Starch/Solute Interaction in Water Sorption as Affected by Pretreatment

The effect of the freeze-drying process on the structure of starch and starch-sucrose mixtures was studied. The technique of inverse gas chromatography was used to study the interaction between organic compounds (probes) and starch (hylon 7) as well as starch-sucrose mixtures. The structural and morphological characteristics of the starch-solute mixtures from the thermodynamic parameters of these interactions was also examined. The porous freeze-dried samples interacted more with certain organic probes compared with untreated starch as indicated by higher values of specific retention volumes (Vg_o). Untreated starch apparently interacted only on the surface with organic probes. Freeze-dried starch reacted only with polar organic probes, particularly those with hydrogen bonding propensity. Cluster analysis of the water sorption isotherms correlated with data obtained from the injected probes.     

Crystallinity of Waxy Maize Starch as Influenced by Ambient Temperature Absorption and Desorption, Sucrose Content and Water Activity

Crystallinity of waxy maize starch was determined by X-ray diffraction. Absorption and desorption over the range 0.33-0.84 a_w, were applied to raw, partially gelatinized, and completely gelatinized starches mixed with0–50% sucrose. Increasing aw and moisture content in-creased crystallinity in case of all three starch treatments. A critical moisture content was required for recrystallization of starch. Gelatinized starch showed the greatest crystallinity hysteresis which was much greater than water sorption hysteresis. Sucrose had no effect on starch crystallinity with absorption. With desorption of completely gelatinized starch-sucrose mixtures, the sucrose caused a sharp decrease in crystallinity at0–10% sucrose while, at higher sucrose content, the crystallinity increased.     

Influence of Water on Molecular and Morphological Structure of Various Starches and Starch Derivatives

In this study the influence of water on untreated, pregelatinised, and chemical modified starches was investigated. Because of their different botanical source, the starch products contain various quantities of amylose and amylopectin. The water vapour absorption capacity of the starches was studied by sorption/desorption and thermogravimetrical measurements. Higher absorption capacities were found for potato starch and for starches containing carboxymethyl and hydroxyethyl groups. Characteristic molecular differences found by Raman spectroscopy were evaluated for untreated and modified starches. To this end, the starch raw materials were classified into groups with similar pretreatments and properties based on cluster analysis. Additionally, the gelatinisation of starch‐water mixtures (gels, powders, and films) was continuously studied using temperature‐dependent Raman spectroscopy. In comparison with powder spectra, the Raman spectra of the starch films showed shifts in band positions in the range of the CH deformation and CH stretching modes. With the exceptions of high‐amylose maize starch and carboxymethylated starch, all starches form films. Starch films differ in their surface structures, water contact angles, and rates of water drop absorption, which might be caused by the different retrogradation properties. The swelling and shrinking behaviour of starch films was investigated at the morphological level by in situ environmental scanning electron microscopy (ESEM) experiments and evaluated by grey value analysis. Films of untreated starch show stronger swelling and shrinking than films of pregelatinised products.     

Gelatinization and Retrogradation Properties of Native and Hydroxypropylated Crosslinked Tapioca Starches with Added Sucrose and Sodium Chloride

The effects of sucrose and sodium chloride on the gelatinization and retrogradation of native and hydroxypropylated crosslinked tapioca starches were investigated by using Differential Scanning Calorimetry (DSC). Hydroxypropylated crosslinked tapioca starches showed low gelatinization temperature and enthalpy compared to the native tapioca starch. Sucrose and sodium chloride increased the gelatinization temperatures of all starch samples. The enthalpy to melt retrograded amylopectin of hydroxypropylated crosslinked tapioca starches were low, compared to that of the native starch. Sucrose did not have much effect on retrogradation of the starch, while sodium chloride decreased retrogradation of all starch samples.     

Interaction of Sucrose with Starch During Dehydration as Shown by Water Sorption

Component interactions in the sucrose-starch-water system were investigated. Starch, sucrose, a mechanical starch:sucrose mixture and four powders obtained by freeze drying dilute aqueous mixtures were equilibrated to a_w ranging from 0.33–0.93. Both raw and gelatinized starch were included. Sucrose-starch interaction was determined by measuring the reduction in water sorption as compared to theoretical. Only the freeze-dried mixtures showed interaction. Interacted sucrose, calculated as the sucrose that did not bind water, (1) decreased from a maximum at 0.86 a_w to zero at 0.936 a_w, and (2) rose sharply with increasing sucrose-starch ratio to a maximum at a ratio of 0.4 and decreased to zero with further increase in ratio to 1.5. More sucrose interacted with gelatinized than raw starch.     

