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).     

Acid thinned jicama and maize starches as fat substitute in stirred yogurt

Jicama and maize starches were hydrolyzed with HCl (1.5, 3.0 or 4.5 g/100 g of starch), at a temperature of 40 °C using two hydrolysis times (3 and 6 h). The acid degradation of both starches was not excessive as revealed by the positive blue value, amylose content, gel formation and gel thermo-reversibility. Jicama starches were more susceptible to acid hydrolysis than maize starches. Hydrolyzed jicama starches showed low values of gel strength and water solubility index, and high values of damaged starch, total sugar content and water absorption index. Stirred yogurt formulated with hydrolyzed starches showed different properties of syneresis index according to the starch type and hydrolysis conditions. Yogurt samples with hydrolyzed jicama starches added did not show significant differences in pH and viscosity. Sensorial testing showed that it is possible to produce yogurt with good functional and sensorial properties using hydrolyzed jicama starches as a fat substitute.     

Effect of maize type and extrusion‐cooking conditions on starch digestibility profiles

This study aimed at evaluating the influence of screw speed (250–600 rpm), barrel temperature (100–160 °C) and water content (16.4–22.5%) on rapidly digestible (RDS), slowly digestible (SDS) and resistant (RS) starch levels of waxy, normal and high‐amylose maize starches. In native starches, an increase in amylose content was correlated with lower SDS content. After extrusion, this trend was reversed. Both waxy and normal maize starches became rapidly digested. However, for normal maize starch, some SDS fraction remained. In contrast, the high‐amylose maize starch showed a significant increase in digestibility and an increase in SDS content from 20.4% in the native starch up to 27.5% after extrusion. This high level of SDS may be attributed to the presence of some remaining granular structures and formation of crystalline orders, which have slow digestion properties.     

Characteristics of rennet–casein-based model processed cheese containing maize starch: Rheological properties,meltabilities and microstructures

The rheological properties, meltabilities and microstructural properties of rennet–casein-based model processed cheese slices containing normal maize starch, waxy maize starch and high amylose (70%) maize starch (HAMS) were investigated as a function of the ratio of starch to protein. The storage modulus (G′) increased with increasing ratio of normal maize starch to protein in the processed cheeses, whereas G′ decreased with the addition of waxy maize starch. The tan δ values at high temperature (90 °C) decreased with the addition of both normal maize starch and waxy maize starch, but normal maize starch caused a greater reduction in the tan δ values. These properties were influenced to a lesser extent in processed cheeses containing HAMS. Processed cheeses containing normal maize starch lost meltability at ratios of starch to protein > 0.16; waxy maize starch and HAMS had less influence on the meltability. The effect of starch on the properties of the processed cheeses was attributed to phase behaviours between the protein and the starch, which was shown in confocal laser scanning micrographs.     

Production and physicochemical properties of resistant starch from hydrolysed wrinkled pea starch

The content and physicochemical properties of resistant starches (RS) from wrinkled pea starch obtained by different molecular mass reduction processes were evaluated. Native and gelatinised starches were submitted to acid hydrolysis (2 m HCl for 2.5 h) or enzymic hydrolysis (pullulanase, 40 U g^?1 for 10 h), followed by hydrothermal treatment (autoclaving at 121 °C for 30 min), refrigeration (4 °C for 24 h) and lyophilisation. Native starch showed RS and total dietary fibre contents of 39.8% and 14.3%, respectively, while processed ones showed values from 38.5% to 54.6% and from 22.9% to 37.1%, respectively. From these, the highest contents were among acid‐modified starches. Processed starches showed endotherms between 144 and 166 °C, owing to the amylose retrogradation. Native and processed starches showed low viscosity, which is inversely proportional to the RS concentration in samples. The heat treatment promoted an increase in the water absorption index. The pea starch is a good source for obtaining resistant starch by acid hydrolysis.     

