Functional properties of pregelatinized and cross-linked cassava starch obtained by extrusion with sodium trimetaphosphate

Cassava starch was cross-linked with sodium trimetaphosphate (STMP) on a Cerealtec single-screw extruder at different extrusion temperatures and concentrations of STMP and NaOH. The effect of variables on functional properties of the products was analysed by the response–surface methodology. The degree of substitution (DS) was influenced by NaOH and phosphorus level, and increased when their concentration increased. Extrusion temperature affected water absorption, cold viscosity and gel characteristics. The introduction of phosphate groups by cross-linking, with maximum DS of 1.5×10⁻⁴, increased the gel strength, water absorption index, resistance to high temperature and shear, and decreased gel cohesiveness, starch clarity and water solubility index. The products had different DS and degree of gelatinization and thus can be applied in several kinds of foods.     

High moisture twin-screw extrusion of sago starch: 1. Influence on granule morphology and structure

Effects of barrel temperature (81–149°C) and screw speed (315–486rpm) on extrusion processing of sago starch in a co-rotating twin-screw extruder under a high moisture system (34–47%) were investigated using response surface methodology. Structural changes were characterised by measuring water solubility index (WSI), water absorption index (WAI), degree of gelatinisation (DG), dextrose equivalent (DE) and high performance size-exclusion chromatography (HPSEC) profiles of the extradates. Thermomechanical processing of sago starch in the twin-screw extruder at the high moisture (34–47%) system led to shearinduced limited degradation and starch phase transitions (a composite melting gelatinisation process). Strong positive correlations between WAI, WSI and DG showed that gelatinisation was the fundamental mechanism in this high moisture system rather than dextrinisation. Processing-induced solubility increased at the expense of water absorption. Low WSI (4.5–18.1%) is ascribed to the presence of structures of either granular crystallite remnants or rearrangement of bonds during extrusion.     

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.     

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.     

Studies on the hydrothermal modifications of new cocoyam (Xanthosoma sagittifolium) starch

Native new cocoyam starch (nNCS) was subjected to annealing (aNCS) and heat moisture treatment at 18% moisture level (h₁₈NCS), 21% moisture level (h₂₁NCS), 24% moisture level (h₂₄NCS) and 27% moisture level (h₂₇NCS) as hydrothermal treatments. Scanning electron and light microscopy revealed round and polygonal shapes with sizes ranging from 15 to 40 μm for native and modified starches. nNCS showed “A” pattern X-ray diffraction and no significant differences were observed in the X-ray pattern of the modified starches. Swelling power and solubility reduced following heat moisture treatment. At all pH studied (2–12), unmodified new cocoyam starch exhibited higher swelling capacity and solubility than the modified derivatives. Hydrothermal modifications improved water absorption capacity but reduced oil absorption capacity. Pasting temperature of native starch shifted to higher values following annealing and heat moisture treatment. Hot paste viscosity (Hv), viscosity after 30 min holding at 95 °C (Hv₃₀) and cold paste viscosity (Cv) reduced after annealing and heat moisture treatment. The result also indicates that hydrothermal treatments reduced the tendency for setback. As the number of days of storage of starch paste increased from 1 to 10, light transmittance of all the starches reduced but marked reduction of light transmittance was observed in native starch. DSC studies revealed increase in gelatinization temperature following annealing and heat moisture treatment. Starch hydrothermal modifications reduced retrogradation as enthalpies of regelatinization reduced following modifications. The regelatinization peak in the second day scanning shifted to lower temperature than the gelatinization peak in first run heating DSC curve for all samples. The regelatinization peak also became larger and shifted to higher temperature range when the storage days increased from 2 to 7.     

