Water Redistribution and Structural Changes of Starch During Storage of a Gluten‐free Bread

The objective of the present work was to analyze molecular and supramolecular changes of bread starch and to relate bread firmness increase during storage with starch recrystallization and water hydration levels and migration in gluten‐free bread. At the studied conditions starch was in the supercooled region of the state diagram, at a temperature between T_g (glass transition temperature) and T_m (melting temperature), feasible to crystallize. The crystalline degree during storage was followed by the intensity increase in the X‐ray diffraction peaks. During bread storage, water migration occurred from the crumb towards the crust. Water amount and redistribution affected the kind of starch crystallites formed and firmness of aged bread. It was not the total amount of crystalline fraction that determined bread firmness, but the type of crystallites formed. These observations are a further evidence that bread firmness development and starch recrystallization, although being related phenomena, are obviously separate events.     

Effect of Heat‐Moisture Treatment on Structural and Thermal Properties of Rice Starches Differing in Amylose Content

Starches from glutinous rice (1.4% amylose), Jasmine rice (15.0% amylose) and Chiang rice (20.2% amylose) were exposed to heat‐moisture treatment (HMT) at 100 °C for 16 h and at different moisture levels (18, 21, 24 and 27%). The effect of heat‐moisture treatment on structural and thermal properties of these three rice starches was investigated. The HMT did not change the size, shape and surface characteristics of rice starch granules. The A‐type crystalline pattern of rice starches remained unchanged after HMT. The relative crystallinity (RC) and the ratio of short‐range molecular order to amorphous (RSA) of heat‐moisture treated glutinous and Jasmine rice starches decreased with increasing moisture level of the treatments. In contrast, the RC of the treated Chiang rice starch remained practically unchanged. A peak of crystalline V‐amylose‐lipid complexes was clearly presented in all treated Chiang rice starches. The peak became progressively stronger with increasing moisture level of the treatment. Differential scanning calorimetry (DSC) of all treated rice starches showed a shift of the gelatinization temperature to higher values. Increasing moisture level of the treatments increased the onset gelatinization temperature (T_o) but decreased the gelatinization enthalpy (ΔH) of rice starches. A broad gelatinization temperature range (T_c‐T_o) with a biphasic endotherm was found for all treated Chiang rice starches and Jasmine rice starch after HMT₂₇ (HMT at 27% moisture level). Additionally the (T_c‐T_o) of treated Chiang rice starches increased linearly with increasing moisture level of the treatments.     

Aliphatic Amidediol and Glycerol as a Mixed Plasticizer for the Preparation of Thermoplastic Starch

The synthesis of 2‐hydroxy‐N‐[2‐(2‐hydroxy‐propionylamino)‐ethyl]propionamide (“aliphatic amidediol”) is described. Aliphatic amidediol and glycerol were used as a novel mixed plasticizer for corn starch to prepare thermoplastic starch. Fourier transform infrared (FT‐IR) spectroscopy proved that the mixture of aliphatic amidediol and glycerol could form more stable and strong hydrogen bonds with starch molecules than glycerol alone. By scanning electron microscopy (SEM) and X‐ray diffraction (XRD) it was proven that native starch granules and crystalline structures were broken and starch was plasticized. Tensile testing revealed that TPS plasticized by aliphatic amidediol and glycerol (AGPTPS) showed a better mechanical properties than TPS plasticized by glycerol (GPTPS). Furthermore, the water resistance of AGPTPS was better than that of GPTPS. In addition, dynamic mechanical thermal analysis (DMTA) showed that both storage modulus and glass transition temperature (T_g) of AGPTPS were higher than those of GPTPS.     

