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.     

Production and characterization of digestion‐resistant starch by the reaction of Neisseria polysaccharea amylosucrase

Recombinant amylosucrase (200 U/mL) from Neisseria polysaccharea was used to produce digestion‐resistant starch (RS) using 1–3% (w/v) corn starches and 0.1–0.5 M sucrose incubated at 35°C for 24 h. Characterization of the obtained enzyme‐modified starches was investigated. Results show that the yields of the enzyme‐modified starches were inversely proportional to the original amylose contents of corn starches. After enzymatic reaction, insoluble RS contents increased by 22.3 and 20.7% from 6.9% of waxy and 7.7% of normal corn starches, respectively, using 3.0% starch as acceptor and 0.3 M sucrose as donor, while amylomaize VII showed the lowest increase (8.5%) in RS content. The crystalline polymorph of these enzyme‐modified starches resulted in the B‐type immediately after enzymatic reaction. The enzyme‐modified starches displayed higher melting peak temperatures (85.6–100.6°C) compared to their native starch counterparts (70.1–78.4°C). After enzymatic reaction, pasting temperature increased in waxy (71.9 → 77.6°C) and normal corn starches (75.3 → 80.6°C), and the peak viscosity of waxy corn starches increased from 264 to 349 RVU, whereas that of normal corn starches decreased from 235 to 66 RVU.     

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.     

Physicochemical Properties of Non‐thermally Cross‐linked Corn Starch with Phosphorus Oxychloride using Ultra High Pressure (UHP)

Corn starch (20%, w/w) was non‐thermally and conventionally cross‐linked with phosphorus oxychloride (POCl₃; 0.01, 0.05, or 0.1%, based on dry weight of starch) at 400 MPa for 5, 15 and 30 min and at 45°C for 2 h, respectively. Swelling power and solubility of both non‐thermally and conventionally cross‐linked corn starches were relatively lower than those of native corn starch. The pressure holding time did not affect the solubility and swelling power of non‐thermally cross‐linked corn starches. X‐ray diffraction patterns and relative crystallinity were not significantly altered by both conventional and non‐thermal cross‐linking. DSC thermal characteristics of both non‐thermally and conventionally cross‐linked corn starches were not significantly changed indicating that the double helical structure of amylopectin was not influenced by both conventional and non‐thermal cross‐linking reactions. Both non‐thermal and conventional cross‐linking greatly affected the Rapid Visco Analyser (RVA) pasting properties, such as increase in pasting temperature and decrease in peak viscosity compared to native starch. This result suggests that in case of cross‐linking using POCl₃, both non‐thermal and conventional methods result in similar physicochemical properties and non‐thermal cross‐linking with POCl₃ can reduce the reaction time from 2 h to 15 min. This work shows the potential and possibility of non‐thermal starch modification and provides the basic and scientific information on the physicochemical properties of non‐thermally cross‐linked corn starches with phosphorus oxychloride using UHP.     

Physicochemical and structural characteristics of cross‐linked banana starch using three cross‐linking reagents

Banana starch was cross‐linked using different cross‐linking reagents, phosphoryl chloride (POCl₃), sodium trimetaphosphate (STMP), and epichlorohydrin (ECH), under alkaline conditions. The reaction conditions were selected to produce similar pasting profiles. The effects of the different cross‐linking reagents on the physicochemical and structural characteristics of cross‐linked starches were evaluated. The microscopy study did not show difference on the surface of the granules. Slight decrease in the peak temperature and enthalpy were found in the cross‐linked banana starch. The chemical groups introduced in the starch molecules by the diverse reagents promoted the re‐association of starch chains during storage. The rheological analysis of all starch dispersion at 10% (flow curves) showed a non‐Newtonian shear‐thinning; pastes obtained were time‐independent, suggesting an important contribution of the continuous phase. Structural study showed that the cross‐linked STMP‐starch had the lowest level of amylose and the ratio short/long amylopectin chains. The three reagents used for cross‐linking presented different action mode on starch granule and its components.     

