Investigation on morphological structure and crystal transition of maize starch gelatinized in pure glycerol

The gelatinization phenomena and crystalline structure of maize starch gelatinized in pure glycerol were investigated using confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). Starch granules were firstly treated in water system, CLSM and SEM micrographs displayed that they were completely broken and the characteristic birefringence of the starch granules disappeared at 70 °C. As for pure glycerol system, the starch granules swelled but maintained granular shape with the increasing of temperature. The crystalline structure of starch granules was partially destroyed at 130 °C and completely destroyed at 140 °C. The DSC thermogram showed that the gelatinization temperature of starch in glycerol started at 123.7 °C, peaked at 128.4 °C, and concluded at 135.2 °C. The X-ray diffractograms indicated that the crystalline structure of maize starch was partially destroyed at 130 °C and completely destroyed at 140 °C. Thus, glycerol served an alternative solvent to destroy crystalline structure of maize starch, which may be helpful for hydrolysis of starch granules by amylase in food industry.     

Glass transition temperature of starches with different amylose/amylopectin ratios

The glass transition temperatures (T_g) of starch with different amylose/amylopectin ratios were systematically studied by a high-speed DSC. The cornstarches with different amylose contents (waxy 0; maize 23, G50 50 and G80 80) were used as model materials. The high heating speed (up to 300 °C/min) allows the weak T_g of starch to be visible and the true T_g was calculated by applying linear regression to the results from different heating rates. It is confirmed for the first time, that the higher the amylose content is, the higher the T_g is for the same kind of starch. The sequence of true T_g of cornstarch is G80 > G50 > maize > waxy when samples contain the same moisture content, which corresponds to their amylose/amylopectin ratio. It was found that T_g was increased from about 52 to 60 °C with increasing amylose content from 0 to 80 for the samples containing about 13% moisture. The microstructure and phase transition were used to explain this phenomenon, in particular the multiphase transitions that occur in high-amylose starches at higher temperatures, and the gel-ball structure of gelatinized amylopectin.     

Properties of maize starch modified by ball milling in ethanol medium and low field NMR determination of the water molecular mobility in their gels

Ethanol as moisturizing agent and ball-milling treatment, has been combined in order to determine their impacts on the improvement of the properties of physically modified maize (Zea mays) starch granules. The content of ethanol has been set respecting a ratio of starch to ethanol varying from 1:0 to 1:3 (w:v), and the ball-milling time varied between 0 and 72 h. We observed that the increase of the amylose content varied in a more effective way with increase of the milling time (p < 0.05) than with the variation of the starch to ethanol ratios. As expected, modified starches were more transparent, more soluble, less crystalline, and presented damaged structures. In all cases, the starch granule sizes were better distributed at ratios of starch to ethanol of 1:0 and 1:3 (w:v) respectively. In addition, the impact of the combination of these treatments on the mobility of water molecules in starch gels characterized by the transverse relaxation time (T₂), as well as the abundance of protons (¹H T₂) in each populations were determined by low field NMR. Mobility of water molecules within starch gels increased at high temperature. Nonetheless, the proton population at T₂ > 10 ms (characterized by T₂₂) for the modified starch (starch/ethanol, 1:3 w:v) was fundamental in the different water concentrations, and accounts for 70 to 90% of total protons, at temperatures >60 °C.     

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.     

Improved viscoelastic zein–starch doughs for leavened gluten-free breads: Their rheology and microstructure

Gluten-free bread was prepared from commercial zein (20 g), maize starch (80 g), water (75 g), saccharose, NaCl and dry yeast by mixing above zein's glass transition temperature (T_g) at 40°C. Addition of hydroxypropyl methylcellulose (HPMC, 2 g) significantly improved quality, and the resulting bread resembled wheat bread having a regular, fine crumb grain, a round top and good aeration (specific volume 3.2 ml/g). In model studies, HPMC stabilized gas bubbles well. Additionally, laser scanning confocal microscopy (LSCM) revealed finer zein strands in the dough when HPMC was present, while dynamic oscillatory tests showed that HPMC rendered gluten-like hydrated zein above its T_g softer (i.e. |G*| was significantly lower). LSCM revealed that cooling below T_g alone did not destroy the zein strands; however, upon mechanical impact below T_g, they shattered into small pieces. When such dough was heated above T_g and then remixed, zein strands did not reform, and this dough lacked resistance in uniaxial extension tests. When within the breadmaking process, dough was cooled below T_g and subsequently reheated, breads had large void spaces under the crust. Likely, expanding gas bubbles broke zein strands below T_g resulting in structural weakness.     

