Effects of multi-functional additives during foam extrusion of wheat gluten materials.

To broaden the range in structures and properties, and therefore the applicability of sustainable foams based on wheat gluten expanded with ammonium-bicarbonate, we show here how three naturally ocurring multifunctional additives affect their properties. Citric acid yields foams with the lowest density (porosity of ~50%) with mainly closed cells. Gallic acid acts as a radical scavenger, yielding the least crosslinked/ aggregated foam. The use of a low amount of this acid yields foams with the highest uptake of the body-fluid model substance (saline, ~130% after 24 hours). However, foams with genipin show a large and rapid capillary uptake (50% in one second), due to their high content of open cells. The most dense and stiff foam is obtained with one weight percent genipin, which is also the most crosslinked. Overall, the foams show a high energy loss-rate under cyclic compression (84-92% at 50% strain), indicating promising cushioning behaviour. They also show a low compression set, indicating promising sealability. Overall, the work here provides a step towards using protein biofoams as a sustainable alternative to fossil-based plastic/rubber foams in applications where absorbent and/or mechanical properties play a key role.

Nanostructures of etherified arabinoxylans and the effect of arabinose content on material properties.

To further our understanding of a thermoplastic arabinoxylan (AX) material obtained through an oxidation-reduction-etherification pathway, the role of the initial arabinose:xylose ratio on the material properties was investigated. Compression molded films with one molar substitution of butyl glycidyl ether (BGE) showed markedly different tensile behaviors. Films made from low arabinose AX were less ductile, while those made from high arabinose AX exhibited elastomer-like behaviors. X-ray scattering confirmed the presence of nanostructure formation resulting in nano-domains rich in either AX or BGE, from side chain grafting. The scattering data showed variations in the presence of ordered structures, nano-domain sizes and their temperature response between AX with different arabinose contents. In dynamic mechanical testing, three transitions were observed at approximately -90 °C, -50 °C and 80 °C, with a correlation between samples with more structured nano-domains and those with higher onset transition temperatures and lower storage modulus decrease. The mechanical properties of the final thermoplastic AX material can therefore be tuned by controlling the composition of the starting material.

Coarse-Grained Model for Prediction of Hole Mobility in Polyethylene.

Electrical conductivity measurements of polyethylene indicate that the semicrystalline structure and morphology influence the conductivity. To include this effect in atomistic charge transport simulations, models that explicitly or implicitly take morphology into account are required. In the literature, charge transport simulations of amorphous polyethylene have been successfully performed using short oligomers to represent the polymer. However, a more realistic representation of the polymer structure is desired, requiring the development of fast and efficient charge transport algorithms that can handle large molecular systems through coarse-graining. Here, such a model for charge transport simulations in polyethylene is presented. Quantum chemistry calculations were used to define six segmentation rules on how to divide a polymer chain into shorter segments representing localized molecular orbitals. Applying the rules to amorphous systems yields distributions of segments with mode and median segment lengths relatively close to the persistence length of polyethylene. In an initial test, the segments of an amorphous polyethylene were used as hopping sites in kinetic Monte Carlo (KMC) simulations, which yielded simulated hole mobilities that were within the experimental range. The activation energy of the simulated system was lower compared to the experimental values reported in the literature. A conclusion may be that the experimental result can only be explained by a model containing chemical defects that generate deep traps.

Stretchable, Strong, Recyclable Helicide Elastomer Based on Dynamic Covalent Interactions.

Current methods for making and disposing synthetic polymers have been widely pursued and are largely unsustainable. As a part of the solution, the reversible nature of dynamic covalent bonds emerges as an extraordinarily diverse and valuable feature in the development of exotic molecules and extended structures. With these bonds, it should be possible to construct recyclable and mechanically interlocked molecular structures using relatively simple precursors with preorganized geometries. A new helicide-based elastomer network is developed here with self-healing, recycling, and degradation features using a similar concept. The best self-healing performance (100%) was noted over 10-20 min, with various H2O, HCl, and NaOH solutions that delivered mechanical properties in the 1-1.4 MPa range. For hydrolytic degradation, the parameters are defined based on the type of binding, the pH of the solutions, and the copolymer network, which endowed a degradation time of approximately 4-11 h for each prepared sample. However, due to the reversible nature of the dynamic bonds, the material showed good recyclable mechanical properties compared to the pristine samples after five consecutive cycles, which meet the requirements of recyclable materials and recyclable packaging.