Improving gel formation of rice starch added with cross‐linked resistant starch prepared from rice starch

The gel formation properties of non‐waxy rice starch with cross‐linked resistant starch with phosphate (RS4, 10, 20, and 30% based on rice starch) prepared from three rice varieties with different amylose (AM) content were investigated to increase dietary fiber content, improve gel structure, and reduce the glycemic index of rice products. The AM contents of rice starches were 1.71% in Hanganchal1, 22.47% in Nampyeong, and 33.39% in Goamy. All RS4 showed A‐type crystallinity and their RS levels were 46.91, 54.54, and 66.01%, respectively. The initial pasting temperatures of RS4 added rice starches increased as RS4 contents increased, but peak and breakdown viscosities and enthalpy change (△H) reduced. The RS4 addition improved gel shape and texture properties including hardness, cohesiveness, and gumminess, except the 30% Goamy RS4 added gel. The 20% RS4 addition was appropriate to form rice starch gels. The network structure of RS4 added gel formed more regular and firmer than that of control, because RS4 granules were entrapped within the gel matrix like observed by light microscope and scanning electron microscopy. It is suggested that RS4 not only assist in forming a rigid network structure but also increasing a dietary fiber content.

     

The effect of chemically‐modified resistant starch,RS type‐4, on body weight and blood lipid profiles of high fat diet‐induced obese mice

This study was conducted to investigate the effects of feeding chemically‐modified resistant starch type‐4 (RS4) of normal (NCS) and high‐amylose corn starch (HACS) on weight gain and plasma and liver lipid profiles of mice fed a high‐fat diet (HFD). The experimental four groups were, respectively, fed following diets: A 40% HFD with NCS, HACS, NCS‐ and HACS‐RS4. A normal diet (ND) group of mice fed the standard diet was also used as control. In order to produce RS4 by chemical modification, corn starches were treated with STMP/STPP. Total RS (TRS) and total dietary fiber (TDF) levels of chemically‐modified NCS were 26.4 and 44.0%, respectively, while TRS and TDF levels in chemically‐modified HACS were 78.1 and 78.5%, respectively. Onset gelatinization temperatures of both modified corn starches clearly shifted to higher temperatures after STMP/STPP treatment. At the end of the diet trial, the mice on the HACS diet decreased body weight gain compared to the NCS‐fed mice. Adding NCS‐ and HACS‐RS4 to the diet significantly reduced the weight gain relative to NCS and HACS groups. Both RS4 diets were effective in improving the lipid profile compared to their respective controls. They significantly reduced the level of total lipid and total cholesterol.     

Physicochemical and Functional Properties of Cross‐linked Banana Resistant Starch. Effect of Pressure Cooking

A resistant starch (RS)‐rich powder was prepared from phosphate cross‐linked banana starch. Serial autoclaving and cooling treatments of this cross‐linked material were also made. The powders were evaluated for chemical composition, resistant starch content, thermal characteristics, as well as for swelling and solubility properties. The parental cross‐linked starch had similar lipid and protein contents than its autoclaved counterpart, but the ash content decreased after autoclaving, a pattern that is in agreement with the low phosphorus index and degree of substitution recorded in the autoclaved preparation. Although the RS content in the autoclaved cross‐linked product was lower than in the non‐autoclaved starch, the autoclaved product still exhibited a remarkable indigestibility. The peak temperatures of gelatinization were 86.6 and 68.5ºC for cross‐linked and autoclaved cross‐linked starch, respectively. At low temperatures the autoclaved modified starch exhibited greater swelling values than its cross‐linked counterpart. The pattern of solubility values resembled the swelling behavior of both samples. The autoclaved cross‐linked banana starch appears suitable for the formulation of foods requiring none or moderate further heat treatment.     

The effects of annealing and acid hydrolysis on resistant starch level and the properties of cross‐linked RS4 rice starch

The effects of ANN prior to cross‐linking of non‐wx rice starches on a RS level and granular shape were investigated to apply them for a fat replacer with RS in a liquid food system. Acid hydrolysis and sonication were also evaluated to improve RS quality. The RS level was also compared with AOAC and P/G methods. The RS levels of CRS analyzed with the AOAC method were higher than those analyzed with the P/G method, but the differences in the RS level of CRS affected an ANN condition and starch content during cross‐linking. When ANN was conducted at 50°C for 12 h using the AOAC method, and starch content (40%) used in cross‐linking was at 45°C for 3 h, the highest RS level of CRS treated with ANN was 69.4% compared to 38.3% RS level of CRS without ANN. The 1 h acid hydrolysis (pH 4.0) of CRS treated ANN increased 114.5% of the RS level (79.4% compared to 69.4% in CRS treated ANN), regardless of which analytical methods were used. CRS granules remained the same as native ones with a polygonal shape and A type crystallinity even after being treated with ANN, and acid hydrolysis. The sonication before cross‐linking reaction increased the RS level and prevented increase in size from aggregating CRS granules.     

