Mechanism and enzymatic contribution to in vitro test method of digestion for maize starches differing in amylose content

To determine the rapidly digestible starch (RDS), slowly digestible starch (SDS), and resistant starch (RS) contents in a starch sample, the addition of amyloglucosidase is often used to convert hydrolyzates from α-amylase digestion to glucose. The objectives of this study were to investigate the exact role of amyloglucosidase in determining the digestibility of starch and to understand the mechanism of enzymatic actions on starch granules. Four maize starches differing in amylose content were examined: waxy maize (0.5% amylose), normal maize (≈27% amylose), and two high-amylose starches (≈57 and ≈71% amylose). Notably, without amyloglucosidase addition, the RS content increased from 4.3 to 74.3% for waxy maize starch, 29.7 to 76.5% for normal maize starch, 65.8 to 88.0% for starch with 57% amylose, and 68.2 to 90.4% for the starch with 71% amylose. In the method without α-amylase addition, less RS was produced than without added amyloglucosidase, except in maize at 71% amylose content. Scanning electron microscopy (SEM) revealed the digestive patterns of pinholes with α-amylase and burrowing with amyloglucosidase as well as the degree of digestion between samples. To understand the roles of amyloglucosidase and α-amylase in the in vitro test, multiple analytical techniques including gel permeation chromatography, SEM, synchrotron wide-angle X-ray diffraction, and small-angle X-ray scattering were used to determine the molecular and crystalline structure before and after digestion. Amyloglucosidase has a significant impact on the SDS and RS contents of granular maize starches.     

Understanding the Physicochemical and Functional Properties of Wheat Starch in Various Foods

This report highlights the structure and myriad properties of wheat starch in various food systems. Granule shape, size, and color, plus the proportion of A‐ and B‐granules, amylose content, and molecular structure largely determine its functionality in food. The role of wheat starch is portrayed in three categories of flour‐based foods that differ in water content. Wheat starch influences the appearance, cooking characteristics, eating quality, and texture of pasta and noodles, and its role is more than a filler in yeast‐leavened bread products. Recent developments in the properties and applications of commercially important wheat pyrodextrins and RS4‐type resistant wheat starches are reported, along with their use to produce fiber‐fortified foods. Gluten‐free foods are also discussed.     

White Pan Bread and Sugar‐Snap Cookies Containing Wheat Starch Phosphate,A Cross‐Linked Resistant Starch

Pup‐loaf bread was made with 10, 30, and 50% substitution of flour with wheat starch phosphate, a cross‐linked resistant starch (XL‐RS4), while maintaining flour protein level at 11.0% (14% mb) by adding vital wheat gluten. Bread with 30% replacement of flour with laboratory‐prepared XL‐RS4 gave a specific volume of 5.9 cm³/g compared with 6.3 g/cm³ for negative control bread (no added wheat starch), and its crumb was 53% more firm than the control bread after 1 day at 25°C, but 13% more firm after 7 days. Total dietary fiber (TDF) in one‐day‐old bread made with commercial XL‐RS4 at 30% flour substitution increased 3–4% (db) in the control to 19.2% (db) in the test bread, while the sum of slowly digestible starch (SDS) plus resistant starch (RS), determined by a modified Englyst method, increased from 24.3 to 41.8% (db). The reference amount (50 g, as‐is) of that test bread would provide 5.5 g of dietary fiber with 10% fewer calories than control bread. Sugar‐snap cookies were made at 30 and 50% flour replacement with laboratory‐prepared XL‐RS4, potato starch, high‐amylose (70%) corn starch, and commercial heat‐moisture‐treated high‐amylose (70%) corn starch. The shape of cookies was affected by the added starches except for XL‐RS4. The reference amount (30 g, as‐is) of cookies made with commercial XL‐RS4 at 30% flour replacement contained 4.3 g (db) TDF and 3.4 g (db) RS, whereas the negative control contained 0.4 g TDF and 0.6 g RS. The retention of TDF in the baked foods containing added XL‐RS4 was calculated to be >80% for bread and 100% for cookies, while the retention of RS was 35–54% for bread and 106–113% for cookies.     