Large-scale synthesis of 2D-silica (SiOx) nanosheets using graphene oxide (GO) as a template material.

Graphene oxide (GO) was used in this study as a template to successfully synthesize silicon oxide (SiOx) based 2D-nanomaterials, adapting the same morphological features as the GO sheets. By performing a controlled condensation reaction using low concentrations of GO (<0.5 wt%), the study shows how to obtain 2D-nanoflakes, consisting of GO-flakes coated with a silica precursor that were ca. 500 nm in lateral diameter and ca. 1.5 nm in thickness. XPS revealed that the silanes had linked covalently with the GO sheets at the expense of the oxygen groups present on the GO surface. The GO template was shown to be fully removable through thermal treatment without affecting the nanoflake morphology of the pure SiOx-material, providing a methodology for large-scale preparation of SiOx-based 2D nanosheets with nearly identical dimensions as the GO template. The formation of SiOx sheets using a GO template was investigated for two different silane precursors, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS), showing that both precursors were capable of accurately templating the graphene oxide template. Molecular modeling revealed that the choice of silane affected the number of layers coated on the GO sheets. Furthermore, rheological measurements showed that the relative viscosity was significantly affected by the specific surface area of the synthesized particles. The protocol used showed the ability to synthesize these types of nanoparticles using a common aqueous alcohol solvent, and yield larger amounts (∼1 g) of SiOx-sheets than what has been previously reported.

Green Chemistry to Modify Functional Properties of Crambe Protein Isolate-Based Thermally Formed Films.

Proteins are promising precursors to be used in production of sustainable materials with properties resembling plastics, although protein modification or functionalization is often required to obtain suitable product characteristics. Here, effects of protein modification were evaluated by crosslinking behavior using high-performance liquid chromatography (HPLC), secondary structure using infrared spectroscopy (IR), liquid imbibition and uptake, and tensile properties of six crambe protein isolates modified in solution before thermal pressing. The results showed that a basic pH (10), especially when combined with the commonly used, although moderately toxic, crosslinking agent glutaraldehyde (GA), resulted in a decrease in crosslinking in unpressed samples, as compared to acidic pH (4) samples. After pressing, a more crosslinked protein matrix with an increase in ß-sheets was obtained in basic samples compared to acidic samples, mainly due to the formation of disulfide bonds, which led to an increase in tensile strength, and liquid uptake with less material resolved. A treatment of pH 10 + GA, combined either with a heat or citric acid treatment, did not increase crosslinking or improve the properties in pressed samples, as compared to pH 4 samples. Fenton treatment at pH 7.5 resulted in a similar amount of crosslinking as the pH 10 + GA treatment, although with a higher degree of peptide/irreversible bonds. The strong bond formation resulted in lack of opportunities to disintegrate the protein network by all extraction solutions tested (even for 6 M urea + 1% sodium dodecyl sulfate + 1% dithiothreitol). Thus, the highest crosslinking and best properties of the material produced from crambe protein isolates were obtained by pH 10 + GA and pH 7.5 + Fenton, where Fenton is a greener and more sustainable solution than GA. Therefore, chemical modification of crambe protein isolates is effecting both sustainability and crosslinking behavior, which might have an effect on product suitability.

Molecular Dynamics Simulations of Cellulose and Dialcohol Cellulose under Dry and Moist Conditions.

The development of wood-based thermoplastic polymers that can replace synthetic plastics is of high environmental importance, and previous studies have indicated that cellulose-rich fiber containing dialcohol cellulose (ring-opened cellulose) is a very promising candidate material. In this study, molecular dynamics simulations, complemented with experiments, were used to investigate how and why the degree of ring opening influences the properties of dialcohol cellulose, and how temperature and presence of water affect the material properties. Mechanical tensile properties, diffusion/mobility-related properties, densities, glass-transition temperatures, potential energies, hydrogen bonds, and free volumes were simulated for amorphous cellulosic materials with 0-100% ring opening, at ambient and high (150 °C) temperatures, with and without water. The simulations showed that the impact of ring openings, with respect to providing molecular mobility, was higher at high temperatures. This was also observed experimentally. Hence, the ring opening had the strongest beneficial effect on "processability" (reduced stiffness and strength) above the glass-transition temperature and in wet conditions. It also had the effect of lowering the glass-transition temperature. The results here showed that molecular dynamics is a valuable tool in the development of wood-based materials with optimal thermoplastic properties.

