A Study of Annealing and Freeze‐Thaw Stability of Acid‐Modified Tapioca Starches by Differential Scanning Calorimetry (DSC)

Tapioca starch was partially hydrolyzed by 6% (w/v) hydrochloric acid at room temperature for various lengths of time. Annealing and freeze‐thaw stability of the acid‐modified starches were studied using Differential Scanning Calorimetry (DSC). In the annealing study, as the hydrolysis time increased, the effect of annealing on narrowing and shifting the endothermic peak to a higher temperature was decreased. The endothermic transition of annealed 48‐h acid‐modified tapioca starch showed a narrow peak and a broad shoulder, corresponding to the melting of the amylopectin double helices (crystalline regions) and the retrograded partially hydrolyzed amylose, respectively. This effect of annealing on the sharpening of the endotherm was less pronounced on acid‐modified tapioca starches annealed for 192 h and 768 h, respectively. These results indicated that annealing leads to more homogeneous crystallites and this effect is enhanced when the material contains more amorphous and homogeneous domains. In the case of the freeze‐thaw stability study, the melting endotherm of recrystallized amylopectin became larger with increasing hydrolysis time. The first detectable endotherm of native tapioca retrograded gel was observed after five cycles, while all acid‐modified retrograded gels showed the melting endotherm after only one cycle. Increasing hydrolysis time may increase the proportion of short chain amylose and amylopectin molecules, which are able to form double helices, resulting in an increase in the enthalpy and a higher retrogradation rate of the gel.     

Effect of repeated freezing-thawing on structural,physicochemical and digestible properties of normal and waxy starch gels

The normal and waxy corn starch gels were subjected to repeated freeze–thaw treatment at 0, 1, 2, 3, 4,5 and 6 cycles with an interval of 24 h, and the effects on structural, physicochemical and digestible properties were investigated. The normal starch gels formed a honeycomb structure while waxy starch gels exhibited a lamellar structure, and the number of holes and lamellas increased with increasing cycles. The X-ray analysis showed that the A-type pattern of starches was converted into the B-type after treatment, and their relative crystallinity increased with the number of increased freeze–thaw cycles. The hardness increased in both normal and waxy starch. The solubility and pasting breakdown viscosity decreased in normal starch while they increased in waxy starch. The pasting peak time, peak viscosity, and setback viscosity increased in normal starch but decreased in waxy starch. The rapidly digested starch (RDS) and slowly digested starch (SDS) content in normal starch increased and non-digestible starch (RS) content decreased whereas the RDS, SDS and RS content in waxy starch was almost unchanged as the freeze–thaw cycles increased. In the meantime, the molecular weight of both normal and waxy starch decreased with freeze–thaw treatment. Therefore, the repeated freeze–thaw treatment can change the physicochemical and digestible properties which could be a basis for starch-based food processing.     

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.     

Effect of single and dual hydrothermal treatments on the crystalline structure,thermal properties,and nutritional fractions of pea,lentil, and navy bean starches

Pea, lentil and navy bean starches were annealed at 50 °C (70% moisture) for 24 h and heat-moisture treated at 120 °C (30% moisture) for 24 h. These starches were also modified by a combination of annealing (ANN) and heat-moisture treatment (HMT). The impact of single and dual modifications (ANN–HMT and HMT–ANN) on the crystalline structure, thermal properties, and the amounts of rapidly digestible starch (RDS), slowly digestible starch (SDS), and resistant starch (RS) were investigated. Birefringence remained unchanged on ANN but decreased on HMT. Granular swelling and amylose leaching decreased on ANN and HMT. Relative crystallinity, gelatinization enthalpy, and short-range order on the granule surface increased on ANN but decreased on HMT. Gelatinization transition temperatures increased on ANN and HMT. Gelatinization temperature range decreased and increased on ANN and HMT, respectively. ANN and HMT increased SDS and decreased RS levels in all starches. However, RDS levels increased on ANN and HMT in pea and lentil starches but decreased in navy bean starch. In gelatinized starches, ANN and HMT decreased RDS level and increased SDS and RS levels. Changes to crystalline structure, thermal properties and amounts of RDS, SDS, and RS were modified further on ANN–HMT and HMT–ANN.     

