Rheological and mechanical properties of bioplastics based on gluten- and glutenin-rich fractions

The present work aims to investigate the dynamic rheology at small strains and the equibiaxial extensional deformation at large strain of the glycerol plasticized dough of gluten- and glutenin-rich fractions and their mixture as well as the uniaxial tension deformation behavior of the compression molded bioplastics. The influence of glutenin-to-gluten ratio (GGR) on the rheological properties of the glycerol plasticized doughs and the crosslinked bioplastics were investigated. The results showed that the glutenin dough exhibits higher moduli and lower loss factor and equibiaxial deformability in comparison with the gluten dough. Addition of a glutenin-rich fraction to the gluten dough can improve elasticity at small deformation and extensional deformational stress at large deformations but result in reductions in extensibility of the compression molded bioplastics.     

Influence of reducing agents on properties of thermo-molded wheat gluten bioplastics

The present work aims to study the influence of reducing agents of sodium bisulfite, sodium sulfite and thioglycolic acid on the equibiaxial extensional deformation of glycerol plasticized wheat gluten and the properties of gluten bioplastics thermo-molded at 125 °C. Moisture absorption, weight loss and water uptake, uniaxial tensile properties (Young's modulus, tensile strength, elongation at break and tensile set), and morphology observations were performed to characterize the physical properties of the thermo-molded gluten bioplastics. The results showed that reducing agents facilitated the viscous flow and restrained the elastic recovery of the plasticized gluten while not hindering the crosslinking reaction of gluten proteins during thermo-molding. On the contrary, reducing agents do not significantly influence moisture absorption, Young's modulus, tensile strength and the morphology of the gluten bioplastics thermo-molded at 125 °C. It is shown that reducing agents are highly effective for tailoring the flow viscosity of the plasticized gluten dough and the mechanical properties of thermo-molded gluten bioplastics.     

Influence of reducing agents on properties of thermo-molded wheat gluten bioplastics

The present work aims to study the influence of reducing agents of sodium bisulfite, sodium sulfite and thioglycolic acid on the equibiaxial extensional deformation of glycerol plasticized wheat gluten and the properties of gluten bioplastics thermo-molded at 125 °C. Moisture absorption, weight loss and water uptake, uniaxial tensile properties (Young's modulus, tensile strength, elongation at break and tensile set), and morphology observations were performed to characterize the physical properties of the thermo-molded gluten bioplastics. The results showed that reducing agents facilitated the viscous flow and restrained the elastic recovery of the plasticized gluten while not hindering the crosslinking reaction of gluten proteins during thermo-molding. On the contrary, reducing agents do not significantly influence moisture absorption, Young's modulus, tensile strength and the morphology of the gluten bioplastics thermo-molded at 125 °C. It is shown that reducing agents are highly effective for tailoring the flow viscosity of the plasticized gluten dough and the mechanical properties of thermo-molded gluten bioplastics.     

Influence of gliadin removal on strain hardening of hydrated wheat gluten during equibiaxial extensional deformation

The aim of the present work has been to study the equibiaxial extensional deformation of doughs of gluten- and glutenin-rich fractions containing 40 wt% water subjected to lubricated squeezing flow with four different crosshead speeds at room temperature. The gluten dough shows strain softening and hardening in succession whilst the dough where the gliadins have been removed by alcohol extraction does not show strain hardening behavior but breaks immediately after strain softening. The equibiaxial extensional viscosity decreases with increasing strain rate at given strains, appearing as strain rate thinning behavior, which is stronger in the glutenin dough than in the gluten dough. The large extensibility with strain hardening in the gluten dough is due to the presence of gliadins acting as both plasticizers and promoters for the more extensible networks.     

Preparation and properties of thermo-molded bioplastics of glutenin-rich fraction

The present work aims to prepare bioplastics from a glutenin-rich fraction; that is, the gluten residue insoluble in 70% (v/v) ethanol. The influence of reducing agents of sodium bisulfite, sodium sulfite and thioglycolic acid on the properties of the glycerol plasticized doughs and the cross-linked bioplastics were investigated. The results showed that reducing agents can be applied to reduce the Young's modulus of the plasticized dough and to improve the Young's modulus of the cross-linked bioplastics. Moisture absorption, weight loss in water, tensile strength, elongation at break and tensile set were studied to characterize the physical properties of the cross-linked bioplastics.     

