Highly magnetic hybrid foams based on aligned tannic acid-coated iron oxide nanoparticles and TEMPO-oxidized cellulose nanofibers.

Lightweight iron oxide nanoparticle (IONP)/TEMPO-oxidized cellulose nanofibril (TOCNF) hybrid foams with an anisotropic structure and a high IONP content were produced using magnetic field-enhanced unidirectional ice-templating. Coating the IONP with tannic acid (TA) improved the processability, the mechanical performance, and the thermal stability of the hybrid foams. Increasing the IONP content (and density) increased the Young's modulus and toughness probed in compression, and hybrid foams with the highest IONP content were relatively flexible and could recover 14% axial compression. Application of a magnetic field in the freezing direction resulted in the formation of IONP chains that decorated the foam walls and the foams displayed a higher magnetization saturation, remanence, and coercivity compared to the ice-templated hybrid foams. The hybrid foam with an IONP content of 87% displayed a saturation magnetization of 83.2 emu g-1, which is 95% of the value for bulk magnetite. Highly magnetic hybrid foams are of potential interest for environmental remediation, energy storage, and electromagnetic interference shielding.

Plant biomechanics and resilience to environmental changes are controlled by specific lignin chemistries in each vascular cell type and morphotype.

The biopolymer lignin is deposited in the cell walls of vascular cells and is essential for long-distance water conduction and structural support in plants. Different vascular cell types contain distinct and conserved lignin chemistries, each with specific aromatic and aliphatic substitutions. Yet, the biological role of this conserved and specific lignin chemistry in each cell type remains unclear. Here, we investigated the roles of this lignin biochemical specificity for cellular functions by producing single cell analyses for three cell morphotypes of tracheary elements, which all allow sap conduction but differ in their morphology. We determined that specific lignin chemistries accumulate in each cell type. Moreover, lignin accumulated dynamically, increasing in quantity and changing in composition, to alter the cell wall biomechanics during cell maturation. For similar aromatic substitutions, residues with alcohol aliphatic functions increased stiffness whereas aldehydes increased flexibility of the cell wall. Modifying this lignin biochemical specificity and the sequence of its formation impaired the cell wall biomechanics of each morphotype and consequently hindered sap conduction and drought recovery. Together, our results demonstrate that each sap-conducting vascular cell type distinctly controls their lignin biochemistry to adjust their biomechanics and hydraulic properties to face developmental and environmental constraints.

A Stiff, Tough, and Thermally Insulating Air- and Ice-Templated Plant-Based Foam.

By forming and directionally freezing an aqueous foam containing cellulose nanofibrils, methylcellulose, and tannic acid, we produced a stiff and tough anisotropic solid foam with low radial thermal conductivity. Along the ice-templating direction, the foam was as stiff as nanocellulose-clay composites, despite being primarily methylcellulose by mass. The foam was also stiff perpendicular to the direction of ice growth, while maintaining λr < 25 mW m-1 K-1 for a relative humidity (RH) up to 65% and <30 mW m-1 K-1 at 80% RH. This work introduces the tandem use of two practical techniques, foam formation and directional freezing, to generate a low-density anisotropic material, and this strategy could be applied to other aqueous systems where foam formation is possible.

Sclerotization-Inspired Aminoquinone Cross-Linking of Thermally Insulating and Moisture-Resilient Biobased Foams.

Thermally insulating foams and aerogels based on cellulose nanofibrils (CNFs) are promising alternatives to fossil-based thermal insulation materials. We demonstrate a scalable route for moisture-resilient lightweight foams that relies on sclerotization-inspired Michael-type cross-linking of amine-modified CNFs by oxidized tannic acid. The solvent-exchanged, ice-templated, and quinone-tanned cross-linked anisotropic structures were mechanically stable and could withstand evaporative drying with minimal structural change. The low-density (7.7 kg m-3) cross-linked anisotropic foams were moisture-resilient and displayed a compressive modulus of 90 kPa at 98% relative humidity (RH) and thermal conductivity values close to that of air between 20 and 80% RH at room temperature. Sclerotization-inspired cross-linking of biobased foams offers an energy-efficient and scalable route to produce sustainable and moisture-resilient lightweight materials.