韧化处理对3种晶型淀粉消化特性的影响

比较玉米淀粉(A型)、马铃薯淀粉(B型)和锥栗淀粉(C型)韧化处理前后的颗粒形貌、结晶特性和热特性变化,探究韧化处理对3种晶型淀粉消化特性的作用机理。SEM图片显示,韧化处理后玉米淀粉表面出现凹坑,马铃薯淀粉表面出现少许裂痕,锥栗淀粉表面变得光滑,褶皱消失;XRD和FTIR分析表明,3种淀粉经韧化后晶型未有改变,但结晶度均显著提高,分子短程有序性增加,晶体结构更趋稳定;DSC分析表明,韧化处理后3种晶型淀粉的糊化温度显著升高,热焓值无显著变化;韧化处理对不同晶型淀粉消化特性的影响存在差异,3种淀粉经韧化后RS含量均显著增加,水解指数HI和血糖指数GI显著降低;玉米淀粉韧化后RDS含量显著增加,SDS含量显著减少,水解平衡浓度由84.81%降至76.79%;马铃薯淀粉中SDS和RDS含量均显著减少,水解平衡浓度由30.59%降至21.84%;韧化处理对锥栗淀粉的RS、SDS、RDS含量及水解平衡浓度变化影响较小。     

Comparison of Thermal and Viscoelastic Properties of Four Waxy Starches and the Effect of Added Surfactant

The waxy starches used in this investigation (maize (WM), barley (WB) and two rice starches RD4 and IR29) showed different gelatinization temperatures (GT) and enthalpies (ΔH_G) measured with differential scanning calorimetry (DSC). The differences in GT and ΔH_G could only partially be related to X-ray crystallinity. The high GT waxy starches WM and RD4 retrograded to a greater extent measured with DSC and the order of increased retrogradation agreed well with the order of X-ray crystallinity of the retrograded waxy starches. The melting temperature (T_C) of the retrograded waxy starches in contrast to GT was very similar for all starches. This indicates that the temperature of the glass transition (T_g) of the amorphous regions in the starch granules controlled the onset GT and perhaps also the extent of retrogradation. Addition of cetyl trimethyl ammonium bromide (CTAB) decreased the extent of retrogradation more than 45% compared to the melting enthalpy (ΔH_C) of the waxy starches without CTAB addition. The rice starch RD4 was most affected by the CTAB addition, and the WM starch the least. The viscoelastic behaviour in the temperature interval 25–90°C of 12%(w/w) gels differed between the waxy starches. The WB starch gels showed the highest storage modulus (G′) value and the lowest phase angle (δ), i. e. strongest and least viscous gels. The WM starch gels showed the lowest G′ value and the highest δ. The rice starches were in between with the RC4 starch (high GT) showing higher G′ value and lower δ than the IR29 (low GT). The viscoelastic parameters changed only slightly with increased temperature. The addition of CTAB to the waxy starch gels changed the viscoelastic behaviour of the stronger and less viscous starch gels of the WB and RD4 as their G′ value decreased and δ increased with increased temperature. The effect on WM and IR29 was only small.     

Starch enzymatic hydrolysis,structural, thermal and rheological properties of pigeon pea (Cajanus cajan) and dolichos bean (Dolichos lab-lab) legume starches

Cajanus Cajans and Dolichos lab-lab legume starches from Argentine cultivars were investigated under a technological and nutritional point of view. Their physico-chemical, structural, thermal and the rheological properties of their gels were evaluated. Rice (RS) and potato (PS) starches were included as references. In vitro digestibility from Englyst method was also evaluated. Legume starches had the highest amylose content and the most stable chemical structure. Their rapidly digestible starch and starch digestibility rate index were very low, similar to PS, and fivefold lower than RS. They had a much higher slowly digestible starch content than PS. Legume starches showed the highest gel stability versus heating and stirring and an intermedium pasting temperature between RS and PS. They formed viscoelastic gels at 6% concentration with stronger elastic-like behaviour and higher yield stress than references. Our results indicate these legumes represent an efficient starch source to provide tailor-made properties to food/industrial applications.     

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.

