Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined.

Selective substitution of long-acyl groups into alcohols of kraft lignin over transesterification using ionic liquid

Kraft lignin is a valuable aromatic renewable resource that is discharged in large quantities during the kraft pulping process. In this study, kraft lignin derivatives with improved solubility and thermal properties were prepared by a facile chemical modification of the aliphatic hydroxy (R-OH) group in kraft lignin with various ester groups. Kraft lignin was subjected to homogeneous transesterification with vinyl esters as acyl donors using an ionic liquid as a green solvent and catalyst. The selective introduction of acyl groups into the R-OH group was confirmed by nuclear magnetic resonance (NMR) spectroscopy, and it was estimated that approximately 90% of the R-OH group was converted whereas more than 80% of the aromatic hydroxy (Ar-OH) group was retained. The R-OH-selective introduction of long-chain acyl groups of more than six carbons successfully provided superior solubility in common low-boiling solvents, such as chloroform and tetrahydrofuran, and sufficient heat-meltability to be molded into films by hot-pressing. All the kraft lignin derivatives showed high glass transition temperatures of over 100 °C, indicating their potential to be heat-resistant materials. The kraft lignin derivatives, in which only the R-OH group was acylated, retain their inherently rich Ar-OH groups and thus, can be applied as desirable precursors in a wide range of further chemical treatments for functional polymer materials.

Propionic Anhydride Modification of Cellulosic Kenaf Fibre Enhancement with Bionanocarbon in Nanobiocomposites

The use of chemical modification of cellulosic fibre is applied in order to increase the hydrophobicity, hence improving the compatibility between the fibre and matrix bonding. In this study, the effect of propionic anhydride modification of kenaf fibre was investigated to determine the role of bionanocarbon from oil palm shell agricultural wastes in the improvement of the functional properties of bionanocomposites. The vinyl esters reinforced with unmodified and propionic anhydride modified kenaf fibres bio nanocomposites were prepared using 0, 1, 3, 5 wt% of bio-nanocarbon. Characterisation of the fabricated bionanocomposite was carried out using FESEM, TEM, FT-IR and TGA to investigate the morphological analysis, surface properties, functional and thermal analyses, respectively. Mechanical performance of bionanocomposites was evaluated according to standard methods. The chemical modification of cellulosic fibre with the incorporation of bionanocarbon in the matrix exhibited high enhancement of the tensile, flexural, and impact strengths, for approximately 63.91%, 49.61% and 54.82%, respectively. The morphological, structural and functional analyses revealed that better compatibility of the modified fibre–matrix interaction was achieved at 3% bionanocarbon loading, which indicated improved properties of the bionanocomposite. The nanocomposites exhibited high degradation temperature which signified good thermal stability properties. The improved properties of the bionanocomposite were attributed to the effect of the surface modification and bionanocarbon enhancement of the fibre–matrix networks.

Neural Network Optimization Algorithms to Predict Wind Turbine Blade Fatigue Life under Variable Hygrothermal Conditions

Moisture and temperature are the most important environmental factors that affect the degradation of wind turbine blades, and their influence must be considered in the design process. They will first affect the resin matrix and then, possibly, the interface with the fibers. This work is the first to use a series of metaheuristic approaches to analyze the most recent experimental results database and to identify which resins are the most robust to moisture/temperature in terms of fatigue life. Four types of resin are compared, representing the most common types used for wind turbine blades manufacturing. Thermoset polymer resins, including polyesters and vinyl esters, were machined as coupons and tested for the fatigue in air temperatures of 20 °C and 50 °C under “dry” and “wet” conditions. The experimental fatigue data available from Sandia National Laboratories (SNL) for wind turbine-related materials have been used to build, train, and validate an artificial neural network (ANN) to predict fatigue life under different environmental conditions. The performances of three algorithms (Backpropagation BP, Particle Swarm Optimization PSO, and Cuckoo Search CS) are compared for adjusting the synaptic weights of the ANN and evaluating the efficiency in predicting the fatigue life of the materials studied, under the conditions mentioned above. For accuracy evaluation, the mean square error (MSE) is used as an objective function to be optimized by the three algorithms.

Palladium Catalyzed α,β-Homodiarylation of Vinyl Esters in Aqueous Medium

A palladium catalyzed 1,2-diarylation of vinyl esters with sustainable arylbornic acids in water has been developed. This newly elaborated protocol features good functional group tolerance and provides a one-step access to 1,2-diaryletahol derivatives under mild reaction conditions. The presented reaction can be carried out in water smoothly without the addition of any ligands at ambient temperature what makes this procedure environmentally benign. The transformation occurs within a single catalytic cycle and is feasible due to the modification of transition metal catalytic activity through the influence of π-acceptor olefin (benzoquinone) as well as the polar protic reaction medium (water in particular). Moreover, the protocol allows to generate entire compounds libraries (highly profitable in medicinal chemistry) and utilizes sustainable arylboronic acid as coupling partners under mild conditions.