Characteristics of mung bean starch isolated by using lactic acid fermentation solution as the steeping liquor

Physicochemical properties of commercial mung bean starch isolated with lactic acid fermentation solution (LFS) and starches laboratory-prepared by using NaOH, Na₂SO₃ and distilled water as steeping liquors were examined with the aim of elucidating the effect of different steeping liquors on the properties of starches. Results indicated that the amylose content, granular morphology and X-ray diffraction pattern of starches isolated with different steeping liquors did not show obvious differences. However, the LFS-isolated starch had significantly (p < 0.05) higher weight percentage of longer B chains and B₁ chains, a lower weight percentage of A chains and a lower ratio of short-to-long chains in amylopectin than those of the other preparations. Moreover, the LFS-isolated starch showed significantly (p < 0.05) lower pasting viscosity, a higher onset temperature, a narrower temperature range and a lower enthalpy of gelatinization than the other preparations. No significant differences on the physicochemical properties mentioned above were found among the laboratory-prepared starches. The results suggest that mung bean starch is degraded during isolation with lactic acid fermentation solution, which leads to the loss of starch granules with less integrity.     

Structural characterizations and digestibility of debranched high-amylose maize starch complexed with lauric acid

Structural characterizations and digestibility of debranched high-amylose maize starch complexed with lauric acid (LA) were studied. The cooked starch was debranched by using pullulanase and then complexed. Light microscopy showed that the lipids complexed starches had irregularly-shaped particles with strong birefringence. Gel-permeation chromatograms revealed that amylopectin degraded to smaller molecules during increasing debranching time, and the debranch reaction was completed at 12 h. Debranching pretreatment and prolonged debranching time (from 2 h to 24 h) could improve the formation of starch lipids complex. X-ray diffraction pattern of the amylose–lipid complexes changed from V-type to a mixture of B- and V-type polymorphs and relative crystallinity increased as the debranching time increased from 0 to 24 h. In DSC thermograms, complexes from debranched starch displayed three separated endotherms: the melting of the free lauric acid, starch–lipid complexes and retrograded amylose, respectively. The melting temperature and enthalpy changes of starch–lipid complex were gradually enhanced with the increasing of debranching time. However, no significant enthalpy changes were observed from retrograded amylose during the starch–lipid complex formation. Rapidly digestible starch (RDS) content decreased and resistant starch (RS) content increased with the increasing of debranching time, while the highest slowly digestible starch (SDS) content was founded at less debranching time of 2 h. The crystalline structures with dense aggregation of helices from amylose-LA complex and retrograded amylose could be RS, while SDS mostly consisted of imperfect packing of helices between amylopectin residue and amylose or LA.     

Microstructural and physicochemical properties of heat-moisture treated waxy and normal starches

Starches from normal rice (21.72% amylose), waxy rice (1.64% amylose), normal corn (25.19% amylose), waxy corn (2.06% amylose), normal potato (28.97% amylose) and waxy potato (3.92% amylose) were heat-treated at 100 °C for 16 h at a moisture content of 25%. The effect of heat-moisture treatment (HMT) on morphology, structure, and physicochemical properties of those starches was investigated. The HMT did not change the size, shape, and surface characteristics of corn and potato starch granules, while surface change/partial gelatinization was found on the granules of rice starches. The X-ray diffraction pattern of normal and waxy potato starches was shifted from B- to C-type by HMT. The crystallinity of the starch samples, except waxy potato starch decreased on HMT. The viscosity profiles changed significantly with HMT. The treated starches, except the waxy potato starch, had higher pasting temperature and lower viscosity. The differences in viscosity values before and after HMT were more pronounced in normal starches than in waxy starches, whereas changes in the pasting temperature showed the reverse (waxy > normal). Shifts of the gelatinization temperature to higher values and gelatinization enthalpy to lower values as well as biphasic endotherms were found in treated starches. HMT increased enzyme digestibility of treated starches (except waxy corn starch); i.e., rapidly and slowly digestible starches increased, but resistant starch decreased. Although there was no absolute consistency on the data obtained from the three pairs of waxy and normal starches, in most cases the effects of HMT on normal starches were more pronounced than the corresponding waxy starches.     

