Influence of Amylose-Amylopectin Ratio on Properties of Extruded Starch Plastic Sheets

Abstract

Starch plastic sheets were prepared by extrusion processing of mixtures of granular high-amylopectin and high-amylose starches in the presence of glycerol and water as plasticizers. Amylose content varied between 0 and 70% (w/w). Structural characterization and determination of the mechanical properties of the sheets were performed after aging the materials between 40–65% relative humidity for 2 and 35 weeks and at 90% relative humidity for two weeks. The materials were semicrystalline and viscoelastic. The materials were described as complex heterogeneous multiphase materials. They consisted of amorphous and crystalline phases of amylose and amylopectin as well as granular structures and domains of amylose, amylopectin and amylose-amylopectin helices. Single-helical type crystallinity was formed solely by amylose directly after processing while B-type crystallinity was rapidly formed in amylose-rich materials and slowly during aging of amylopectin-rich materials.

The stress-strain and stress-relaxation properties were related to differences in amylose content, degree of crystallization and water content. The amorphous amylopectin rich materials were flexible and soft but showed an increase in stiffness and a decrease in elongation due to crystallization. Amylopectin-rich materials showed unfavorable relaxation, shrinkage and cracking during aging. The materials rich in amylopectin were sensitive to water content while the amylose-rich materials were not sensitive to water in the range of 9–13% (w/w). Stress-strain relaxation behaviors of the materials were dependent on starch structure and on experimental conditions such as strain rate and extension by which the ratio of elastic and viscous response were varied. An increase in relaxation times was found with increasing amylose content and water content for the materials with solely amylose crystallinity.     

Flocculation and binding properties of highly substituted cationic starches

The flocculation properties of a series of cationic starches with the substitution degree of 0.25–1.54 in kaolin dispersions were studied, and the dependence of the kaolin retention with fiber on the surface content of starch, degree of its substitution, and amylose: amylopectin ratio was evaluated.     

Structure of starch-bentonite gels

Mixed gels of starch and bentonite are investigated in the interval 0.056–0.089 of total solids/water ratio and 0-100% starch in the solids. The bentonite was a sodium calcium bentonite with a Na/Ca ratio of 1.76. In water it forms gels consisting of a network of band-type structures. Starch forms gels through hydrogen bonds between granules and/or amylose and amylopectin present on the external surfaces of granules and/or in fully stretched form. Mixed gels of bentonite and starch were obtained by adding corn starch granules to the already formed bentonite gels and heating the mixture above the Kofler gelatinization temperature. Amylose and amylopectin were adsorbed on strands of band-type structures of mont-morillonite lamellae. Starch gellation, e.g. diffusion of amylose out of the granule, was facilitated in the presence of bentonite. On the other hand, the presence of starch favored delamination of the montmorillonite particle into thinner lamellae. Maximum gelatinization and polymer adsorption were observed for gels with 20% starch and 80% bentonite. Montmorillonite networks formed the continuous phase for 0-80% starch. At higher starch concentrations, montmorillonite flakes were dispersed within the polymer network. Increase in the water content of the gels caused segregation of the bentonite and starch.     

Branching ratios of starch via proton nuclear magnetic resonance and their use in determining amylose/amylopectin content: Evidence for three types of amylopectin

The branching (α-1,4)/(α-1,6) ratio of starch from a number of sources can be quickly and accurately determined by proton nuclear magnetic resonance (NMR). This NMR ratio, with standard ratios for isolated amylose and amylopectin, can then be used to determine the amylose/amylopectin content of starches. In the course of determining the amylose/amylopectin content of various starches, it was discovered that two different types of amylopectin standards were required to obtain results comparable to those obtained from iodine-binding amylose determinations. These two types were a waxy amylopectin, with a high level of branching, and a potato amylopectin, with a lower level of branching. A third type of amylopectin, with a still lower level of branching, is apparently present in high amylose cornstarches, leading to the conclusion that starches with higher amylose contents generally contain amylopectin with a lower level of branching. The three amylopectin types are referred to as amylopectin I, II and III, with the higher numeral coinciding with higher branching (α-1,4)/(α-1,6) ratio, or less branching.     