Solubility Behavior of Granular Corn Starches in Methyl Sulfoxide (DMSO) as Measured by High Performance Size Exclusion Chromatography

The extent of corn starch dispersibility and the relative molecular solubility of amylose and amylopectin in methyl sulfoxide (DMSO) were determined. Granular corn starches with <l, 25, 53, and 70% amylose were dispersed in 0–100% DMSO (in water) solutions at 30°C for 30 min. Maximum dispersibility for all starches (98%) was obtained when 90% DMSO/10% water was used; regular (normal) dent corn starch was equally dispersed in solutions with 88–94% DMSO. Molecular solubility, the presence of individual molecules of amylose and amylopectin, of starches was also measured (after centrifugation and filtration) by high performance size-exclusion chromatography (HPSEC). Starches were dispersed in 90% DMSO and heated for 10 min at temperatures of 35–120ºC. At low temperatures, high coefficients of variation resulted from additional DMSO solubilization after treatment. At 120ºC, 70% amylose starch was >90% solubilized, while waxy starch was only 47% solubilized. When starches were treated for 18–89 h in 90ºC DMSO, solubility stopped increasing after 67 h. High amylose starch (70%) was mostly solubilized, but 53% amylose, waxy and regular starches could only be fully solubilized after exposure to shear. Amylopectin molecules appeared more susceptible to shear induced depolymerization than amylose. The percent amylopectin in the high amylose starches reflected that as determined by iodine binding analysis and the manufacturer; while the percent amylopectin in regular starch was too low (manufacturers: 75%, HPSEC: 65%). Undispersed components were mostly amylopectin. Since amylose is fully solubilized, however, the HPSEC can be used to quickly determine percent amylose in starch.     

Physicochemical properties of pressure moisture treated (PMT) and heat moisture treated (HMT) starches

Physicochemical properties of pressure moisture treated (PMT, 550 MPa, 10 min) and heat moisture treated (HMT, 100 °C, 10 h) starches were investigated. Effects of PMT and HMT were different depending on starch type. PMT starches showed dramatic changes in moisture sorption isotherm, pasting properties, thermal characteristics, solubility and swelling power (at 90 °C), and in vitro digestibility. The most dramatic difference between PMT and HMT starches was amylopectin melting transition, i.e., broadening in PMT and shift to high temperature in HMT starches. Moreover, B- and C-type starches revealed the more increase in amylopectin melting enthalpy than A-type starch. Both PMT and HMT did not increase the crystallinity but reorganized the amorphous area to compact, resulting in lower rapidly digestible starch and higher slowly digestible starch than those of native starches. Consequently, PMT changed the digestibility and physicochemical properties of starches with different modes of action compared with HMT.     

Effect of high pressure on binding aroma compounds by maize starches with different amylose content

Hylon VII, waxy maize starch and their mixtures were subjected to high pressure treatment (650 MPa/9 min). To obtain starch-odorants products: (i) the pressurised and native starches were incubated with odorants; and (ii) the native starches mixed with odorants were treated under high pressure (650 MPa/9 min). The sorption capacity of odorants by investigated starches was studied using capillary gas chromatography.The sorption capacity of odorants by native starches was found to stronger depend on hydrophobicity and molecular structure of odorants rather than the starch botanical origin. The highest sorption was observed for polar hydrophobic compounds (hydrocarbons) and for aliphatic esters, whereas the lower one—for guaiacol and methyl anthranilate. The high pressure-treated Hylon VII demonstrated slight changes in melting enthalpy and degree of gelatinisation compared to other starches and it showed the highest sorption capacity of the majority of odorants. The treatment of a starch with odorant under 650 MPa for 9 min resulted in a diminished average sorption of the aroma compounds. However hexanol, guaiacol and methyl antrinilate, that were slightly or not sorbed by native and high pressure-treated starches, demonstrated the highest degree of binding with waxy starch and its mixtures under high pressure conditions.     

