Physicochemical Properties of Different Types of Starch Phosphate Monoesters

Different types of starch were phosphorylated to different degrees of substitution using monosodium and disodium hydrogen orthophosphate at 160 °C under vacuum. Generally, phosphation enhanced the physicochemical properties of the modified starches compared to their native counterparts. Solubility and swelling power greatly increase when phosphorylation was carried out to a low degree of substitution, while the solubility and swelling power decreased gradually by increasing the degree of substitution. However, the values of the monoesters were still higher than those of the corresponding native polysaccharides. Viscosities of different starch types except corn amylose showed the highest values at the lowest degree of substitution, when the degree of phosphation increased the viscosity values decreased. Native potato starch formed a clear paste (96% transmittance) due to the presence of phosphate groups while the paste clarity of potato starch decreased gradually by increasing the degree of phosphation. Generally, phosphorylation increased the light transmittance of the other starches investigated at the lowest degree of substitution but the clarity decreased by increasing the degree of substitution.     

Characterization of Different Starches Oxidized by Hypochlorite

The effects of starch origin (potato, corn, and rice starches) and hypochlorite level (NaOCl, 0.8% and 2% w/w) on the structures and physicochemical properties of oxidized starches were investigated. Carboxyl and carbonyl group contents of oxidized starches increased with increasing NaOCl level, with potato starch having the highest and corn starch having the lowest carboxyl groups content at both NaOCl levels. Oxidation generally reduced the pasting temperature and viscosity of native starches as demonstrated by using a Rapid Visco Analyser. The peak viscosities of oxidized rice and corn starches were higher than those of their native counterparts at 0.8% NaOCl. The morphology of starches was not altered and X‐ray diffraction patterns of all the starches remained unchanged after oxidation. Oxidized starch batters exhibited greater adhesions than did native starch batters, with rice starch batter exhibiting the greatest adhesion. Carbohydrate profiles by high‐performance size‐exclusion chromatography indicated that both amylopectin and amylose were degraded during oxidation. The level of oxidation was largely dependent on the degree of crystallinity of starch and the degree of polymerization of amylose, whereas the adhesion property of oxidized starch was mainly attributed to its granular size and shape.     

Degradability of Different Phosphorylated Starches and Thermoplastic Films Prepared from Corn Starch Phosphomonoesters

Different starch types (corn, rice, potato, corn amylose and corn amylopectin) were phosphorylated to varying degrees of substitution (DS) and tested both for acid hydrolysis during 3 h in a boiling bath and for enzymatic hydrolysis with a thermostable bacterial α‐amylase (Bacillus licheniformis) for 30 min at 95 °C. Generally, phosphorylated starches showed a reduced degree of acid hydrolysis during the entire time of hydrolysis (3 h) as well as reduced susceptibility to α‐amyIase hydrolysis. The enzyme action was inhibited by the presence of phosphate groups in the modified starch molecules and the extent of inhibition increased with increasing degree of phosphate substitution, regardless of the starch type. Thermoplastic films were fabricated by blending modified corn starches of different DS with polyacrylate, urea and water at a ratio of 4:5:1:50, heating for 30 min at 95 °C before casting and allowing to cool, stand and dry at room temperature. The plastic films prepared from phosphorylated corn starch showed both higher disintegration rate and a greater degradability by thermostable bacterial α‐amylase than the ones prepared from non‐phosphorylated starch. These new acquired properties can meet the increasing demand for biodegradable disposable plastic bags.     

Starch Paste Stickiness is a Relevant Native Starch Selection Criterion for Wet‐end Paper Manufacturing

The correct choice of selection and quality criteria is critical for most starch applications. In this study, a set of different potato starches, selected for a large variation in natural phosphate content and final viscosity, was cationised and tested in a laboratory scale wet‐end paper manufacturing process. Analysis of further parameters expected to be critical for processing, including amylose content and starch granule size, was also performed. Since no significant correlation was found between any of these parameters and paper processing, further attempts were made to find structural or physico‐chemical explanations for the paper processing performance. Hence, several additional parameters of the starches were determined including amylopectin chain length pattern, phosphate substitution, molecular size distribution, pasting‐texture properties and fragility of the gelatinised granules. Among these parameters, the best correlation found to paper filler retention was stickiness of the starch as measured by texture analysis. The starches that performed best in the paper trials showed rapid granule bursts that could be readily estimated from the width of the pasting curve peaks. Light microscopy of non‐soluble remnant starch obtained after gelatinisation of starch under dilute conditions revealed a high proportion of broken granular structures. It is hypothesised that the degree of phosphorylation, together with a hitherto unknown molecular parameter that is related to starch granule fragility, determines starch paste stickiness, which in turn is an important parameter for wet‐end paper manufacturing.     

