Structural characterization of Peruvian carrot (Arracacia xanthorrhiza) starch and the effect of annealing on its semicrystalline structure

Structural characteristics of native and annealed Peruvian carrot (Arracacia xanthorrhiza) starches were determined and compared to those of cassava and potato starches. Peruvian carrot starch presented round and irregular shaped granules, low amylose content and B-type X-ray pattern. Amylopectin of this starch contained a large proportion of long (DP > 37) and short (DP 6-12) branched chains. These last ones may contribute to its low gelatinization temperature. After annealing, the gelatinization temperatures of all starches increased, but the ΔH and the crystallinity increased only in Peruvian carrot and potato starches. The annealing process promoted a higher exposure of Peruvian carrot amylose molecules, which were more quickly attacked by enzymes, whereas amylopectin molecules became more resistant to hydrolysis. Peruvian carrot starch had structural characteristics that differed from those of cassava and potato starches. Annealing affected the semicrystalline structure of this starch, enhancing its crystallinity, mainly due to a better interaction between amylopectin chains.     

Physicochemical and structural properties of maize and potato starches as a function of granule size

Chemical composition, molecular structure and organization, and thermal and pasting properties of maize and potato starches fractionated on the basis of granule size were investigated to understand heterogeneity within granule populations. For both starches, lipid, protein, and mineral contents decreased and apparent amylose contents increased with granule size. Fully branched (whole) and debranched molecular size distributions in maize starch fractions were invariant with granule size. Higher amylose contents and amylopectin hydrodynamic sizes were found for larger potato starch granules, although debranched molecular size distributions did not vary. Larger granules had higher degrees of crystallinity and greater amounts of double and single helical structures. Systematic differences in pasting and thermal properties were observed with granule size. Results suggest that branch length distributions in both amylose and amylopectin fractions are under tighter biosynthetic control in potato starch than either molecular size or amylose/amylopectin ratio, whereas all three parameters are controlled during the biosynthesis of maize starch.     

Characterization of Maize Starch Nanoparticles Prepared by Acid Hydrolysis

Starch nanoparticles (SNP) from maize starches of varying amylose content (0–71%) were prepared by acid hydrolysis (3.16M H₂SO_4, at 40°C up to 6 days) followed by repeated water washings. During the washing cycles, nonwaxy starches (normal, Hylon V, and Hylon VII) had suspended particles in the water washings, which were not evident in waxy starch. Microscopic examination revealed the presence of SNP in the “cloudy supernatants” of nonwaxy starches and in the “final washed residue” of waxy maize. The objective of this study was to collect SNP fractions accordingly and determine whether variation in the native starch amylose content would influence the yield, morphology, and crystallinity of the SNP. In nonwaxy starches, the yield of SNP increased up to 26.6% with hydrolysis time and was proportional to the amylose content. Morphology of SNP differed with starch type: flat/elliptical (500 nm) in waxy, oval/irregular (50–200 nm) in normal, oval/round (40–50 nm) in Hylon V, and square/polygonal (50–100 nm) in Hylon VII. X‐ray diffraction confirmed the presence of A‐type crystals in SNP from all starch types and a crystalline transformation from B‐ to A‐type in Hylon starches. The relative crystallinity of SNP was higher than their native starch counterparts.     

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.     

Structural properties of hydrolyzed high-amylose rice starch by α-amylase from Bacillus licheniformis

High-amylose cereal starch has a great benefit on human health through its resistant starch (RS) content. Enzyme hydrolysis of native starch is very helpful in understanding the structure of starch granules and utilizing them. In this paper, native starch granules were isolated from a transgenic rice line (TRS) enriched with amylose and RS and hydrolyzed by α-amylase. Structural properties of hydrolyzed TRS starches were studied by X-ray powder diffraction, Fourier transform infrared, and differential scanning calorimetry. The A-type polymorph of TRS C-type starch was hydrolyzed faster than the B-type polymorph, but the crystallinity did not significantly change during enzyme hydrolysis. The degree of order in the external region of starch granule increased with increasing enzyme hydrolysis time. The amylose content decreased at first and then went back up during enzyme hydrolysis. The hydrolyzed starches exhibited increased onset and peak gelatinization temperatures and decreased gelatinization enthalpy on hydrolysis. These results suggested that the B-type polymorph and high amylose that formed the double helices and amylose-lipid complex increased the resistance to BAA hydrolysis. Furthermore, the spectrum results of RS from TRS native starch digested by pancreatic α-amylase and amyloglucosidase also supported the above conclusion.     

