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.     

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.     

A Study of Some Physicochemical Properties of High‐Crystalline Tapioca Starch

Tapioca starch was partially hydrolyzed in hydrochloric acid solution at room temperature for various lengths of time to obtain high‐crystalline starches. RVA viscoamylograms of acid‐modified starches demonstrated a very low viscosity as compared to that of native tapioca starch. The relative crystallinity of native and acid‐modified tapioca starches were measured by X‐ray diffraction ranging from 39.53% to 57.75%. The native and acid‐modified tapioca starches were compressed into tablets using various compression forces. The % relative crystallinity of starch increased with the increase in hydrolysis time and the crushing strength of the tablet was also increased in line with the crystallinity while the amylose content decreased when the crystallinity increased. These results suggested that the erosion of amylose might cause the rearrangement of starch structure into a new more tightly packed form, which provided the higher crushing strength for the tablets.     

Characterization and Utilization of Acid‐modified Rice Starches for Use in Pharmaceutical Tablet Compression

Acid modified, agglomerated starches offer specific advantages as fillers in production of pharmaceutical tablets. Spray drying can improve processing of tablet mixtures significantly. In order to investigate prerequisites in utilization of rice starch, non‐waxy and waxy types were partially hydrolyzed in 6% (w/v) HCl solution at room temperature for varied length of time to obtain rice starches with increased crystallinity (so‐called crystalline rice starches). Scanning electron micrographs of native and highly crystalline starches were used to study the morphological changes and to suggest the mode of acid attack during hydrolysis. Exo‐corrosion distributed over the surface of acid‐modified waxy rice starch (AWRS) was observed after 192 h of hydrolysis. In contrast, the surface of acid‐modified rice starch (ARS) remained unchanged at 192 h of acid hydrolysis. The amylose content and the median particle size (diameter) were reduced with increasing hydrolysis time. It was found by X‐ray diffraction that the relative crystallinity of acid‐modified starches at >95% relative humidity was clearly increased with prolonged hydrolysis time. For studying tablet properties spherical agglomerates of the native and acid modified starches were directly compressed at 4 kN to obtain tablets. Crushing strength and disintegration time of tablets increased with relative crystallinity. In contrast, tablet friability was reduced. Concerning tablet functionality, the crystalline starches were positioned in overlapping ranges between the common commercial tablet fillers (microcrystalline cellulose, pregelatinized starch and lactose, respectively).     

Ordered structure and thermal property of acid-modified high-amylose rice starch

High-amylose cereal starch has a great benefit on human health. Acid modification is very helpful for application of high-amylose starch in food and non-food industries. In this study, the ordered structure of acid-modified high-amylose rice starch was investigated by GPC, HPAEC, ¹³C CP/MAS NMR and XRD. Acid preferentially degraded the amylose, then A chain and short B chain of amylopectin. Relative double helix content and crystallinity both initially increased sharply and then progressively with acid hydrolysis. The relative crystallinity of starches obtained from ¹³C CP/MAS NMR was higher than that from XRD. The onset gelatinisation temperature decreased, while the peak and conclusion temperatures increased with increasing hydrolysis time. The endothermic value initially increased and then decreased with acid hydrolysis. The swelling power decreased while solubility increased after acid hydrolysis. These results add to our understanding of the effect of acid hydrolysis on the high-amylose rice starch.     

酸解对不同链/支比含量玉米淀粉特性的影响

以4种不同链/支比含量的玉米淀粉为原料,酸解处理不同时间,以酸解玉米淀粉的形貌特性、冻融稳定性、膨胀度、溶解度、晶体性质为指标衡量不同酸解时间对玉米淀粉结构性质的影响。结果表明:4种玉米淀粉酸水解程度的顺序为:蜡质玉米普通玉米淀粉G50G80。酸解后,同品种的4种玉米淀粉的析水率随着酸解天数的增加而增加;溶解度增加,膨胀度降低。酸解并未改变淀粉的晶型,随着酸解时间的延长,蜡质玉米淀粉和普通玉米的相对结晶度先增大后保持不变,G50和G80的相对结晶度随着酸解时间的增加而增大。表明酸解对低直链淀粉(蜡质玉米淀粉和普通玉米淀粉)的结构、性能影响最大。     

