Model approach to starch functionality in bread making

We used modified wheat starches in gluten-starch flour models to study the role of starch in bread making. Incorporation of hydroxypropylated starch in the recipe reduced loaf volume and initial crumb firmness and increased crumb gas cell size. Firming rate and firmness after storage increased for loaves containing the least hydroxypropylated starch. Inclusion of cross-linked starch had little effect on loaf volume or crumb structure but increased crumb firmness. The firming rate was mostly similar to that of control samples. Presumably, the moment and extent of starch gelatinization and the concomitant water migration influence the structure formation during baking. Initial bread firmness seems determined by the rigidity of the gelatinized granules and leached amylose. Amylopectin retrogradation and strengthening of a long-range network by intensifying the inter- and intramolecular starch-starch and possibly also starch-gluten interactions (presumably because of water incorporation in retrograded amylopectin crystallites) play an important role in firming.     

Effects of Rice Flour Blends on Bread Texture and Staling

The effects of blending rice flour with wheat flour on bread texture and staling were investigated with three rice varieties with different amylose contents. For the texture analysis of bread crumb, the compression test, puncture test, and tensile test were performed. A flour blend containing rice flour suppressed the recovery of the crumb after compression. For the puncture test, blends with rice flour increased the distance to penetrate the crumb. The rupture strain measured with the puncture test decreased with staling of the bread crumb for all samples tested. The fresh bread crumb sample containing waxy rice flour had much greater extensibility in the tensile test than the other samples tested, but it was dramatically decreased after one day of storage. Endothermic enthalpies corresponding to retrograded amylopectin, which is part of the staling process, were also measured. The enthalpy of bread crumb from the blended flour was lower than that of wheat flour bread up to three days but was higher on day 4. A blend of rice flour thus reduced amylopectin retrogradation during early storage, but it was accelerated later. Bread blended with waxy rice flour showed the lowest enthalpy during storage.     

Pulsed Nuclear Magnetic Resonance (PNMR) Study of Rice Starch Retrogradation

Although pulsed NMR (PNMR) has been used for qualitative study of starch retrogradation in selected systems, validation is necessary for its application to new systems. PNMR was used to analyze the retrogradation of rice starches in purified form, in rice flour, and in cooked rice grains. The standard curves between the relative solid content (S′, %) by PNMR and the percentage of gelatinized starch (GS, %) were determined for common rice flour, common rice starch, and waxy rice starch at different moisture contents. The coefficients of linear regression for these curves (R²) were all >0.997. Starches with different amylose contents were tested for S′ values at the stages of freshly gelatinized, retrograded (4°C, 18 days), and reheated (90°C, 20 min). The S′ of reheated starch (S′_reheat) was similar to the S′ of freshly gelatinized starch (S′₀), so we concluded that the increase in S′ during storage corresponded to amylopectin retrogradation. The effect of moisture content on retrogradation of rice starch, rice flour, and cooked rice grains was studied by PNMR, and the data were interpreted using the Avami equation. Decreasing the moisture content increased the rate of retrogradation and led to a higher parameter k and a lower parameter n. For moisture content in the range studied, PNMR can be used to follow amylopectin retrogradation of different rice starch systems.     

Retrogradation of Rice Flour Gel and Dough: Plasticization Effects of Some Food Additives

Certain food additives commonly used in flour products also have a plasticization effect on product shelf life regarding retrogradation. Sucrose, sorbitol, glycerol, citric acid, and acetic acid at 25, 25, 25, 0.5, and 0.5%, respectively, were added to two different starch gel systems: slurry (high‐amylose rice flour gel) and dough (waxy rice flour dough). All plasticizers increased gelatinization temperature, decreased enthalpy (ΔH), and promoted a more homogeneous system. Sucrose had the greatest effect on gelatinization increase. Rice dough was more susceptible to plasticizers, resulting in higher moisture content and a more amorphous structure. Retrogradation was highly positively correlated with amylose content, moisture retention, ratio of protons of water/starch, and previous occurrence of retrogradation. Moisture retention was increased in plasticizer‐added samples, especially waxy rice dough. Over a longer storage period, sucrose and sorbitol showed an antiplasticization effect in waxy rice flour dough, but glycerol and acid caused higher retrogradation in high‐amylose rice flour gel.     

