Effect of Cooling,and Freezing on the Digestibility of Debranched Rice Starch and Physical Properties of the Resulting Material

Ten percent non‐waxy and waxy starch suspensions were debranched with pullulanase followed by heating and cooling (1 °C) to crystallize and/or gel. Products with a range of textures can be made depending on the type (waxy and non‐waxy) of starch used. The water holding capacity was 35% and 84% for waxy and non‐waxy cooled debranched starch, respectively, at 4 h of cooling and did not change. The hardness of the debranched waxy and non‐waxy starch continued to increase beyond 24 h up to 45 g and 245 g of force, respectively. The particle size of precipitates of non‐waxy and waxy debranched starch was 45 μm and 4 μm after 4 h of cooling and did not change. Cooling of debranched non‐waxy starch at 1 °C for 12 h without agitation decreased digestibility by 59%; with stirring digestibility decreased by 42% after 24 h of cooling. Freezing of debranched cooled waxy and non‐waxy starch does not effect the decreases in digestibility. Particle size of debranched, cooled/freeze‐thawed, dried, and milled starch affects digestibility.     

Effect of Osmotic Pressure on Starch: New Method of Physical Modification of Starch

A new method of physical modification of starch in the presence of high concentrated salt solution is presented, called “Osmotic Pressure Treatment” (OPT). OPT was introduced in order to produce the same physically modified products as obtained by conventional heat‐moisture treatment (HMT) of starch. Potato starch was selected for the comparative study of the two methods. For the OPT method, potato starch was suspended in a saturated solution of sodium sulfate and heated in an autoclave at 105°C and 120°C ,which corresponded to the calculated osmotic pressures of 328 and 341 atm (332 and 345 bar, respectively) (assuming sodium sulfate dissociates completely) for 15, 30 and 60 min, respectively. For the HMT method, starch with 20% moisture content was placed in a Duran bottle, then the same heat treatment method in the autoclave was applied. Light and scanning electron microscopy (SEM) showed that OPT of starch changed the shape of the starch granules to a folded structure, while the starches remained unchanged after HMT. The RVA viscogram for the OPT starch exhibited a decrease in the peak viscosity without a breakdown and an increase of the pasting temperature when increasing the temperature and time, which was in an agreement with the viscosity patterns for the HMT starches. X‐ray diffraction patterns were altered from B to A+B for the HMT and from B to A type for the OPT starch when treated at 120°C. After OPT, the gelatinization temperatures (T_o, T_p, and T_c) of the starch increased significantly with increasing temperature and time, whereas only the T_c of starch increases after HMT. The biphasic broadening of the peaks (high T_c‐T_o) can be explained by an inhomogeneous heat transfer during HMT. Narrow peaks in the DSC curve can be an indication for a better homogeneity of the OPT samples. However, both methods provide a similar decrease in the gelatinization enthalpy (ΔH). The amylose‐amylopectin ratio calculated from the HPSEC patterns was strongly increased for HMT starches at 105°C for 60 min and 120°C for 30 min and decreased after treatment at 120°C for 60 min. For OPT starches the ratio was strongly increased at 120°C for 15 min and decreased after prolong heating. The OPT provides a uniform heat distribution in the starch suspension. This allows the modified starch to be produced on a larger scale.     

Structural Transformation of Sago Starch by Heat‐Moisture and Osmotic‐Pressure Treatment

Sago starch was modified by osmotic‐pressure treatment (OPT) and heat‐moisture treatment (HMT) and physicochemical characteristics were compared. In OPT, sago starch was suspended in saturated sodium sulfate solution and heated for 1 h at 100, 110 and 120°C, corresponding to a calculated osmotic pressure of 32,728, 33,640 and 34,552 kPa (assuming sodium sulfate dissociates completely), respectively, and in HMT, sago starch with 20% moisture content was used. Change of X‐ray diffraction pattern from C‐type to A‐type was obtained for OPT and HMT starch at 110°C and 120 °C, respectively. RVA viscograms of both OPT and HMT starch exhibited a decrease of peak and breakdown viscosity but increase of final viscosity and pasting temperature. Onset (T_o), peak (T_p), and conclusion temperature (T_c) of gelatinization of both OPT and HMT starch increased significantly with increase of treatment temperature. Biphasic broadening of T_p was observed for HMT starch indicating an inhomogeneous heat transfer during HMT. The observed narrow peaks of DSC curves indicated better homogeneity of OPT. These properties suggest that OPT starch is more suitable for large‐scale production.     

