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.     

Amylopectin structure of heat–moisture treated starches

The effects of heat–moisture treatment (HMT; moisture content of 25%, at 100°C for 24 h) on starch chain distribution and unit chain distribution of amylopectin in normal rice, waxy rice, normal corn, waxy corn, normal potato, and waxy potato starches were investigated. After HMT, starch chain distribution (amylose and amylopectin responses) of waxy corn and potato starches were identical to those of untreated starches, whereas the chromatographic response of waxy rice starch showed a slight decrease, but with a slight increase in peak tailing. This result indicated that HMT had no (or very limited) effect on the degradation of amylopectins. Analysis of unit chain distribution of amylopectins revealed that waxy characteristics affected the molecular structure of amylopectin in untreated starches, i.e., the CL of normal‐type starches was greater than that of waxy‐type starches. After HMT, the CL and unit chain distribution of all starches were no different than those of untreated starches. The results implied that changes in the physico‐chemical properties of HMT starches would be due to other phenomena rather than the degradation of amylopectin molecular structure. However, the thermal degradation of amylopectin molecules of waxy starches could occur by HMT at higher treatment temperatures (120 and 140°C).     

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.     

Effect of heat-moisture treatment on rice starch of varying amylose content

The effect of heat-moisture treatment (HMT) on the properties of rice starches with high-, medium- and low-amylose content was investigated. The starches were adjusted to 15%, 20% and 25% moisture levels, and heated at 110 °C for 1 h. The swelling power, solubility, pasting properties, morphology, enzymatic susceptibility and X-ray crystallinity of the starches were evaluated. HMT reduced the swelling power and solubility of the starches. The strongest effect of HMT occurred on the high-amylose starch; the pasting temperature was increased and the peak viscosity, breakdown, final viscosity and the setback were reduced. HMT increased the starch’s susceptibility to α-amylase and promoted a reduction in the starch relative crystallinity.     

Effect of gelatinisation on slowly digestible starch and resistant starch of heat-moisture treated and chemically modified canna starches

The effects of gelatinisation on slowly digestible (SDS) and resistant starch (RS) of native and modified canna starches were investigated. Starch slurries (10% w/w) were gelatinised at 100 °C for 5, 10, 20 and 40 min using a rapid visco analyzer (RVA). Significant change in the degree of gelatinisation (DG) values of all starch samples was observed during the initial 10 min of gelatinisation; after that the DG values increased gradually with gelatinisation time. The RS contents in all gelatinised starches decreased with increasing gelatinisation time, while the SDS values fluctuated. Chemical modification affected DG values as well as RS/SDS contents. The RS contents in 10% (w/w) acetylated, hydroxypropylated, octenyl succinylated and cross-linked canna starches gelatinised at 100 °C for 40 min were 26.6%, 32.0%, 45.3% and 19.8%, respectively, which were higher than that of the native starch (12.4%). Canna starch modified by crosslinking had the highest SDS content when gelatinised for 20-40 min. Modification of canna starch by heat-moisture treatment resulted in a lower content of RS for all treated samples. However, the Vt-HMT25 (canna starch containing moisture content of 25% during heat treatment) when gelatinised for 5-20 min contained a higher amount of SDS, compared to unmodified starch. The most effective modification method for RS and SDS formation was octenyl succinylation, where the sum of RS and SDS approached that of Novelose260.     

Influence of heat–moisture treatment and annealing on functional properties of sorghum starch

Sorghum starch was annealed in excess water at 50 °C for 24 h. Starch was also modified under heat–moisture treatment at 110 °C after adjusting various moisture contents (20, 30 and 40%) for 8 h. Significant decrease in chain lengths of amylose fraction in HMT starches was observed. Heat moisture treated (HMT) and annealed (ANN) starches showed lower granule sizes, swelling power, peak and setback viscosity but higher retrogradation as compared to native starch. HMT starch with addition of 40% moisture showed a decrease in relative crystallinity. HMT and ANN starch gels were observed to be harder than native starch gel.     

