Rice Starch Molecular Size and its Relationship with Amylose Content

The composition and starch molecular structure of eight rice varieties were studied. Waxy and non‐waxy (long‐, medium‐, and short‐grain) rice varieties from California and Texas were used. The amylose contents were measured using the Concanavalin A method and were found to be related to the type of rice: waxy ≈ 1.0%, short and medium grain 8.7–15.4%, and long grain 17.1–19.9%. The weight‐average molar masses (M_w) of the starches varied from 0.52 to 1.96×10⁸ g/mol. As would be expected, a higher M_w of rice starch correlated to lower amylose content. The range of M_w of amylopectin was 0.82 to 2.50 ×10⁸ g/mol, and there was also a negative correlation of amylopectin M_w with amylose content. Amylose M_w ranged from 2.20 to 8.31×10⁵ g/mol. After debranching the amylopectin with isoamylase, the weight‐average degree of polymerization (DP_w) for the long‐chain fraction correlated positively with a higher amylose content. California and Texas varieties were significantly different in their amylose content, starch M_w (short‐ and medium‐grain only), and amylopectin M_w (p < 0.05).     

The Influences of Chain Length of Amylopectin on Resistant Starch in Rice (Oryza sativa L.)

Amylopectin is the principle component of starch. To elucidate the relationships between amylopectin and resistant starch content, six rice mutants with altered fine structure of amylopectin were selected for comparative studies with the primary wild type and two types of amylose‐extender (ae) mutants. Significant differences in resistant starch content were observed among mutants with similarity or differences in amylose levels. Mutants high in resistant starch had significantly increased proportions of short amylopectin chains with DP≤12, decreased levels of intermediate chains with size of 13≤DP≤36, and decreased fractions of long chains with DP≥37. Additionally, there was a mutant different to ae, which was characterized by an increased level of short chains with 8≤DP≤12 and 13≤DP≤24, and a decreased proportion of long chains with DP≥37. The increased contents of short chains with 8≤DP≤12 and decreased of intermediate and long chains with 24≤DP were clearly associated with the increase of resistant starch in rice.     

Chemometric Analysis of the Gelatinization and Pasting Properties of Long‐grain Rice Starches in Relation to Fine Structure

Chemometric tests were carried out to better understand the multidimensional facet of starch fine structure‐relationship concerning gelatinization and pasting properties. With Ward's hierarchical cluster analysis 20 long‐grain rice starch samples were sorted out into three clusters based on similarities in functional properties, particularly, paste peak (PV) and final viscosity (FV). The three clusters (arbitrarily named Clusters A, B, and C) exhibited a pasting profile trend of PV<FV, PV˜FV, and PV>FV, respectively. Cluster A samples were also lower in peak temperature, range and enthalpy of gelatinization, and swelling power. These attributes were associated with higher amylose content (AM), β‐amylolysis limit, and percentage of B1 chains (DP13‐24), but lower amylopectin weight‐average molar mass (M_w) and percentage of A chains (DP6‐12). A 5‐variable linear discriminant function correctly predicted 85% of the Ward's cluster membership of the individual cultivars. The discriminant function included the variables A, B1, and B2 (DP25‐36) chains, average chain length (ACL), and gyration radius (R_z). Fine structure variance was fully explained by a total of nine principal components, with the first three components cumulatively accounting for 74%. The leading variables included in the three rotated components pertained to amylopectin chain length distribution (A, B2, and B3+ or DP≥37 chains, and ACL) and amylopectin molar mass (M_w, R_z, and polydispersity). AM and M_w were loaded most frequently in the 4‐variable, best‐fit linear regression models for predicting gelatinization and pasting properties. A combination of at least two fine structure variables controls the functionality of rice starch.     