Preparation of Polyvinyl Pyrrolidone-Based Hydrogels by Radiation-Induced Crosslinking with Potential Application as Wound Dressing

Polyvinyl pyrrolidone/polyethylene glycol hydrogels (PVP/PEG) and PVP/PEG/Starch were prepared by irradiating the mixtures of aqueous solutions of PVP, PEG and starch with electron beam at different doses. Their properties were evaluated to identify their usability in wound dressing applications. The physical properties of the prepared hydrogels, such as gel content, swelling, water content and degree of water evaporation with varying composition and irradiation dose were examined to evaluate the usefulness of the hydrogels for wound dressing. The gel content increases with increasing PVP concentration due to increased crosslink density, and decreases with increasing the PEG concentration. PEG seems to act not only as plasticizer but also to modify the gel properties as gelation% and maximum swelling. Mechanical experiments were conducted for both PVP/PEG and PVP/PEG/Starch. The adding of PEG and starch to PVP significantly improves elongation and tensile strength of prepared hydrogels, respectively. The crystallinity of both prepared hydrogels was investigated with varying their components, XRD studies indicated that the crystallinity in the gel was mainly due to PVP and mainly decreased with enhanced starch content. The prepared hydrogels had sufficient strength to be used as wound dressing and could be considered as a good barrier against microbes.     

Rapid analysis of starch, amylose and amylopectin by high-performance size-exclusion chromatography

Starch components, amylose and amylopectin, were analyzed by high-performance size-exclusion chromatography. These two-components were separated using a two-column system (E-Linear and E-1000) and dimethyl sulphoxide as the mobile phase. The void volume (V0 = 2.22 ml) was measured using tobacco mosaic virus. Column calibration was accomplished with dextrans of known average molecular weight (Mw range = 10,100-2,000,000). The elution volume of amylopectin (Ve = 2.5 ml) indicated that this starch component was fractionated on the column system despite its very large molecular size. Standard curves were prepared from various mixtures of purified corn and wheat amylose and amylopectin. From the linear relationships obtained, the percentages of both components in corn and wheat starches were determined. The method developed proved useful to monitor the purity of amylose and amylopectin preparations, and to estimate rapidly the amylose:amylopectin ratio of starch samples.     

Structure of starches extracted from near-isogenic wheat lines

High-sensitivity differential scanning calorimetry (HSDSC) and small-angle X-ray scattering (SAXS) were used to investigate the structural characteristics of starch granules with different amylose content extracted from near-isogenic wheat lines with different combinations of active granule-bound starch synthase (GBSS I) isoforms. Paracrystalline diffraction model, ‘two-state’ model of starch melting and other physico-chemical approaches were used to estimate the sizes of amylopectin clusters, the thicknesses of crystalline lamellae and the structure of amylopectin defects for investigated wheat starches. The joint analysis of SAXS and DSC data has shown that the size of amylopectin cluster, the thickness of crystalline lamellae and the structure of amylopectin defects do not depend on the differences in combinations of active GBSS I isozymes. The data obtained supposed that the amylopectin cluster size and the thickness of crystalline lamellae are, generally, the universal structural parameters for wheat starches. Additionally, the data obtained suggest that increase of amylose content is accompanied by accumulation of both amylose tie-chains, located as defects in crystalline lamellae, and amylose chains oriented transversely to the lamella stack within amorphous lamellae. Disordered ends of amylopectin double helices and/or pre-existing double helices not participating in formation of crystals are considered as amylopectin defects arranged in crystalline lamellae. The relationship between structure of wheat starches extracted from near-isogenic lines and their thermodynamic properties was recognized.     

Effect of the grafting ratio of poly(N‐isopropylacrylamide) on thermally responsive polymer brush surfaces

Four kinds of poly(N‐isopropylacrylamide)‐grafted silicas with different grafting ratios and the same grafting density were prepared by atom transfer radical polymerization. The chemical groups in the stationary phase was verified by FTIR spectroscopy, and the content of elements was measured by elemental analysis. The grafting ratio of thermoresponsive chromatographic materials was measured by thermogravimetric analysis and was 2.36–21.10% mg/m². The retention behaviors of the stationary phase with different grafting ratios were evaluated by separating five kinds of steroids and ten kinds of different hydrophobic properties compounds. With the increase in grafting ratio, the retention time of analytes was prolonged in high‐performance liquid chromatography. The results showed that grafting ratio had a significant influence on the separation effect under the same grafting density. And the optimal grafting ratio of poly(N‐isopropylacrylamide) was 5.81–13.15%.     

