This book systematically describes the green engineering, chemistry and manufacture of bio-based polymers and composites derived from plants. This book gives a thorough introduction to bio-based ...material resources, availability, sustainability, bio-based polymer formation, extraction and refining technologies, and the need for integrated research and multi-disciplinary working teams. It provides an in-depth description of adhesives, resins, plastics, and composites derived from plant oils, proteins, starches, and natural fibers in terms of structures, properties, manufacturing, and product performance. This is an excellent book for scientists, engineers, graduate students and industrial researchers in the field of bio-based materials.
A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in ...copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10−4 S cm−1 at −30 °C up to ∼1.5 × 10−2 S cm−1 at 80 °C) with good electrochemical stability window (−2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from −30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g−1 at 0.18 A g−1 and 138 F g−1 at 8 A g−1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.
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•Gel polymer electrolyte based on SN and IL has been prepared for supercapacitors.•Supercapacitor with new gel electrolytes has been fabricated and characterized.•Presence of SN in gel electrolyte improves the device performance significantly.•The cell with SN based electrolyte shows high specific capacitance of 176 F g−1.
•Improvement was achieved on adhesion properties of camelina protein to make it as a value added ingredient for biobased adhesives.•Chemical agents were identified for modification to increase ...adhesion strength to the benchmark following industrial wood adhesive standard.•Physiochemical properties of modified adhesives were characterized to reveal the underlying mechanism of higher adhesion property.
Camelina protein is a major by-product created after oil extraction from camelina seeds; it has drawn research attention as an economical material for bio-industrial implications. The present study investigates the influence of polyelectrolyte interaction on camelina protein structure and effects on wood bonding performance when used as a bio-adhesive. Infrared spectroscopy (IR) and transmission electron microscopy (TEM) images revealed that after interacting with polymeric amine epichlorohydrin (PAE), a cationic polyelectrolyte, camelina protein is partly unfolded with more flexible chain structures. PAE works as a bridge among different protein molecules primarily through electrostatic and hydrophobic interactions. Separation by size exclusion chromatography showed that soluble PAE modified proteins are smaller in molecular size. Polymeric amine epichlorohydrin modified proteins had reduced solubility, possibly indicating increased hydrophobicity. The PAE treatment of camelina protein greatly improved both dry and wet adhesion strength when used as an adhesive. Dry bond strength increased from 2.39 ± 0.52 MPa to 5.39 ± 0.50 MPa with 100% wood failure and wet bond strength was dramatically increased from 0.37 ± 0.22 to 2.35 ± 0.17 MPa on two layer cherry wood tests. Two aliphatic structures with hydrophobic chains were introduced into the PAE modified protein system to further improve water resistance and get wet bond strength increase from 0 to 1.30 ± 0.23 MPa on three layer yellow pine wood tests. This study demonstrates the possibility of camelina as a green resource for the adhesive industry.
•Novel bio-based acrylate was synthesized using cardanol and camelina oil.•Phenolic compound with two alkyl side chains provided strength with flexibility.•Good alternative to bio-based acrylates ...using feedstocks such as soybean oil.
Novel bio-based acrylate was designed through the epoxy ring-opening reaction of cardanol glycidyl ether (CGE) with fatty acids from camelina oil (FACO), followed by epoxidation of unsaturated chains and then acrylation of the epoxides. Cardanol- and camelina oil-based acrylates were also respectively synthesized for comparison purposes. The bio-based acrylate coatings were then produced under UV-radiation from the acrylates monomers with an addition of a photoinitiator. Polymerization of the acrylates and synthesis of the monomers were observed using Fourier transform infrared (FTIR) spectroscopy, and the chemical structures and acryl contents of the acrylates were confirmed by proton nuclear magnetic resonance (1H NMR). The mechanical and thermal properties of the cured acrylates were evaluated using tensile test, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). Observation of resistances to water, solvent, and hydrolytic degradation were conducted to water and toluene uptake test, methyl ethyl ketone (MEK) rub test, and a degradation test under sodium hydroxide solution. Gel content was measured to evaluate performance of the coatings, and other coating performances including gloss, adhesion, and pencil hardness were determined using the wood panel coated with the cured acrylates. Compared to acrylated epoxidized soybean oil (AESO) coating, the acrylate derived from the cardanol modified fatty acids showed higher tensile strength, hardness, glass transition temperature, thermal decomposition temperature at maximum degradation rate, and resistances to solvent and hydrolytic condition of the cured coating. Therefore, the newly designed acrylate is a great alternative to AESO.
The aim of this study was to enhance the water resistance of soy protein (SP) adhesives using laccase/TEMPO-modified lignin. Kraft lignin was depolymerized by laccase enzyme in the presence of TEMPO ...to expand the oxidation reaction of both phenolic and non-phenolic compounds. This simplified process has the distinct advantage of enhancing lignin-protein interaction. Compared with SP adhesives, lignin-protein adhesives showed a stronger elastic modulus, higher thermal stability, and increased wet adhesion performance. Wet shear strength increased by 106% from 0.693 to 1.429 MPa, and partial wood failure was observed after the test. Better performance was also observed in the three-cycle soaking test. At the same time, the stronger interactions between -COO- and -NH2 groups of protein and lignin led to a decrease in flowability and spreadability.
•We unfolded camelina protein isolate by two reagents: NaHSO3 (cleave SS) and guanidine–HCl (destroy hydrogen bond).•Both treatment decreased camelina protein isolate dispersion's viscosity and ...protein-protein interaction.•NaHSO3 modified camelina protein isolate was more hydrophobic than guanidine–HCl modified camelina protein.•NaHSO3 was more efficient in destroying the structure of camelina protein isolate, while Gdm-HCl treatment reduced more viscosity and water resistant.
