Benchmarking the Humidity-Dependent Mechanical Response of (Nano)fibrillated Cellulose and Dissolved Polysaccharides as Sustainable Sand Amendments.

Soil quality is one of the main limiting factor in the development of the food sector in arid areas, mainly due to its poor mechanics and lack of water retention. Soil's organic carbon is nearly absent in arid soils, though it is important for water and nutrient transport, to soil mechanics, to prevent erosion, and as a long-term carbon sink. In this study, we evaluate the potential benefits that are brought to inert sand by the incorporation of a range of, mainly, cellulosic networks in their polymeric or structured (fiber) forms, analogously to those found in healthy soils. We explore the impact of a wide range of nonfood polysaccharide-based amendments, including pulp fibers, nanocellulose, cellulose derivatives, and other readily available polysaccharide structures derived from arthropods (chitosan) or fruit peels (pectin) residues. A practical methodology is presented to form sand-polymer composites, which are evaluated for their soil mechanics as a function of humidity and the dynamics of their response to water. The mechanics are correlated to the network of polymers formed within the pores of the sandy soil, as observed by electron microscopy. The response to water is correlated to both the features of the network and the individual polysaccharides' physicochemical features. We expect this work to provide a rapid and reproducible methodology to benchmark sustainable organic amendments for arid soils.

Controlling the critical parameters of ultrasonication to affect the dispersion state, isolation, and chiral nematic assembly of cellulose nanocrystals.

Cellulose nanocrystals (CNCs) are typically extracted from plants and present a range of opto-mechanical properties that warrant their use for the fabrication of sustainable materials. While their commercialization is ongoing, their sustainable extraction at large scale is still being optimized. Ultrasonication is a well-established and routinely used technology for (re-) dispersing and/or isolating plant-based CNCs without the need for additional reagents or chemical processes. Several critical ultrasonication parameters, such as time, amplitude, and energy input, play dominant roles in reducing the particle size and altering the morphology of CNCs. Interestingly, this technology can be coupled with other methods to generate moderate and high yields of CNCs. Besides, the ultrasonics treatment also has a significant impact on the dispersion state and the surface chemistry of CNCs. Accordingly, their ability to self-assemble into liquid crystals and subsequent superstructures can, for example, imbue materials with finely tuned structural colors. This article gives an overview of the primary functions arising from the ultrasonication parameters for stabilizing CNCs, producing CNCs in combination with other promising methods, and highlighting examples where the design of photonic materials using nanocrystal-based celluloses is substantially impacted.

Supramolecular nanoarchitectonics of phenolic-based nanofiller for controlled diffusion of versatile drugs in hydrogels.

Drug-dependent design of hydrogels is currently required for engineering the controlled release of therapeutics, which is a major contributor to the technical challenges relating to the clinical translation of hydrogel-drug systems. Herein, by integrating supramolecular phenolic-based nanofillers (SPFs) into hydrogel microstructures we developed a facile strategy to endow a range of clinically relevant hydrogels with controlled release properties for diverse therapeutic agents. The assembly of multiscale SPF aggregates leads to tunable mesh size and multiple dynamic interactions between SPF aggregates and drugs, which relaxes the available choices of drugs and hydrogels. This simple approach allowed for the controlled release of 12 representative drugs evaluated with 8 commonly used hydrogels. Moreover, the anesthetic drug lidocaine was loaded into SPF-integrated alginate hydrogel and demonstrated sustained release for 14 days in vivo, validating the potential for long-term anesthesia in patients.

Versatile Assembly of Metal-Phenolic Network Foams Enabled by Tannin-Cellulose Nanofibers.

Metal-phenolic network (MPN) foams are prepared using colloidal suspensions of tannin-containing cellulose nanofibers (CNFs) that are ice-templated and thawed in ethanolic media in the presence of metal nitrates. The MPN facilitates the formation of solid foams by air drying, given the strength and self-supporting nature of the obtained tannin-cellulose nanohybrid structures. The porous characteristics and (dry and wet) compression strength of the foams are rationalized by the development of secondary, cohesive metal-phenolic layers combined with a hydrogen bonding network involving the CNF. The shrinkage of the MPN foams is as low as 6% for samples prepared with 2.5-10% tannic acid (or condensed tannin at 2.5%) with respect to CNF content. The strength of the MPN foams reaches a maximum at 10% tannic acid (using Fe(III) ions), equivalent to a compressive strength 70% higher than that produced with tannin-free CNF foams. Overall, a straightforward framework is introduced to synthesize MPN foams whose physical and mechanical properties are tailored by the presence of tannins as well as the metal ion species that enable the metal-phenolic networking. Depending on the metal ion, the foams are amenable to modification according to the desired application.