Granule Sizes of Canna (Canna edulis) Starches and their Reactivity Toward Hydration,Enzyme Hydrolysis and Chemical Substitution

Small and large granule fractions were isolated from canna starch (Canna edulis, green leaf cultivar), and their morphology, physicochemical properties, susceptibility towards granular starch hydrolyzing enzymes and chemical reaction with propylene oxide were investigated. Canna starch consisted of a mixed population of large, medium and small granules; the mean of granule diameter was 47.4 μm. The small granules presented round and polygonal shapes, whereas the large granules had oval and elliptical shapes. Significant variations in digestibility of the various granules size by granular starch hydrolyzing enzymes were observed. During the first 24 h, the hydrolysis rate of small granules was higher than that of native and large granule starches. After 72 h, however, the degree of hydrolysis of small granule, large granule and native starches had reached the extent of 19.6%, 32.0% and 27.2%, respectively. The larger the granule size, the higher the MS obtained when modified with propylene oxide, which was due to the higher swelling power of the large granules. The results obtained from this study suggest that small granules had lower water and chemical affinity when compared with the bigger ones. The difference in the reactivity of small and large granules could be presumably attributed to the starch components (amylose and amylopectin) and their organization of glucan chains in ordered and/or less ordered structure of these two fractions.     

Morphological,Physicochemical and Structural Characteristics of Oxidized Barley and Corn Starches

Barley starch was oxidized to different levels and the morphological, physicochemical and structural of the resultant oxidized barley starch were determined and compared with oxidized corn starch at the same oxidation level. The amylose content in oxidized starches decreased with increasing oxidation level, and the extent of decrease was similar for both starch types. No evidences of alteration in morphology and X‐ray diffraction pattern were noted after oxidation. The crystallinity of barley starch increased with increasing oxidation but corn starch displayed a reduced crystallinity at 5% NaOCl. The onset and peak gelatinization temperatures of oxidized starches as measured by differential scanning calorimetry showed a slight increase up to 3% NaOCl and then decreased at 5% NaOCl, whereas gelatinization enthalpy gradually decreased with increasing oxidation level. The melting temperature of retrograded oxidized starches increased with increasing oxidation. Both amylose and amylopectin were degraded during oxidation, but a higher degradation in both components as determined by high‐performance size‐exclusion chromatography (HPSEC) was noted for barley starch than for corn starch. Results of amylopectin chain‐length distribution showed that the proportions of A and B1 chains significantly increased while that of B2+ chains significantly decreased. These results suggest that differences in the structure of barley and corn starches affected their responses to oxidation. Barley starch seemed to be more susceptible to oxidation with more significant reduction in pasting temperature, viscosity, and molecular size than corn starch.     

Gel Textural Characteristics of Corn,Cassava and Yam Starch Blends: A Mixture Surface Response Methodology Approach

Blends of native starches can be used to obtain special sensory properties avoiding the use of chemically modified starches. The mixture design approach was used to analyze the textural properties (hardness, adhesiveness, cohesiveness and gumminess) of gels obtained with different proportions of yam, corn and cassava starches (6% total solids) and related to microstructural characteristics. Maximum limits of 60% yam starch and 70% corn starch and minimum level of 30% cassava starch were fixed to minimize syneresis under storage. Hardness, adhesiveness and gumminess increased with the proportion of corn starch in the blends. The lowest values of hardness corresponded to the blends containing higher proportions of cassava starch, that has the lowest amylose content. Corn starch was the component that less contributed to cohesiveness. The characteristic high cohesiveness of cassava starch pastes (related to its higher amylopectin content) was reduced when it was mixed in adequate proportions with yam and/or corn starches. Gels containing only yam starch presented syneresis values close to 40% after 24° h storage at 4°C; the decrease of the maximum level of yam starch to 60% as well as the inclusion of cassava starch in the blends reduced weight losses. Disadvantages found in gels containing individual starches, such as exudate in yam and corn starch gels, and excessive cohesiveness in cassava starch gels, are minimized improving their possible applications, when blends are used.     

