes typical of α‐amylase‐treated large barley starch granules could not be seen. Lipid addition during partial gelatinization decreased the formation of soluble carbohydrates during α‐amylolysis. Also free amylose remained in the granule residues and mostly amylopectin hydrolyzed into soluble carbohydrates. These findings indicate that lysophospholipid (LPL) complexation with amylose occurred either during pretreatment or after hydrolysis, and free amylose was now part of otherwise complexed molecules instead of being separate molecules. Partial gelatinization caused the granules to swell somewhat less during heating 2% starch‐water suspensions up to 90°C, and lipid addition prevented the swelling completely. α‐Amylolysis changed the microstructure of heated suspensions. No typical twisting of the granules was seen, although the extent of swelling appeared to be similar to the reference starch. The granules with added LPL were partly fragmented after hydrolysis.     

甘薯淀粉性质与其粉丝品质的关系

为了弄清不同品种甘薯淀粉所制粉丝品质差异的原因,该研究通过对各种甘薯淀粉的理化性质、热力学特性、分子结构与甘薯粉丝品质的测定,并以绿豆淀粉做对照,对三者与其粉丝品质进行了相关性分析。结果表明：淀粉理化性质对粉丝品质影响较大,按相关系数大小依次是：膨润力＞溶解度＞表观直链淀粉含量＞蛋白质含量＞颗粒大小。回生对粉丝品质的影响远远大于糊化对其的影响。快速黏度分析参数与粉丝品质有显著的相关性,可作为预测其相应的粉丝品质的重要手段之一。淀粉分子结构对粉丝品质影响更大,按显著程度依次是：直链淀粉（A _m ）含量＞支链淀粉（A _P ）短链量＞A_P长链量＞A_m分支数＞A_P短链长度＞A_m链长＞A_P长链长度。     

Influence of amylopectin structure and amylose content on the gelling properties of five cultivars of cassava starches

Five cassava genotypes were investigated to identify the fine amylopectin structures and granule chemical compositions, which differentiated the starches into high (T(o) = 63.7 degrees C on average) and low (57.3 degrees C on average) gelatinization temperatures. The amylose contents (15.9-22.4%) and granular dimensions (12.9-17.2 microm) significantly differed among the starches. Diverse amylopectin structural elements resulted in significant swelling power, viscoelastic properties, and gel firmness. Debranched starches revealed a trimodal amylopectin distribution of three fractions: FIII (DP 12), FII (DP 24.31), and FI (DP 63) and FIII (DP 12), FII (DP 24.69), and FI (DP 67) for the low and high gelatinization starch groups, respectively. The higher proportion of FI long chain entanglement with amylose chain lengths to form longer helical structures was confirmed in the high gelatinization starch group, which developed "true" gels with better shear resistance, frequency independence, and higher gel firmness. Significant amounts of resistant starch fractions revealed the potential for application of these genotype starches in diverse foods.     

Structural characterization of Peruvian carrot (Arracacia xanthorrhiza) starch and the effect of annealing on its semicrystalline structure

Structural characteristics of native and annealed Peruvian carrot (Arracacia xanthorrhiza) starches were determined and compared to those of cassava and potato starches. Peruvian carrot starch presented round and irregular shaped granules, low amylose content and B-type X-ray pattern. Amylopectin of this starch contained a large proportion of long (DP > 37) and short (DP 6-12) branched chains. These last ones may contribute to its low gelatinization temperature. After annealing, the gelatinization temperatures of all starches increased, but the ΔH and the crystallinity increased only in Peruvian carrot and potato starches. The annealing process promoted a higher exposure of Peruvian carrot amylose molecules, which were more quickly attacked by enzymes, whereas amylopectin molecules became more resistant to hydrolysis. Peruvian carrot starch had structural characteristics that differed from those of cassava and potato starches. Annealing affected the semicrystalline structure of this starch, enhancing its crystallinity, mainly due to a better interaction between amylopectin chains.     

