Chemical and Physical Characterisation of Grain Tef [Eragrostis tef (Zucc.) Trotter] Starch Granule Composition

Chemical and physical properties of starch granules isolated from five grain tef (Eragrostis tef) varieties were characterised and compared with those of maize starch. Endogenous starch lipids extracted with hot water‐saturated n‐butanol and total starch lipids extracted with n‐hexane after HCl hydrolysis were 7.8 mg/g (mean) and 8.9 mg/g (mean), respectively, slightly lower than in the maize starch granules. The starch phosphorus content (0.65 mg/g) was higher than that of maize starch but virtually the same as reported for rice starch. The starch granule‐swelling factor was lower than that of maize starch and extent of amylose leaching was higher. The starch X‐ray diffraction pattern was characteristic of A type starch with a mean crystallinity of 37%, apparently lower than the crystallinity of maize starch and more similar to that reported for rice and sorghum starches. The starch DSC gelatinisation temperature was high, like for other tropical cereals; T_o, T_p, T_c and ΔH were in the range 63.8—65.4, 70.2—71.3, 81.3—81.5 °C and 2.28—7.22 J/g, respectively. The lower swelling, apparently lower percentage crystallinity and lower DSC gelatinisation endotherms than maize starch suggest that the proportion of long amylopectin A chains in tef starch is smaller than in maize starch.     

Measurement of electrical conductivity,differential scanning calorimetry and viscosity of starch and flour suspensions during gelatinisation process

Electrical conductivity measurements were applied to analyse the gelatinisation process of 12 starch or flour suspensions. The electrical conductivity of starch suspensions was found to increase upon gelatinisation because of the release of ions from starch granules. The initiation temperature of ion release, T_i, correlated well with the onset temperature in the DSC thermogram (R = 0.868), while the completion temperature of ion release, T_f, correlated with the temperature at the start of viscosity increase (R = 0.865). Thus T_i and T_f corresponded to the beginning and ending temperatures of gelatinisation respectively. The electrical conductivity measurement will be used as an on‐line technique to monitor the whole process of starch gelatinisation. © 2001 Society of Chemical Industry     

Structural properties and gelatinisation characteristics of potato and cassava starches and mutants thereof

The molecular size of amylopectin (AP) and amylose (AM), AP chain length distribution, crystallinity and granular structure (morphology and granule size distribution) of five wild type potato starches (wtps), five AM free potato starches (amfps), four high-AM potato starches (haps), one wild type cassava starch (wtcs) and one AM free cassava starch (amfcs) were investigated and related to their gelatinisation characteristics. Starches with higher levels of short chains [degree of polymerisation (DP) 6–9 and DP 10–14)] had lower gelatinisation onset (T_o), peak (T_p) and conclusion (T_c) temperatures, whereas higher contents of longer chains (DP 18–25 and DP 25–80) led to higher gelatinisation temperatures. Gelatinisation enthalpies (ΔH) increased with degree of crystallinity. The granules of wtps were larger than those of amfps and haps, respectively. No differences in morphology were observed between wtps and amfps granules, but the haps granules had more irregular surfaces and showed multi-lobed granules.     

Resistant starch and thermal,morphological and textural properties of heat‐moisture treated rice starches with high‐, medium‐ and low‐amylose content

This study investigated the effects of heat‐moisture treatment (HMT) on the resistant starch content and thermal, morphological, and textural properties of rice starches with high‐, medium‐ and low‐amylose content. The starches were adjusted to 15, 20 and 25% moisture levels and heated at 110°C for 1 h. The HMT increased the resistant starch content in all of the rice starches. HMT increased the onset temperature and the gelatinisation temperature range (T_finish–T_onset) and decreased the enthalpy of gelatinisation of rice starches with different amylose contents. This reduction increased with the increase in the moisture content of HMT. The morphology of rice starch granules was altered with the HMT; the granules presented more agglomerated surface. The HMT affected the textural parameters of rice starches; the high‐ and low‐amylose rice starches subjected to 15 and 20% HMT possessed higher gel hardness.     