Rheological Properties of Short Doughs at Large Deformation

Large deformation rheological properties of short doughs of various composition were determined in uniaxial compression. Apart from a sugar-free dough, all doughs studied showed pronounced yielding and flow behaviour. Yielding occurred at very small strain, indicating strong strain dependence. At small strain, systems were predominantly solid-like; at large strain they behaved more like strain-rate thinning liquids. The doughs showed large differences in apparent biaxial extensional viscosity, depending on fat and sucrose contents. It is concluded that yielding behaviour is strongly influenced by intact flour particles that act as defects in the material. The occurrence of such particles is determined by the presence of sucrose, which delays gluten development through its effect on solvent quality. The sucrose also facilitates formation of a non-fat continuous phase, since it increases the quantity of solvent.     

Rheological Properties of Dough During Mechanical Dough Development

During mechanical development dough is subjected to both shear and extensional deformations. Thus, it is expected that both flow conditions contribute to the development of dough. In order to monitor rheological changes, occurring during mixing, shear and extensional properties of dough prepared with two flours of different strength and various levels of mixing energy were determined using fundamental rheological methods. Rheological measurements included: small deformation and large deformation (shear test), planar extensional flow and a combined shear/extensional flow test, namely extrusion test. Results obtained in this research showed that, during mixing, dough develops with an increase in both apparent shear and extensional viscosities. For all the tests, plots of the measured rheological properties as a function of the mixing energy resembled typical mixing curves. This indicated that the increase in the power drawn by the mixer motor is due to the increase in both apparent shear and extensional viscosities. After peak dough development these properties decreased synchronously with the mixing curves. Results from small deformation shear tests exhibited large variability, particularly when non-mixed and underdeveloped doughs were tested. This variability was associated with poor water distribution in the sample due to insufficient mixing. Results of large deformation tests, including shear, planar extensional flow and the extrusion test, were less variable and showed that mixing and type of flour affect the rheological properties of dough.     

Large Deformation Properties of Short Doughs: Effect of Sucrose in Relation to Mixing Time

Large deformation rheological properties of short doughs of various composition prepared under various mixing times were determined in uniaxial compression. Sucrose-syrup doughs exhibited prominent yielding and flow behaviour. Their apparent biaxial extensional viscosity decreased with increasing sucrose content. The stress-strain curves for the sugar-free doughs indicated a stronger elastic contribution to deformation than did those for the sucrose-syrup doughs. The deformability of the former doughs increased with increasing water content. Regardless of dough type, mixing time had a pronounced effect on dough consistency. In addition, it drastically changed the shape of the stress-strain curve for a sugar-free dough. These results are discussed in terms of the structure of short doughs. It is concluded that sucrose delays, if not inhibits, gluten development and promotes formation of a non-fat continuous phase, whereas mixing promotes formation of a continuous fat phase.     

The effect of sodium chloride on gluten network formation and rheology

Gluten samples were obtained from two wheat flours with different levels of total protein in the presence or absence of sodium chloride (2% flour base). The dynamic oscillation rheology, large extensional deformation, confocal laser scanning microscopy (CLSM), transmission electron microscopy (TEM) and chemical analysis of disulfide bond linkages and the ratio of polymeric glutenins and monomeric gliadins were used to investigate the effect of salt on the structure and rheological properties of gluten. CLSM and TEM images showed that NaCl caused the gluten to form fibrous structure. The presence of NaCl increased non-covalent interactions and β-sheet structure, measured by FTIR, in gluten proteins. The gluten matrix formed with salt resulted in higher tan δ values corresponding to a less elastic network when measured using oscillatory rheometry. Large deformation extensional measurements showed that the maximum force to fracture were lower for the gluten samples prepared in the presence of NaCl. The results from this study indicate that changes in the solvent quality due to the presence of NaCl during dough mixing result in different molecular conformation and network structure of gluten proteins which contributed to the differences in the rheological properties.     

