Intermolecular interactions and phase structures of plasticized wheat proteins materials

The intermolecular interactions and phase structures of thermally processed wheat proteins with glycerol and water as plasticizers were studied by dynamic mechanical analysis and solid-state high-resolution NMR spectroscopy. The results of phase structures at scales of molecular level to tens of nanometers were correlated with the mechanical properties of the materials. The strong hydrogen bonding intermolecular interactions between the components in wheat proteins and the plasticizers resulted in a significant change in molecular motions of wheat protein materials. The plasticized systems, however, still presented a wide distribution of chain mobility at a scale from the molecular level to 20-30 nm, and the plasticizing effect was different for each wheat protein system. High protein content systems tended to be plasticized relatively easily especially when lipid content is high, but the existence of residual starch would require more plasticizers to reach a similar level of chain mobility. On a scale of 20-30 nm, plasticized vital wheat gluten (WG) and the deamidated wheat proteins (WP-I) were heterogeneous with each component exhibiting its individual mobility, whereas the plasticized insoluble protein system (WP-II) with poor mechanical properties was homogeneous. Both WG and WP-I systems showed excellent mechanical polymeric properties in tensile strength and elasticity despite the heterogeneity. The strong intermolecular hydrogen bonding interactions and soluble protein components in the materials could provide an adhesion among different components and act as a continuous matrix in the systems. Therefore, these materials displayed excellent mechanical properties via coordination effects among different components.     

Wheat gluten-based renewable and biodegradable polymer materials with enhanced hydrophobicity by using epoxidized soybean oil as a modifier

Epoxidized soybean oil (ESO) was applied as an additive for wheat gluten (WG) to modify the properties of the renewable and biodegradable natural polymer materials. Optimum intermolecular interactions and crosslinking between ESO chains and the WG matrix were achieved under alkaline conditions. The WGESO materials were heterogeneous on a scale of 20-30 nm, but the homogeneity was improved upon increasing the amount of glycerol as a plasticizer in the materials. The combination of plasticization and crosslinking effects derived from ESO resulted in good retention in mechanical strength for the plasticized WGESO materials as compared to those without 10 wt % of mobile ESO additives. The hydrophobicity of the plasticized WG materials was also enhanced significantly by using the ESO additives.     

Wheat-gluten-based natural polymer nanoparticle composites

A series of wheat-gluten-based nanocomposites were produced by dispersing Cloisite-30B nanoclay particles into plasticized wheat gluten systems under thermal processing conditions. The exfoliation of the nanoparticles as confirmed by wide-angle X-ray diffraction and transmission electron microscopy has resulted in significant enhancement of the mechanical properties for both deamidated proteins and vital gluten systems under 50% relative humidity (RH). Such strength improvement was also pronounced for wheat gluten (WG) systems under a high humidity condition (RH = 85%). A similar level of further strength enhancement was obtained for the WG systems that had been strengthened by blending with poly(vinyl alcohol) (PVA) and cross-linking with glyoxal. Although the nanoclay modifier, a quaternary ammonium, caused an additional plasticization to the materials, the interactions between the gluten matrix and the nanoparticles were predominant in all of these nanocomposites. A solid-state NMR study indicated that the polymer matrix in all of these nanocomposites displayed a wide distribution of chain mobilities at a molecular level (less than 1 nm). The interactions between the nanoparticles and the natural polymer matrix resulted in motional restriction for all components in the mobile phases including lipid, plasticizers, and plasticized components, although no significant influence from the nanoparticles was obtained in the mobility of the rigid phases (unplasticized components). On a scale of 20-30 nm, the deamidated protein systems tended to be homogeneous. The small domain size of the matrix resulted in modifications of the spin-lattice relaxation of these systems via spin diffusion. The residual starch seemed to remain in a relatively larger domain size in WG systems. The nanoparticles could enhance the miscibility between the starch and the other components in the WG nanocomposite, but such miscibility enhancement did not occur in the WG/PVA blend and the cross-linked system. These polymer matrixes were still heterogeneous on a scale of 20-30 nm.     

Plasticization and crosslinking effects of acetone-formaldehyde and tannin resins on wheat protein-based natural polymers

Efficient plasticization and sufficient crosslinking were achieved by using an acetone-formaldehyde (AF) resin as an additive in the thermal processing of wheat protein-based natural polymers. The mobile AF resin and its strong intermolecular interactions with a wheat protein matrix produced sufficient flexibility for the plastics, while the covalent bonds formed between AF and the protein chains also caused the water-soluble resin to be retained in the materials under wet conditions. The mechanical properties of the materials were also enhanced as an additional benefit due to the formation of crosslinked networks through the polymer matrix. Tensile strength was further enhanced when using AF in conjunction with tannin resin (AFTR) in the systems as rigid aromatic structures were formed in the crosslinking segments. Different components in wheat proteins (WPs) or wheat gluten (WG) (e.g., proteins, residual starch and lipids) displayed different capabilities in interaction and reaction with the AFTR additives, and thus resulted in different performances when the ratio of these components varied in the materials. The application of the AFTR additives provides a feasible methodology to thermally process wheat protein-based natural polymers with improved mechanical performance and water-resistant properties.     