     

Digestibility and physicochemical properties of granular sweet potato starch as affected by annealing

The effects of annealing on the digestibility, morphology, and physicochemical characteristics of four types of granular sweet potato starches [Yulmi (YM), Yeonwhangmi (YHM), sweet potato starch from Samyang Genex (SSPS), and commercial sweet potato starch (CSPS)] were investigated. Annealing was performed at 55°C and 90% moisture content for 72 h. Morphology, the branched chain distribution of amylopectin, and the X-ray diffraction pattern remained unchanged during the annealing process. The slowly digestible starch content in annealed YM, YHM, and SSPS starches increased, but did not change in annealed CSPS. The gelatinization temperatures increased, but the gelatinization temperature range decreased with annealing. The swelling factor and amylose leaching decreased, while the close packing concentration increased. Rapid Visco Analyser analysis revealed that annealed starches possessed thermal stability and higher pasting temperatures. It is suggested that the enhanced packing arrangement formed during annealing impacts the digestibility and physicochemical properties of sweet potato starches.     

Gel texture and chain structure of amylomaltase-modified starches compared to gelatin

Amylomaltase (AM) (4-α-d-glucanotransferase; E.C. 2.4.1.25) from Thermus thermophilus was used to modify starches from various botanical sources including potato, high amylose potato (HAP), maize, waxy maize, wheat and pea, as well as a chemical oxidized potato starch (Gelamyl 120). Amylopectin chain length distribution, textural properties of gels and molecular weight of 51 enzyme and 7 non-enzyme-modified starches (parent samples) were analyzed. Textural data were compared with the textural properties of gelatin gels. Modifying starch with AM caused broadening of the amylopectin chain length distribution, creating a unimodal distribution. The increase in longer chains was supposedly a combined effect of amylose to amylopectin chain transfer and transfer of cluster units within the amylopectin molecules.Exploratory principal component analysis (PCA) data analysis revealed that the data were composed of two components explaining 94.2% of the total variation. Parent starches formed a cluster separated from that of the AM-modified starches.Extended AM treatments reduced the apparent molecular weight and the gel texture without changing the amylopectin chain length distribution. However, the gel texture was typically increased as compared to the parent starch. AM-modified HAP gels were about twice as hard as gelatin gels at identical concentration, whereas gels of pea starch were comparable to gelatin gels. Modifying Gelamyl 120 and waxy maize with AM did not change the textural properties. Branching enzyme (BE) (1,4-α-d-glucan branching enzyme; EC 2.4.1.18) from Rhodothermus obamensis was used in just one modification and in combination with AM. The combined AM/BE modification of pea starch resulted in starches with shorter amylopectin chains and pastes unable to form gel network even at concentration as high as 12.0% (w/w). The PCA model of all gel texture data gave suggestive evidence for starch structural features being important for generating a gelatin-like texture.     

In vitro starch bioavailability of corn tortillas with hydrocolloids

Tortillas were prepared using commercial hydrocolloids, stored for 7 and 14 days and their available, resistant and retrograded resistant starches, were evaluated alongside their in vitro starch digestibility. Available starch (AS) decreased with storage time and tortillas with hydrocolloids had lower values than the control sample. Tortillas elaborated with TC-20 gum did not present substantial differences in AS. Control tortilla had resistant starch (RS) content that increased with storage time but, in general, tortillas with hydrocolloids did not show any change in RS values with storage time, except tortillas with TC-1 gum that presented a slight increase after 7 storage days. Approximately 50% of RS is due to the retrogradation phenomenon as it was shown by the amount of retrograded resistant starch (RRS). Tortillas with added hydrocolloids had lower hydrolysis percentage and the hydrolysis was slower than in the control. In general, tortillas prepared with hydrocolloids had a lower tendency for retrogradation than control tortillas; it is important to consider this to obtain tortillas with better texture and lower RS content.     

Annealing processing technique divergently affects starch crystallinity characteristic related to resistant starch content: a literature review and meta-analysis

Annealing is one of starch physical modification techniques that can increase resistant starch (RS) content. However, the effect of annealing on RS varies based on botanical sources. Starch crystal type and relative crystallinity are two important characteristics of starch. This study aimed to compare the influence of annealing on starch crystallinity and different starch crystal type (A, B and C) and investigate its effect on RS content by literature meta-analysis study. The literature review was carried out using 22 research articles and 101 data points. The result showed relative crystallinity increase from the highest changes to the lowest, respectively; C-type crystal (18.98%) followed by B (13.60%) and A-type crystal (8.17%). Meta-analysis study results showed a significant increase of RS content on starches with A-type crystal (SMD = 6.46; 95% CI: 3.22–9.70; P < 0.01) and a positive relationship between the degree of crystallinity and RS content after annealing modification.     