Flocculation and coalescence of droplets in oil-in-water emulsions formed with highly hydrolysed whey proteins as influenced by starch

The effects of added unmodified amylopectin starch, modified amylopectin starch and amylose starch on the formation and properties of emulsions (4 wt.% corn oil) made with an extensively hydrolysed commercial whey protein (WPH) product under a range of conditions were examined. The rate of coalescence was calculated based on the changes in the droplet size of the emulsions during storage at 20 degrees C. The rates of creaming and coalescence in emulsions containing amylopectin starches were enhanced with increasing concentration of the starches during storage for up to 7 days. At a given starch concentration, the rate of coalescence was higher in the emulsions containing modified amylopectin starch than in those containing unmodified amylopectin starch, whereas it was lowest in the emulsions containing amylose starch. All emulsions containing unmodified and modified amylopectin starches showed flocculation of oil droplets by a depletion mechanism. However, flocculation was not observed in the emulsions containing amylose starch. The extent of flocculation was considered to correlate with the rate of coalescence of oil droplets. The different rates of coalescence could be explained on the basis of the strength of the depletion potential, which was dependent on the molecular weight and the radius of gyration of the starches. At high levels of starch addition (>1.5%), the rate of coalescence decreased gradually, apparently because of the high viscosity of the aqueous phase caused by the starch.     

Rheological properties of native and hydrolyzed starches in dependence on composition and concentration

The structure formation of starch polysaccharides in aqueous solutions is determined by the ratio of amylose to amylopectin and the molecular properties of these components. Our research is focused on establishing defined correlations between composition, molecular structure in diluted solutions and rheological properties of concentrated aqueous starch polysaccharide solutions. Diluted solutions were investigated by size exclusion chromatography with multi angle laser light scattering detector. Measurements of concentrated aqueous solutions were carried out by a Bohlin cs-rheometer with programmed stress using a cone-plate geometry of 40 mm diameter and a cone angle of 4 degrees. Gels were characterized by oscillatory measurements taking into account the frequency dependence of the storage and loss moduli and the influence of a stress sweep on the moduli. The concentration dependence was investigated with starches of potato, wheat, maize and wrinkled pea. Starches with quite similar amylose content as from potato, wheat and maize, show different behavior in rheological properties. Further differences in structure formation were obtained by enzymatic hydrolysis of potato and wheat starch with bacterial α-amylase. The hydrolyzing conditions were chosen such that the degradation led to molecular weights between 5*10⁵ and 10⁷ g/mol. Detailed information about molecular composition was obtained by fractionation of degraded starches. The amylopectin was found to be degraded more strongly than the contained amylose. In comparison to native starch polysaccharide fractions the amylopectin hinders the gelation process in dependence on its molecular weight distribution and the length of the outer chains.     

Baked hydrogel from corn starch and chitosan blends cross‐linked by citric acid: Preparation and properties

Citric acid (CA)–modified hydrogels from corn starch and chitosan were synthesized using a semidry condition. This strategy has great benefits of friendly environment because of the absence of organic solvents and compatible with the industrial process. The hydrogel blends were prepared with starch/chitosan ratios of 75/25, 50/50, and 25/75. The thermal stability, morphology, water absorption, weight loss in water, and methylene blue absorption were determined. Multi‐carboxyl structure of CA could result in a chemical cross‐linking reaction between starch, chitosan, and CA. The cross‐linking reaction between free hydroxyl groups of starch, amino groups of chitosan, and carboxyl groups of CA has been confirmed by attenuated total reflectance infrared (ATR‐IR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) analysis. The water absorption properties of CA‐modified hydrogel blends were increased significantly compared with the native starch and chitosan. Moreover, the hydrogel blends modified with CA showed good water resistance and gel content. The morphology study confirmed the complete chemical cross‐linking and porous structure of hydrogel blends. The hydrogel blend with the starch/chitosan ratio of 50/50 presented powerful absorption of methylene blue as well as chemical cross‐linking reaction and dense structure. In sum, the hydrogel blend comprising 50% starch and 50% chitosan has the potential to be applied for water maintaining at large areas, for example, in agriculture.     