Effect of Acid‐Methanol Treatment on the Physicochemical and Structural Characteristics of Cassava and Maize Starches

Physicochemical, structural and morphological characteristics of maize and cassava starches treated with 0.36% concentrated HCl in anhydrous methanol at 54ºC for 1–8 h were analyzed and compared. Average yield of modified starch was about 97% for both starches. The solubility of the acid‐methanol treated starches increased with temperature and after 3 h of treatment reached 93% for maize starch and 97% for cassava starch at 95ºC. After 8 h of treatment, the average size of the cassava starch granules decreased from 14.9 to 11.1 µm. The action of acid‐methanol on the maize starch was more subtle, reducing the granule average size from 11.8 to 11.3 µm. Scanning electron micrographs showed that the granule surfaces were rough and exfoliated after treatment suggesting exocorrosion that was more evident for cassava starch. From GPC, it was noted that amylose and amylopectin were partially degraded during treatment. Starch crystallinity gradually increased with duration of treatment. The amylose content decreased from 21.4 to 18.8% and from 26.3 to 23.0% and the intrinsic viscosity was reduced from 2.36 to 0.21 and from 1.85 to 0.04 for cassava and maize starches, respectively. The gelatinization temperatures increased whereas pasting viscosities decreased with reaction time, especially for cassava starch. These results suggested that the attack of acid‐methanol, which was more effective on cassava starch granules, occurred preferentially in the amorphous areas located in the granule periphery and composed of amylose and amylopectin.     

Pea Starch Annealing: New Insights

Three different pea starches were annealed in excess water at 45 °C for 24 and 72 h, and the changes in their structure and functionality were determined. Annealing resulted in slightly irreversible swelling with leaching of some amylose molecules, which was accompanied by small changes in granular morphology and relative crystallinity, but significant changes in functionality such as decreased swelling power and starch solubility and increased thermal transition temperatures, enthalpy changes, pasting viscosities and in vitro digestibility. Annealing led to an increase in proportion of B-type polymorphs within C-type pea starches, which was explained as being due to a polymorphic transition from A to B. Annealing mainly acts on the amorphous regions of starch granules, leading to amylose leaching. The removal of amylose molecules can reduce the long-range forces within the granule and thereby weakening the overall granule structure and leading to significant changes to functional properties. This study showed that annealing is a mild but important physical modification of starch, which can be used as a pretreatment technique to tailor the starch functionality for specific industrial application.     

酸解时间对大米淀粉结构性质的影响

以4种不同直链淀粉含量的大米淀粉(0%的优糯3号、10.90%的稻花灿、21.03%的聚两优、28.46%的华优香占)为原料,酸解处理不同时间,以酸解大米淀粉的酸解率、颗粒形貌、结晶性质、溶解度的变化为指标衡量不同酸解时间对大米淀粉结构及性质的影响。结果表明,不同直链淀粉含量的大米淀粉具有不同的耐酸性,酸解时间对不同直链淀粉含量大米淀粉的结构和性质有着不同的影响。大米淀粉酸解率与直链淀粉含量成反比,优糯3号为50%而华优香占仅为30%;所有淀粉颗粒在酸解后均产生一定程度的破碎,偏光十字变形直至消失,酸解相同时间,直链淀粉含量高的大米淀粉破碎率低;酸解未改变淀粉的晶型,仍为A晶型;随着酸解时间的延长相对结晶度增加;淀粉的溶解度随着酸解时间的增加而增大。     