Gelatinization and Pasting Properties of Waxy and Non‐waxy Rice Starches

Gelatinization and pasting properties of diverse rice types grown in two locations were examined by differential scanning calorimetry (DSC) and rotational rheometry, respectively. The data were compared to previously reported molecular starch properties for these samples: specifically, amylose content, starch molecular weight (M_w), and amylopectin side‐chain‐length distributions. Significant correlations were observed between amylose content, starch M_w, and the weight degree of polymerization of the long side chains of amylopectin F₁(DP_w) and many of the gelatinization and pasting properties measured. Higher amylose content corresponded with increased gelatinization onset (T_o) and peak temperatures (T_p), pasting onset and peak temperatures, and decreased peak and trough viscosity. Starch M_w correlated negatively with T_o, T_p, pasting onset, and peak temperature and positively with peak, trough, final, and breakdown viscosity. Amylopectin with DP_w 59‐78 of F₁(DP_w) correlated with increased T_o, T_p, pasting onset and peak temperature, and decreased peak, trough, final and breakdown viscosity. Pasting properties were also somewhat related to DP_w 21 of shorter side chains of amylopectin (F₂(DP_w)). Significant correlations between F₂(DP_w) and peak, final, and breakdown viscosity were observed (r = −0.447*, −0.391*, −0.388*, peak, final, and breakdown viscosity, respectively).     

Molecular Distribution and Pasting Properties of UV-Irradiated Corn Starches

Suspension (30 %, w/w) of corn starch (25 % amylose) in water was irradiated by UV-light with wavelength greater than 250 nm at 25°C, under a stream of nitrogen or air, for time intervals ranging from 5 to 25 h. Effects of the irradiation on the transition enthalpy and temperature for melting, and the pasting viscosity profile of the irradiated starch were examined. Weight-average molecular weight (M_w) and radius of gyration (R_g) of the irradiated starch molecules were measured by high performance size exclusion chromatography coupled with multiangle laser light scattering and differential refractive index detectors (HPSEC-MALLS-RI). In the case of starch irradiated under nitrogen, the transition enthalpy (ΔH) decreased with increasing irradiation time whereas the melting temperature was not changed. Similarly, the peak paste viscosity (P_v) decreased from 97 to 56 RVU by 25 h irradiation. Average M_w and R_g of amylopectin and amylose fractions, which were 93 × 10⁶ and 144 nm, and 2.0 × 10⁶ and 104 nm, respectively, were decreased by irradiation to 32.2 × 10⁶ and 93.7 nm, and 0.7 × 10⁶ and 83.6 nm by the irradiation for 15 h under nitrogen, respectively. When the starch was irradiated with aeration, sharp drops of all measured parameters were observed in 5 h of irradiation (ΔH 11.4 J/g, P_v 53.2 RVU, amylopectin M_w 50 × 10⁶). After 15 h under air, however, all measured values increased (ΔH 16.8 J/g, P_v 65.5 RVU, amylopectin M_w 63.1 × 10⁶). Molecular size distribution profiles confirmed oxidative the photodegradation in the early stage (up to 5 h), and cross-linking reactions in the late stage (5—15 h) of irradiation under aeration.     

Effect of Gamma Irradiation on Molecular Structure and Physicochemical Properties of Corn Starch

ABSTRACT:  Carboxyl content and amylose leaching of gamma-irradiated corn starch increased and swelling factor decreased with increasing radiation dose. The apparent amylose content decreased gradually from 28.7% for native starch to 20.9% for 50 kGy irradiated starch. The proportion of short amylopectin branch chains (DP 6 to 12) increased, while the proportion of longer branch chains (DP ≥ 37) decreased with increasing radiation dose. The relative crystallinity and the degree of granule surface order decreased from 28.5% and 0.631 in native starch to 26.9% and 0.605 in 50 kGy irradiated starch, respectively. Pasting viscosity and gelatinization temperatures decreased with an increase in radiation dose. At a high dose (50 kGy), melting of amylose–lipid complex in DSC thermogram was not observed. The rapidly digestible starch (RDS) content slightly decreased up to 10 kGy but increased at 50 kGy. The resistant starch (RS) content slightly decreased at 2 kGy and then increased up to 50 kGy. The slowly digestible starch (SDS) content showed the opposite trend to RS content. Slower irradiation dose rate reduced carboxyl content, swelling factor, and amylose leaching. The apparent amylose content and amylopectin chain length distribution were not significantly affected by dose rate of gamma irradiation. However, the relative crystallinity and gelatinization enthalpy increased with slower dose rate. Slower dose rate decreased RDS and SDS contents, and increased RS content.     

