Selected morphological and functional properties of extruded acetylated starch-cellulose foams

Starch acetates with degrees of substitution (DS) of 1.68 and 2.3 were extruded with 10%, 20% and 30% (w/w) cellulose and 20% (w/w) ethanol in a twin screw extruder at 150, 160 and 170 degrees C barrel temperatures and 170, 200 and 230 rpm screw speeds. X-ray diffractogram (XRD), differential scanning calormetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the morphological properties of extruded foams. A central composite response surface design was applied to analyze the effects of starch type, cellulose content, barrel temperature and screw speed on specific mechanical energy requirement of extruding foams and the radial expansion ratio and compressibility of the extruded foams. XRD showed losses of DS starch and cellulose crystallinity and the formation of new complexes. FTIR spectra revealed that functional groups and chemical bonds were maintained after extrusion. Melting temperatures changed significantly when higher DS starch acetate was used. Cellulose content, barrel temperature and screw speed showed significant effects on thermal, physical and mechanical properties of extruded foams and the specific mechanical energy requirement.     

Structural transformations during gelatinization of starches in limited water: combined wide- and small-angle X-ray scattering study

Rice flour (18-25% moisture) and potato starch (20% moisture) were heated with continuous recording of the X-ray scattering during gelatinization. Rice flours displayed A-type crystallinity, which gradually decreased during gelatinization. The development of the characteristic 9 nm small-angle X-ray scattering (SAXS) peak during heating at sub-gelatinization temperatures indicated the gradual evolution into a stacked lamellar system. At higher temperatures, the crystalline and lamellar order was progressively lost. For potato starch (B-type crystallinity), no 9 nm SAXS peak was observed at ambient temperatures. Following the development of lamellar structures at sub-gelatinization temperatures, B-type crystallinity and lamellar order was lost during gelatinization. On cooling of partially gelatinized potato starch, A-type crystallinity steadily increased, but no formation of stacked lamellar structures was observed. Results were interpreted in terms of a high-temperature B- to A-type recrystallization, in which the lateral movement of double helices was accompanied by a shift along their helical axis. The latter is responsible for the inherent frustration of the lamellar stacks.     

Physicochemical characteristics and fine structure of high-amylose wheat starches isolated from Australian wheat cultivars

High-amylose starch is a source of resistant starch (RS) which have great impact on human health like dietary fiber. Nowadays, high-amylose wheat has been produced by genetic backcrossing, which enhances apparent amylose content and generates altered amylopectin. In this study, the high-amylose wheat starches isolated from various high-amylose wheat cultivars grown in Australia were characterized for understanding their physicochemical properties and fine structure of starch. The physicochemical characteristics of the high-amylose wheat starches are significantly different among the cultivars. Amylose contents of these cultivars were in a range of 28.0–36.9%, which is significantly higher than that of the normal wheat starch (25.6%). The high-amylose wheat starches also had higher blue value but lower λ_max than the normal wheat starch. Gelatinization temperature of the high-amylose wheat starches is higher than that of the normal wheat starch but transition enthalpy is lower. X-ray diffraction showed that the high-amylose wheat starch had C-type crystals close to A-type crystal. Pasting properties of the high-amylose wheat starches were varying depending on the cultivars. However, almost high-amylose wheat starches had lower peak and final viscosities and higher setback viscosity than did the normal wheat starch. Fine structure of amylose and amylopectin was different among the high-amylose wheat cultivars and related to the physicochemical properties of starch. These results help to understand well the characteristics of the high-amylose wheat starches before application for food processing.     

Effect of γ-irradiation on pasting and emulsification properties of octenyl succinylated rice starches

Octenylsuccinylated (OS) starches from waxy rice or high-amylose rice (28.1% amylose) (DS 0.023 and 0.025, respectively) were gamma-irradiated at 10, 30, or 50kGy and their pasting and thermal properties, crystallinity, and emulsification property were examined. When the OS starches were irradiated, the degrees of substitution gradually decreased as irradiation dose increased. A significant decrease in pasting viscosity was observed with an increase in irradiation dose, indicating the presence of chain degradation induced by the radiation. The melting temperature and enthalpy determined by differential scanning calorimetry increased slightly by irradiating at 10 or 30kGy. Little change in crystallinity was observed in the X-ray diffraction analysis for the OS high-amylose rice starch regardless of irradiation doses, whereas a decrease in crystallinity was observed with the OS waxy starch irradiated at 50kGy. Chain degradation induced by irradiation occurred mainly in the amorphous regions, but some loss of crystallinity occurred when the irradiation was excessive. The OS starches showed greater emulsion capacity and stability than the native counterparts due to their amphipathic nature. The irradiation further improved the emulsification properties of OS starches. The irradiation at 10kGy was optimal, and treating at higher doses decreased the emulsion capacity and stability of the OS starches.     

