Ultralight, reusable biopolymer aerogels: Formation mechanisms to applications in selective fluid sorption and oil spill remediation

Highly porous (99.7 %), ultra-light (4.3 mg/ml) and mechanically robust cellulose ester aerogels with tailored hydrophobicity are synthesized. The aerogels achieve maximum compression strain of 92 % without failure and reach a compressive stress of 350 kPa, which is 100 times higher than that reported for cellulosic aerogels. In its native, unmodified state, the aerogels are hydrophilic and display unprecedented water uptake (45-90 g/g) while affording wet strength. Further adjustment of the aerogels towards hydrophobicity and oleophilicity via chemical vapor deposition with an organo-silane species reveal them to exhibit high oil retention (20-30 g/g aerogel) while maintaining mechanical integrity for fast oil cleanup from aqueous media under marine conditions. The modified aerogels are reusable and durable as they retain their hydrophobicity for months under ambient conditions. The Zisman and Fowkes theoretical frameworks are used to identify the selectiveness of the aerogel and establish a criterion for separation of various non-polar fluids from water media

Super-stretchable paper-based materials for 3D forming

Paper is renewable, recyclable, sustainable and biodegradable material and, as a result, paper-based materials are widely used in the world packaging market. However, paper-based materials cannot compete with plastics in terms of processability into various 3D shapes. This is due to poor formability of paper, which is closely associated with its toughness. To improve paper formability, we report on a facile and green method that combines fiber and paper mechanical modifications at different structural levels as well as biopolymer treatment via spraying. As a result, a remarkable elongation of ∼30% was achieved after proposed combined approach on the laboratory scale. At the same time, a significant increase in tensile strength and stiffness (by ∼306% and ∼690%, respectively) was observed. Overall, an inexpensive, green, and scalable approach is introduced to improve formability of fiber networks that in turn allows preparation of 3D shapes in the processes with fixed paper blanks such as vacuum forming, hydroforming, hot pressing, etc

Lignin particles for multifunctional membranes, antioxidative microfiltration, patterning and 3D structuring

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.9b16931We introduce a new type of particle-based membrane based on the combination of lignin particles (LPs) and cellulose nanofibrils (CNF), the latter of which are introduced in small volume fractions to act as networking and adhesive agents. The synergies that are inherent to lignin and cellulose in plants are re-engineered to render materials with low surface energy (contact angle measurements) and can be rendered water-resistant with the aid of wet-strength agents (WSAs). Importantly, they are most suitable for antioxidative separation (ABTS•+ radical inhibition): membranes with uniform porous structures (air permeability and capillary flow porosimetry) allow effluent oxidation at 95 mL/cm2, demonstrating, for the first time, the use of unmodified lignin particles in flexible membranes for active microfiltration. Moreover, the membranes are found to be nonfouling (protein adhesion and activity rate). The inherent properties of lignin, including UV radiation blocking capacity (UV transmittance analysis) and reduced surface energy, are further exploited in the development of tailorable and self-standing architectures that are almost entirely comprised of nonbonding LP (solids content as high as 92 w/w%). Despite such composition, the materials develop high toughness (oscillatory dynamic mechanical analysis), owing to the addition of minor amounts of CNF. Multifunctional materials based on thin films (casting), 3D structures (molding), and patterned geometries (extrusion deposition) are developed as a demonstration of the potential use of lignin particles as precursors of new material generation. Remarkably, our observations hold for spherical LPs since a much poorer performance was observed after using amorphous powder, indicating the role of size and shape in related applicationsPostprint (author's final draft

Alternative chemo-enzymatic treatment for homogeneous and heterogeneous acetylation of wood fibers

A new chemo-enzymatic treatment is proposed to produce cellulosic fibers suitable for heterogeneous- or homogeneous-phase acetylation. The procedure included enzymatic (laccase–violuric acid) lignin removal from the precursor fibers (unbleached sulfite pulp) followed by hydrogen peroxide treatment. An optional intermediate stage included partial hydrolysis (endoglucanase) to increase fiber reactivity. The obtained ‘‘biobleached’’ fibers were acetylated in the heterogeneous phase with acetic anhydride in nonpolar solvents, yielding various acetyl group contents, depending on the severity of the reaction. The degree of acetylation was highly sensitive to the treatment conditions, mainly the acetic anhydride activity in the system. The results were compared to those obtained after acetylation of commercial, dissolving-grade fibers, used as reference. The effect of the inherent nature of the fibers tested were elucidated as far as hemicellulose content, fiber length, fine content and crystallinity. Acetyl group content of up to 24% were determined after heterogeneous reaction with the chemoenzymatic fibers. The substitution of hydroxyl groups by acetyl moieties resulted in a lower hydrophilicity, as assessed by measurement of the water contact angle. Homogeneous acetylation of the chemo-enzymatic and reference fibers resulted in relatively similar acetyl group content (up to 36 and 33%, respectively). These samples were soluble in acetone and produced transparent films (via solvent casting), with enhanced dry strength and lower hydrophilicity. Overall, it is concluded that the proposed chemo-enzymatic treatment is a feasible alternative for the production of fibers that are suitable for efficient acetylationPostprint (author's final draft

Oil-in-water Pickering emulsions via microfluidization with cellulose nanocrystals: 1. Formation and Stability

