Effect of Sucrose on Glass Transition,Gelatinization, and Retrogradation of Wheat Starch

Differential scanning calorimetry (DSC) was used to study the effect of sucrose on wheat starch glass transition, gelatinization, and retrogradation. As the ratio of sucrose to starch increased from 0.25:1 to 1:1, the glass transition temperature (T_g, T_g′) and ice melting enthalpy (ΔH_ice) of wheat starch‐sucrose mixtures (with total moistures of 40–60%) were decreased to a range of −7 to −20°C and increased to a range of 29.4 to 413.4 J/g of starch, respectively, in comparison with wheat starch with no sucrose. The T_g′ of the wheat starch‐sucrose mixtures was sensitive to the amount of added sucrose, and detection was possible only under conditions of excess total moisture of >40%. The peak temperature (T_m) and enthalpy value (ΔH_G) for gelatinization of starch‐sucrose systems within the total moisture range of 40–60% were increased with increasing sucrose and were greater at lower total moisture levels. The T_g′ of the starch‐sucrose system increased during storage. In particular, the significant shift in T_g′ ranged between 15 and 18°C for a 1:1 starch‐sucrose system (total moisture 50%) after one week of storage at various temperatures (4, 32, and 40°C). At 40% total moisture, samples with sucrose stored at 4, 32, and 40°C for four weeks had higher retrogradation enthalpy (ΔH) values than a sample with no sucrose. At 50 and 60% total moisture, there were small increases in ΔH values at storage temperature of 4°C, whereas recrystallization of samples with sucrose stored at 32 and 40°C decreased. The peak temperature (T_p), peak width (δT), and enthalpy (ΔH) for the retrogradation endotherm of wheat starch‐sucrose systems (1:0.25, 1:0.5, and 1:1) at the same total moisture and storage temperature showed notable differences with the ratio of added sucrose. In addition, T_p increased at the higher storage temperature, while δT increased at the lower storage temperature. This suggests that the recrystallization of the wheat starch‐sucrose system at various storage temperatures can be interpreted in terms of δT and T_p.     

Effects of Starch Isolation,Drying, and Grinding Techniques on Its Gelatinization and Retrogradation Properties

The effects of two different methods of starch isolation, drying, and grinding on gelatinization and retrogradation properties were investigated. Starch was isolated from whole wheat and flour of four hard red spring wheat cultivars. Portions of each starch isolate were freeze-dried or air-dried and portions of each dried starch were ground using a mortar and pestle or a Wiley Jr. mill. Less starch damage was obtained for freeze-dried starch regardless of isolation method or grinding technique and for all starches derived from whole wheat. Highest starch damage was obtained for air-dried starch isolates. Wiley-milled starch isolates showed higher water-binding. Whole wheat starch isolates had higher peak, lower trough, and lower final viscosities, as determined by starch paste viscosity analysis, than did starch isolates derived from flour. Major effects of all treatments on differential scanning calorimetry gelatinization properties showed lower onset temperature for flour starch isolates, lower peak temperature for freeze-dried starches, and no effects due to grinding. Endotherms of all starches after refrigerated storage and freezethaw cycling were lower than those for gelatinization.     

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.     

Quality Characteristics of Waxy Hexaploid Wheat (Triticum aestivum L.): Properties of Starch Gelatinization and Retrogradation

The viscoelastic properties and molecular structure of the starch isolated from waxy (amylose-free) hexaploid wheat (WHW) (Triticum aestivum L.) were examined. WHW starch generally had lower gelatinization onset temperature, peak viscosity, and setback than the starch isolated from normal hexaploid wheat (NHW). Differential scanning calorimetry (DSC) showed that WHW starch had higher transition temperatures (T_o, T_p, and T_c) and enthalpy (ΔH) than NHW starch. However, when compared on the basis of amylopectin (AP) content, ΔH of WHW starch was almost statistically identical to that of its parental varieties. Typical A-type X-ray diffraction patterns were observed for the starches of WHW and its parental varieties. Somewhat higher crystallinity was indicated for WHW starch. WHW starch was also characterized by having greater retrogradation resistance. The high-performance size-exclusion chromatography (HPSEC) of amylopectin showed that each amylopectin yielded two fractions after debranching. Although WHW amylopectin had somewhat long B chains, little difference was observed in the ratio of Fr.III/ Fr.II between WHW and its parental varieties.     

