Influence of hydroxypropylation on retrogradation properties of native,defatted and heat-moisture treated potato starches

Recent studies have shown that defatting and heat-moisture treatment cause structural changes within the amorphous and crystalline regions of potato starch. Furthermore, the alkaline reagents (NaOH and Na₂SO₄) used during hydroxypropylation has been shown to cause structural changes within the amorphous and crystalline regions of native, defatted and heat-moisture treated starches. In this study, we have compared (using different techniques) the retrogradation properties of potato starch before and after physical (defatting and heat-moisture treatment), and chemical (alkaline treatment and hydroxypropylation) modification. Turbidity measurements showed that changes in turbidity during storage (4°C for 24 h and then at 40°C for 29 days) of native, defatted and heat-moisture treated gelatinized starch pastes were influenced by the interplay of two factors: (1) interaction between leached starch components (amylose–amylose, amylose–amylopectin, amylose–amylopectin), and (2) interaction between granule remnants and leached amylose and amylopectin. In alkali treated gelatinized native, defatted and heat-moisture treated starch pastes, turbidity changes on storage was influenced by aggregation of granule remnants. Hydroxypropylation decreased the rate and extent of increase in turbidity during storage of native, defatted and heat-moisture treated starches. The change in turbidity during storage of hydroxypropylated starch pastes was influenced by the interplay between: (1) steric effects imposed by hydroxypropyl groups on chain aggregation, (2) aggregation between small granule remnants, and (3) settling of large granule remnants beneath the path of the spectrophotometer beam. Stored gelatinized pastes of native, defatted and heat-moisture treated starches gave a `B' type X-ray pattern. A similar pattern was also observed after alkaline treatment, and hydroxypropylation. However, the X-ray intensity of the strong reflection at 5.2 Å decreased after alkaline treatment and hydroxypropylation. The retrogradation endotherm (monitored by differential scanning calorimetry) occurred after 2 days storage in native, defatted and heat-moisture treated starches. A similar trend was also observed after alkaline treatment. However, the retrogradation endotherm appeared only after 7 days in hydroxypropylated starches. The enthalpy of retrogradation in all starches decreased on alkaline treatment and hydroxypropylation.     

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.     

The impact of heat-moisture treatment on molecular structures and properties of starches isolated from different botanical sources

Heat-moisture treatment is a hydrothermal treatment that changes the physicochemical properties of starches by facilitating starch chain interactions within the amorphous and crystalline domains and/or by disrupting starch crystallites. The extent of these changes is influenced by starch composition, moisture content and temperature during treatment, and by the organization of amylose and amylopectin chains within native starch granules. During heat-moisture treatment starch granules at low moisture levels [(<35% water (w/w)] are heated at a temperature above the glass transition temperature (T(g)) but below the gelatinization temperature for a fixed period of time. Significant progress in heat-moisture treatment has been made during the last 15 years, as reflected by numerous publications on this subject. Therefore, this review summarizes the current knowledge on the impact of heat-moisture treatment on the composition, granule morphology, crystallinity, X-ray pattern, granular swelling, amylose leaching, pasting properties, gelatinization and retrogradation parameters, and susceptibility towards α-amylase and acid hydrolysis. The application of heat-moisture treatment in the food industry is also reviewed. Recommendations for future research are outlined.     

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.     

Effect of the Heat-Moisture Treatment on the Enzymatic Susceptibility of Corn Starch Granules

Normal and waxy corn starches were isolated, adjusted to different levels of moisture and heated at 100°C for 16h. The heat treated starches were hydrolysed with α-amylase and amyloglucosidase. The starch samples were studied by determining their water-binding capacity, pasting properties, X-ray diffraction and by optical and scanning electron microscopy. The results showed that the heat-moisture treatment produced an increase in the degree of crystallinity of normal and waxy corn starches at the level of 18% moisture. This result, in conjunction with a significant decrease in the enzymatic susceptibility, suggested a rearrangement of the starch molecules with strengthening of the linkages within the granules. On the other hand, the heat-moisture treatment caused a rupture with further rearrangment of linkages within the granules for normal and waxy corn starches adjusted to the 27% moisture level. This produced a certain degree of starch degradation increasing the accessible regions of the granule to amylolysis.     

Physico-Chemical Properties of Defatted Heat-Moisture Treated Starches

Physico-chemical properties of wheat- and potato starch, defatted before or after heat-moisture treatment, were compared with those of untreated starches. Effects on waterbinding capacity, swelling power, solubility, enzyme susceptibility, gelatinization temperature range, viscograph consistency and on functional properties such as cake baking performance and thickening power are reported. X-ray diffraction patterns of samples defatted before heating appeared slightly sharper than those of non-defatted, then heat-moisture treated samples. Defatting of wheat starch combined with heat-moisture treatment caused less reduction in relative crystallinity than heat-moisture treatment alone, enzyme susceptibility was reduced, viscograph consistencies increased and cake baking performance and thickening power of the starches improved. Defatting of potato starch combined with heat treatment had some positive effects on enzyme susceptibility, solubility and thickening power.     

