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.     

Effect of hydroxypropyl β-cyclodextrin on physical properties and transition parameters of amylose–lipid complexes of native and acetylated starches

The effect of hydroxpropyl β-cyclodextrin (HPβ-CD) on physical properties and digestibility of wheat, potato, waxy maize and high-amylose maize starches before and after acetylation was studied. Effect of HPβ-CD on amylose–lipid complexes in native and acetylated potato starches synthesized using α-lysophosphatidylcholine was also studied. Acetylation increased swelling factor, amylose leaching, peak viscosity and susceptibility to α-amylase hydrolysis, but decreased gelatinization temperature and enthalpy and gel hardness in all starches. HPβ-CD markedly increased swelling factor and amylose leaching in native and acetylated wheat starches but had little or no impact on other starches. Wheat starch gelatinization enthalpy decreased in the presence of HPβ-CD but gelatinization temperature of all the starches was slightly increased. HPβ-CD had no influence on enzymatic hydrolysis. Melting enthalpy of amylose–lipid complex in both native and acetylated wheat starches was decreased by HPβ-CD. Acetylation also decreased the melting enthalpy of amylose–lipid complex in wheat starch. Similar trend of thermal transitions was observed in the presence of HPβ-CD for the amylose–lipid complexes synthesized in potato starch. Acetylation reduces the complex formation ability of the amylose polymer. Similar to gelatinization, acetylation widened the melting temperature range of amylose–lipid complexes while shifting it to a lower temperature. Higher swelling and amylose leaching, and decreased gelatinization temperature and enthalpy resulting from acetylation of wheat starch is consistent with its influence on starch hydration. Similar effects resulting from the inclusion of HPβ-CD were consistent with the disruption of amylose–lipid complex by HPβ-CD which promotes granular hydration.     

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.     

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.     

Relationship between α-amylase degradation and physico-chemical properties of sweet potato starches

Six varieties of sweet potatoes, grown under identical conditions, produced starches that displayed different characteristics. Susceptibility to pancreatic α-amylase varied between starches produced by the different clones. Structural characteristics at various levels, such as ratio of major fractions, size of amylose, gelatinization temperature and granule morphology, were also different between clones. Correlating structural attributes with susceptibility led to the suggestion that granule structure, including amylopectin: amylose ratio and molecular associations, were important critical factors in the hydrolysis of sweet potato starch granules. High amylopectin content of sweet potato starch was associated with a high gelatinization temperature and correspondingly less susceptibility to α-amylase attack. The hydrolysis pattern was correlated with degree of hydrolysis. Extensive surface erosion was shown to indicate a high degree of hydrolysis, whereas less surface erosion indicated less degradation.     

Substituent distribution within cross-linked and hydroxypropylated sweet potato starch and potato starch

Revealing the substituents distribution within starch can help to understand the changes of starch properties after modification. The distribution of substituents over cross-linked and hydroxypropylated sweet potato starch was investigated and compared with modified potato starch. The starches were cross-linked with sodium trimetaphosphate and/or hydroxypropylated with propylene oxide. The native and modified starches were gelatinized and hydrolysed by pullulanase, β-amylase, α-amylase and a combination of pullulanase, α-amylase and amyloglucosidase. The hydrolysates were analysed by HPSEC, HPAEC and MALDI-TOF mass spectrometry. Cross-linking had only a slight effect on the enzymatic hydrolysis, where hydroxypropylation evidently limited the enzymatic hydrolysis. The results obtained suggest that the hydroxypropyl substituents are not distributed regularly over the starch chains. Although the average substitution was around 2 hydroxypropyl groups per 10 glucose units, in the enzyme digests of hydroxypropylated starches, oligomer fragments of 10–15 glucose units, carrying 5–8 hydroxypropyl groups, were identified. It is hypothesised that higher levels of substituents are present in the amorphous regions and periphery of clusters of starch granules. This is the first time that the location of hydroxypropyl groups within sweet potato starch has been examined in this detail. Despite significant differences in granule architecture between starches from potato and sweet potato, similar patterns of hydroxypropylation have been found.     