Retrogradation Mechanism of Rice Starch

The non‐Newtonian behavior and dynamic viscoelasticity of rice starch (Akihikari, 18.8% amylose content) solutions after storage at 25 and 4°C for 24 hr were measured with a rheogoniometer. The flow curves, at 25°C, of Akihikari starch showed plastic behavior >3.0% (w/v) after heating at 100°C for 30 min. The dynamic viscoelasticity of the starch increased after storage at 25 and 4°C for 24 hr and stayed at a constant value with increasing temperature. A small dynamic modulus of rice starch was observed upon addition of urea (4.0M) at low temperature (0°C), but it produced a sigmoid curve when plotted against increasing temperature. A small dynamic modulus was also observed in 0.05M NaOH solution. However, it increased rapidly after the temperature reached 70°C. Possible models of retrogradation mechanism of rice starch were proposed.     

Starch Retrogradation in Cooked Pasta and Rice

Effect of cooking time on starch retrogradation and water distribution was studied in pasta (spaghetti) and rice (parboiled and arborio) using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) Optimum cooking times (OCT) were 8, 16, and 18.5 min for spaghetti, parboiled, and arborio rice, respectively. Swelling was observed by image analysis. OCT spaghetti and rice showed various starch retrogradation rates at various aging times and temperatures. Based on the classical Avrami function, the retrogradation rate at 5°C followed the order spaghetti > parboiled rice > arborio rice, while extent was in the opposite order. At higher temperature (20°C), the rates decreased by 20× in all cases. Thermogravimetric analysis (TGA) investigations were undertaken to check the distribution of water within these products and its relationship to starch retrogradation. During heating, water was released in two distinguishable steps at ≈80 and 100°C. Results supported the conclusion that the more tightly bound water might not participate or facilitate starch retrogradation. In this study, the overall water content did not change during storage, and water appeared to migrate from sites of stronger binding to sites of weaker binding. The temperature dependence of the Avrami constant was described with the Vogel‐Tamman‐Fulcher empirical expression.     

Gelatinization,Pasting, and Gelling Properties of Sweetpotato and Wheat Starch Blends

Sweetpotato starch is high yielding but has very limited uses. It is possible to expand its application by blending it with other starches to obtain novel properties. In this study, functional properties of the blends of native sweetpotato starch with native, acid‐thinned, and hydroxypropylated wheat starch were studied at different ratios (75:25, 50:50, 25:75). The swelling factor, extent of amylose leaching, pasting, and gel textural properties of the blends were nonadditive of their individual components, and could be mathematically modeled by quadratic equations in relation to the ratios. Two peaks during pasting were observed for some starch mixtures studied by Rapid ViscoAnalyser (RVA). The gelatinization and retrogradation enthalpies (ΔH) of the blends were additive of their individual components and could be modeled by linear equations. All starch mixtures exhibited two peaks during differential scanning calorimetry (DSC) scan for gelatinization, but a single peak for retrograded starches. This study may provide basis for formulation of mixtures using starch from diverse sources to develop more natural starch systems with a range of physicochemical properties.     

Sources of Variation for Starch Gelatinization,Pasting, and Gelation Properties in Wheat

