Extrusion of Cross‐Linked Hydroxypropylated Corn Starches II. Morphological and Molecular Characterization

A series of cross‐linked hydroxypropylated corn starches were extruded with a Leistritz micro‐18 co‐rotating extruder. Extrusion process variables including moisture (30, 35, and 40%), barrel temperature (60, 80, and 100°C), and screw design (low, medium, and high shear) were investigated. Scanning electron microscopy (SEM) of extruded starches showed a gel phase with distorted granules and granule fragments after extrusion at 60°C. After extrusion at 100°C only a gel phase was observed with no granular structures remaining. High performance size exclusion chromatography (HPSEC) equipped with multiangle laser light‐scattering (MALLS) and refractive index (RI) detectors showed extruded starches degraded to different extents, depending on extrusion conditions. The average molecular weight of the amylopectin of unextruded native corn starch was 7.7 × 10⁸. Extrusion at 30% moisture, 100°C, and high shear reduced the molecular weight of amylopectin to 1.0 × 10⁸. Hydroxypropylated normal corn starch extruded at identical conditions showed greater decreases in amylopectin molecular weight. With the addition of cross‐linking, the amylopectin fractions of the extruded starches were less degraded than those of their native and hydroxypropylated corn starch counterparts. Similarly, increasing moisture content during extrusion lowered amylopectin degradation in the extruded starches. Increasing temperature during extrusion of cross‐linked hydroxypropylated starches at high moisture content (e.g., 40%) lowered amylopectin molecular weights of the extruded starches, whereas increasing extrusion temperature at low moisture content (30%) resulted in less degraded molecules. This difference was attributed to the higher glass transition temperatures of the cross‐linked starches.     

Molecular Structure and Some Physicochemical Properties of Buckwheat Starches

The molecular structure and pasting properties of starches from eight buckwheat cultivars were examined. Rapid viscograms showed that buckwheat starches had similar pasting properties among cultivars. The actual amylose content was 16–18%, which was lower than the apparent amylose content (26–27%), due to the high iodine affinity (IA) of amylopectin (2.21–2.48 g/100 g). Amylopectins resembled each other in average chain‐length (23–24) and chain‐length distributions. The long‐chains fraction (LC) was abundant (12–13% by weight) in all the amylopectins, which was consistent with high IA values. The amyloses were also similar among the cultivars in number‐average DP 1,020–1,380 with 3.1–4.3 chains per molecule. The molar‐based distribution indicated that all the amyloses comprised two molecular species differing in molecular size, although the weight‐based distribution showed a single species. A comparison of molecular structures of buckwheat starches to cereal starches indicated buckwheat amylopectins had a larger amount of LC, and their distributions of amylose and short chains of amylopectin on molar basis were similar to those of wheat and barley starches.     

Physicochemical Properties and Molecular Structures of Starches from Millet (Pennisetum typhoides) and Sorghum (Sorghum bicolor L. Moench) Cultivars in Nigeria

Some physicochemical properties and molecular structures of starches from millet (Pennisetum typhoides, Doro and Gero) and sorghum (Sorghum bicolor, red and white) in Nigeria were examined. Starch granules of millet and sorghum were 3–14 μm and 4–26 μm in diameter, respectively. Millet cultivars had similar peak viscosities (204–205 RVU) on pasting, while sorghum showed similar minimum viscosities (155–156 RVU). The actual amylose content (%) calculated from iodine affinity (IA, g/100 g) was 20.1 and 21.4 for sorghum and 21.3 for millet. The IA of amylopectin was high (1.27–1.42) and its average chain lengths were 20–21 with β‐amylolysis limit of 56%. Amylopectins showed a polymodal molecular weight distribution on a molar basis. The distributions differed among the samples with a higher amount of larger molecules in Doro and red sorghum. Weight‐ and molar‐based distributions of debranched amylopectins on HPSEC were polymodal with weight‐based distribution showing presence of long chains. Peak DP values for A+B₁ and B₂+B₃ chain fractions were 13–16 and 42–43, respectively. The (A+B₁)/(B₂+B₃) ratio on molar basis (9.0–11.5) was similar to maize and rice amylopectins. Peak DP on molar‐based distribution for white sorghum and millet amyloses were similar (490–540) and the DP_n range was narrow (1,060–1,300), but weight‐based distribution profiles differed. The average chain lengths were 260–270 with 3.9–4.8 chains per molecule.     