Comparative susceptibilities of sago,potato and corn starches to alkali treatment

The effects of steeping starch (sago, corn, and potato), in 0.025 M of sodium hydroxide for 0, 15, and 30 days at 30 °C, on its granular structure and other physicochemical properties were investigated. Changes in the morphology of starch granules indicated that the alkaline solution affected the granular structure of the starch. Pasting studies showed that the peak viscosity, breakdown, and setback of sago and potato starch decreased significantly, whereas that of corn starch increased significantly, when steeping time was prolonged. Swelling power increased significantly for treated potato and corn starches, but it decreased for sago starch. The amylose content of all alkali-treated starches also decreased significantly after treatment. Onset and peak temperatures of gelatinization (as analyzed with a differential scanning calorimeter) increased significantly, but the enthalpy decreased, for both gelatinization and retrogradation. The results showed that the physicochemical properties of starch of various botanical origins were affected to variable degrees when it was treated with alkaline solution.     

Hydroxypropylation of pigeon pea (Cajanus cajan) starch: Preparation, functional characterizations and enzymatic digestibility

Hydroxypropyl starch derivatives were prepared from pigeon pea starch (NPPS) which is an unconventional starch source. Functional parameters and characterization of both native and modified starches were carried out. The starch granules appeared oval or elliptical in shape with sizes ranging from 7 to 40 μm in width and 10 − 30 μm in length. Hydroxypropylation did not alter the shape of the starch granules in a pronounced way. Generally, the x-ray diffractograms of native pigeon pea starch showed the “A” pattern. However, slight reductions in the diffraction intensity of starches after modification were observed. At all temperatures studied (30-90 °C), swelling and solubility of hydroxypropylated starches were higher than the NPPS. Progressive increases in swelling capacity and solubility were observed as the molar substitution (MS) increased among the hydroxypropylated starches. Hydroxypropylation reduced starch paste turbidity on storage. Also, studies showed that syneresis reduced after hydroxypropylation. In addition, syneresis reduced as the MS of the hydroxypropyl starches increased. The results indicate that pasting temperature and peak temperature reduced after modification but peak viscosity increased in hydroxypropylated starch derivatives compared with the native starch. Setback reduced in hydroxypropylated starches compared with the native starch. Enthalpy of gelatinization and percentage retrogradation reduced after hydroxypropylation and progressive reductions were observed as the MS increased among the starch derivatives. Hydroxypropylation increased enzymatic digestibility.     

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.     

Low temperature post-harvest storage of New Zealand Taewa (Maori potato): Effects on starch physico-chemical and functional characteristics

Fresh tubers from four traditional Taewa (Maori potato) cultivars (Karuparera, Tutaekuri, Huakaroro and Moemoe) and one modern potato cultivar (Nadine) of New Zealand, were stored at 4 °C and 80–90% relative humidity for six months after harvest. Starch was isolated from tubers after every three month period, and its physico-chemical and functional properties measured. Considerable changes in these properties occurred during storage. The extent of changes varied significantly from cultivar to cultivar. Starch swelling power, solubility and light transmittance decreased during tuber storage while a slight increase was observed in starch amylose content. The starch granule size distribution shifted to smaller granule size during tuber storage. Scanning electron micrographs showed degradation/erosion and pitting on the surfaces of many of the starch granules isolated from stored tubers. Transition temperatures and enthalpies of gelatinization of the starches increased somewhat during tuber storage, suggesting that changes in the stability of starch crystalline structures had occurred. Pasting, viscoelastic and texture profile analysis (TPA) characteristics of starch gels were found to have been influenced by tuber storage time for all the cultivars, but to the greatest extent for Nadine and Huakaroro. Gels made from starches from the stored tubers had a reduced tendency towards retrogradation as evidenced by the decrease in syneresis (%) during gel storage at 4 °C.     

交联酯化甘薯淀粉特性研究

采用示差扫描量热仪(DSC)、扫描电子显微镜(SEM)和X-射线衍射仪(X-ray)研究了交联酯化甘薯淀粉的特性,结果表明,甘薯淀粉经过不同的交联酯化作用后,其糊化特性、颗粒形态外观特征和X-衍射图谱等发生明显的变化,并对其变化机理进行了分析。     

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.     