Staling Effects When Adding Low Amounts of Normal and Heat‐Treated Barley Flour to a Wheat Bread

The properties of a white wheat bread could be changed by adding normal or heat‐treated barley flour in small amounts (2 and 4%) to a white wheat bread recipe. Differences regarding gelatinization as well as retrogradation properties were found when analyzing the two flours in model systems. The heat‐treated flour was fully gelatinized due to prior time, temperature, and pressure treatment and could therefore absorb larger amounts of water than the other flours. In gelatinized model systems with 40% flour (dwb), the heat‐treated barley flour contained less retrograded amylopectin as compared with normal barley flour after storage for up to 14 days, whereas no differences were found with 20% flour (dwb). However, stored breads showed an increased retrogradation of amylopectin (as measured by differential scanning calorimetry [DSC]) when 2% pretreated barley flour was added as compared with addition of 2% normal barley flour. On the other hand, there were no significant differences at the 4% level. Addition of either of the barley flours resulted in less firm breads during storage as compared with the control breads. Increased water absorption in barley flour and thus increased water content in the breads or different water‐binding capacities of the flour blends could explain these results. The present study indicated that water had a stronger influence on bread firmness than the retrogradation of amylopectin. This conclusion was based on breads with pretreated barley flour being less firm than breads with normal barley flour, although the retrogradation, as determined by DSC, was higher.     

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.     

Partial beta-amylolysis retards starch retrogradation in rice products

Starch retrogradation is the main cause of quality deterioration of starch-containing foods during storage. The current work investigated the effect of partial beta-amylolysis on the retrogradation of rice starch and the potential of beta-amylase in preparing rice products with extended shelf life. Isolated amylopectin, whole rice starch, and rice flour from a regular rice cultivar were partially hydrolyzed by either reagent-grade or food-grade beta-amylase. The degree of beta-amylolysis was expressed as average external chain length () for isolated amylopectin or the degree of hydrolysis (%) for other starch systems. Pulsed nuclear magnetic resonance was used to monitor starch retrogradation during storage at 4 degrees C. The results indicated that partial beta-amylolysis using reagent-grade beta-amylase retarded amylopectin retrogradation by shortening the of amylopectin. When was below DP 11.6, the amylopectin retrogradation was essentially inhibited. Partial beta-amylolysis had a similar effect on the amylopectin retrogradation in the whole starch system. The maltose produced in beta-amylolysis might slightly attenuate the retrogradation-retarding effect of partial beta-amylolysis. The effect of food-grade beta-amylase on starch retrogradation was also evident, although less effective than that of reagent-grade beta-amylase. The retrogradation-retarding effect of food-grade beta-amylase was also demonstrated in rice flour system, indicating a potential method for controlling the starch retrogradation of rice products.     

Influence of Bran Particle Size on Bread‐Baking Quality of Whole Grain Wheat Flour and Starch Retrogradation

The influence of bran particle size on bread‐baking quality of whole grain wheat flour (WWF) and starch retrogradation was studied. Higher water absorption of dough prepared from WWF with added gluten to attain 18% protein was observed for WWFs of fine bran than those of coarse bran, whereas no significant difference in dough mixing time was detected for WWFs of varying bran particle size. The effects of bran particle size on loaf volume of WWF bread and crumb firmness during storage were more evident in hard white wheat than in hard red wheat. A greater degree of starch retrogradation in bread crumb stored for seven days at 4°C was observed in WWFs of fine bran than those of coarse bran. The gels prepared from starch–fine bran blends were harder than those prepared from starch–unground bran blends when stored for one and seven days at 4°C. Furthermore, a greater degree of starch retrogradation was observed in gelatinized starch containing fine bran than that containing unground bran after storage for seven days at 4°C. It is probable that finely ground bran takes away more water from gelatinized starch than coarsely ground bran, increasing the extent of starch retrogradation in bread and gels during storage.     