Influence of heat–moisture treatment and annealing on functional properties of sorghum starch

Sorghum starch was annealed in excess water at 50 °C for 24 h. Starch was also modified under heat–moisture treatment at 110 °C after adjusting various moisture contents (20, 30 and 40%) for 8 h. Significant decrease in chain lengths of amylose fraction in HMT starches was observed. Heat moisture treated (HMT) and annealed (ANN) starches showed lower granule sizes, swelling power, peak and setback viscosity but higher retrogradation as compared to native starch. HMT starch with addition of 40% moisture showed a decrease in relative crystallinity. HMT and ANN starch gels were observed to be harder than native starch gel.     

Structural characterizations and digestibility of debranched high-amylose maize starch complexed with lauric acid

Structural characterizations and digestibility of debranched high-amylose maize starch complexed with lauric acid (LA) were studied. The cooked starch was debranched by using pullulanase and then complexed. Light microscopy showed that the lipids complexed starches had irregularly-shaped particles with strong birefringence. Gel-permeation chromatograms revealed that amylopectin degraded to smaller molecules during increasing debranching time, and the debranch reaction was completed at 12 h. Debranching pretreatment and prolonged debranching time (from 2 h to 24 h) could improve the formation of starch lipids complex. X-ray diffraction pattern of the amylose–lipid complexes changed from V-type to a mixture of B- and V-type polymorphs and relative crystallinity increased as the debranching time increased from 0 to 24 h. In DSC thermograms, complexes from debranched starch displayed three separated endotherms: the melting of the free lauric acid, starch–lipid complexes and retrograded amylose, respectively. The melting temperature and enthalpy changes of starch–lipid complex were gradually enhanced with the increasing of debranching time. However, no significant enthalpy changes were observed from retrograded amylose during the starch–lipid complex formation. Rapidly digestible starch (RDS) content decreased and resistant starch (RS) content increased with the increasing of debranching time, while the highest slowly digestible starch (SDS) content was founded at less debranching time of 2 h. The crystalline structures with dense aggregation of helices from amylose-LA complex and retrograded amylose could be RS, while SDS mostly consisted of imperfect packing of helices between amylopectin residue and amylose or LA.     

The impact of coupled acid or pullulanase debranching on the formation of resistant starch from maize starch with autoclaving–cooling cycles

Maize starch was treated by autoclaving–cooling cycles, coupled with acid or pullulanase hydrolysis to prepare resistant starch (RS). Debranching of retrograded or gelatinized maize starch with acid or pullulanase was studied to show the corresponding impact on RS formation. When maize starch was treated with three autoclaving–cooling cycles and retrograded maize starch was hydrolyzed at room temperature, with 0.1 mol L⁻¹ citric acid for 12 h, analysis results showed that debranching of citric acid was helpful in RS formation for RS yield increased from 8.5 to 11%. Debranching of gelatinized or retrograded maize starch at 60 °C with pullulanase at addition level of 3 PUN g⁻¹ starch showed a more favorable effect on RS formation. When gelatinized maize starch was hydrolyzed by pullulanase for 12 h and then treated with two autoclaving–cooling cycles, RS yield increased to 23.5%. If retrograded maize starch subjected to one autoclaving–cooling cycle was hydrolyzed by pullulanase for 10 h and then followed by two autoclaving–cooling cycles, RS yield elevated to 32.4%. The debranching effect of pullulanase on retrograded maize starch to help RS formation is obvious and most effective, indicating this treatment is applicable in RS preparation to increase the RS yield.     