Physical properties of octenyl succinic anhydride modified rice,wheat, and potato starches

The physical properties of octenyl succinic anhydride (OSA) starches prepared from rice, wheat, and potato starches were studied. Rice and wheat OSA starches had significantly higher peak viscosity (PV), hot paste viscosity (HPV), and cool paste viscosity (CPV), but potato OSA starch had only significantly higher CPV, relative to the native starch. The gel hardness was higher with lower degree of substitution (DS) but lower with higher DS OSA compared to native starch. The swelling volumes (SV) of rice and wheat OSA starches were significantly higher compared to native starch, but the SV of potato OSA starch was slightly lower at high DS. The gelatinization temperature (GT) of rice OSA starches was sharply lower at low DS; for wheat OSA starch it was slightly lower even at high DS, but potato OSA starches had higher GT than the native starch. The enthalpy of all the OSA starches decreased gradually with increased DS. This study showed that the magnitude of changes in physical properties of OSA-modified starches depends not only on their DS but also on the botanical origin of the native starches.     

Morphological, structural, thermal, and rheological characteristics of starches separated from apples of different cultivars

The starches were separated from unripe apples of five cultivars (Criterion, Ruspippum, Red Spur, Skyline Supreme, and Granny Smith) and evaluated using scanning electron microscopy (SEM), gel permeation chromatography (GPC), X-ray diffraction, differential scanning calorimetry (DSC), and dynamic viscoelasticity. SEM showed the presence of round granules as well as granules that had been partially degraded, probably by amylases. The starch granules in different apple starches ranged between 4.1 and 12.0 mum. Debranching of starch with isoamylase and subsequent fractionation of debranched materials by GPC revealed the presence of an apparent amylose, an intermediate fraction (mixture of amylose and amylopectin), long side chains of amylopectin, and short side chains of amylopectin in the range of 28-35.2, 3.6-4.4, 20-21.3, and 39.9-47.1%, respectively. The swelling power of starches ranged between 14.4 and 21.3 g/g. X-ray diffraction of apple starches showed a mixture of A- and B-type patterns. All apple starches showed peak intensities lower than that observed for normal corn and potato starch, indicating the lower crystallinity. The transition temperatures (onset temperature, T(o); peak temperature, T(p); and conclusion temperature, T(c)) and enthalpy of gelatinization (deltaH(gel)) determined using DSC ranged between 54.7 and 56.2 degrees C, between 57.1 and 59.1 degrees C, between 60.2 and 63.5 degrees C, and between 3.3 and 4.2 J/g, respectively. The viscoelastic properties of starch from different cultivars measured during heating and cooling using a rheometer differed significantly. Red Spur and Criterion starches with larger granule size showed higher G' and G' ' values, whereas those containing smaller size and amylolytically degraded granules showed lower G' and G' '.     

Thermomechanical Behavior of Concentrated Starch-Water Preparations

The rheological behavior of concentrated starch preparations from various origins was studied by dynamic mechanical thermal analysis (DMTA). Four types of starch were used: wheat, potato, normal, and waxy corn adjusted to moisture contents in the 42–49% (w/w) range. The thermal treatments of the starch-water mixtures consisted of heating to 85°C and cooling to room temperature, both at a rate of 1°C/min. During heating, the storage modulus (E′) appearance was first characterized by an increase with a maximum at ≈70°C (or potato starch at 63°C) followed by a decrease to 85°C. During cooling, storage modulus increased steadily down to room temperature. The magnitude of these variations depended on the starch type. Despite some differences, all the loss tangent curves showed a decrease during heating from 60–70°C to 85°C, followed by a plateau during cooling. To propose an interpretation for the DMTA results, we measured, by laser-light diffraction, the influence of heating (up to the maximum E′ peak) on the distribution of the granule sizes of the different starches. Moreover, differential scanning calorimetry (DSC) was used to measure the temperature range where the melting of starches ordered regions occurred. Partial melting enthalpies were plotted against temperature. The hypothesis of a relationship between swelling and an increase in rigidity during heating seemed to be confirmed by laser-light diffraction, whereas DSC indicated the decrease in rigidity was caused predominantly by order-disorder transitions. During cooling, amylose gelation plays a major role in the rigidity increase, but a contribution of amylopectin is not excluded.     

