Investigation of the high-amylose maize starch gelatinization behaviours in glycerol-water systems

The effect of glycerol on gelatinization behaviours of high-amylose maize starch was evaluated by confocal laser scanning microscopy (CLSM), scanning electronic microscope (SEM), differential scanning calorimetry (DSC), texture analyzer (TPA) and rheometer. Gelatinization of the high-amylose maize starches with glycerol content of 10% (w/w) began at 95.4 °C (T_o), peaked at 110.3 °C (T_p), and completed at 118.9 °C (T_c). The birefringence began to disappear at around 100 °C and finished at 120 °C which corresponded well to the onset and conclusion temperatures obtained by DSC. The high-amylose maize starch granules maintained original morphological structure at 100 °C and swelled to a great degree at 110 °C. The high-amylose maize starch paste formed at 100 °C showed the lowest hardness (39.92 g), while at 120 and 130 °C, showed the highest hardness (610.89 g and 635.43 g, respectively). It should be noted that in going from 100 °C to 110 °C there is a significant increase in the viscosity of the slurry solution. The identical apparent viscosity was observed when the shear rate exceed 100 s⁻¹, resulting from the high-amylose maize starch granules were completely gelatinized at 120 °C, which was consistent with DSC analysis.     

Interaction of granular maize starch with lysophosphatidylcholine evaluated by calorimetry, mechanical and microscopy analysis

In this study we evaluated the thermo-mechanical properties of maize starch pastes (80% wt/wt) under the effect of exogenous lysophosphatidylcholine (LPC) using differential scanning calorimetry (DSC), dynamic mechanical spectrometry (DMS), and scanning electron microscopy (SEM). Particular attention was paid to the development of the amylose-LPC inclusion complex. Results from SEM and DSC showed that with no exogenous LPC, granular maize starch developed the amylose network structure for starch gelling at 80–95 °C. In comparison, at 1.86 and 3.35% of LPC, heating up to 130 °C was needed to develop the three-dimensional network required for starch gelling. Results showed that at these LPC concentrations LPC interacted mainly with amylose within the starch granule. At concentrations ≥8.26% the LPC interacted with amylose both inside the granule and on the granule's surface. At such LPC concentrations heating to 130 °C did not fully develop the starch network structure for gelling. These results suggested that a higher thermal stability was achieved by starch granules because of LPC inclusion complex formation. DSC or DMS did not detect the development of this complex, probably because its formation took place below the onset of gelatinization under conditions of limited molecular mobility. Subsequently, a lower level of organization (i.e. complex in form I) was achieved than in the complex developed at high temperature and water excess (i.e. complex in form II). On the other hand, the changes in the starch granule structure observed by SEM as a function of the time–temperature variable were well described by the phase shift angle (δ) rheograms for starch pastes with and without addition of LPC.     

Structural,rheological and gelatinization properties of wheat starch granules separated from different noodle-making process

In this study, three typical wheat cultivars (ZM366, AK58, and ZM103) with high, medium, and low gluten strength, respectively, were selected as the raw material. The starch granules separated from different stages of the noodle-making process, including kneading, resting, sheeting, cutting, and drying, were used to explore the structure, dynamic rheology, and quality of the noodles. The D50 (median diameter) of the starch granules decreased during the noodle-making process, and the reduction was enhanced by an increase in the gluten strength of the flour. Between steps 4 and 5 of the noodle-making process, the solubility of ZM103 variety increased from 4.3% to 5.0% at 80 °C, while the peak viscosity decreased from 3626 to 3386 mPa s, which resulted in a decrease in the cooking loss of noodles. Similar trend was observed in the ZM366 and AK58 varieties. The gelatinization enthalpy was reduced, suggesting that the crystalline regions of the starch granules were destroyed during the kneading process. Between steps 4 and 5 of the noodle-making process, the elastic modulus of the starch granules significantly increased, while the temperature at which maximum elastic modulus was decreased, indicating an increase in the crystalline stability of starch during the drying process. Correlation analysis indicated that the changes occurred to the gelatinization property was primarily due to the change in the particle size.     