Effects of Low Moisture Extrusion on the Structural and Physicochemical Properties of Adlay (Coix lacryma-jobi L.) Starch-Based Polymers

This study investigated the changes in the structural and functional properties of various adlay starch-based polymers that occur during low moisture extrusion. The water absorption index, water solubility index, color, and morphological, pasting, and thermal properties of the adlay flours were investigated. Extrusion significantly decreased their contents (starch > protein > fiber > lipids). The color of the adlay flour darkened after extrusion, primarily due to the Maillard reaction and caramelization. Scanning electron microscopy revealed various cracks, pits, and holes on the surface of the extruded flour without defatting for both the extruded brown adlay and the extruded polished adlay. Extrusion caused molecular degradation of the extruded starch, decreasing its swelling power in hot water. The ΔH values (0.19-0.71 J/g) of the extrudates revealed that the starch granules were not fully gelatinized. These results provide a theoretical basis for further explorations of the interactions of adlay macromolecules by extrusion.     

Preparation and characterization of biodegradable copolyester-starch based foams

Regular (25% amylose) and waxy corn starches blended to various ratios with Eastar Bio Copolyester 14766 (EBC) were extruded into loose-fill foams using a twin screw extruder. Included in this study were two types of corn starch, three levels of EBC content, and three levels of starch moisture content. Waxy starch produced foams with greater radial expansions and lower unit and bulk densities than regular starch. Regular starch foams had lower water solubility indices (WSIs) than waxy starch foams. Foams made of both types of starch possessed similar mechanical properties. No differences were observed in compressibilities and spring indices of either waxy or regular starch foams. Higher levels of EBC addition resulted in less radial expansion and higher unit and bulk densities. Foams made with 10% EBC had higher compressibility than foams containing 25% EBC. Spring indices of single-piece samples and compressibilities and spring indices of bulk samples were not affected by the differences in the level of EBC addition. At 19% and 22% of moisture contents, foams had greater radial expansion than at 25% moisture content. Unit and bulk densities were not affected by variations in moisture content. At 22% moisture content, a lower WSI of 18.5% was obtained. At 22% moisture content, softer foams were produced. At all three levels of moisture content, no differences were detected in the spring indices.     

Cross-linking of wheat starch and hydroxypropylated wheat starch in alkaline slurry with sodium trimetaphosphate

Wheat starch was cross-linked at 40 °C and pH 11.0 by slurrying the starch (30% solids) in a solution of sodium trimetaphosphate (STMP), sodium hydroxide, and sodium sulfate. The extent of cross-linking was determined by an increase in alkaline fluidity or by a decrease in alkaline clarity. Response surface analysis showed that cross-linking increased with increasing levels of STMP (0.5-1.5%, based on starch, bos) and sodium sulfate (0–4.0%, bos) over a reaction period of 120–720 min. A regression equation with first and second order terms showed that STMP and sodium sulfate concentrations and the reaction time accounted for 99% of the variability in alkaline fluidity. Wheat starch (37% slurry) was hydroxypropylated by reaction with propylene oxide (8%, bos) for 24h at 45 °C in alkali (pH 11.5) containing 16.0% sodium sulfate (bos). The hydroxypropylated (4.5wt%) wheat starch (DS 0.12-0.13) was not isolated but was cross-linked with STMP (0.1-0.5%, bos) over a 10–40 min reaction period. A comparison of pasting curves at pH 3.5 showed that some of the cross-links produced by STMP were less stable than those produced by phosphoryl chloride, indicating a low level of pyrophosphate as well as monophosphate cross-links. The less stable cross-links were diminished by changing reaction conditions with STMP.     

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.     

Effects of glyoxal cross-linking on baked starch foam

Starch trays and plates were prepared from native corn starch and corn starch cross-linked with glyoxal at different concentrations (0.126, 0.269, 0.271, 0.468 g/kg) using a foam baking process. The effect of cross-linking on baking parameters, including density, colour, water absorption, and tensile and flexural properties, was determined. Also, the morphologies of the trays were examined using a scanning electron microscope. Cross-linking considerably reduced the baking time, density and water absorption of the trays. Trays made from starch cross-linked with 0.126 and 0.269 g/kg glyoxal presented the best properties, with a homogenous microstructure and smooth surface quality. These trays had the lowest density (0.27 g/cm³) and had approximately 53% reduction in water absorption. Moreover, both the tensile and flexural strain of these foams was significantly higher than other foams.     