Effects of β-amylolysis on the resistant starch formation of debranched corn starches

Retrograded amylose is resistant to digestion by amylolytic enzymes, which is known as resistant starch type III (RS3). In this study we investigated the effect of β-amylase hydrolysis on the formation and physicochemical properties of RS3 from debranched corn starches. Three types of corn starch (Hylon VII, Hylon V, and common corn) were first gelatinized and then hydrolyzed using β-amylase to varying degrees. The resultant hydrolyzed starch was debranched with isoamylase and then exposed to temperature cycling to promote RS formation. A broad endotherm from approximately 45 to 120 °C and a small endotherm above 150 °C were noted for all retrograded starches. All three corn starches had increased RS contents after moderate β-amylolysis, with Hylon V having the highest RS content at 70.7% after 4 h of β-amylolysis. The results suggest that RS3 formation is affected by the starch composition as well as the starch structure and can be increased by moderate β-amylolysis.     

Hot‐Water Solubilities and Water Sorptions of Resistant Starches at 25°C

Resistant starches (RS) were prepared from wheat starch and lintnerized wheat starch by autoclaving and cooling and by cross‐linking. Heat‐moisture treatment also was used on one sample to increase RS. The experimental resistant starches made from wheat starch contained 10–73% RS measured as Prosky dietary fiber, whereas two commercial resistant starches, Novelose 240 and 330, produced from high‐amylose maize starch, contained 58 and 40%, respectively. At 25°C in excess water, the experimental RS starches, except for the cross‐linked wheat starch, gained 3–6 times more water than the commercial RS starches, and at 95°C gained 2–4 times more. Cross‐linked RS4 wheat starch and Novelose 240 showed 95°C swelling powers and solubilities of 2 g/g and 1%, and 3 g/g and 2%, respectively. All starches showed similar water vapor sorption and desorption isotherms at 25°C and water activities (a_w) < 0.8. At a_w 0.84–0.97, the resistant starches made from wheat starch, except the cross‐linked wheat starch, showed ≈10% higher water sorption than the commercial resistant starches.     

Cross‐Linked Resistant Starch: Preparation and Properties

Resistant starches (RS) were prepared by phosphorylation of wheat, waxy wheat, corn, waxy corn, high‐amylose corn, oat, rice, tapioca, mung bean, banana, and potato starches in aqueous slurry (≈33% starch solids, w/w) with 1–19% (starch basis) of a 99:1 (w/w) mixture of sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) at pH 10.5–12.3 and 25–70°C for 0.5–24 hr with sodium sulfate or sodium chloride at 0–20% (starch basis). The RS₄ products contain ≤100% dietary fiber when assayed with the total dietary fiber method of the Association of Official Analytical Chemists (AOAC). In vitro digestion of four RS₄ wheat starches showed they contained 13–22% slowly digestible starch (SDS) and 36–66% RS. However after gelatinization, RS levels fell by 7–25% of ungelatinized levels, while SDS levels remained nearly the same. The cross‐linked RS₄ starches were distinguished from native starches by elevated phosphorus levels, low swelling powers (≈3g/g) at 95°C, insolubilities (<1%) in 1M potassium hydroxide or 95% dimethyl sulfoxide, and increased temperatures and decreased enthalpies of gelatinization measured by differential scanning calorimetry.     

Composition,Molecular Structure,Properties, and In Vitro Digestibility of Starches from Newly Released Canadian Pulse Cultivars