Blood compatibility of novel poly(gamma-glutamic acid)/polyvinyl alcohol hydrogels

Sodium poly(gamma-glutamic acid) (PGA), a water-soluble and biodegradable polypeptide, was reacted with polyvinyl alcohol (PVA) to form hydrogel without any chemical treatment. The gelation occurred probably due to physical cross-linking of polymer chains by interpenetrating hydrogen bonding. From the results of thermal analysis, PGA/PVA exhibited better thermal stability than native PVA. Although the swelling ratio decreased with the increase of PGA content, however, the water resistance and retention were improved. The tensile strength of the PGA/PVA hydrogel membranes was about 15-30% lower than that of the native PVA, whereas the elongation was increased 2.0-2.6 times. The amount of protein adsorbed and platelets adhered on the PGA/PVA membranes were significantly curtailed with increasing PGA content, thereby showing improved blood compatibility. The as-fabricated hydrogels were proven to be non-cytotoxic evaluated in vitro by L-929 fibroblast incubation. Overall results demonstrate that the non-cytotoxic PGA/PVA hydrogels, due to better water resistance, mechanical properties and blood compatibility could be very promising candidates for blood-contacting medical devices.     

Isothermal microcalorimetric studies on starch retrogradation

In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After 10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.The authors thank Eva Qvarnström at the Dept. of Thermochemistry and Eva Tjerneld at the Dept. of Food Technology for valuable practical assistance. Financial support was obtained from the Swedish Council for Forestry and Agricultural Research (SJFR) and the Swedish Farmer's Foundation for Agricultural Research (Stiftelsen Lantbruksforskning).     

Electrosprayed maize starch and its constituents (amylose and amylopectin) nanoparticles

Starch consists of amylose and amylopectin. Properties such as being natural and highly hygroscopic as well as biodegradability have opened a considerable range of applications for amylose, amylopectin and starch. The performance of particles is highly dependent on their size which in turn determines the specific surface area. This work studies the application of electrospraying to fabricate maize starch and its constituents: amylose and amylopectin nanoparticles. This study showed that electrospraying technique is capable of producing amylose, amylopectin and starch nanopowder with an average particle size around 100 nm. FTIR analysis showed no reaction or interaction occurring in amylose, amylopectin and starch nanoparticle compared with their natural form. Basically, lower concentration, lower viscosity and lower surface tension of the electrospraying solution as well as higher nozzle–collector distance, higher voltage and lower feed rate lead to smaller nanoparticle size. Copyright © 2015 John Wiley & Sons, Ltd.     

Assessment of waxy and non-waxy corn and wheat cultivars as starch substrates for ethanol fermentation

The amylose/amylopectin ratio in cereal substrates is one of the parameters affecting starch hydrolysis and fermentation process. Waxy (less than 1 mass % of amylose) starch seems to be suitable for improving the fuel ethanol production. The main aim of this paper was to characterize the fermentation performance of corn and wheat waxy and non-waxy cultivars in terms of simultaneous saccharification and fermentation (SSF) as well as of the separated hydrolysis and fermentation (SHF) type. Two corn (waxy and non-waxy) and two wheat (waxy and non-waxy) cultivars were used for the comparison applying separate enzymatic hydrolysis and fermentation. In the SHF process, the glucose content was higher after saccharification in the waxy corn and wheat compared to that in non-waxy corn and wheat. In the SSF of waxy varieties, the glucose content after the pre-saccharification was also higher than in the non-waxy ones. Although the starch content did not vary significantly, differences in the glucose content after saccharification were observed. The ethanol yield obtained after the distillation of mash varied from 229.2–262.3 L per ton for the SHF fermentation, while it was in the range of 311.5–347.9 L per ton for the SSF process.     

Fabrication of starch blend films with different matrices and their mechanical properties

The objective of the study was to determine the effects of molecular sizes of amylose (AM) and starch granules on the mechanical properties of thermoplastic starch (TPS) blend films. Leached amylose solution from cassava (CS_ AM) and mung bean (MB_AM), and two forms of amylopectin (AP) (granular; g and non-granular; ng) of waxy cassava (WxCS) starch were used. Four types of film matrices were fabricated and all TPS blend films contained same amount of AM and glycerol. Results displayed that molecular weight profiles of starch films and presence of granule remnants significantly controlled the film matrix formation, types of crystal formation, and percent of relative crystallinity (%RC) (p < 0.05). Tensile property of TPS films was controlled by %RC and presence of granule remnants. Percent elongation at break (%E_b) of TPS films increased when the films had a large range of molecular weight distribution (from 5.5 × 10⁷ g/mol to 0.4 × 10⁵ g/mol) and contained a high weight fraction (~58%) of starch molecules with M_w~0.4 × 10⁵ g/mol.     