Morphological, structural, thermal, and rheological characteristics of starches separated from apples of different cultivars

The starches were separated from unripe apples of five cultivars (Criterion, Ruspippum, Red Spur, Skyline Supreme, and Granny Smith) and evaluated using scanning electron microscopy (SEM), gel permeation chromatography (GPC), X-ray diffraction, differential scanning calorimetry (DSC), and dynamic viscoelasticity. SEM showed the presence of round granules as well as granules that had been partially degraded, probably by amylases. The starch granules in different apple starches ranged between 4.1 and 12.0 mum. Debranching of starch with isoamylase and subsequent fractionation of debranched materials by GPC revealed the presence of an apparent amylose, an intermediate fraction (mixture of amylose and amylopectin), long side chains of amylopectin, and short side chains of amylopectin in the range of 28-35.2, 3.6-4.4, 20-21.3, and 39.9-47.1%, respectively. The swelling power of starches ranged between 14.4 and 21.3 g/g. X-ray diffraction of apple starches showed a mixture of A- and B-type patterns. All apple starches showed peak intensities lower than that observed for normal corn and potato starch, indicating the lower crystallinity. The transition temperatures (onset temperature, T(o); peak temperature, T(p); and conclusion temperature, T(c)) and enthalpy of gelatinization (deltaH(gel)) determined using DSC ranged between 54.7 and 56.2 degrees C, between 57.1 and 59.1 degrees C, between 60.2 and 63.5 degrees C, and between 3.3 and 4.2 J/g, respectively. The viscoelastic properties of starch from different cultivars measured during heating and cooling using a rheometer differed significantly. Red Spur and Criterion starches with larger granule size showed higher G' and G' ' values, whereas those containing smaller size and amylolytically degraded granules showed lower G' and G' '.     

Nutritional property of endosperm starches from maize mutants: a parabolic relationship between slowly digestible starch and amylopectin fine structure

The relationship between the slow digestion property of cooked maize starch and its molecular fine structure was investigated. Results of the in vitro Englyst assay showed a range of rapidly digestible starch (RDS) (70.1-98.9%), slowly digestible starch (SDS) (0.2-20.3%), and resistant starch (RS) (0.0-13.7%) among the tested maize mutant flour samples. Further analysis showed that amylose content was significantly correlated ( R = 0.763, P < 0.001) with RS amount but not with that of SDS, indicating that amylopectin is the starch molecule associated with SDS. Total starch debranching analysis revealed a parabolic relationship between SDS content and the weight ratio of amylopectin short chains (DP < 13, named SF) to long chains (DP >/= 13, named LF), which means amylopectin with a higher amount of either short chains or long chains can produce relatively high amounts of SDS. Furthermore, debranching analysis of the SDS materials from samples with the highest and lowest weight ratios of SF/LF (both had a high amount SDS) showed significantly different profiles, indicating there is not a uniform molecular structure for SDS. Thus, genetic mutants of maize samples have a good potential to provide raw starch materials of high nutritional quality. An additional finding showed that a simple and comparably high-throughput technique of Rapid Visco-Analyzer (RVA) can be used to screen genetic mutants on the basis of their RVA profiles.     

Effects of Environmental Temperature on Structure and Gelatinization Properties of Wheat Starch

The effects of environmental temperature on gelatinization properties and amylopectin structures of wheat endosperm starch were examined by isolating starches from four wheat cultivars matured in growth chambers at daytime temperatures of 15, 20, 25, or 30°C. Kernel weight and starch content per kernel were reduced by high maturation temperature. Amylose content showed no significant change at high maturation temperature in some cultivars; in other cultivars, there was a slight increase. Principal component analysis of data on relative peak areas of debranched amylopectin showed that amylopectin from wheat grown at a lower temperature had a greater proportion of shorter chains. Amylopectin branch chains were classified into three groups based on the correlation coefficients between the data of branch chain length distribution and principal component scores, degree of polymerization (DP) of 6–12, DP 13–34, and DP ≥ 35. The gelatinization temperature of starches increased markedly at a higher maturation temperature, with increases exceeding 10°C at high maturation temperatures. Gelatinization properties correlated significantly with amylopectin chain length distribution.     

Slowly digestible state of starch: mechanism of slow digestion property of gelatinized maize starch