The objective of this research was to investigate the unfolding behaviors of camelina protein isolate (CPI) induced by sodium bisulfite (NaHSO3) and guanidine–HCl (Gdm.Cl). Protein was extracted from defatted camelina meal through alkali solubilization and acid precipitation and modified with varying amount of NaHSO3 (0–12% of the protein dry basis) and Gdm.Cl (0–250% of the protein, dry basis). NaHSO3 treatment broke the disulfide bonds of the CPI and increased free sulfhydryl content and surface hydrophobicity. As NaHSO3 concentration increased, the viscosity, elastic modulus (G’) and water resistant of NaHSO3-modified camelina protein (SMCP) dispersion decreased, and the protein became aggregated due to high surface hydrophobicity. Gdm.Cl treatment broke the CPI's hydrogen bonds but decreased their surface hydrophobicity. Similarly, viscosity, G’, and water resistant of Gdm.Cl-modified camelina protein (GMCP) dispersions decreased as Gdm.Cl increased and protein aggregation formed. The reducing effect of NaHSO3 was greater than Gdm.Cl for CPI’s protein–protein interaction and less obvious for the viscosity and water resistant. Gdm.Cl reduced CPI's decomposing temperature at high concentration, but no remarkable effect was observed for NaHSO3 treatment. These findings on physicochemical changes of SMCPs and GMCPs may contribute to the application of camelina proteins in the biodegradable materials products.
Protein N-terminal methylation catalyzed by N-terminal methyltransferase 1 (NTMT1) is an emerging methylation present in eukaryotes, playing important regulatory roles in various biological and ...cellular processes. Although dysregulation of NTMT1 has been linked to many diseases such as colorectal cancer, their molecular and cellular mechanisms remain elusive due to inaccessibility to an effective cellular probe. Here we report the design, synthesis, and characterization of the first-in-class NTMT1 degraders based on proteolysis-targeting chimera (PROTAC) strategy. Through a brief structure-activity relationship (SAR) study of linker length, a cell permeable degrader 1 involving a von Hippel-Lindau (VHL) E3 ligase ligand was developed and demonstrated to reduce NTMT1 protein levels effectively and selectively in time- and dose-dependent manners in colorectal carcinoma cell lines HCT116 and HT29. Degrader 1 displayed DC50 = 7.53 μM and Dmax > 90% in HCT116 (cellular IC50 > 100 μM for its parent inhibitor DC541). While degrader 1 had marginal cytotoxicity, it displayed anti-proliferative activity in 2D and 3D culture environment, resulting from cell cycle arrested at G0/G1 phase in HCT116. Label-free global proteomic analysis revealed that degrader 1 induced overexpression of calreticulin (CALR), an immunogenic cell death (ICD) signal protein that is known to elicit antitumor immune response and clinically linked to a high survival rate of patients with colorectal cancer upon its upregulation. Collectively, degrader 1 offers the first selective cellular probe for NTMT1 exploration and a new drug discovery modality for NTMT1-related oncology and diseases.
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•New PROTAC-based degrader selective to N-terminal methyltransferase 1.•First-in-class cellular probe to study N-terminal methylation in a selective manner.•Anti-proliferative activity of the degrader in colorectal carcinoma cell line HCT116.•Degrader-induced upregulation of cell death signal protein calreticulin in HCT116.
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•EDC-induced crosslink reaction stabilized camelina protein’s structures.•The newly-formed amide bond stimulated protein’s intermolecular interaction.•The stabilized camelina protein ...structure became more rigid and water resistant.•Ultrasound unfolding pretreatment increased protein’s crosslink degree.•Molecular characteristics of cross-linked camelina protein were discussed.
Camelina protein showed poor water resistance, which restrained its industrial application, such as for adhesives or coatings. In this research, the effect of ultrasound pretreatment and carbodiimide coupling on water resistance of camelina protein isolate (CPI) was discussed. Camelina protein was extracted from defatted camelina meal by alkali solubilization and acid precipitation and treated by high intensity ultrasound. Both CPI and ultrasound-modified CPI (UCPI) were cross-linked by Ethyl-3-(3-dimethyl-aminopropyl-1-carbodiimide) (EDC). The cross-linked CPI exhibited increased molecular weight and particle size due to the amide bond formation between free amino groups and carboxyl groups. Accordingly, microstructures of the coupled protein became rigid and condensed with increased aqueous stability. The crosslink degree of UCPI was higher than CPI, leading to UCPI’s better water resistance, more compact microstructures and larger particle size.
•CG consists of 75.1% polysaccharides 12.3% of protein.•CG had high apparent viscosity, and strong temperature and pH tolerance.•CG also showed higher viscosities, G’, and G than commercial gums ...studied.•CG exhibited the potential as thickener or stabilizer.
Camelina gum (CG) was characterized on the physicochemical properties including rheological properties, chemical compositions, morphological property, and thermal properties. The results showed that dried CG has porous structure and polysaccharides and protein content of 75.1% and 12.3%, separately. CG solution showed high apparent viscosity, strong temperature and pH tolerance. CG also showed higher viscosities, storage (G’), and viscous modulus (G”) than commercial gums such as κ-carrageenan and hydroxyethylcellulose (HEC) gums. At concentration of 1.0%, the viscosity of CG was more than 2 times and 4 times higher than that of κ-carrageenan and HEC gums (0.01 1/s), respectively, and G’ was more than 3 times and 30 times higher than that of κ-carrageenan and HEC gums (0.01Hz), respectively. CG showed modulus reversibility, 100% of G’ could be recovered in 180s. Those properties indicate camelina gum is an excellent candidate for food and industrial uses as thickener or stabilizer.