底物浓度对三种不同来源的脱支重结晶淀粉的影响

以三种不同来源淀粉（普通玉米淀粉、木薯淀粉、豌豆淀粉）为研究对象,对样品进行脱支重结晶处理,分析底物浓度对三类脱支重结晶淀粉的形态、大小、结晶结构、热性质和凝胶性质等功能特性的影响。结果表明,原淀粉表面光滑无孔洞,脱支重结晶淀粉完整性均被破坏且受浓度影响不明显;粒径随底物浓度增加而增大;相对结晶度随底物浓度增加呈先减小后增大的趋势;与原淀粉相比,三种改性淀粉的储能模量（G'）高于损耗模量（G"）,凝胶强度增强,热稳定性和有序度（DO）均下降而双螺旋度（DD）均上升。改性玉米淀粉和木薯淀粉在较低底物浓度（6%、10%）表现出较弱的粘弹性,而豌豆淀粉在中等底物浓度（10%、14%）表现为较高的粘弹性;DD值随底物浓度增加而减小（底物浓度为18%样品除外）;热稳定性随底物浓度增大有所改善,但仍低于原淀粉。由此可见,调节底物浓度可以选择性地获取理想的脱支重结晶淀粉,这将为不同品种淀粉的综合利用提供思路。     

Production and physicochemical properties of resistant starch from hydrolysed wrinkled pea starch

The content and physicochemical properties of resistant starches (RS) from wrinkled pea starch obtained by different molecular mass reduction processes were evaluated. Native and gelatinised starches were submitted to acid hydrolysis (2 m HCl for 2.5 h) or enzymic hydrolysis (pullulanase, 40 U g^?1 for 10 h), followed by hydrothermal treatment (autoclaving at 121 °C for 30 min), refrigeration (4 °C for 24 h) and lyophilisation. Native starch showed RS and total dietary fibre contents of 39.8% and 14.3%, respectively, while processed ones showed values from 38.5% to 54.6% and from 22.9% to 37.1%, respectively. From these, the highest contents were among acid‐modified starches. Processed starches showed endotherms between 144 and 166 °C, owing to the amylose retrogradation. Native and processed starches showed low viscosity, which is inversely proportional to the RS concentration in samples. The heat treatment promoted an increase in the water absorption index. The pea starch is a good source for obtaining resistant starch by acid hydrolysis.     

Characterization of Pea Starches in the Presence of Alkali and Borax

Refined field pea (Pisum sativum L.) starches were prepared from air‐classified pea starch by washing or from whole pea by wet milling, and analyzed for their physicochemical and pasting characteristics in the presence of alkali and borax. Commercial corn and high amylose corn starches were included in the study for comparative purposes. The two pea starches exhibited similar physicochemical characteristics. Amylose content markedly influenced pasting and other characteristics of the corn starches. Pea starch and high amylose corn starch exhibited little viscosity development during pasting in deionized water. The presence of alkali or borax significantly altered the peak viscosities and cold paste stabilities of all four starches in a concentration dependent manner. Alkali and borax increased peak and cold paste viscosity and reduced syneresis in all cases.     

Lactic acid assisted wet fractionation of field pea (Pisum sativum L.) flour

The use of lactic acid (LA) in the isolation of starch from field pea (Pisum sativum L.) flour was investigated. The yield, purity, morphology, and the physicochemical properties (color, swelling, pasting and gelatinization characteristics, X‐ray diffraction pattern, and crystallinity) of the starches isolated with and without LA were determined. When compared to the control (0% LA), addition of LA at concentrations ranged from 0.5 to 7.0% v/v significantly increased the purity of the isolated starches up to 4% w/w and reduced the residual protein content by 6% w/w. The resistant starch and apparent amylose contents of the isolated starches using LA were significantly higher (up to 25 and 42.5%, w/w, respectively). Furthermore, the starches produced by LA assisted extraction showed significantly lower swelling factor and pasting viscosities, but generally insignificant changes were observed in the gelatinization parameters as compared to that of control. Marginal differences were observed in the X‐ray diffractograms between control and the LA processed starches. However, the relative crystallinity of LA processed starches was significantly higher than the control. The present study revealed that the use of LA in pea starch extraction show benefits in terms of starch purity, brightness, resistance to amylolysis, and apparent amylose content.     