Chain‐length Distribution Profiles of Amylopectin Isolated from Endosperm Starch of Waxy and Low‐amylose Bread Wheat (Triticum aestivum L.) Lines with Common Genetic Background

Large A‐type endosperm starch granules were isolated from near‐isogenic waxy and non‐waxy lines and low‐amylose mutant lines of bread wheat with a common genetic background. The amylose contents of A‐type starch ranged from 2.6% to 23.6%. Amylopectin was isolated by concanavalin A (Con A) precipitation from the isolated starch. The λ_max (range: 532‐538 nm) and blue values at 680 nm (range: 0.026‐0.037) of the iodine‐amylopectin complex were not significantly different among the isolated amylopectins, indicating that amylopectins from non‐waxy and low‐amylose lines did not contain such long chains as amylose or extra‐long chains of amylopectin affecting iodine complex properties. Chain‐length distribution profiles measured by both high‐performance size‐exclusion chromatography (HPSEC) and high‐performance anion‐exchange chromatography (HPAEC) showed that the amylopectin structures of these lines were indistinguishable from each other. Extra‐long chains were not detected in the amylopectins by HPSEC measurement. The side‐chains measured by HPAEC were classified into four groups according to their degree of polymerization (DP), and the proportion of each group were in the following ranges: DP 6‐12, 26.5‐27.5%; DP 13‐24, 43.6‐44.1%; DP 25‐36, 13.6‐14.2%, and DP 37‐60, 11.0‐11.7%. The alleles on the Wx‐D1 locus, i.e., Wx‐D1a, Wx‐D1d, Wx‐D1f, and Wx‐D1g, responsible for granule‐bound starch synthase (GBSS I) biosynthesis had no influence on the properties of iodine‐amylopectin complex and the chain‐length distribution profiles of amylopectin.     

Granule‐bound SSIIa Protein Content and its Relationship with Amylopectin Structure and Gelatinization Temperature of Rice Starch

Starch characteristics such as gelatinization properties determine the quality of various products of rice. The eating, cooking and processing qualities of rice are a function of the gelatinization of rice starch. The gelatinization temperature (GT) of rice is controlled by the starch synthase IIa (SSIIa) gene. In the present study, the amount of the starch‐associated SSIIa protein and its relationship with amylopectin structure and GT were investigated. The results indicated that the starch associated SSIIa protein content was positively correlated with GT and level of amylopectin chains with degree of polymerization 12‐24 (DP12‐24), and negatively correlated with the fraction of chains with DP6‐11 and short chain ratio (SCR), i.e. DP6‐11/DP12‐24 (P<0.001). GT was also negatively correlated with DP6‐11 SCR, and positively correlated with DP12‐24. The SSIIa protein content and amylopectin structure showed significant difference between the two SSIIa single nucleotide polymorphisms (SNPs, i.e. guanine‐cytosine/thymine‐thymine (GC/TT)) groups. Rice with GC and TT SNPs had average SSIIa protein contents of 1.076 and 0.681, respectively. Rice with the GC SNPs displayed a lower amount of chains with DP6‐11 and more chains with DP 12‐24 than those with TT SNPs. A mechanism is postulated to explain how SSIIa could determine the distribution of amylopectin side‐chains, which affects the gelatinization temperature of rice starch.     

Structural modification and characterization of rice starch treated by Thermus aquaticus 4-α-glucanotransferase