Subzero Glass Transition of Waxy Maize Starch Studied by Differential Scanning Calorimetry

A mixture of waxy maize starch and water (1:2, w/w) was heated in a differential scanning calorimeter (DSC) pan to different temperatures to obtain different degrees of gelatinization. Each pan was then quenched to ‐30°C and rescanned, and the subzero glass transition temperature (T_g′) of the content was determined. A three‐phase model of a starch granule—a mobile amorphous phase, a rigid amorphous phase, and a crystalline phase—was used to interpret results and explain the glass transitions in starch. Waxy maize starch had an onset gelatinization temperature (T_o) of 61.5°C, peak temperature (T_p) of 70.3°C, and completion temperature (T_c) of 81.7°C. The T_g′ was clearly noted after the starch and water mixture was heated to T_p and T_c, but was small and barely observable when the mixture was heated up to T_o and immediately cooled to ‐30°C. When the starch and water mixture was heated to 55°C, which was 6°C below the T_o, and held for 2 h, a T_g′ was observed. Moreover, T_g′ began to appear and was observable if the starch and water mixture was heated to 10°C below gelatinization onset temperature (51°C) and annealed for 2 h without any gelatinization. Further holding at ‐7°C showed a clear subzero glass transition of annealed native starch granules.     

Rheological and Thermal Properties of Extruded Mixtures of Rice Starch and Isolated Soy Protein

Many foods gain new mechanical, thermal and textural properties after being processed due to interactions between carbohydrates and proteins. This effect is characteristic for each foodstuff. The properties of extruded isolated soy protein (ISP) and rice starch were studied considering the following extrusion variables: starch proportion with respect to ISP (0–100%), pH (3–9), moisture content (20–30%) and temperature (140–180ºC). The following characteristics were measured: Water absorption index (WAI), water solubility index (WSI), glass transition temperature (T_g), melting temperature (T_m), viscosity at 90ºC and at 50ºC, storage (G′), loss modulus (G′′) and tan δ. The results indicate that the extruded starch exhibits higher WAI and WSI values than untreated starch. For extruded ISP these values are much lower than for untreated ISP. Extrudates with higher starch proportion had higher T_g and T_m values; pH has a significant effect (p<0.05), at pH 3 higher T_g values were observed, and at pH 9 higher values of T_m. The highest viscosities at 90ºC and 50ºC were observed for extrudates with a higher starch proportion and pH 9. Extruded mixtures showed a more elastic than viscous behavior and an extruded 1:1 blend of starch‐ISP exhibited the behavior of a viscous liquid.     

INFLUENCE OF GLASS TRANSITION TEMPERATURE ON RATE OF RICE STARCH RETROGRADATION DURING LOW-TEMPERATURE STORAGE

An increasing amount of research suggests a relationship between the glass‐transition temperature (T_g) and the optimum storage temperature for a frozen food. In addition, the T_g for a frozen food is related to the cooling rate through the temperature range of phase transition for water. The objectives of this study were to investigate the influence of T_gon the rate of starch retrogradation during low‐temperature storage. Rice starch with 65% w/w water content was heated to obtain starch gel as a model food. The influences of cooling rate, storage temperature and time on rate of retrogradation were evaluated. Differential scanning calorimetry was used to measure the T_gand the enthalpy during retrogradation. Results indicated that the retrogradation rate during storage was reduced at a slower cooling rate. The retrogradation rates at storage temperatures above T_gwere higher than at storage temperatures below T_g.     

The effect of starch gelatinization and solute concentrations on T g′ of starch model system

The effect of starch gelatinization on glass transitions in a starch/water model system and how the concentrations of added solutes (sucrose and sodium chloride) affect the glass transition temperatures of the gelatinized starch solution was investigated. The starch suspension samples were heat treated in a Differential Scanning Calorimeter (DSC) under different time and temperature regimes to achieve different degrees of gelatinization. The gelatinization characteristics (onset, peak and end temperatures and enthalpy) and the glass transition values of a potato starch were determined using the DSC. The results showed that the starch concentrations had no effect on gelatinization characteristics and the T_g′ of the gelatinized potato starch but had clearly increased their ΔC_p in the T_g′ region. Annealing at a temperature slightly below the T_g′ of −5 °C, led to maximal freeze‐concentration in the total/partial gelatinized starch and a higher T_g′ value at about −3 °C was obtained. The T_g′ values of the totally gelatinized starch samples were slightly lower than those of partially gelatinized samples. The T_g′ of the gelatinized starch decreased with increasing concentrations of sucrose or sodium chloride. Sodium chloride had a stronger depressing effect on T_g′ than sucrose. © 2000 Society of Chemical Industry     