Sustainable Wheat Protein Biofoams: Dry Upscalable Extrusion at Low Temperature.

Glycerol-plasticized wheat gluten was explored for producing soft high-density biofoams using dry upscalable extrusion (avoiding purposely added water). The largest pore size was obtained when using the food grade ammonium bicarbonate (ABC) as blowing agent, also resulting in the highest saline liquid uptake. Foams were, however, also obtained without adding a blowing agent, possibly due to a rapid moisture uptake by the dried protein powder when fed to the extruder. ABC's low decomposition temperature enabled extrusion of the material at a temperature as low as 70 °C, well below the protein aggregation temperature. Sodium bicarbonate (SBC), the most common food-grade blowing agent, did not yield the same high foam qualities. SBC's alkalinity, and the need to use a higher processing temperature (120 °C), resulted in high protein cross-linking and aggregation. The results show the potential of an energy-efficient and industrially upscalable low-temperature foam extrusion process for competitive production of sustainable biofoams using inexpensive and readily available protein obtained from industrial biomass (wheat gluten).

Robust Assembly of Cross-Linked Protein Nanofibrils into Hierarchically Structured Microfibers.

Natural, high-performance fibers generally have hierarchically organized nanosized building blocks. Inspired by this, whey protein nanofibrils (PNFs) are assembled into microfibers, using flow-focusing. By adding genipin as a nontoxic cross-linker to the PNF suspension before spinning, significantly improved mechanical properties of the final fiber are obtained. For curved PNFs, with a low content of cross-linker (2%) the fiber is almost 3 times stronger and 4 times stiffer than the fiber without a cross-linker. At higher content of genipin (10%), the elongation at break increases by a factor of 2 and the energy at break increases by a factor of 5. The cross-linking also enables the spinning of microfibers from long straight PNFs, which has not been achieved before. These microfibers have higher stiffness and strength but lower ductility and toughness than those made from curved PNFs. The fibers spun from the two classes of nanofibrils show clear morphological differences. The study demonstrates the production of protein-based microfibers with mechanical properties similar to natural protein-based fibers and provides insights about the role of the nanostructure in the assembly process.

Clustering and cross-linking of the wheat storage protein α-gliadin: A combined experimental and theoretical approach.

Our aim was to understand mechanisms for clustering and cross-linking of gliadins, a wheat seed storage protein type, monomeric in native state, but incorporated in network while processed. The mechanisms were studied utilizing spectroscopy and high-performance liquid chromatography on a gliadin-rich fraction, in vitro produced α-gliadins, and synthetic gliadin peptides, and by coarse-grained modelling, Monte Carlo simulations and prediction algorithms. In solution, gliadins with α-helix structures (dip at 205 nm in CD) were primarily present as monomeric molecules and clusters of gliadins (peaks at 650- and 700-s on SE-HPLC). At drying, large polymers (Rg 90.3 nm by DLS) were formed and ß-sheets increased (14% by FTIR). Trained algorithms predicted aggregation areas at amino acids 115-140, 150-179, and 250-268, and induction of liquid-liquid phase separation at P- and Poly-Q-sequences (Score = 1). Simulations showed that gliadins formed polymers by tail-to-tail or a hydrophobic core (Kratky plots and Ree = 35 and 60 for C- and N-terminal). Thus, the N-terminal formed clusters while the C-terminal formed aggregates by disulphide and lanthionine bonds, with favoured hydrophobic clustering of similar/exact peptide sections (synthetic peptide mixtures on SE-HPLC). Mechanisms of clustering and cross-linking of the gliadins presented here, contribute ability to tailor processing results, using these proteins.

Bio-based thermoplastic natural rubber based on poly(lactic acid)/thermoplastic starch/calcium carbonate nanocomposites.