Impacts of acid-methanol treatment and annealing on the enzymatic resistance of corn starches

Normal corn, Hylon V and Hylon VII starches were acid-methanol-treated at 25 °C for 1–30 days in methanol containing 0.36% HCl, and then annealing at 50 °C for 72 h in excess water. The rapid digestible starch (RDS), slow digestible starch (SDS) and resistant starch (RS) contents of starch before and after treatments were determined. The molecular structure, thermal properties, double helix content and relative crystallinity of starch were observed for elucidating the impacts of acid-methanol treatment and annealing, as well as the molecular structure, on the enzymatic resistance of starch. Results showed that the weight-average degree of polymerization of acid-methanol-treated corn starches ranged from 884 × 10³ to 404, 778 × 10³ to 299 and 337 × 10³ to 250 anhydrous glucose units for normal corn, Hylon V and Hylon VII starches, respectively. Annealing increased the RS content of starch, and the increment of RS increased with decreasing molecular size of starch. Furthermore, the change in RS content after treatments depended on the content and weight-average chain length of amylose fraction of starch. The RS content of starch after treatments increased from 19.2 to 56.2%, 69.9 to 86.1%, and 73.1 to 89.1% for normal corn, Hylon V and Hylon VII starches, respectively. The gelatinization peak temperature and double helix content of starch increased after acid-methanol treatment or annealing. Results demonstrate that the degradation of starch, causing by acid-methanol treatment, enhances the mobility and realignment of starch chains in molecules during treatments and further increases the enzymatic resistance of starch granules.     

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.     

Properties of Cassava Starch Modified by Amylomaltase from Corynebacterium glutamicum

Amylomaltase (α‐1,4‐glucanotransferase, AM; EC 2.4.1.25) from Corynebacterium glutamicum expressed in Escherichia coli was used to prepare the enzyme‐modified cassava starch for food application. About 5% to 15% (w/v) of cassava starch slurries were incubated with 1, 3, or 5 units of amylomaltase/g starch. Apparent amylose, amylopectin chain length distribution, thermal properties, freeze–thaw stability, thermo‐reversibility, and gel strength of the obtained modified starches were measured. The apparent amylose content and retrogradation enthalpy were lower, whereas the retrogradation temperatures, freeze–thaw stability, and thermo‐reversibility were higher than those of the native cassava starch. However, when amylomaltase content was increased to 20 units of amylomaltase/g starch and for 24 h, the modified starch showed an improvement in the thermo‐reversibility property. When used in panna cotta, the gel strength of the sample using the 20 units/24 h modified cassava starch was similar to that of using gelatin.     

Resistant starch and potential glycaemic index of raw and cooked legumes (lentils, chickpeas and beans)

 The amount of resistant starch (RS) in raw and processed legumes, lentils, chickpeas and beans was analysed. In addition, the effect of cooking on the availability of legume starches to enzymes, which may influence the glycaemic response, was studied. Raw legumes were found to have higher RS values (16–21%) than retrograded or cooked ones (4–8%). Cooling increased RS yields, whereas reheating maintained or decreased the value depending on the sample. On the other hand, the kinetics of starch hydrolysis revealed that the rate of digestion was higher for cooked seeds and retrograded flours (15–21% of total starch digested) than for raw flours (5–8% of total starch digested). The estimated glycaemic indices (GIs), i.e. GI₁ from the Hydrolysis Index (HI) and GI₂ from the percentage of hydrolysis within 90 min (H ₉₀), were well correlated with the reported GI values (r = 0.96 and r = 0.95 respectively, P≤ 0.05). Received: 22 September 1997 / Revised version: 24 November 1997     

Functional,thermal and molecular behaviours of ozone-oxidised cocoyam and yam starches

Ozone-oxidised starches were prepared from the native starches isolated from white and red cocoyam, and white and yellow yam cultivars. The native and oxidised starches were evaluated for functional, thermal and molecular properties. The correlations between the amount of reacted ozone and carbonyl and carboxyl contents of the starches were positive, as ozone generation time (OGT) increased. Significant differences were obtained in terms of swelling power, solubility, pasting properties and textural properties of the native starches upon oxidation. The DSC data showed lower transition temperatures and enthalpies for retrograded gels compared to the gelatinized gels of the same starch types. The native starches showed C_B-type XRD patterns while the oxidised starches resembled the C_A-type pattern. As amylose content increased, amylopectin contents of the starches decreased upon oxidation. Similarly, an increase in M_w values were observed with a corresponding decrease in M_n values upon oxidation.