Effects of ball‐milling on the glass transition of wheat flour constituents

BACKGROUND: Starch and gluten, the major components of wheat flour, greatly influence the structural characteristics of food products made with wheat flour. The effects of ball‐milling on the change in the semicrystalline structure of starch granules to the amorphous state have been reported. However, the effects of ball‐milling of native wheat flour on physicochemical changes in wheat flour constituents have not been elucidated. Therefore in this study the effects of ball‐milling on the glass transition of wheat flour constituents were investigated. RESULTS: Crude gluten, non‐gluten proteins and separated starch were obtained from wheat flour ball‐milled for 0–10 h, and the glass transition temperature (T_g) of these constituents was evaluated. The T_g of all wheat flour constituents decreased with increasing ball‐milling time. Sodium dodecyl sulfate polyacrylamide gel electrophoresis revealed that changes in band position and intensity did not occur for gluten but did occur for non‐gluten proteins. X‐ray diffraction revealed decreased crystallinity and greater plasticisation by water in separated starch as the ball‐milling time was prolonged. CONCLUSION: The results showed that the ball‐milling process decreased the T_g of wheat flour constituents as a function of milling time. The decrease in T_g was probably due to changes in conformation of protein subunits in gluten and depolymerisation of the non‐gluten protein fraction. The information obtained here about the physical alteration of wheat flour constituents may enhance the ability to successfully use ball‐milled wheat flour in food applications. Copyright © 2008 Society of Chemical Industry     

Determining the effects of annealing time on the glass transition temperature of Pueraria lobata (Willd.) Ohwi starch

To probe the effects of annealing time on the glass transition temperature (T_g) and digestibility of Pueraria lobata (Willd.) Ohwi starch, the starch crystal structure and moisture distribution through the components of P. lobata (Willd.) Ohwi starch were investigated. Annealing times of 0, 1, 3, 6, 12 and 24 h were employed to determine the effect of starch T_g using differential scanning calorimetry (DSC) with the support of ¹H low‐field NMR, polarised light microscopy and ¹³C CP/MAS NMR. The T_g values of the starch increased with longer annealing times. The ¹H low‐field NMR results showed that the T₂ relaxation time decreased and starch–water interactions increased as the annealing time increased. Compared with native starch, annealed starch had higher contents of slowly digested starch (SDS) and resistant starch (RS). The starch crystal structure was not destroyed after annealing, but the relative crystallinity percentage increased slightly.     

Original article: Encapsulation of ascorbic acid in amorphous maltodextrin employing extrusion as affected by matrix/core ratio and water content

Ascorbic acid (AA) was encapsulated in glassy low‐dextrose equivalent maltodextrin matrix by extrusion. The effects of formulation parameters, i.e., core/matrix ratio and water content were mainly investigated on T_g of extrudate. The AA yield, AA content and water content of the products together with extrusion parameters were also determined and compared for different formulations. The T_g of extrudates containing water content from 7.860% to 10.430% ranged from 43.17 to 27.48 °C, and the T_g of extrudates which core to matrix from 1:4 to 1:8 ranged from 35.79 to 41.64 °C. AA yield of all extrudates is above 96%, and with increasing water content, there was a slight decrease in the AA yield. The increased water level and core/matrix ratio reduce specific mechanical energy and die head pressure. X‐ray diffraction and scanning electron microscopy suggested that AA was most likely molecularly dispersed within the maltodextrin indicating the miscibility of AA and maltodextrin.     