Drying stresses in cellulose nanocrystal coatings: Impact of molecular and macromolecular additives.

The industrial implementation of cellulose nanocrystals (CNCs) in films and coatings requires thorough evaluation of the internal stresses post-consolidation, as they cause fracturing and peeling. Characterizing the impact of plasticizing additives on stress is therefore critical. Herein, we use the deflection of thin glass substrates to measure drying stresses in consolidating CNC films, and benchmark the impact of five additives (glucose, glycerol, poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA) and bovine serum albumin). Glycerol and PEG reduced drying stresses effectively, while PEG of increased molecular weight (from 0.2 to 10 kDa), PVA, and BSA were less effective. We analyzed the temporal aspects of the process, where stress relaxation of up to 30 % was observed 2 years after coating formation. Finally, we provide a framework to evaluate the impact of CNC morphology on residual stresses. The introduced approach is expected to fast-track the optimization and implementation of coatings based on biocolloids.

Spatioselective surface chemistry for the production of functional and chemically anisotropic nanocellulose colloids.

Maximizing the benefits of nanomaterials from biomass requires unique considerations associated with their native chemical and physical structure. Both cellulose nanofibrils and nanocrystals are extracted from cellulose fibers via a top-down approach and have significantly advanced materials chemistry and set new benchmarks in the last decade. One major challenge has been to prepare defined and selectively modified nanocelluloses, which would, e.g., allow optimal particle interactions and thereby further improve the properties of processed materials. At the molecular and crystallite level, the surface of nanocelluloses offers an alternating chemical structure and functional groups of different reactivity, enabling straightforward avenues towards chemically anisotropic and molecularly patterned nanoparticles via spatioselective chemical modification. In this review, we will explain the influence and role of the multiscale hierarchy of cellulose fibers in chemical modifications, and critically discuss recent advances in selective surface chemistry of nanocelluloses. Finally, we will demonstrate the potential of those chemically anisotropic nanocelluloses in materials science and discuss challenges and opportunities in this field.

Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase.

Gas-phase acylation is an attractive and sustainable method for modifying the surface properties of cellulosics. However, little is known concerning the regioselectivity of the chemistry, i.e., which cellulose hydroxyls are preferentially acylated and if acylation can be restricted to the surface, preserving crystallinities/morphologies. Consequently, we reexplore simple gas-phase acetylation of modern-day cellulosic building blocks - cellulose nanocrystals, pulps, dry-jet wet spun (regenerated cellulose) fibres and a nanocellulose-based aerogel. Using advanced analytics, we show that the gas-phase acetylation is highly regioselective for the C6-OH, a finding also supported by DFT-based transition-state modelling on a crystalloid surface. This contrasts with acid- and base-catalysed liquid-phase acetylation methods, highlighting that gas-phase chemistry is much more controllable, yet with similar kinetics, to the uncatalyzed liquid-phase reactions. Furthermore, this method preserves both the native (or regenerated) crystalline structure of the cellulose and the supramolecular morphology of even delicate cellulosic constructs (nanocellulose aerogel exhibiting chiral cholesteric liquid crystalline phases). Due to the soft nature of this chemistry and an ability to finely control the kinetics, yielding highly regioselective low degree of substitution products, we are convinced this method will facilitate the rapid adoption of precisely tailored and biodegradable cellulosic materials.

Nanochitin: Chemistry, Structure, Assembly, and Applications.

Chitin, a fascinating biopolymer found in living organisms, fulfills current demands of availability, sustainability, biocompatibility, biodegradability, functionality, and renewability. A feature of chitin is its ability to structure into hierarchical assemblies, spanning the nano- and macroscales, imparting toughness and resistance (chemical, biological, among others) to multicomponent materials as well as adding adaptability, tunability, and versatility. Retaining the inherent structural characteristics of chitin and its colloidal features in dispersed media has been central to its use, considering it as a building block for the construction of emerging materials. Top-down chitin designs have been reported and differentiate from the traditional molecular-level, bottom-up synthesis and assembly for material development. Such topics are the focus of this Review, which also covers the origins and biological characteristics of chitin and their influence on the morphological and physical-chemical properties. We discuss recent achievements in the isolation, deconstruction, and fractionation of chitin nanostructures of varying axial aspects (nanofibrils and nanorods) along with methods for their modification and assembly into functional materials. We highlight the role of nanochitin in its native architecture and as a component of materials subjected to multiscale interactions, leading to highly dynamic and functional structures. We introduce the most recent advances in the applications of nanochitin-derived materials and industrialization efforts, following green manufacturing principles. Finally, we offer a critical perspective about the adoption of nanochitin in the context of advanced, sustainable materials.