Amylose content and chemical modification effects on thermoplastic starch from maize – Processing and characterisation using conventional polymer equipment

A design of experiments was performed on extruded starch based materials studied in a recently published article [Chaudhary, A. L., Miler, M., Torley, P. J., Sopade, P. A., & Halley, P. J. (2008). Amylose content and chemical modification effects on the extrusion of thermoplastic starch from maize. Carbohydrate Polymers, 74(4), 907–913] highlighting the effects of amylose content, chemical modification and extrusion on a range of maize starches. An investigation into the effects of starch type (unmodified 0–80% amylose starch; hydroxypropylated 80% amylose starch), screw speed and ageing after moulding on final product properties such as mechanical properties (Young’s modulus, maximum stress and strain at break), moisture absorption, morphology and retrogradation are included. A full factorial design was used to study these starch type, processing and final product property relationships. Microscopy was used to observe any morphological difference between the various starch types in thermoplastic starch (TPS) blends and X-ray diffraction (XRD) was used to observe changes in crystallinity over time (retrogradation). The results show that 0% amylose (waxy maize) and hydroxypropylated 80% amylose thermoplastic starches have mechanical properties comparable to that of low density polyethylene (LDPE) and high density polyethylene (HDPE), therefore these materials have the potential to be an environmentally friendly alternative to current polymer resins.     

Effect of the alkaline treatment on the ultrastructure of C-type starch granules

The effect of alkaline treatment on the ultrastructure of C-type starch granules was investigated during the alkaline extraction of Araucaria angustifolia (pinhao) starch. The efficiency in protein removal was evaluated using intrinsic fluorescence and Kjeldahl's method. In parallel, morphological changes of starch granules were observed using scanning electron microscopy and atomic force microscopy. The starch crystallinity was monitored by wide-angle X-ray scattering and the lamellar structure was studied by small-angle X-ray scattering (SAXS). The paracrystalline model was employed to interpret the SAXS curves. It was found that the granular organization was significantly altered when alkaline solutions were used during the extraction. A partial degradation of B-type allomorph of starch and a significant compression of semicrystalline growth rings were observed.     

Structure-properties relationship in cross-linked high-amylose starch for use in controlled drug release

Cross-linked high-amylose starch (CLHAS), obtained by high-amylose starch cross-linking, was recently introduced as an excipient (Contramid) for monolithic dosage forms that are able to control drug release over 18-24 h. These control properties are related to tablet swelling and are strongly dependent on the degree of the cross-linking of CLHAS. The permeability of solutes through CLHAS hydrogels depends on the chemical structure of the polymer. The aim of this study was to obtain a better understanding of how modifications in CLHAS molecular structures at the level of long-range and short-range order during the cross-linking and processing conditions relate to the release properties of the CLHAS matrices. Structural parameters such as crystallinity contribute significantly to the physical and mechanical aspects of starch products. X-ray diffractometry, FTIR spectroscopy, dissolution tests in vitro, and mechanical hardness (of dry tablets) were found to be sensitive to the cross-linking degree (cld) variation. Best release properties and highest mechanical hardness were obtained from CLHAS matrices with low-to-moderate crystallinity, where the V- and the B-type structures coexist with amorphous regions. X-ray and FTIR profiles of dry CLHAS powders were found to be predictive for release properties of CLHAS tablets.     

Structure study of cellulose fibers wet-spun from environmentally friendly NaOH/urea aqueous solutions

In this study, structure changes of regenerated cellulose fibers wet-spun from a cotton linter pulp (degree of polymerization approximately 620) solution in an NaOH/urea solvent under different conditions were investigated by simultaneous synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). WAXD results indicated that the increase in flow rate during spinning produced a better crystal orientation and a higher degree of crystallinity, whereas a 2-fold increase in draw ratio only affected the crystal orientation. When coagulated in a H2SO4/Na2SO4 aqueous solution at 15 degrees C, the regenerated fibers exhibited the highest crystallinity and a crystal orientation comparable to that of commercial rayon fibers by the viscose method. SAXS patterns exhibited a pair of meridional maxima in all regenerated cellulose fibers, indicating the existence of a lamellar structure. A fibrillar superstructure was observed only at higher flow rates (>20 m/min). The conformation of cellulose molecules in NaOH/urea aqueous solution was also investigated by static and dynamic light scattering. It was found that cellulose chains formed aggregates with a radius of gyration, Rg, of about 232 nm and an apparent hydrodynamic radius, Rh, of about 172 nm. The NaOH/urea solvent system is low-cost and environmentally friendly, which may offer an alternative route to replace more hazardous existing methods for the production of regenerated cellulose fibers.     

