Magnetic cellulose: does extending cellulose versatility with magnetic functionality facilitate its use in devices?

Magnetism is certainly one of the most intriguing properties of materials. It provides a means for manipulating macroscopic and microscopic positioning and alignment of materials and is a characteristic that is essential for the creation of numerous devices and appliances. Cellulose is a renewable resource that encompasses a diverse portfolio of material hierarchies: the cellulose molecule, molecular clusters, fibrils, fibers, films, and wood products. Cellulose is exploited in materials due to its impressive intrinsic properties of non-toxicity, low density, and low cost as well as due to the extraordinary material properties of thermal stability and strength. However, many devices operate on electrical or magnetic signals, a functionality that cellulose lacks. To exploit cellulose in such applications, cellulose is often modified by ferromagnetic particles. Ferromagnetic cellulose fibers are not only demonstrated for separation of biomolecules and environmental accumulations but also in electrical textiles, loudspeakers, magnetic shielding, and optical and medical devices. This review focuses on presenting the current selection of methods for rendering cellulose magnetic; its demonstrated use in devices; and an outlook on the challenges, application, and gaps in knowledge of creating the requisite materials

Review: Periodate oxidation of wood polysaccharides—Modulation of hierarchies

Periodate oxidation of polysaccharides has transitioned from structural analysis into a modification method for engineered materials. This review summarizes the research on this topic. Fibers, fibrils, crystals, and molecules originating from forests that have been subjected to periodate oxidation can be crosslinked with other entities via the generated aldehyde functionality, that can also be oxidized or reduced to carboxyl or alcohol functionality or used as a starting point for further modification. Periodate-oxidized materials can be subjected to thermal transitions that differ from the native cellulose. Oxidation of polysaccharides originating from forests often features oxidation of structures rather than liberated molecules. This leads to changes in macro, micro, and supramolecular assemblies and consequently to alterations in physical properties. This review focuses on these aspects of the modulation of structural hierarchies due to periodate oxidation

Calcium Ion-Induced Structural Changes in Carboxymethylcellulose Solutions and Their Effects on Adsorption on Cellulose Surfaces

The adsorption of carboxymethylcellulose (CMC) on cellulose surfaces is one of the most studied examples of the adsorption of an anionic polyelectrolyte on a like-charged surface. It has been suggested that divalent ions can act as a bridge between CMC chains and the surface of cellulose and enhance the CMC adsorption: they can, however, also alter the structure of CMCs in the solution. In previous investigations, the influence of cations on solution properties has been largely overlooked. This study investigates the effect of Ca2+ ions on the properties of CMC solutions as well as the influence on cellulose nanofibers (CNFs), which was studied by dynamic light scattering and correlated with the adsorption of CMC on a cellulose surface probed using QCMD. The presence of Ca2+ facilitated the multichain association of CMC chains and increased the hydrodynamic diameter. This suggests that the adsorption of CMCs at high concentrations of CaCl2 is governed mainly by changes in solution properties rather than by changes in the cellulose surface. Furthermore, an entropy-driven mechanism has been suggested for the adsorption of CMC on cellulose. By comparing the adsorption of CMC from H2O and D2O, it was found that the release of water from the cellulose surface is driving the adsorption of CMC

Fundamental aspects of the non-covalent modification of cellulose via polymer adsorption

The increasing need for new material applications based on cellulose demands increased functional diversity and thus new functionalisation/modification approaches. The non-covalent modification of cellulose fibres via the adsorption of functional polymers has emerged as a promising route for tailoring the properties of material. This review focuses on fundamental aspects of polymer adsorption on cellulose surfaces, where the adsorption of polyelectrolytes and non-polyelectrolytes are treated separately. Adsorption studies on model surfaces as well as cellulose macro-fibres are reviewed. A correlation of the adsorption findings with the Scheutjens-Fleer polymer adsorption theory is provided, allowing the fundamentals behind the polymer adsorption phenomenon and its context in utilization of cellulose fibres to be understood

Cellulose Nanocrystal Liquid Crystal Phases: Progress and Challenges in Characterization Using Rheology Coupled to Optics, Scattering, and Spectroscopy

Cellulose nanocrystals (CNCs) self-assemble and can be flow-assembled to liquid crystalline orders in a water suspension. The orders range from nano- to macroscale with the contributions of individual crystals, their micron clusters, and macroscopic assemblies. The resulting hierarchies are optically active materials that exhibit iridescence, reflectance, and light transmission. Although these assemblies have the potential for future renewable materials, details about structures on different hierarchical levels that span from the nano- to the macroscale are still not unraveled. Rheological characterization is essential for investigating flow properties; however, bulk material properties make it difficult to capture the various length-scales during assembly of the suspensions, for example, in simple shear flow. Rheometry is combined with other characterization methods to allow direct analysis of the structure development in the individual hierarchical levels. While optical techniques, scattering, and spectroscopy are often used to complement rheological observations, coupling them in situ to allow simultaneous observation is paramount to fully understand the details of CNC assembly from liquid to solid. This Review provides an overview of achievements in the coupled analytics, as well as our current opinion about opportunities to unravel the structural distinctiveness of cellulose nanomaterials