Comparative study of the retrogradation of intermediate water content waxy maize, wheat, and potato starches

The retrogradation of extruded starches from three different botanical sources was studied in concentrated conditions (34 +/- 1% water) at 25 degrees C using differential scanning calorimetry (DSC) and isothermal calorimetry, Fourier transform infrared spectroscopy (FTIR), and wide-angle X-ray scattering. Potato starch showed the highest rate of retrogradation (approximately 0.17 h(-1)) followed by waxy maize (approximately 0.12 h(-1)), while the retrogradation of wheat starch was the slowest (approximately 0.05 h(-1)). In addition to the kinetics, the extent of molecular order in the retrograded samples was studied in detail in terms of "short-range" (helical) and "long-range" (crystalline) distance scales. The amylopectin crystallinity indices were essentially the same (approximately 47-51% amylopectin basis) for the three starches. However, significant differences were found in the enthalpy of melting measured by DSC after "full" retrogradation (potato, 11.6 +/- 0.7; waxy maize, 9.0 +/- 0.5; and wheat, 6.1 +/- 0.3 J/g of amylopectin). The degree of short-range molecular order in the retrograded state determined by FTIR was waxy maize > potato > wheat. The effect of amylopectin average chain length and the polymorphism of the crystalline phase were taken into account to explain the differences in the retrogradation enthalpies.     

Properties and Structures of Flours and Starches from Whole,Broken, and Yellowed Rice Kernels in a Model Study

The objective of this study was to compare the structure and properties of flours and starches from whole, broken, and yellowed rice kernels that were broken or discolored in the laboratory. Physicochemical properties including pasting, gelling, thermal properties, and X‐ray diffraction patterns were determined. Structure was elucidated using high‐performance size‐exclusion chromatography (HPSEC) and high‐performance anion‐exchange chromatography with pulsed amperometric detection (HPAEC‐PAD). The yellowed rice kernels contained a slightly higher protein content and produced a significantly lower starch yield than did the whole or broken rice kernels. Flour from the yellowed rice kernels had a significantly higher pasting temperature, higher Brabender viscosities, increased damaged starch content, reduced amylose content, and increased gelatinization temperature and enthalpy compared with flours from the whole or the broken rice kernels. However, all starches showed similar pasting, gelling, thermal properties, and X‐ray diffraction patterns, and no structural differences could be detected among different starches by HPSEC and HPAEC‐PAD. α‐Amylase may be responsible for the decreased amylopectin fraction, decreased apparent amylose content, and increased amounts of low molecular weight saccharides in the yellowed rice flour. The increased amount of reducing sugars from starch hydrolysis promoted the interaction between starch and protein. The alkaline‐soluble fraction during starch isolation is presumed to contribute to the difference in pasting, gelling, and thermal properties among whole, broken, and yellowed rice flours.     

Effects of Amylopectin Branch Chain Length and Amylose Content on the Gelatinization and Pasting Properties of Starch

Structures and properties of starches isolated from different botanical sources were investigated. Apparent and absolute amylose contents of starches were determined by measuring the iodine affinity of defatted whole starch and of fractionated and purified amylopectin. Branch chain-length distributions of amylopectins were analyzed quantitatively using a high-performance anion-exchange chromatography system equipped with a postcolumn enzyme reactor and a pulsed amperometric detector. Thermal and pasting properties were measured using differential scanning calorimetry and a rapid viscoanalyzer, respectively. Absolute amylose contents of most of the starches studied were lower than their apparent amylose contents. This difference correlated with the number of very long branch chains of amylopectin. Studies of amylopectin structures showed that each starch had a distinct branch chain-length distribution profile. Average degrees of polymerization (dp) of amylopectin branch chain length ranged from 18.8 for waxy rice to 30.7 for high-amylose maize VII. Compared with X-ray A-type starches, B-type starches had longer chains. A shoulder of dp 18–21 (chain length of 6.3–7.4 nm) was found in many starches; the chain length of 6.3–7.4 nm was in the proximity of the length of the amylopectin crystalline region. Starches with short average amylopectin branch chain lengths (e.g., waxy rice and sweet rice starch), with large proportions of short branch chains (dp 11–16) relative to the shoulder of dp 18–21 (e.g., wheat and barley starch), and with high starch phosphate monoester content (e.g., potato starch) displayed low gelatinization temperatures. Amylose contents and amylopectin branch chain-length distributions predominantly affected the pasting properties of starch.     