Effect of extrusion on trypsin inhibitor activity and nutrient digestibility of diets based on fish meal, soybean meal and white flakes

The effects of moist extrusion processing of diets containing fish meal (FM) and conventional defatted soybean meal (SBM) or untoasted defatted soybean meal (white flakes [WF]) on amino acid composition, trypsin inhibitor activity (TIA), and apparent total tract digestibility of nutrients were studied. Three diets with the nutritional characteristics of feeds for salmonid fish were formulated: one control based on FM as protein source and two others where 40% of total amino acids from FM were substituted by either SBM or WF. Each diet was fed to mink either as an unextruded mixture of the ingredients or as extruded pellets in order to determine the effect of extrusion processing. Extrusion did not change the amino acid composition of the diets significantly, but reduced the TIA of both diets containing soy products by approximately 76%. Intake of the unextruded WF diet was only one-third compared with the other diets. The dry matter concentration in faeces from mink fed diets containing soy products was significantly lower than in mink fed the FM diet. Digestibility of crude protein, all amino acids and fat was lower, but starch higher, in the unextruded WF diet than in the FM and SBM diets, whereas no significant differences were found among the extruded diets. Extrusion of the WF diet increased digestibility of protein and all amino acids. The greatest increase in digestibility after extrusion of the WF diet was observed for cysteine followed by tryptophan. Extrusion of the FM and SBM diets had no significant effect on amino acid digestibility. Digestibility of starch was, in general, increased by extrusion. It is concluded that the heat treatment involved in typical moist extrusion processing used for fish feed may be sufficient to inactivate most of the TIA in unheated soybean meal, and to increase digestibility of the protein in WF to approximately the same level as found for SBM and FM. Still, extrusion is a lenient process with minor effects on nutrient digestibility of diets containing fish meal or toasted soybean meal as major protein sources.     

Effects of processing high amylose maize starches under controlled conditions on structural organisation and amylase digestibility

The amylase digestibility of high-amylose maize starches has been compared before and after thermo-mechanical processing. Starches were analysed for enzyme-resistant starch yield, apparent amylose content, crystallinity (X-ray diffraction), and molecular order (NMR and FTIR), both before and after treatment with α-amylase. All samples had significant (>10%) enzyme-resistant starch levels irrespective of the type and extent of thermal or enzymic processing. Molecular or crystalline order was not a pre-requisite for enzyme resistance. Near-amorphous forms of high amylose maize starches are likely to undergo recrystallisation during the enzyme-digestion process. The mechanism of enzyme resistance of granular high-amylose starches is found to be qualitatively different to that for processed high-amylose starches. For all samples, measured levels of enzyme resistance are due to the interruption of a slow digestion process, rather than the presence of completely indigestible material.     

Structural memory of natively unfolded tau protein detected by small-angle X-ray scattering

Small-angle X-ray scattering (SAXS) is a universal low-resolution method to study size and shape of globular proteins in solution but recent developments facilitate the quantitative characterization of the structure and structural transitions of metastable systems like partially or completely unfolded proteins. We present here a study of temperature induced transitions in tau, a natively unfolded protein involved in Alzheimer's disease. Previous studies on full length tau and several disease-related mutants provided information about the residual structure in different domains revealing a specific role and extended conformations of the so-called repeat domains, which are considered to be responsible for the formation of amyloid-like fibrils ("paired helical filaments"). Here, we employ SAXS to investigate the temperature dependent properties of tau. Slow heating/cooling of the full length protein from 10°C to 50°C did not lead to detectable changes in the overall size. Surprisingly, quick heating/cooling caused tau to adopt a significantly more compact conformation, which was stable over up to 3 h and represents a structural "memory" effect. This compaction is not observed for the shorter tau constructs containing largely the repeat domains. The structural and functional implications of the observed unusual behavior of tau under nonequilibrium conditions are discussed.     

