Modeling of Retrogradation of Waxy and Normal Corn Starches

Retrogradation behavior of waxy and normal corn starch gels stored at 5 and 21°C were investigated for 50 days by differential scanning calorimetry. The extend of retrogradation can be expressed as the ratio of retrogradation and gelatinization enthalpy values and these were 70–78% for normal corn starch and 39–68% for amioca stored at two temperatures. Higher retrogradation rates were observed at 5°C for both waxy and normal corn starch. Kinetic data were evaluated by considering retrogradation as consecutive reactions in series and by Avrami Equation. High R² values (0.97–0.98) indicated that both models can be used for prediction. The comparison of rate constants obtained by Avrami Equation indicated that both temperature and amylose content of starch affected the recrystallization rate. By the kinetic model based on consecutive reactions in series, it was proven mathematically that the rate limiting step in recrystallization of starch gels is the nucleation.     

Cationization of Waxy and Normal Corn and Barley Starches by an Aqueous Alcohol Process

When an aqueous alcoholic-alkaline solvent was used, cationization of normal and waxy corn and barley starches was achieved with high degrees of substitution (DS) and reaction efficiency (RE) in the absence of gelatinization inhibitor salts. Ethanol was a more effective solvent than methanol or 2-propanol, and alcohol concentrations could vary between 35–65%. Maintaining a starch to water ratio of 1:1 (w/w) was critical, but DS values were proportional to the concentration of cationic reagent, 3-chloro-2-hydroxypropyltrimethylammonium chloride. At 50°C, cationization was essentially complete within 6h but nearly the same DS could be achieved in 1h at 70°C.     

Endosperm Structure and Physicochemical Properties of Starches from Normal,Waxy, and Super-Sweet Maize

Maize is a main botanical source used for extraction of starch in the world market. New maize cultivars with different amylose contents and special starch metabolism characteristics have been generated. Three types of maize cultivars, namely, normal maize, waxy maize (wxwx homozygous mutant), and super-sweet maize (sh2sh2 homozygous mutant), were investigated to determine differences in endosperm structures, morphologies, and physicochemical properties of starches. Maize kernels exhibited significantly different contents of total starch, soluble sugar, and amylose. Normal maize kernels contained the largest proportion of floury endosperm, followed by waxy maize and then super-sweet maize. Normal maize starch and waxy maize starch were larger in size than super-sweet maize starch. Normal maize starch and waxy maize starch were spherical and polygonal in floury and vitreous endosperms, respectively. Super-sweet maize starch was spherical both in floury and vitreous endosperms. Waxy maize starch showed the strongest birefringence patterns, the highest crystallinity and the largest proportion of ordered structure in external region of granules, and the largest proportion of double helix components, followed by normal maize starch and then super-sweet maize starch. Waxy maize starch showed the highest peak viscosity, trough viscosity, breakdown viscosity, gelatinization temperatures (i.e., gelatinization conclusion temperature, gelatinization onset temperature, gelatinization peak temperature, and gelatinization enthalpy). By contrast, super-sweet maize starch showed the lowest corresponding values for these parameters.     

Physicochemical Properties of Waxy and Normal Maize Starches Irradiated at Various pH and Salt Concentrations

Waxy and normal maize starches of various pH values and salt contents were prepared, irradiated with gamma rays (5–20 kGy) and their molecular structure, pasting viscosity and rheological properties determined. Average molar mass and size of both waxy and normal maize starches decreased considerably by irradiation from >338.0×10⁶ to <39.4×10⁶ g/mol and from >237.5 to <125.2 nm, respectively. Adjustments of pH had little influence on the average molar mass and size of irradiated starch, whereas incorporation of salt greatly reduced the molar mass and size of irradiated waxy and normal maize starches. As the pH increased from 4 to 8, the pasting viscosity of the irradiated starches decreased from 1032 to 279 mPa s in waxy and from 699 to 381 mPa s in normal starches. Pasting viscosity of both irradiated waxy and normal starch decreased from 689 to 358 mPa s and from 327 to 184 mPa s as the salt concentration increased from 1 to 5%. The G′ of gels, determined during cooling from 90 to 10°C or storage for 8 h, decreased in irradiated waxy and normal starches by pre‐conditioning at pH 8 and in irradiated waxy starches by pre‐conditioning at 5% NaCl. With 5% NaCl, G′ of irradiated normal maize starch during cooling increased up to the irradiation level of 10 kGy, and increased during storage for 8 h at all levels of irradiation. Incorporated salt prior to irradiation appears to induce incremental modifications in the molecular structure, rheological and retrogradation properties of starch by boosting the degradation of molecules.     