Hydrothermal treatments of rice starch for improvement of rice noodle quality

Two types of hydrothermal treated rice starches were prepared by annealing and heat-moisture treatment (HMT). Annealing of starch slurry was conducted at 55 °C for 24 h and HMT was applied in starch with 20 g/100 g moisture at 110 °C for 1.5 h, based on the optimization of the treatment conditions. The apparent changes on gelatinization, swelling, RVA paste viscosities and gel hardness of starch were observed. The study on 50% substitution of rice flour with untreated (UR), annealed (AR) or heat-moisture treated (HR) rice starches proved that the cooking and texture quality of rice noodle was substantially affected by the treatments. The composite noodles of flour and hydrothermal treated rice starches exhibited quality parameters which were closer to those of commercial noodles. The results revealed the possibility of utilizing these starches with low quality rice flour so as to produce noodles of acceptable quality. The study also inferred that characterization of RVA paste viscosities and gel texture of flour could become a practical method for predicting the quality of the derived noodle.     

Heat‐Moisture Treatment and Enzymatic Digestibility of Peruvian Carrot,Sweet Potato and Ginger Starches

The aim of this work was to study the effects of heat‐moisture treatment (27% moisture, 100°C, 16 h) and of enzymatic digestion (alpha‐amylase and glucoamylase) on the properties of sweet potato (SP), Peruvian carrot (PC) and ginger (G) starches. The structural modification with heat‐moisture treatment (HMT) affected crystallinity, enzyme susceptibility and viscosity profile. The changes in PC starch were the most pronounced, with a strong decrease of relative crystallinity (from 0.31 to 0.21) and a shift of X‐ray pattern from B‐ to A‐type. HMT of SP and G starch did not change the X‐ray pattern (A‐type). The relative crystallinity of these starches changed only slightly, from 0.32 to 0.29 (SP) and from 0.33 to 0.32 (G). The extent of these structural changes (PC > SP > G) altered the susceptibility of the starches to enzymatic attack, but not in same order (PC > G > SP). HMT increased the starches digestion, probably due to rearrangement of disrupted crystallites, increasing accessible areas to attack of enzymes. The viscosity profiles and values changed significantly with HMT, resulting in higher pasting temperatures, decrease of viscosity values and no breakdown, i.e., stability at high temperatures and shear rates. Changes in pasting properties appeared to be more significant for PC and SP starch, whereas the changes for G starch were small. Setback was minimized following HMT in SP and G starches.     

Effects of microwave heat-moisture treatment on properties of waxy and non-waxy rice starches

Waxy and non-waxy rice starches adjusted to 20% moisture (wet basis, w.b.) were heat-moisture treated in a microwave oven to determine the effects of the microwave heating characteristics on digestibility, pasting, and morphological properties of the heated starches. Microwave heating produced only minimal changes in digestibility as well as the physical characteristics of heated starches. Significant changes in viscosity properties after microwave heat treatment were observed for both waxy and non-waxy starches heat-treated in a microwave oven, relative to non-treated samples. Non-waxy starch heated in microwave oven showed an increase in breakdown viscosity from 29.8 RVU (non-treated starch) to 35.8 RVU after heating for 60 min. However, for waxy starch, breakdown viscosity decreased from 112.7 to 35.9 RVU after 60 min of microwave heat treatment, reflecting an increased stability of microwave heat-treated starch under cooking. The data obtained in this study indicate that there was much higher re-aggregation of starch granules in waxy starch after microwave heat treatment than occurred in non-waxy starch, suggesting a re-association of amylopectin branch chains in the heat-treated waxy starch.     

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.     

Digestibility of common native starches with reference to starch granule size,shape and surface features towards guidelines for starch-containing food products

Influence of diverse botanical sources (wheat, maize, waxy maize, cassava, potato, rice or waxy rice) on in vitro native starch digestibility has been investigated. Physicochemical properties (chemical composition, particles size and shape, surface features) of starch granules were determined with a view to explaining digestibility differences between samples. Rapidly digestible starch (RDS), slowly digestible starch (SDS) and resistant starch (RS) contents were measured according to Englyst method. Potato starch was shown to be composed of large rounded granules having smooth surfaces, which explains its slow enzymatic breakdown. Potato starch displayed the highest RS (86%) content and the lowest RDS content (9.9%). Since RS positively influences health and SDS may result in cell, tissue and/or organ damages, potato starch is an ideal starch nutrient. Conversely, waxy rice starch was rich in amylopectin and displayed small diameters and angular shapes, which are both known to facilitate enzymatic starch hydrolysis. It exhibited a near-zero RS content (0.9%) and a high RDS fraction (60%). According to this study, potato starch exhibited the best nutrient profile, followed up in this order by cassava, waxy maize, wheat, maize and waxy rice starches.     

