Retrogradation of Maize Starch After Thermal Treatment Within and Above the Gelatinization Temperature Range

Studies of starch retrogradation have not considered the initial thermal treatment. In this article, we explore the effect of heating to temperatures within and above the gelatinization range on maize starch retrogradation. In the first experiment, 30% suspensions of waxy (wx) starch were initially heated to final temperatures ranging from 54 to 72°C and held for 20 min. On reheating in the differential scanning calorimeter immediately after cooling, the residual gelatinization endotherm peak temperature increased, the endotherm narrowed, and enthalpy decreased. Samples stored for seven days at 4°C showed additional amylopectin retrogradation endotherms. Retrogradation increased dramatically as initial holding temperature increased from 60 to 72°C. In a second experiment, wx starch was initially heated to final temperatures from 54 to 180°C and rapidly cooled, followed by immediate reheating or storage at 4°C. Maximum amylopectin retrogradation enthalpy after storage was observed for initial heating to 82°C. Above 82°C, retrogradation enthalpy decreased as initial heating temperature increased. A similar effect for ae wx starch was observed, except that retrogradation occurred more rapidly than for wx starch. These experiments show that heating to various temperatures above the range of gelatinization may profoundly affect amylopectin retrogradation, perhaps due to varying extents of residual molecular order in starch materials that are commonly presumed to be fully gelatinized. This article shows that studies of starch retrogradation should take into account the thermal history of the samples even for temperatures above the gelatinization temperature range.     

Retrogradation of du wx and su2 wx Maize Starches After Different Gelatinization Heat Treatments

Retrogradation of du wx and su2 wx starches after different gelatinization heat treatments was studied by differential scanning calorimetry. Suspensions of 30% (w/w) starch were initially heated to final temperatures of 55–180°C. Gelatinized starch was cooled and stored at 4°C. Starch retrogradation in the storage period was influenced by initial heat treatments. Retrogradation of du wx starch was rapid: when initially heated to 80–105°C, retrogradation enthalpy was ≈10 J/g after one day at 4°C. The retrogradation enthalpy was ≈15 J/g after 22 days of storage, and reached a maximum of 16.2 J/g after 40 days of storage. For du wx starch, application of the Avrami equation to increases in retrogradation enthalpy suggests retrogradation kinetics vary with initial heating temperature. Furthermore, starch retrogradation may not fit simple Avrami theory for initial heating ≤140°C. Retrogradation of su2 wx starch was slow. After 30 days of storage at 4°C, the maximum retrogradation enthalpy for all initial heating temperatures tested was 7.0 J/g, for the initial heating to 80°C. This work indicates that gelatinization heat treatment in these starches is an important factor in amylopectin retrogradation, and that the effect of initial heat treatment varies according to the genotype.     

Effect of sucrose on the thermomechanical behavior of concentrated wheat and waxy corn starch-water preparations

The rheological behavior of concentrated starch preparations from two different origins (wheat and waxy corn) was studied in the presence of sucrose by dynamic mechanical thermal analysis (DMTA). Moisture contents ranged from 30 to 60% (w/w wsb), and samples contained 0, 10, or 20 g of sucrose for 100 g of the starch-water mixture. The storage modulus (G') changes during heating depended strongly on water content (in the moisture range studied), and the importance of these variations was dependent upon the starch type. Sucrose addition resulted in a shift to higher temperatures of the increase in G' during heating. Differential scanning calorimetry (DSC) and electron-spin resonance (ESR) analyses were performed in parallel in order to relate the viscoelastic changes to water migrations and to structural disorganization of starch. Sucrose was found to increase the gelatinization temperature and enthalpy of both starches, implying a stabilization of the granular structure during heating. The sugar-water interactions do not appear to be the only way by which sucrose delays starch gelatinization. The obtained results suggest that sugar-starch interactions in the amorphous and/or the crystalline regions of the starch granules should be envisaged.     