Best Practice for Reporting Wet Mechanical Properties of Nanocellulose-Based Materials.

Nanocellulose-based materials and nanocomposites show extraordinary mechanical properties with high stiffness, strength, and toughness. Although the last decade has witnessed great progress in understanding the mechanical properties of these materials, a crucial challenge is to identify pathways to introduce high wet strength, which is a critical parameter for commercial applications. Because of the waterborne fabrication methods, nanocellulose-based materials are prone to swelling by both adsorption of moist air or liquid water. Unfortunately, there is currently no best practice on how to take the swelling into account when reporting mechanical properties at different relative humidity or when measuring the mechanical properties of fully hydrated materials. This limits and in parts fully prevents comparisons between different studies. We review current approaches and propose a best practice for measuring and reporting mechanical properties of wet nanocellulose-based materials, highlighting the importance of swelling and the correlation between mechanical properties and volume expansion.

Antioxidant and UV-Blocking Leather-Inspired Nanocellulose-Based Films with High Wet Strength.

The mechanical performance in the wet state needs to be significantly improved and the intrinsic functionalities should be fully utilized to promote the replacement of fossil-based plastics with renewable biobased materials. We demonstrate a leather-inspired approach to produce multifunctional materials with a high wet strength that is based on tannin-induced precipitation of gelatin grafted onto surface-modified cellulose nanofibrils (CNF). The leather-inspired CNF-based films had a wet tensile strength of 33 MPa, a Young's modulus of 310 MPa, and a strain at failure of 22%, making the wet materials stronger than, for example, dry conventional low-density polyethylene and more ductile than paper-based food packaging materials. The tannin-containing films displayed excellent antioxidant and UV-blocking properties, rapidly scavenging more than 90% of added free radicals and absorbing 100% of light in the UV-B/UV-C range. This work illustrates the prospect of combining renewable materials in a leather-inspired approach to form wet strong and multifunctional films with potential application in food packaging.

Functionalization and patterning of nanocellulose films by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions.

Inspired by the Bogolanfini dyeing technique, we report how flexible nanofibrillated cellulose (CNF) films can be functionalized and patterned by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions with tunable colors. Molecular dynamics simulations show that gallic acid (GA) and ellagic acid (EA) rapidly adsorb and assemble on the CNF surface, and atomic force microscopy confirms that nanosized GA assemblies cover the surface of the CNF. CNF films were patterned with tannin-metal ion nanoparticles by an in-fibre reaction between the pre-impregnated tannin and the metal ions in the printing ink. Spectroscopic studies show that the FeIII/II ions interact with GA and form surface-bound, stable GA-FeIII/II nanoparticles. The functionalization and patterning of CNF films with metal ion-hydrolyzable tannin nanoparticles is a versatile route to functionalize films based on renewable materials and of interest for biomedical and environmental applications.

Irreversible thermochromism in copper chloride Imidazolium Nanoparticle Networks.

In this work Imidazolium Nanoparticle Networks (INNs) with chloride counter-ions were used to complex copper dichloride. This complexation reaction leads to the formation of a green material. The properties of the copper INN material were compared to: first, copper imidazolium complexes, without the presence of silica nanoparticles, which are not thermochromic; second, chloride-containing INN material. The copper INN material showed irreversible thermochromic behaviour, with a clear colour change from green to yellow at 180 °C, which is due to a configuration change of the copper complex from planar to tetragonal. This structural change was studied using DSC and in situ SAXS measurements during heat treatment. The thermochromic material is stable under air up to 250 °C. This preliminary study opens the door of optical sensors for INN materials.