Wheat starch carbamate: Production, molecular characterization, and film forming properties.

Wheat starch carbamates of different degrees of substitution were produced in laboratory experiments and for the first time their film forming performance were investigated. The carbamation reaction between urea and starch was investigated using a factorial design. Long reaction time, 2h, and high urea content, 10 and 25%, resulted in a high degree of substitution, 0.07 and 0.15, respectively. These starch carbamates were assumed to be cross-linked and showed best film forming properties resulting in continuous and firm films. Furthermore, a high degree of carbamate substitution favored a decrease in glass transition temperature (Tg) in cast films. The addition of acid as a catalyst for carbamation of starch produced inconsistent results and mainly lead to degradation of starch molecules that caused brittle films. FTIR and 13C NMR analyses confirmed the covalent bonding between urea and starch in starch carbamates. In a final step, production of starch carbamates was successfully scaled up. A potential industrial use of these starches is as oxygen barrier in multilayer food packaging.

Film Extrusion of Crambe abyssinica/Wheat Gluten Blends.

Crambe abyssinica is a plant with potential for use in industrial (non-food) plant oil production. The side stream from this oil production is a high-protein crambe meal that has limited value, as it is not fit for food or feed use. However, it contains proteins that could potentially make it a suitable raw material for higher-value products. The purpose of this study was to find methods of making this side stream into extruded films, showing that products with a higher value can be produced. The study mainly considered the development of material compositions and methods of preparing and extruding the material. Wheat gluten was added as a supportive protein matrix material, together with glycerol as a plasticizer and urea as a denaturant. The extrudate was evaluated with respect to mechanical (tensile testing) and oxygen barrier properties, and the extrudate structure was revealed visually and by scanning electron microscopy. A denser, more homogeneous material had a lower oxygen transmission rate, higher strength, and higher extensibility. The most homogeneous films were made at an extruder die temperature of 125-130 °C. It is shown here that a film can be extruded with promising mechanical and oxygen barrier properties, the latter especially after a final compression molding step.

Unusual effects of monocarboxylic acids on the structure and on the transport and mechanical properties of chitosan films.

The purpose of this study was to study the transport of monocarboxylic acids in chitosan films, since this is important for understanding and predicting the drying kinetics of chitosan from aqueous solutions. Despite the wealth of data on chitosan films prepared from aqueous monocarboxylic acid solutions, this transport has not been reported. Chitosan films were exposed to formic, acetic, propionic and butyric acid vapours, it was found that the rate of uptake decreased with increasing molecular size. The equilibration time was unexpectedly long, especially for propionic and butyric acid, nine months. A clear two-stage uptake curve was observed for propionic acid. Evidently, the rate of uptake was determined by acid-induced changes in the material. X-ray diffraction and infrared spectroscopy indicated that the structure of the chitosan acetate and buffered chitosan films changed during exposure to acid and during the subsequent drying. The dried films previously exposed to the acid showed less crystalline features than the original material and a novel repeating structure possibly involving acid molecules. The molar mass of the chitosan decreased on exposure to acid but tensile tests revealed that the films were always ductile. The films exposed to acid vapour (propionic and butyric acid) for the longest period of time were insoluble in the size-exclusion chromatography eluent, and they were also the most ductile/extensible of all samples studied.

Improved material properties of solution-cast starch films: Effect of varying amylopectin structure and amylose content of starch from genetically modified potatoes.

High-amylose potato starches were produced through genetic modification resulting in changed granule morphology and composition, with higher amylose content and increased chain length of amylopectin. The increased amylose content and structural changes in amylopectin enhanced film-forming behavior and improved barrier and tensile properties in starch films. The molecular structure in these starches was related to film-forming properties. Solution-cast films of high-amylose starch revealed a homogeneous structure with increasing surface roughness at higher amylose content, possibly due to amylose aggregation. Films exhibited significantly higher stress and strain at break compared with films of wild-type starch, which could be attributable to the longer chains of amylopectin being involved in the interconnected network and more interaction between chains, as shown using transmission electron microscopy. The oxygen permeability of high-amylose starch films was significantly decreased compared with wild-type starch. The nature of the modified starches makes them an interesting candidate for replacement of non-renewable oxygen and grease barrier polymers used today.

Macromolecular changes and nano-structural arrangements in gliadin and glutenin films upon chemical modification: Relation to functionality.