Structure–properties relationship in cross-linked high amylose starch cast films

Cross-linked high amylose starch cast films were prepared to study the effect of cross-linking degree on various properties in normal environmental conditions. Mechanical tensile properties (Young's modulus, elongation at break, tensile strength), water vapour transmission rate (WVTR) and oxygen permeability coefficients of cast films were determined as a function of cross-linking degree and percentage of free humidity. Cross-linking degree and degree of crystallinity are closely related and seem to have non-negligible opposite effect on the properties of interest. By using increased amounts of cross-linking agents, the effect of cross-linking degree tends to reduce the degree of crystallinity modulating thus mechanical properties, water vapour permeability and oxygen permeability coefficients. Yield strength, tensile strength at break, WVTR versus cross-linking degree showed a non-monotonous behaviour. Maximal values for these properties were reached for moderate cross-linking degree. Optimal crystalline/amorphous ratio in the films may induce interactions and balanced effects, which would be responsible for the non-linear behaviour of some of the investigated properties. By cross-linking with epichlorohydrin in the range 1–10 g crosslinker/100 g polymer, the mechanical properties of films are still related to water content and water vapour permeability remains high compared to some synthetic polymeric materials.     

Preparation of clear noodles with mixtures of tapioca and high-amylose starches

Ways to simulate the making of clear noodles from mung bran starch were investigated by studying the molecular structures of mung bean and tapioca starches. Scanning electron micrographs showed that tapioca starch granules were smaller than those of mung bean starch. X-ray diffraction patterns of mung bean and tapioca starch were A- and C_A-patterns, respectively. Iodine affinity studies indicated that mung bean starch contained 37% of apparent amylose and tapioca starch contained 24%. Gel permeation chromatograms showed that mung bean amylopectin had longer peak chain-length of long-branch chains (DP 40) than that of tapioca starch (DP 35) but shorter peak chain-length of short-branch chains (DP 16) than that of tapioca starch (DP 21). P-31 n.m.r. spectroscopy showed that both starches contained phosphate monoesters, but only mung bean starch contained phospholipids. Physical properties, including pasting viscosity, gel strength, and thermal properties (gelatinization), were determined. The results of the molecular structure study and physical properties were used to develop acceptable products using mixtures of cross-linked tapioca and high-amylose maize starches. Tapioca starch was cross-linked by sodium trimetaphosphate (STMP) with various reaction times, pH values, and temperatures. The correlation between those parameters and the pasting viscosity were studied using a visco/amylograph. Starches, cross-linked with 0.1% STMP, pH 11.0, 3.5 h reaction time at 25, 35, and 45°C (reaction temperature), were used for making noodles. High-amylose maize starch (70% amylose) was mixed at varying ratios (9, 13, 17, 28, 37, and 44%) with the cross-linked tapioca starches. Analysis of the noodles included: tensile strength, water absorption, and soluble loss. Noodle sensory properties were evaluated using trained panelists. Noodles made from a mixture of cross-linked tapioca starch and 17% of a high-amylose starch were comparable to the clear noodles made from mung bean starch.     

Optimization of conditions for production of sago starch-based foam

Production of sago starch-based foam involved mixing of sago starch with polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP) followed by preparation of electron beam irradiated sago starch/PVA and sago starch/PVP sheets and expanding them in a microwave. The results revealed that good foams with high linear expansion and closed cell structure can be produced from 25:15 of sago starch:PVA and 30:10 of sago starch:PVA blends prepared at 80 °C and electron beam irradiated at 15 kGy or 10 kGy for the cross-linking process. An increment of sago starch in the blends enhanced the linear expansion of the foams produced. Change in the blend morphology was observed when it was exposed to higher irradiation doses as electron beam irradiation induced the cross-linking in PVA and PVP, and leaching of amylose and amylopectin from the starch granules. Sago starch/PVA blend is more suitable for foam production because it produced flexible and glossy foam as compared to sago starch/PVP blend which produced very rigid foam.     