Physicochemical Properties and In Vitro Starch Digestibility of Cooked Rice from Commercially Available Cultivars in Canada

The influence of amylose content, cooking, and storage on starch structure, thermal behaviors, pasting properties, and rapidly digestible starch (RDS), slowly digestible starch (SDS), and resistant starch (RS) in different commercial rice cultivars was investigated. Long grain rice with high‐amylose content had a higher gelatinization temperature and a lower gelatinization enthalpy than the other rice cultivars with intermediate amylose content (Arborio and Calrose) and waxy type (glutinous). The intensity ratio of 1047/1022 cm^–1 determined by Fourier Transform Infrared (FT‐IR), which indicated the ordered structure in starch granules, was the highest in glutinous and the lowest in long grain. Results from Rapid ViscoAnalyser (RVA) showed that the rice cultivar with higher amylose content had lower peak viscosity and breakdown, but higher pasting temperature, setback, and final viscosity. The RDS content was 28.1, 38.6, 41.5, and 57.5% in long grain, Arborio, Calrose, and glutinous rice, respectively, which was inversely related to amylose content. However, the SDS and RS contents were positively correlated with amylose content. During storage of cooked rice, long grain showed a continuous increase in pasting viscosity, while glutinous exhibited the sharp cold‐water swelling peak. The retrogradation rate was greater in rice cultivars with high amylose content. The ratio of 1047/1022 cm^–1 was substantially decreased by cooking and then increased during storage of cooked rice due to the crystalline structure, newly formed by retrogradation. Storage of cooked rice decreased RDS content and increased SDS content in all rice cultivars. However, no increase in RS content during storage was observed. The enthalpy for retrogradation and the intensity ratio 1047/1022 cm^–1 during storage were correlated negatively with RDS and positively with SDS (P ≤ 0.01).     

Influence of storage conditions on the structure, thermal behavior, and formation of enzyme-resistant starch in extruded starches

Starch structures from an extrusion process were stored at different temperatures to allow for molecular rearrangement (retrogradation); their thermal characteristics (DSC) and resistance to amylase digestion were measured and compared. The structure of four native and processed starches containing different amylose/amylopectin compositions (3.5, 30.8, 32, and 80% amylose content, respectively) before and after digestion was studied with small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD). Rearrangement of the amylose molecules was observed for each storage condition as measured by the DSC endotherm at around 145 degrees C. The crystalline organization of the starches after processing and storage was qualitatively different to that of the native starches. However, there was no direct correlation between the initial crystallinity and the amount of enzyme-resistant starch (ERS) measured after in vitro digestion, and only in the case of high-amylose starch did the postprocess conditioning used lead to a small increase in the amount of starch remaining after the enzymatic treatment. From the results obtained, it can be concluded that retrograded amylose is not directly correlated with ERS and alternative mechanisms must be responsible for ERS formation.     

A Better Understanding of Factors That Affect the Hardness and Stickiness of Long‐Grain Rice

Eight U.S. long‐grain rice cultivars were studied for chemical compositions, physicochemical properties, and leaching characteristics in relation to hardness and stickiness of rice flour paste and cooked rice. There were differences in the chemical composition of rice kernels among the eight rice cultivars, including crude protein (6.6–9.3%), crude fat (0.18–0.51%), and apparent amylose content by iodine colorimetry (19.6–27.0%). Differences were also observed in gelatinization temperatures and enthalpies, pasting temperatures and viscosities, leached/insoluble amylose, soluble solids, and hardness and stickiness of rice flour pastes and cooked rice kernels. The quantity and molecular size distribution of the leached starch molecules varied greatly among the samples. Protein and crude lipid contents negatively correlated with hardness of rice flour paste and cooked rice, but positively correlated with stickiness. Apparent amylose content correlated with gel properties but not cooked rice texture, whereas the ratio of A and short B chains to long B chains of amylopectin correlated significantly with cooked rice texture.     