Physicochemical,crystalline, and thermal properties of native,oxidized, acid,and enzyme hydrolyzed Chinese yam (Dioscorea opposite Thunb) starch

Native yam starch was modified by oxidation (with sodium hypochlorite), acid, and enzyme (with gluco‐amylase), respectively. Ash content, fat content, protein, and AM contents were reduced following modifications. All the modifications reduced swelling capacity whereas improved the solubility. The SEM of the native starch showed the presence of large oval or spherical to small irregular‐shaped granules, however, oxidation and hydrolysis caused collapse of the granules. From the XRD, the typical C‐type XRD pattern of the native starch changed to the typical A‐type XRD pattern of the three modified starches. The above results also demonstrated that amorphous region of yam starch granules was preferentially degraded than crystalline region of granules. DSC showed that oxidation and acid/enzyme hydrolysis reduced peak temperature of gelatinization (T_p) of native starch significantly. Enthalpy of gelatinization (ΔH) of oxidation and enzyme starch was reduced but it has no obviously change following acid modification.     

Morphological,thermal, rheological and retrogradation properties of potato starch fractions varying in granule size

The physicochemical properties of small, medium and large starch granules separated from four potato cultivars were investigated to reveal whether functional properties differed among the various size classes of the starches. Large‐size fractions showed higher amylose content and light transmittance and lower swelling power than small‐size fractions. The granules from the three fractions had diameters of 5–20, 25–40 and 40–85 µm respectively. The large and medium granules were ellipsoidal to irregular or cuboidal while the small granules were spherical or ellipsoidal in shape. The transition temperatures and gelatinisation temperature range of the fractionated starches increased while the enthalpy of gelatinisation decreased with decreasing granule size. Rheological parameters such as peak storage (G′) and loss (G″) moduli increased in the order small‐, medium‐ and large‐granule starches when subjected to temperature sweep testing. The breakdown in peak G′ during the heating cycle and retrogradation during storage were found to be highest for large‐ and lowest for small‐size fractions. The differences in functional properties among the different size fractions suggested that the granule size distribution is an important parameter that can influence the behaviour of potato starch during processing. Copyright © 2004 Society of Chemical Industry     

Formation of starch spherulites: Role of amylose content and thermal events

Commercial maize starches and potato starches of two cultivars differing in physicochemical composition (granule size distribution; amylose to amylopectin ratio) and crystallinity were heated to 180 °C and then cooled by fast quench using a differential scanning calorimeter (DSC), in order to produce spherulitic starch morphologies. Among the raw maize starches, waxy maize starch had highest relative crystallinity (49%) whereas a lowest crystallinity of 33–39% was calculated for high-amylose maize starches. Potato starches showed a relative crystallinity of 50%. The temperatures and enthalpies of gelatinisation and melting varied among all the starches. High-amylose maize starches showed higher transition temperatures of gelatinisation (T_gel), whereas waxy maize starch had lowest T_gel and enthalpy of gelatinisation (ΔH_gel). Similarly, a considerable variation in parameters related with crystalline melting (T_m1, T_m2 and ΔH_m1, ΔH_m2) was observed for different starches. The superheated gels of different starches treated using DSC were subjected to polarised microscopy, to confirm the formation of spherulites. Both the high-amylose starch gels showed the presence of spherulites exhibiting birefringence and a weak crystalline pattern. No birefringence was observed for waxy maize starch gel, while potato starch gels had some birefringence. The particle size distribution of high-amylose maize starch gels analysed through Zetasizer showed the sizes of spherulitic particles fall in the range of 300 nm–900 nm. The scanning electron micrographs of the dried high-amylose maize starch gels showed the presence of round spherulites consisting of several aggregated spherulitic particles. Amylose content and melting of crystallites during heating play an important role during recrystallisation of amylose (spherulite morphologies).     

Characterization of Dextrins obtained by Enzymatic Treatment of Cationic Potato Starch

The substitution pattern of cationic potato starches was studied using starch hydrolyzing enzymes and a characterization of the hydrolysis products. Native and cationic starch samples were hydrolyzed with pullulanase, isoamylase, and α‐amylase and the molecular‐weight distributions of the resulting dextrins were studied using gel permeation chromatography. Isoamylase hydrolyzed the native potato starch sample readily, whereas hydrolysis with pullulanase was incomplete. Pullulanase hydrolyzed, however, cationic starch with higher DS (degree of substitution) more efficiently than isoamylase. The hydrolysis products obtained with pullulanase were separated according to charge using cation‐exchange chromatography into one unbound and two bound fractions. The unbound fraction possessed an increasing number of short chains from amylopectin with increasing DS of the starch sample. The bound material contained amylose and dextrins with sizes corresponding to the long B‐chains. The high portion of uncharged dextrins after α‐amylolysis suggested that the substitution pattern, on the molecular level, was non‐random. The composition of the unbound and bound material, obtained by ion‐exchange chromatography of α‐amylase treated starches, suggested a more intense fragmentation with increasing DS of the sample. Possibly, the substituents influence substrate conformation and thereby alter the hydrolysis patterns. It is concluded that a thorough understanding of the enzymatic hydrolysis patterns is of ultimate importance in structural studies of modified starch.     