Pulse starches were isolated from different cultivars of pea, lentil, and chickpea grown in Canada under identical environmental conditions. The in vitro digestibility and physicochemical properties were investigated and the correlations between the physicochemical properties and starch digestibility were determined. Pulse starch granules were irregularly shaped, ranging from oval to round. The amylose content was 34.9–39.0%. The amount of short A chains (DP 6‐12) of chickpea starch was much higher than the other pulse starches, but the proportions of B1 and B2 chains (DP 13‐24 and DP 25‐36, respectively) were lower. The X‐ray pattern of all starches was of the C type. The relative crystallinity of lentil (26.2–28.3%) was higher than that of pea (24.4–25.5%) and chickpea starches (23.0–24.8%). The swelling factor (SF) in the temperature range 60–90°C followed the order of lentil ≈ chickpea > pea. The extent of amylose leaching (AML) at 60°C followed the order of pea ≈ chickpea > lentil. However, in the temperature range 70–90°C, AML followed the order of lentil > pea > chickpea. The gelatinization temperatures followed the order of lentil > pea > chickpea. The peak viscosity, setback, and final viscosity of pea starch were lower than those of the other starches. Lentil starch exhibited lower rapidly digestible starch (RDS) content, hydrolysis rate, and expected glycemic index (eGI). The resistant starch (RS) content of both lentil cultivars was nearly similar. However, pea and chickpea cultivars exhibited wide variations in their RS content. Digestibility of the pulse starches were significantly correlated (P < 0.05) with swelling factor (60°C), amylose leaching (60°C), gelatinization temperature, gelatinization enthalpy, relative crystallinity, and chain length distribution of amylopectin (A, B1, and B2 chains).     

Physicochemical and digestibility properties of double-modified banana ( Musa paradisiaca L.) starches

Banana starch was chemically modified using single (esterification or cross-linking) and dual modification (esterification-cross-linking and cross-linking-esterification), with the objective to increase the slowly digestible starch (SDS) and resistant starch (RS) concentrations. Physicochemical properties and in vitro digestibility were analyzed. The degree of substitution of the esterified samples ranged from 0.006 to 0.020. The X-ray diffraction pattern of the modified samples did not show change; however, an increase in crystallinity level was determined (from 23.79 to 32.76%). The ungelatinized samples had low rapidly digestible starch (RDS) (4.23-9.19%), whereas the modified starches showed an increase in SDS (from 10.79 to 16.79%) and had high RS content (74.07-85.07%). In the cooked samples, the esterified starch increased the SDS content (21.32%), followed by cross-linked starch (15.13%). Dual modified starch (cross-linked-esterified) had the lowest SDS content, but the highest RS amount. The esterified and cross-linked-esterified samples had higher peak viscosity than cross-linked and esterified-cross-linked. This characteristic is due to the fact that in dual modification, the groups introduced in the first modification are replaced by the functional group of the second modification. Temperature and enthalpy of gelatinization decreased in modified starches (from 75.37 to 74.02 °C and from 10.42 to 8.68 J/g, respectively), compared with their unmodified starch (76.15 °C and 11.05 J/g). Cross-linked-esterified starch showed the lowest enthalpy of gelatinization (8.68 J/g). Retrogradation temperature decreased in modified starches compared with unmodified (59.04-57.47 °C), but no significant differences were found among the modified samples.     

抗性淀粉及预防糖尿病和肥胖症功能稻米研究进展

抗性淀粉(RESISTANT STARCH,RS)是指不被健康人体小肠所吸收的淀粉及其降解产物的总称。本文在简述RS的定义、分类、检测及其生理功能与影响RS形成因素的基础上,介绍了富含RS功能食品的研发途径、富含RS稻米制品及利用诱变技术选育富含RS水稻品种的最新进展。     

电子束辐照预处理对辛烯基琥珀酸改性芋艿淀粉性质的影响研究

为探究不同剂量电子束辐照预处理对辛烯基琥珀酸改性芋艿淀粉颗粒结构和功能特征的影响,本研究以奉化芋艿淀粉为材料,对其进行电子束辐照预处理,分析处理前后改性淀粉的颗粒结构、热力学性质、溶胀特性、消化性和乳化性。结果表明,电子束辐照预处理显著改变了辛烯基琥珀酸改性芋艿淀粉酯的理化与功能特性。随着辐照剂量从2 kGy逐步增加至50 kGy,辛烯基琥珀酸改性淀粉(OSTS)颗粒屑状点逐渐增多、表面形成的皱痕和突起加深,并出现颗粒破裂;快消化淀粉(RDS)含量和水溶性指数不断增加,结晶度、缓慢消化淀粉(SDS)、糊化峰值温度(T_p)不断下降;直链淀粉含量和溶胀力呈现先增加后减少的趋势,糊化焓、抗性淀粉、乳化稳定性和FTIR光谱中1 047 cm^-1/1 022 cm^-1 峰强度呈现先降低后升高的趋势。本研究为采用电子束辐照预处理技术改善辛烯基琥珀酸改性淀粉的功能特性提供了一定的理论依据。     

