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.     

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.     

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.     

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.     

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.     

Influence of the Cross‐linking Agent on the Gel Structure of Starch Derivatives

Hydrogels were synthesized through cross‐linking of carboxymethyl starch (CMS; Degree of Substitution DS = 0.45) using polyfunctional carboxylic acids (malic, tartaric, citric, malonic, succinic, glutaric and adipic acid). The syntheses used a cross‐linking agent ratio (ratio of the number of cross‐linking agent molecules to the number of monomer units constituting the polymer) of F_Z = 0.05. After cross‐linking the gels were dried, ground and then hydrogels of a polymer concentration of 4 mass‐% were produced. These CMS‐hydrogels were then rheologically characterized using dynamic oscillatory measurements. From measurements of the plateau region storage modulus G'_P, the network parameters molar mass between two entanglement points M_e (M_e ranging from 9.318 (citric acid) to 281.397 g/mol (tartaric acid)), the cross‐link density ν_e and the distance between two entanglement points ξ were calculated. Using carboxylic acids without other functional groups, a maximum in gel sturdiness is found at a spacer length of two CH₂‐groups. The evaluation of the loss factor tan δ for the CMS‐hydrogels showed that values of tan δ = 0.2 varied only slightly with the frequency ω. Flow curves showed a pseudopIastic flow behavior for all CMS‐hydrogels (the shear viscosity η declining over five decades in the range of the shear rate γ of 10⁻³ to 10³ s⁻¹) The different polyfunctional carboxylic acids have a strong influence on the sturdiness of the synthesized CMS‐hydrogels.     

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.

     

Heat‐Moisture Treatment and Enzymatic Digestibility of Peruvian Carrot,Sweet Potato and Ginger Starches

The aim of this work was to study the effects of heat‐moisture treatment (27% moisture, 100°C, 16 h) and of enzymatic digestion (alpha‐amylase and glucoamylase) on the properties of sweet potato (SP), Peruvian carrot (PC) and ginger (G) starches. The structural modification with heat‐moisture treatment (HMT) affected crystallinity, enzyme susceptibility and viscosity profile. The changes in PC starch were the most pronounced, with a strong decrease of relative crystallinity (from 0.31 to 0.21) and a shift of X‐ray pattern from B‐ to A‐type. HMT of SP and G starch did not change the X‐ray pattern (A‐type). The relative crystallinity of these starches changed only slightly, from 0.32 to 0.29 (SP) and from 0.33 to 0.32 (G). The extent of these structural changes (PC > SP > G) altered the susceptibility of the starches to enzymatic attack, but not in same order (PC > G > SP). HMT increased the starches digestion, probably due to rearrangement of disrupted crystallites, increasing accessible areas to attack of enzymes. The viscosity profiles and values changed significantly with HMT, resulting in higher pasting temperatures, decrease of viscosity values and no breakdown, i.e., stability at high temperatures and shear rates. Changes in pasting properties appeared to be more significant for PC and SP starch, whereas the changes for G starch were small. Setback was minimized following HMT in SP and G starches.     

Radiation‐Modified Carboxymethyl Starch Derivative as Metal Scavenger in Aqueous Solutions

Corn starch was chemically modified using sodium chloroacetate to yield carboxymethyl starch (CMS). The aqueous solutions of CMS at 15 and 50% (w/w) concentration were then irradiated by electron beam (EB) at various dosages (1, 2, 3, 5, 10, 20, and 50 kGy), resulting in a cross‐linked carboxymethyl starch (CCMS). The maximum gel fraction, i.e. the highest degree of cross‐linking, was achieved with a 50% (w/w) aqueous CMS solution irradiated at 2 kGy EB dosage. Metal removal efficiency of the CCMS was then evaluated for the extraction of copper (Cu) and cadmium (Cd) ions from aqueous solutions. Our results showed that the metal adsorption is pH dependent and the adsorption increases with increase of the pH of the metal solution from acidic towards neutral. The adsorption efficiency also showed the maximum value at the highest gel content, demonstrating the enhancement of adsorption by the physical entrapment of the ions in the CCMS network in addition to the primary chemical adsorption.     

Lintnerization of Two Amylose‐free Starches of A‐ and B‐Crystalline Types,Respectively

Waxy maize starch (WMS) and potato amylopectin starch (PAPS), representing amylose‐free A‐ and B‐crystalline granules, respectively, were subjected to hydrolysis in diluted hydrochloric acid (lintnerization). The solubilization rate of the granules was dependent on the temperature, but there were only small differences between the samples. The compositions of the lintners obtained at 29°C were also similar, though the sensitivity to enzymatic debranching was different. The degree of debranching increased significantly if pullulanase and isoamylase were used successively. Because some branches remained resistant to enzymatic attack, the degree of scattered branching was difficult to estimate. The amount and composition of β‐limit dextrins suggested, however, that both starches contained scattered branches. Long chains and the shortest chains in the amylopectin molecules were sensitive to lintnerization and therefore probably located outside the crystallites. The composition of the PAPS lintners was dependent on the temperature of the lintnerization, whereas that of WMS lintners was not. The composition of a lintner from normal potato starch was compared with PAPS, and it is concluded that the presence of amylose has a higher effect than the type of crystallinity on the lintnerization results.     

Thermal and Rheological Properties of Dough and Bread as Affected by Various Cross‐linked Cornstarch Substitutions

Various kinds of cross‐linked cornstarches (CLCSs) were used to substitute for wheat flour (5 and 10%), and thermal and rheological properties of dough and bread were examined. The pastes of the substituted flours had lower gelatinization temperatures and higher viscosities than those of the control. The substitution with low‐swelling waxy CLCS (L‐CWCS) had higher paste consistency and lower transition enthalpy than those with high‐ or low‐swelling non‐waxy CLCS (H‐CNCS or L‐CNCS) or the control. The substitutions with L‐CNCS made harder doughs and higher firmness of breadcrumbs during storage than the others. The specific volumes of breads with cross‐linked cornstarch substitutions were slightly smaller than that of the control because of the lack of gluten. The firmness of bread substituted with L‐CWCS was softer than that with H‐ or L‐CNCS. In addition, the breads with H‐CNCS were softer than that with L‐CNCS. The results showed that the compression stress of dough was highly positively correlated with firmness of breads after storage for one and three days (r = 0.876, P < 0.01 and r = 0.809, P < 0.05, respectively). Also, significant positive correlations were detected between the transition enthalpy of dough and firmness of breads after storage for one and three days (r = 0.840, P < 0.05 and r = 0.853, P < 0.05, respectively), whereas no correlation between transition enthalpies of breadcrumbs and firmness of breads was observed.     

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.