SENSORY PROPERTIES OF EXTRUDED CORN MEAL RELATED TO THE SPATIAL DISTRIBUTION OF PROCESS CONDITIONS

The quality determining factors of extruded products are affected by the temperature, shear and pressure generated by any input to the extruder during the short residence time (< 120s). Although the relationship of process history to measurable product qualities has been established, sensory qualities have not been well correlated to these process responses. Sensory attributes of extruded corn meal products were investigated and correlated to measured physical properties in this study. Corn meal was extruded in a twin screw extruder (Baker Perkins MPF 50/25; LD ratio 15:1) with step increases in screw speed from 200-400 rpm, and moisture from 16-22%. Principal component analysis (PCA) of main factors from sensory color, crispness, and adhesiveness was correlated to process torque, pressure and temperature. Spatial distribution of process response and product attributes showed crispness to be dependent on extrusion temperature. Porosity and adhesiveness were not correlated to any measured process response. PCA analysis identified significant differences in the effects of moisture and screw speed input to the extruder on product properties.     

Effect of the cross-linked reagent type on some morphological,physicochemical and functional characteristics of banana starch (Musa paradisiaca)

Cross-linked starches have increased their importance due to their applications such as adsorbents of heavy metals. In this work the effect the reagent used in the chemical modification of banana starch and its impact on some morphological, physicochemical and functional characteristics was evaluated. The reagent used in the cross-linked of starch decreased the fat and protein content, whereas ash level were higher. The morphology of the granules, observed by scanning electron microscopy, was more affected when a blend of sodium trimetaphosphate (STMP)/sodium tripolyphosphate (STPP) and epichlorohydrin (EPI) were used in the modification. The cross-linked starches presented a bimodal distribution and the effect was more conspicuous in those starches modified with STMP/STPP and EPI. The swelling value (60 °C) increased with the cross-linking and the highest value was obtained in those starches modified with STMP/STPP and EPI. However, at higher temperatures the swelling values of cross-linked starches with STMP/STPP and EPI decreased as temperature increased (80 °C), and there after the value was constant. The cross-linked starches with STMP/STPP and EPI showed the lowest solubility values. The cross-linked starch with POCl₃ (phosphorous oxychloride) showed a slight decrease in the onset and peak temperatures compared with its native counterpart, but those modified with STMP/STPP and EPI presented an increase in the three transition temperatures, but a decrease in enthalpy value. The results obtained can be used to determine the type of reagent used for cross-linked in order to obtain a starch with specific characteristics.     

Oxidized and acid thinned starch derivatives of hybrid maize: functional characteristics, wide-angle X-ray diffractometry and thermal properties

Starch isolated from hybrid maize (8535-23) was subjected to oxidation and acid thinning. Proximate analyses revealed that moisture, ash, protein, fat, fibre, and pH reduced after oxidation and acid thinning. Percentage amylose content reduced from 20.42% in native starch to 18.76 and 17.65% in oxidised and acid thinned starch derivatives, respectively. Wide-angle X-ray diffraction patterns indicated strong peaks at 15.9 degrees, 17.2 degrees, 18.8 degrees, and 25.0 degrees 2theta. No significant difference was observed between the X-ray pattern of the native and modified starches. Both swelling power and solubility increased with increase in temperature. Oxidation and acid thinning reduced swelling power and increased solubility starch. At all pHs, both oxidation and acid thinning reduced the swelling capacity of the native starch. Oxidation increased water and oil absorption capacity of the native starch, while both hydrophilic and hydrophobic properties reduced following acid thinning. Least gelation concentration reduced in acid thinned starch but increased in oxidised derivative. Pasting temperature (Tp), peak viscosity (Pv), hot paste viscosity (Hv), and viscosity after 30 min holding at 95 degrees C (H(v30)) reduced following both modifications. However, values for cold paste viscosity (Cv) and setback (SB) reduced in oxidised derivative and increased in acid thinned starch. Light transmittance of the starch pastes reduced with increase in storage days, however, reduction was more pronounced in native and acid thinned starches. Onset temperature (To), peak temperature (Tp) and conclusion temperature (Tc) of gelatinisation reduced in modified starches compared with native hybrid maize starch. Also, gelatinisation enthalpy reduced after oxidation and acid thinning. Enthalpy of regelatinisation increased as days of storage of starch paste increased.     