Hydrolysis of granular corn starch with controlled pore size

Native corn (Zea mays L.) starch granules were hydrolyzed using glucoamylase at 50 °C for 1–8 h. The degree of hydrolysis over time was analyzed by the concentration of glucose released into solution. The pore sizes of hydrolyzed starch granules increased gradually with the degree of hydrolysis, as evidenced by scanning electron micrographs. It was deduced that every pore on the surface of granules was formed by hydrolysis of one enzyme molecule, so the size of pores distributed on the surface of starch granules was almost homogeneous for the same hydrolysis time. The specific surface area (S_BET), porosity, adsorptive capacity and mean pore radius of porous starch granules were determined to analyze the effect of digestion time on granule properties.     

A Continuous Measurement of Swelling of Rice Starch During Heating

The changes in size distribution of rice starch granules during heating have been determined continuously using a polarised light microscope in combination with a hot stage and an image analysis system. The size of starch granules increased slightly as the temperature was raised from 35°C to 55°C, with a 3·9% increase in average area; however, a dramatic increase in size of starch granules occurred at 65°C. The swelling of the starch granules reached a maximum 54·7% increase in average area at 75°C which is coincidental with the peak temperature (T_p) of DSC thermograms. Starch granules proceeded to disrupt/dissolve above 75°C. Loss of birefringence occurred at a lower temperature than granule rupture.T_pappeared to be the critical point in the phase change between the stages of swelling and disruption/dissolution of rice starch granules during heating.     

Extensive degradation of native starch granules by alpha-amylase from aspergillus fumigatus

Starch granules of various botanical origins were subjected to enzymic degradation by purified alpha-amylases from pig pancreas, Bacillus sp. and Aspergillus fumigatus (Aspergillus sp. K-27). With the A. fumigatus enzyme, glucose in alpha-anomeric configuration was the sole end degradation product regardless of the starch tested. The efficiency of this enzyme was very high on all native starch granules. Starches from normal and waxy maize, smooth pea and wheat were completely solubilised within 30 h using 1·34 nKat/mg of substrate. High-amylose maize, wrinkled pea and potato starches were degraded to lower extents (50, 70 and 45%, respectively). Such high enzymic efficiency was not observed with alpha-amylases from pig pancreas or Bacillus sp. With alpha-amylase from A. fumigatus, normal and waxy maize starches displayed highly eroded layered structures when observed by scanning or transmission electron microscopy during degradation. In contrast, potato and high-amylose maize starches produced a minor fraction of endo-eroded granules, whereas the rest of the granules exhibited superficial porosity.     

Effects of Amylose/Amylopectin Ratio and Baking Conditions on Resistant Starch Formation and Glycaemic Indices

The possible improvement of the nutritional properties of starch in barley flour-based bread by using barley genotypes varying in amylose content (3–44%) was evaluated. Breads were made from 70% whole-meal barley flour and 30% white wheat flour. Test breads were baked from waxy barley (WB), ordinary barley (OB), ordinary Glacier barley (OGB) and high-amylose barley (HAB). Each bread was baked either at conventional baking conditions (45 min, 200 °C) or at pumpernickel conditions (20 h, 120 °C). A white wheat bread (WWB) was used as reference. The resistant starch (RS) content and rate of starch hydrolysis were measuredin vitro. The glycaemic index (GI) and the insulinaemic index (II) of the high-amylose breads were determined in healthy subjects. The amount of RS (total starch basis) varied from <1% (WB) to approximately 4% (HAB) in conventionally baked bread, and from about 2% to 10% in the corresponding long-time/low-temperature baked products. The long-time/low-temperature baked HAB displayed a significantly lower rate of starch hydrolysisin vitrocompared with WWB and reduced the incremental blood-glucose response in healthy subjects (GI=71). In contrast, the GI of the conventionally baked HAB was similar to that for WWB. It is concluded that a barley flour-based bread of low GI and high RS content can be obtained by choosing high-amylose barley and appropriate baking conditions.     

Water mobility,rheological and textural properties of rice starch gel

Three rice starches from indica (TNuS19), japonica (TNu67) and waxy (TCW70) were used as samples to investigate the water mobility, viscoelasticity and textural properties of starch gels using pulsed nuclear magnetic resonance (PNMR), dynamic rheometer and texture analyzer. The spin–spin relaxation time (T₂), showed water mobility of starch gels was detected with starch concentrations 10–30%. Generally, the TNuS19 and TNu67 at ≥20% showed two components (T_2a and T_2b) in water mobility, where T_2a and T_2b related to solid-like and liquid-like water molecules in starch gels, respectively. However, the TCW70 over the concentrations examined had only T_2b component, higher than those of corresponding TNuS19 and TNu67. The storage (G′) and loss (G″) moduli of starch gels were in the order of TNuS19 > TNu67 > TCW70. Texture analyzer analysis indicated that TNuS19 had higher hardness, stickiness and adhesiveness than did the TNu67 and TCW70, and changed significantly with the starch concentration increase. The value of T_2b was highly correlated with physical properties of starch gels, especially with dynamic rheological parameters. It is suggested that amylose content may play a major role to influence the water mobility of starch gels which affects the specific viscoelasticity and textural properties of starch gels.     

