Simple functionalization of cellulose beads with pre-propargylated chitosan for clickable scaffold substrates

Concerning the increased market for bio-based materials and environmentally safe practices, cellulose-based beads are one of the more attractive alternatives. Thus, this work focuses on the generation of functional cellulose-based beads with a relatively simple and direct method of blending a pre-modified chitosan bearing the targeted functional groups and cellulose, prior to the formation of the beads, as a mean to have functional groups in the formed structure. To this end, chitosan was chemically modified with propargyl bromide in homogenous reaction conditions and then combined with cellulose in sodium hydroxide/urea solution and coagulated in nitric acid to produce spherical shaped beads. The successful chemical modification of chitosan was assessed by elemental analysis, as well as by Fourier-transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The alkynyl moieties from the chitosan derivative, served as reactive functional groups for click-chemistry as demonstrated by the tagging of the commercial fluorophore Azide-Fluor 488 via CuI-catalysed alkyne-azide cycloaddition reaction, in aqueous media. This work demonstrates the one-step processing of multiple polysaccharides for functional spherical beads as a template for bio-based scaffolds such as enzyme immobilization for stimuli-response applications and bioconjugations.

     

Mechanically-induced dimensional extensibility of fibers towards tough fiber networks

The beneficial effect of materials with high aspect ratio as composite reinforcement has prompted continuous interest towards cellulosic fibers. Besides providing stiffness, fibers can potentially contribute to composite extensibility. While mechanical treatments are typically used to adjust the physical and surface properties of fibers, less is known about ensuing effects on their extensibility and that of associated networks. Fiber network dimensional extensibility of 16% was achieved by processing the precursor aqueous fiber dispersions following a simple mechanical treatment with a judicious combination of low (PFI refining) and high concentrations and temperatures (Wing defibrator). Consequently, deformation of fibers and increased inter-fiber bonding resulted in a three-fold increase in strength to rupture of the fiber network leading to the structures with unprecedented toughness.     

Effect of residual lignin and heteropolysaccharides in nanofibrillar cellulose and nanopaper from wood fibers

Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and <1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm³, higher than that from FB NFC (0.7 g/cm³). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m²/g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides.     

In situ production of nanocomposites of poly(vinyl alcohol) and cellulose nanofibrils from Gluconacetobacter bacteria: effect of chemical crosslinking

Nanocomposites of poly(vinyl alcohol) (PVA) reinforced with bacterial cellulose (BC) were bioproduced by Gluconacetobacter genus bacteria. BC was grown from a culture medium modified with water-soluble PVA to allow in situ assembly and production of a novel nanocomposite that displayed synergistic property contributions from the individual components. Chemical crosslinking with glyoxal was performed to avoid the loss of PVA matrix during purification steps and to improve the functional properties of composite films. Reinforcement with BC at 0.6, 6 and 14 wt% content yielded nanocomposites with excellent mechanical, thermal and dimensional properties as well as moisture stability. Young’s modulus and strength at break increased markedly with the reinforcing BC: relative to the control sample (in absence of BC), increases of 15, 165 and 680 % were determined for nanocomposites with 0.6, 6 and 14 % BC loading, respectively. The corresponding increase in tensile strengths at yield were 1, 12 and 40 %, respectively. The results indicate an exceptional reinforcing effect by the three-dimensional network structure formed by the BC upon biosynthesis embedded in the PVA matrix and also suggest a large percolation within the matrix. Bonding (mainly hydrogen bonding) and chemical crosslinking between the reinforcing phase and matrix were the main contributions to the properties of the nanocomposite.     

Titrimetric methods for the determination of surface and total charge of functionalized nanofibrillated/microfibrillated cellulose (NFC/MFC)

Total and surface charge of three different carboxymethylated nanofibrillated/microfibrillated cellulose (NFC/MFC) samples were investigated by using titrimetric methods (conductometric and polyelectrolyte (PE) titrations). Conductometric titration was found to be suitable method for the NFC total charge measurements when the back titration with HCl was applied. Surface charge measurements of NFC/MFC were conducted by using both indirect and direct PE titrations. The direct PE titration was found to be a more suitable method for the surface charge determination of NFC/MFC whereas the indirect PE titration produced too high surface charge values. This is presumably due to kinetically locked polyelectrolyte conformations on the NFC/MFC surfaces or entrapment of residual polymer after adsorption onto the NFC/MFC gel network. Finally, NFC was propargyl-functionalized and the changes in surface and total charge were successfully monitored and compared to those of propargyl-functionalized pulp. A good correlation between the titrimetric methods and elemental analysis was observed.