Differences in Carbohydrate Composition and Digestion In Vitro of Selected Barley Cultivars as Influenced by Pearling and Cooking

Among common cereals, barley is a low glycemic index food. In an attempt to better understand this character, the nutritional properties of glycemic carbohydrates and dietary fiber concentrations of nine cultivars were evaluated. The cultivars were selected based on botanical variations and commercial value to investigate the impact of pearling and cooking on nutritional properties. Each cultivar was pearled into four fractions ranging from hull removal only to hull, bran, germ, and crease removal. The study showed that botanical class and degree of pearling significantly affect the carbohydrate composition and digestion indices of barley. Waxy starch cultivars had less total starch and more rapidly digestible starch (RDS), rapidly available glucose (RAG), and β‐glucan than the other nonwaxy cultivars. Regardless of the barley type, the less pearled kernels had significantly lower total starch and higher total low molecular weight sugars, insoluble, and total fiber. However, β‐glucan content was fairly comparable in the whole grain and pearled fractions. Cooking had a significant effect on nutritional properties of Celebrity and AC Klinck cultivars. The only consistent significant difference between raw and cooked barley was resistant starch (RS), which increased after cooking regardless of cultivar or fraction. The study showed that barley cultivar and carbohydrate composition significantly affected starch digestion with some cultivar fractions holding a promise for the development of low glycemic index foods.     

Characterization of Resistant Starch Samples Prepared from Two High‐Amylose Maize Starches Through Debranching and Heat Treatments

The aim of the present study was to investigate effects of debranching, autoclaving‐storing cycles, and drying processes (oven‐drying or freeze‐drying) on RS contents, thermal, pasting, and functional properties of high‐amylose maize starches (Hylon V and Hylon VII). The resistant starch (RS) contents increased (≤57.8%) with increasing autoclaving‐storing cycles. RS contents of oven‐dried samples were higher than those of freeze‐dried samples due to ongoing retrogradation of starch during oven drying at 50°C. Debranching caused a significant decrease in peak transition temperature and enthalpy values as compared with native starches. Solubility and water binding values of RS preparations were higher than those of native starches. Addition of native and autoclaved samples had improving effect on emulsion properties of albumin. Cold viscosity values of oven‐dried samples were lower as compared with freeze‐dried samples; this might be due to higher number of H‐bonds in the oven‐dried samples expected to be formed during drying. Debranching and autoclaving‐storing cycles caused decreases in peak, breakdown, and final viscosity values. The results of present study showed that debranching and heat treatments increased the RS contents and improved the functional properties of high‐amylose maize starches.     

In Vitro Digestion of RS4‐Type Resistant Wheat and Potato Starches,and Fermentation of Indigestible Fractions

RS4‐type resistant wheat starch (RWS) and resistant potato starch (RPS) were subjected successively to in vitro digestion with pepsin and pancreatin‐bile, and the indigestible residues (82.1% db and 74.1% db, respectively) were recovered and subsequently fermented by in vitro techniques using fresh human fecal microbiota as inoculum. Scanning electron microscopy of the indigestible residues showed surface erosion on the residual granules. Total gas production during the in vitro fermentation increased almost linearly over time with the two resistant starches exhibiting similar gas production rates, as well as a similar rate of production of total short‐chain fatty acids (SCFA). The indigestible fractions from both starches produced acetate as the major SCFA and relatively higher levels of butyrate than propionate, but wheat starch tended to produce more butyrate over time than potato starch. Fractional molar ratios of acetate, propionate, and butyrate from the RWS and RPS were 0.586:0.186:0.228 and 0.577:0.200:0.223, respectively. The calculated caloric contributions of the RWS and RPS are ≈33% lower than for unmodified starch and are comparable to those reported in the literature for RS2 and RS3 high‐amylose maize starches.     