Effect of acid‐ethanol treatment followed by ball milling on structural and physicochemical characteristics of cassava starch

Structural and physicochemical characteristics of cassava starch treated with 0.36% HCl in anhydrous ethanol during 1 and 12 h at 30, 40, and 50°C followed by ball milling for 1 h were analyzed. Average yield of acid‐ethanol starches reached 98% independent of the treatment conditions. Solubility of acid‐ethanol starches increased with reaction temperature and time, but it did not change after ball milling. Granule average size reduced with chemical treatment from 25.2 to 20.0 µm after 12 h at 50°C. Ball milling decreased the granule average diameter of the native starch and those chemically treated at 30°C/1 h or 40°C/1 h, but it did not alter the starches treated for 12 h, independent of temperature. From scanning electron microscopy (SEM), starch granules presented round shape and after modification at 50°C/12 h, before and after ball milling, showed a rough and exfoliated surface. Some granules were deformed, suggesting partial gelatinization that was more intense after milling. Starch crystallinity increased as temperature and time of chemical treatment were increased, while amylose content, intrinsic, and pasting viscosities decreased. Gelatinization temperatures increased for all chemical starches. The findings can be related to the preferential destruction of amorphous areas in the granules, which are composed of amylose and amylopectin. After ball milling, the starch crystallinity decreased, amylose content, intrinsic, and pasting viscosities kept unchanged and gelatinization temperatures and enthalpy reduced. Ball milling on native and chemical starches caused the increase of amorphous areas with consequent weakening and decreasing of crystalline areas by breaking of hydrogen bonds within the granules.     

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.     

Effect of acid treatment on the physicochemical and structural characteristics of starches from different botanical sources

Starch and starch derivatives (maltodextrins) are used as encapsulating materials. Starch for use as encapsulating material could be subjected to mild acid treatment. However, the granule size and organization of starch components (AM and AP) play an important role in the acid treatment. The aim of this research was to produce modified starch that might be used as encapsulate material, applying moderate acid‐treatment with 3 N sulphuric acid in a ratio 1:5 w/v for 3 h at 60°C, in starches from different granule size, evaluating their morphological, physicochemical, and structural features. Acid treatment has an effect in the AM content and the outcome was higher in starch with larger granule size. Bimodal granule size distribution was found in acid‐treated rice and maize starches. Erosion and exo‐corrosion were observed in acid‐treated starches with SEM. The XRD pattern did not change with the acid treatment, the native and acid‐treated samples showed similar crystallinity values, except rice starch. The branching degree was higher for modified potato starch, showing higher branching points, modified starches had shorter chains with increased A‐chains, and decreased B3+ chains, and the effect was higher in cereal starches; modified starches had a higher degree of retrogradation and they did not show pasting properties. The internal organization given by the granule size is an important parameter in the acid treatment of starches as it affected their physicochemical and structural features, and in the end, their functionality as encapsulate agent.     

Influence of Heat‐Moisture Treatment and Acid Modifications on Physicochemical,Rheological, Thermal and Morphological Characteristics of Indian Water Chestnut (Trapa natans) Starch and its Application in Biodegradable Films

Water chestnut starch was subjected to acid modification and heat‐moisture treatment. Hydrochloric acid was used for acid modification at three different concentrations (0.25 M, 0.5 M and 1 M) for 2 h. Modifications did not alter the granule morphology. Heat‐moisture treatment (HMT) resulted in slight reduction in the granular size of the starch granules. Acid modification lowered the amylose content, swelling power, water‐ and oil‐binding capacity but improved the solubility of starch to a considerable level. Light transmittance of acid‐modified (AM) starches improved significantly. A significant reduction in peak, trough, final and setback viscosity was observed by acid‐thinning. In case of heat‐moisture treated starch the final viscosity (F_v) was found to be even higher than the peak viscosity (P_v). Native water chestnut starch exhibited a lower onset temperature (T_o) and peak temperature (T_p) of gelatinization than the corresponding acid‐treated starches. Starch films prepared from native starch exhibited excellent pliability, whereas those prepared from AM and HMT starches showed good tensile strength. Starch films prepared from acid‐treated starches provided better puncture and tensile strength.     