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

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

Effect of autoclave–cooling cycles combined pullulanase on the physicochemical and structural properties of resistant starch from black Tartary buckwheat

A starch-rich portion is produced as a by-product of black Tartary buckwheat processing. The effect of enzymatic combined with autoclaving–cooling cycles (one, two, or three times) on the physicochemical and structural properties of black Tartary buckwheat type 3 resistant starch (BRS) was evaluated. The autoclaving–cooling cycles enhanced solubility and reduced swelling, with the BRS content increasing from 14.12% to 25.18%. The high crystallinity of the BRS reflected a high molecular order. However, increasing the number of autoclaving–cooling cycles did not result in higher BRS content. The highest BRS yield in the autoclaved starch samples was 25.18% after double-autoclaving–cooling cycles. Furthermore, the autoclaving–cooling cycles altered the crystalline structure of black Tartary buckwheat, and the subsequent crystallinity changed from 36.33% to 42.05% to 38.27%. Fourier-transform infrared spectroscopy shows that the number of cycles results in more efficient double-helical packing within the crystalline lamella. Principal component analysis showed that the autoclaving–cooling cycle treatment leads to significant changes in the molecular structure of resistant starch (RS). These results indicated that autoclaving–cooling cycles might be a feasible way for producing RS from black Tartary buckwheat starch with better structural stability to expand their application range.     

Effect of Cross‐linking with Epichlorohydrin on the Properties of Cassava (Manihot esculenta Crantz) Starch

Cassava starch was cross‐linked with epichlorohydrin (EPI) at 45°C for 2 h in three different media which include water, water in the presence of a phase transfer catalyst (PTC) and N,N‐dimethylformamide (DMF). The products were characterized by determining their physicochemical, thermal and retrogradation properties. In aqueous medium, the use of a PTC, tetrabutylammonium bromide (TBAB) produced derivatives with higher degree of cross‐linking than those prepared without the use of the catalyst. The degree of cross‐linking was found to be higher using the same concentration of EPI when the reaction was carried out in DMF. At low levels of cross‐linking, the peak viscosity of the cross‐linked starches increased in comparison to that of the native starch. With increasing degree of cross‐linking, the peak viscosity showed a significant reduction. The swelling volume, solubility and light transmittance of the starch pastes were lower for the modified starches. The cross‐linked starches showed slightly reduced values for the gelatinization temperatures, T_onset, T_peak and T_end. The enthalpy of gelatinization of the modified starches increased with increase in the degree of cross‐linking. The modified starches exhibited higher water‐binding capacities (WBC) than the native starch; but with increase in the degree of cross‐linking, there was a gradual decrease in WBC. The in vitro alpha amylase digestibility of the modified starches decreased gradually with increase in the level of cross‐linking.     

In vitro Digestibility of Cross‐Linked Starches – RS4

In vitro digestibility of cross‐linked starches (RS4 type), which were prepared from wheat, corn, rice, potato, and high‐amylose corn starches, was determined by Prosky AOAC and pancreatin gravimetric (P/G) methods. The RS levels of RS4 starches obtained by the AOAC method were higher than those by the P/G method. Pronase treatment before digestion with heat‐stable α‐amylase (AOAC method) gave similar RS levels as those by P/G method. The shapes of residues after digestion by the AOAC method were not different from untreated ones, but those after digestion by the P/G method showed irregular and fluffy forms. It was found that the P/G method provided more exhaustive digestion of RS4 starches than the AOAC method.     