Effect of Pullulanase Debranching of Sago (Metroxylon sagu) Starch at Subgelatinization Temperature on the Yield of Resistant Starch

The effects of pullulanase debranching of sago (Metroxylon sagu) starch in the granular state and subsequent physical treatments on the formation and yield of type III resistant starch (RS 3) have been investigated. Sago starch was enzymatically debranched with pullulanase at 60°C and at pH 5.0 using different enzyme concentrations (24, 30, 40, 50 PUN/g dry starch) which was added to 20% (w/v) starch slurry and incubated for 0 to 48 h. Optimum enzyme concentration of 40 PUN/g dry starch and three debranching times (8, 16 and 24 h) have been selected for subsequent preparation of RS. Granule morphology and molecular weight distribution (MWD) of the debranched and resistant starch were examined. Debranched starch samples showed blurred birefringence patterns, a decrease in amylopectin fraction, an increase in low molecular weight fraction and a broadening of MWD. Debranched starch samples with a maximum RS yield of 7% were obtained at 8 h debranching time. Temperature cycling and incubation at certain temperature and storage time enhanced the formation of RS. Under the conditions used in this study, the optimum conditions to obtain the highest RS yield (11.6%) were 8 h of debranching time, followed by incubation at 80°C for seven days. The MWD analysis showed that RS consisted of material with relatively low degree of polymerization. This study showed that pullulanase treatment of starch in the granular state resulted in limited debranching of amylopectin but the subsequent physical treatments (incubation time/temperature) can be manipulated to promote crystallization and enhance formation of RS 3.     

Effect of debranching and storage condition on crystallinity and functional properties of cassava and potato starches

Debranching starch by pullulanase is considered to improve the RS content of starch which is widely used to produce the starch‐based foods with high‐health benefit impacts. In this study, the cassava and potato starches were debranched by pullulanase, followed by an autoclave treatment and storage at −18°C, 4°C, or 25°C to investigate their crystallinity and functional properties. After debranching, the potato starch contained significantly higher CL (35.4 glucose units) than did the cassava starch (32.4 glucose units). The debranched cassava and potato starches after retrogradation at the storage temperatures had a typical B‐type crystalline structure although the native cassava and potato starches exhibited the different crystalline forms (A‐ and B‐type, respectively). The RS contents of the debranched cassava and potato starches significantly improved with higher RS content of the debranched potato starch than that of the debranched cassava starch at the same storage condition. The storage temperature significantly affected the RS formation of the debranched starches with the highest RS content at storage temperature of −18°C (35 and 48% for the debranched cassava and potato starches, respectively). The debranched starches had significantly lower viscosities and paste clarities but higher solubilities than did the native starches. As a result, the debranched cassava and potato starches can be considered for use not only in functional foods with enhanced health benefits but also in pharmaceutical and cosmetic industries.     

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.     

Molecular structure and granule morphology of native and heat‐moisture‐treated pinhão starch

Pinhão seed is an unconventional source of starch and the pines grow up in native forests of southern Latin America. In this study, pinhão starch was adjusted at 15, 20 and 25% moisture content and heated to 100, 110 and 120 °C for 1 h. A decrease in λ max (starch/iodine complex) was observed as a result of increase in temperature and moisture content of HMT. The ratio of crystalline to amorphous phase in pinhão starch was determined via Fourier transform infra red by taking 1045/1022 band ratio. A decrease in crystallinity occurred as a result of HMT. Polarised light microscopy indicated a loss of birefringence of starch granules under 120 °C at 25% moisture content. Granule size distribution was further confirmed via scanning electron microscopy which showed the HMT effects. These results increased the understanding on molecular and structural properties of HMT pinhão starch and broadened its food and nonfood industrial applications.     

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).     

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.     