Rice starch was modified using Thermus aquaticus 4-α-glucanotransferase (TAαGTase) in this study. The changes in the molecular structure and the effect on the starch retrogradation by TAαGTase treatment were investigated on isolated rice starch. By treating TAαGTase, molecular weight profile of amylopectins shifted to higher elution time from 1.0 × 10⁸ to 2.4 × 10⁷ or 0.8 × 10⁷, depending on the level of enzyme dosage. Meanwhile, there were huge increases in the proportions of content corresponding to amylose size and even smaller molecules. On treating with TAαGTase, short branch chains (DP 1–8) increased, and longer branch chains (>DP 19) increased significantly as well, with a broader distribution up to DP 46 compared to the control rice starch. Amylose content decreased from 30.0 to 21.8–23.7%. This indicated that the amylose could be transferred to the amylopectin branch chain by the disproportionation of TAαGTase, resulting in lowering the amylose content and the formation of amylopectin with a broader branch-chain length distribution. TAαGTase modified rice starch showed that X-ray diffraction pattern of the B-type crystalline even before cold storage, and that a variety of cyclic glucans (DP 5–19) were produced by enzymatic reaction. In particular, the accelerated rate of starch retrogradation was clearly observed compared to the control due to an overall increase in the number of elongated long-branch chains, decrease in the amount of amylose–lipid complex, and the possible synergistic effects of these factors.     

Effect of gamma‐ray irradiation on the physicochemical properties of flour and starch granule structure for wheat

Effect of gamma irradiation on the physicochemical properties of flour and starch granule structure of wheat was compared to non‐irradiated wheat. The moisture content of wet gluten and titratable acidity of wheat flour were significantly affected by gamma irradiation. This treatment also destroyed the starch granules of wheat grain and their breakage augmented as the dose of gamma irradiation increased, apparently resulting in the increase of small starch granules. Probably, these results were due to the disruption of large molecule, such as proteins, lipids and starch. The irradiated wheat flour for RVA pasting properties (flour viscosity) was also evaluated. Besides the difference in RVA profile, starch pasting curves showed a considerable decrease for six main parameters as gamma irradiation dose at different velocity increased.     

Isolation and Molecular Characterization of Makal (Xanthosoma yucatanensis) Starch

Starch was isolated from a non‐conventional source: makal (Xanthosoma yucatanensis) and molecular characteristics were determined using X‐ray diffraction, light scattering and chain length determination. The granules had an oval shape with sizes between 8 and 20 μm, with an average size of 12.4 μm. Amylose content was 22.4% and amylopectin content 77.6%. The granules presented a C‐type X‐ray diffraction pattern, with a degree of polymerization (DP) of 5–19 for branch chain lengths and an average molar mass of 5.4×10⁶ g/mol. The R_H and the R_G was 61.7 and 92.7 nm, respectively. Gelatinization temperature was 72.6 to 84.2°C and transition enthalpy was 15 J/g, which may be related to the X‐ray diffraction pattern and to the small granule size of makal starch. The retrogradation of makal starch increased during storage.     

Thermo‐rheological and functional properties of gamma‐irradiated wholewheat flour

The effects of different doses (0, 0.5, 1, 2.5, 5 and 10 kGy) of gamma irradiation on the thermal, rheological and functional properties of the wholewheat flour were evaluated. Water and oil absorption capacity of the flour increased from 85.92% to 91.44% and 1.10 to 1.91 g g^?1 of flour, respectively, with increase in irradiation dose. The dough development time decreased with dose from 4.0 to 3.0 min. The transition temperatures (T_o, T_p and T_c) decreased as the dose increased; enthalpy of gelatinisation (?H) decreased from 5.18 to 4.27 J g^?1 with dose. The flow behaviour showed a shear‐thinning behaviour, and the hysteresis area decreased with dose. The structural recovery decreased with dose. FTIR did not show formation of any new chemical groups.     

Properties of Cast Films Made of HCl‐Methanol Modified Corn Starch

The molecular and physicochemical properties of the studied starches modified with 0.36% HCl in methanol at 25 °C and 45 °C were related to the film properties of these starches. The weight‐averaged molecular weight (M_w) and the number of long‐chain branches (DP 13‐36) of HCl‐methanol modified starch decreased with increasing degree of acid modification, but the number of short‐chain branches (DP < 6) increased. HCl‐methanol modification significantly decreased the ghost formation in gelatinized starch dispersions and the viscosity of starch film‐forming dispersions. Thus, the homogeneity of the produced starch films was improved and their opacity reduced. Proper HCl‐methanol modification produced corn starch films with lower moisture absorption rate and maximum moisture content under high relative humidity (RH = 97%) condition.     