Production of hydrolysate with antioxidative activity by enzymatic hydrolysis of extruded corn gluten

Hydrolysate of extruded corn gluten with higher solubility and antioxidative property was prepared. Extrusion and starch removal of corn gluten were applied as pretreatment before enzymatic hydrolysis by Alcalase. The amylase hydrolysis of starch at 70°C for 3 h resulted in the removal of the starch from the extruded corn gluten. The best hydrolysis results can be obtained by conducting the hydrolysis at 60°C with water addition 20 g/g protein, enzyme addition 0.048 Ansen units/g protein, pH 8.5, and 120 min. Degree of hydrolysis of extruded and nonextruded corn gluten reached 39.54 and 31.16%, respectively, under the optimal condition. Sodium dodecyl sulfate polyacrylamide gel electrophoresis of the optimal hydrolysate revealed that proteolysis of extruded corn gluten was more extensive than proteolysis of its counterpart which was not subjected to extrusion. The molecular weight of the peptides in the optimal hydrolysate was mainly over 3,710–660 Da as determined by gel filtration chromatography. The hydrolysates displayed good solubility and antioxidative activity. The separation profile of the hydrolysate on an ion exchange chromatography of Q-Sepharose Fast Flow showed that many kinds of peptides had antioxidative effect. A new peptide with antioxidative activity was purified, and its amino acid sequence was Phe-Pro-Leu-Glu-Met-Met-Pro-Phe, which was identified by Q-TOF2 mass spectrometry.     

Segmental mobility of polymers in starch granules at low moisture contents

The objective of this study was to determine the moisture content at which the segmental mobility of polymers within a starch granule is restricted. Common corn, waxy corn and high amylose corn starch samples were equilibrated to a final water activity of 0.15, 0.33, 0.75 or 0.97. The samples were then exposed to iodine vapor for 24 h and the color, absorption spectra and X-ray diffraction patterns were measured. Stained and unstained granules were also viewed under a bright field and polarized light microscope. The results demonstrate that successive local transitions occur within a granule with increasing moisture contents. Furthermore, the data shows that at moisture contents of about 13%, iodine is able to penetrate the granule and the resulting complex disrupts the crystalline arrangement within the granules. The differences in extent of mobility of polymers between different starch types can potentially illuminate differences in starch structure and architecture.     

Surface esterification of corn starch films: Reaction with dodecenyl succinic anhydride

Surface of corn starch films was modified through esterification using dodecenyl succinic anhydride (DDSA) as reactant. The effects of reaction temperature and time, concentration of alkaline aqueous solution for activating starch, concentration of ethanol diluted DDSA, and time of alkaline aqueous solution treatment on the physical properties related to material’s hydrophilic nature, such as moisture absorption and surface water contact angle, were investigated. It was found that the surface esterification modification significantly reduced the moisture sensitivity and surface hydrophilic character of starch film. Due to the hydroxyl groups in the film surface layer were reacted with DDSA, the equilibrium moisture content of the starch film under 95% RH declined 22% and the surface water contact angle increased up to 82% after surface esterification modification.     

Influence of drying temperature on functional properties of wet-milled starch granules

Relationships between swelling capacities, pasting properties, rotational flow behaviour and textural properties of hydro-thermally heated wet-milled starch granules from corn dried between 60 and 130 °C were investigated. High-drying temperatures applied during the corn drying process conferred to the wet-milled starch granules (WSG) such a rigidity which reduced their swelling capacities, their water binding capacities and their water solubility index after gelatinization. These granules changes affected their pasting characteristics, their flow behaviour and several textural parameters of gel formed from the wet-milled starch granule after gelatinization. The rigidity of granules was a major factor determining the formation of either starch pastes or gels.