Mild hydrolysis of resistant starch from maize

To investigate structural changes of resistant starch (RS) caused by mild-acid treatment, native maize starch, retrograded (RS3), and cross-linked (RS4) resistant starches, prepared from maize starch, were hydrolyzed with 0.1 M HCl at 35 °C for 30 days. The hydrolysis rate of RS3 was shown to be the highest, at 44.1% after 30 days of the hydrolysis. The hydrolysis rapidly progressed upto 10 days but gradually changed after that. Native starch and RS4 showed less than 5% of hydrolysis during the period of hydrolysis. As for the RS level of the residue after the hydrolysis, RS4 did not show any significant change, but RS3 exhibited an increase of up to 25.9% after 30 days, which led to 88% increase in comparison with 13.8% at the initial stage. As a result of examining the molecular weight (MW) of RS3 by the SEC-MALLS-RI system, the non-hydrolyzed RS3 exhibited three peaks, having MW 53.4 × 10⁶, 7.4 × 10⁶, and 0.8 × 10⁶, respectively, but the MW of the molecules decreased to 4.9 × 10⁶ and 0.6 × 10⁶ after 7 days of hydrolysis. It was difficult to verify the MW of RS4 because this was not dispersed in 1 M NaOH. The crystallinity of native starches, RS3 and RS4, by X-ray diffractometry of the residue hydrolyzed with 0.1 M HCl was equal to that of the non-hydrolyzed starch. The peak intensity at 2θ = 17° of RS3 increased sharply after hydrolysis.     

Comparative Studies on Some Physico-chemical, Thermal, Morphological, and Pasting Properties of Acid-thinned Jicama and Maize Starches

Comparative studies on acid hydrolysis of jicama and maize starch were carried out using concentrations of hydrochloric acid of 1.5%, 3.0%, and 4.5% (w/v), for 3 and 6 h, at 40°C. Native maize and jicama starches showed important morphological, thermal, and structural differences from those of tubers and cereals which potentially offer diverse industrial applications. Jicama starch showed low amylose content (12%) and small size of starch granules. Due to these characteristics, jicama starch was more susceptible to degradation during hydrolysis process than maize starch. Under the experimental conditions employed, the acid degradation was not particularly severe, as shown by scanning electronic microscopy analysis which showed small degraded zones and similar X-ray patterns in both starches. However, jicama starch was more susceptible to acid hydrolysis than maize starch, as revealed by the considerable increase in water solubility index, damaged starch, and crystallinity values. Also, the higher susceptibility of jicama starch than maize starch to the hydrolysis conditions was reflected in the sugar content release during hydrolysis. The relative crystallinity of hydrolyzed maize starches decreased during hydrolysis, while those of hydrolyzed jicama starches increased attributable to the lower amylose content of jicama starch in relation to maize starch. Maize and jicama hydrolyzed starches showed low viscosity values with relation to their native starch counterparts. However, native jicama starch showed lower viscosity values than maize starch, suggesting a lower internal stability of the starch granules during hydrolysis. Both native and hydrolyzed maize starches showed higher enthalpy, T _o, T _p, and T _c values than jicama starch and the broadening of the endotherms decreased during the hydrolysis of both starches.     