Granule Sizes of Canna (Canna edulis) Starches and their Reactivity Toward Hydration,Enzyme Hydrolysis and Chemical Substitution

Small and large granule fractions were isolated from canna starch (Canna edulis, green leaf cultivar), and their morphology, physicochemical properties, susceptibility towards granular starch hydrolyzing enzymes and chemical reaction with propylene oxide were investigated. Canna starch consisted of a mixed population of large, medium and small granules; the mean of granule diameter was 47.4 μm. The small granules presented round and polygonal shapes, whereas the large granules had oval and elliptical shapes. Significant variations in digestibility of the various granules size by granular starch hydrolyzing enzymes were observed. During the first 24 h, the hydrolysis rate of small granules was higher than that of native and large granule starches. After 72 h, however, the degree of hydrolysis of small granule, large granule and native starches had reached the extent of 19.6%, 32.0% and 27.2%, respectively. The larger the granule size, the higher the MS obtained when modified with propylene oxide, which was due to the higher swelling power of the large granules. The results obtained from this study suggest that small granules had lower water and chemical affinity when compared with the bigger ones. The difference in the reactivity of small and large granules could be presumably attributed to the starch components (amylose and amylopectin) and their organization of glucan chains in ordered and/or less ordered structure of these two fractions.     

THE FLOW PROPERTIES OF NATIVE, HEAT-MOISTURE TREATED, AND ANNEALED STARCHES FROM WHEAT, OAT, POTATO AND LENTIL

The effect of heat-moisture treatment (30% moisture, 100C, 16 h) and annealing (75 % moisture, 50C, 72 h) on the flow behavior of gelatinized starch pastes from wheat, oat, lentil and potato starches were studied at a concentration of 6% starch with a cone and plate viscometer (Wells Brookfield RVTDV II CP 200). The power law rheological model (σ=Kγⁿ) was used to describe the flow behavior of the above starch pastes. All native starches exhibited a non-Newtonian shear thinning behavior. A thixotropic loop was evident only in oat starches and native potato starch. Among native starches, the magnitude of the shear thinning index (n) followed the order: oat > wheat > lentil > potato, while the corresponding order for the consistency index (K) was: potato > lentil > wheat > oat. Heat-moisture treatment decreased the K value of all starches. On annealing, K decreased in wheat and lentil starches, but increased in potato and oat starches. Heat-moisture treatment and annealing increased the n value of wheat, lentil and potato starches, but decreased that of oat starch. In all starches, the modification to the flow behavior was more marked on heat-moisture treatment than on annealing.     

Scanning Electron Microscopy of Chemically and Enzymatically Treated Black Gram (Phaseolus mungo) and Ragi (Eleusine coracana) Starch Granules

Amylolysis of chemically - treated starch granules of black gram and ragi was followed colorimetrically and by scanning electron microscopy. From the percent hydrolysis values it was evident that oxidation with periodate resulted in considerable resistance, whereas urea treatment resulted in granule susceptibility towards in vitro amylolysis. The action of α-amylase and/or glucoamylase on periodate oxidised black gram starch showed on SEM sufficient enlargement of the granules and hollow craters as well; whereas similar treatment on oxidised ragi starch resulted in folded, distorted and deformed granules. Treatment with 8M urea resulted in the total loss of characteristic granular shape and formation of the socalled amylopectin “sacs”. Like waxy starches the latter showed an increase in enzymic activity. Particularly, the synergistic action of α-amylase and glucoamylase on ureatreated starches virtually collapsed the granules, forming innumerable “flat” ribbon like fragments.     

Kinetic Studies During Enzyme Hydrolysis of Potato and Cassava Starches

The hydrolysis of raw potato and cassava starches by bacterial α-amylase depends on the time of action, temperature and on the specific starch involved. The molecular weight of the trade α-amylase (Termamyl 60L), determined by SDS-PAGE, was found to be 55–65 kDa. The properties of α-amylase such as kinetic parameters, inhibition, stability, and thermostability were studied. The constants K_m and maximum reaction rate V_max for α-amylase were fitted to Michaelis-Menten models with these two starches. Differences in response of potato and cassava starches to hydrolysis by Termamyl 60L can explain differences found in K_m and V_max values and inhibition properties.     

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.     

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.     

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.     