Effect of Moisture Content on Thermomechanical Behavior of Concentrated Wheat Starch-Water Preparations

The rheological behavior of wheat starch preparations at intermediate moisture contents (25–60%, w/w) was studied by dynamic mechanical thermal analysis (DMTA). Differential scanning calorimetry (DSC) and electron spin resonance (ESR) experiments were also performed in parallel. Upon heating wheat starch preparations from 25 to 85°C, DMTA showed first a slight decrease in storage modulus (G′) to 45–60°C, then an increase of the shear modulus (predominant effect of swelling) to 68–74°C, followed by a decrease (predominant effect of melting-softening) to 85°C. In this 25–85°C temperature range, the initial swelling and subsequent softening were less pronounced with decreasing moisture content. The 45% moisture content level appeared critical, since there was a radical change in the thermomechanical behavior below this concentration. DSC showed that gelatinization did not appear as a single endotherm but as two endotherms. Whatever the moisture content, the melting started within a quite narrow temperature range, while the end of melting shifted progressively to higher temperatures as moisture content was decreased. ESR showed first a slight decrease in the water-soluble probe (Tempol) mobility as temperature was increased to 47–50°C, followed by a pronounced decrease to 57–60°C. Then, a progressive increase in probe mobility was observed to 85°C. These changes in probe mobility suggest some modifications of the kinetic and thermodynamic properties of the aqueous phase associated with changes in the starch physical state. For the lowest moisture contents, the probe mobility was quite stable during heating.     

Frozen and Unfrozen Water Contents of Wheat Flours and Their Components

The properties of frozen and unfrozen water in two different wheat flours (hard and soft), and in their main components (gluten, starch, damaged starch, water‐soluble and water‐insoluble pentosans), were described using modulated differential scanning calorimetry (DSC). As a reference, enthalpy values of crystallization (298 J/g) and melting (335 J/g) of pure water were determined from the total heat flow curves. The separation of thermal events between the reversing and nonreversing heat flows with modulated DSC was not effective due to disturbances in the modulated temperature scan. For wheat flours and their components, linear regressions described well the changes in frozen water content calculated from enthalpies of freezing (R² = 0.970–0.982) or melting (R² = 0.783–0.996). The unfrozen water content (UFWC) calculated for the hard wheat flour (29–31%, db) was close to that calculated for the soft wheat flour (30–32%). The UFWC of wheat gluten (38–47%), starch (38–42%), damaged starch (37–40%), water‐soluble pentosans (51%), and water‐insoluble pentosans (40–44%) were higher than the corresponding values for the flours. The simple summation of the contributions of each component cannot be used to estimate the overall behavior of flours.     

莲子热风干燥过程对其淀粉热特性及凝胶化的影响

为解决莲子干燥过程中淀粉形态结构变化造成莲子结壳、硬化,不利于干燥以及复水难、易返生问题,该文利用差示扫描量热技术(differential scanning calorimetry,DSC)对新鲜莲子以及不同热风干燥(70、80、90℃)莲子的淀粉热特性与凝胶化过程进行了研究.研究发现,莲子淀粉在低水分环境(42.2%,以质量比计)时存在2个明显的吸热峰,高水分环境(71.1%,以质量比计)时存在1个明显的吸热峰;莲子在干燥过程中不断失水,并伴随着淀粉凝胶化.方差分析(analysis of variance,ANOVA)表明,高温干燥显著影响莲子淀粉的热特性,其淀粉凝胶化温度(峰起温度To、峰顶温度Tp以及峰止温度Te)部分显著升高.相同干燥条件下,莲子淀粉糊化焓ΔH受水分显著影响,但干燥温度、升温速率对其影响不显著(P>0.01).采用Kissinger、Crane方程获得了淀粉凝胶化动力学参数(活化能Ea、指前因子Z以及反应级数n).莲子淀粉的非等温凝胶化反应可近似为一级反应,高温干燥后其Ea值出现增加,并随着水分增加呈现降低趋势.研究结果可为确定莲子高品质干燥工艺以及干莲子、莲子淀粉后续加工过程提供技术支持.     