Modification of granular corn starch with 4-alpha-glucanotransferase from Thermotoga maritima: effects on structural and physical properties

ABSTRACT:  Corn starch was converted using α-1,4-glucanotransferase from Thermotoga maritima (TmαGT), a hyperthermophilic bacterium, without inducing gelatinization, and the structural changes and physical properties of the modified starches were investigated. Enzyme modification was induced at 65 °C for 8, 16, or 24 h, and the morphology of the modified starches was observed with light and scanning electron microscopy. Granule integrity was mostly maintained after enzyme treatment, although some granules were partially fragmented as evidenced by enlarged surface pores and some cracks. The modified starches had lower apparent amylose levels than raw starch. The molecular weights of amylose and amylopectin molecules in the treated starches were lower than those of raw starch, and the amount of branched molecules, which had much lower molecular weights, also increased in the treated starches. The chain-length distribution of amylopectin showed an increased number of shorter branched chains. The modified starches showed a wider melting temperature range and a lower melting enthalpy than that of raw starch. The X-ray diffraction pattern of the modified starches showed typical A-type starch peaks, but the relative crystallinities were lower than that of raw starch. The solubility and paste clarity of the modified starches were much higher than those of raw starch. The modified starch gels maintained their rigidity over the whole frequency range tested and showed thermoreversibility between 4 and 75 °C. These results suggest that TmαGT can be used to produce granular corn starch, which contains amylose and amylopectin having lower molecular weights and a thermoreversible gelation property.     

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.     

Characterization of amorphous granular starches prepared by high hydrostatic pressure (HHP)

Amorphous granular starches (AGS) and non-granular amorphous starches (non-AGS) of corn, tapioca and rice were prepared using high hydrostatic pressure (HHP) treatment with ethanol and water washing, respectively and their physicochemical properties were investigated. Water holding capacity and apparent viscosity of AGS and non-AGS were higher than those of native one in all starches. In RVA pasting properties, AGS and non-AGS showed higher pasting temperature and lower peak viscosity than those of native one. Furthermore, non-AGS showed distinctively lower peak viscosity compared to that of AGS possibly due to its non-granular structure. Apparent viscosity of non-AGS revealed relatively lower than commercial pre-gelatinized starch because of heat and pressure-induced gelatinization. Maintaining granular structure in HHP treated pre-gelatinized starch provide a distinctive physicochemical characteristics compared to native starch and preparation of gelatinized starch with different gelatinization and washing methods could cause big differences in their physicochemical properties.     

韧化处理对不同玉米淀粉理化特性的影响

以不同直/支链比例的普通玉米淀粉和蜡质玉米淀粉为材料,在40、50、60℃进行韧化处理,研究韧化处理对玉米淀粉理化特性的影响。结果表明：韧化处理的两种玉米淀粉颗粒形貌有较小变化。韧化处理后,两种淀粉的溶解度和膨胀度随着处理温度的升高而降低;所有韧化处理过的玉米淀粉黏度低于原淀粉,起糊温度高于原淀粉;韧化处理后淀粉的糊化温度升高,热焓变化不大。     

改性玉米淀粉的物理化学研究

对天然玉米淀粉和五种化学改性玉米淀粉的糖化性质进行了比较。改性玉米淀粉包括下列五种,磷酸淀粉,交联磷酸淀粉,醋酸淀粉A,醋酸淀粉B和羟丙基淀粉。使用差热扫描量热计测定了糊化的热力学参数,同时用显微镜观察了糊化过程。研究表明,五种改性玉米淀粉的糊化热都比天然的玉米淀粉小,测量冷的淀粉糊的流动性质表明只有羟丙基玉米淀粉比天然玉米淀粉的帖度高。     

α-Amylolysis of native potato and corn starches - SEM, AFM, nitrogen and iodine sorption investigations

Scanning electron microscopy (SEM), atomic force microscopy (AFM), as well as iodine and nitrogen sorption measurements were applied to investigate potato and corn starch granules surface after an action of Bacillus subtilis α-amylase. The SEM images revealed holes and pits (corn starch) or scratches (potato starch) on the surface of modified granules. These results were confirmed by AFM investigation which showed the presence of depressions of approximately 121 nm in diameter. Structure of the surface was not uniform. It consisted of small particles, amylopectin blocklets, of approximately 20 nm in diameter. They became more distinctive after α-amylolysis. Values of iodine binding capacity (IBC) obtained for hydrolyzed granules were lower than for native ones which indicated that the amylose and amylopectin chains building their surface were shortened. Specific surface area, volume and average diameter of mesopores increased for both starches after α-amylolysis.     