Injection-molded nanocomposites and materials based on wheat gluten

This is, to our knowledge, the first study of the injection molding of materials where wheat gluten (WG) is the main component. In addition to a plasticizer (glycerol), 5 wt.% natural montmorillonite clay was added. X-ray indicated intercalated clay and transmission electron microscopy indicated locally good clay platelet dispersion. Prior to feeding into the injection molder, the material was first compression molded into plates and pelletized. The filling of the circular mold via the central gate was characterized by a divergent flow yielding, in general, a stronger and stiffer material in the circumferential direction. It was observed that 20-30 wt.% glycerol yielded the best combination of processability and mechanical properties. The clay yielded improved processability, plate homogeneity and tensile stiffness. IR spectroscopy and protein solubility indicated that the injection molding process yielded a highly aggregated structure. The overall conclusion was that injection molding is a very promising method for producing WG objects.     

Chemical modification of wheat-protein-based natural polymers: formation of polymer networks with alkoxysilanes to modify molecular motions and enhance the material performance

The mechanical performance of plasticized wheat gluten (WG) materials was significantly modified through the formation of different chemical and network structures with alkoxysilanes. The epoxy-functionalized alkoxysilanes were grafted to segments of WG, and then the condensation reactions between alkoxysilane segments occurred during thermal processing to form WG-siloxane networks. The mechanical properties and molecular motions of the networks were dependent on the amount and type of alkoxysilanes applied. A lower amount of alkoxysilanes caused the alkoxysilane molecules to predominately graft onto WG chains without forming linkages between WG segments, which produced an additional plasticizing effect on the WG systems with a longer elongation value and weaker tensile strength at relative humidity (RH) = 50% as compared to the WG system. However, such grafting improved the hydrostability of the materials and generated an improvement in tensile strength at RH = 85%. Increasing the amount of alkoxysilanes in the systems led to the formation of cross-linked WG-siloxane networks via linkages between alkoxysilane segments. Remarkable strength improvement was obtained for the networks with elongation values still higher than the original plasticized WG due to the flexible nature of the siloxane components. A more significant strength improvement was obtained for the WG-SiA systems at both RH = 50% and 85%, where SiA could form three-dimensional networks from siloxane condensation and generate highly cross-linked network structures with relatively low mobility. For WG-SiB systems, SiB could only form linear linkages, and the higher mobility of the SiB phase caused the systems to display a lower strength improvement with a longer elongation value.     

An Insight into the Role of Glycerol in Chitosan Films

This work was focused on assessing the influence of the glycerol in chitosan matrices, analyzing the changes produced in the molecular mobility, mechanical, thermal, barrier and structural properties. The addition of glycerol in the matrix decreased the stress values, increasing the elasticity and water vapor permeability of the films, with a marked decrease in glass transition temperature; Detailed analyses of Fourier Transform IR Spectroscopy spectra supported the observed changes, especially in the spectral windows 1700–1500 cm^?1 revealing the modifications at molecular level caused by hydrogen bond interactions between chitosan and water in the presence of glycerol. Positron annihilation spectroscopic (PALS) measurements allowed determining the free volume assuming spherical holes as well as monitoring the structural changes in chitosan films caused by the addition of both, glycerol and water molecules. It was possible to infer that for unplasticized matrices, a sustained increase of the radius between 0.06 and 0.2 of X_water was observed, followed by a plateau up to 0.35. In the other case, with the addition of glycerol, there were two plateaus, the first between 0.25 and 0.37 of X_water, and the second from 0.41 to 0.47. For higher glycerol concentrations, the plasticizer would be mainly bounded to the chitosan pack more efficiently and the water present in the system would be predominantly free in the matrix causing its swelling. Findings on molecular mobility contributed to the understanding of the role of water and glycerol in the structural arrangement and its influence on film properties.     