Material Properties and Glass Transition Temperatures of Different Thermoplastic Starches After Extrusion Processing

Four different starch sources, namely waxy maize, wheat, potato and pea starch were extruded with the plasticizer glycerol, the latter in concentrations of 15, 20 and 25% (w/w). The glass transition temperatures of the resulting thermoplastic products were measured by Dynamic Mechanical Thermal Analysis (DMTA). Beside mechanical and structural properties also the transition temperatures of the materials were evaluated during tensile and impact tests. Above certain glycerol contents, dependent on the starch source, a lower glass transition temperature T_g resulted in decreased modulus and tensile strengths and increased elongations. Lowering the T_g at different glycerol contents did not influence the impact strength. When the amylose/amylopectin ratio increased a decrease in T_g was found. For pea, wheat, potato and waxy maize starch the T_g was 75 °C, 143 °C, 152 °C and 158 °C, respectively. Therefore products with higher percentages of amylose are more flexible. The shrinkage of the specimens made by injection molding was considerable compared to the specimens made by pressing.     

Effects of Heating,Vacuum Drying and Steeping on Gelatinization Properties and Dynamic Viscoelasticity of Various Starches

Starches having A‐ and B‐type X‐ray diffraction patterns (A‐ and B‐type starches) were modified by heating at 120 °C for 2 h (HT), vacuum drying at room temperature for 20 h (VD) and steeping at 50 °C for 20 h (ST). The properties of starches were compared using differential scanning calorimetry (DSC) and dynamic viscoelasticity behavior during heat processing (G' behavior). As observed by DSC, HT rarely changed the gelatinization properties for A‐type starches, but decreased the gelatinization temperatures and enthalpies (ΔH) for B‐type starches. A shift of the X‐ray diffractograms from B‐type to A‐type patterns was not detected after HT. Similar changes in gelatinization properties were observed for B‐type starches after VD. ST increased the gelatinization temperatures and also narrowed the gelatinization temperature range irrespective of crystal type. Both HT and VD decreased the peak temperature (T_p) in G' behavior and increased the peak G' value for B‐type starches. ST increased T_p and also decreased the peak G' value irrespective of starch crystal type. G' values after reaching T_p — which indicate the viscoelasticity of the swollen starch granules without breakdown — showed significant increases only for B‐type starches after HT.     

Effects of molecular characteristics of on konjac glucomannan glass transitions of potato amylose, amylopection and their mixtures

BACKGROUND: The purpose of this study was to explore further the functions of konjac glucomannan (KGM) in starch‐based foods. Experiments were carried out using the mixed amylose/amylopectin/KGM system as a model. High‐speed differential scanning calorimetry (hyper‐DSC) with the support of high‐performance size exclusion chromatography (HPSEC) equipped with multi‐angle laser light scattering (MALLS) and differential refractive index (RI), X‐ray diffractometry (XRD) and viscosimetry was used to investigate the effects of KGM on glass transition temperatures (T_gs) of mixtures with different amylose/amylopectin ratios. RESULTS: Hyper‐DSC results showed that the T_gs of amylose, amylopection and their mixtures decreased with increasing concentration of KGM. Based on the molecular characteristics of KGM, HPSEC‐MALLS‐RI, viscosimetry and XRD results showed that the molar masses of KGM ranged from 1.023 × 10⁶ to 1.329 × 10⁶ g mol^?1; the root mean square (RMS) radii were distributed from 110.5 to 129.6 nm, and M_w/M_n was 1.017. KGM was a linear molecule with random‐coil conformation in solution and the crystallinity was 0.00%. CONCLUSION: It is suggested that the addition of KGM has plasticizing effects on the structures of amylose and amylopectin, which can increase free volume and molecular movement of amylose and amylopectin chains, resulting in a decrease in their T_gs. Copyright © 2010 Society of Chemical Industry     

Suppression of Fusarium graminearium growth by differently structured starch types