Influence of modified starches on properties of gluten-free dough and bread. Part II: Quality and staling of gluten-free bread

The aim of the study was to check the quality of gluten-free bread produced basing on the recipes, in which part of native starch was replaced with high amylose corn starch (HACS), acetylated distarch adipate (ADA), and hydroxypropyl distarch phosphate (HDP). The application 10 or 15% of chemically modified starches (HDP, ADA) caused the increase in volume of the obtained gluten-free loaves. The changes were accompanied by a decrease of average cell size, and an increase in their number. Due to the addition of modified starch crumb structure became more elastic, which was revealed in the results of stress relaxation. A slight decrease in hardness and chewiness of the crumb was also observed on the day of baking, and its extent depended on the level of modified starch, and was a little more pronounced in case of starch adipate. In comparison to the chemically modified starches, HACS deteriorated structural and mechanical properties of the crumb, which is probably related to their resistance to pasting and divergence in retrogradation pattern, where amylose component is more important than amylopectin.     

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.     

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

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

Effects of sodium dodecyl sulphate and sonication treatment on physicochemical properties of starch

Effects of sodium dodecyl sulphate (SDS) and sonication treatment on physicochemical properties of starch were studied on four types of starch, namely, corn, potato, mung bean, and sago. The SDS and sonication treatments caused a significant reduction of protein content for all the starches. The SDS treatment did not cause apparent damage on granular structure but sonication appeared to induce changes such as rough surface and fine fissures on starch granules. The combination of SDS and sonication increased amylose content for all starches. This could be attributed to the removal of surface protein by SDS and structural weakening by sonication which facilitated amylose leaching from swollen starch granule. The X-ray pattern for all starches remained unchanged after SDS treatment, suggesting no complexation of amylose–SDS had occurred. Combined SDS-sonication treatment increased swelling and solubility of corn, mung bean, and potato starch. The treated starches showed significant increase in peak viscosity with reduction in pasting temperature, except for potato starch. Results of the present study indicate the possibilities of exploring SDS and sonication treatments for starch modifications.     

Physicochemical characterization of chemically modified corn starches related to rheological behavior,retrogradation and film forming capacity

An integral approach of chemical modification effects on physicochemical and functional properties of corn starch was performed using different and complementary techniques. Acetylated, acetylated crosslinked, hydroxypropylated crosslinked, and acid modified corn starches were analyzed. Substitution and dual modification reduced significantly amylose concentration. Chemical modification decreased granules crystallinity degree. A significant increase in swelling power was observed in substituted and dual modified starches at 90 °C, besides these treatments decreased gelatinization temperature and enthalpy. Acid modified starch pastes showed a Newtonian behavior while substituted and dual modified ones exhibited a viscoelastic response. Dynamic rheological properties of modified starch pastes were not affected by post gelatinization time while native starch pastes developed a more rigid structure during storage. Retrogradation of substituted starch pastes after 12 days at 4 °C was reduced, since syneresis degree and hardness increase were significantly lower than those of native pastes. It was demonstrated that only substituted and native starches exhibited film forming capacity.     

Thermal,rheological, and mechanical properties of normal corn and potato starch blends

Native corn and potato starches were mixed in different proportions. Blends presented similar values to potato starch at onset temperature and at ending temperature to corn starch. CS20PS80 blend had the highest values for hardness between blends due to the formation of a three-dimensional network with corn starch granules that act as composite material. Some blends exhibited higher recovery viscosity than native starches, possibly due to interactions. Gelatinization temperature, swelling power, phosphorous content, granule size, and x-ray pattern played an important role in the resulting properties, however, the amylose content did not show influence due to both starches having a similar content.     

Effect of high hydrostatic pressure on modified noncrystalline granular starch of starches with different granular type and amylase content

Waxy corn (A-type pattern, amylopectin with trace amounts of amylase) and tapioca starch (C-type pattern, 17 g/100 g amylase content) were modified by High Hydrostatic Pressure (HHP) to produce noncrystalline granular (NCG) starch, respectively. The changes in the starch structure and properties occurring upon modified NCG after high-pressure treatment (300–600 MPa/30 min) were analyzed using polarized light microscopy (LM), differential scanning calorimetry (DSC), particle size distribution and scanning electronic microscopy (SEM). The resulting modified NCG starch took place when the 50 g/100 g starch suspension was treated under 450 MPa for the waxy corn starch with swelling degree of 57.07%, whereas 600 MPa for the tapioca starch with restricted starch swelling degree of 16.48%, indicating the stabilization effect of amylase. Also, they had reduced gelatinization temperatures, and lower pasting viscosities, which suggested that HHP had an effect on the physicochemical properties of native starch by destabilization, hydration and swelling.