Rational design and characterization of bioplastics from Hermetia illucens prepupae proteins

In this study proteins extracted from prepupae of Hermetia illucens, also known as black soldier fly, are investigated as promising base for a new type of bioplastics for agricultural purposes. Design of experiments techniques are employed to perform a rational study on the effects of different combination of glycerol as plasticizer, citric acid as cross-linking agent and distilled water as solvent on the capability of proteins to form a free-standing film through casting technique, keeping as fixed the quantity of proteins. Glycerol shows interesting properties as plasticizer contributing to the formation of homogenous and free-standing film. Moreover, mechanical and thermal characterizations are performed to estimate the effect of increasing amounts of proteins on the final properties and thickness of the specimens. Proteins derived from H. illucens can be successfully employed as base for bioplastics to be employed for agricultural purposes.     

Mechanical and Barrier Properties of Avenin, Kafirin, and Zein Films

Biodegradable and renewable materials can be manufactured from prolamins, which are the major storage protein fraction of cereals. This paper investigates the material properties of oat prolamin (avenin), corn prolamin (zein), and sorghum prolamin (kafirin). Glass transition temperature, dry solid content, stress at break, strain at break, oxygen permeability, and water vapor permeability were analyzed at different plasticizer contents. Avenin was plasticized with glycerol, and kafirin and zein were plasticized with a mixture of polyethylene glycol, glycerol, and lactic acid. Avenin displayed potential, although it did not exhibit the mechanical qualities of gluten, which resembles avenin at the molecular level. Compared to kafirin and zein, avenin was more extensible at low plasticizer contents, while kafirin and especially zein were more extensible at the highest plasticizer content. Avenin was far weaker than the other two at all plasticizer contents. Kafirin and zein displayed similar barrier properties, whereas avenin was notably more permeable.     

Plasticized waxy maize starch: effect of polyols and relative humidity on material properties

The plasticizing effect of different polyols such as glycerol, xylitol, sorbitol, and maltitol on waxy maize starch was investigated. The concentration of plasticizer was fixed at 33 wt % (dry basis of starch). The structure and mechanical performance of resulting films conditioned at different relative humidity levels were studied in detail. The effect of the plasticizer on the glass-rubber transition temperature (T(g)) and crystallinity was characterized using differential scanning calorimetry. It was found that T(g) decreases with increasing moisture content and decreasing molecular weight of the plasticizer. The water resistance of starch increased steadily with the molecular weight of the plasticizer and was directly proportional to the ratio of the end to total hydroxyl groups. As the molecular weight of the plasticizer increased, the brittleness of the dry system increased. However, the use of high molecular plasticizer allowed good mechanical properties of the moist material to be obtained in terms of both stiffness and elongation at break.     

The effect of citric acid on the structural properties and cytotoxicity of the polyvinyl alcohol/starch films when molding at high temperature

A series of starch/polyvinyl alcohol (PVA) films, denoted SP films, with varying concentrations (5–30 wt%) of citric acid (CA) were solvent cast at 140 °C. The effects of CA on the chemical structure, thermal properties, swelling degree, mechanical properties, crystallinity, and cytotoxicity were investigated. Fourier-transform infrared (FT-IR) spectroscopy showed that an esterification took place between CA and starch (or PVA) during molding at 140 °C. This esterification and the multi-carboxyl structure of CA resulted in a chemical cross-linking of the blended system. Furthermore, the esterification occurred more easily between starch and CA as opposed to between the PVA and CA. The residual-free CA acted as a plasticizer for the starch and PVA. As compared to the hydroxyl groups on glycerol, the carboxyl groups on CA were capable of forming stronger hydrogen bonds between CA and other components, and this cross-linking and strong hydrogen bonding enhanced the thermal stability of the SP films. Consequently, the water absorbance decreased from 33% to 20% as the CA percentage increased from 5 to 30 wt%. When 5 wt% CA was added, the tensile strength of the sample increased from 39 to 48 MPa, but when even more CA was added (from 5 to 30 wt%), the tensile strength decreased from 48 to 42 MPa and the elongation at break increased from 102% to 208%. This was caused by the plasticizing effect of the residual-free CA in the blend. The cell relative growth rates of samples with varying CA concentrations exceeded 80% after 7 days of incubation, and this demonstrated that there was no significant toxicity on the cells’ growth when the CA content was less than 20 wt%.     

Rheological behaviour and physical properties of controlled-release gluten-based bioplastics

Bioplastics based on glycerol, water and wheat gluten have been manufactured in order to determine the effect that mechanical processing and further thermal treatments exert on different thermo-mechanical properties of the biomaterials obtained. An “active agent”, KCl was incorporated in these matrices to develop controlled-release formulations. Oscillatory shear, dynamic mechanical thermal analysis (DMTA), diffusion and water absorption tests were carried out in order to study the influence of the above-mentioned treatments on the physico–chemical characteristics and rheological behaviour of these bioplastic samples. Wheat gluten protein-based bioplastics studied in this work present a high ability for thermosetting modification, due to protein denaturation, which may favour the development of a wide variety of biomaterials. Bioplastic hygroscopic properties depend on plasticizer nature and processing procedure, and may be a key factor for industrial applications where water absorption is required. On the other hand, high water absorption and slow KCl release from bioplastic samples (both of them suitable properties in agricultural applications) may be obtained by adding citric acid to a given formulation, at selected processing conditions.     