Rheological Behaviour of Wheat Glutens at Small and Large Deformations. Comparison of Two Glutens Differing in Bread Making Potential

The rheological characteristics of hydrated cv. Obelisk and Katepwa glutens, with poor and good baking potential, respectively, were studied at small and large deformations. Dynamic (oscillatory) measurements at small deformations over a frequency range of 0·03 to 3 rad/s showed that cv. Katepwa gluten had a higher dynamic modulus and a lower loss tangent than cv. Obelisk gluten. Overmixing resulted in increases in the dynamic moduli of both glutens. Measurements at different water contents indicated that the lower dynamic moduli at higher water contents resulted mainly from a concentration effect and were not due to water acting as a plasticiser. The apparent biaxial extensional viscosities of the glutens were determined by uniaxial compression of cylindrically shaped test pieces at various cross-head speeds. This proved to be a very useful method of providing information about the rheological behaviour of glutens at large deformations as a function of different strain rates. At every biaxial strain rate tested, the apparent biaxial extensional viscosity of cv. Katepwa gluten was higher than that of cv. Obelisk gluten. A thin layer of biaxially extended gluten showed a higher resistance to further biaxial extension than a less biaxially extended, thicker layer. Cv. Katepwa gluten exhibited this strain hardening behaviour to a greater extent than cv. Obelisk gluten. Possible consequences for baking performance are discussed.     

Feather meal-based thermoplastics: Methyl vinyl ether/maleic anhydride copolymer improves material properties

The poultry meat processing industry produces large amounts of feather meal, which is traditionally used as lowvalue plant fertilizer or fish nutrient. A higher value application for feather meal is described in this paper - a thermal blending and compression molding method to create compostable composites out of environmentally friendly materials: feather meal, glycerol, and a biodegradable copolymer of methyl vinyl ether and maleic anhydride (MVEMA). The composite’s mechanical, microstructural and chemical characteristics are described. Feather meal plasticized only with glycerol is mechanically fragile, with average tensile strength of 1.7 MPa, Young’s modulus of 296 MPa and strain-at-failure of 0.6 %. With the addition of MVEMA copolymer, feather meal is transformed into a ductile plastic composite, with tensile modulus reduced 2- to 5-fold and strain-at-failure increased 4- to 25-fold. These properties are ideal for creating feather mealbased compostable bioplastics for agricultural and industrial applications.     

Effect of sodium chloride on gluten network formation,dough microstructure and rheology in relation to breadmaking

Sodium chloride (NaCl) is an essential ingredient to control the functional properties of wheat dough and bread quality. This study investigated the effect of NaCl at 0, 1 and 2%, (w/w, flour base) on the gluten network formation during dough development, the dough rheology, and the baking characteristics of two commercial flours containing different levels of protein (9.0 and 13.5%) and with different glutenin-to-gliadin ratios. Examination of the dough structure by confocal microscopy at different stages of mixing show that the gluten network formation was delayed and the formation of elongated fibril protein structure at the end of dough development when NaCl was used. The fibril structure of protein influenced the dough strength, as determined by strain hardening coefficient and hardening index obtained from the large deformation extension measurements. NaCl had a greater effect on enhancing the strength of dough prepared from the low protein flour compared to those from the high protein flour. The effect of NaCl on loaf volume and crumb structure of bread followed a similar trend. These results indicate that the effect of NaCl on dough strength and bread quality may be partially compensated by choosing flour with an appropriate amount and quality of gluten protein.     

Surface properties and locations of gluten proteins and lipids revealed using confocal scanning laser microscopy in bread dough

Surface properties of gluten proteins were measured in a dilation test and in compression and expansion tests. The results showed that monomeric gliadin was highly surface active, but polymer glutenin had almost no surface activity. The locations of those proteins in bread dough were investigated using confocal scanning laser microscopy and compared with polar and nonpolar lipids. Added gluten proteins participated in the formation of the film or the matrix, surrounding and separating individual gas cells in bread dough. Gliadin was found in the bulk of dough and gas ‘cell walls’. Glutenin was found only in the bulk dough. Polar lipids were present in the protein matrix and in gas ‘cell walls’, as well as at the surface of some particles, which appeared to be starch granules. However, nonpolar lipid mainly occurred on the surface of particles, which may be starch granules and small lipid droplets. It is suggested that the locations of gluten proteins in bread dough depends on their surface properties. Polar lipid participates the formation of gluten protein matrix and gas ‘cell walls’. Nonpolar lipids may have an effect on the rheological properties by associating with starch granule surfaces and may form lipid droplets.     