We investigated the growth behavior and amylolytic enzymes of Fusarium graminearum cultivated on different types of native starch granules including barley (A‐type crystalline polymorph), potato and Curcuma zedoaria (B‐type crystalline polymorph), cassava (C‐type crystalline polymorph), and high AM maize (A + Vh‐type crystalline polymorphs). F. graminearum grew poorly on B‐type starches and the accumulation of biomass was similar to that obtained for fungi cultivated under carbohydrate starvation conditions. In comparison, three‐ to fivefold higher accumulation of fungal biomass was observed for growth on the A‐, C‐ and A + Vh‐type starches. Fungal glucoamylase and α‐amylase activity increased over time in the presence of native starch granules. Interestingly, resistant B‐type starches induced the highest amylolytic activity indicating that F. graminearum interacts with B‐type granules although only limited degradation occur. Starch degradation products maltose and malto‐oligosacharides was found to increase glucoamylase and α‐amylase activity, whereas glucose acted as a catabolite repressor.     

Resistant starch and thermal,morphological and textural properties of heat‐moisture treated rice starches with high‐, medium‐ and low‐amylose content

This study investigated the effects of heat‐moisture treatment (HMT) on the resistant starch content and thermal, morphological, and textural properties of rice starches with high‐, medium‐ and low‐amylose content. The starches were adjusted to 15, 20 and 25% moisture levels and heated at 110°C for 1 h. The HMT increased the resistant starch content in all of the rice starches. HMT increased the onset temperature and the gelatinisation temperature range (T_finish–T_onset) and decreased the enthalpy of gelatinisation of rice starches with different amylose contents. This reduction increased with the increase in the moisture content of HMT. The morphology of rice starch granules was altered with the HMT; the granules presented more agglomerated surface. The HMT affected the textural parameters of rice starches; the high‐ and low‐amylose rice starches subjected to 15 and 20% HMT possessed higher gel hardness.     

Influence of Heat‐Moisture Treatment and Acid Modifications on Physicochemical,Rheological, Thermal and Morphological Characteristics of Indian Water Chestnut (Trapa natans) Starch and its Application in Biodegradable Films

Water chestnut starch was subjected to acid modification and heat‐moisture treatment. Hydrochloric acid was used for acid modification at three different concentrations (0.25 M, 0.5 M and 1 M) for 2 h. Modifications did not alter the granule morphology. Heat‐moisture treatment (HMT) resulted in slight reduction in the granular size of the starch granules. Acid modification lowered the amylose content, swelling power, water‐ and oil‐binding capacity but improved the solubility of starch to a considerable level. Light transmittance of acid‐modified (AM) starches improved significantly. A significant reduction in peak, trough, final and setback viscosity was observed by acid‐thinning. In case of heat‐moisture treated starch the final viscosity (F_v) was found to be even higher than the peak viscosity (P_v). Native water chestnut starch exhibited a lower onset temperature (T_o) and peak temperature (T_p) of gelatinization than the corresponding acid‐treated starches. Starch films prepared from native starch exhibited excellent pliability, whereas those prepared from AM and HMT starches showed good tensile strength. Starch films prepared from acid‐treated starches provided better puncture and tensile strength.     

Comparison of the morphological,crystalline, and thermal properties of different crystalline types of starches after acid hydrolysis

A‐type maize starch, B‐type Fritillaria ussurensis, and C‐type Rhizoma dioscorea starches were hydrolyzed (32 days) with 2.2 N HCl. Regardless of the crystallinity level, starch with predominant B‐crystalline type was less susceptible to acid degradation than A‐type and C‐type starches, and initial rates of hydrolysis in B‐type was lower than others. The SEM and XRD results revealed that different types of starch displayed different hydrolysis mechanisms. The acid corrosion started from the exterior surface of A‐type and B‐type starches followed by the core of granules. However, the hydrogen ions primarily attacked the interior of the C‐type R. dioscorea starch granules and then the exterior. FT‐IR results confirmed that the amorphous regions in the starch granules were hydrolysed first. After 8–32 days of hydrolysis, the acid‐modified C‐type starch showed typical A‐type characteristics upon analysis of the XRD pattern. The average particle size of hydrolytic starch decreased with increasing hydrolysis time. The thermal results revealed that the hydrolytic starch showed lower ΔH than the native starch, while displaying higher peak width (T_c − T_o) value.     