Morphologies and microstructures of cornstarches with different amylose–amylopectin ratios studied by confocal laser scanning microscope

The morphologies and microstructures of cornstarches with different amylose–amylopectin ratios (waxy: 0/100; maize: 23/77; Gelose 50: 50/50; and Gelose 80: 80/20) were studied by a confocal laser scanning microscope (CLSM). The temperature-induced changes of the cornstarch granules in excess of water were also studied under CLSM. Acid hybridization of starch by HCl was used to enhance the difference between amorphous and crystalline ranges. It was found that the high-amylose starches (G50 and G80) were brighter than those of low-amylopectin starches (waxy and maize) under confocal laser light, and the average (decreasing) fluorescence intensity sequence of the granules was G80 > G50 > maize > waxy. Waxy and maize starches showed clear internal cavities and channels, whilst G50 and G80 had bright cores. Sharp growth ring structures can be clearly observed for low-amylose starches (waxy and maize) after acid hydrolysis. Gelatinization of all starches starts at the hilum and the adjacent of the channels, and spreads rapidly to the periphery. This work is the first time that three-dimensional images of partly gelatinized granules have been constructed and presented from different confocal images, which allows further exploration of the mechanisms of gelatinization.     

Modification of physicochemical properties and in vitro digestibility of wheat flour through superheated steam processing

Native and moistened wheat flours (moisture contents were 13.5 and 27.0%, respectively) were treated with superheated steam (SS) at different temperatures (140 and 170 °C) and times (1, 2 and 4 min). Their physicochemical and digestive properties were analyzed. For native flour, SS treatment altered the starch molecular structure and behavior slightly. While for moistened flour, crystalline degree, gelatinization enthalpy, amylose leaching (AML) and falling number significantly decreased, but thermal transition temperatures increased with the rise of treating severity. Clumping of starch granules, aggregation of proteins and formation of amylose-lipid complexes occurred in both native and moistened flours. Broader pasting temperature ranges and higher viscosities were found on SS-modified flours. Additionally, SS treatment on moistened flours increased resistant and slowly digestible starch contents. In general, SS treatment induced changes in starch molecular structure and reactions among flour components leading to more stable structures, thus affecting their pasting behavior, thermal properties and in vitro digestion.     

A comparison study on phase transition and structure of cornstarch in dimethyl sulfoxide and ionic liquid systems

A comparison study of the phase transition and structure of waxy cornstarch in DMSO and AMIMCl systems was conducted using a differential scanning calorimeter, an optical microscope, a scanning electron microscope, X-ray diffraction and thermogravimetric analysis. A full disruption and dissolution of starch granules was completed in 10 h at room temperature in pure DMSO, which was faster and more effective than that in ionic liquid 1-allyl-3-methylimidazolium chloride (AMIMCl). When dispersed in DMSO/water and AMIMCl/water at various ratios, respectively, different phase transitions were clearly exhibited, and the appearance and crystal structure of starch granules were significantly damaged with an increase in the concentration. Basing on the study of the decomposition temperature change through TGA measurements, a decreased temperature was observed in both DMSO and AMIMCl system, meaning starch degradation occurred with different levels. The huge temperature change from 357 to 328 °C were found in AMIMCl system, which most likely induced the distinct exothermic phenomenon in the DSC observation due to a significant depolymerization of starch.     

Effect of jet-cooked wheat gluten/lecithin blends on maize and rice starch retrogradation