The mechanism underlying the previously reported parabolic relationship between amylopectin fine structure, represented by the weight ratio of linear short chains [degree of polymerization (DP < 13) to long chains (DP >/= 13], and slowly digestible starch (SDS) content was investigated from the viewpoint of starch retrogradation and substrate susceptibility to enzyme hydrolysis. A maize mutant sample, termed "highest long-chain starch" (HLCS) representing group I samples with a higher proportion of long chains, showed a bell-shaped SDS pattern with retrogradation time, whereas insignificant changes in SDS were found for the sample termed "highest short-chain starch" (HSCS) representing group II samples with a higher proportion of short chains. This corresponded to results from X-ray powder diffraction and differential scanning calorimetry that showed a rapid increase of crystallinity and enthalpy for HLCS during retrogradation, but negligible changes for sample HSCS. Therefore, retrogradation was associated with SDS content for group I samples, but not for group II samples. Analysis of amylopectin fine structure, SDS content, retrogradation enthalpy, SDS material debranching profile, and hydrolysis pattern demonstrated, for group I samples, that linear branched chains of DP 9-30 of amylopectin may act as anchor points to slow the digestion of branced-chain fractions of DP > 30, which constitute the major slowly digestible portion, whereas for group II samples, it is the inherent molecular structure of amylopectin with a higher amount of branches and shorter chains that is not favorable for rapid enzyme digestion. The concept of a slowly digestible starch state (SDS state) that could be a chemical or physical entity is proposed to better describe the mechanistic underpinning of the slow digestion property of starches.     

Characteristics of taro (Colocasia esculenta) starches planted in different seasons and their relations to the molecular structure of starch

Physico-chemical properties and molecular structure of starches from three cultivars (Dog hoof, Mein, and KS01) of taro tubers planted in summer, winter, and spring were investigated. The effects of the planting season on the physico-chemical properties and the molecular structure of starch were determined, and the relations between the physico-chemical properties and the molecular structure of starch are discussed. Results indicate that taro starches from tubers planted in summer had the largest granule size, a low uniformity of gelatinization, and a high tendency to swell and collapse when heated in water. Taro starch planted in summer also showed an elasticity during gelatinization that was higher than that of starches planted in the other seasons. In addition to the planting season and the variety, rheological and pasting properties of taro starches studied are influenced not only by the amylose content but also by the chain-length distribution of amylopectin, whereas swelling power and solubility only depend on the amylose content of starch. Taro starch with relatively high amylose content, high short-to-long-chain ratio, and long average chain length of long-chain fraction of amylopectin displayed high elasticity and strong gel during heating.     

Physicochemical and structural properties of maize and potato starches as a function of granule size

Chemical composition, molecular structure and organization, and thermal and pasting properties of maize and potato starches fractionated on the basis of granule size were investigated to understand heterogeneity within granule populations. For both starches, lipid, protein, and mineral contents decreased and apparent amylose contents increased with granule size. Fully branched (whole) and debranched molecular size distributions in maize starch fractions were invariant with granule size. Higher amylose contents and amylopectin hydrodynamic sizes were found for larger potato starch granules, although debranched molecular size distributions did not vary. Larger granules had higher degrees of crystallinity and greater amounts of double and single helical structures. Systematic differences in pasting and thermal properties were observed with granule size. Results suggest that branch length distributions in both amylose and amylopectin fractions are under tighter biosynthetic control in potato starch than either molecular size or amylose/amylopectin ratio, whereas all three parameters are controlled during the biosynthesis of maize starch.     

Oil Binding of Heat‐Treated Waxy Wheat Starch Granules and Starch Granule Ghosts Produced with Concentrated KI and I2

Dry waxy wheat starch granules were heat‐treated at 120°C for 5 hr, and then shaken vigorously in a biphasic system of oil and water. Non‐heat‐ treated starch remained in the aqueous phase, whereas the heat‐treated starch granules showed a strong oil‐binding ability that was lost by trypsin treatment. This result showed that the starch granule surface protein changed from hydrophilic to hydrophobic due to the heat treatment. The presence of starch granule surface protein was ascertained by staining with fluorescamine and fluorescence microscopic observation. Heat‐treated waxy wheat starch granules were incubated with a 25% KI/10% I₂ (w/v) solution, which produced “ghosts” (exterior and interior) structures. The exteriors stained red‐brown, whereas the interiors stained black‐brown. Sonication (20 kHz for 255 sec) followed by centrifugation separated the structures, which were then shaken vigorously in an oil and water system. Only the exterior ghosts exhibited a remarkable emulsification property, which disappeared after trypsin treatment. The ghosts from unheated control granules did not show emulsification. The presence of protein in the exterior ghost fraction was further substantiated by fluorescamine treatment. No protein was detectable in the interior fraction with this dye. From these results, we suggest that the ghost fraction of the waxy wheat starch contained the starch granule surface protein that was made hydrophobic by heat treatment. Also, the nature of the induced emulsification property of the exterior fraction (ghosts) and the oil‐binding ability of the heat‐treated waxy wheat starch granules coincided. Both were due to the hydrophobic nature of the same starch granule surface protein, which showed that the ghosts were the swollen form of the outer region of the waxy starch granule.     