Structure and functional properties of sorghum starches differing in amylose content

Starches were isolated from grains of waxy, heterowaxy, and normal sorghum. To study the relationship between starch structure and functionality and guide applications of these starches, amylose content, amylopectin chain-length distributions, gelatinization and retrogradation, pasting properties, dynamic rheological properties, and in vitro enzyme digestion of raw starches were analyzed. Heterowaxy sorghum starch had intermediate amylose content, pasting properties, and dynamic rheological properties. Stress relaxation was a useful indicator of cooked starch cohesiveness. Cooked heterowaxy sorghum starch (10% solids) had a viscoelastic-solid type of character, whereas cooked waxy sorghum starch behaved like a viscoelastic liquid. Amylopectin of normal sorghum starch had a slightly higher proportion of chains with degree of polymerization (DP) of 6-15 (45.5%) compared with amylopectin of heterowaxy starch (44.1%), which had a gelatinization peak temperature 2 degrees C higher than normal sorghum starch. Heterowaxy sorghum starch contained significantly lower rapidly digestible starch (RDS) and higher resistant starch (RS) than waxy sorghum starch.     

Resistant Starch Content Is Related to Granule Size in Barley

Physical properties of resistant starch (RS) were examined in a range of barley genotypes to determine the contribution of starch and seed physical characteristics to the RS component. Thirty‐three barley genotypes were studied, which varied significantly in their RS, amylose, and starch contents and grain yield. From 33 genotypes, 13 exhibiting high RS were selected for detailed physicochemical analysis of starch. In high‐RS varieties, granule size and number were unimodal, compared with normal starches from a reference genotype, which showed a bimodal distribution. Principal component analysis (PCA) showed that a higher content of granules <15 µm was positively correlated with RS and amylose content, whereas the proportion of granules 15–45 µm was negatively correlated with the RS and amylose contents. Physical fractionation of starches by centrifugation into different population sizes demonstrated that size alone is not an accurate indicator of the population of A‐type and B‐type granules within a given genotype. PCA also showed that large 15–45 µm granules were positively correlated with seed thickness and that thousand grain weight was positively correlated with seed width. High‐RS and high‐amylose genotypes showed variation in overall yield and starch content, with some genotypes showing yield comparable to the reference genotype. Analysis of amylopectin chain length distribution showed that high amylose or RS content was not associated with a higher proportion of amylopectin long chains when compared with either waxy or reference (normal) barley genotypes. This study highlights useful markers for screening barley genotypes with favorable starch characteristics.     

Effect of Partial Acid Hydrolysis and Heat‐Moisture Treatment on Formation of Resistant Tuber Starch

Structural characteristics of resistant starch (RS) were investigated. Tuber starches, hydrolyzed with 1N HCl at 35°C for 8 hr followed by autoclaving‐cooling treatment, were heated at 100°C for 16 hr after adjusting the moisture content to 20 or 30%. RS content of the tuber starches ranged from 5.4 to 22.7% depending on the source and type of treatment. Gelatinization parameters of RS isolated from partially acid‐hydrolyzed starch with autoclaving‐cooling followed by heat‐moisture treatment (HMT) showed higher enthalpy (ΔH) values and lower peak temperature (T_p) compared with non‐acid‐hydrolyzed RS. R values, the difference between completion and initial temperatures, and ΔH of RS increased by HMT. The X‐ray diffraction patterns of potato and sweet potato RS isolated from partially acid‐hydrolyzed starch with autoclaving‐cooling showed distinct sharp peaks at 15, 25, 27, and 28°, which decreased by HMT.     

In Vitro Starch Digestibility and Expected Glycemic Index of Kodo Millet (Paspalum scrobiculatum) as Affected by Starch–Protein–Lipid Interactions