Effect of Small and Large Wheat Starch Granules on Thermomechanical Behavior of Starch

The physicochemical properties of small‐ and large‐granule wheat starches were investigated to reveal whether gelatinization properties and rheological behavior differ between size classes of wheat starch. All samples contained 60% water (w/w, wb). The starch granule size and shape were examined by scanning electron microscopy in the separated A‐ and B‐type granule populations and in the whole wheat starch granule population. Differential scanning calorimetry (DSC) and electron spin resonance (ESR) analyses were performed in parallel with rheological measurements using dynamic mechanical thermal analysis (DMTA) to relate the viscoelastic changes to modifications in dynamic properties of aqueous solutions and structural disorganization of starch. The small (B‐type) granules had slightly higher gelatinization temperature and lower gelatinization enthalpy than did the large (A‐type) granules. Also, B‐type granules had higher enthalpy for the amylose‐lipid complex transition. Moreover, our results suggested that small granules have higher affinity for water at room temperature. It seems that there is a less ordered arrangement of the polysaccharide chains in the smaller granules when compared with the larger ones. These differences in functional properties of small and large granules suggested that the granule size distribution is an important parameter in the baking process.     

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

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

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.     

Influence of drying temperature, water content, and heating rate on gelatinization of corn starches

The gelatinization properties of starch extracted from corn and waxy corn dried at different temperatures were determined at various water contents and heating rates by differential scanning calorimetry. All gelatinization transition temperatures increased with drying temperature and heating rate. Onset and peak temperatures remained relatively constant, whereas end temperature decreased in the presence of excess water. The gelatinization enthalpy (deltaH(g)) of corn starch decreased with drying temperature at 50% water; however, it remained constant for waxy corn starch. The effects of water content and heating rate on deltaH(g) were dependent on each other. The minimum water levels required for gelatinization of starch extracted from corn dried at 20 and 100 degrees C are 21 and 29%, respectively. The activation energy (E(a)) was calculated using an Arrhenius-type equation and two first-order models; the degree of conversion (alpha) was predicted using a newly proposed model that produced good results for both E(a) and alpha.     

Relationships Between Soybean 11S Globulin Content and Thermal and Retrogradation Properties of Nonwaxy Maize Starch

In the present study, the relationships of soybean 11S globulin content, thermal properties, and retrogradation properties of nonwaxy maize starch in starch–globulin mixtures were investigated by differential scanning calorimetry. The onset and peak temperatures of maize starch were positively related to soybean 11S globulin content, whereas the thermal enthalpy was negatively related to it. However, the onset temperature, peak temperature, and thermal enthalpy of soybean 11S globulin were negatively related to maize starch content of mixtures. On the other hand, the onset and peak temperatures of retrograded maize starch were positively related to soybean 11S globulin content, whereas the retrogradation enthalpy was negatively related to it during storage. Therefore, adding soybean 11S globulin was an effective method to control maize starch gelatinization and retrogradation properties, which will be helpful for the food industry to produce high‐quality products based on starch and soybean protein.     

Thermal Modifications of Starch During High‐Temperature Drying of Pasta

Changes in starch at the molecular level during high‐temperature (HT) drying of pasta were studied with differential scanning calorimetry (DSC). Pasta was manufactured from durum wheat semolina into the shape of spaghetti on a pilot‐plant installation. The HT phase (100°C) was applied at relatively high (27 g/100 g, wb), intermediate (20 g/100 g), and low (15 g/100 g) product moisture, respectively. Spaghetti dried at 55°C served as reference samples. The changes in the thermal properties of starch during drying were dependent on the drying conditions. The gelatinization enthalpy of pasta dried at 55°C was reduced by 30% during drying, which indicates a partial melting of the starch crystallites. With the beginning of the HT phase, the gelatinization enthalpy increased to final values that were close to or higher than those of freshly extruded pasta. In general, HT drying of pasta induced a broadening of the gelatinization range. Starch crystallinity remained unchanged during extrusion and drying at HT. Based on a state diagram of starch and on DSC measurements of pasta during drying, it is hypothesized that HT drying favors molecular rearrangements of starch polymers at the double helical level.     