Starch-Lipid Interactions in Common,Waxy, ae du,and ae su2 Maize Starches Examined by Differential Scanning Calorimetry

Four maize genotypes (common, waxy, ae du, and ae su2) were examined by differential scanning calorimetry (DSC) in the presence of four surfactants (sodium dodecyl sulfate [SDS], dodecyltrimethylammonium bromide [DOTAB], sodium hexadecyl sulfate [SHS], 1-monolauroyl-rac-glycerol [ML]) to characterize the starch-lipid complexes produced and provide evidence of differences in starch structure. The ionic surfactants with a C₁₂ hydrocarbon tail reduced the gelatinization onset temperature, a phenomenon that does not occur typically with neutral surfactants or with surfactants with longer hydrocarbon tails. Subtracting the DSC curves, the exotherm we suspected was caused by starch-lipid complexation, which occurs concomitantly with the gelatinization endotherm, was identified and provided evidence of the existence of amylopectin-lipid interactions. Apparent starch amylose content correlated well with enthalpies of amylose-lipid complexes. Complexes formed from DOTAB produced DSC endotherms that were broad and shallow and that shifted to lower temperatures as the DOTAB concentration increased. This was in contrast to other surfactants that normally produce amylose-lipid complex endotherms at temperatures independent of surfactant concentration.     

Effects of Growing Environment on Properties of Starch from Five Australian Wheat Varieties

The effects of growing conditions on properties of starch from wheat grain were examined. Growing conditions affected starch and amylose content, granule size distribution, protein associated with starch granules, and starch swelling power in grains from five commercial Australian milling wheat varieties grown at multiple locations in two years in crop production systems. Soil nitrogen and meteorological conditions were major contributors to variability in grain yield and grain protein and starch contents. The volume proportion of B‐granules was positively affected by warmer temperatures before flowering but negatively correlated with high temperatures during grain filling. Genotype was the main source of variability in the proportion of B‐granules and granule dimensions, starch‐granule proteins, and starch swelling power, although there were also significant contributions to variability from the growing conditions. Seasonal effects and interactions between genotype and season and location were significant sources of variability in amylose content, proportion of short chains of amylopectin, and flour swelling power. The positive relationships between starch content and the number of clear days and atmospheric temperatures before flowering indicate that conditions that enhance accumulation of assimilates before anthesis influence the deposition of reserves in developing grain.     

Composition,Molecular Structure,Properties, and In Vitro Digestibility of Starches from Newly Released Canadian Pulse Cultivars

Pulse starches were isolated from different cultivars of pea, lentil, and chickpea grown in Canada under identical environmental conditions. The in vitro digestibility and physicochemical properties were investigated and the correlations between the physicochemical properties and starch digestibility were determined. Pulse starch granules were irregularly shaped, ranging from oval to round. The amylose content was 34.9–39.0%. The amount of short A chains (DP 6‐12) of chickpea starch was much higher than the other pulse starches, but the proportions of B1 and B2 chains (DP 13‐24 and DP 25‐36, respectively) were lower. The X‐ray pattern of all starches was of the C type. The relative crystallinity of lentil (26.2–28.3%) was higher than that of pea (24.4–25.5%) and chickpea starches (23.0–24.8%). The swelling factor (SF) in the temperature range 60–90°C followed the order of lentil ≈ chickpea > pea. The extent of amylose leaching (AML) at 60°C followed the order of pea ≈ chickpea > lentil. However, in the temperature range 70–90°C, AML followed the order of lentil > pea > chickpea. The gelatinization temperatures followed the order of lentil > pea > chickpea. The peak viscosity, setback, and final viscosity of pea starch were lower than those of the other starches. Lentil starch exhibited lower rapidly digestible starch (RDS) content, hydrolysis rate, and expected glycemic index (eGI). The resistant starch (RS) content of both lentil cultivars was nearly similar. However, pea and chickpea cultivars exhibited wide variations in their RS content. Digestibility of the pulse starches were significantly correlated (P < 0.05) with swelling factor (60°C), amylose leaching (60°C), gelatinization temperature, gelatinization enthalpy, relative crystallinity, and chain length distribution of amylopectin (A, B1, and B2 chains).     