Microstructure formation and rheological behaviour of dough under simple shear flow

In a z-blade mixer, both shear and extensional deformations contribute to the development of dough structure. I effect of simple shearing versus z-blade mixing at similar levels of work input, on the microstructure and uniaxial extensional properties of two doughs prepared from flours of different strengths. With respect to microstructure, mixing initially increased the formation of coarse protein patches, leading to a heterogeneous dough structure with a high fracture stress (σ_max) and significant strain hardening. These parameters decreased with prolonged mixing. This was accompanied by loss of glutenin macro polymer (GMP) wet weight and formation of a more homogenous microstructure. Prolonged mixing typically led to an over-mixed state. In contrast, prolonged simple shearing did not affect GMP content or strain hardening and gave enhanced shear banding. Confocal scanning laser microscopy revealed that short-term simple shearing induced structure formation in the direction of the shear flow for both flour types, followed by formation of shear-banded gluten structures both parallel and perpendicular to the direction of shear flow. Uniaxial extension of dough oriented parallel or perpendicular to the shear field did not reveal anisotropy. Apparently, the observed heterogeneity on a scale of ‘mm’ was not relevant for this type of rheology. Nevertheless, a relative weakening of dough strength (reduced fracture stress) was observed as a function of long-term shearing. This seems to be related to a local segregation effect caused by differences in visco-elasticity between the gluten phase and the starch granules. The results of this study reveal important features of the dough processing and underline the importance of not only work input, but also the type of deformation applied.     

Dough processing in a Couette-type device with varying eccentricity: Effect on glutenin macro-polymer properties and dough micro-structure

Dough mixing involves a combination of different deformation flows, e.g. shear and elongation. The complicated nature of mixing process makes it difficult to understand dough processing at a mechanistic level. A new Couette device allowed the effects of shear flow on the physical properties of glutenin macro-polymer (GMP) and micro-structure formation of the dough to be studied. Steady shear deformation using concentric Couette-type flow did not decrease GMP content or size of glutenin particles. Confocal scanning laser microscopy revealed the formation of interconnected gluten domains indicating the development of a gluten network. In an eccentric Couette configuration the results depended on the degree of eccentricity. A higher degree of eccentricity and a longer processing time led to considerable reduction in GMP content and size of glutenin particles. The micro-structural change in the narrow gap regions of the eccentric cell occurred early in processing, leading to a break up of large protein domains, and a microscopically more homogeneous dough. Transient high shear flow led to elongation and break up of the macroscopic gluten network. In low shear regions of the eccentric cell (wider gap settings), reformation or aggregation of protein domains was observed. Thus, the gluten aggregation–break up mechanisms are strongly influenced by the local flow profile in a conventional mixer. The impact of different types of shear flow must be taken into account in the design of dough mixers.     

Heterologous Expression and Dough Mixing Studies of Wild-Type and Mutant C Hordeins

Wild type and mutant (cysteine-containing) forms of C hordein were expressed inEscherichia coli. Incorporation of a mutant form with N- and C-terminal cysteine residues into dough using a 2 g Mixograph showed similar positive effects on dough strength to the incorporation of HMW subunit 1Bx7. Co-incorporation showed that the effects of the two proteins were additive. In contrast, the incorporation of wild type C hordein or mutants with single cysteines at the N- or C-terminus resulted in decreased dough strength, with the two mutant forms inhibiting the positive effect of 1Bx7. Analysis of total protein extracts from the doughs indicate that the differences resulted from alterations in the proportions of gluten monomers, small gluten polymers and large gluten polymers.     