Protein macromolecules adopted for biological and bio-based material functions are known to develop a structured protein network upon chemical modification. In this study, we aimed to evaluate the impact of chemical additives such as, NaOH, NH4OH and salicylic acid (SA), on the secondary and nano-structural transitions of wheat proteins. Further, the effect of chemically induced modifications in protein macromolecular structure was anticipated in relation to functional properties. The gliadin-NH4OH-SA film showed a supramolecular protein organization into hexagonal structures with 65 Å lattice parameter, and other not previously observed structural entities having a characteristic distance of 50 Å. Proteins in gliadin-NH4OH-SA films were highly polymerized, with increased amount of disulfide crosslinks and ß-sheets, causing improved strength and stiffness. Glutenin and WG proteins with NH4OH-SA showed extensive aggregation and an increase in ß-sheet content together with irreversible crosslinks. Irreversible crosslinks hindered a high order structure formation in glutenins, and this resulted in films with only moderately improved stiffness. Thus, formation of nano-hierarchical structures based on ß-sheets and disulfide crosslinks are the major reasons of high strength and stiffness in wheat protein based films.

Nanostructural morphology of plasticized wheat gluten and modified potato starch composites: relationship to mechanical and barrier properties.

In the present study, we were able to produce composites of wheat gluten (WG) protein and a novel genetically modified potato starch (MPS) with attractive mechanical and gas barrier properties using extrusion. Characterization of the MPS revealed an altered chain length distribution of the amylopectin fraction and slightly increased amylose content compared to wild type potato starch. WG and MPS of different ratios plasticized with either glycerol or glycerol and water were extruded at 110 and 130 °C. The nanomorphology of the composites showed the MPS having semicrystalline structure of a characteristic lamellar arrangement with an approximately 100 Å period observed by small-angle X-ray scattering and a B-type crystal structure observed by wide-angle X-ray scattering analysis. WG has a structure resembling the hexagonal macromolecular arrangement as reported previously in WG films. A larger amount of ß-sheets was observed in the samples 70/30 and 30/70 WG-MPS processed at 130 °C with 45% glycerol. Highly polymerized WG protein was found in the samples processed at 130 °C versus 110 °C. Also, greater amounts of WG protein in the blend resulted in greater extensibility (110 °C) and a decrease in both E-modulus and maximum stress at 110 and 130 °C, respectively. Under ambient conditions the WG-MPS composite (70/30) with 45% glycerol showed excellent gas barrier properties to be further explored in multilayer film packaging applications.

Effect of additives on the tensile performance and protein solubility of industrial oilseed residual based plastics.

Ten chemical additives were selected from the literature for their proposed modifying activity in protein-protein interactions. These consisted of acids, bases, reducing agents, and denaturants and were added to residual deoiled meals of Crambe abyssinica (crambe) and Brassica carinata (carinata) to modify the properties of plastics produced through hot compression molding at 130 °C. The films produced were examined for tensile properties, protein solubility, molecular weight distribution, and water absorption. Of the additives tested, NaOH had the greatest positive effect on tensile properties, with increases of 105% in maximum stress and 200% in strain at maximum stress for crambe and a 70% increase in strain at maximum stress for carinata. Stiffness was not increased by any of the applied additives. Changes in tensile strength and elongation for crambe and elongation for carinata were related to changes in protein solubility. Increased pH was the most successful in improving the protein aggregation and mechanical properties within the complex chemistry of residual oilseed meals.

Structure and morphology of wheat gluten films: from polymeric protein aggregates toward superstructure arrangements.

Evaluation of structure and morphology of extruded wheat gluten (WG) films showed WG protein assemblies elucidated on a range of length scales from nano (4.4 Å and 9 to 10 Å, up to 70 Å) to micro (10 µm). The presence of NaOH in WG films induced a tetragonal structure with unit cell parameters, a = 51.85 Å and c = 40.65 Å, whereas NH(4)OH resulted in a bidimensional hexagonal close-packed (HCP) structure with a lattice parameter of 70 Å. In the WG films with NH(4)OH, a highly polymerized protein pattern with intimately mixed glutenins and gliadins bounded through SH/SS interchange reactions was found. A large content of ß-sheet structures was also found in these films, and the film structure was oriented in the extrusion direction. In conclusion, this study highlights complexities of the supramolecular structures and conformations of wheat gluten polymeric proteins in biofilms not previously reported for biobased materials.

Properties of wheat gluten/poly(lactic acid) laminates.