Morphological,thermal, rheological and noodle‐making properties of potato and corn starch

A comparison between the morphological, thermal, rheological and noodle‐making properties of corn starch and potato starches separated from five different potato cultivars was made. The granule size and shape of all starches differed significantly. Potato starch granules were comparatively larger than corn starch granules, while the transition temperatures were found to be higher for corn starch. Consistency coefficients and flow behaviour indices measured by back extrusion were higher for potato starches than for corn starch. Stickiness of cooked starch pastes was observed to depend upon their consistency coefficient. The gels made from all potato starches showed higher gel strength than those from corn starch. The gel strength of starches from both corn and potato increased during refrigerated storage. The amylose content, swelling power, solubility and light transmittance values of potato starches were significantly higher than those of corn starch. Noodles made from potato starches had higher cooked weight and cooking loss than corn starch noodles. Texture profile analysis revealed that potato starch noodles also had higher hardness and cohesiveness than corn starch noodles. Hardness of cooked noodles from all starches increased and cohesiveness decreased during storage. Noodles made from starches of higher viscosity exhibited higher hardness and cohesiveness. Textural differences among cooked starch noodles appeared to be associated with morphological, thermal and rheological properties of corn starch and potato starches. © 2002 Society of Chemical Industry     

Resistant Starch‐rich Powders Prepared by Autoclaving of Native and Lintnerized Banana Starch: Partial Characterization

Powdered preparations enriched in resistant starch (RS) were obtained from native and lintnerized (prolonged acid treatment) banana starches by consecutive autoclaving/cooling treatments. The preparations were tested for indigestible starch content, swelling and solubility properties, thermal analysis and pasting profile. The autoclaved samples had higher RS content than their parental counterparts, but the chemical modification (lintnerization process) allowed development of higher RS proportions (19%, dry matter basis, dmb). The autoclaved samples (RS‐enriched products) showed similar swelling values (α = 0.05) at the temperatures assessed. These RS‐rich products exhibited a lower solubility in water than the corresponding raw materials. The peak temperatures of the thermal transition were 155.5 and 145.8°C for native autoclaved and lintnerized autoclaved starch, respectively. These values indicate that RS products have a marked thermal stability. The pasting behavior of the RS products was less pronounced than that of the raw counterparts. Hence, their potential use as processed food ingredients should not impact final product viscosity. These RS‐enriched products appear suitable for the formulation of functional foods.     

Effects of Granule Sizes on Physicochemical Properties of Cross‐linked and Acetylated Wheat Starches

Large and small wheat starch granules were used for cross‐linking and acetylation to determine effects of granule sizes on physicochemical properties of the modified starches. The native and cross‐linked starches from the small granules showed higher phosphorus contents than did those from the large granules. However, the level of phosphate substituents in the modified starches was not significantly different between the large and small granules under the same conditions. In contrast, the large granules had a higher reactivity with acetic anhydride than did the small granules. The phosphate group cross‐linked starch (CS), acetylated starch (AS) and acetylated cross‐linked starch (ACS) from the large granules had lower gelatinization temperatures and higher enthalpies than those from the small granules. The paste viscosities of the CSs from the large granules decreased rapidly, whereas those of the AS or ACS increased significantly as compared with those from the small granules. The pastes of cross‐linked starches from the small granules were more stable than those from the large granules, whereas the pastes of AS and ACS from the large and small granules had similar resistance to freeze‐thaw treatment. Scanning electron microscopy (SEM) also showed that the small granules were less damaged after modification than the large ones. Thus, the different granule sizes resulted in different physicochemical properties of starch after modification.     

Structures and Physicochemical Properties of Acid‐Thinned Corn,Potato and Rice Starches

The structures and physicochemical properties of acid‐thinned corn, potato, and rice starches were investigated. Corn, potato, and rice starches were hydrolyzed with 0.14 N hydrochloric acid at 50 °C until reaching a target pasting peak of 200—300 Brabender Units (BU) at 10% solids in the Brabender Visco Amylograph. After acid modification the amylose content decreased slightly and all starches retained their native crystallinity pattern. Acid primarily attacked the amorphous regions within the starch granule and both amylose and amylopectin were hydrolyzed simultaneously by acid. Acid modification decreased the longer chain fraction and increased the shorter chain fraction of corn and rice starches but increased the longer chain fraction and decreased the shorter chain fraction of potato starch, as measured by high‐performance size‐exclusion chromatography. Acid‐thinned potato starches produced much firmer gels than did acid‐thinned corn and rice starches, possibly due to potato starch's relatively higher percentage of long branch chains (degree of polymerization 13—24) in amylopectin. The short‐term development of gel structure by acid‐thinned starches was dependent on amylose content, whereas the long‐term gel strength appeared dependend on the long branch chains in amylopectin.     