Preparation and Characterisation of Thermoplastic Starches from Cassava Starch,Cassava Root and Cassava Bagasse

Summary: Thermoplastic starches (TPS) based on cassava starch have been produced by extrusion at 120 °C, using glycerol as plasticizer. Three forms of cassava starch were employed, viz: cassava root (CR), cassava bagasse (CB) and purified cassava starch (PCS). The main differences between these are the presence of sugars and a few fibres in CR and high fibre concentration in CB. Conditions of processing and characteristics such as amylose and fibre content, crystallinity, water absorption and mechanical behaviour in the tension x deformation test were evaluated. The results demonstrated that the PCS and CR had amylose contents consistent with literature values (14–18%) and that CB is a material constituted mainly by amylopectin. It was found that fibres in high proportions (as in the bagasse) can confer reinforcement properties and are thus able to generate natural composites of TPS with cellulose fibre. The sugars naturally found in the root reduce the elongation of the TPS under tension. The PCS and CR TPS were stable with respect to indices of crystallinity after processing; and during a period of 90 d in a relative humidity of 53%, while the CB TPS tended to vary its crystallinity, probably because its amylose chain had low degree of polymerization.     

Effect of Microwave Irradiation on Acid Hydrolysis of Faba Bean Starch: Physicochemical Changes of the Starch Granules

Starch is the most abundant carbohydrate in legumes (22–45 g/100 g), with distinctive properties such as high amylose and resistant starch content, longer branch chains of amylopectin, and a C-type pattern arrangement in the granules. The present study concentrated on the investigation of hydrolyzed faba bean starch using acid, assisted by microwave energy, to obtain a possible food-grade coating material. For evaluation, the physicochemical, morphological, pasting, and structural properties were analyzed. Hydrolyzed starches developed by microwave energy in an acid medium had low viscosity, high solubility indexes, diverse amylose contents, resistant starch, and desirable thermal and structural properties to be used as a coating material. The severe conditions (moisture, 40%; pure hydrochloric acid, 4 mL/100 mL; time, 60 s; and power level, 6) of microwave-treated starches resulted in low viscosity values, high amylose content and high solubility, as well as high absorption indexes, and reducing sugars. These hydrolyzed starches have the potential to produce matrices with thermo-protectants to formulate prebiotic/probiotic (symbiotic) combinations and amylose-based inclusion complexes for functional compound delivery. This emergent technology, a dry hydrolysis route, uses much less energy consumption in a shorter reaction time and without effluents to the environment compared to conventional hydrolysis.     

ESR investigation of starch gelatinization using novel spin probes

The spin probes 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) and the sodium salt of its sulfonate, 1,1,3,3-tetramethylisoindolin-2-yloxyl-5-sulfonate (NaTMIOS) were used to monitor the microviscosity changes of water during starch gelatinization. In cereal starch, which contains mainly A-type polymorphs, evidence was found for the amylopectin and amylose regions, the latter undergoing a transition at about 55 degrees C and a large increase in the microviscosity on cooling. Pea starch contains both A-and B-type polymorphs and this was also found to have two domains and the 55 degrees C transition was observed for the amylose phase: the less mobile amylopectin showed a reversible decrease in water microviscosity on heating.     

Characterization of starch polysaccharides by flow field-flow fractionation-multi-angle laser light scattering-differential refractometer index

The coupling between flow field-flow fractionation (FFF), multi-angle laser light scattering and differential refractometer index provides a promising technique for fractionation of starch polysaccharides in aqueous conditions. Native starches with different amylose/amylopectin levels (0-70%) as well as a pure amylose sample were characterized. By applying a sudden drop in the cross-flow-rate, clear separation was achieved between amylose (which elutes first) and amylopectin. Flow FFF produced correct relationships between the molecular mass or the gyration radius versus elution volume for the fractionated amylopectin population. The results are also considered in terms of the macromolecular composition of starches.