Studies on Quality of Potato Flour Blends with Rice Flour for Making Extruded Noodles

The effects of rice flour on the physicochemical properties of the raw material system and the quality of extruded potato–rice noodles were studied. The results demonstrated that the amylose content, pasting viscosities, storage modulus (G′), and loss modulus (G″) gradually increased with the included levels of rice flour, whereas the swelling power, solubility, and pasting temperature decreased with increasing rice flour content. The extruded potato–rice noodles exhibited desirable cooking qualities and textural properties with rice flour contents of up to 40%. Additionally, sensory evaluations revealed that the scores for chewiness, firmness, slipperiness, elasticity, and overall acceptability increased gradually with increasing rice flour content in the blends. Additionally, the results indicated the possibility of replacing potato flour with rice flour at a ratio of 6:4 to produce extruded potato–rice noodles of acceptable quality.     

Using Visible and Near‐Infrared Reflectance Spectroscopy and Differential Scanning Calorimetry to Study Starch,Protein, and Temperature Effects on Bread Staling

Starch, protein, and temperature effects on bread staling were investigated using visible and near‐infrared spectroscopy (NIRS) and differential scanning calorimetry (DSC). Bread staling was mainly due to amylopectin retrogradation. NIRS measured amylopectin retrogradation accurately in different batches. Three important wavelengths, 970 nm, 1,155 nm, and 1,395 nm, were associated with amylopectin retrogradation. NIRS followed moisture and starch structure changes when amylopectin retrograded. The amylose‐lipid complex changed little from one day after baking. The capability of NIRS to measure changes in the retrograded amylose‐lipid complex was limited. Two important wavelengths, 550 nm and 1,465 nm, were key for NIRS to successfully classify the starch‐starch (SS) and starch‐protein (SP) bread based on different colors and protein contents in SS and SP. Low temperature dramatically accelerated the amylopectin retrogradation process. Protein retarded bread staling, but not as much as temperature. The starch and protein interaction was less important than the starch retrogradation. Protein hindered the bread staling process mainly by diluting starch and retarding starch retrogradation.     

Partial Characterization of Buckwheat (Fagopyrum esculentum) Starch

Laboratory-isolated buckwheat (Fagopyrum esculentum) starch was compared to commercial corn and wheat starches. Buckwheat starch granules (2.9–9.3 μm) were round and polygonal with some holes and pits on the surface. Buckwheat starch had higher amylose content, waterbinding capacity, and peak viscosity, and it had lower intrinsic viscosity when compared with corn and wheat starches. Buckwheat starch also showed restricted swelling power at 85–95°C and lower solubility in water at 55–95°C and was more susceptible to acid and enzymatic attack. Gelatinization temperatures, determined by differential scanning calorimetry, were 61.1–80.1°C for buckwheat starch compared to 64.7–79.2°C and 57.1–73.5°C for corn and wheat starches, respectively. A second endotherm observed at 84.5°C was an amylose-lipid complex attributed to the internal lipids in buckwheat starch, as evidenced by selective extraction. The retrogradation of buckwheat, corn, and wheat starch gels was examined after storage at 25, 4, and -12°C for 1–15 days. In general, buckwheat starch retrogradation was slower than that of corn and wheat starch, but it increased as storage time increased, as did that of the other starch pastes. When the values of the three storage temperatures were averaged for each storage period analyzed, buckwheat starch gels showed a lower percentage of retrogradation than did corn and wheat starch gels. Buckwheat starch also had a lower percentage of water syneresis when stored at 4°C for 3–10 days and had better stability to syneresis after three freeze-thaw cycles at -12 and 25°C.     