Physicochemical Properties of Pueraria Root Starches and Their Effect on the Improvement of Buckwheat Noodle Quality

The physicochemical properties of starches from cultivated Pueraria thomsonii Benth were examined and compared with those of P. lobata (Willd.) Ohwi and other root starches, and the effect of pueraria root starches on the improvement of buckwheat noodle quality was investigated. The total content of isoflavones in P. thomsonii root starches was higher than in P. lobata root starches, and the size and uniformity of those particles displayed a significant difference. The gel stabilities of pueraria root starches were similar and more favorable than those of potato starch and sweet potato starch. For the amylose molecular properties of pueraria root starches, the λ_max and blue value index were higher than those of the potato starch and the sweet potato starch, whereas the amylose content and degree of polymerization were much lower in comparison. However, amylopectin branch lengths of pueraria root starches were shorter. Thus, pueraria root starches could improve the quality of buckwheat noodles and enhance their nutritional function. Therefore, pueraria root starches may be regarded as raw materials that influence the quality of buckwheat noodles.     

Influence of Botanical Source and Processing on Formation of Resistant Starch Type III

Influence of botanical source and gelatinization procedure (autoclaving or boiling) on resistant starch (RS) formation was investigated in starches from wheat, corn, rice, and potato. RS yields did not vary within the same sample but differed among samples with different starch botanical sources. Differences also existed in RS contents in native and retrograded starches. Slight or minor variations in RS values were found after both gelatinization procedures, although no clear pattern was found in the behavior of samples based on gelatinization procedure. The degree of polymerization (DP) of retrograded samples was assigned using high-performance anion exchange chromatography with pulsed amperometric detector (average DP 50–60), with no differences between autoclaved and boiled samples.     

Octenyl succinic anhydride modified early indica rice starches differing in amylose content

Seven early indica rice starches with different amylose contents were modified by octenyl succinic anhydride (OSA) in aqueous suspension systems to evaluate the effect of amylose contents on starch esterification. The crystalline structure and pasting properties of starches were investigated using X-ray diffraction and a Rapid Visco Analyzer (RVA). The results indicated that the amylose content had a positive impact on the OSA modification. As the amylose content increased from 0 to 39.6%, the degree of substitution increased from 0.024 to 0.030 and the reaction efficiency increased from 62.8 to 77.5%. X-ray diffraction scans confirmed that the amylose was mainly present in the amorphous domain of the granule and was highly substituted after the OSA treatment. The RVA profiles demonstrated that the OSA starches had higher viscosities than their native counterparts. Moreover, negative correlations were observed between the amylose content and the major RVA parameters (e.g., peak viscosity, hot paste viscosity, cool paste viscosity, and breakdown viscosity).     

Determination of the molecular and structural characteristics of okenia, mango, and banana starches

Starches were isolated from nonconventional sources (banana, mango, and okenia) and their characteristics were examined using polarized light microscopy, X-ray diffraction pattern, Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). Banana starch granules were of an ellipsoidal shape with size between approximately 8 and 20 microm; okenia had the smallest granule size, between approximately 2 and 5 microm. The three starches showed the Maltese cross, indicative of an intact granule structure. Okenia and mango starches had the A-type X-ray diffraction pattern, common to native cereal starches, whereas banana starch showed a mixture between A- and B-type pattern. Banana starch had the highest temperature (77.6 degrees C) and enthalpy (23.4 J/g) of gelatinization in excess water conditions; okenia had the lowest temperature (71.2 degrees C) and enthalpy (15 J/g), which may be related to the X-ray diffraction pattern and its small granule size. Both the okenia and mango starches had a higher molar mass and gyration radius than banana starch, which may be related to the differences determined in their crystalline structures.     

General Application of Raman Spectroscopy for the Determination of Level of Acetylation in Modified Starches

A method using Raman spectroscopy was recently developed for the determination of the degree of acetylation in modified wheat starch. In this article, we show that the method can be generalized to a wide range of starches of different botanical origin and amylose content. Calibration sets were used to develop regression equations for 11 types of acetylated starches, including cereal (rice, maize, wheat) and noncereal (potato and sweetpotato) sources. The calibration lines were then used to predict the level of acetylation of starch samples with unknown level of acetylation using their Raman spectra. In each case, R² > 0.98 for linear regression of Raman vs. titrimetric determination of acetylation. The Raman-based calibration curves allow fast and nondestructive determination of the degree of acetylation for different types of starches.     