Interaction of Guar and Xanthan Gums with Starch in the Gels Obtained from Normal,Waxy and High‐amylose Corn Starches

The objectives of the present study were to analyze the chemical interactions between guar and xanthan gums and starches. Gels were obtained from normal (NCS), waxy (WCS) and high‐amylose (HACS) corn starches containing gums. The gels were evaluated according to their pasting properties and infra‐red absorption. The guar (GG) and xanthan (XG) gums affected the properties of the NCS paste more significantly than those of the WCS paste. In the infra‐red absorption spectra, no covalent bonds between the starches and gums were observed under the conditions studied, so probably the only interactions occurring between them were hydrogen bonds.     

The Structure of Waxy Corn Starch: Effect of Granule Size

The granules of waxy corn starch were isolated and various samples were separated by size and classified according to their average diameter in: non-separated granules (N), granules with diameter < 15 μm (S) and granules with diameter ≥ 15 μm (L). The samples were hydrolyzed by bacterial α-amylase and fungal amyloglucosidase. The starch granules remaining after enzymatic hydrolysis were analysed by X-ray diffraction and optical and scanning electron microscopy. Sephadex G-50 gel permeation chromatography of the dissolved residues from the hydrolysis of the N and S samples was performed directly and after successive enzymatic digestion with pullulanase and β-amylase. The results showed that the percentage of hydrolysis increased with a decrease in diameter. No apparent differences in waxy corn starch when observed under light and scanning electronic microscope were observed, regardless of diameter and enzyme action, although both large and small granules showed extensive surface corrosion after enzymatic attack. X-ray analysis suggested a decrease in the quantity of crystalline areas in the smaller granules, which would explain the high percentage of hydrolysis evidenced by these granules. The elution patterns of the α-glucans of both starches (N and S) were similar and reveled the presence of two fractions which were not susceptible to α-amylase and amyloglucosidase attack suggesting that these fractions were involved in the waxy corn starch crystalline regions. Debranching with pullulanase followed by gel-permeation chromatography showed that the amylopectins from the starch granules studied contained three groups of unit chains instead of the two reported in the literature.     

反应程序和淀粉浓度对糯玉米和普通玉米淀粉快速黏度测定谱特征值的影响

以糯玉米品种渝糯7号和普通玉米品种农大108为材料,研究了不同的反应程序和淀粉浓度对其快速黏度测定(RVA)谱特征值的影响,同时比较了糯玉米和普通玉米淀粉在不同反应程序和淀粉浓度条件下的差异。结果表明:(1)玉米淀粉的RVA特征值在不同反应程序下发生了改变,但其没有改变糯玉米和普通玉米之间的差异,在不同反应程序下,相对于普通玉米淀粉,糯玉米淀粉的峰值黏度和沉降值较高,而谷值黏度、终值黏度、回复值、峰值时间和糊化温度较低。(2)糯玉米和普通玉米淀粉的RVA特征值受到浓度影响,随着淀粉浓度的增加,峰值黏度、谷值黏度、沉降值、终值黏度和回复值随之增加,峰值时间略有降低,浓度太低时淀粉不能糊化,在能糊化条件下则随着浓度的增加而降低。在低浓度条件下,糯玉米淀粉的峰值黏度高于普通玉米,而在较高浓度(11%)条件下,糯玉米淀粉的峰值黏度则低于普通玉米淀粉。     

Effect of Aqueous Ethanol Cationization on Functional Properties of Normal and Waxy Starches

Cationic starch ethers of normal and waxy corn, normal and waxy barley and normal pea starch were prepared by an aqueous alcoholic process for evaluation of their functional properties as compared to the native starch controls. The native starches exhibited a wide range in average granule size (10–21 μm diameter), amylose content (0–34%) and swelling power (13–31). Cationization to degrees of substitution (DS) of 0.030–0.035 with 3-chloro-2-hydroxypropyltrimethylammonium chloride resulted in marked increases in swelling power of all starches, with little corresponding increases in starch solubility. Cationization also decreased the onset of endothermic transitions and pasting temperatures quite substantially, and promoted the development of sharp peak viscosities in the amylographs of all normal and waxy starches, including that of pea starch. Final cold viscosities of the cationic starches exhibited positive setbacks, and the cooked starch gels, after storage for 7 days at 4°C and −15°C, showed no syneresis. All cationic starches except for waxy corn were more susceptible to α-amylase hydrolysis than native control starches. The general improvement in functional properties, especially in the waxy corn, waxy barley and pea starches, due to the aqueous alcoholic-alkaline cationization process would greatly enhance their industrial applications.     