Properties of protease-treated maize starches

Commercially produced maize starches were treated with protease (Promod 25P) and their composition and properties were compared with untreated controls. It was found that, although protease treatment reduced the starch protein contents by 41%, 21% and 37% for the waxy, normal and amylomaize starches, respectively, it also caused some pits on the granule surfaces, which were evident by scanning electron microscopy (SEM), but no obvious decrease in granule dimensions (Coulter Counter Multisizer). The protein extraction was associated with decreases in starch lipid content by 42%, 40% and 45% (waxy, normal and amylomaize starches, respectively) and a decrease in total amylose content (30.7–26.0%) for the normal maize starch. The gelatinisation parameters of the starches by differential scanning calorimetry (DSC) in water, 0.001 M HCl or NaOH were less obviously affected by protease treatment in common with the swelling factors at 80 °C. The amount of α-glucan leached by the swollen (80 °C) granules was, however, increased by the protease treatment by factors of 3.8, 1.4, and 1.1, for the waxy, normal and amylomaize starches, respectively. Although proteases provide a useful tool for the purification of native starches, commercial protease preparations need to be controlled in terms of amylase content to prevent modifications to starch structure and properties during industrial processing.     

Enzymatic production of linear long-chain dextrin from sago (Metroxylon sagu) starch

Pullulanase (EC.3.2.1.41) was used to generate more linear-chain dextrin from sago starch (24.9% amylose) such that the resulting product could act as a high amylose starch. A starch suspension of 5.0% (w/v) sago starch was heated at 100 °C for 45 min and, after cooling, the gelatinized sago starch was hydrolyzed with 2.0% (v/dry weight starch) pullulanase (Promozyme 400L, Novozymes A/S, Denmark) for 24 h. The linear long-chain dextrin (LLD) content of the hydrolysate after drying, was then compared with the initial LLD content. The surface morphology of the starch granules was observed with a scanning electron microscope (SEM). The effects of gelatinization, time of reaction, pretreatment with different strengths of hydrochloric acid prior to enzyme hydrolysis, and starch and enzyme concentrations were studied. Raw sago starch was resistant to the action of pullulanase, but caused an increase in the LLD of that sago starch from an initial concentration of 24.9–33.2% following gelatinization. The best conditions to maximize the amount of LLD were 5.0% (w/v) sago starch, 2.0% (v/w) enzyme and 12 h reaction time. Acid pretreatment of the sago starch did not cause greater improvement in the accessibility and susceptibility of pullulanase as the LLD content, following pullulanase action did not change significantly. Shrinkage on the surface of the starch granules was observed with the SEM.     

Molecular structure,rheological and thermal characteristics of ozone-oxidized starch

The effects of oxidation by ozone gas on the molecular structure, rheological and thermal properties of starch (corn, sago and tapioca) were investigated. Starch, in dry powder form, was exposed to ozone for 10 min at different ozone generation times (OGTs). Average molecular weight decreased in oxidized corn and sago starches but increased in oxidized tapioca starch. All oxidized starches exhibited non-Newtonian shear-thinning behaviour. Starch viscosity decreased drastically with increasing OGT. Young’s modulus for all oxidized corn and sago starch gels stored for 1 and 7 days at 4 °C increased significantly compared to unmodified starch. No differences were noted in gelatinization temperatures and gelatinization enthalpies of all oxidized starches compared to unmodified starch. Retrogradation enthalpy increased markedly in corn starch after 1 min OGT. These results show that the extent of starch oxidation varies among starches of different botanical origins under similar ozone treatment conditions.     

Physicochemical characterization of chemically modified corn starches related to rheological behavior,retrogradation and film forming capacity

An integral approach of chemical modification effects on physicochemical and functional properties of corn starch was performed using different and complementary techniques. Acetylated, acetylated crosslinked, hydroxypropylated crosslinked, and acid modified corn starches were analyzed. Substitution and dual modification reduced significantly amylose concentration. Chemical modification decreased granules crystallinity degree. A significant increase in swelling power was observed in substituted and dual modified starches at 90 °C, besides these treatments decreased gelatinization temperature and enthalpy. Acid modified starch pastes showed a Newtonian behavior while substituted and dual modified ones exhibited a viscoelastic response. Dynamic rheological properties of modified starch pastes were not affected by post gelatinization time while native starch pastes developed a more rigid structure during storage. Retrogradation of substituted starch pastes after 12 days at 4 °C was reduced, since syneresis degree and hardness increase were significantly lower than those of native pastes. It was demonstrated that only substituted and native starches exhibited film forming capacity.     