The starch of wheat (Triticum aestivum L.) flour affects food product quality due to the temperature-dependent interactions of starch with water during gelatinization, pasting, and gelation. The objective of this study was to determine the fundamental basis of variation in gelatinization, pasting, and gelation of prime starch derived from seven different wheat cultivars: Kanto 107, which is a partial waxy mutant line, and six near-isogenic lines (NILs) differing in hardness. Complete pasting curves with extended 16-min hold at 93°C were obtained using the Rapid Visco Analyser (RVA). Apparent amylose content ranged from 17.5 to 23.5%; total amylose content ranged from 22.8 to 28.2%. Starches exhibited significant variation in onset of gelatinization. However, none of the parameters measured consistently correlated with onset or other RVA curve parameters that preceded peak paste viscosity. Peak paste viscosity varied from 190 to 323 RVA units (RVU). Higher peak, greater breakdown, lower final viscosity, negative setback, and less total setback were associated with lower apparent and total amylose contents. Each 1% reduction in apparent or total amylose content corresponded to an increase in peak viscosity of about 22 and 25 RVU, respectively, at 12% starch concentration. Of the seven U.S. cultivars, the lower amylose cultivars Penawawa and Klasic were missing the granule-bound starch synthase (GBSS; ADPglucose starch glycosyl transferase, EC 2.4.4.21) protein associated with the Waxy gene locus on chromosome 4A (Wx-B1 locus). Kanto 107 was confirmed as missing both the 7A and 4A waxy proteins (Wx-A1 and Wx-B1 loci). The hardness NIL also were shown to be null at the 4A locus. Apparent and total amylose contents of prime starch generally corresponded well to the number of GBSS proteins; although the hardness NIL tended to have somewhat higher amylose contents than did the other GBSS 4A nulls. We concluded that reduced quantity of starch amylose due to decreased GBSS profoundly affects starch gelatinization, pasting, and gelation properties.     

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.     

Effects of Rough Rice Storage Conditions on Gelatinization and Retrogradation Properties of Rice Flours

Changes in gelatinization and retrogradation properties of two rice cultivars, Bengal and Kaybonnet, during rough rice storage were studied using differential scanning calorimetry (DSC). The storage variables included two storage moisture contents (12 and 14%), three storage temperatures (4, 21, and 38°C), and four storage durations (0, 3, 9, and 16 weeks). Rough rice cultivar, storage temperature, moisture content, and duration affected (P < 0.05) the enthalpies and temperatures of gelatinization and retrogradation of rice flour. Bengal had a higher gelatinization enthalpy (P < 0.005) but lower gelatinization temperatures (P < 0.0001) than the long-grain Kaybonnet. Rice stored at 38°C exhibited higher gelatinization enthalpy and temperatures (P < 0.05) than those stored at 4 or 21°C. Storage duration affected the gelatinization and retrogradation properties through a higher order, rather than a linear, relationship.     

Modeling Starch Gelatinization Kinetics of Milled Rice Flour

Milled long‐grain rice samples were evaluated by differential scanning calorimetry (DSC) to determine the kinetics of starch gelatinization. The experiments were conducted with milled rice flour with a 10.6% degree of milling. DSC thermograms were obtained from 35 to 110°C using heating rates between 1°C/min and 15°C/min. The rate constants were evaluated, and two activation energies were found for different temperature ranges. At <70.1°C gelatinization was not completed. It was assumed that at <70.1°C gelatinization would only affect the amorphous regions. During the subsequent phase the crystalline regions destabilized by the amorphous component begin to gelatinize. For moisture content of 70%, wet basis, and a heating rate of 12°C/min, the enthalpy of gelatinization reaches a constant value of 7.3 J/g.     

Influence of Milk,Corn Starch,and Baking Conditions on the Starch Digestibility,Gelatinization, and Fracture Stress of Biscuits

Dough for nontraditional semisweet biscuits—prepared with wheat flour or replacing part of the wheat flour with corn starch, with or without skim milk—was baked at two oven temperatures, 120 or 170°C, until reaching moisture content and water activity lower than 6% and 0.5, respectively. Assays of fracture stress, differential scanning calorimetry, X‐ray diffraction, and starch digestibility were performed. Results showed that biscuits containing milk had the highest fracture stress, and biscuits baked at low temperature were harder than biscuits baked at high temperature. The degree of starch gelatinization during baking was higher when dough was baked at 170°C, compared with dough baked at 120°C. The decrease in gelatinization coincides with the decrease in the height and surface of peaks at 15 and 23° in the X‐ray diffraction patterns. Milk and corn starch did not affect the starch digestibility of biscuits, but biscuits baked at 170°C presented lower fracture stress and higher starch digestibility than biscuits baked at 120°C.     