Isolation and Characterization of Atriplex hortensis and Sweet Chenopodium quinoa Starches

Starches from garden orach (Atriplex hortensis) and sweet quinoa (Chenopodium quinoa Willd. ‘Surumi’) seeds were isolated, examined for compositional characteristics, and compared with bitter quinoa (Cheno‐podium quinoa Willd.) starch. Garden orach and sweet quinoa seeds were similar in fat and ash contents, while garden orach seeds contained ≈10% more protein. Starches were isolated from seeds following a 12‐hr soak in dilute alkaline solution using a series of grinding, screening, centrifugation, and washing steps. Isolated starches viewed by scanning electron microscopy yielded angular, polygonal granules ≈1–2 μm in diameter. Starches displayed typical A‐type crystalline packing arrangements as determined by X‐ray powder diffractometry. Apparent amylose contents for garden orach (21.2%), sweet quinoa (20.6%), and bitter quinoa (19.8%) were determined according to colorimetric procedure. Differential scanning calorimetry data indicated a higher and wider gelatinization temperature range for garden orach as compared with sweet and bitter quinoa starches. Starch pasting profiles generated using a Rapid Visco Analyser indicated a reduced peak paste viscosity for garden orach starch relative to sweet and bitter quinoa and common corn starches.     

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.     

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.     

Molecular Structure and Some Physicochemical Properties of High‐Amylose Barley Starches

The molecular structure and some physicochemical properties of starches from two high‐amylose cultivars of barley, high‐amylose Glacier A (HAG‐A) and N (HAG‐N), were examined and compared with those of a normal cultivar, Normal Glacier (NG). The true amylose contents of HAG‐A, HAG‐N, and NG were 41.0, 33.4, and 23.0%, respectively. Iodine affinities before and after defatting of starch, and thermograms of differential scanning calorimetry, indicated that HAG‐A and HAG‐N starches had a higher proportion of amylose‐lipid complex than did NG starch. The amylopectins from HAG‐A and HAG‐N were similar to NG amylopectin in average chain length (18–19), β‐amylolysis limit (β‐AL 56–57%), number‐average degrees of polymerization (DP_n 6,000–7,500) and chain length distribution. Very long chains (1–2%) were found in amylopectins from all cultivars. HAG‐A amylopectin had a larger amount of phosphorus (214 ppm) than the others. The amyloses from HAG‐A and HAG‐N resembled NG amylose in DP_n (950–1,080) and β‐AL (70–74%). However, HAG‐A and HAG‐N had a larger number of chains per molecule (NC 2.4–2.7) than NG amylose (1.8) and contained the branched amylose with a higher NC (9.5–10.6) than that of NG amylose (5.8), although molar fractions of the branched amylose (15–20%) were similar.     

Solubilization Effects on Molecular Weights of Amylose and Amylopectins of Normal Maize and Barley Starches