Laminates of compression-molded glycerol-plasticized wheat gluten (WG) films surrounded and supported by poly(lactic acid) (PLA) films have been produced and characterized. The objective was to obtain a fully renewable high gas barrier film with sufficient mechanical integrity to function in, for example, extrusion-coating paper/board applications. It was shown that the lamination made it possible to make films with a broad range of glycerol contents (0-30 wt %) with greater strength than single unsupported WG films. The low plasticizer contents yielded laminates with very good oxygen barrier properties. In addition, whereas the unsupported WG films had an immeasurably high water vapor transmission rate (WVTR), the laminate showed values that were finite and surprisingly, in several cases, also lower than that of PLA. Besides being a mechanical support (as evidenced by bending and tensile data) and a shield between the WG and surrounding moisture, the PLA layer also prevented the loss of the glycerol plasticizer from the WG layer. This was observed after the laminate had been aged on an "absorbing" blotting paper for up to 17 weeks. The interlayer adhesion (peel strength) decreased with decreasing glycerol content and increasing WG film molding temperature (130 degrees C instead of 110 degrees C). The latter effect was probably due to a higher protein aggregation, as revealed by infrared spectroscopy. The lamination temperature (110-140 degrees C) did not, however, have a major effect on the final peel strength.

Properties of extruded vital wheat gluten sheets with sodium hydroxide and salicylic acid.

This paper presents a novel approach to improve the barrier and mechanical properties of extruded glycerol-plasticized vital wheat gluten sheets. The sheets were extruded with a single screw extruder at alkaline conditions using 3-5 wt % NaOH. Salicylic acid (SA), known to improve the extrudability of wheat gluten, was also added alone or in combination with NaOH. Oxygen transmission rate and volatile mass measurements, tensile tests, protein solubility, glycerol migration, infrared spectroscopy, and electrophoresis were used to assess the properties of the extrudate. Electrophoresis showed that the gluten/glycerol sheet and the sheet with 3 wt % NaOH and 1 wt % SA contained the same building blocks in terms of proteins and protein subunits, although the protein solubility in these samples was different. The oxygen barrier, at dry conditions, was improved significantly with the addition of NaOH. On the other hand, the addition of salicylic acid yielded poorer barrier properties. The extrudate was placed on a blotting paper and its aging properties were investigated during the first 120 days. It was observed that the extrudate with 3 wt % NaOH had the most suitable combination of properties (low oxygen permeability, large strain at break, and relatively small aging-induced changes in mechanical properties); the reason is probably due to low plasticizer migration and an optimal protein aggregation/polymerization.

Enhancement of the wet properties of transparent chitosan-acetic-acid-salt films using microfibrillated cellulose.

This report presents a new route to enhance the wet properties of chitosan-acetic-acid-salt films using microfibrillated cellulose (MFC). The enhancement makes it easier to form chitosan-acetic-acid-salt films into various shapes at room temperature in the wet state. Chitosan with MFC was compared with the well-known buffer treatment. It was observed that films containing 5 wt % MFC were visually identical to the buffered/unbuffered films without MFC. Field-emission scanning electron microscopy indicated that MFC formed a network with uniformly distributed fibrils and fibril bundles in the chitosan matrix. The addition of MFC reduced the risk of creases and deformation in the wet state because of a greater wet stiffness. The wet films containing MFC were also extensible. Although the stiffness, strength and extensibility were highest for the buffered films, the wet strength of the MFC-containing unbuffered films was sufficient for wet forming operations. The effects of MFC on the mechanical properties of the dry chitosan films were small or absent. It was concluded that the addition of MFC is an acceptable alternative to buffering for shaping chitosan films/products in the wet state. The advantages are that the "extra" processing step associated with buffering is unnecessary and that the film matrix remains more water-soluble.

Aging properties of films of plasticized vital wheat gluten cast from acidic and basic solutions.

In order to understand the mechanisms behind the undesired aging of films based on vital wheat gluten plasticized with glycerol, films cast from water/ethanol solutions were investigated. The effect of pH was studied by casting from solutions at pH 4 and pH 11. The films were aged for 120 days at 50% relative humidity and 23 degrees C, and the tensile properties and oxygen and water vapor permeabilities were measured as a function of aging time. The changes in the protein structure were determined by infrared spectroscopy and size-exclusion and reverse-phase high-performance liquid chromatography, and the film structure was revealed by optical and scanning electron microscopy. The pH 11 film was mechanically more stable with time than the pH 4 film, the latter being initially very ductile but turning brittle toward the end of the aging period. The protein solubility and infrared spectroscopy measurements indicated that the protein structure of the pH 4 film was initially significantly less polymerized/aggregated than that of the pH 11 film. The polymerization of the pH 4 film increased during storage but it did not reach the degree of aggregation of the pH 11 film. Reverse-phase chromatography indicated that the pH 11 films were to some extent deamidated and that this increased with aging. At the same time a large fraction of the aged pH 11 film was unaffected by reducing agents, suggesting that a time-induced isopeptide cross-linking had occurred. This isopeptide formation did not, however, change the overall degree of aggregation and consequently the mechanical properties of the film. During aging, the pH 4 films lost more mass than the pH 11 films mainly due to migration of glycerol but also due to some loss of volatile mass. Scanning electron and optical microscopy showed that the pH 11 film was more uniform in thickness and that the film structure was more homogeneous than that of the pH 4 film. The oxygen permeability was also lower for the pH 11 film. The fact that the pH 4 film experienced a larger and more rapid change in its mechanical properties with time than the pH 11 film, as a consequence of a greater loss of plasticizer, was presumably due to its initial lower degree of protein aggregation/polymerization. Consequently, the cross-link density achieved at pH 4 was too low to effectively retain volatiles and glycerol within the matrix.