Glycerol-enhancing heat-moisture treatment of A-type rice and cassava starches and B-type potato and canna starches

Effects of glycerol on the heat-moisture treatment (HMT) of A-type rice and cassava starches and B-type potato and canna starches were investigated. Starch samples were soaked in water or glycerol solution, adjusted to 25% moisture, and then subjected to HMT at 100 °C for 1, 6, and 16 h. Pasting profiles of all four starches plasticised with water clearly showed the B-type potato and canna starches were more susceptible to HMT than the A-type rice and cassava starches. The effect of HMT on the pasting properties of glycerol-plasticised samples was inconclusive; the B-type canna and A-type cassava starches were altered, but not the B-type potato and A-type rice starches, which remained comparable to the water-plasticised samples. Thus, the type of plasticiser as well as the environment surrounding the crystalline region, which is specific to each starch type, also affect the alteration of starch during HMT.     

Influence of moisture content on the degradation of waxy and normal corn starches acid-treated in methanol

Waxy and normal corn starches with different moisture contents, 5.1-16.9% and 4.8-15.9%, respectively, were prepared and treated in methanol containing 0.36% HCl at 45 °C for 1 h. Recovery of all the treated starches was found to be above 90%. Peak viscosity, gelatinization temperature and enthalpy change of gelatinization of waxy and normal corn starches decreased after treatment and this decrement was found to be more in treated starches having lower initial moisture content. The weight-average degree of polymerization and chain length (CL) of waxy and normal corn starches decreased upon acid-methanol treatment. The decrement ratio of molecular weight of modified starches was found to be negatively correlated with the initial moisture content of the starches. The decrement ratio of normal corn starch was higher than waxy corn starch with similar moisture content of starch. The content and CL of long chain fraction of amylopectin for waxy corn starch slightly decreased after treatment, while no obvious trend was found among starches with different moisture contents. CL of amylose for acid-methanol-treated normal corn starch decreased and this change was found to be higher in starches with lower initial moisture contents. Results demonstrated that the initial moisture content of starch granules strongly influenced the functional properties and degradation of starch treated by acid in methanol.     

Characterisation of low‐digestible starch fractions isolated from amylosucrase‐modified waxy corn starch

Amylosucrase (AS) modification of starch increases the slowly digestible (SDS) and resistant starch (RS) fractions. However, the characteristics and formation mechanism of each fraction of AS‐modified starch have not been determined yet. Therefore, this study isolated SDS and/or RS from AS‐modified waxy corn starches and investigated their structural characteristics. The amount of SDS+RS and RS had a positive correlation with the proportion of the medium length (13–24 of degree of polymerisation) branched chains of amylopectin. The relative crystallinity increased in the order of AS‐modified starch < SDS+RS < RS, while maintaining the B‐type crystalline structure. The thermal transition temperature ranges of the isolated fractions were also higher than those of undigested starches. The medium branched chains of amylopectin were presumably the clincher for the SDS and/or RS formation in AS‐modified starches. The principal causes of SDS and RS formation were the chain length elongation and the subsequent retrogradation‐like process, respectively.     

Effect of single and dual hydrothermal treatments on the crystalline structure,thermal properties,and nutritional fractions of pea,lentil, and navy bean starches

Pea, lentil and navy bean starches were annealed at 50 °C (70% moisture) for 24 h and heat-moisture treated at 120 °C (30% moisture) for 24 h. These starches were also modified by a combination of annealing (ANN) and heat-moisture treatment (HMT). The impact of single and dual modifications (ANN–HMT and HMT–ANN) on the crystalline structure, thermal properties, and the amounts of rapidly digestible starch (RDS), slowly digestible starch (SDS), and resistant starch (RS) were investigated. Birefringence remained unchanged on ANN but decreased on HMT. Granular swelling and amylose leaching decreased on ANN and HMT. Relative crystallinity, gelatinization enthalpy, and short-range order on the granule surface increased on ANN but decreased on HMT. Gelatinization transition temperatures increased on ANN and HMT. Gelatinization temperature range decreased and increased on ANN and HMT, respectively. ANN and HMT increased SDS and decreased RS levels in all starches. However, RDS levels increased on ANN and HMT in pea and lentil starches but decreased in navy bean starch. In gelatinized starches, ANN and HMT decreased RDS level and increased SDS and RS levels. Changes to crystalline structure, thermal properties and amounts of RDS, SDS, and RS were modified further on ANN–HMT and HMT–ANN.     