Vital wheat gluten and lecithin (GL) (50:50, w/w) were dry blended in a coffee grinder and a 9.5% (w/v) aqueous slurry was jet-cooked (steam pressures of 65 psi/g inlet and 40 psi/g outlet) to disaggregate wheat gluten and facilitate better dispersion of the two components. The jet-cooked material was freeze-dried and stored at 0 °C for future use. The GL blend was added to pure food grade common maize and rice starch at concentrations of 0 (control), 6, 11, 16, and 21%. Starch gelatinization and retrogradation temperature transitions were determined using Differential Scanning Calorimetry (DSC). From the DSC profiles, the change in the ΔH value was used as an indication of starch retrogradation, where a higher ΔH value indicated higher retrogradation. The ΔH values of the blends at 4 °C had higher values than the −20 °C and the ambient (25 °C) storage temperatures. Overall, the 21% GL/starch blends reduced retrogradation by 50%. The lower amylose content of rice starch relative to maize starch was reflected in Rapid Visco Amylograph (RVA) measurements of peak viscosity, and similarly, Texture Analyzer (TA) measurements indicated that maize starch gel is firmer than rice starch gel. Retrogradation was also evaluated by observing G′, the shear storage modulus, as a function of time after running a standard pasting curve. Using this method, it appears that GL has a significant effect on maize starch retrogradation, since low concentrations (<0.4%, w/w) reduced G′ up to 40%. The opposite behavior was seen in rice starch, where G′ increased directly with added GL. It appears that the amylose level in the rice starch is too low to be affected by the GL, and the increase seen in G′ is most likely due to added solids.     

Effect of glutathione on gelatinization and retrogradation of wheat flour and starch

Reduced glutathione (GSH) commonly exists in wheat flour and has remarkable influence on gluten properties. In this study, effect of GSH on the gelatinization and retrogradation of wheat flour and wheat starch were investigated to better understand the GSH-gluten-starch interactions in wheat flour. Compared with wheat starch, wheat flour showed significant decreases in peak and final viscosity, and gelatinization onset temperature with increasing GSH concentration. GSH depolymerized gluten and thereby broke down the protein barrier around starch granules to make the starch easily gelatinized. However, the interaction between GSH and wheat starch restrained starch swelling. GSH addition resulted in weakened structure with higher water mobility in freshly gelatinized wheat flour dispersions but decreased water mobility in wheat starch dispersions. After storage at 4 °C for 7 d, GSH increased elasticity and retrogradation degree in wheat flour dispersions but retarded retrogradation in wheat starch dispersions. The results indicated that GSH promoted retrogradation of wheat flour, which mainly attributed to the depolymerized gluten embedding in the leached starch chains, and inhibiting the re-association of amylose, and subsequently promoted the starch intermolecular associations and starch retrogradation. This study could provide valuable information for the control of the quality of wheat flour-based products.     

Crystallinity changes in wheat starch during the bread-making process: Starch crystallinity in the bread crust

The crystallinity of starch in crispy bread crust was quantified using several different techniques. Confocal scanning laser microscopy (CSLM) demonstrated the presence of granular starch in the crust and remnants of granules when moving towards the crumb. Differential scanning calorimetry (DSC) showed an endothermic transition at 70 °C associated with the melting of crystalline amylopectin. The relative starch crystallinity, as determined by X-ray and DSC, from different types of breads was found to lie between 36% and 41% (X-ray) and between 32% and 43% (DSC) for fresh bread crust. Storage of breads in a closed box (22 °C) for up to 20 days showed an increase in crust crystallinity due to amylopectin retrogradation both by X-ray and DSC. However, DSC thermograms of 1-day old bread crust showed no amylopectin retrogradation and after 2 days storage, amylopectin retrogradation in the crust was hardly detectable. ¹³C CP MAS NMR was used to characterize the physical state of starch in flour and bread crumb and crust. The intensity of the peaks showed a dependence on the degree of starch gelatinization.     

Changes in the thermal and structural properties of maize starch during nixtamalization and tortilla-making processes as affected by grain hardness

The objective of this work was to evaluate the changes in the thermal and structural properties of maize starch during nixtamalization and the tortilla-making process and their relationship with grain hardness. Three maize types with varying hardness (hard, intermediate, soft) were processed by three nixtamalization processes (classic, traditional and ecological). Starch from the three maize types showed an A-type pattern and two endotherms corresponding to gelatinization and melting of the Type I amylose-lipid complexes. After cooking and steeping, in intermediate and soft grains the partial gelatinization and the annealing affected the starch properties and promoted the formation of amylose-lipid complexes. These effects were not observe in hard grains. The increase in melting enthalpy and the intensity of the peak 2θ∼20° from nixtamal to tortillas demonstrated the formation of amylose-lipid complexes. A third endotherm above 114 °C in some treatments of nixtamal and tortilla starch demonstrated the transformation of some amylose-lipid complexes in a most ordered structures (Type II complexes). The V-type polymorph structure found in native starch, nixtamal, and tortilla corresponds to a coexistence of Type I and Type II complexes. Formation of amylose-lipid complexes in tortillas had a partial effect on decreasing starch retrogradation (r = −0.47, P < 0.05).     