Preparation and characterization of a thermostable and biodegradable biopolymers using natural cross-linker

The present study describes preparation and characterization of a thermally stable and biodegradable biopolymer using collagen and a natural polymer, alginic acid (AA). Required concentration of alginic acid and collagen was optimized and the resulting biopolymer was characterized for, degree of cross-linking, mechanical strength, thermal stability, biocompatibility (toxicity) and biodegradability. Results reveal, the degree of cross-linking of alginic acid (at 1.5% concentration) with collagen was calculated as 75%, whereas it was 83% with standard cross-linking agent, glutaraldehyde (at 1.5% concentration). The AA cross-linked biopolymer was stable up to 245°C and Exhibits 5-6-fold increase in mechanical (tensile) strength compared to plain collagen (native) materials. However, glutaraldehyde cross-linked material exhibits comparatively less thermal stability and brittle in nature (low tensile strength). With regard to cell toxicity, no cytotoxicity was observed for AA cross-linked material when tested with mesenchymal cells and found degradable when treated with collagenase enzyme. The nature of bonding pattern and the reason for thermal stability of AA cross-linked collagen biopolymer was discussed in detail with the help of bioinformatics. A supplementary file on efficacy of AACC as a wound dressing material is demonstrated in detail with animal model studies.     

On the Plasticization Process of Potato Starch: Preparation and Characterization

This study aimed to gain a deep understanding of the preparation mechanism of the thermoplastic potato starch (TPPS) by using melt-mixing as a production method, to pursue the changes occurred on the microstructure, morphology and thermal properties of potato starch, TPPS was prepared using a mixture of potato starch with glycerol and water as plasticizer in an internal mixer. The steps of the phase transition, happening by applying harsh conditions (60 rpm, 160 °C, and 7 min), were followed by monitoring the evolution of torque during the mixing time. It was shown that the granules structure was destroyed and a new phase was formed. This was proved by SEM which gave the evidence that the morphology of the TPPS was homogeneous with the smooth surface means that the mixing conditions used in this work were good enough to obtain the thermoplastic starch with a high level of homogeneity in all dimensions. FTIR analysis allowed deducing the formation of new H-bonds between the starch and plasticizers molecules instead of intra and intermolecular H-bonds in the native starch that was destructed through the melt-mixing process., These caused starch chains gain mobility and as the results decreasing in crystallinity, where the XRD analysis exhibited that the crystallinity decreased from 14.5% resulting from B-type in native potato starch to 9% resulting from B-type and VH-type in TPPS. TGA and DSC analysis proved a decreasing in the thermal stability in the TPPS as compared to the starch granules.     

Water-induced hydrophobicity of soy protein materials containing 2,2-diphenyl-2-hydroxyethanoic acid

Biodegradable soy protein isolate (SPI), containing 2,2-diphenyl-2-hydroxyethanoic acid, films (SB) were successfully prepared with bis-(2-hydroxyethyl)sulfide as a plasticizer by compression molding at 155 degrees C and 15 MPa. By immersing the SB in distilled water for 26 h, we prepared the films (coded as SB-WM) having good water resistance. The films were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical thermal analysis, and tensile testing to evaluate their structure and properties. Moreover, the surface of the SB-WM films was analyzed by X-ray photoelectron spectroscopy and contact angle measurement. SB-WM films exhibited significantly higher contact angle than SB. The results revealed that a lotus-like nanoscale structure was created in SB-WM films, with increased hydrophobicity, through the process of the solvent-induced microphase separation during the immersion in water. More stable compound diphenylhydroxymethane could form from 2,2-diphenyl-2-hydroxyethanoic acid of SB in water, leading to the hydrophobicity of the SB-WM materials. A "green" and easy method for fabricating hydrophobic materials from soy protein has been provided in this work.     

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.     