Bio-based thermoplastic natural rubber (TPNR) has recently received much attention due to its sustainability. TPNR based on natural rubber (NR), poly(lactic acid) (PLA), thermoplastic starch (TPS), and nano-precipitated calcium carbonate (NPCC) was fabricated using a twin-screw extruder with two different mixing sequences: MI (NPCC was first compounded with PLA) and MII (NPCC was initially compounded with TPS), and then converted to a sheet through cast sheet extrusion. A constant weight ratio of NR:PLA:TPS at 30:40:30 and varying concentrations of NPCC at 0.5, 1, 3, and 5 wt% were employed. The effects of NPCC and mixing sequence on the properties of NR/PLA/TPS/NPCC nanocomposites were investigated. The NR and TPS phases were dispersed in the PLA matrix. The nanocomposites loaded with a small amount of NPCC (0.5 and 1 wt%) showed increased tensile strength and Young's modulus. NPCC enhanced melt flowability, slightly improved the water vapor barrier property of the NR/PLA/TPS blend and caused decreased Tg, Tcc, and Tm of PLA in the nanocomposites. The PLA phase of the MI nanocomposites contained a higher amount of NPCC, consequently having greater PLA chain scission and poorer tensile properties than that of the MII nanocomposites.

Hierarchical propagation of structural features in protein nanomaterials.

Natural high-performance materials have inspired the exploration of novel materials from protein building blocks. The ability of proteins to self-organize into amyloid-like nanofibrils has opened an avenue to new materials by hierarchical assembly processes. As the mechanisms by which proteins form nanofibrils are becoming clear, the challenge now is to understand how the nanofibrils can be designed to form larger structures with defined order. We here report the spontaneous and reproducible formation of ordered microstructure in solution cast films from whey protein nanofibrils. The structural features are directly connected to the nanostructure of the protein fibrils, which is itself determined by the molecular structure of the building blocks. Hence, a hierarchical assembly process ranging over more than six orders of magnitude in size is described. The fibril length distribution is found to be the main determinant of the microstructure and the assembly process originates in restricted capillary flow induced by the solvent evaporation. We demonstrate that the structural features can be switched on and off by controlling the length distribution or the evaporation rate without losing the functional properties of the protein nanofibrils.

Millions of microplastics released from a biodegradable polymer during biodegradation/enzymatic hydrolysis.

In this article, we show that enzymatic hydrolysis of a biodegradable polyester (poly(ε-caprolactone)) by Amano Lipase PS in an aqueous (buffer) environment yielded rapidly an excessive number of microplastic particles; merely 0.1 g of poly(ε-caprolactone) film was demonstrated to yield millions of particles. There were also indications of non-enzymatic hydrolysis at the same conditions, but this did not yield any particles within the time frame of the experiment (up to 6 days). Microplastic particles formed had irregular shapes with an average size of around 10 µm, with only a few reaching 60 µm. The formation of microplastic particles resulted from the uneven hydrolysis/erosion rate across the polymer film surface, which led to a rough and undulating surface with ridge, branch, and rod-shaped micro-protruding structures. The consequent detachment and fragmentation of these micro-sized protruding structures resulted in the release of microplastics to the surroundings. Together with microplastics, hydrolysis products such as acidic monomers and oligomers were also released during the enzymatic hydrolysis process, causing a pH decrease in the surrounding liquid. The results suggest that the risk of microplastic pollution from biodegradable plastics is notable despite their biodegradation. Special attention needs to be paid when using and disposing of biodegradable plastics, considering the enormous impact of the paradigm shift towards more biodegradable products on the environment.

Innovative Green Way to Design Biobased Electrospun Fibers from Wheat Gluten and These Fibers' Potential as Absorbents of Biofluids.

In this study, a new method was developed to successfully design sustainable microfibers from wheat gluten proteins using a nonreducing solvent and electrospinning. We explored the morphology by X-ray tomography, scanning electron microscopy (SEM), and confocal laser scanning microscopy (CLSM), protein chemistry and cross-linking by size exclusion-high-performance liquid chromatography (SE-HPLC), and secondary structure by Fourier transform infrared spectroscopy (FT-IR) of fibers containing 15 and 20% of gluten. The impact of heat (130 °C) post-treatment on the polymerization properties of fibers and their absorption performance in different biofluids were also evaluated. The fibers with 20% gluten showed a uniform architecture supported by a relatively stronger fibrous network as compared to irregular and brittle fibers from 15% gluten. Heat treatment of fibers increased the protein cross-linking in all electrospun fibers as compared to the non-heat-treated fibers, as evidenced by SE-HPLC. An increase in the amount of α-helices and random coils was observed in the proteins of all of the heat-treated fibers compared to the nontreated fibers by FT-IR. This suggested that the heat treatment contributed positively to the gluten protein's chemical rearrangements, e.g., aggregation, new hydrogen and isopeptide bonding, and conversion of some of the sulfhydryl groups into disulfide cross-links, contributing positively to the functional performance. The heat-treated electrospun fibers with 20% gluten showed a very attractive blood absorption capacity (323%) and reasonable stability in phosphate-buffered saline (PBS) buffer compared to 15% gluten fibers and non-heat-treated fibers. Cotton-like fiber architecture, high blood absorption capacity, and reasonable stability in PBS buffer are properties desired for absorbents of biofluids and should be further explored in healthcare and medical applications.

