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 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.     

In vitro Digestibility of Hydroxypropylated and Cross-linked Waxy and Non-waxy Rice Starches

In vitro digestibility of hydroxypropylated and cross-linked waxy and non-waxy rice starches was investigated to find the proper resistant starch (RS) assaying method for chemically modified starches. RS and total dietary fiber (TDF) content of hydroxypropylated and cross-linked waxy and non-waxy rice starches were measured using the approved AOAC RS assay procedure (AOAC method 2002.02) and the AOAC TDF assay procedure (AOAC method 985.29). Hydroxypropylation did not alter the RS content of waxy and non-waxy rice starches (less than 1% of RS). Cross-linking also did not change the RS content of waxy and non-waxy rice starches (less than 1% of RS). It is interesting to note that non-RS content decreased with increasing hydroxypropylation (97-80%) and cross-linking (99-95%) in both waxy and non-waxy rice starches. This indicates that some fraction of RS in hydroxypropylated and cross-linked waxy and non-waxy rice starches cannot be measured using approved AOAC RS and TDF assay procedures. Therefore, the RS and TDF assay procedures performed in this study are not appropriate to determine the RS content of chemically modified starch. Further investigation is needed to develop a method to determine the RS content of chemically modified starch.     

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.     

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.     

Combined effect of autoclaving‐cooling and cross‐linking treatments of normal corn starch on the resistant starch formation and physicochemical properties

Normal corn starch (NCS) was treated by both autoclaving‐cooling and cross‐linking to produce resistant starch (RS). The RS yield, crystalline structure, as well as other physicochemical properties of the modified starch were investigated. The yield of RS was 12.2% by four autoclaving‐cooling cycles, and it could be further increased up to 31.0% by the subsequent cross‐linking using sodium trimetaphosphate/sodium tripolyphosphate. The scanning electron microscopy images clearly illustrated that the granular structure of native starch was disrupted and a continuous network with irregular shape was formed after autoclaving‐cooling cycles. The subsequent chemical cross‐linking appeared to make the network structure more compact and dense. X‐ray diffraction patterns showed that B‐ and V‐types coexisted in all the modified corn starches, and all these modified starches exhibited very low viscosity which remained almost constant regardless of temperature changes.     

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.     

Structural and some nutritional characteristics of Velvet bean (Mucuna pruriens) and Lima bean (Phaseolus lunatus) starches

Velvet bean (Mucuna pruriens) and lima bean (Phaseolus lunatus) starches were isolated from seeds and their structural characteristics evaluated using XRD, size‐exclusion chromatography and light scattering analyzes. Total starch, available starch, RS and in vitro digestibility were also determined. Structural and nutritional characteristics of Velvet bean and Lima bean starches were compared to those of commercial corn starch. The legumes starches presented a C‐type XRD pattern and crystallite sizes of 43.1 Å for velvet bean and 48.3 Å for lima bean. Lima bean starch average molar mass (4.9 × 10⁶ g/mol) was slightly higher than the velvet bean starch (3.04 × 10⁶ g/mol). Size‐exclusion chromatography indicated structural similarity between the lima bean and corn starches which differed from that of the velvet bean starch. Hydrodynamic radius (R_H) for the velvet bean and lima bean starches was 45.5 and 55 nm, respectively, and their radius of gyration (R_G) was 67.7 and 82.5 nm, respectively. Total starch content in all three starches was greater than 98%. Their complex crystalline structure provided the legume starches lower in vitro digestibility values than the corn starch. RS content in both the velvet bean starch (7.72%) and lima bean starch (5.66%) was higher than in the corn starch, essentially qualifying these polysaccharides as natural dietary fiber sources, with the associated physiologic advantages.     

Structural characteristics and in vitro digestibility of Mango kernel starches (Mangifera indica L.)

Structural characteristics and digestibility of starches isolated from the kernels of two mango cultivars (Chausa and Kuppi) were studied and compared with those of a commercial normal corn starch. Mango kernel starches showed an A-type X-ray diffraction pattern, with relative crystallinities of 35.4% and 38.3%, respectively for Kuppi and Chausa cultivars. The structural characterisation obtained, using high performance size exclusion column chromatography connected to multi-angle laser light scattering and refractive index detectors (HPSEC-MALLS-RI), revealed that the mango kernel starches had lower molecular weight (M_w) and radius of gyration (R_g) of amylopectin and amylose compared to those of corn starch. The M_w of amylopectin for Chausa and Kuppi starches were 179 × 10⁶ and 140 × 10⁶ g/mol, respectively. The amounts of readily digestible starch (RDS) and slowly digestible starch (SDS) were lower for mango kernel starch than those of corn starch. Resistant starch (RS) contents in the mango kernel starches (75.6% and 80.0%, respectively) were substantially higher than those of corn starch (27.3%). The glycemic index (GI) values for mango kernel starches were 48.8 and 50.9 (for Chausa and Kuppi, respectively), whereas that of corn starch was 74.8, indicating that the mango kernel starch granules were highly resistant to digestion with significant contents of RS.     

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.