In vitro starch digestibility and predicted glycaemic indexes of buckwheat,oat, quinoa,sorghum, teff and commercial gluten-free bread

The in vitro starch digestibility of five gluten-free breads (from buckwheat, oat, quinoa, sorghum or teff flour) was analysed using a multi-enzyme dialysis system. Hydrolysis indexes (HI) and predicted glycaemic indexes (pGI) were calculated from the area under the curve (AUC; g RSR/100g TAC*min) of reducing sugars released (RSR), and related to that of white wheat bread. Total available carbohydrates (TAC; mg/4 g bread “as eaten”) were highest in sorghum (1634 mg) and oat bread (1384 mg). The AUC was highest for quinoa (3260 g RSR), followed by buckwheat (2377 g RSR) and teff bread (2026 g RSR). Quinoa bread showed highest predicted GI (95). GIs of buckwheat (GI 80), teff (74), sorghum (72) and oat (71) breads were significantly lower. Significantly higher gelatinization temperatures in teff (71 °C) and sorghum flour (69 °C) as determined by differential scanning calorimetry (DSC) correlated with lower pGIs (74 and 72). Larger granule diameters in oat (3–10 μm) and sorghum (6–18 μm) in comparison to quinoa (1.3 μm) and buckwheat flour (3–7 μm) as assessed with scanning electron microscopy resulted in lower specific surface area of starch granules. The data is in agreement with predictions that smaller starch granules result in a higher GI.     

Effect of annealing from traditional nixtamalisation process on the microstructural,thermal, and rheological properties of starch and quality of pozole

Eleven maize landraces were evaluated for pozole quality. The microstructural, thermal and rheological properties of annealed starch granules determine most of the quality of pozole. Annealed starch in traditional nixtamalisation has an important role in increasing gelatinisation onset (To), peak (Tp) and final (Tf) temperatures; peak, setback and final viscosity as well as the stability of the starch granule, all of which significantly affect pozole quality. Annealed starch in Cacahuacintle nixtamal (pozole end-use) increased temperatures To, Tp and Tf by >5.2, >3.8 and >4.1 °C respectively, and narrowed the range Tf − To from 13.78 to 12.62 °C. The enthalpy was reduced from 6.76 to 5.85 J/g, while the nixtamal starch in tortilla maize landraces presented fewer annealing effects. The annealing effect in nixtamal starch seems to stabilize the starch granules and avoid their collapse, compared to native starch, as shown by the X-ray diffraction peak intensity and pattern that is similar to unprocessed maize. Starch in nixtamal changes from Type A to Type V pattern in pozole. Kernel physical parameters, although important, affected the quality to a lesser extent, with the exception of the flotation index. Cacahuacintle maize landrace showed the best quality and yield as well as a short pozole cooking time.     

Starch gelatinization distribution and peripheral cell disruption in cooking rice grains monitored by microscopy

Starch gelatinization kinetics governs rice cooking behaviour (cooking time and texture). Starch gelatinization however occurs unevenly in the cooking grain. The aim of this study was to investigate the dynamics of starch gelatinization topography in rice kernels cooked in excess water at two temperatures: 75 °C and 95 °C, for times ranging from 5 to 30 min. Gelatinization front position was assessed over time on 40 μm cross sections using four different tracking methods: directly or after iodine staining using a microscope or a stereomicroscope under normal or polarized light. The four methods gave similar results and the obtained kinetics can be used to model starch gelatinization during grain cooking.In parallel, changes in the structure of the peripheral area of cooked grains were investigated on 3 μm cross sections under the same cooking conditions. Microscopic observations by auto fluorescence and after iodine staining revealed dynamic peripheral cell disruption at the same time as starch gelatinization, which may have a major impact on starch leaching and hence on the textural properties of the cooked grain.     