Effect of Hydrothermal Treatment on Formation and Structural Characteristics of Slowly Digestible Non‐pasted Granular Sweet Potato Starch

The formation and structural characteristics of slowly digestible non‐pasted granular starch in sweet potato starch were investigated under various hydrothermal treatment conditions. The moisture content of the sweet potato starch was adjusted to 20, 50 or 90%, and the starch was heated at 40, 55 or 100°C for 12 h in a dry oven. The relative crystallinity of the hydrothermally treated samples was decreased with increasing temperature, and the X‐ray diffraction patterns of the samples were altered from C_b‐type to A‐type. Microscopic observations did not reveal any changes in the starch granules of any samples except those with moisture contents of 50 and 90% that were heated at 100°C. When gelatinization parameters were examined, samples with moisture contents of 50 and 90% that were heated at 55°C and samples of all moisture contents that were heated at 100°C had peak temperatures higher than that of raw starch but gelatinization enthalpies lower than that of raw starch. The swelling factor of the samples heated at 40°C did not change significantly, whereas that of samples heated at 55 and 100°C was decreased at increased moisture levels. The sweet potato starch with 50% moisture content that was heated at 55°C had the highest content of granular slowly digestible starch, about 200% that of raw starch, although our study did not involve further hydrothermal treatment conditions. Further study is required to complete a process for more efficient production of heat stable and slowly digestible starch.     

Effect of Heat‐Moisture Treatment on Structural and Thermal Properties of Rice Starches Differing in Amylose Content

Starches from glutinous rice (1.4% amylose), Jasmine rice (15.0% amylose) and Chiang rice (20.2% amylose) were exposed to heat‐moisture treatment (HMT) at 100 °C for 16 h and at different moisture levels (18, 21, 24 and 27%). The effect of heat‐moisture treatment on structural and thermal properties of these three rice starches was investigated. The HMT did not change the size, shape and surface characteristics of rice starch granules. The A‐type crystalline pattern of rice starches remained unchanged after HMT. The relative crystallinity (RC) and the ratio of short‐range molecular order to amorphous (RSA) of heat‐moisture treated glutinous and Jasmine rice starches decreased with increasing moisture level of the treatments. In contrast, the RC of the treated Chiang rice starch remained practically unchanged. A peak of crystalline V‐amylose‐lipid complexes was clearly presented in all treated Chiang rice starches. The peak became progressively stronger with increasing moisture level of the treatment. Differential scanning calorimetry (DSC) of all treated rice starches showed a shift of the gelatinization temperature to higher values. Increasing moisture level of the treatments increased the onset gelatinization temperature (T_o) but decreased the gelatinization enthalpy (ΔH) of rice starches. A broad gelatinization temperature range (T_c‐T_o) with a biphasic endotherm was found for all treated Chiang rice starches and Jasmine rice starch after HMT₂₇ (HMT at 27% moisture level). Additionally the (T_c‐T_o) of treated Chiang rice starches increased linearly with increasing moisture level of the treatments.     

Development and Physicochemical Characterization of New Resistant Citrate Starch from Different Corn Starches

Resistant starch has drawn broad interest for both potential health benefits and functional properties. In this study, a technology was developed to increase resistant starch content of corn starch using esterification with citric acid at elevated temperature. Waxy corn, normal corn and high‐amylose corn starches were used as model starches. Citric acid (40% of starch dry weight) was reacted with corn starch at different temperatures (120–150°C) for different reaction times (3–9 h). The effect of reaction conditions on resistant starch content in the citrate corn starch was investigated. When conducting the reaction at 140°C for 7 h, the highest resistant starch content was found in waxy corn citrate starch (87.5%) with the highest degree of substitution (DS, 0.16) of all starches. High‐amylose corn starch had 86.4% resistant starch content and 0.14 DS, and normal corn starch had 78.8% resistant starch and 0.12 DS. The physicochemical properties of these citrate starches were characterized using various analytical techniques. In the presence of excess water upon heating, citrate starch made from waxy corn starch had no peak in the DSC thermogram, and small peaks were found for normal corn starch (0.4 J/g) and Hylon VII starch (3.0 J/g) in the thermograms. This indicates that citrate substitution changes granule properties. There are no retrogradation peaks in the thermograms when starch was reheated after 2 weeks storage at 5°C. All the citrate starches showed no peaks in RVA pasting curves, indicating citrate substitution changes the pasting properties of corn starch as well. Moreover, citrate starch from waxy corn is more thermally stable than the other citrate starches.     