Processing stability of cross-linked starches in acid sauce applications and identification of some of the molecular factors involved

The thickening functionality of four acetylated di-starch adipates with variations in starch source and amylose and adipate contents was evaluated in a simplified small-scale model sauce system at fourteen processing conditions with variations in temperature, shear, and pH. A processing stability factor for a given starch was defined as a normalised standard deviation of model sauce viscosities calculated over all fourteen treatments. Adipate and acetate substituents were stable at all processing conditions. The processing stability of modified starches was found to decrease in the order waxy maize> amylopectin potato > normal potato. The release of solubles increased in that order and the solubles from the normal potato starches were enriched in amylose. Molar mass determinations of the soluble fraction before and after saponification of the cross-links revealed that processing at high temperature caused much more molecular degradation than at high shear and that in all cases the soluble fraction was only scarcely cross-linked. These results suggest that the negative effect of amylose on processing stability is due to its ineffective cross-linking in the intact starch. Distinct morphological changes were induced by processing: generally, swollen cross-linked starches respond to processing by the common swelling and leaching pattern, but amylopectin-starch granules subjected to high shear are disintegrated into tiny particles. Presumably, these morphological responses are related to the effectiveness of cross-linking in the processed starch granules.     

In vitro Digestibility of Hydroxypropyl Maize,Waxy Maize and High Amylose Maize Starches

Hydroxypropyl derivatives of maize, waxy maize and high amylose maize starches were prepared and characterized. The in vitro digestibility of the raw and gelatinized starches and their derivatives was compared using porcine pancreatic α-amylase. Digestibility of the unmodified starches decreased in the order waxy maize > maize > high amylose maize. Increasing molar substitution (MS) caused a decrease in digestibility for all starch types after gelatinization. Raw maize and high amylose maize starch derivatives showed an initial decrease in digestibility followed by increases at higher MS levels. The digestibility of the raw waxy maize starch derivatives showed a continuing drop as MS increased.     

Effect of heat-moisture treatment on the formation and physicochemical properties of resistant starch from mung bean (Phaseolus radiatus) starch

Mung bean starch was subjected to a range of heat-moisture treatments (HMT) based on different moisture contents (15%, 20%, 25%, 30%, and 35%) all heated at 120 °C for 12 h. The impact on the yields of resistant starch (RS), and the microstructure, physicochemical and functional properties of RS was investigated. Compared to raw starch, the RS content of HMT starch increased significantly, with the starch treated at 20% moisture having the highest RS content. After HMT, birefringence remained at the periphery of the granules and was absent at the center of some granules. The shape and integrity of HMT starch granules did not change but concavity was observed under scanning electronic microscopy. Apparent amylose contents of HMT starch increased and the HMT starch was dominated by high molecular weight fraction. Both the native and HMT starches showed A-type X-ray diffraction pattern. Relative crystallinity increased after HMT. The gelatinization temperatures (To, Tp, and Tc), gelatinization temperature range (Tc–To) and enthalpies of gelatinization (ΔH) increased significantly in HMT starch compared to native starch. The solubility increased but swelling power decreased in HMT starches. This study clearly shows that the HMT exhibited thermal stability and resistance to enzymatic hydrolysis owing to stronger interactions of starch chains in granule.     

Relationship between the structure,physicochemical properties and in vitro digestibility of rice starches with different amylose contents