Changes in Retrogradation Properties of Rice Starches with Amylose Content and Molecular Properties

The increases in storage modulus (G′), retrogradation enthalpy change (ΔH) and ΔH‐related Avrami kinetic parameters of gelatinized rice starch dispersions at 25% (w/w) were investigated with respect to storage period, amylose content (AC), and molecular properties. Three high‐AC and five low‐AC rice cultivars were compared for understanding the multiple influences of AC and molecular properties involved. After refining the results of correlation analysis, the G′ of just‐cooled samples changed positively, mainly with AC and additionally with the average chain length of amylose (CL_AM) and the weight ratio of extra‐long plus long chains to short chains of amylopectin (AP) (r_APchain). The developed ΔH on short‐term storage (10 days) elevated with increasing AC and CL_AM and decreasing degree of polymerization of AP (DP_AP), but after long‐term aging for one to three months with increasing r_APchain, especially for the low‐AC cultivars examined. Greater Avrami rate constants for retrogradation could be attributed to the combination of a lower DP_AP and r_APchain or AP chain length and a greater CL_AM. The polynomials using these critical factors to describe the retrogradation parameters were elucidated and could account for 85–99.6% of data deviations.     

Structural and Retrogradation Properties of Rice Endosperm Starch Affect Enzyme Digestibility of Steamed Milled-Rice Grains Used in Sake Production

Structural and physicochemical characteristics of endosperm starch from milled rice grains of seven Japanese cultivars used in sake production were examined. Amylose content was 15.2–20.2%, number-average degree of polymerization (DP_n) of amylose was 900–1,400, and the ratio of short-to-long chain amylopectin was 2.7–3.5, respectively. The degree of retrogradation of purified starch stored for seven days at 4°C after gelatinization was 20–31%. The degree of retrogradation correlated negatively with the ratio of short-to-long chain amylopectin. The effect of holding time after steaming on enzyme digestibility and starch retrogradation of steamed rice grains was investigated. The longer the holding time after steaming, the greater the extent of retrogradation, and the less the degree of enzymatic digestibility. The decreased rate of enzyme digestibility correlated with amylopectin chain length distribution. Samples with short-chain amylopectin exhibited a slow decrease in enzyme digestibility. It was determined that the structure and retrogradation properties of endosperm starch in Japanese rice cultivars affect the decreasing rate of enzyme digestibility of the steamed, milled rice grains.     

Freeze‐Thaw Stability of Bualoy Thai Dessert Using Waxy Rice Flour

Frozen food products are gaining acceptance in Thai food industry and frozen bualoy dessert is a good opportunity for marketing in domestic and for exports. One important factor affecting quality of frozen starchy foods is retrogradation of starch gels. Thus freeze‐thaw stability of a frozen bualoy made from total waxy rice flour was studied and compared among the samples modified by 20 and 30% cross‐linked tapioca starch (CTS) derivatized with phosphorylation and 0.25% propylene glycol alginate (PGA). The waxy rice flour was pregelatinized by adding boiled water before shaping as a ball, then boiled and mixed with coconut syrup. All samples were subjected to five freeze‐thaw cycles over 60 days in a conventional freezer (–18°C). Texture analysis firmness and stickiness of the nonfrozen gels substituted with 20% CTS (382 ± 43, 20.5 ± 7.1 g·f) and 30% CTS (493 ± 37, 31.1 ± 7.0 g·f) were significantly different as compared with the control (329 ± 22, 14.8 ± 3.1 g·f). Similar results were observed for the samples continuously frozen for 60 days. The effects of freeze‐thaw stability to the frozen gels of the control, CTS, and PGA substituted samples appeared after two cycles and exhibited a large increase in firmness and stickiness at the fourth cycle. The firmness values obtained from the control and the samples substituted with 20% and 30% CTS were 2,397 ± 197, 2,182 ± 203, and 2,104 ± 200 g·f, respectively. This evidence was also observed with the samples containing PGA, but the effect was slightly less. This might account for the recrystallization of amylopectin molecules induced by freeze‐thawings. With DSC, the waxy rice gels showed a significant increase in the melting enthalpy (2.39 ± 0.23 J/g) at the fifth cycle from the nonfrozen gels (0.11 ± 0.02 J/g). The sensory tests of the bualoys were correlated with textural qualities that were acceptable to the panelists when the freeze‐thawing went no further than the second cycle.     