Structural characteristics of starches have been important to determine their physicochemical and functional properties. Solubilization procedures were tested to find a higher solubilization percentage and thereafter to study the structural characteristics of amylose and amylopectin. Size‐exclusion chromatography with refractive index (SEC‐RI) system using a pullulan standard curve was tested to study the amylose molar mass. Also, a microbatch system using a MALLS detector was used to determine the molar mass and gyration radius of starch and amylopectin. Microwave heating produced higher solubility percentages than autoclaving, and there was a difference between both starches. The sample solubilized with microwave heating presented higher molar mass and gyration radius values than autoclave samples, showing that this process for structural studies provided information representative of the initial starch sample. When starch components were separated, amylose showed lower purity than amylopectin. Lower purity was obtained for amylose separated from barley starch, but no difference was obtained for purity of amylopectin separated from both starches. Barley amylopectin had a higher solubility percentage than maize amylopectin. Molar mass of barley amylose was 1.03 × 10⁵ g/mol and for maize of 2.25 × 10⁵ g/mol. Molar mass values of amylopectin separated from both starches were lower than the starch counterparts, although the same solubilization procedure (microwave heating) was used. The difference might be due to depolymerization during separation of starch components.     

Evaluation of the Entanglement Molecular Weights of Maize Starches from Solution Rheological Measurements

The entanglement molecular weights of waxy maize (WM) and normal maize (NM) starches were calculated from solution rheological data. The viscoelastic behavior of both WM and NM starches were measured at several different concentrations and then shifted to produce a master curve for each of the materials. The theory of Doi and Edwards was used to calculate the plateau moduli from which values for the entanglement molecular weights for WM and NM starches were calculated. The entanglement molecular weights were 100 ± 15 kg/mol for WM starch and 96 ± 8 kg/mol for NM starch. These two values were within experimental error of one another and represent the entanglement molecular weight of amylopectin, the major component of WM and NM starches. The entanglement degrees of polymerization for WM and NM starch, using a value of 162 g/mol for the monomer molecular weight of amylopectin, were 617 ± 92 and 592 ± 49, respectively. The values for the entanglement molecular weight and the entanglement degrees of polymerization for WM and NM starch were markedly higher than those quoted for many commercial polymers. This finding indicates that molecular weights of >1 million are required to produce starch-based materials with consistent physical properties.     

Characterization of Thermal Traits of Starches from Argentinian Maize Inbreds: Genotypic and Crop Year Variability

Thermal properties are among the most important end‐use characteristics of starch from maize (Zea mays L.). Knowledge of the contribution of genotype and environment to the total variance for starch thermal properties is needed to aid in defining a testing strategy for selecting maize with desirable thermal starch properties. Thus, the objectives of this study were 1) to characterize the thermal properties of starches from a group of recently developed Argentine maize inbred lines, and 2) to assess the variability in starch properties attributable to genetic and crop year effects. Twelve inbred lines developed by the National Institute of Agricultural Technology (INTA) in Argentina derived from a wide array of germplasm sources were evaluated. Gelatinization and retrogradation properties were measured by differential scanning calorimetry. Enthalpy means for gelatinization were below means reported in the literature, suggesting possible energy savings when using these starches. The ratio between change in enthalpy for retrogradation and gelatinization was above the mean reported in the literature, suggesting a starch that may be useful as a dietary fiber. Significant environmental effects caused by crop year were detected. Some inbred lines, with smaller observed ranges and standard deviations across environments, may be more stable for some properties.     

糜子分子遗传研究进展与展望

糜子是最古老的驯化栽培作物之一,具有抗旱、耐瘠、水分利用效率高、营养丰富等特点,在北方旱作农业区特色粮食生产中占有重要地位。为深入推动糜子农艺、产量及品质相关性状遗传解析,在介绍国内糜子遗传研究现状基础上,通过文献分析综述了糜子分子遗传研究进展,并展望了未来发展趋势。     

Impact of Treated Industrial Effluent on Physical and Chemical Properties of Three Subtropical Soils and Millet Nutrition

The use of treated industrial effluents to irrigate plants is an alternative, because of nutrients that can increase yield of the agricultural crops. This study was conducted to determine irrigation with treated effluent and gypsum application, which changes the chemical and physical characteristics of soils and the growth and nutrition of millet (Pennisetum glaucum). Thus, an experiment was conducted on PVC columns with three soil classes, Typic Hapludox, Typic Hapludult, and Arenic Hapludult. Nutrient and Na⁺ concentrations in the millet biomass reflected concentrations of elements in the effluent and soil. In the control, low N levels were found in the biomass, while higher leaf N concentrations were observed, due to irrigation with treated effluent. In the short term, irrigation with treated industrial effluent by controlled application could be an alternative and a complementary source of nutrients for plants, reducing the volume of nutrients and organic materials discharged into water bodies.     