Enzymatic hydrolysis of granular native and mildly heat-treated tapioca and sweet potato starches at sub-gelatinization temperature

The effect of mild heat treatment (below gelatinization temperature) towards the susceptibility of granular starch to enzymatic hydrolysis was investigated. Tapioca and sweet potato starches were subjected to enzymatic hydrolysis with a mixture of fungal α-amylase and glucoamylase at 35 °C for 24 h. Starches were hydrolyzed in native (granular) state and after heat treatment below gelatinization temperature (60 °C for 30 min). The dextrose equivalent (DE) value of heat-treated starch increased significantly compared to native starch, i.e., 36–50% and 27–34% for tapioca and sweet potato starch, respectively. Scanning electron microscopy examination showed that enzymatic erosion occurred mainly at the surface of starch granules. Hydrolyzed heat-treated starch exhibited rougher surface and porous granules compared to native starch. X-ray analysis suggested that enzymatic erosion preferentially occurred in amorphous areas of the granules. The amylose content, swelling power and solubility showed insignificant increase for both starches. Evidently, heating treatment below gelatinization temperature was effective in enhancing the degree of hydrolysis of granular starch.     

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.     

湿热处理对不同晶型淀粉理化性质及消化性的影响

采用三种不同晶型淀粉即玉米淀粉(A型)、马铃薯淀粉(B型)、豌豆淀粉(C型)为原料,在水分含量为25%、温度120℃条件下湿热处理13 h,研究湿热处理对不同晶型淀粉的理化性质及消化性的影响。研究表明,与原淀粉相比,经湿热处理的三种淀粉的结晶结构均发生了改变,玉米淀粉由A型变为了A+V型,马铃薯淀粉和豌豆淀粉分别由B型和C型变为了A型;三种淀粉颗粒表面均出现了不同程度的破损;三种淀粉的部分颗粒的偏光十字的中心强度有所减弱;三种淀粉样品的糊化温度均升高,但A型和B型淀粉的焓值降低,而C型淀粉的焓值升高;三种淀粉的抗性组分含量均有所升高,抗消化性显著增强,其中C型淀粉变化最明显。     

Hydrolysis of Tropical Tuber Starches by Bacterial and Pancreatic α-Amylases

Action of porcine pancreatic and Bacillus subtilis α-amylases on native tuber starches of yam (Dioscorea alata), sweet potato (Ipomea batatas) and tannia (Xanthosoma sagittifolium) was studied in comparison with the well known potato and cassava starches. Large differences in enzymes susceptibilities were observed when studied on 24h. Yam starch was 3.5% hydrolysed with 2,8 μkat amylase/g starch, three times less than potato and tannia starches while sweet potato starch was 53% hydrolysed, two times less than cassava starch. Except yam, level of hydrolysis was higher with porcine pancreatic amylase than with the Bacillus subtilis amylase while initial hydrolysis rate was lesser. Microscopic observations and image analysis pointed out that the polyhedric shaped granules of tannia, sweet potato and cassava starches were much more damaged than the spherical ones. Pitting occured preferentially on the edges of the granules and the enzymes penetrated into the starch granule by pores and canals of corrosion. Conversely to other starches, hydrolysis of yam starches evidenced greater differences between action of Bacillus subtilis and pancreatic α-amylases. The enzymes acted by pitting some parts of the granules surface, the number of pores and their size being related to enzyme source.     

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.     

Functional Properties and Retrogradation of Heat‐Moisture Treated Wheat and Potato Starches in the Presence of Hydroxypropyl β‐cyclodextrin

Some functional and retrogradation properties of native and heat‐moisture treated potato and wheat starches were examined in the presence of hydroxypropyl β‐cyclodextrin (HPβ‐CD). HPβ‐CD increased swelling factor, amylose leaching, and solubility of both native and heat‐moisture treated wheat starches but it had less impact on corresponding potato starches. Gelatinization enthalpy of native wheat starch was decreased in the presence of HPβ‐CD but was increased in potato starch with increasing concentration. Reduction of amylose‐lipid complex endotherm in both native and heat‐moisture treated wheat starch was observed in the presence of HPβ‐CD. Heat‐moisture treatment did not change the transition parameters of amylose‐lipid complex showing its resistance to hydrothermal treatment. HPβ‐CD greatly decreased the pasting temperature of wheat starch. Cold paste viscosity of both native and heat‐moisture treated wheat starch was increased by HPβ‐CD to a greater extent than corresponding potato starch. Amylopectin retrogradation of all the starches was unaffected in the presence of HPβ‐CD but heat‐moisture treatment slightly decreased retrogradation of potato starch. These results suggest that HPβ‐CD can disrupt the amylose‐lipid complex within the starch granule in both native and heat‐moisture treated wheat starch but has no influence on amylopectin retrogradation. However, greatly increased wheat starch setback with HPβ‐CD indicates its greater effect on wheat starch amylose retrogradation.     

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.