Unexpected microphase transitions in flow towards nematic order of cellulose nanocrystals

Organization of nanoparticles is essential in order to control their light-matter interactions. We present cellulose nanocrystal suspension organization in flow towards a unidirectional state. Visualization of evolving polarization patterns of the cellulose nanocrystal suspensions is combined with steady and oscillatory shear rheology. Elucidation of the chiral nematic mesophase in a continuous process towards unidirectional order enables control of alignment in a suspension precursor for structural films and reveals thus far in situ unrevealed transition states that were not detectable by rheology alone. The coupled analytics enabled the suspensions of interest to be divided into rheological gels and rheological liquid crystal fluids with detailed information on the microtransition phases. Both populations experienced submicron organization and reached macro-scale homogeneity with unidirectional ordering in continued shear. We quantify the time, shear rate, and recovery time after shear to design an optimizing formation process for controlled wet structures as precursors for dry products

Oxidized xylan additive for nanocellulose films – A swelling modifier

Polymeric wood hemicelluloses are depicted to join cellulose, starch and chitosan as key polysaccharides for sustainable materials engineering. However, the approaches to incorporate hemicelluloses in emerging bio-based products are challenged by lack of specific benefit, other than the biomass-origin, although their utilization would contribute to sustainable material use since they currently are a side stream that is not valorized. Here we demonstrate wood-xylans as swelling modifiers for neutral and charged nanocellulose films that have already entered the sustainable packaging applications, however, suffer from humidity sensitivity. The oxidative modification is used to modulate the water-solubility of xylan and hence enable adsorption in an aqueous environment. A high molecular weight grade, hence less water-soluble, adsorbed preferentially on the neutral surface while the adsorbed amount on a negatively charged surface was independent of the molecular weight, and hence, solubility. The adsorption of the oxidized xylans on a neutral cellulose surface resulted in an increase in the amount of water in the film while on the negatively charged cellulose the total amount of water decreased. The finding of synergy of two hygroscopic materials to decrease swelling in hydrophilic bio-polymer films demonstrates the oxidized macromolecule xylan as structurally functional component in emerging cellulose products

Carboxylation of sulfated cellulose nanocrystals by family AA9 lytic polysaccharide monooxygenases

Lytic polysaccharide monooxygenases (LPMOs) from the auxiliary activity 9 (AA9) family act on cellulose through an oxidative mechanism that improves cellulose saccharification in concert with other cellulolytic enzymes. Degradation and solubilization of cellulose chains are known to take place when various cellulose hierarchies, fibers, nanofibers, and cellulose nanocrystals (CNCs) are subjected to LPMOs, either alone or in combination with other cellulose acting enzymes. The use of LPMOs to modify and prepare CNCs has been proposed mostly in top-down synthesis from larger hierarchies. Here, we attempted a direct surface modification of CNCs with LPMOs with the aim of investigating the role played by the charged sulfate groups on CNCs. Sulfate half-ester\ua0groups are introduced during the preparation of CNCs from cellulose using sulfuric acid. It has been proposed that the charged sulfate groups hinder the binding of enzymes or affinity of charged reactants on the surface and hence reduce enzymatic and chemical reaction efficiency. We demonstrate the modification of commercial sulfated CNCs using a family AA9 LPMO. Conductometric titration and spectrometric characterization of the oxidized particles indicate that carboxylation of up to 10% was possible without degradation of the crystals. Unexpectedly, the carboxyl groups could only be introduced to the crystals containing\ua0sulfate groups, while desulfated crystals remained unfunctionalized. This was deemed to be due to that the sulfate groups limit the adsorption of the enzymes and hence modulate the cuts facilitated by the enzymes on the surface. This limits the release of chains from the surface and enables the carboxylation of the insoluble substrate rather than the release of the solubilized chains. This study highlights the importance of analyzing both the solid and soluble reaction products to gain insights into the oxidation mechanism. We demonstrated that 10% functionalization suffices for the use of CNCs in coupling chemistry

Self-Standing, Robust Membranes Made of Cellulose Nanocrystals (CNCs) and a Protic Ionic Liquid: Toward Sustainable Electrolytes for Fuel Cells

Energy-conversion devices based on the phenomenon of proton conduction, for example, polymer electrolyte membrane fuel cells (PEMFCs), require low cost and sustainable electrolytes with high ionic conductivity and good mechanical properties under anhydrous conditions and at temperatures up to 150 \ub0C. Biopolymers possess an intrinsic thermomechanical stability but an insufficient proton conductivity in the dry state, which however may be imparted by a protic ionic liquid (PIL). This work presents the preparation and properties of composite membranes made of cellulose nanocrystals (CNCs) and a PIL. The membranes are thermally stable and display an ionic conductivity within the range 10-4-10-3 S/cm for temperatures between 120 and 160 \ub0C. Moreover, the analysis of the biopolymer\u27s apparent dimensions at nanoscale reveals a dependence of the CNCs\u27 defects, twisting, and aggregation in the presence of the PIL. Preliminary tests using a simple fuel cell setup demonstrate a response of the membranes to the inlet of H2 gas, with a generation of electrical current. These findings provide a solid groundwork for further development and future studies of biopolymer/PIL electrolytes for energy applications