Structure and Functionality of Barley Starches

Amylose contents of prime starches from nonwaxy and high-amylose barley, determined by colorimetric method, were 24.6 and 48.7%, respectively, whereas waxy starch contained only a trace (0.04%) of amylose. There was little difference in isoamylase-debranched amylopectin between nonwaxy and high-amylose barley, whereas amylopectin from waxy barley had a significantly higher percentage of fraction with degree of polymerization < 15 (45%). The X-ray diffraction pattern of waxy starch differed from nonwaxy and high-amylose starches. Waxy starch had sharper peaks at 0.58, 0.51, 0.49, and 0.38 nm than nonwaxy and high-amylose starches. The d-spacing at 0.44 nm, characterizing the amylose-lipids complex, was most evident for high-amylose starch and was not observed in waxy starch. Differential scanning calorimetry (DSC) thermograms of prime starch from nonwaxy and high-amylose barley exhibited two prominent transition peaks: the first was >60°C and corresponded to starch gelatinization; the second was >100°C and corresponded to the amylose-lipid complex. Starch from waxy barley had only one endothermic gelatinization peak of amylopectin with an enthalpy value of 16.0 J/g. The retrogradation of gelatinized starch of three types of barley stored at 4°C showed that amylopectin recrystallization rates of nonwaxy and high-amylose barley were comparable when recrystallization enthalpy was calculated based on the percentage of amylopectin. No amylopectin recrystallization peak was observed in waxy barley. Storage time had a strong influence on recrystallization of amylopectin. The enthalpy value for nonwaxy barley increased from 1.93 J/g after 24 hr of storage to 3.74 J/g after 120 hr. When gel was rescanned every 24 hr, a significant decrease in enthalpy was recorded. A highly statistically significant correlation (r = 0.991) between DSC values of retrograded starch of nonwaxy barley and gel hardness was obtained. The correlation between starch enthalpy value and gel hardness of starch concentrate indicates that gel texture is due mainly to its starch structure and functionality. The relationship between the properties of starch and starch concentrate may favor the application of barley starch concentrate without the necessity of using the wet fractionation process.     

Chemical and Physical Characteristics of Proso Millet (Panicum miliaceum)‐Based Products

Celiac disease and gluten sensitivities, as well as obesity and overweight‐related disorders, have led to the investigation of gluten‐free grains and development of new food products. To address this, refined proso millet and refined corn (control), both gluten‐free grains, were used to produce four different product types (muffin, couscous, extruded snack, and porridge). The products contained four different grain combinations (100% proso millet, 75% proso millet/25% corn, 25% proso millet/75% corn, and 100% corn). All products were evaluated for their nutritional composition, in vitro starch digestibility, and expected glycemic index (eGI). Products made with refined proso millet had increased protein (7.6–11.3%), lipid (1.2–6.1%), fiber (7.0–8.8%), and phenolic content (323.5–425 μg/g) compared with those incorporating corn flour (2.5–9.0%, 0.8–4.0%, 2.1–4.1%, and 213–315 μg/g, respectively). As the proso millet content increased, the eGI decreased significantly (P < 0.05). Products made from refined proso millet appear to be good candidates for producing low‐GI, gluten‐free foods.     