Starch properties of various potato (Solanum tuberosum L) Cultivars susceptible and resistant to low-temperature sweetening

Properties of starch granules isolated from different varieties and selections of potato (which vary in their degree of chill sweetening) were examined. Differential scanning calorimetry (DSC) showed an increase in resistance to gelatinisation of isolated starch granules which correlated (r = 0.911) with higher chip scores following storage at 4°C and 12°C. Varying water level content during DSC studies resulted in significantly lower water content required to produce two endotherms for starch isolated from varieties resistant to chill sweetening. These data strongly suggest that starch granule composition might be a factor differentiating the low temperature sweetening sensitive from resistant cultivars, and may provide a screening method for predicting chip colour of potatoes out of storage.     

玉米淀粉退火处理及其性质变化

采用扫描电子显微镜(SEM)、激光粒度分析仪(LPA)、X射线粉末衍射仪(XRD)和差示扫描量热仪(DSC)研究退火处理对玉米淀粉颗粒形貌、粒径大小、晶体结构和热力学性质的影响。结果显示:退火处理会改变玉米淀粉颗粒的外貌,使其微孔增多,孔径增大;退火处理会增加玉米淀粉颗粒粒径;退火处理不涉及玉米淀粉晶体结构的变化;退火处理会使玉米淀粉糊化温度显著增高,糊化温度范围变窄;原玉米淀粉(NC)和退火处理玉米淀粉(AC)的溶解度和膨胀率都随着温度的升高而增大,在相同温度条件下,退火处理玉米淀粉(AC)溶解度和膨胀率均小于原玉米淀粉(NC)。     

Comparison of the morphological,crystalline, and thermal properties of different crystalline types of starches after acid hydrolysis

A‐type maize starch, B‐type Fritillaria ussurensis, and C‐type Rhizoma dioscorea starches were hydrolyzed (32 days) with 2.2 N HCl. Regardless of the crystallinity level, starch with predominant B‐crystalline type was less susceptible to acid degradation than A‐type and C‐type starches, and initial rates of hydrolysis in B‐type was lower than others. The SEM and XRD results revealed that different types of starch displayed different hydrolysis mechanisms. The acid corrosion started from the exterior surface of A‐type and B‐type starches followed by the core of granules. However, the hydrogen ions primarily attacked the interior of the C‐type R. dioscorea starch granules and then the exterior. FT‐IR results confirmed that the amorphous regions in the starch granules were hydrolysed first. After 8–32 days of hydrolysis, the acid‐modified C‐type starch showed typical A‐type characteristics upon analysis of the XRD pattern. The average particle size of hydrolytic starch decreased with increasing hydrolysis time. The thermal results revealed that the hydrolytic starch showed lower ΔH than the native starch, while displaying higher peak width (T_c − T_o) value.     

Hydration and physicochemical properties of small‐particle cassava starch

Acid hydrolysis followed by ball milling was applied to cassava starch in order to fracture the granules. Lintnerisation led to degradation first in the amorphous domains and increased the crystallinity. The resulting increase in internal defects and brittleness made the granules more susceptible to breakage upon milling. Ball milling, although leading to some degree of crystallinity loss, could effectively reduce the size of acid‐hydrolysed starch while the total double helix remained relatively unchanged. The resulting small‐particle starch was structurally more heterogeneous (wider T_m range). Swelling of small‐particle starch was accompanied by solubilisation of water‐soluble fragments at a temperature greater than 60 °C. The properties of individual granules are strongly influenced by the hydration and physicochemical properties of their amorphous and crystalline domains. © 2002 Society of Chemical Industry     

Effect of heat treatment on quality, thermal and pasting properties of sweet potato starch during yearlong storage