Properties of starches separated from potatoes stored under different conditions

Starches from 11 potato cultivars stored at five temperatures (4, 8, 12, 16 and 20 °C) for 120 days were evaluated for physicochemical, thermal and pasting properties. Amylose content and swelling power increased with increase in storage temperatures. The proportion of small size granules was higher in starches from potatoes stored at 4 °C. The starch granules of stored potatoes were slightly rough-surfaced and pitted; the effect was pronounced in those stored at 4 °C. Starches from potatoes stored at 4 °C showed lower onset gelatinization temperature and conclusion temperature than did starches from potatoes stored between 8 and 20 °C. Starches from potatoes stored at higher temperature (20 °C) showed higher peak viscosity, set back, as well as gel hardness, chewiness and gumminess than did starches from those stored between 4 and 16 °C. Amylose content showed significant positive correlation with gumminess and setback while swelling power showed significant positive correlation with peak viscosity and hot-paste viscosity.     

Impacts of acid-methanol treatment and annealing on the enzymatic resistance of corn starches

Normal corn, Hylon V and Hylon VII starches were acid-methanol-treated at 25 °C for 1–30 days in methanol containing 0.36% HCl, and then annealing at 50 °C for 72 h in excess water. The rapid digestible starch (RDS), slow digestible starch (SDS) and resistant starch (RS) contents of starch before and after treatments were determined. The molecular structure, thermal properties, double helix content and relative crystallinity of starch were observed for elucidating the impacts of acid-methanol treatment and annealing, as well as the molecular structure, on the enzymatic resistance of starch. Results showed that the weight-average degree of polymerization of acid-methanol-treated corn starches ranged from 884 × 10³ to 404, 778 × 10³ to 299 and 337 × 10³ to 250 anhydrous glucose units for normal corn, Hylon V and Hylon VII starches, respectively. Annealing increased the RS content of starch, and the increment of RS increased with decreasing molecular size of starch. Furthermore, the change in RS content after treatments depended on the content and weight-average chain length of amylose fraction of starch. The RS content of starch after treatments increased from 19.2 to 56.2%, 69.9 to 86.1%, and 73.1 to 89.1% for normal corn, Hylon V and Hylon VII starches, respectively. The gelatinization peak temperature and double helix content of starch increased after acid-methanol treatment or annealing. Results demonstrate that the degradation of starch, causing by acid-methanol treatment, enhances the mobility and realignment of starch chains in molecules during treatments and further increases the enzymatic resistance of starch granules.     

Impact of γ-irradiation,CIPC treatment,and storage conditions on physicochemical and nutritional properties of potato starches

In the present study, three potato varieties were treated with chlorpropham (CIPC, 35 ppm), γ-irradiated (0.1 kGy) and stored for up to 5 months at 8 °C, and the physicochemical properties and in vitro starch digestibility of native and cooked starches were investigated. Sprouting was found to be satisfactorily suppressed by γ-irradiation and CIPC treatment. However, irradiation increased total free glucose content in two potato varieties, and decreased the thermal transition and pasting temperature of starch. The crystallinity of starch in irradiated potatoes decreased significantly (p ? 0.05) which may explain its decreased resistant starch content. Sprout inhibiting treatments and storage had no effect on in vitro starch digestibility in cooked starches, but cooling cooked starch significantly (p ? 0.05) increased its resistant starch content.     

甘薯交联抗性淀粉热力学性质与消化性研究

根据膨胀度、糊化度及差示扫描量热仪(DSC)测得热力学参数,综合分析甘薯交联抗性淀粉和原淀粉热力学性质,并采用Jenkins提出In–vitro模型测定淀粉体外消化性。结果表明:在同一温度下,甘薯交联抗性淀粉膨胀度和糊化度均较原淀粉低,且交联剂用量越高,淀粉膨胀度和糊化度越小;DSC测试结果显示,甘薯交联抗性淀粉相转变温度To、Tp、Tc随交联剂用量增加而升高,Tc–To和△H均比原淀粉低。In–vitro消化模拟实验表明,甘薯交联抗性淀粉消化性比原淀粉低,并随交联剂含量增加,消化产物量减少,消化速度降低。     

Characteristics of native and enzymatically hydrolyzed Zea mays L., Fritillaria ussuriensis Maxim. and Dioscorea opposita Thunb. starches