Selected functional properties of waxy corn and potato starches after illumination with linearly polarised visible light

Aqueous suspensions (30%) of waxy corn and potato starches were illuminated for 5–50 h with linearly polarised visible light (λ > 500 nm). Molecular weights (M?_w) and radii of gyration (R?_g) of the amylopectin and amylose fractions of illuminated waxy corn starch, and the amylopectin, intermediate, and amylose fractions of illuminated potato starch were measured by high‐performance size exclusion chromatography coupled with multiangle laser light scattering and refractive index detection. The weight‐average molecular weight (M?_w) and radius of gyration (R?_g) of the amylopectin fraction of native waxy corn starch were 14.45 × 10⁷ and 161.1 nm respectively. After 15 h of illumination a decrease in M?_w (5.80 × 10⁷) and R?_g (117.6 nm) was observed. Illumination for 25 h, led to an increase in M?_w (7.60 × 10⁷) and R?_g (134.0 nm). Further illumination, up to 50 h resulted in a slight decrease in M?_w (6.74 × 10⁷). The molecular weight and radius of gyration of the amylopectin fraction of native potato starch were 21.30 × 10⁷ and 207 nm respectively. Illumination for 15 h led to a decrease in M?_w (14.87 × 10⁷) and R?_g (141.5 nm), followed by an increase in both values after 25 h (18.97 × 10⁷, 146.6 nm) and 50 h (19.69 × 10⁷, 207.1 nm) of illumination. Illumination influenced the swelling power, solubility, susceptibility to α‐amylolysis and X‐ray diffractogram of the starches. A varying increase in the solubility passed through a minimum after 25 h of illumination. The X‐ray diffraction pattern and susceptibility to enzymatic hydrolysis of waxy corn starch did not change, but in potato starch a gradual, illumination time‐dependent increase in the amylolysis rate took place. This effect could result from the reduction in crystallinity of the starch as indicated by the X‐ray diffraction pattern. Copyright © 2003 Society of Chemical Industry     

Influence of γ-irradiation on antioxidant,thermal and rheological properties of native and irradiated whole grain millet flours

Millets of different types like Barnyard (Echinochloa utilis), Finger (Eleusine coracana), Foxtail (Setaria italic), Kodo (Paspalum setaceum) Little (Panicum sumatrense), Pearl (Pennisetum glaucum) and Proso millets (Penicum miliaceum) are staple foods for Indian and African diets. The germination, fungal and microbial contamination leads to postharvest losses mainly due to poor warehouse storage in Asia and Africa. Six millet varieties conditioned at 12% and 14% moisture content and irradiated at a dosage of 2.5 and 5 kGy and then milled into flours. The flour was analysed for composition, antioxidant and the rheological and thermal properties. Pearl, Proso, Finger Kodo at 12% moisture contents showed significant (P ≤ 0.05) increase in Phenolic contents at 2.5 kGy level of irradiation treatments compared with native and 5% irradiation treatment level. The DPPH activity showed an interesting results (42.77–72.65%) with wide variation and a mixed trend of high and low results with irradiation. Thermal transition temperatures showed that the irradiation decreased the transition temperatures primarily due to loss of the crystalline and amorphous starch structure due to radiation that lead to rapid water uptake and shorter time to reach peak viscosity. We are further studying the application of the irradiated flours in different food products to understand the influence of irradiation on nutritional, sensory and functional properties in cereal-based products.     

Starch Structure and Digestibility of Rice High in Resistant Starch

Starch digestibility and starch structure of a high‐resistant starch (RS) rice (RS111) was compared to that of a wild rice type (R7954). RS111 exhibited high RS content and incomplete starch hydrolysis in both cooked rice and retrograded rice flour. High RS rice RS111 had a higher λ_max of absorbance and blue value of iodine‐binding starch complex and contained a higher percentage of intermediate chains of amylopectin than R/954. X‐ray diffraction pattern of RS isolated from cooked high RS rice displayed a mixture of B‐ and V‐type that was more resistant to starch hydrolysis by alpha‐amylase. Resistant starch in RS111 is composed mainly of linear amylose and some low‐molecular‐weight amylopectin.     