Successive Reduction Dry Milling of Normal and Waxy Corn: Grain,Grit, and Flour Properties

Dry milling of different corn types resulted in varied proportions of germ, pericarp, grit and flour. Grit and flour produced during different reduction stages varied in particle size and chemical constituents, hence applications in food industry. In this study, recovery of different fractions and variation in physicochemical and pasting properties of grit and flour fractions obtained during 3 successive reduction dry millings of 2 normal (African tall, HQPM1) and 1 waxy corn (IC 550353) were evaluated. Waxy corn grains had the highest L*, a*, b*, ash, fat, and protein content and the lowest weight. Waxy and African tall gave the highest recovery of germ and pericarp, respectively. Waxy corn showed lower grit and flour recovery as compared to normal corn. Flour fractions showed higher L* and lower a* and b* values than grit fractions. Particle size of grit and flour fractions ranged from 840 to 982 μm and 330 to 409 μm, respectively. Fractions with larger particle size showed lower L* value. The b* value showed positive correlation with yellow pigment content. Grit and flour from the 1st reduction stage showed higher ash and fat content. Protein content was correlated positively with ash content and negatively with L* value. Grit and flour fractions with higher protein content had lower pasting viscosities. Pasting viscosities were higher for flours than their corresponding grits. Protein profiling of grit and flour fractions from different stages showed quantitative and qualitative differences in medium (22, 28, and 35 kDa) and low molecular weight (16, 17, and 19 kDa) polypeptides and were related to grit and flour yield.     

不同分子量辛烯基琥珀酸蜡质玉米淀粉酯的制备及其性能

以蜡质玉米淀粉为原料,辛烯基琥珀酸酐(OSA)为酯化剂,β-淀粉酶为酶解剂,制备了不同分子量辛烯基琥珀酸蜡质玉米淀粉酯(OSAS),并测定了其理化特性。结果表明:不同分子量(1.0×10⁴~2.0×10⁵ Da) OSAS的黏度在0.0035~0.0010 Pa·s范围内随分子量下降显著(P<0.05)降低,糊透明度自28.6%降低至23.1%,凝沉性和膨胀度也均随分子量降低而下降;辛烯基琥珀酸酐对蜡质玉米淀粉的酯化作用主要发生在蜡质玉米淀粉颗粒表面,酶解处理不会引入新基团。本研究初步揭示了OSAS分子量与其理化性质间的相互关系。     

Studies on the Starches of Barley Genotypes: The Waxy Starch

Two varieties of waxy barley originating from Japan, Sumiremochi and Mochimugi, have been characterized in detail for the first time. These two glutinous starches were found to be essentially identical. Both contained less than 0.5% of amylose, had a β-amylolysis limit of 53% conversion into maltose, and an average length of unit-chain of about 23 glucose units. The weight average molecular weight was 300 × 10⁶. These properties are characteristic of amylopectin. The iodine binding capacity of six other varieties of Japanese waxy barley has been measured and apparent amylose contents of 3 to 13% were obtained. Possible reasons for the presence of this amount of amylose are discussed.     

食盐对普通玉米杂交种淀粉糊化性质的影响

采用快速粘度分析仪（RVA）研究了食盐对18种普通玉米杂交种淀粉糊化性质的影响。结果表明：食盐显著降低了所有普通玉米杂交种淀粉的峰值、破损值和回生值;提高了谷值、终粘度、出峰时间和成糊温度。但对不同的普通玉米杂交种淀粉的糊化性质的影响程度有显著差别。随着食盐溶液质量分数的增加,普通玉米杂交种淀粉的谷值、终粘度、出峰时间和成糊温度也逐渐增加,破损值和回生值则显著降低,峰值受食盐溶液质量分数的影响很小。     

Fractionation and Characterization of Dent Corn and Amylomaize Starch Granules

Starch granules of dent corn and Classes V and VII amylomaizes were fractionated according to size by an aqueous differential sedimentation procedure. The sized fractions were characterized by microscopy and by a modified method for determining their iodine binding capacities. Results show an inverse relationship between granule size and iodine binding capacity in the amylomaizes. Ordinary dent corn does not show this. The percent apparent amylose in the fractions of amylomaize V starch amounted to 40% for the largest size particles and 52% for the smallest ones; for amylomaize VII starch, 46% for the large particles and 70% for the small particles. Dent corn averaged 23% apparent amylose.     