Modelling starch phase transitions and water uptake of rice kernels during cooking

To model the cooking processes of rice, starch gelatinization, the level of fusion of the amylose-lipid complex, and equilibrium water uptake have to be known for any given condition. Starch phase transitions were measured by DSC in two milled Korean round rice kernels whose water contents ranged from 0.18 to 4.7 g g⁻¹ db. Two to three partially overlapping transitions were assessed. Starch thermal transitions were modelled using a double step approach. First, a mechanistic double sigmoid model was fitted with DSC data for any water content value. Each parameter of the mechanistic model was then modelled with conservative empirical water content functions. In this way we obtained an explicit form of phase transition levels as a function of both temperature and water content. In parallel, the water uptake kinetics of rice kernels was determined in the temperature range of 50 °C–100 °C. Equilibrium water uptake was found to be linked to starch phase transitions and a model was built to calculate equilibrium water uptake as a function of modelled starch gelatinization and amylose-lipid complex fusion levels.     

The Effect of Heat–Moisture Treatment on the Structure and Physicochemical Properties of Normal Maize,Waxy Maize,Dull Waxy Maize and Amylomaize V Starches

Normal maize, waxy maize, dull waxy maize and amylomaize V starches were heat treated at 100 °C for 16 h at a moisture content of 30%. The results showed that the X-ray intensities of the major d-spacings of all starches increased on heat–moisture treatment (waxy maize > normal maize > dull waxy maize > amylomaize V). This treatment decreased the apparent amylose content (amylomaize V > normal maize), swelling factor (amylomaize V > waxy maize > dull waxy maize > normal maize), amylose leaching (amylomaize V > normal maize), pasting viscosities (amylomaize V > normal maize), acid hydrolysis (amylomaize V > normal maize > waxy maize > dull waxy maize), enzyme hydrolysis (amylomaize V > normal maize > dull waxy maize > waxy maize) and syneresis (amylomaize V > normal maize > waxy maize ≈ dull waxy maize). The gelatinization transition temperatures of all starches increased on heat–moisture treatment (amylomaize V > normal maize > waxy maize > dull waxy maize). However, the gelatinization temperature range increased only in normal maize and amylomaize V starches (amylomaize V > normal maize), while it remained unchanged in both the waxy starches. The enthalpy of gelatinization remained unchanged on heat–moisture treatment in all starches and the pasting viscosities of the two waxy starches were also unaffected. The foregoing data showed that starch chains within the amorphous and crystalline regions of the granule associate during heat–moisture treatment. However, the extent of this association was of a greater order of magnitude within the amorphous regions. DSC studies have indicated associations involving amylose chains (amylose–amylose and amylose–native starch lipids) resulted in the formation of new crystallites of different stabilities. In contrast, associations involving amylopectin chains (amylopectin–amylopectin) did not lead to crystallite formation.     

Synthesis and characterization of polyurethane-based side-chain cholesteric liquid crystal polymers

Polyurethane-based side-chain cholesteric liquid crystalline polymers (ChLCPs) with variable clearing temperatures were synthesized in a two-step reaction. The chemical structures of ChLCPs were confirmed by FT-IR and ¹H-NMR spectroscopy. The mesogenic properties and phase transition behavior were investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction measurements. The DSC studies show that the melting temperature and isotropic transition temperature of the ChLCPs increased with the weight percentage of cholesterol in the polymer. POM shows that the ChLCPs had a distinct spherulite structure that melted at about 140 °C, and these results are consistent with those of the DSC studies. The thermogravimetric studies show that the ChLCPs were stable up to 200 °C, though there was a reduction in the thermal stability as the weight proportion of cholesterol and glycerol in the polymer increased.     