     

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 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,structural, and digestibility properties of enzymatic modified plantain and mango starches

The effect of two enzymatic treatments (increasing the branch density of starch and shortening of AP and amylose chains) on the fraction of slowly digestible starch (SDS) and resistant starch (RS) of plantain (Musa paradisiaca L.) and mango (Mangifera indica L.) starches was investigated. The enzymatic modifications were carried out using β‐amylase (β‐AMY) and β‐amylase‐transglucosidase (β‐AMY‐TGs), in gelatinized starches. Plantain starch showed an increase from 10.9 to 18.5% of SDS, when it was modified by β‐AMY‐TGs, while the treatment with β‐AMY alone showed reduction from 10.9 to 7.1% in SDS. RS content increased with both treatments. On the other hand, mango starch showed an increase in SDS from 6.3 to 22.3% using β‐AMY treatment and from 6.3 to 11.7% using β‐AMY‐TGs treatment. The latter treatment also increased RS content. The enzyme modified starches showed a reduction in the values of molar mass and gyration radius compared with the native starch. The content of short chains of AP, particularly in the DP range 5–12, increased, the percentage of crystallinity decreased in treated starches, and ¹H NMR spectra showed a significant increase of α‐(1 → 6) linkages in the starches modified with β‐AMY‐TGs. These characteristics were related to an increase in the slow and resistant digestion properties of plantain and mango starches.     

Quantification of Resistant Starch in Several Starch Sources Treated Thermally

The purpose of the research was to determine the effect of heat-moisture treatment at different phases and temperatures on resistance starch (RS) level on native starches samples of several botanical sources and to evaluate the thermal stability of different granules. Samples of potato, cassava, wheat, and corn starches were moisturized up to 30% wet basis and then treated in a convection oven at 80, 100, and 120°C during 40 and 60 minutes. RS was determined gravimetrically by a modification of Method 991.43 of the AOAC for the determination of total dietary fibre. All samples were submitted to different thermal analysis in a range from 40 to 180°C at 10°C/min. Overall, in the treated samples an increase of RS was observed, being the corn starch sample treated at 120°C and 60 minutes – the one that presented the highest content of RS (4.2%). Other treated samples showed a decrease in the gelatinization enthalpies with the presence of granular fusion, indicating internal re-arrangement, an increase in the gelatinization temperature and the thermo stability below 95°C.     

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).     

Thermal behavior of resistant starches RS 2, RS 3, and RS 4

ABSTRACT:  The thermal behaviors of 3 resistant starch types—RS 2, RS 3, and RS 4—were investigated. Samples were heated in excess water to specific temperatures, from 35 to 85 °C at 5 °C intervals, and freeze-dried. The treated samples were analyzed using SEM, DSC, XRD, and HPSEC to determine the structural changes at granular and molecular levels. Light microscopy was used to determine real-time thermal behavior of the starches. Although the resistant starches did not show significant morphological changes, as revealed by microscopy, they underwent internal structural changes at low temperatures before complete phase transitions occurred. The structural changes were less in RS 2 compared to the other 2 starches studied. The nongranular material of RS 3's crystallinity decreased gradually from 35 to 85 °C and showed microscopically visible changes at >80 °C. Cross-linking might have prevented RS 4 from becoming completely amorphous within the temperature range (35 to 85 °C) tested. The study indicated that the extent of structural changes depended on the treatment temperature and RS type.     

Effect of raw and heat–moisture‐treated high‐amylose corn starches on the process of digestion in the rat digestive tract

High‐amylose corn starch (HAS) is widely known as a resistant starch foodstuff. We developed heat–moisture‐treated high‐amylose corn starch (HMT‐HAS) that was more resistant to enzymatic hydrolysis. Resistant starch contents of HAS and HMT‐HAS using the enzymatic–gravimetric method were found to be 30% and 65% respectively. Rats were given 10% ordinary corn starch (CS), HAS or HMT‐HAS by meal feeding for 10 days. The caecum contents increased and the caecal pH was lower after their diets were supplemented with HAS and HMT‐HAS. Starch contents increased in the upper and the lower small intestine with HAS and HMT‐HAS. Caecal starch with HAS and HMT‐HAS was more than that with CS. Particularly, caecal starch with HMT‐HAS was seven times more than that with HAS. There were no differences in starch content in the large bowel between CS and HAS, but the content increased with HMT‐HAS. These results suggested that HAS and HMT‐HAS were resistant to digestion and absorption in the small intestine, and any indigestible starches reached the caecum. In the caecum, HAS was hydrolysed almost completely by intestinal bacteria; however, some HMT‐HAS escaped bacterial hydrolysis. This escaped HMT‐HAS reached the large bowel and was excreted in the faeces. © 1999 Society of Chemical Industry     

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.     

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.     

Comparison between Size Exclusion Chromatography and Micro‐Batch Analyses of Corn Starches in DMSO using Light Scattering Detector

The molecular structure of corn starches different in amylose content (waxy, normal, and high‐amylose) was analyzed in 90% dimethyl sulfoxide (DMSO) solution by refractive index (RI) and multi‐angle laser light scattering (MALLS) detectors. The starch sample solutions were measured either by medium‐pressure size exclusion chromatography (MPSEC) or by the micro‐batch mode. For waxy corn starch, the average molar mass (M_w) and radius of gyration (R_g) values were similar in both methods. However, for normal and high‐amylose corn starches, M_w measured by the micro‐batch mode was 2–4 times greater than that by the chromatographic method, although R_g values obtained from both methods were not very different. The M_w difference was the greater the higher the amylose content of starch.