Physicochemical and Pharmaceutical Properties of Carboxymethyl Rice Starches Modified from Native Starches with Different Amylose Content

Carboxymethyl rice starches (CMRS) were prepared from nine strains of native rice starches with amylose contents of 14.7–29.1%. The reaction was conducted at 50°C for 120 min using monochloroacetic acid as a reagent under alkaline conditions and 1-propanol as a solvent. After determining the degree of substitution (DS), the physicochemical properties including water solubility, pH, and viscosity of 1% (w/v) solution, scanning electron microscopy (SEM), and X-ray diffraction (XRD) analyses of the granules, as well as some pharmaceutical properties of CMRS powders and pastes were investigated. The DS range was 0.25–0.40. All CMRS dissolved in unheated water and formed viscous gel. A good positive correlation was observed between amylose content and DS (r = 0.9278) but not viscosity. SEM and XRD concurrently revealed significant physical alteration of CMRS granules compared with those of native starches, which reflected the changes in the properties of CMRS. At 3% (w/w), CMRS can function as tablet binder in the wet granulation of both water-soluble and water-insoluble diluents. The tablets compressed from these granules showed good hardness with fewer capping problems compared with those prepared using the pregelatinized native rice starch as a binder. In addition, most CMRS pastes formed clear films with varying film characteristics, depending upon the amylose content of the native starches. This type of modified rice starch can potentially be employed as a tablet binder and film-former for pharmaceutical dosage formulations.     

Composition,Molecular Structure,Properties, and In Vitro Digestibility of Starches from Newly Released Canadian Pulse Cultivars

Pulse starches were isolated from different cultivars of pea, lentil, and chickpea grown in Canada under identical environmental conditions. The in vitro digestibility and physicochemical properties were investigated and the correlations between the physicochemical properties and starch digestibility were determined. Pulse starch granules were irregularly shaped, ranging from oval to round. The amylose content was 34.9–39.0%. The amount of short A chains (DP 6‐12) of chickpea starch was much higher than the other pulse starches, but the proportions of B1 and B2 chains (DP 13‐24 and DP 25‐36, respectively) were lower. The X‐ray pattern of all starches was of the C type. The relative crystallinity of lentil (26.2–28.3%) was higher than that of pea (24.4–25.5%) and chickpea starches (23.0–24.8%). The swelling factor (SF) in the temperature range 60–90°C followed the order of lentil ≈ chickpea > pea. The extent of amylose leaching (AML) at 60°C followed the order of pea ≈ chickpea > lentil. However, in the temperature range 70–90°C, AML followed the order of lentil > pea > chickpea. The gelatinization temperatures followed the order of lentil > pea > chickpea. The peak viscosity, setback, and final viscosity of pea starch were lower than those of the other starches. Lentil starch exhibited lower rapidly digestible starch (RDS) content, hydrolysis rate, and expected glycemic index (eGI). The resistant starch (RS) content of both lentil cultivars was nearly similar. However, pea and chickpea cultivars exhibited wide variations in their RS content. Digestibility of the pulse starches were significantly correlated (P < 0.05) with swelling factor (60°C), amylose leaching (60°C), gelatinization temperature, gelatinization enthalpy, relative crystallinity, and chain length distribution of amylopectin (A, B1, and B2 chains).     

Characterization of Resistant Starch Samples Prepared from Two High‐Amylose Maize Starches Through Debranching and Heat Treatments

The aim of the present study was to investigate effects of debranching, autoclaving‐storing cycles, and drying processes (oven‐drying or freeze‐drying) on RS contents, thermal, pasting, and functional properties of high‐amylose maize starches (Hylon V and Hylon VII). The resistant starch (RS) contents increased (≤57.8%) with increasing autoclaving‐storing cycles. RS contents of oven‐dried samples were higher than those of freeze‐dried samples due to ongoing retrogradation of starch during oven drying at 50°C. Debranching caused a significant decrease in peak transition temperature and enthalpy values as compared with native starches. Solubility and water binding values of RS preparations were higher than those of native starches. Addition of native and autoclaved samples had improving effect on emulsion properties of albumin. Cold viscosity values of oven‐dried samples were lower as compared with freeze‐dried samples; this might be due to higher number of H‐bonds in the oven‐dried samples expected to be formed during drying. Debranching and autoclaving‐storing cycles caused decreases in peak, breakdown, and final viscosity values. The results of present study showed that debranching and heat treatments increased the RS contents and improved the functional properties of high‐amylose maize starches.     