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 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.     

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.     

压热-冻融循环处理对甘薯淀粉结构及物化特性的影响

为了探索压热冻融循环处理对甘薯淀粉结构及物化性质的影响,以甘薯淀粉为原料,并在不同淀粉乳浓度(5%、10%、20%,w/w)条件下进行重复的压热-冻融循环处理。结果表明,与甘薯原淀粉相比,经重复的压热-冻融处理后,甘薯淀粉颗粒形态消失,破裂熔融,最终呈不规则形状;甘薯淀粉衍射吸收峰强度减弱,晶型由A型向B型转化。随着淀粉乳浓度以及压热-冻融循环次数的增加,甘薯淀粉的膨胀势和溶解度均有所降低。在淀粉乳浓度为10%、压热-冻融循环1次处理后,甘薯淀粉中缓慢消化淀粉与抗性淀粉含量达到最高,分别为29.83%和39.82%。本研究为甘薯缓慢消化及抗性淀粉的制备提供了科学依据,为其在功能性食品领域中的应用提供了基础数据。     

Gelatinization and Retrogradation Kinetics of High‐Fiber Wheat Flour Blends: A Calorimetric Approach

The impact of dietary fiber (DF) mixtures on dough thermal properties needs to be investigated when designing high‐fiber wheat bread. Effects of flour replacement at different levels (6–34%) by soluble (inuline [FN]), partially soluble (sugar beet [FX], pea cell wall [SW]), and insoluble (pea hull [EX]) DF on wheat dough thermal profiles have been investigated by simulating baking, cooling, and storage in differential scanning calorimetry (DSC) pans. In general, DF incorporation into water‐flour systems delayed endothermic transition temperatures for both gelatinization and retrogradation phenomena except for the peak temperature (T_p) of retrogradation. With some exception, the pattern of the enthalpy of amylopectin retrogradation was lower and slower (lower constant of proportion, k) over 10 days of storage in gelatinized hydrated flour‐fiber blends when compared with control without DF. FX, a partially soluble fiber, provided major effects on gelatinization (T_p decrease and ΔH increase) and retrogradation kinetics (the Avrami exponent, n, increase). Single presence of EX allowed a significant reduction in the Avrami exponent n leading to slower kinetics for amylopectin retrogradation when included in the blends.     

高压对玉米淀粉糊化度影响的研究

采用差热扫描量热法（ＤＳＣ）研究了不同压力及保压时间对玉米淀粉糊化度的影响。在７００ＭＰａ压力下，保压２ｍｉｎ即可使８６．８％玉米淀粉糊化，达到一般食品加工要求；保压５ｍｉｎ，可使玉米淀粉１００％糊化，这是高压食品加工的一大优点     

Gelatinization Profiles of Triticale Starch in Cookies as Influenced by Moisture and Solutes

Starch physicochemical parameters and phase transitions were determined in flours of 10 advanced lines and cultivars of triticale (Cananea, Currency, Eronga, LA 24 Bve, LA 20 FCA, LA 83 FCA, Tatú, Tehuelche, Quiñé, and Yagan). Starch behavior was also analyzed during the baking of cookies prepared with triticale flours. Starch granule size, crystal type patterns, and size distribution were determined by light microscopy, X-ray diffraction, and gel-permeation chromatography, respectively. Two types and sizes of starch granules with characteristic A-form crystals were obtained in all samples tested. The Quiñé cultivar showed the lowest extent of starch crystallinity. Only a monophasic endotherm was found by differential scanning calorimetry for water content >50–60%. Gelatinization temperature and enthalpy values varied significantly among samples. A biphasic endotherm was detected for water contents between 35 and 60%, and no endothermic transitions were observed for water levels <35%. Only one endotherm corresponding to starch gelatinization was detected in baked cookies prepared with five triticale flours. In all samples, the highest enthalpy of gelatinization of starch was detected for the cookie surface, whereas the highest gelatinization temperature was observed for the center. These differences may be attributed to the presence and content of the solutes in cookie dough and also to the degree of starch gelatinization during the cooking process.     

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.