Comparison of the gelatinization behavior of organic and conventional spelt starches assessed by thermal and rheological analyses

The objective of this study was to compare gelatinization properties and molecular composition of starches extracted from locally grown organic and conventional spelt using thermal, rheological, and SEC analyses, along with Concanavalin A method. Organic and conventional spelt was planted in six replicated plots, and the extracted starch was analyzed for their gelatinization properties. DSC showed that the gelatinization temperature ranged from 56.7 to 68.8 °C with an average peak of 62.4 °C, with no evidence for statistical difference in gelatinization properties between treatments. Rheological behavior variation among samples was more pronounced than that between the two growing conditions. The amylose content ranged from 23.0% to 29.8%. There was no significant difference in the molecular weight of amylose and amylopectin irrespective of the plot locations, although a significant difference was found between the amylopectin molecular weight of organic and conventional spelt starches when analyzed collectively. The organic spelt starch studied may substitute the conventional starch when gelatinization behavior is considered.     

Investigation of Digestibility In Vitro and Physicochemical Properties of A‐ and B‐Type Starch from Soft and Hard Wheat Flour

In this study, the functional properties of A‐ and B‐type wheat starch granules from two commercial wheat flours were investigated for digestibility in vitro, chemical composition (e.g., amylose, protein, and ash content), gelatinization, retrogradation, and pasting properties. The branch chain length and chain length distribution of these A‐ and B‐type wheat starch granules were also determined using high‐performance anion exchange chromatography (HPAEC). Wheat starches with different granular sizes not only had different degrees of enzymatic hydrolysis and thermal and pasting properties, but also different molecular characteristics. Different amylose content, protein content, and branch chain length of amylopectin in A‐ and B‐type wheat starch granules could also be the major factors besides granular size for different digestibility and other functional properties of starch. The data indicate that different wheat cultivars with different proportion of A‐ and B‐type granular starch could result in different digestibility in wheat products.     

Why do gelatinized starch granules not dissolve completely? Roles for amylose, protein, and lipid in granule "ghost" integrity

After gelatinization in water, starch granules persist in swollen hydrated forms known as ghosts. Three potential mechanisms for ghost formation are tested. Proteins and lipids on the granule surface are found to be a determinant of ghost robustness, but not ghost formation. Proteins inside pre-made maize or wheat starch ghosts are degraded extensively by proteases without any apparent change in ghost properties, making an internal protein cross-linking mechanism unlikely. Waxy maize mutants with a range of amylose contents have ghost integrities that correlate with (low) apparent amylose levels. It is hypothesized that ghost formation is due to cross-linking of polysaccharide chains within swollen granules, most likely involving double helices formed from polymer chains that become free to move following heat-induced granule swelling. The size and robustness of granule ghosts is proposed to be determined by the relative rates of swelling and cross-linking, modulated by surface non-polysaccharide components.     

Effect of Lime on Gelatinization of Corn Flour and Starch

Analysis of swelling power, water retention capacity, and degree of gelatinization of corn flour cooked in water with and without lime indicated, over a concentration range of 0–1% (w/v), that at low concentrations, lime increases swelling and digestibility of starch granules. Measurement of starch solubility revealed an increase in the amount of starch dissolved by lime cooking. Swelling, retention, and gelatinization exhibited maxima at or near 0.2% (w/v) lime, and then decreased as lime concentration increased. Hot-stage polarized light microscopy and differential scanning calorimetry of isolated starch revealed increasing gelatinization temperatures with increasing lime concentrations. It is hypothesized that the high pH of the system causes starch hydroxyl groups to ionize, thereby creating binding sites for Ca⁺⁺/CaOH⁺ and producing Ca-starch crosslinks. It is also suggested that, at low lime levels (<0.4%, w/v), granule crystalline regions are disrupted and the granule matrix is stretched by exchange of protons for calcium ions; when the lime level surpasses 0.4% (w/v), the granule shell becomes stabilized by Ca⁺⁺-starch interactions, producing stronger, more rigid granules.     

From Molecules to Products: Some Aspects of Structure–Function Relationships in Cereal Starches

In this review, starch behavior is described from molecules in solution to the use of starch in products. The determination of molecular characteristics with asymmetrical flow field‐flow fractionation is described, and the behavior of starch in binary solutions is discussed. The organization of starch in granules and the changes in organization during gelatinization and retrogradation are then described. The role of starch retrogradation in bread staling is described in some detail, and the influence of water mobility and distribution is discussed in relation to amylopectin retrogradation. Finally, the use of starch as emulsifier is described. Hydrophobically modified starch is one possibility for emulsion stabilization; also, the starch granule as such can be used to stabilize emulsions (so‐called Pickering emulsions).