Extruding foams from corn starch acetate and native corn starch

Because of the hydrophilic characteristics of native starch foams and the cost of modifying starch, the uses of starch and modified starch foams are hindered. To decrease hydrophilicity and cost of starch foams, native corn starch was blended with starch acetate and extruded. A twin-screw mixing extruder was used to produce the foams. Native starch content, screw speed, and barrel temperature had significant effects on molecular degradation of starches during extrusion. The melting temperature of extruded starch acetate/native starch foam was higher (216 degrees C) than that for starch acetate (193.4 degrees C). Strong peaks in the X-ray diffractograms of extruded starch acetate/native starch foam suggested new crystalline regions were formed. Optimum conditions for high radial expansion ratio, high compressibility, low specific mechanical energy requirement, and low water absorption index were 46.0% native starch content, 163 rpm screw speed, and 148 degrees C barrel temperature.     

Extrusion of pectin and glycerol with various combinations of orange albedo and starch

Microstructural and mechanical properties of extruded pectin and glycerol films with various combinations of orange albedo and starch were determined by universal mechanical testing (UMT), dynamic mechanical analysis (DMA), optical microscopy (OM) and scanning electron microscopy (SEM). A glass transition and a second order transition attributed to the onset of translational motion of the pectin molecules was observed in all films. Observation by OM suggested that extrusion in the presence of dilute HCl was more effective in disintegrating albedo than either water or dilute citric acid. UMT, DMA and SEM analysis revealed that extruded pectin/albedo/starch/glycerol films provided better mechanical properties than pectin/albedo/glycerol films and were comparable in mechanical properties to extruded pectin/starch/glycerol films.     

Effect of extrusion on trypsin inhibitor activity and nutrient digestibility of diets based on fish meal,soybean meal and white flakes

Abstract

The effects of moist extrusion processing of diets containing fish meal (FM) and conventional defatted soybean meal (SBM) or untoasted defatted soybean meal (white flakes [WF]) on amino acid composition, trypsin inhibitor activity (TIA), and apparent total tract digestibility of nutrients were studied. Three diets with the nutritional characteristics of feeds for salmonid fish were formulated: one control based on FM as protein source and two others where 40% of total amino acids from FM were substituted by either SBM or WF. Each diet was fed to mink either as an unextruded mixture of the ingredients or as extruded pellets in order to determine the effect of extrusion processing. Extrusion did not change the amino acid composition of the diets significantly, but reduced the TIA of both diets containing soy products by approximately 76%. Intake of the unextruded WF diet was only one-third compared with the other diets. The dry matter concentration in faeces from mink fed diets containing soy products was significantly lower than in mink fed the FM diet. Digestibility of crude protein, all amino acids and fat was lower, but starch higher, in the unextruded WF diet than in the FM and SBM diets, whereas no significant differences were found among the extruded diets. Extrusion of the WF diet increased digestibility of protein and all amino acids. The greatest increase in digestibility after extrusion of the WF diet was observed for cysteine followed by tryptophan. Extrusion of the FM and SBM diets had no significant effect on amino acid digestibility. Digestibility of starch was, in general, increased by extrusion. It is concluded that the heat treatment involved in typical moist extrusion processing used for fish feed may be sufficient to inactivate most of the TIA in unheated soybean meal, and to increase digestibility of the protein in WF to approximately the same level as found for SBM and FM. Still, extrusion is a lenient process with minor effects on nutrient digestibility of diets containing fish meal or toasted soybean meal as major protein sources.     

Extrusion processing of high amylose potato starch materials

Thermoplastic starch was prepared by mixing native high amylose potato starch and normal potato starch in a Buss co-kneading extruder at starch to glycerol ratios of 100:45 and 100:30. The materials were also conditioned to different moisture contents at different relative humidities at 23 °C. After the mixing, the compounds were extruded into sheets with a Brabender laboratory extruder. The thermoplastic high amylose materials exhibited a higher melt viscosity than the normal potato starch materials when conditioned at 53% relative humidity. Increasing the moisture content in HAP from 27% to 30% (by weight) lowered the melt viscosity to the same level as that of normal potato starch with a moisture content of 28%. In general, the high amylose materials were more difficult to extrude than the thermoplastic material based on normal starch. The main extrusion problems encountered with the high amylose starch were unstable flow, insufficient melt tenacity and clogging of the die. By increasing the moisture content, increasing the compression ratio of the screw and increasing the rotation rate of the screw, the problems were reduced or eliminated. However, only with a starch to glycerol ratio of 100:45 was an acceptable extrusion result obtained. Extruded sheets of such high amylose materials had a stress at break of about 5 MPa at room temperature and 53% relative humidity, whereas the corresponding value for normal potato (thermoplastic) starch was 3 MPa. The elongation at break was also higher in the case of the high amylose material. The results are discussed in terms of residual crystallinity of the starch materials.     