Strain Hardening Properties and Extensibility of Flour and Gluten Doughs in Relation to Breadmaking Performance

The mechanical properties of flour–water doughs and hydrated gluten of different wheat cultivars were determined. Measurements were performed at small deformations (dynamic measurements) as well as at large deformations (biaxial extension measurements). Results of dynamic measurements of flour doughs related poorly to breadmaking quality. For hydrated gluten doughs, all having the same water content, it was found that glutens from wheat cultivars with good baking quality had higher values for the storage modulus,G, and lower values for the loss tangent. The relevant type of deformation around an expanding gas bubble is biaxial extension. Wheats with a good baking performance exhibited greater strain hardening and greater extensibility. The differences in strain hardening observed at 20 °C were also present at 55 °C. No clear effects of NaCl or emulsifiers on the biaxial extension properties of flour dough were found. Extensograms as well as Alveograms from the flour doughs showed that, in general, good baking flours exhibited stronger resistance to extension and a greater extensibility, but differences found were not directly related to the results of the baking tests. The results indicate that the baking performance of dough is related to a combination of at least three different rheological characteristics.     

Thermoplastic films from wheat proteins

We show that the wheat proteins gluten, gliadin and glutenin can be compression molded into thermoplastic films with good tensile strength and water stability. Wheat gluten is inexpensive, abundantly available, derived from renewable resource and therefore widely studied for potential thermoplastic applications. However, previous reports on developing thermoplastics from wheat proteins have used high amounts of glycerol (30-40%) and low molding temperature (90-120 °C) resulting in thermoplastics with poor tensile properties and water stability making them unsuitable for most thermoplastic applications. In this research, we have developed thermoplastic films from wheat gluten, gliadin and glutenin using low glycerol concentration (15%) but high molding temperatures (100-150 °C). Our research shows that wheat protein films with good tensile strength (up to 6.7 MPa) and films that were stable in water can be obtained by choosing appropriate compression molding conditions. Among the wheat proteins, wheat gluten has high strength and elongation whereas glutenin with and without starch had high strength and modulus but relatively low elongation. Gliadin imparts good extensibility but decreased the water stability of gluten films. Gliadin films had strength of 2.2 MPa and good elongation of 46% but the films were unstable in water. Although the tensile properties of wheat protein films are inferior compared to synthetic thermoplastic films, the type of wheat proteins and compression molding conditions can be chosen to obtain wheat protein films with properties suitable for various applications.     

Oat malt as a baking ingredient – A comparative study of the impact of oat,barley and wheat malts on bread and dough properties

Oat malt is a nutritionally rich ingredient mainly used in a small number of speciality products. The aim of this study was to evaluate the suitability of oat malt in wheat baking. The effect of oat malt on bread and dough properties at levels ranging from 0.5% to 5% was studied and compared with barley and wheat malts. The addition of all malts increased loaf specific volumes. Barley and wheat malts at levels above 2.5% led to a sticky and coarse crumb, but the effect of oat malt on the crumb grain was negligible. Rheological characterisation could not explain the superior baking performance of oat malt, as it increased extensibility and decreased resistance extensively indicating weakening of the extensional properties of the gluten network. The high lipolytic activity may have compensated for the loss of dough strength by improving the surface properties of gas cells. The results show that oat malt can be used in wheat baking to improve the loaf volume and nutritional quality without the detrimental effects associated with the excess amylolytic activity of barley and wheat malts.     

Rheological properties of kafirin and zein prolamins

The possibility of forming dough from kafirin was investigated and laboratory prepared kafirin was formed into a viscoelastic dough system. Measurements with Contraction Flow showed that dough systems prepared from kafirin and from commercial zein had the required extensional rheological properties for baking of leavened bread. The extensional viscosity and strain hardening of the kafirin and zein dough systems were similar to those of gluten and wheat flour doughs. The kafirin dough system, however, unlike the zein dough system rapidly became very stiff. The stiffening behaviour of the kafirin dough system was presumed to be caused by cross-linking of kafirin monomers. SDS-PAGE showed that the kafirin essentially only contained α- and γ-kafirin, whereas the zein essentially only contained α-zein. Since γ-kafirin contains more cysteine residues than the α-prolamin it is more likely to form disulphide cross-links, which probably caused the differences in stiffening behaviour between kafirin and zein dough systems. Overall the kafirin dough system displayed rheological properties sufficient for baking of porous bread. Kafirin like zein appears to have promising properties for making non-gluten leavened doughs.