Molecular Size Distribution and Amylase Resistance of Maize Starch Nanoparticles Prepared by Acid Hydrolysis

The molecular size distribution of maize starch nanoparticles (SNP) prepared by acid hydrolysis (3.16M H₂SO₄) and their amylase‐resistant counterparts, before and after debranching, was investigated. The weight average molecular weight (M_w) and linear chain length distribution were determined by high‐performance size‐exclusion chromatography (HPSEC) and high‐performance anion‐exchange chromatography (HPAEC), respectively. The objective was to understand the role of amylose involvement in the formation of SNP showing different crystalline structures (A‐ and B‐types). The HPSEC profiles of SNP before debranching from waxy, normal, and high‐amylose maize starches showed broad monomodal peaks. Debranched SNP from waxy maize eluted in a single narrow peak, whereas those from nonwaxy starches showed a multimodal distribution. Similar trends were also observed for the chain length distribution patterns, for which the longest detectable chains (degree of polymerization [DP] 31) in waxy maize were significantly lower than those of nonwaxy maize starches (DP 55–59). This indicated the potential amylose involvement in the SNP structure of normal and high‐amylose starches. Further evidence of amylose involvement was ascribed to the resistance of SNP toward amylolysis (Hylon VII > Hylon V > normal > waxy). The amylase‐resistant residues of SNP from high‐amylose maize starches were composed of both low M_w linear and branched chains.     

Physicochemical Properties of Zero Amylose Hull-less Barley Starch

Zero amylose starch isolated from hull-less barley (HB) showed a typical A-type diffraction pattern. The X-ray analysis suggested that granules of zero amylose (SB94794) and 5% amylose (CDC Candle) HB starches had lower crystallinity than did commercial waxy corn starch. Differential scanning calorimetry showed lower transition temperatures and endothermal enthalpies for the HB starches than for the waxy corn starch. The zero amylose HB starch showed a Brabender pasting curve similar to that of waxy corn starch, but with lower pasting and peak temperatures and a higher peak viscosity. Noteworthy characteristics of zero amylose HB starch were its low pasting temperature and high paste clarity and freezethaw stability, which make this starch useful for many food and industrial applications.     

碾轧时间和频率对玉米淀粉机械力化学效应的影响

为了研究碾轧对玉米淀粉机械力化学效应的影响,该研究以玉米淀粉为原料,采用扫描电镜、偏光显微镜、激光共聚焦显微镜、X-射线衍射、傅立叶变换红外光谱仪、差示扫描量热仪、快速黏度分析仪等手段来研究碾轧处理时间和转速对样品的表面形貌、粒度分布、结晶结构、糊化特性和热特性等结构和性质的影响。结果表明,在频率为20 Hz条件下,碾轧处理3~9 h时,碾轧对淀粉结晶结构破坏作用较弱,主要是对颗粒的无定型区产生了破坏作用,破坏了无定型区的双螺旋结构,中央腔变大,孔道模糊。碾轧处理3~6 h时,淀粉颗粒形状发生不规则变化,粒径也发生了相应的变化,热焓值下降,而结晶度下降不显著。在碾轧处理9 h时,球状凸起变大,水溶指数、膨胀度、透光率、峰值黏度和热焓值都有所减小,而淀粉乳稳定性增强。碾轧处理12~24 h时,淀粉颗粒表面球状凸起变的不明显,淀粉颗粒结晶区内部双螺旋结构破坏,孔道增多变粗,粒径增大,热焓值下降。总之,频率为20 Hz时的碾轧处理对淀粉颗粒的无定形区、结晶区产生不同程度的机械力化学作用,导致玉米淀粉颗粒内部依次发生了受力、聚集和团聚效应。而频率为30 Hz时,由于剪切力更强,碾轧处理对淀粉结构和性质的影响更为显著。     

Effect of Dry Heating on Physicochemical Properties of Pregelatinized Rice Starch

Japonica and indica rice starches (10% w/w) were pregelatinized in a boiling water bath for 5 or 10 min and subsequently heat‐treated in a dry state for 0, 1, 2, or 3 h at 130°C to examine the effects of dry heating on pasting viscosity, paste clarity, thermal properties, X‐ray diffraction pattern, and gel strength of pregelatinized starches. Heat treatment obviously changed the physicochemical properties of pregelatinized rice starch. The pregelatinized rice starches had higher peak viscosity and final viscosity than the corresponding native rice starches. Heat treatment of pregelatinized rice starch for 1 h increased the peak viscosity, but treatment for 2 or 3 h decreased the peak viscosity compared with the unheated pregelatinized rice starch. The indica rice starch exhibited more substantial changes in pasting viscosity than did japonica rice starch during heat treatment. The melting enthalpy of the endothermic peak occurred at 90–110°C, and the intensity of the X‐ray diffraction peak at 20° was increased by dry heating, possibly owing to the enhanced amylose‐lipid complexes. The dry heat treatment of pregelatinized starch caused an increase in paste clarity and a decrease in gel strength.