Structure‐Functionality Changes in Starch Following Rough Rice Storage

The molecular‐level features of starch in relation to the changes in rice functionality during storage are not yet fully elucidated. This work investigated the effects of rough rice storage conditions on starch fine structures and physicochemical properties. Dried rough rice samples (medium‐grain Bengal and long‐grain Cypress) were stored at 4, 21, and 38°C in temperature‐controlled chambers and then periodically removed and evaluated after 1, 3, 5, 7, and 9 months. Flour (powdered head rice) and starch (extracted from head rice by alkali steeping) samples were evaluated for pasting and thermal properties. High‐performance size‐exclusion chromatography and high‐performance anion exchange chromatography were used to characterize starch molecular size and amylopectin chain‐length distribution, respectively. Significant changes in starch fine structure were observed primarily on the 38°C lots, and to some extent on the 21°C lots. The decreased amylose: amylopectin ratio, shortened amylopectin average chain length, and the shift in chain‐length distribution to shorter branch chains were implicative of molecular‐level starch degradation. The flour and starch samples showed inconsistent trends in pasting and thermal properties, thus suggesting the role of not only starch but also its interaction with non‐starch components in rice aging.     

Comparison between Size Exclusion Chromatography and Micro‐Batch Analyses of Corn Starches in DMSO using Light Scattering Detector

The molecular structure of corn starches different in amylose content (waxy, normal, and high‐amylose) was analyzed in 90% dimethyl sulfoxide (DMSO) solution by refractive index (RI) and multi‐angle laser light scattering (MALLS) detectors. The starch sample solutions were measured either by medium‐pressure size exclusion chromatography (MPSEC) or by the micro‐batch mode. For waxy corn starch, the average molar mass (M_w) and radius of gyration (R_g) values were similar in both methods. However, for normal and high‐amylose corn starches, M_w measured by the micro‐batch mode was 2–4 times greater than that by the chromatographic method, although R_g values obtained from both methods were not very different. The M_w difference was the greater the higher the amylose content of starch.     

Thermal and Pasting Properties of Microwaved Corn Starch

Corn starch with 15–40% moisture was irradiated at 0.17 or 0.5 W/g for 1 h using the sophisticated Ethos 1600 microwave apparatus that accurately controls temperature and wattage. Temperature of irradiated starch was measured during microwaving. Thermal and pasting properties were studied on dehydrated starch after microwave irradiation. Temperature increases were greatest during the first 10 min for starch at all moisture contents at both microwave power levels. Starch irradiated at 0.17 W/g had a temperature below onset gelatinization temperature (T_o) after 1 h. Higher temperatures were observed for starch with higher moisture content and microwaved at 0.5 W/g. Compared to native starch, starch with 15–40% moisture had higher T_o (measured using differential scanning calorimetry) and with 35–40% moisture had higher peak gelatinization temperature and lower enthalpy change of gelatinization. All paste viscosity parameters measured by the Rapid Visco Analyser were reduced and pasting temperature was elevated for starch irradiated at 0.5 W/g compared to native starch.     

Physicochemical Properties of Pin Oak (Quercus palustris Muenchh.) Acorn Starch

Physicochemical properties of acorn (Quercus palustris) starch were studied. Acorn starch granules were spherical or ovoid, with diameters ranging from 3–17 μm. Acorn starch exhibited A‐type X‐ray diffraction pattern, an apparent amylose content of 43.4% and absolute amylose content of 31.4%. Relative to other A‐type starches, acorn amylopectin had a comparable weight‐average molar mass (3.9×10⁸ g/mol), gyration radius (288 nm) and density (16.3 g mol⁻¹nm⁻³). Average amylopectin branch chain‐length corresponded to DP 25.5. Onset gelatinization temperature was 65.0°C and peak gelatinization temperature was considerably higher (73.7°C). The enthalpy change of gelatinization was very high compared to non‐mutant starches (20.8 J/g). An amylose‐lipid thermal transition was not observed. Starch retrograded for 7 d at 4°C had very high peak melting temperature (54.2°C) relative to other A‐type starches. Final (260 RVU) and setback (138 RVU) viscosity of an 8% acorn starch paste was high relative to other starches and pasting temperature was 71.5°C.