Physicochemical properties of pressure moisture treated (PMT) and heat moisture treated (HMT) starches

Physicochemical properties of pressure moisture treated (PMT, 550 MPa, 10 min) and heat moisture treated (HMT, 100 °C, 10 h) starches were investigated. Effects of PMT and HMT were different depending on starch type. PMT starches showed dramatic changes in moisture sorption isotherm, pasting properties, thermal characteristics, solubility and swelling power (at 90 °C), and in vitro digestibility. The most dramatic difference between PMT and HMT starches was amylopectin melting transition, i.e., broadening in PMT and shift to high temperature in HMT starches. Moreover, B- and C-type starches revealed the more increase in amylopectin melting enthalpy than A-type starch. Both PMT and HMT did not increase the crystallinity but reorganized the amorphous area to compact, resulting in lower rapidly digestible starch and higher slowly digestible starch than those of native starches. Consequently, PMT changed the digestibility and physicochemical properties of starches with different modes of action compared with HMT.     

Thermal Transitions in Gelatinized Wheat Starch at Different Moisture Contents by Dynamic Mechanical Analysis

Gelatinized starch was analyzed by DMA and the resulting overlapped tan 5 curve was characterized. At high moisture contents (>30% w/w), transitions around ice melting region of tan 5 peak (>50°C wide) showed skewness at the low temperature side. After deconvolution, a symmetrical, sharp, main peak was correlated with the ice melting endotherm but the cause of the lower temperature asymmetrical peak was not identified. At <30% moisture, two deconvoluted Gaussian peaks indicated at least two separate, broadly distributed domains (slightly frequency dependent). Transitions (other than ice melting), if caused by glassy rubbery transitions, were small in tan 5 and broad (50–100°C wide).     

Canavalia ensiformis Tailing Starch: A Functional Source of Dietary Fiber

Physicochemical and functional characteristics of the tailing starch isolated from the legume Canavalia ensiformis were determined. Proximal composition was 2.86% protein, 4.05% fiber, 0.37% fat, 1.51% ash and 91.33% carbohydrates as nitrogen‐free extract. Total dietary fiber content was 21.3%, soluble fiber was 2.2%, and insoluble fiber was 19.1% as determined by the Prosky method. Amylose content as quantified by differential scanning calorimetry (DSC) was 39.35%. Gelatinization temperature range as determined by DSC was from 77.9 °C to 88.1 °C, with 81.6 °C being the peak temperature. Transition enthalpy was 10.1 J/g. Swelling power ranged from 4.36 g water/g starch at 60 °C to 11.87 g water/g starch at 90 °C. Water solubility, analyzed within the same temperature interval, ranged from 3.29% to 16.93%. Water absorption capacity was 4.22 g water/g starch at 60 °C and 10.33 g water/g starch at 90 °C. Syneresis in a 6% gel stored at 4 °C for 24 h was 25.66 mL water/50 mL gel. Clarity, expressed as transmittance, was 10.46%. Initial pasting temperature was 93 °C, breakdown was —22 Brabender Units (BU), consistency was ‐5 BU, and setback was 17 BU.     

Formation of Resistant Starch in Corn Starch and Estimation of its Content from Physicochemical Properties

The effect of autoclaving temperatures (100‐120°C) on yields of enzyme‐resistant starch (RS) from normal corn starch and the physicochemical properties of autoclaved‐cooled starches were studied. The RS content increased linearly with increasing autoclaving temperature (R² = 0.993) and the number of autoclaving‐cooling cycles at an autoclaving temperature of 120°C. The effect of the number of autoclaving‐cooling cycles was more pronounced than that of temperature. The swollen starch weight measured at 60°C slightly increased as the RS content increased, and then drastically decreased with the continous increase of the RS content (R² = ‐0.969). As the RS content increased, all parameters of Rapid Visco Analyser (RVA) viscosity except breakdown decreased. Log RVA peak viscosity showed a negative correlation with the RS content (R² = ‐0.986). The enthalpy in the differential scanning calorimetry (DSC) endotherm corresponding to the transitions of RS linearly increased as the RS content increased (R² = 0.988). The RS content of the heat‐treated starch estimated from the relationship between RS content and swollen starch weight at 60°C, log RVA peak viscosity or DSC enthalpy was in good agreement with that determined with the standard method.     