Physicochemical properties,resistant starch content and enzymatic digestibility of unripe banana,edible canna,taro flours and their rice noodle products

Unripe banana, edible canna and taro flours, which have been reported to contain significant amounts of fibre, were investigated for their physicochemical properties, resistant starch (RS) content and in vitro starch digestibility, and compared with commercial high‐fibre‐modified starches from corn and tapioca. Differential scanning calorimetry showed a single endothermic peak located around 70–83 °C for the samples except the modified starches, which exhibited no transition enthalpy. The samples showed different pasting behaviours in the Rapid Visco‐Analyser (RVA) ranging from full to restricted swelling. The RS content varied from 1–26 g per 100 g dry sample, and the estimated glycaemic indices (GIs) of the samples were from 67% to 99%. Generally, samples with high RS were low in GI values. The starches produced acceptable rice noodles but with reduced rate of starch digestion and GI. The effects of the unripe banana, edible canna and taro flours on starch digestibility were either comparable or better than the commercial modified starches. These flours can substitute commercial modified starches to lower GIs of noodles and identical foods.     

Effects of cross‐linking on the rheological and thermal properties of sweet potato starch

Sweet potato starches were modified with three different concentrations of phosphorus oxychloride (POCl₃) (0.01, 0.02, and 0.03%, based on dry weight of starch) as a cross‐linking agent. The effects of crosslinking on rheological and thermal properties of sweet potato starch (SPS) pastes were evaluated. Cross‐linking considerably reduced the swelling power, consistency index (K), apparent viscosity (η_a), and yield stress (σ_oc) values of SPS, which significantly decreased with increase in POCl₃ concentration. The gelatinization temperature (T_p) and enthalpy (ΔH) values of the cross‐linked SPS, which were determined using differential scanning calorimetry, were higher than those of native SPS. Storage modulus (G′), loss modulus (G″), and complex viscosity (η*) of the cross‐linked SPS pastes determined using small deformation oscillatory rheometry, were higher than native starch, and they also decreased with increase in POCl₃ concentration from 0.01 to 0.03%. The tan δ (ratio of G″/G′) values (0.15–0.19) of the cross‐linked SPS samples were much lower than that (0.37) of the native SPS, indicating that the elastic properties of the SPS pastes were strongly influenced by modifications from cross‐linking. Finally, Cox–Merz plots showed that η* was much higher than η_a for the cross‐linked SPS pastes.     

Preparation of highly substituted carboxymethyl starch using a twin‐screw extruder

Carboxymethyl starch was prepared by reacting corn starch with sodium mono chloro acetate (SMCA) in a Brabender TSE‐20 co‐rotating twin screw extruder. The effects of the SMCA/starch ratio (theoretical degrees of substitutions 2.73, 3.62, and 4.53), aqueous ethanol/(starch + SMCA) ratio (0.13 and 0.25) and the screw configuration (0, 1, and 2 kneading blocks) on the degree of substitution (DS) and reaction efficiency were studied. A 3 × 2 factorial design with 3 levels of the starch/SMCA ratio and 2 levels of the aqueous ethanol/(starch + SMCA) ratio were used. This 3 × 2 factorial design was blocked, with the screw configuration as the blocking variable. The effects of the SMCA/starch ratio and the screw configuration were found to be significant. The carboxymethylated starches were characterized using FTIR, SEM, and XRD. The microstructure of the carboxymethylated starches, studied using SEM, revealed that the integrity of the starch granules was partially preserved at low aqueous ethanol levels when no kneading block was used. However, for all other reaction conditions either granule agglomeration or fusion was observed. XRD analysis indicated substantial loss of crystallinity in the carboxymethylated starches, irrespective of the damage to the granule structure. The highest DS and the highest reaction efficiency obtained were 1.54 and 0.42, respectively.