Oil-in-water Pickering emulsions were successfully prepared via high-energy microfluidization using cellulose nanocrystals (CNC) as interfacial stabilizers. The influence of microfluidization pressure, CNC concentration, and oil type on droplet size and emulsion stability was determined. Under optimized homogenization conditions, CNC formed and stabilized emulsions based on corn, fish, sunflower, flax, orange, and MCT oils. The droplet size decreased with increasing microfluidization pressure from 9 to 17 kpsi, but then increased slightly at 19 kpsi. The creaming stability of the emulsions increased with CNC concentration, which was mainly attributed to the decrease in droplet size (mean particle diameter \u3c 1 μm at CNC-to-oil ratios greater than 1:10) and slightly increased viscosity. The Pickering emulsions were stable to droplet coalescence, presumably due to strong electrostatic and steric repulsions between the lipid droplets carrying adsorbed nanoparticles. The Pickering emulsions had good stability over a range of environmental stresses: pH 3 to 10; NaCl ≤ 100 mM; temperature from 30 to 90 °C. Droplet flocculation was, however, observed under more acidic conditions (pH 2) and at high ionic strength (200–500 mM NaCl), owing to electrostatic screening. Our results indicate that microfluidization is an effective method for forming CNC-stabilized Pickering emulsions suitable for utilization in the food industry

Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions. The efficiency of chemical reactions in biological systems is often connected to the properties of confined water, but the developments and applications of artificial mimicking systems are impeded by the complexity of the biological systems. Here, the authors show how surface bound water in nanoporous cellulosic fibers can increase the reaction rate of surface acetylation reactions and enable regioselectivity of the reactionPeer reviewe

Plasticized Cellulosic Films by Partial Esterification and Welding in Low-Concentration Ionic Liquid Electrolyte

Alternatives to petroleum-based plastics are of great significance not only from the point of view of their scientific and practical impact but to reduce the environmental footprint. Inspired by the composition and structure of wood's cell walls, we used phenolic acids to endow cellulosic fibers with new properties. The fiber dissolution and homogeneous modification were performed with a recyclable ionic liquid (IL) (tetrabutylammonium acetate ([N-4444][OAc]):dimethyl sulfoxide) to attain different levels of reaction activity for three phenolic acids (p-hydroxybenzoic acid, vanillic acid, and syringic acid). The successful autocatalytic Fischer esterification reaction was thoroughly investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, elemental analysis, and nuclear magnetic resonance spectroscopy (C-13-CP-MAS, diffusion-edited H-1 NMR and multiplicity-edited heteronuclear single quantum coherence). Control of the properties of cellulose in the dispersed state, welding, and IL plasticization were achieved during casting and recrystallization to the cellulose II crystalline allomorph. Films of cellulose carrying grafted acids were characterized with respect to properties relevant to packaging materials. Most notably, despite the low degree of esterification (DS 90%), and water resistance (WCA similar to 90 degrees). Moreover, the measured water vapor barrier was found to be similar to that of poly(lactic acid) composite films. Overall, the results contribute to the development of the next-generation green, renewable, and biodegradable films for packaging applications.Peer reviewe

Cellulose dissolution and gelation in NaOH(aq) under controlled CO2 atmosphere : supramolecular structure and flow properties

We investigate the interplay between cellulose crystallization and aggregation with interfibrillar interactions, shear forces, and the local changes in the medium's acidity. The latter is affected by the CO2 chemisorbed from the surrounding atmosphere, which, combined with shear forces, explain cellulose gelation. Herein, rheology, nuclear magnetic resonance (NMR), small and wide-angle X-ray scattering (SAXS/WAXS), and focused ion beam scanning electron microscopy (FIB-SEM) are combined to unveil the fundamental factors that limit cellulose gelation and maximize its dissolution in NaOH(aq). The obtained solutions are then proposed for developing green and environmentally friendly cellulose-based materials.Peer reviewe

Inverse Thermoreversible Mechanical Stiffening and Birefringence in a Methylcellulose/Cellulose Nanocrystal Hydrogel

We show that composite hydrogels comprising methyl cellulose (MC) and cellulose nanocrystal (CNC) colloidal rods display a reversible and enhanced rheological storage modulus and optical birefringence upon heating, i.e., inverse thermoreversibility. Dynamic rheology, quantitative polarized optical microscopy, isothermal titration calorimetry (ITC), circular dichroism (CD), and scanning and transmission electron microscopy (SEM and TEM) were used for characterization. The concentration of CNCs in aqueous media was varied up to 3.5 wt % (i.e, keeping the concentration below the critical aq concentration) while maintaining the MC aq concentration at 1.0 wt %. At 20 degrees C, MC/CNC underwent gelation upon passing the CNC concentration of 1.5 wt %. At this point, the storage modulus (G') reached a plateau, and the birefringence underwent a stepwise increase, thus suggesting a percolative phenomenon. The storage modulus (G') of the composite gels was an order of magnitude higher at 60 degrees C compared to that at 20 degrees C. ITC results suggested that, at 60 degrees C, the CNC rods were entropically driven to interact with MC chains, which according to recent studies collapse at this temperature into ring-like, colloidal-scale persistent fibrils with hollow cross-sections. Consequently, the tendency of the MC to form more persistent aggregates promotes the interactions between the CNC chiral aggregates towards enhanced storage modulus and birefringence. At room temperature, ITC shows enthalpic binding between CNCs and MC with the latter comprising aqueous, molecularly dispersed polymer chains that lead to looser and less birefringent material. TEM, SEM, and CD indicate CNC chiral fragments within a MC/CNC composite gel. Thus, MC/CNC hybrid networks offer materials with tunable rheological properties and access to liquid crystalline properties at low CNC concentrations.Peer reviewe