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.     

Study of kernel structure of high-amylose and wild-type rice by X-ray microtomography and SEM

Rice kernels of a transgenic high-amylose rice line and its wild type were examined by a high-resolution X-ray microtomography (XMT) and an environmental scanning electron microscope. Two-dimensional (2-D) cross-sectional images and 3-D objects from XMT were reconstructed and analyzed to elucidate their structural features. The lack of two isoforms of starch branching enzyme, termed SBEI and SBEIIb in high-amylose rice (HAR), resulted in a distinctly different grain inner density than wild-type rice (WTR). HAR had smaller, elongated starch granules with air spaces inside the kernels resulting in an opaque grain, whereas WTR had a tight endosperm with little air space and polygonal starch granules. XMT allowed a full 3-D characterization of the rice kernel structure and revealed that air space distribution was not uniform in the HAR kernel.     

Thermal requirements for barley maturation and leaf development in interior Alaska

Spring barley (Hordeum vulgare L.) is well adapted to the cool and short growing season of interior Alaska but little is known about thermal requirements for development and maturation of barley at such latitudes. Air temperature and barley development were monitored over the course of six growing seasons at Fairbanks (65°N) and Delta Junction (64°N), Alaska. These data were used to assess the base temperature (T_b) in the linear, thermal-unit model using the least variable, x-intercept, and regression coefficient methods. These methods indicated a range in T_b from 0°C to 1.5°C. At a T_b of 0°C, barley required nearly 1100°C d to mature. The phyllochron differed between early and late sowings and averaged 75°C d leaf⁻¹. Sowing date appeared to influence the phyllochron during early vegetative growth due to differences in daylength as well as temperature.     

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.     

Thermoplastic starch modified during melt processing with organic acids: The effect of molar mass on thermal and mechanical properties

Thermoplastic starch (TPS) was modified with ascorbic acid and citric acid by melt processing of native starch with glycerol as plasticizer in an intensive batch mixer at 160 °C. It was found that the molar mass decreases with acid content and processing time causing the reduction in melting temperature (T_m). As observed by the results of X-ray diffraction and DSC measurements, crystallinity was not changed by the reaction with organic acids. T_m depression with falling molar mass was interpreted on the basis of the effect of concentration of end-chain units, which act as diluents. FTIR did not show any appreciable change in starch chemical compositions, leading to the conclusion that the main changes observed were produced by the variation in molar mass of the material. We demonstrated that it is possible to decrease melt viscosity without the need for more plasticizer thus avoiding side-effects such as an increase in water affinity or relevant changes in the dynamic mechanical properties.     

Comparison of structural features of reconstituted doughs affected by starches from different cereals and other botanical sources

Starch, as the main component of flour products, determines the physicochemical properties of dough. This work investigated the relationship of the physical properties of seven types of starches from various cereals with the structural features of reconstituted dough. Results of mixing and tensile properties analysis and scanning electron microscopy displayed that rice reconstituted flour exhibited maximum water absorption; pea reconstituted flour had higher dough stability; sweet potato dough had higher tensile resistance; highland barley dough had the greatest extensibility. Moisture distribution analysis revealed that various model dough showed remarkably different water distribution, which was distributed at T₂₁ (0.07–0.11 ms), T₂₂ (0.8–2.66 ms) and T₂₃ (10.0–20.82 ms). Correlation analysis indicated that large starch granules associated with good dough stability; amylose content of starch positively affected tensile resistance of dough; crystallinity of starch showed negative effects on water absorption; starch with higher crystallinity associated with greater dough stability.     

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

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

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.     

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.     

Thermal stability and pyrolysis kinetics of organosolv lignins obtained from Eucalyptus globulus

In the present work, thermogravimetric analysis of 17 organosolv lignin samples was carried out to determine their thermal stability and calculate the kinetic parameters of their pyrolysis. The thermal stability has been estimated by the measurement of the degradation temperature (T_d), calculated according to the maximum reaction rate. In addition, degradation temperature at 10% of conversion (T_10%) has been obtained in order to compare the initial stability of the samples with T_d for all samples. The values of T_d are comprised between 262 and 389 °C and the average value is 340 °C. The range for T_10% is 251–320 °C and the average value is 270 °C. The ashes content of the samples has been analyzed and all the residues presented values lower than 4 wt%. Kinetic parameters of lignin pyrolysis were calculated by Borchardt–Daniels’ method assuming nth order reaction. The activation energy values obtained are comprised between 17.9 and 42.5 kJ/mol and the average value is 28.1 kJ/mol. These results are in agreement with the bibliography.