Interaction of Sucrose with Gelatin, Egg Albumin and Gluten in Freeze-Dried Mixtures as Shown by Water Sorption

The objective was to study sucrose-protein interactions in freeze-dried mixtures as shown by water binding data. Gelatin, egg albumin and gluten were included. Sucrose content was varied. Each sample was mixed with water and dried. The powder was equilibrated against known water activity (a_w) ranging from 0.58 to 0.93. The experimental water sorption data at a given a_w was then compared to calculated values obtained from the Lang-Steinberg mass balance equation. Contrary to other systems, samples sorbed more rather than less water than calculated. This was ascribed to sucrose-protein interaction which increased water binding by protein. Amount of interaction at a given a_w was found to be linearly related to the sucrose content. A critical sucrose content was needed to trigger the interaction.     

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.     

Amylose and β‐Glucan Content of New Waxy Barleys

Starch was isolated from four new waxy barleys and compared with normal and high‐amylose barley starch. The waxy barley samples were selected lines from crosses of Swedish hulled and naked barley cultivars with the cultivar Azhul as donor of the waxy gene. The starches from the waxy barley samples were found to contain 0.7–2.6% amylose when determined iodimetrically by amperometric titration and 0.0–0.9% when determined by size exclusion chromatography after debranching. However, Sepharose CL‐2B elution profiles of the starches detected by iodine staining showed that all four waxy samples were free from detectable amounts of amylose. The amylopectin starches were found to contain a small polysaccharide fraction with molecular size smaller than amylopectin, with an iodine staining λ_max range of 550–600 nm. The water extractable and acid extractable β‐glucan contents in the waxy barley cultivars were generally found to be higher than those in normal barley.     

Drying Kinetics of Hydrated and Gelatinized Corn Starches in the Presence of Sucrose and Sodium Chloride

Drying behavior of the hydrated corn starch, hydrated starch/sucrose, and hydrated starch/sodium chloride mixture and their gels were investigated. Drying data were obtained on slabs of samples in a laboratory tunnel dryer at 40 to 70 °C. The rate-of-drying curves for hydrated starches with or without sucrose showed that the moisture movement may be the result of capillary action rather than diffusion. In the hydrated starches containing sodium chloride, case-hardening was the controlling mechanism. In gelatinized samples, however, diffusion was the main mechanism. The effective diffusivity was estimated by the methods of slopes. Gelatinization of starch reduced the moisture diffusivity significantly. The presence of sucrose or sodium chloride decreased the coefficient significantly in hydrated starch, but their effect was small in gelatinized samples.     

Amylopectin: Structural, gelatinisation and retrogradation studies

Amaranth, waxy corn, and commercial corn amylopectins were enzymically debranched and their fractions separated by gel filtration. In all cases a bimodal distribution of chain lengths was found, containing a high proportion of short chains. Amaranth, waxy corn starches and commercial corn amylopectin displayed an A-type X-ray diffraction pattern, which is characteristic of cereal starches, whereas amaranth amylopectin did not show a well-defined pattern, suggesting that the former samples have granular structure. Gelatinisation and retrogradation data, by differential scanning calorimetry, showed a good agreement between starches and amylopectins of the same source. Amaranth starch and its amylopectin presented a lower tendency to undergo these changes compared to the remaining tested materials. The temperature effiect on retrogradation was more drastic for amaranth and waxy corn amylopectins.     

Physicochemical Characteristics of Starches from Unripe Fruits of Mango and Banana

Mango and banana starches were isolated from unripe fruits and their morphology; thermal and pasting properties; molar mass and chain length distribution were determined. Mango starch granules were spherical or dome‐shaped and split, while banana starch had elongated granules with a lenticular shape. Amylopectin of both fruit starches had a lower molar mass than maize starch amylopectin; however, mango amylopectin had the highest gyration radius. Banana amylopectin showed the lowest percentage of short chains [degree of polymerization (DP) 6–12] and the highest level of long chains (DP ≥ 37); mango amylopectin presented the highest fraction of short chains, but the level of longest chains was intermediate between those of banana and maize amylopectins. Banana starch presented the highest average gelatinization temperature followed by mango starch and maize starch had the lowest value; a similar pattern was found for the gelatinization enthalpy. The two fruit starches had a lower pasting temperature than maize starch, but the former samples showed higher peak and final viscosities than maize starch. Structural differences identified in the fruit starches explain their physicochemical characteristics such as thermal and pasting behavior.     