In vitro availability of starch in heat‐treated potatoes as related to genotype,weight and storage time

The objective of the study was to determine the influence of potato variety, weight and storage time after lifting on the glycaemic index (GI) and resistant starch (RS) content predicted from measurement of the rate and extent of in vitro starch hydrolysis, respectively. The potatoes were either boiled, or boiled and subjected to different heat‐cycling conditions selected to promote retrogradation of amylose or amylopectin, respectively. The hydrolysis indices (HI) and predicted GIs of all 19 potato products were high and fell within narrow ranges of 122–144 and 118–138, respectively. No correlation between average weight of the potato tuber and HI was found. Furthermore, there was no difference in HI between potatoes stored for 1–3 or 8–10 months, nor between varieties of new potato and winter potato. However, the HI was significantly lowered by temperature cycling at conditions known to promote retrogradation of amylopectin (6 °C, 48 h) compared with 6 °C for 24 h followed by 70 °C for 24 h. RS content was already substantial in boiled potatoes, 4.5 g 100 g^?1 (starch basis), and could be increased further by temperature cycling, the highest yield obtained, 9.8 g 100 g^?1 (starch basis), following heat treatment at 6 °C for 24 h followed by 70 °C for 24 h; that is at conditions known to favour amylose retrogradation. Copyright © 2004 Society of Chemical Industry     

湿热处理对大米淀粉多层次结构及消化特性的影响

为了明晰湿热处理前后大米淀粉多层次结构与消化性能之间的关系,本研究采用体外模拟法测定湿热处理前后大米淀粉的消化性能,并通过小角X射线散射（SAXS）、X射线衍射（XRD）和凝胶渗透色谱-多角度激光光散射（GPC-MALS）等现代分析技术考察湿热处理前后大米淀粉不同层次结构的变化。研究表明,湿热处理可引起大米淀粉半结晶片层的有序化程度下降,降低其结晶程度和分子量;同时,伴随着淀粉颗粒内部层状、结晶及分子链结构的破坏,淀粉-脂质复合物的形成及Mw >2×107 g/mol的高分子量片段的降低和Mw<5×106 g/mol的低分子量片段比例的增加（0%增至21.3%）有利于大米淀粉慢消化和抗消化性能的提高,而当Mw<5×106 g/mol比例增至32.1%时,可能由于低分子量片段较多,反而阻碍了慢消化和抗消化性能的提高。研究结果为湿热处理加工技术调控淀粉及淀粉质食品的消化性能提供了理论支撑和基础数据。     

Physicochemical,crystallinity, pasting and thermal properties of heat‐moisture‐treated pinhão starch

The effect of heat‐moisture treatment (HMT) on the properties of pinhão starches under different moisture and heat conditions was investigated. The starches were adjusted to 15, 20 and 25% moisture levels and heated to 100, 110 and 120°C for 1 h. The X‐ray diffractograms, swelling power, solubility, gel hardness, pasting properties and thermal properties of the native and HMT pinhão starches were evaluated. Compared to native starch, there was an increase in the X‐ray intensity and gel hardness of HMT starches, with the exception of the 25% moisture‐treated and 120°C heat‐treated starch. HMT reduced the swelling power and solubility of the pinhão starches when compared to native starch. There was an increase in the pasting temperature, final viscosity and setback and a decrease in the peak viscosity and breakdown of HMT pinhão starches compared to native starch. HMT increases the gelatinisation temperature of native pinhão starch and reduces gelatinisation enthalpy.     

Effect of heating rate at different moisture contents on starch retrogradation and starch–water interactions during gelatinization

The objective of this research was to investigate the effect of heating rate at different moisture contents on starch retrogradation and gelatinization process. Starch retrogradation was not influenced by either moisture content (water/starch ratio of 0.7 or 2.0) or heating rate (5°C/min, 20°C/min, or 40°C/min). In order to further understand the effects of heating rate on starch–water interactions, starch suspensions at a water/starch ratio ranging from 0.7 to 3.0 were heated at 5, 15, or 25°C/min by using a DSC to different final temperatures and rescanned. The deconvoluted G and M1 endotherms and the corresponding additional unfrozen water (AUW) were determined. The results showed that the G and M1 endotherms merged at higher heating rates and at higher moisture contents as expected. A significant interaction was observed between moisture content and heating rate. The results suggest that the gelatinization process is governed by moisture content at the lower heating rate (5°C/min) and by heating rate at the higher heating rates (15 or 25°C/min). Results from the AUW data suggest that the M1 component of gelatinization dominated at moisture content below water/starch ratio of 1.5 and at 5°C/min heating rate. However, at moisture contents above water/starch ratio 1.0, an interaction was observed between moisture content and heating rate. The data suggest that at higher moisture content (>1.5 water/starch ratio) and at higher heating rate (≥15°C/min), there is still a kinetic limitation to the complete melting of the M1 endotherm.