The in vitro digestibility and molecular and crystalline structures of rice starches (Long-grain, Arborio, Calrose, and Glutinous) differing in amylose content were investigated and the relationship between the structure and in vitro digestibility of starch was studied. Long-grain showed the highest amylose content (27.2%), whereas Glutinous showed the lowest amylose content (4.2%). Long-grain had the highest average amylopectin branch chain length (18.8) and proportion (8.7%) of long branch chains (DP ≥ 37), and the lowest proportion (26.9%) of short branch chains (DP 6–12). Among the non-waxy rice starches (Long-grain, Arborio, and Calrose), Calrose had the lowest average chain length (17.7) and the lowest proportion (7.1%) of long branch chains (DP ≥ 37). The relative crystallinity of rice starch followed the order: Glutinous (33.5%) > Calrose (31.4%) > Arborio (31.0%) > Long-grain (29.9%). Long-grain had the highest gelatinization temperature and the lowest gelatinization temperature range, whereas Glutinous showed the highest gelatinization temperature range and gelatinization enthalpy. Arborio had the highest melting enthalpy for amylose–lipid complex among the tested rice starches. Pasting temperature, setback, and final viscosity increased with increasing amylose content, whereas the peak viscosity and breakdown showed negative correlations with amylose content. The rapidly digestible starch (RDS) content of the tested rice starches followed the order: Glutinous (71.4%) > Calrose (52.2%) > Arborio (48.4%) > Long-grain (39.4%). Contrary to this, the slowly digestible starch (SDS) and resistant starch (RS) contents showed an opposite trend compared to RDS. Digestibility (RDS, SDS, and RS) of the rice starches was significantly correlated (p ≤ 0.05) with amylose content, proportions of DP 6–12 and DP 13–24, relative crystallinity, intensity ratio (of 1047 cm⁻¹ to 1022 cm⁻¹ from Fourier transform infrared spectroscopy), swelling factor, amylose leaching, onset temperature of gelatinization, gelatinization temperature range, gelatinization enthalpy, pasting temperature, peak viscosity, breakdown, setback, and final viscosity.     

Enzymatic hydrolysis of potato starches containing different amounts of phosphorus

The rapid hydrolysis of potato starches differing in phosphorus content, as well as sweet potato, cassava and yam starches, was accomplished by treatment of gelatinised starches with bacterial liquefying α-amylase at 50 °C for 1 h, followed by Bacillus licheniformis α-amylase at 55 °C up to 24 h, and then by glucoamylase at 40 °C for a further 24 h. Among the potato starches, the high-phosphorus starches showed higher starch resistant capacity than the medium-phosphorus starches, as well as other tuber and root starches. The hydrolysis rate of tuber and root starches was not greatly influenced by their amylose content and median granule size. Only glucose was detected in the almost completely hydrolysed tuber and root starch samples, indicating that the concomitant enzymes treatment could hydrolyse both the α-1,4 and α-1,6 linkages of the starches examined.     

The effect of starch isolation method on physical and functional properties of Portuguese nuts starches. I. Chestnuts (Castanea sativa Mill. var. Martainha and Longal) fruits

The functionality of starch from chestnut (Castanea sativa Mill.) fruits isolated by alkaline and enzymatic methods were assessed. The studied properties included: solubility, swelling power, pasting properties, synaeresis, turbidity, and thermal and rheological behaviours. In addition amylose and resistant starch content were also evaluated. Results showed that the starch isolation method induced changes in most of those properties. Extracted starches (with high contents of amylose and resistant starch) showed low and similar swelling solubility values for all of the samples. Gelatinisation temperatures were also similar (61.5-63.0 °C), but the enzymatic method induced lower consistencies at 95 °C and after holding at this temperature. High values of setback were found, which were clearly affected by the isolation method. This parameter presented lower values for starches isolated by alkaline method (160 BU and 235 BU, respectively for Martainha and Longal). Starches did not present a peak consistency during pasting. Turbidity and synaeresis values were low at room temperature. Synaeresis increased when pastes were stored at low temperatures. This effect was more evident for the material isolated by enzymatic method. All of the isolation starches presented low enthalpy values (3.0-3.5 J/g), but the activation energy was higher for Martainha starches and for starches isolated by A3S method. Pastes showed viscoelastic behaviour, with a predominance of elastic property, forming strong gels after cooling. Longal variety seems to be less resistant to the effect of isolation method. In general starches isolated by the alkali method present the best functional properties as a food ingredient.