Morphological and structural studies of thermally treated starch-fatty acid systems

A series of starch-fatty acid samples were prepared using three types of starches differing in their amylose content i.e. maize, pea and amylomaize and three fatty acids differing in their chain length; i.e. myristic, palmitic and stearic. Two different modes of heating the starch systems were employed; i.e. either prior to the addition of the acid to starch aqueous dispersions or after heating the dispersions at the predetermined temperatures 75, 85 or 98 °C. Light and SEM microscopic examination indicated that amylose-fatty acid interactions taken place during starch gelatinization retarded the destruction of the granules depending on the heating temperature. XRD studies revealed that the degree of crystallinity exhibited by the starch samples was dependent on the amylose content, the fatty acid chain length and the modes of heating employed.     

Effects of Early- and Late-Sowing on Starch Accumulation and Associated Enzyme Activities During Grain Filling Stage in Rice

The environmental temperature occurring during the grain filling stage is an important factoraffecting starch synthesis and accumulation in rice. We investigated starch accumulation, amylaseactivity and starch granule size distribution in two low-amylose japonica rice varieties, Nanjing 9108 andFujing 1606, grown in the field at different filling temperatures by manipulating sowing date. The two ricevarieties exhibited similar performances between two sowing dates. Total starch, amylose andamylopectin contents were lower at the early-filling stage of T1 treatment (Early-sowing) compared withthose at the same stage in T2 treatment (Late-sowing). In contrast, at the late-filling stage, when fieldtemperatures were generally decreasing, total starch and amylopectin contents in T1 were highercompared to those in T2. The ideal temperature for strong activity of ADP-glucose pyrophosphorylaseand soluble starch synthase was about 22℃. A higher temperature from the heading to maturity stagesin T1 increased the activities of starch branching enzyme and suppressed the activities of granule boundstarch synthetase and starch debranching enzyme. We found that rice produced larger-sized starchgranules under the T1 treatment. These results suggested that due to the early-sowing date, the hightemperature (30℃) occurring at the early-filling stage hindered starch synthesis and accumulation,however, the lower temperatures (22 ℃) at the late-filling stage allowed starch synthesis and accumulationto return to normal levels.     

Effect of quick-freezing temperature on starch retrogradation and ice crystals properties of steamed oat roll

Oat roll is one of the traditional oat wholemeal foods. The purpose of this work was to investigate the effects of quick freezing at −20 °C, −40 °C and −80 °C for 90 min before frozen storage on the quality of frozen steamed oat roll. Quick freezing at −40 °C and −80 °C inhibited the increase of peak gelatinization temperature, enthalpy and the ordered degree of oat roll starch, therefore postponing starch retrogradation. The cross-section microstructure confirmed that reducing the quick-freezing temperature could prevent the increase of ice crystals size, ruptured structures and maintain the integrity of internal structure. As the storage time extend, the ice recrystallization led to an increase in size of ice crystals, while a decrease in their number. Frozen steamed oat roll starch had the highest swelling power at the quick-freezing temperature of −80 °C, that indicated strongest water absorption and binding ability when gelatinized again. Texture analysis demonstrated that hardness increased during frozen storage, quick freezing at −80 °C had the best texture properties. Therefore, declining the quick-freezing temperature could obtain a higher quality of frozen steamed oat roll, by means of delaying the starch retrogradation and minimising the size of ice crystals.     

Gelation characteristics of Mesona chinensis polysaccharide-maize starches gels: Influences of KCl and NaCl

An investigation was conducted into the effects of potassium chloride (KCl) and sodium chloride (NaCl) on the gelation properties of maize starch-Mesona chinensis polysaccharide (MCP) gels. Waxy maize starch (WS), normal maize starch (NS), and high amylose maize starch (HS) were used to compare the effects of different amylose contents on the gel properties of maize starch-MCP gels. The results showed that KCl and NaCl have similar effects on the gelation, rheological, and structural properties of maize starch-MCP gels. The addition of KCl and NaCl increased the pasting viscosity, breakdown values, setback values, dynamic modulus, and apparent viscosity of maize starch-MCP gels, especially for HS-MCP gels. LF-NMR (Low-field nuclear magnetic resonance) showed that salts reduced bound water content while increasing the free water content of maize starch-MCP gels. CLSM (Confocal laser scanning microscopy) results also indicated that salt can restrict the expansion and maintain the integrity of starch granules, especially for WS-MCP gels.