Comparative studies on glucoamylase hydrolysis of A-type Zea mays L., B-type F. ussuriensis Maxim., and C-type Dioscorea opposita Thunb. were carried out by scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared (FT-IR) spectra and differential scanning calorimetry (DSC). Maize, Fritillaria, Dioscorea starches were hydrolyzed with glucoamylase for 2, 4, 8, 12 and 24 h, respectively. The SEM and XRD results revealed that A-type, B-type starch and C-type starch displayed different hydrolysis mechanisms. A-type starch was digested with enzyme penetrating into starch granules through natural pores on the surface and disrupted the interior of the starch granules. The glucoamylase worked by attacking the surface of B-type starch and forming cracks. When endo-corrosion occurred, the internal part of the granule was corroded through small cracks. However, the glucoamylase primarily attacked the interior of the C-type starch granules and then the exterior of starch granules. FT-IR confirmed that the amorphous regions in the starch granules are firstly hydrolyzed and could be hydrolyzed completely as long as the hydrolysis time is sufficient. The transition temperatures and enthalpy of gelatinization (ΔH_gel) were determined using DSC. According to the gelatinization parameters, it could be further proved amorphous and crystalline structures were hydrolyzed.     

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.     

Impact of annealing on the molecular structure and physicochemical properties of normal,waxy and high amylose bread wheat starches

Starch from normal (CDC teal), high amylose (line 11132) and waxy (99 WAX 27) bread wheat cultivars was isolated and its morphology, composition, structure and properties were studied before and after annealing. Granule diameters, total phosphorus, total amylose, lipid complexed amylose chains, crystallinity, gelatinization temperature range, gelatinization enthalpy, swelling factor (at 90 °C), and amylose leaching (at 90 °C), in the above starches ranged from 2–38 μm, 0.007–0.058%, 26.9–32.3%, 13.4–18.7%, 28.6–42.8%, 12.7–14.3 °C, 11.3–13.3 J/g, 27.6–72.2 and 22.2–26.2%, respectively. Peak viscosity, thermal stability, set-back and susceptibility towards acid hydrolysis followed the order: 99WAX27 > CDC teal > 11132, 11132 > CDC teal > 99WAX27, CDC teal > 99 WAX 27 > 11132, and 99WAX27 > 11132 > CDC teal, respectively. Susceptibility towards α-amylase hydrolysis followed the order: 99 WAX 27 > 11132 > CDC teal (<24 h) and 11132 > CDC teal > 99WAX27 (>24 h). The extent of retrogradation measured by spectroscopy and differential scanning calorimetry followed the order: 11132 > CDC teal > 99WAX27 and 99WAX27 > CDC teal > 11132, respectively. In all starches, concentration of amylose, lipid complexed amylose chains, gelatinization temperature range, swelling factor, amylose leaching, peak viscosity, final viscosity, set-back, light transmission, susceptibility towards α-amylase and acid hydrolysis and the proportion of small (2–8 μm) B-type granules decreased on annealing. Thermal stability and crystallinity increased on annealing. In all starches, gelatinization, enthalpy, retrogradation rate and amylopectin chain length distribution remained unchanged on annealing. Pores and indentations were formed on the granule surfaces of CDC teal and 99WAX27 starches on annealing.     

Digestibility and physicochemical properties of granular sweet potato starch as affected by annealing

The effects of annealing on the digestibility, morphology, and physicochemical characteristics of four types of granular sweet potato starches [Yulmi (YM), Yeonwhangmi (YHM), sweet potato starch from Samyang Genex (SSPS), and commercial sweet potato starch (CSPS)] were investigated. Annealing was performed at 55°C and 90% moisture content for 72 h. Morphology, the branched chain distribution of amylopectin, and the X-ray diffraction pattern remained unchanged during the annealing process. The slowly digestible starch content in annealed YM, YHM, and SSPS starches increased, but did not change in annealed CSPS. The gelatinization temperatures increased, but the gelatinization temperature range decreased with annealing. The swelling factor and amylose leaching decreased, while the close packing concentration increased. Rapid Visco Analyser analysis revealed that annealed starches possessed thermal stability and higher pasting temperatures. It is suggested that the enhanced packing arrangement formed during annealing impacts the digestibility and physicochemical properties of sweet potato starches.