BACKGROUND: Proper postharvest handling and storage of sweet potato is an important link in the chain from producer to consumer or manufacturing industry. Heat treatments have been used as a non‐chemical means to modify the postharvest quality and reduce pathogen levels and disease development of a wide variety of horticultural products. The objective of this study was to investigate the effects of hot water treatment (HWT) on the quality, gelatinisation enthalpy and pasting properties of sweet potato starch during long‐term storage. The weight loss, sprouting, spoilage and sugar content of sweet potato were also determined. RESULTS: HWT significantly inhibited the sprouting and decay of sweet potato during the storage period. There were no significant differences (P < 0.05) in the pasting properties and onset (T_O), peak (T_P) and endset (T_E) temperatures of gelatinisation of sweet potato starch among all treatments, especially between heat‐treated and non‐heat‐treated samples. HWT also had no significant impact on the quality of the internal components of the roots. Less than 4% of the yearlong‐stored roots were discarded owing to spoilage. HWT supplied a lethal dose of heat to surface pathogens and black spot without damaging the nutritional and processing qualities of sweet potato. CONCLUSION: HWT was an effective method to reduce root sprouting and deterioration without significant impact on the quality of the internal components of sweet potato. This novel technique will open a new avenue to extend the storage life of sweet potato with good quality and minimal waste. Copyright © 2011 Society of Chemical Industry     

Changes in Crystallinity and Gelatinization Phenomena of Potato Starch by Acid Treatment

The hydrolysis of potato starch by 1-N H₂SO₄/30% ethanol aqueous solution at 45°C increased linearly with increasing of hydrolysis time for 14 d. The relative crystallinity of native starch showed 0.343 and 0.350 by symmetrical reflection and transmission techniques, resp. The increasing ratio of relative crystallinity to hydrolysis time corresponded very closely with that of 1/hydrolysis residue up to 14 d. These facts suggest that only the amorphous region of the starch granules will be hydrolyzed by the acid. By differential scanning calorimetry the calorimetric enthalpy of potato starch containing about 200% moisture content was found to stay largely unchanged by acid treatment for 6 d. The swelling power at 70° and 80°C of potato starch reached to the minimum value and, moreover, from the gel-chromatogram patterns of the acid-treated starches, the crystalline region of the starch granules may begin to deteriorate slightly by acid treatment for more than 6 d, although the relative crystallinity by the X-ray diffraction method increased slightly with passing of hydrolysis time.     

Effects of time/temperature treatments on potato (Solanum tuberosum) starch: a comparison of isolated starch and starch in situ

Previously, time/temperature treatments of starch have been performed mainly on starch/water systems. In this study the same time/temperature treatments were applied to starch/water systems and to potato starch in situ. Two potato varieties (Solanum tuberosum cultivars Asterix and Bintje) were used. The effect of time/temperature treatments on gelatinisation behaviour was evaluated using differential scanning calorimetry (DSC). A blanching process was simulated by heating samples to 74 °C and then cooling them to 6 °C. A DSC scan showed that starch was completely gelatinised after this treatment. Retrogradation of amylopectin increased during storage at 6 °C from 0 to 24 h after blanching. Annealing of starch, with the aim of altering cooking properties, was performed by heating samples to temperatures below the gelatinisation onset temperature. Treating samples at 50 °C for 24 h caused a shift in gelatinisation onset temperature of 11–12 °C for isolated starch and 7–11 °C for in situ samples. The extent of the annealing effect depended on the difference between onset and annealing temperatures, and prolonged treatment time increased the effect. Starch/water systems and tissue samples behaved similarly when exposed to time/temperature treatments. The most apparent difference was the shift of gelatinisation to higher temperatures in tissue samples. Copyright © 2003 Society of Chemical Industry     

Effect of temperature on the synthesis,composition and physical properties of potato microtuber starch

Potato microtubers (cv Maris Piper) were grown at 10, 16 and 24°C in total darkness for 28 days. Soluble and insoluble starch synthase, ADPglucose pyrophosphorylase, sucrose synthase and fructokinase were assayed in extracts of the microtubers and, in the case of soluble and insoluble starch synthase, activity was found to be particularly sensitive to increasing growth temperature. The starch content of the microtubers increased slightly with increasing growth temperature, but with little effect on the number of granules per microtuber and a small increase in the average granule size. The microtuber starch granules were much smaller than those found in commercial potato starch (c 8–9 μm modal diameter compared to c 21 μm). Although the amylose content of the microtuber starches tended to increase with increasing growth temperature, the phosphorus content was variable. Gel permeation chromatographic elution profiles of native and debranched microtuber and a commercial potato starch showed that no differences could be detected in either amylose or amylopectin molecular size, polydispersity or unit chain distribution of amylopectin (which contained two major unit chain fractions at DP 21 and 56). The onset, peak and conclusion temperatures of the DSC gelatinisation endotherm increased linearly as a function of growth temperature whilst the enthalpy of gelatinisation decreased. It is suggested that elevated temperature during starch biosynthesis facilitates ordering of amylopectin double helices into crystalline domains. © 1998 SCI.     