普通玉米杂交种间淀粉糊化过程中热力学性质的差异研究

采用湿法在试验室条件下提取了52种普通玉米杂交种淀粉。采用差示扫描量热仪(DSC)分析了这些玉米杂交种淀粉的糊化过程中的热力学性质。结果表明:52种普通玉米杂交种间淀粉糊化过程中的热力学性质存在明显区别:热焓值变化范围为8.95~15.54 J/g,起始糊化温度、峰值糊化温度、终止糊化温度及温度变幅的变化范围分别为64.72~70.28℃、70.37~75.03℃、77.16~84.16℃及9.49~17.43℃;52种普通玉米杂交种淀粉平均热焓值、起始糊化温度、峰值糊化温度、终止糊化温度及温度变幅分别为10.87 J/g、68.17℃、72.68℃、81.01℃和12.85℃;某些热力学性质参数间存在显著的相关性;依据热焓值大小,可以将52种普通玉米杂交种分为5个组别。     

Fine Structure,Thermal and Viscoelastic Properties of Starches Separated from Indica Rice Cultivars

Starches were separated from indica rice cultivars (PR‐113, Basmati‐370, Basmati‐386, PR‐115, IR‐64, and PR‐103) and evaluated using gel permeation chromatography (GPC), X‐ray diffraction, differential scanning calorimetry (DSC) and dynamic viscoelasticity . Debranching of starch with isoamylase and subsequent fractionation by GPC revealed 9.7–28.3% apparent amylose content, 3.7–5.0% intermediate fraction (mixture of short amylose and long side‐chains of amylopectin), 20.6–26.6% long side‐chains of amylopectin and 45.8–59.4% short side‐chains of amylopectin). IR‐64 starch with the highest crystallinity had the highest gelatinization temperatures and enthalpy, T_o, T_p, T_c, and ΔH_gel being 71.8, 75.9, 82.4°C and 5.1 J/g, respectively, whereas PR‐113 starch with lower crystallinity showed the lowest gelatinization temperatures (T_o, T_p, T_c, of 60.8, 65.7 and 72.2°C, respectively). Basmati‐386 starch exhibited two endotherms during heating, the first and second endotherm being associated with the melting of crystallites and amylose‐lipid complexes, respectively. T_o, T_p, T_c and ΔH_gel of the second endotherm of Basmati‐386 starch were 99.0, 100.1, 101.1°C and 2.0 J/g, respectively. During cooling, Basmati‐386 also showed an exotherm at a peak temperature of 87°C. PR‐113 starch with the highest amylose content and the lowest content of short side‐chains of amylopectin had the highest peak storage modulus (G′= 1.6×10⁴ Pa). The granules of PR‐113 starch were the least disintegrated after heating. The effects of heating starch suspensions at different temperatures (92°C, 130°C and 170°C) on intrinsic viscosity [η], transmittance and viscoelasticity were also studied to evaluate the extent of breakdown of the molecular structure. The intrinsic viscosity of starch suspensions heated at 92, 130 and 170°C ranged between 103–114, 96–110 and 28–93 mL/g. Transmittance value of starches cooked at 92°C decreased with increase in storage duration. All starches except PR103, cooked at 130°C also showed decrease in transmittance during storage, however, at lower rate. PR103 starch heated at 130°C did not show any change in transmittance up to a storage time of 48 h. The changes in viscoelasticity of starch pastes cooked at different temperatures during cooling and reheating were also evaluated. G′ and G′′ increased with decrease in temperature during cooling cycle. Starches heated at 130°C with apparent amylose content ≤ 21.2% showed an improvement in G′ and G′′ in comparison to the corresponding starches heated at 92°C, this improvement was observed to be higher in starches with lower amylose content. All starches heated at 170°C had a higher proportion of breakdown in molecular structure as indicated by lower G′ and G′′ than the same starches heated at 130 and 92°C.     

Extrusion of Rice,Bean and Corn Starches: Extrudate Structure and Molecular Changes in Amylose and Amylopectin

The objective of this study was to evaluate the effects of starch source and amylose content on the expansion ratio, density, and texture of expanded extrudates, as well as to investigate the structural and molecular changes that occur in starch granules as a function of extrusion. The starches employed were rice starches (8%, 20%, and 32% amylose), carioca bean starch (35% amylose), and Hylon V^® corn starch (55% amylose). The extrudates from rice starches containing 20% and 32% amylose exhibited the highest expansion ratio, while, extrudates from Hylon V^® corn starch containing 55% amylose exhibited the lowest expansion ratio. The hardness values of the extrudates with 55% amylose were twice those of the extrudates with 20%, 32%, and 35% amylose. An additional finding was that although the amylopectin promoted the expansion of the gelatinized starch matrix, it failed to strengthen and sustain the walls of the extrudate bubbles during expansion.     