High-amylose rice improves indices of animal health in normal and diabetic rats

A high-amylose rice with 64.8% amylose content (AC) was developed by transgenic inhibition of two isoforms of starch branching enzyme (SBE), SBEI and SBEIIb, in an indica rice cultivar. The expression of SBEI and SBEIIb was completely inhibited in the transgenic line, whereas the expression of granule-bound starch synthase was normal. Compared with wild-type rice, drastic reductions in both SBEs in the transgenic rice increased apparent AC in flour from 27.2% to 64.8%, resistant starch (RS) content from 0% to 14.6% and total dietary fibre (TDF) from 6.8% to 15.2%. Elevated AC increased the proportion of long unit chains in amylopectin and increased onset gelatinization temperature and resistance to alkaline digestion; however, kernel weight was decreased. A rat feeding trial indicated that consumption of high-amylose rice decreased body weight gain significantly (P < 0.01); increased faecal mass, faecal moisture and short-chain fatty acids; and lowered the faecal pH. An acute oral rice tolerance test revealed that the high-amylose rice had a positive effect on lowering the blood glucose response in diabetic Zucker fatty rats. This novel rice with its high AC, RS and TDF offers potential benefits for its use in foods and in industrial applications.     

Extrusion of pectin/starch blends plasticized with glycerol

The microstructural and thermal dynamic mechanical properties of extruded pectin/starch/glycerol (PSG) edible and biodegradable films were measured by scanning electron microscopy (SEM) and thermal dynamic mechanical analysis (TDMA). SEM revealed that the temperature profile (TP) in the extruder and the amount of water present during extrusion could be used to control the degree to which the starch was gelatinized. TDMA revealed that moisture and TP during extrusion and by inference the amount of starch gelatinization had little effect on the mechanical properties of PSG films. Furthermore, TDMA revealed that PSG films underwent a glass transition commencing at about −50°C and two other thermal transitions above room temperature. Finally, it was concluded that the properties of extruded PSG films were comparable to those cast from solution.     

Characterization of Molecular Structure of Starch Granules in Suspension-cultured Cells from Ipomoea cordatotriloba Denn.

The molecular structure of starch granules formed in suspension-cultured cells of Ipomoea cordatotriloba Denn. was characterized by its chain length distribution, which was compared to those of the starches from the root and leaf of the original plant. The cultured cell starches were spherical and had a very small granule size (about 2 μm). The debranched starches roughly separated into three fractions during gel-permeation chromatography, and the fractions were defined as Fr.1, 2, and 3, respectively. The chain length distribution of the debranched cultured cell starch showed that the high molecular weight fraction (Fr.1), referred to as an amylose fraction, was much less than those of the root and leaf starches. The ratio of the two lower fractions (Fr.3/Fr.2) of the cultured cell starch, which was mainly derived from unit chains of amylopectin, was greatest among the starches, suggesting that the amylopectin from the cultured cell starch has much shorter unit chains. By X-ray diffraction analysis, it was found that both cultured cell and leaf starch granules have low crystallinity.     

The effect of lintnerisation on wheat and potato starch granules

Wheat and potato starches were hydrolysed with 2·2 n hydrochloric acid at 35°C for a period of time up to 15 days. The residues (lintnerised starches) were washed and freeze dried, and studied by differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), small-angle light scattering (SALS), small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). These techniques showed that profound changes took place in the first day of hydrolysis (during which time the extent of hydrolysis was 7·7% for potato starch and 12·5% for wheat starch). In particular, the gelatinisation enthalpy (ΔH) decreased, the X-ray crystallinity increased and the SANS and SAXS peaks (indicative of a regular spacing between crystalline and amorphous regions) virtually disappeared. The reduction in ΔH is surprising and is discussed at length. It was also shown that freeze drying results in a considerable lowering of the gelatinisation temperature of potato starch (and also of ΔH) while that of wheat starch is only slightly affected.