Determining the effects of annealing time on the glass transition temperature of Pueraria lobata (Willd.) Ohwi starch

To probe the effects of annealing time on the glass transition temperature (T_g) and digestibility of Pueraria lobata (Willd.) Ohwi starch, the starch crystal structure and moisture distribution through the components of P. lobata (Willd.) Ohwi starch were investigated. Annealing times of 0, 1, 3, 6, 12 and 24 h were employed to determine the effect of starch T_g using differential scanning calorimetry (DSC) with the support of ¹H low‐field NMR, polarised light microscopy and ¹³C CP/MAS NMR. The T_g values of the starch increased with longer annealing times. The ¹H low‐field NMR results showed that the T₂ relaxation time decreased and starch–water interactions increased as the annealing time increased. Compared with native starch, annealed starch had higher contents of slowly digested starch (SDS) and resistant starch (RS). The starch crystal structure was not destroyed after annealing, but the relative crystallinity percentage increased slightly.     

Gelatinisation properties of native and annealed potato starches

The relationship between the gelatinisation parameters of native and annealed starches extracted from ten different potato varieties grown at the same site at the same time was studied. The objective was to identify how native gelatinisation temperatures and enthalpies impacted on annealed starch gelatinisation parameters. Prior to ANN, the initial onset (T_o), peak (T_p) and conclusion (T_c) gelatinisation temperatures ranged from 58.71 to 62.45, 62.52 to 66.05 and 68.67 to 72.27°C, respectively, which increased to 66.15 to 69.12, 70.22 to 72.30 and 76.21 to 77.44°C, respectively, post ANN. Overall, the greater the initial gelatinisation temperatures the smaller the increment (ΔGT) post ANN. Comparable enthalpy values pre‐ and post‐ANN were 15.13 to 18.37 and 15.76 to 18.37 J/g, respectively. These data indicate that the more ‘perfect’ the crystallites were before ANN the less they could be enhanced by the ANN process and that against a constant background of α‐glucan structure, the pattern (rate) of starch deposition might be the primary differentiator of starch architecture across the varieties.     

Physicochemical,crystalline, and thermal properties of native and enzyme hydrolyzed Pueraria lobata (Willd.) Ohwi and Pueraria thomsonii Benth. starches

Starches isolated from the bulbs of Pueraria lobata (Willd.) Ohwi (PLO) and Pueraria thomsonii Benth. (PTB) were hydrolysed by glucoamylase for different lengths of time (2, 4, 8, 12, and 24 h). The hydrolysis results were compared by scanning electron microscope (SEM), X‐ray power diffractometer (XRD), and differential scanning calorimetry (DSC). The SEM results revealed that both of the PLO and PTB starches showed the same hydrolysis mechanism, which indicated that the glucoamylase primarily attacking the exterior of starch granules and then the interior. The results of XRD revealed the crystalline type of PTB starch changed from C‐type to A‐type with crystallinity reducing from 43.5 to 20.9% during the hydrolysis. Unlike PTB starch, the PLO starch did not show marked changes in crystalline style but lower degree of crystallinity was obtained from 32.4 to 13.7% during the hydrolysis. All the XRD results demonstrated that B‐type polymorph was preferentially degraded than A‐type polymorph in the C‐type starch. The DSC results revealed that both of the PLO and PTB starches showed decreased enthalpy of gelatinization (ΔH_gel) and gelatinization temperature range (R)‐value after hydrolysis, while the gelatinization temperature (T_p) indicated different tendency, initially ranging from 68.6 to 64.3°C and then increasing to 67.8°C for PLO starch. While for PTB starch, the T_p‐value showed progressive reduction from 85.4 to 74.3°C during the whole process.     

Hydrothermische Behandlung von Stärke in Gegenwart von α-Amylase Teil 2: Einfluß einer hydrothermischenzymatischen Modifizierung auf die Quellungstemperatur von Weizenstärken

Hydrothermal Treatment of Starch in the Presence of α-Amylase. Part 2: Effect of a Hydrothermal Enzymatic Modification on the Swelling Temperature of Wheat Starches. The hydrothermal treatment of wheat starch in the presence of bacterial-α-amylase is directed to the production of modified residual starches with a maximal shift of swelling temperature T_max (measured by DSC) at high yields. The annealing of granular starch at temperatures below the swelling temperature (50°C) in presence of α-amylase gives no difference regarding the shift of T_max. Because of the hydrolysis of swollen material it is possible to use higher reaction temperatures and the process becomes more effective. The formed maltose syrup retards the shift of T_max and protects the granules. Within 24h wheat starch can be modified with a yield of 70% and a shift of T_max of 8K.