Physicochemical, mechanical and thermal properties of brown rice grain with various moisture contents

The effects of moisture content on the mechanical and thermal properties of either a short‐grain variety (Akitakomachi) or two long‐grain varieties (Delta and L201) of brown rice were studied. Total starch contents of the three varieties were comparable, but the amylose content of L201 was significantly higher than that of the other two varieties. The maximum compressive strength of brown rice grain was much higher than the maximum tensile strength. L201 showed the highest maximum compressive and tensile strengths. The phase transition temperatures (glass transition temperature T_g and melting temperature T_m) were examined by differential scanning calorimetry. The T_g and T_m for L201 were higher than those for Delta and Akitakomachi. The maximum compressive strength, maximum tensile strength, T_g and T_m for the three varieties of brown rice grains decreased with increasing moisture content. The T_g of individual brown rice kernels decreased from 53 to 22 °C as moisture content increased from 12 to 25% wet basis. A statistical model was calculated by using linear regression to describe the change in T_g in terms of moisture content.     

Impact of arabinoxylan with different molecular weight on the thermo‐mechanical,rheological, water mobility and microstructural characteristics of wheat dough

The aim of this study was to investigate the effects of arabinoxylan with different molecular weight on the wheat dough thermo‐mechanical, rheological, microstructural and water mobility properties. Arabinoxylan was extracted from wheat bran and hydrolysed by endo‐1,4‐β‐xylanase (EC 3.2.1.8 from Trichoderma reesei, 10 000 U g^?1) for 2 min (AX_M) and 10 min (AX_L), respectively. The addition of hydrolysed arabinoxylan AX_L increased the stability time, decreased the setback value of wheat dough and enhanced the values of storage modulus (G′) and loss modulus (G″), while unhydrolysed arabinoxylan (AX_H) reduced these values. Meanwhile, unhydrolysed arabinoxylan increased T₂ relaxation time while hydrolysed arabinoxylan AX_L decreased T₂₁ and T₂₂. Confocal laser scanning microscope (CLSM) results showed that the addition of hydrolysed arabinoxylan AX_L promoted the formation of a more compact and continuous protein network in wheat dough. These results revealed that compared with high molecular weight arabinoxylan, hydrolysed arabinoxylan could improve the rheological properties and processing properties of wheat dough by enhancing the interaction among water molecules, starch and gluten in wheat dough.     

AFM Images of Complexes between Amylose and Aspergillus niger Glucoamylase Mutants,Native and Mutant Starch Binding Domains: A Model for the Action of Glucoamylase

Atomic force microscopy has been used to investigate the complexes formed between high molecular weight amylose chains and Aspergillus niger glucoamylase mutants (E400Q and W52F), wild‐type A. niger starch binding domains (SBDs), and mutant SBDs (W563K and W590K) lacking either of the two starch binding sites. The images are interpreted in terms of a favourable binding between the amylose chains and the wild‐type SBDs, leading to the formation of ring‐like structures, in which parallel strands of the amylose molecule bind to both binding sites on the SBDs. The SBDs are seen to form a template for the assembly of an expanded amylosic double helix. This model for amylose‐SBD binding has been used to propose a molecular mechanism for the role of the SBD in the hydrolytic action of glucoamylase on starch granules. The SBDs are considered to recognise the ends of amylosic double helices formed by the short amylosic chains present as branches on the amylopectin molecules, and displayed on the face of crystalline lamellae. This allows the binding and immobilisation of chain ends by the SBD, facilitating binding and cleavage by the exo‐acting catalytic domain.