Properties of Korean Amaranth Starch Compared to Waxy Millet and Waxy Sorghum Starches

Characteristics of waxy type starches isolated from amaranth, waxy millet and waxy sorghum harvested in Korea were evaluated. Shapes of all starch granules were polygonal or slightly round and the surfaces of waxy millet and waxy sorghum starch granules showed visible pores. Amylose contents of the three starches were between 3.2–6.0% and amaranth starch showed the highest water binding capacity (WBC) (130.7%). The swelling power and solubility of amaranth starch studied at 65.0–95.0°C increased about 13.7‐ and 14.0‐fold, respectively, with increase in temperature. Swelling power of waxy sorghum starch was the highest (72.6 at 95°C) among the starches studied, while amaranth starch had a constant swelling power and its rate of solubility increasely only slowly at temperatures higher than 75°C. From RVA data, initial pasting temperatures of amaranth, waxy sorghum and waxy millet starches were 75.7, 73.3 and 75.2°C, respectively. Peak viscosity, breakdown, and setback from trough of amaranth starch were 68.3, 16.7 and 7.5 RVU, respectively, which were the lowest values among the starches investigated. Using DSC, onset temperature of gelatinization of amaranth starch was 1.5–4.0°C higher than those of waxy sorghum and millet starches, corresponding to the RVA result. The enthalpies of gelatinization of the starches studied in our laboratory were in the range of 8.5–12.7 J/g with decreasing order of waxy sorghum > amaranth > waxy millet starch.     

Enhancement of Resistant Starch (RS3) in Amylomaize,Barley, Field Pea and Lentil Starches

Native starches isolated from amylomaize. Glacier high amylose barley, field peas and lentils contained 3–5% (w/w) resistant starch (RS3). Retrograded gels that were prepared from these starches had higher RS3 (6–9%) contents. The effects of gel concentration (% starch), storage temperature and time on the RS3 content of the retrograded gels were investigated; the optimum RS3 content was determined in gels prepared at = 10% (w/v) starch concentration and stored under = 20°C for = 5 days. Annealing of the retrograded starch gels by heating and cooling cycles, further enhanced RS3 content to 9–19%; the effect of annealing temperature and number of heat-cool cycles on the RS3 content of the annealed gel were studied. The hydrolysis of retrograded starch gels by pulanase enzyme or acid (2.2 N HCl), prior to annealing, enhanced the RS3 formation during annealing; the enzyme or acid treatment increased RS3 content of the annealed gel to 15–24% or 17–24%, respectively. The potential molecular mechanism that is responsible for the RS3 increase is discussed.     

Structure and Physicochemical Properties of Endosperm Starches of a Waxy Allelic Series and Their Respective Normal Counterparts in the Inbred Oh43 Maize Background

Research over the past three decades has greatly increased our understanding of the biochemical genetics of various waxy (wx) alleles of maize, but our knowledge about the structure and physicochemical properties of endosperm starches obtained from the wx alleles is still incomplete. We further investigated the structure and physicochemical properties of endosperm starches from a wx allelic series and their normal counterparts in the Oh43 inbred background. Starch granules were prepared from mature kernels of wx mutant alleles; wx-C31, wx-R, wx-90, wx-a, wx-B3, wx-m-1, wx-m-8, and wx-S5, and their respective normal counterparts in the inbred Oh43 maize background. Measurements of absorption spectra of starch-iodine complexes and by gel permeation chromatography of Pseudomonasisoamylase-debranched starches showed that all of the starches from the wx allelic series were uniquely waxy type in characteristics, and their normal counterparts were characteristically normal type. Pasting characteristics of starch granules and retrograded starches of the wx allelic series and their respective normal counterparts were investigated by differential scanning calorimetry (DSC). The peak temperature (Tp) and conclusion temperature (Tc) values from starches of the wx allelic series were slightly higher than those of their respective normal counterparts and the ΔHs of starches of the wx allelic series were greater than those of their respective normal counterparts. The onset temperature (To), Tp, and Tc of all retrograded starches were very similar, however, the ΔHs of the retrograded starches of the wx allelic series were greate than those of their respective normal counterpart. Starch granules of the wx allelic series were hydrolyzed more rapidly than those of their respective normal counterparts.