Impact of structural changes due to heat-moisture treatment at different temperatures on the susceptibility of normal and waxy potato starches towards hydrolysis by porcine pancreatic alpha amylase

The objectives of this study were to determine the impact of structural changes within the amorphous and crystalline domains of normal potato (NP) and waxy potato (WP) starches subjected to heat-moisture treatment (HMT) at 80, 100, 120 and 130 °C for 16 h at a moisture content of 27% and to determine the impact of structural changes at each of the above temperatures on the susceptibility on hydrolysis by porcine pancreatic α-amylase (PPA). The results showed that structural changes due to HMT were influenced by differences in starch chain mobility at the different temperatures of HMT. Starch chain mobility in turn was influenced by the interplay between the extent to which B-type crystallites were transformed into A + B-type crystallites, kinetic energy imparted to starch chains and amylose content. The main type of structural changes influencing physicochemical properties at the different temperatures of HMT was starch chain interactions (at 80 and 100 °C), disruption of hydrogen bonds between amylose (AM)–amylopectin (AMP) and AMP–AMP chains (at 120 and 130 °C), disorganization of AMP chains near the vicinity of the hilum (at 100, 120 and 130 °C) and formation of interrupted helices (at 130 °C). The susceptibility of NP and WP starches towards α-amylase decreased at 80 °C, but increased in the range of 100 to 130 °C. This suggested that α-amylase hydrolysis of HMT starches was influenced by the interplay of: 1) amount of A-type crystallites, 2) starch chain interactions and 3) changes to double helical conformation. Differences in granule morphology in PPA hydrolyzed NP and WP starches were largely influenced by the higher granular swelling in the latter. NP and WP starches exhibited heterogeneity in degradation (NP > WP) in both their native and HMT states.     

Development of oxidised and heat-moisture treated potato starch film

This study investigated the effects of sodium hypochlorite oxidation and a heat-moisture treatment of potato starch on the physicochemical, pasting and textural properties of potato starches in addition to the water vapour permeability (WVP) and mechanical properties of potato starch films produced from these starches. The carbonyl contents, carboxyl contents, swelling power, solubility, pasting properties and gel texture of the native, oxidised and heat-moisture treated (HMT) starches were evaluated. The films made of native, oxidised and HMT starches were characterised by thickness, water solubility, colour, opacity, mechanical properties and WVP. The oxidised and HMT starches had lower viscosity and swelling power compared to the native starch. The films produced from oxidised potato starch had decreased solubility, elongation and WVP values in addition to increased tensile strength compared to the native starch films. The HMT starch increased the tensile strength and WVP of the starch films compared to the native starch.     

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).     

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.     

The effect of rice variety and starch isolation method on the pasting and rheological properties of rice starch pastes

The effect of rice variety and starch isolation method on the pasting and rheological properties of rice starches was evaluated. One waxy and three non-waxy rice varieties from California with a range of amylose contents of 1.6–26.5% and four methods of isolation were evaluated. A rotational rheometer (RR) was used to measure the pasting and rheological properties of starch dispersions (8% w/w). The RR pasting curves had similar shapes to those from a rapid visco-analyzer (RVA). The four treatments used for isolating starch were a protease, NaOH (0.1% and 0.4%), or sodium dodecyl sulfate (SDS) (1.0%). The NaOH (0.4%) and SDS treatments were found to reduce the peak pasting temperatures of the non-waxy starches as compared with the protease and NaOH (0.1%) treatments. The same trend of the treatments was found with the elastic moduli, low shear viscosities, and yield stresses of the non-waxy starch pastes measured at 65 °C, immediately after pasting. The elastic moduli of the waxy starch pastes appeared to be least affected by method of starch isolation, but the low shear viscosity and yield stress of the protease starch paste was significantly higher than the paste from the other three treatments. Overall, the method of rice starch isolation was found to affect the gelatinization and rheological characteristics of hot rice starch paste.