Genotype and Environmental Influences on Pasting Properties of Rice Flour

The pasting behavior of flour from several Australian rice (Oryza sativa L.) cultivars, differing in amylose content and grown in three different locations and three seasons, were determined using the Rapid Visco Analyser. Genotype, growth season, and growth location all affected the pasting behavior of rice flour. The amylose content of the same cultivar was significantly higher in the coolest growing season, resulting in RVA traces with lower peak viscosity and higher setback than samples with lower amylose content. When the same cultivar of rice was grown in different locations in the same season, there were no significant differences in the total starch, protein, lipid, and amylose content of the flour, but there were significant differences in the pasting behavior. This indicates that environmental as well as genetic factors influence the pasting behavior of rice flour. Flour from parboiled and quick‐cooking rice did not paste and had low viscosities compared with unprocessed rice. Results from this study showed that the pasting behavior of rice flour was related to genotype and was influenced by environmental factors that brought about subtle changes in the grains that were not picked up by chemical analyses.     

Molecular and Gelatinization Properties of Rice Starches from IR24 and Sinandomeng Cultivars

The differences in pasting properties involving gelatinization and retrogradation of rice starches from IR24 and Sinandomeng cultivars during heating‐cooling processes were investigated using a Rapid Visco Analyser (RVA)and a dynamic rheometer. The results were discussed in relation to the molecular structure, actual amylose content (AC), and concentration of the starches. Generally, both starches possessed a comparable AC (≈11 wt%), amylose average chain length (CL), iodine absorption properties, and dynamic rheological parameters on heating to 95°C at 10 wt% and on cooling to 10°C at higher concentrations. In contrast to Sinandomeng, IR24 amylose had a greater proportion of high molecular weight species and number‐average degree of polymerization (DP_n). IR24 amylopectin possessed a lower DP_n and greater CL, exterior CL (ECL), and interior CL (ICL). Comparing the results of RVA analysis and dynamic rheology, the gelatinization properties and higher retrogradation tendencies of IR24 starch can be related to the structural properties and depend on starch concentration. In addition, the exponent n of starch concentration for storage moduli at 25°C (G′₂₅ ∝ Cⁿ) increased linearly with increasing AC.     

Physical and Molecular Characterization of Millet Starches

This study investigated the physical and molecular starch characteristics of four Canadian‐grown millet species: pearl, foxtail, proso, and finger millet. The millet starch granules ranged from about 2.5 to 24 μm in size and were mainly polygonal with a few spherical ones. Their amylose contents ranged from 28.6 to 33.9%, with finger and pearl millets having much more of long amylose chains than short amylose chains compared with foxtail and proso millets. Starches also differed in the molecular structure of their branched amylose, with finger and pearl millets having longer glucan chains between branch points. The enthalpy of gelatinization of starch granules ranged from 11.8 to 13.2 J/g, and the enthalpy of melting of the retrograded starches ranged from 2.2 to 5.9 J/g. The onset temperature of gelatinization (T_o) of the starches ranged from 62.8 to 70.6°C. Addition of iodine vapor to the granular starches showed significant (P < 0.05) differences in the ratio of the absorbance to scattering coefficient (K/S) values, indicating differences in the rigidity of the glucan chains present in the granules. Starches with short amylose chains exhibited higher K/S values. Iodine vapor addition resulted in altered X‐ray diffractogram peak intensities. The study suggested differences in the structure and granular architecture of the millet starches.