Starch and Amylopectin - Effects of Solutes on Clarity of Pastes

The effect of sucrose, glucose and sodium chloride at different concentrations on clarity of starch and amylopectin pastes was studied. It was found that clarity of amaranth, waxy corn and normal corn starch pastes tended to increase by increasing carbohydrate concentrations. The percentage of transmittance (%T) values for the same starch sample with sucrose and glucose did not present significantly differences (α=0.05). The starches with sodium chloride did not show a defined pattern. The %T for amaranth and waxy corn amylopectin pastes with all solutes tended to increase by increasing solute concentration. Interestingly, the %T values among all amylopectins at a given solute concentration were significantly different (α=0.05) probably due to different chain length proportion in such amylopectins. The same amylopectin in presence of sucrose and glucose did not show %T significantly different (α=0.05) but with sodium chloride those values were different (α=0.05).     

Effect of pH on aqueous structure of maize starches analyzed by HPSEC-MALLS-RI system

Molecular conformation of maize starches (waxy, normal and high amylose) was examined at different pH values (5–10) using an aqueous medium-pressured size exclusion column chromatography (SEC) connected to multi-angle laser light scattering (MALLS) and refractive index (RI) detectors. The starch molecules were partially degraded at pH 5 and 10, resulting in lower values for molar size and radius of gyration than those in neutral condition. The specific volume data revealed that the structural changes under an alkaline condition such as pH 10 was more significant for amylose than that for amylopectin. Logarithmic ratios between molar size and radius of gyration were similar (0.2–0.3) for the amylopectins in waxy and normal maize starches, but higher (0.4–0.5) for the amylopectin in high amylose starch, indicating that the amylopectins in waxy or normal maize starches had sphere forms whereas that in high amylose starch had a random coil shape.     

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).     

Sorption Behavior of Mechanically Mixed and Freeze-Dried Sucrose/Casein Mixtures

Interactions between sucrose and casein were investigated by adsorption isotherms. Mechanically mixed and freeze-dried sucrose/casein mixtures at sucrose percentages of 1, 5, 10, 15 and 20% (wet basis) were compared to calculated isotherms using the mass balance equation, over the a_w range 0.23–0.93 at 20°C. The mechanical mixtures did not exhibit solute/polymer interactions. The freeze-dried systems showed positive interaction (i.e., sorbed more water than calculated) for 1 and 5% sucrose at all a_w values. For the 10, 15 and 20% sucrose mixtures, positive interaction continued below 0.86 a_w; however, above 0.86 a_w, no interaction was apparent. That is, experimental sorption values equaled calculated values.     

Changes in Starch Pasting Properties Due to Sugars and Emulsifiers as Determined by Viscosity Measurement

The effects of sugars, emulsifiers, and their interactions on starch pasting properties were determined by the Rapid Visco-Analyser (RVA). Solutions of 50% sugars in water were used. The disaccharides, sucrose and lactose, delayed pasting more than did the monosaccharide, dextrose. Sugars’effects on starch pasting delay and on starch paste consistency varied with the starch. Addition of the same emulsifier (1%) to different starches did not result in the same change in paste consistency in the presence of high amounts of sugar. Both sucrose ester F-160 (SE) and polysorbate 60 (PS) reduced the hot paste consistency of starch-sugar mixtures, with SE having a greater effect than PS.     

Water Binding Capacity of Commercial Produced Native and Modified Starches

The water binding capacities of five cereal and three tuberous starches, as well as fourteen modified wheat starches were determined using a Differential Scanning Calorimetry technique. Of the native starches, the tuberous ones had the highest moisture binding capacities. The influence of amylose/amylopectin ratio on water binding capacity was examined using waxy maize, normal maize and high amylose maize starches and increases in amylose level were found to result in reduced water binding. Chemical modification caused a reduction in the water binding capacity of wheat starch presumably as a result of blocking water binding sites on the starch molecules. Pregelatinized wheat starch showed a higher water binding capacity than wheat starch as a consequence of the disruption of the internal structure of the granule.