Structure and Viscoelastic Properties of Starches Separated from Different Legumes

A comparison between the morphological, structural, thermal and viscoelastic properties of starches separated from pigeon pea, chickpea, field pea, kidney bean and blackgram was made. The shape of the starch granules in the different legumes varied from oval to elliptical or spherical. X-ray diffraction of the legume starches indicated a typical C-pattern (mixture of A- and B-type). Granules of blackgram and pigeon pea starch had a higher degree of crystallinity than those of field pea and kidney bean starches. Apparent amylose content of field pea, kidney bean, chickpea, blackgram and pigeon pea starch was 37.9%, 36.0%, 34.4-35.5%, 32.9-35.6% and 31.8%, respectively. Distribution of isoamylase-branched materials among the starches revealed that the proportions of long and short side chains of amylopectin ranged between 13.6-18.5% and 41.7-46.5%, respectively. Field pea and kidney bean starch had the highest apparent amylose content and the lowest amount of long side chains of amylopectin, respectively. Blackgram and pigeon pea starch possessed higher proportions of both long and short side chains of amylopectin than field pea and chickpea starches. The onset, peak and conclusion temperatures of gelatinization (T_o T_p and T_c, respectively) were determined by differential scanning calorimetry. T_o and T_c ranged from 59.3 to 77.3°C, 66.8 to 79.6°C, 55.4 to 67.6°C and 68.3 to 69.3°C, respectively, for chickpea, blackgram, field pea and kidney bean starch. The enthalpy of gelatinization (ΔH_gel) of field pea, kidney bean, chickpea, blackgram and pigeon pea starches was 3.6, 3.0, 2.6-4.2, 1.6-1.7 and 2.6 J/g, respectively. Pastes of blackgram and pigeon pea starches showed lower storage and loss shear moduli G′ than field pea, kidney bean and chickpea starches. The changes in moduli during 10 h at 10°C revealed retrogradation in the order of: field pea> kidney bean> chickpea> blackgram> pigeon pea starch. In blackgram and pigeon pea starches, the lower proportion of amylose plus intermediate fraction and higher proportion of short and long side chains of amylopectin are considered responsible for the higher crystallinity, gelatinization temperature and enthalpy of gelatinization.     

Physicochemical Properties of Field Pea, Pinto and Navy Bean Starches

Legume starches were compared for physicochemical properties that may explain differences in functional properties. Field pea starch had higher amylose, greater swelling power and solubility, and lower pasting temperatures than pinto and navy bean starches. Scanning electron microscopy (SEM) showed that field pea starch had larger, more irregularly shaped granules and more broken large granules than pinto or navy starches. The most starch damage was observed for field pea. Pinto and navy bean starches had greater resistance to swelling at 60°C than field pea indicating a more strongly bonded micellar network. Higher cold paste viscosity was observed for navy bean and field pea.     

The Influence of Acid Hydrolysis of Potato Starch on the Stress-Strain Propoerties of Thermoplastic Starch

Potato starch has been hydrolysed lowering the molecular mass. The influence of starch molecules mass on the mechanical properties of thermoplastic starch has been investigated. Acid hydrolysis was performed with hydrochloric acid in various concentrations and time spans. Acid hydrolysis of the granular potato starch decreased both the molecular mass of amylose and amylopectin. The thermoplastic materials have been made by extrusion processing of the various starches with fixed amounts of water and glycerol. The stress-strain properties showed to be influenced by molecular mass. The materials were rubbery at 20°C and 60% relative humidity. Although the tensile stress did not change significantly, the elastic modulus increased with an decrease in molecular mass. This increase was explained by differences in starch structure and morphology. The higher of the low molecular mass materials could result in a more rapid starch structural ordering. The elongation and tearing energy increased with incrasing molecular mass. Theses effects were explained by the higher amylose chain length and amylopectin endgroups chain length resulting in a more entangled polymer matrix.