Light-Scattering Molecular Weights and Intrinsic Viscosities of Processed Waxy Maize Starches in 90% Dimethyl Sulfoxide and H2O

Waxy maize starch was treated by a variety of gentle and severe methods: direct dispersion-solubilization into 90% dimethyl sulfoxide (DMSO) and H₂O solvent, extrusion followed by dispersion-solubilization of the ground exudate into solvent, or jet-cooking or stirred autoclaving of an aqueous starch slurry followed by transfer into solvent. Intrinsic viscosities [η] and multiangle light-scattering measurements were made in 90% DMSO-H₂O. A Mark-Houwink relation, [η] = (0.28–1.2) M_w^{0.29 ± 0.04}, was obtained over a molecular weight range of ≈30–700 million. However, there was a large amount of scatter in the data when [η] were >140 mL/g. The power law relationship R_g ∝ M_w^0.41±0.04 was noted between radii of gyration and molecular weights. We infer from our data that over the entire range of M_w distributions, the amylopectin existed in solution as relatively compact molecules or aggregates and that in the higher molecular weight region, the size and possibly the shape of the “dissolved” amylopectin was highly sensitive to the method of dispersal and treatment.     

Alkali Debranning of Sorghum and Millet

Aqueous solutions of sodium hydroxide were used to debran whole sorghum and millet grains. The alkali solution was effective in dissolving the pericarp, leaving the kernel free of pericarp. Various combinations of concentration of sodium hydroxide (3, 6, and 10%, w/w) and soaking duration (5, 8, and 10 min) were investigated. Two cultivars of sorghum (Dionje and Jumbo) and one cultivar of pearl millet (IM) were used in the study. A 10% aqueous solution of sodium hydroxide at 60°C was most effective in dissolving the pericarp of both sorghum and millet after 10 min of soaking, resulting in ≈90% yield of clean endosperm for all grain types. The debranning process reduced the fiber content (measured as crude fiber) of sorghum cultivars Dionje and Jumbo by 37.6 and 41.8%, respectively; and pearl millet by 32%.     

谷子SiPSY1基因与米色形成相关性分析

为明确谷子八氢番茄红素合成酶基因与谷子米色形成的相关性,本研究从黄色和白色2种不同米色谷子中克隆出SiPSY1基因的cDNA全长序列,并进行生物信息学分析,同时,利用实时荧光定量PCR方法检测该基因在谷子米色形成过程中的表达模式。结果表明,SiPSY1基因编码序列(CDS)全长为1 248 bp,共编码415个氨基酸。SiPSY1蛋白的理论分子量为46.866 kDa,等电点为8.97,为不稳定亲水性蛋白。该蛋白的二级结构由α螺旋(57.35%)、不规则卷曲(29.64%)、延伸链结构(9.88%)和β转角(3.13%)四种结构组成。SiPSY1蛋白与玉米ZmPSY1的同源性较高,二者的亲缘关系较近。在谷子米色形成的初期和中期,黄色米色品种籽粒中SiPSY1基因的表达水平显著高于白色米色品种,而在米色形成后期,该基因在白色米色品种中的表达水平显著提高,并高于在黄色米色品种中的表达水平。随着籽粒成熟米色的形成,SiPSY1基因在黄色米色品种七月黄中的表达量呈先上升后显著下降的趋势,在白色米色品种中呈逐渐上升的趋势。通过对SiPSY1基因结构和表达特性的分析,初步推测谷子米色差异及形成与SiPSY1基因结构无关,而与基因的表达特性有一定的相关性。本研究结果为进一步阐明SiPSY1基因的功能以及谷子米色形成的分子机制奠定了基础。