Properties of Starches from Near‐Isogenic Wheat Lines with Different Wx Protein Deficiencies

To determine the effect of amylose content on the starch properties, the amylose content, pasting properties, swelling power, enzymatic digestibility, and thermal properties of partial and perfect waxy types along with their wild‐type parent were analyzed. As expected, amylose content decreases differently in response to the loss of each Wx gene, showing the least response to Wx‐A1a. Most of the characteristics, except the thermal properties of the amylose‐lipid complex in differential scanning calorimetry (DSC), differed significantly among the tested types. Furthermore, the breakdown, setback, and pasting temperatures from the Rapid Visco Analyser (RVA) and the enzymatic digestibility, swelling power, peak temperature, and enthalpy of starch gelatinization from DSC showed a correlation with the amylose content. The relationships between the peak viscosity from the RVA and the onset temperature of starch gelatinization determined by DSC with amylose content of the tested materials were not clear. Waxy starch, which has no amylose, showed a contrasting behavior in starch gelatinization compared with nonwaxy starches. Among the nonwaxy starches, lower setback, lower pasting temperature, higher enzyme digestibility, higher peak temperature, higher enthalpy of starch gelatinization, and higher swelling were generally associated with low amylose starches.     

Gelatinization and Retrogradation Traits of Starches from Argentinian Maize Inbred Lines: Patterns of Correlation Among Traits

Efforts are being made to identify sources of starches with unique end-use properties, such as thermal properties, within a wide array of maize germplasm. Because redundancy may exist when evaluating these traits, it would be useful to know the pattern of correlation among traits involved to focus the expensive stage of evaluation of germplasm on traits that do not provide redundant information. The objectives of this study were to analyze the pattern of correlations between starch gelatinization and retrogradation-associated traits in a group of 12 Argentine maize inbred lines and to develop predictive models among traits when possible. Traits measured by differential scanning calorimetry included gelatinization and retrogradation properties. Pearson correlation coefficients among starch thermal properties were determined from univariate analyses, and canonical correlations were determined from multivariate analyses. Canonical correlation analyses were more sensitive in detecting associations between starch gelatinization and retrogradation parameters than univariate analyses. Multiple regression equations to estimate the change in enthalpy of starch gelatinization and retrogradation traits, especially for change in enthalpy and percentage of retrogradation, were obtained and validated with an independent data set.     

Gelation of whey protein concentrate-cassava starch in acidic conditions.

Whey protein concentrate (WPC)-cassava starch (CS) gels were prepared by heating WPC-CS dispersions (0-12.5% protein-0-4.2% starch, w/w; pH 3.75 and 4.2). Gels were characterized by measures of water-holding capacity (WHC), estimation of the relative size and/or density distribution of the gel particles, and light microscopy. Differential scanning calorimetry (DSC) of WPC-CS dispersions was also performed. Results show that CS increased the WHC of gels. Mixed gels presented separate zones of gelatinized starch and aggregated protein and a higher proportion of large/high-density particles. DSC assays showed that starch gelatinization preceded protein denaturation during heating. Starch gelatinization shifted to higher temperatures in dispersions containing WPC, due to the presence of whey proteins, lactose, and calcium.     

Identification of QTL Controlling Thermal Properties of Maize Starch

Starch has many uses and some of these uses would be facilitated by altering its thermal properties. Genetic manipulation of starch thermal properties will be facilitated by a better understanding of the genetic control of starch gelatinization. We used differential scanning calorimetry to characterize the gelatinization parameters of maize (Zea mays L.) kernel starch prepared from two populations of recombinant inbred lines, an intermated B73xMo17 population (IBM) and an F_6:7 Mo17xH99 population. The traits examined were the onset and peak temperatures of gelatinization and the enthalpy of gelatinization. These traits were measured for both native starch and for gelatinized starch allowed to recrystallize, a process called retrogradation. Substantial variation in these traits was found in spite of the narrow genetic base of the populations. We identified several quantitative trait loci (QTL) controlling traits of interest in each population. In the IBM population, a significant QTL for the peak temperature of gelatinization of retrograded starch co‐localized to a molecular marker in the Wx1 gene, which encodes a granule bound starch synthase. The major QTL identified in this study explain, on average, ≈15% of the variation for a given trait, underscoring the complexity of the genetic control of starch functional properties.     