Effect of plasticizers (water and glycerol) on the diffusion of a small molecule in iota-carrageenan biopolymer films for edible coating application

Translational diffusion of a fluorescein probe has been measured in iota-carrageenan edible films containing different amounts of glycerol (0, 15, 30, and 45%), using fluorescence recovery after photobleaching (FRAP) experiments. The effects of this plasticizer as well as the plasticizing effect of water on the diffusion of fluorescein have been studied in this edible coating mainly composed of natural biopolymer. Diffusion coefficients of about 10(-13) m2 s(-1) have been measured in these films for water activity (aw) lower than 0.7. Above this water content threshold, fluorescein translational diffusion coefficient increases up to 10(-12) m2 s(-1). Another interesting information obtained from FRAP experiments on this system is the ratio of the diffusing molecules which are immobilized in the carrageenan matrix at aw lower than 0.98. Moreover, films containing more than 30% glycerol (w/w carrageenan) present a huge increase of the diffusion coefficient of fluorescein at high water activity (about 2 orders of magnitude), this effect being less pronounced at low water activity. The increase of diffusion seems to be only related to the water content, and glycerol only acts through the enhancement of water adsorption. Therefore, in biopolymer films containing polyol plasticizers, the gain in mobility could be devoted to the effect of the ubiquitous plasticizing molecule, water, whose adsorption is increased by the plasticizer.     

Wheat gluten-thiolated poly(vinyl alcohol) blends with improved mechanical properties

A multifunctional macromolecular thiol (TPVA) obtained by esterification of poly(vinyl alcohol) (PVA) with 3-mercaptopropionic acid was characterized by a combination of NMR, IR, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC), and was used as a wheat gluten (WG) reactive modifier. The effect of TPVA molecular weight (M(w) = 2000, 9500, 50 000, and 205 000) and blend composition (5, 20, and 40% w/w TPVA/WG) on the mechanical properties of compression-molded bars indicates that TPVA/WG blends increase the fracture strength by up to 76%, the elongation by 80%, and the modulus by 25% above WG. In contrast, typical WG additives such as glycerol and sorbitol improve flexibility but decrease modulus and strength. Preliminary investigations of suspension rheology, water uptake, molecular weight distribution and electron microscopy of TPVA/WG and PVA/WG blends illustrate the different protein interactions with PVA and TPVA. Further work is underway to determine whether TPVA and WG form protein conjugates or microphase-separated morphologies.     

Cassava bagasse cellulose nanofibrils reinforced thermoplastic cassava starch

Cellulose cassava bagasse nanofibrils (CBN) were directly extracted from a by-product of the cassava starch (CS) industry, viz. the cassava bagasse (CB). The morphological structure of the ensuing nanoparticles was investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), presence of other components such as sugars by high performance liquid chromatography (HPLC), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) experiments. The resulting nanofibrils display a relatively low crystallinity and were found to be around 2–11 nm thick and 360–1700 nm long. These nanofibrils were used as reinforcing nanoparticles in a thermoplastic cassava starch matrix plasticized using either glycerol or a mixture of glycerol/sorbitol (1:1) as plasticizer. Nanocomposite films were prepared by a melting process. The reinforcing effect of the filler evaluated by dynamical mechanical tests (DMA) and tensile tests was found to depend on the nature of the plasticizer employed. Thus, for the glycerol-plasticized matrix-based composites, it was limited especially due to additional plasticization by sugars originating from starch hydrolysis during the acid extraction. This effect was evidenced by the reduction of glass vitreous temperature of starch after the incorporation of nanofibrils in TPSG and by the increase of elongation at break in tensile test. On the other hand, for glycerol/sorbitol plasticized nanocomposites the transcrystallization of amylopectin in nanofibrils surface hindered good performances of CBN as reinforcing agent for thermoplastic cassava starch. The incorporation of cassava bagasse cellulose nanofibrils in the thermoplastic starch matrices has resulted in a decrease of its hydrophilic character especially for glycerol plasticized sample.     

Improved tensile strength of glycerol-plasticized gluten bioplastic containing hydrophobic liquids

The aim of the present work has been to study the influence of hydrophobic liquids on the morphology and the properties of thermo-molded plastics based on glycerol-plasticized wheat gluten (WG). While the total amount of castor oil and glycerol was remained constant at 30 wt%, castor oil with various proportions with respect to glycerol was incorporated with WG by mixing at room temperature and the resultant mixtures were thermo-molded at 120 degrees C to prepare sheet samples. Moisture absorption, morphology, dynamic mechanical properties, and tensile properties (Young's modulus, tensile strength and elongation at break) of the plastics were evaluated. Experimental results showed that the physical properties of WG plastic were closely related to glycerol to castor oil ratio. Increasing in castor oil content reduces the moisture absorption markedly, which is accompanied with a significant improvement in tensile strength and Young's modulus. These observations were further confirmed in 24 wt% glycerol-plasticized WG plastics containing 6 wt% silicone oil or polydimethylsiloxane (PDMS) liquid rubber.