Enlarged processing window of plasticized wheat gluten using salicylic acid.

The temperature window for the extrusion of glycerol-plasticized wheat gluten was increased by the use of salicylic acid, a known scorch retarder and radical scavenger. It was possible to extrude 30 wt % glycerol-wheat gluten films with a die-head temperature as high as 135 degrees C, rather than 95 degrees C, by incorporating only 1 wt % salicylic acid. Small effects of shear-induced heating during extrusion at the higher temperatures suggested that the acid acted as a lubricant and viscosity reducer. The latter was suggested to originate primarily from the salicylic-acid-induced reduction in the degree of protein aggregation/cross-linking, as indicated by size-exclusion high-performance liquid chromatography and chemiluminescence. Electron paramagnetic resonance spectroscopy on extruded films indicated that the beneficial effect of salicylic acid was due to its radical scavenging effect. Tensile tests on extrudates revealed that the materials produced at the substantially higher processing temperature were still ductile. The complex shear modulus increased more slowly with increasing salicylic acid content above 110-120 degrees C, indicating that the aggregation/cross-linking rate was slower with salicylic acid, that is, that it did have a scorch-retarding effect, besides yielding a lower final degree/complexity of aggregation.

Properties of aged montmorillonite-wheat gluten composite films.

The properties of new and aged glycerol-plasticized vital wheat gluten films containing < or =4.5 wt % natural or quaternary ammonium salt modified montmorillonite clay were investigated. The films were cast from pH 4 or pH 11 ethanol/water solutions. The films, aged for < or =120 days, were characterized by tensile testing, X-ray diffraction, and transmission electron microscopy. In addition, water vapor permeability (11% relative humidity) and the content of volatile components were measured. The large reduction in the water vapor permeability with respect to the pristine polymer suggests that the clay platelets were evenly distributed within the films and oriented preferably with the platelet long axis parallel to the film surface. The film prepared from pH 11 solution containing natural clay was, as revealed by transmission electron microscopy and X-ray diffraction, almost completely exfoliated. This film was consequently also the strongest, the stiffest, and the most brittle and, together with the pH 11 film containing modified clay, it also showed the greatest decrease in water vapor permeability. The large blocking effect of the clay had no effect on the aging kinetics of the films. During aging, the pH 4 and pH 11 film strength and the pH 4 film stiffness increased and the pH 4 film ductility decreased at the same rate with or without clay. This suggests that the aging was not diffusion rate limited, that is, that the loss of volatile components or the migration of glycerol or glycerol/wheat gluten phase separation was not limited by diffusion kinetics. The aging rate seemed to be determined by slow structural changes, possibly involving protein denaturation and aggregation processes.

Transport and tensile properties of compression-molded wheat gluten films.

Mechanical and transport properties were assessed on wheat gluten films with a glycerol content of 25-40%, prepared by compression molding for 5-15 min at temperatures between 90 and 130 degrees C. Effects of storing the films up to 24 days, in 0 and 50% relative humidity (RH), were assessed by tensile measurements. The films were analyzed with respect to methanol zero-concentration diffusivity, oxygen permeability (OP), water vapor permeability (WVP), Cobb60 and sodium dodecyl sulfate (SDS) solubility coupled with sonication. The SDS solubility and methanol diffusivity were lower at the higher molding temperature. Higher glycerol content resulted in higher OP (90-95% RH), WVP, and Cobb60 values, due to the plasticizing and hygroscopic effects. Higher glycerol contents gave a lower fracture stress, lower Young's modulus, lower fracture strain, and less strain hardening. The mold time had less effect on the mechanical properties than mold temperature and glycerol content. The fracture stress and Young's modulus increased and the fracture strain decreased with decreasing moisture content.