Characterization of Thermal Traits of Starches from Argentinian Maize Inbreds: Genotypic and Crop Year Variability

Thermal properties are among the most important end‐use characteristics of starch from maize (Zea mays L.). Knowledge of the contribution of genotype and environment to the total variance for starch thermal properties is needed to aid in defining a testing strategy for selecting maize with desirable thermal starch properties. Thus, the objectives of this study were 1) to characterize the thermal properties of starches from a group of recently developed Argentine maize inbred lines, and 2) to assess the variability in starch properties attributable to genetic and crop year effects. Twelve inbred lines developed by the National Institute of Agricultural Technology (INTA) in Argentina derived from a wide array of germplasm sources were evaluated. Gelatinization and retrogradation properties were measured by differential scanning calorimetry. Enthalpy means for gelatinization were below means reported in the literature, suggesting possible energy savings when using these starches. The ratio between change in enthalpy for retrogradation and gelatinization was above the mean reported in the literature, suggesting a starch that may be useful as a dietary fiber. Significant environmental effects caused by crop year were detected. Some inbred lines, with smaller observed ranges and standard deviations across environments, may be more stable for some properties.     

Thermal Properties of Corn Starch Extraction Intermediates by Differential Scanning Calorimetry

Thermal properties of corn starch extraction intermediates from four types of corn were studied using differential scanning calorimetry. Starch at four different stages of extraction, including a standard single-kernel starch isolation procedure and three starch extraction intermediates, was isolated from mature corn kernels of B73 and Oh43 inbreds and the mutants of waxy (wx) and amylose extender (ae) in an Oh43 background. Differences in thermal properties and moisture and protein contents of starch from the extraction stages were statistically analyzed. Most thermal properties (gelatinization and retrogradation onset temperatures, gelatinization and retrogradation ranges, gelatinization and retrogradation peak temperatures, gelatinization and retrogradation enthalpies, peak height index, and percentage of retrogradation) of starches extracted at stage 3 intermediate (a procedure that did not include a final washing step) were similar to those of starch extracted by the standard single-kernel isolation procedure. Values for gelatinization peak temperature, gelatinization enthalpy, and peak height index were different between the standard and the stage 3 intermediate. The values obtained from starches extracted at stage 3, however, were consistent and predictable, suggesting that this extraction intermediate might be used in screening programs in which many starch samples are evaluated. By using the stage 3 extraction, samples could be evaluated in three rather than four days and the procedure saved ≈0.5 hr of labor time. The other two starch extraction intermediates, which excluded filtering and washing or filtering, washing, and steeping, produced starch with thermal properties generally significantly different from starch extracted by the standard single-kernel isolation procedure.     

Effect of Wheat Starch Structure on Swelling Power

Starches were isolated from the endosperm of 12 wheat samples with a wide swelling power range in the wholemeal. Starch amylose content (24.8–34.2%) correlated negatively with the swelling power of isolated starch (18.3–26.9), but starch lipid content showed no such correlation. Higher proportions of long chains (DP ≥ 35) in amylopectins contributed to increased starch swelling. Native starch gelatinization temperatures and enthalpy measured by differential scanning calorimetry correlated positively with swelling power, which also correlated significantly with the regelatinization enthalpy of retrograded starches stored at 5°C for two and four weeks.     

Effect of Dry Heating on Physicochemical Properties of Pregelatinized Rice Starch

Japonica and indica rice starches (10% w/w) were pregelatinized in a boiling water bath for 5 or 10 min and subsequently heat‐treated in a dry state for 0, 1, 2, or 3 h at 130°C to examine the effects of dry heating on pasting viscosity, paste clarity, thermal properties, X‐ray diffraction pattern, and gel strength of pregelatinized starches. Heat treatment obviously changed the physicochemical properties of pregelatinized rice starch. The pregelatinized rice starches had higher peak viscosity and final viscosity than the corresponding native rice starches. Heat treatment of pregelatinized rice starch for 1 h increased the peak viscosity, but treatment for 2 or 3 h decreased the peak viscosity compared with the unheated pregelatinized rice starch. The indica rice starch exhibited more substantial changes in pasting viscosity than did japonica rice starch during heat treatment. The melting enthalpy of the endothermic peak occurred at 90–110°C, and the intensity of the X‐ray diffraction peak at 20° was increased by dry heating, possibly owing to the enhanced amylose‐lipid complexes. The dry heat treatment of pregelatinized starch caused an increase in paste clarity and a decrease in gel strength.