Potential natural polymer-based nanofibres for the development of facemasks in countering viral outbreaks.

The global coronavirus disease 2019 (COVID-19) pandemic has rapidly increased the demand for facemasks as a measure to reduce the rapid spread of the pathogen. Throughout the pandemic, some countries such as Italy had a monthly demand of ca. 90 million facemasks. Domestic mask manufacturers are capable of manufacturing 8 million masks each week, although the demand was 40 million per week during March 2020. This dramatic increase has contributed to a spike in the generation of facemask waste. Facemasks are often manufactured with synthetic materials that are non-biodegradable, and their increased usage and improper disposal are raising environmental concerns. Consequently, there is a strong interest for developing biodegradable facemasks made with for example, renewable nanofibres. A range of natural polymer-based nanofibres has been studied for their potential to be used in air filter applications. This review article examines potential natural polymer-based nanofibres along with their filtration and antimicrobial capabilities for developing biodegradable facemask that will promote a cleaner production.

A collection of the novel coronavirus (COVID-19) detection assays, issues, and challenges.

The global pandemic of COVID-19 has rapidly increased the number of infected cases as well as asymptomatic individuals in many, if not all the societies around the world. This issue increases the demand for accurate and rapid detection of SARS-CoV-2. While accurate and rapid detection is critical for diagnosing SARS-CoV-2, the appropriate course of treatment must be chosen to help patients and prevent its further spread. Testing platform accuracy with high sensitivity and specificity for SARS-CoV-2 is equally important for clinical, regional, and global arenas to mitigate secondary transmission rounds. The objective of this article is to compare the current detection technology and introduce the most accurate and rapid ones that are suitable for pandemic circumstances. Hence, the importance of rapid detection in societies is discussed initially. Following this, the current technology for rapid detection of SARS-CoV-2 is explained and classified into three different categories: nucleic acid-based, protein-based, and point of care (PoC) detection testing. Then, the current issues for diagnostic procedures in laboratories are discussed. Finally, the role of new technologies in countering COVID-19 is also introduced to assist researchers in the development of accurate and timely detection of coronaviruses. As coronavirus continues to affect human lives in a detrimental manner, the development of rapid and accurate virus detection methods could promote COVID-19 diagnosis accessible to both individuals and the mass population at patient care. In this regard, rRT-PCR and multiplex RT-PCR detection techniques hold promise.

Protein Nanofibrils and Their Hydrogel Formation with Metal Ions.

Protein nanofibrils (PNFs) have been prepared by whey protein fibrillation at low pH and in the presence of different metal ions. The effect of the metal ions was systematically studied both in terms of PNF suspension gelation behavior and fibrillation kinetics. A high valence state and a small ionic radius (e.g., Sn4+) of the metal ion resulted in the formation of hydrogels already at a metal ion concentration of 30 mM, whereas an intermediate valence state and larger ionic radius (Co2+, Ni2+, Al3+) resulted in the hydrogel formation occurring at 60 mM. A concentration of 120 mM of Na+ was needed to form a PNF hydrogel, while lower concentrations showed liquid behaviors similar to the reference PNF solution where no metal ions had been introduced. The hydrogel mechanics were investigated at steady-state conditions after 24 h of incubation/gelation, revealing that more acidic (smaller and more charged) metal ions induced ca. 2 orders of magnitude higher storage modulus as compared to the less acidic metal ions (with smaller charge and larger radius) for the same concentration of metal ions. The viscoelastic nature of the hydrogels was attributed to the ability of the metal ions to coordinate water molecules in the vicinity of the PNFs. The presence of metal ions in the solutions during the growth of the PNFs typically resulted in curved fibrils, whereas an upper limit of the concentration existed when oxides/hydroxides were formed, and the hydrogels lost their gel properties due to phase separation. Thioflavin T (ThT) fluorescence was used to determine the rate of the fibrillation to form 50% of the total PNFs (t1/2), which decreased from 2.3 to ca. 0.5 h depending on the specific metal ions added.