The effect of starch–protein–lipid interaction on the in vitro starch digestibility and expected glycemic index (eGI) of kodo millet flour (MF) was investigated. Debranned MF and the flour with lipid removed, protein removed, or both lipid and protein removed (MF‐L‐P) were subjected to digestion assays. The in vitro starch digestibility and eGI of the millet samples and millet starch were compared with rice or wheat flour. Rapidly digestible starch, slowly digestible starch, and resistant starch (RS) of the samples were also calculated. Protease treatment and defatting resulted in significant reduction (P < 0.05) in protein and lipid contents of samples. Significant increases in the in vitro starch digestibility and eGI of samples were observed after removal of protein, lipid, or both. The effect of lipid removal on in vitro starch digestibility of kodo millet was found to be more significant, compared with when proteins were removed. The eGI increased from 49.4 for cooked MF to 62.5 for MF‐L‐P. The eGI of cooked kodo millet starch was significantly lower than that of cooked rice flour. The RS (1.61%) of cooked rice was the least among the samples. The in vitro starch digestibility and eGI of rice were significantly higher than those of MF. Processes applied to kodo millet, such as decortication, that result in the removal of proteins, lipids, or both (especially lipids) would result in an increase in its in vitro starch digestibility and eGI. We therefore advocate for the development of acceptable products from whole millets to maintain its hypoglycemic property.     

Physicochemical and Digestion Characteristics of Starch and Fiber‐Rich Subfractions from Four Pulse Bagasses

The aim of this study was to characterize the physicochemical, functional, and digestion properties of bagasses derived from broad beans, chickpeas, lentils, and white beans, and to isolate the starch and a fiber‐rich fraction that can be used as a food ingredient. The bagasses showed different chemical compositions that were related to their botanical origin. The further processing that involved mechanical separation of starch yielded up to 69.65% with ≥80.12% recovery and high purity (≥94.42%), and a fiber‐rich fraction (total dietary fiber content ≥72.75%) in which the majority was insoluble fiber. The starch digestion fractions of the isolated lentil starch showed the highest amount of slowly digestible starch (30.76%), whereas the white bean contained the highest resistant starch content (15.65%). All starches showed predicted glycemic indexes ≤ 66.90, which classify them as medium glycemic foods. In vitro protein digestion was higher for the bagasse fraction (up to 89.78%), followed by the fiber‐rich fraction (84.36%). This research demonstrates that it is possible to revalorize the use of pulses bagasse, which could contribute to enhance the technological and economic output of the protein isolation process, rendering two potentially functional fractions.     

Production of Boiling‐Stable Granular Resistant Starch by Partial Acid Hydrolysis and Hydrothermal Treatments of High‐Amylose Maize Starch

The purpose of the present work was to examine whether partial acid hydrolysis (PAH) of a high‐amylose maize starch (ae‐VII) would enhance the effects of hydrothermal treatments to produce granular resistant starch (RS) that is stable to further heat treatment at atmospheric pressure. PAH ae‐VII starches were prepared by heating 35% (w/v) suspensions with 1% (w/w) HCl at 25°C for 6, 30, and 78 hr. Native and PAH starches were then treated by annealing (ANN) or heat‐moisture treatment (HMT). ANN was done at 70% moisture at 50, 60, or 70°C for 24 hr, and HMT was done at 30% moisture at 100, 120, or 140°C for 80 min. RS that survives boiling during analysis was determined by a modification of the AOAC method for determining total dietary fiber. RS was also determined by the Englyst method. Little change in the gelatinization enthalpy was found for ae‐VII starch after PAH, ANN, or HMT as individual treatments. After PAH, either ANN or HMT led to decreased gelatinization enthalpy. HMT and ANN alone increased boiling‐stable RS but decreased total RS. After PAH of ae‐VII, either ANN or HMT tended to increase the yield of boiling‐stable granular RS, with the greatest yield (≤63.2%) observed for HMT.     

Influence of Botanical Source and Processing on Formation of Resistant Starch Type III

Influence of botanical source and gelatinization procedure (autoclaving or boiling) on resistant starch (RS) formation was investigated in starches from wheat, corn, rice, and potato. RS yields did not vary within the same sample but differed among samples with different starch botanical sources. Differences also existed in RS contents in native and retrograded starches. Slight or minor variations in RS values were found after both gelatinization procedures, although no clear pattern was found in the behavior of samples based on gelatinization procedure. The degree of polymerization (DP) of retrograded samples was assigned using high-performance anion exchange chromatography with pulsed amperometric detector (average DP 50–60), with no differences between autoclaved and boiled samples.