Benchmarking supramolecular adhesive behavior of nanocelluloses, cellulose derivatives and proteins.

One of the key steps towards a broader implementation of renewable materials is the development of biodegradable adhesives that can be attained at scale and utilized safely. Recently, cellulose nanocrystals (CNCs) were demonstrated to have remarkable adhesive properties. Herein, we study three classes of naturally synthesized biopolymers as adhesives, namely nanocelluloses (CNFs), cellulose derivatives, and proteins by themselves and when used as additives with CNCs. Among the samples evaluated, the adhesion strength was the highest for bovine serum albumin and hydroxypropyl cellulose (beyond 10 MPa). These were followed by carboxymethylcellulose and CNCs (ca. 5 MPa) and mechanically fibrillated CNFs (ca. 2 MPa), and finally by tempo-oxidized CNFs (0.2 MPa) and lysozyme (1.5 MPa). Remarkably, we find that the anisotropy of adhesion (in plane vs out of plane) falls within a narrow range across the bio-based adhesives studied. Collectively, this study benchmarks bio-based non-covalent adhesives aiming towards their improvement and implementation.

Rapid assembly of colorless antimicrobial and anti-odor coatings from polyphenols and silver.

The development of antimicrobial fabrics and textiles that can sustainably inhibit a broad spectrum of microbes is crucial for protecting against pathogens in various environments. However, engineering antimicrobial textiles is challenging due to issues with discoloration and inhibited breathability, the use of harmful or harsh reagents and synthesis conditions, and complex and/or time-consuming processing. Herein, we develop a facile and rapid approach to deposit antimicrobial coatings using universally adherent plant polyphenols and antimicrobial silver ions. Importantly, the coatings are colorless, thin (< 10 nm), rapidly assembled (< 20 min), and can be deposited via immersion or spraying. We demonstrate that these metal-phenolic coatings on textiles can inhibit lipid-enveloped viruses over one thousand times more efficiently than coatings composed of other metal ions, while maintaining their efficacy even after 5 washes. Moreover, the coatings also inhibit Gram positive and negative bacteria, and fungi, and can prevent odors on clothes for at least 10 washes. Collectively, the ease of synthesis, use of simple and safe precursors, and amenability to at-home and industrial application suggests that the coatings will find practical application in various settings.

Superstable Wet Foams and Lightweight Solid Composites from Nanocellulose and Hydrophobic Particles.

Colloids are suitable options to replace surfactants in the formation of multiphase systems while simultaneously achieving performance benefits. We introduce synergetic combination of colloids for the interfacial stabilization of complex fluids that can be converted into lightweight materials. The strong interactions between high aspect ratio and hydrophilic fibrillated cellulose (CNF) with low aspect ratio hydrophobic particles afford superstable Pickering foams. The foams were used as a scaffolding precursor of porous, solid materials. Compared to foams stabilized by the hydrophobic particles alone, the introduction of CNF significantly increased the foamability (by up to 350%) and foam lifetime. These effects are ascribed to the fibrillar network formed by CNF. The CNF solid fraction regulated the interparticle interactions in the wet foam, delaying or preventing drainage, coarsening, and bubble coalescence. Upon drying, such a complex fluid was transformed into lightweight and strong architectures, which displayed properties that depended on the surface energy of the CNF precursor. We show that CNF combined with hydrophobic particles universally forms superstable complex fluids that can be used as a processing route to synthesize strong composites and lightweight structures.

Multifunctional lignin-based nanocomposites and nanohybrids.

Significant progress in lignins valorization and development of high-performance sustainable materials have been achieved in recent years. Reports related to lignin utilization indicate excellent prospects considering green chemistry, chemical engineering, energy, materials and polymer science, physical chemistry, biochemistry, among others. To fully realize such potential, one of the most promising routes involves lignin uses in nanocomposites and nanohybrid assemblies, where synergistic interactions are highly beneficial. This review first discusses the interfacial assembly of lignins with polysaccharides, proteins and other biopolymers, for instance, in the synthesis of nanocomposites. To give a wide perspective, we consider the subject of hybridization with metal and metal oxide nanoparticles, as well as uses as precursor of carbon materials and the assembly with other biobased nanoparticles, for instance to form nanohybrids. We provide cues to understand the fundamental aspects related to lignins, their self-assembly and supramolecular organization, all of which are critical in nanocomposites and nanohybrids. We highlight the possibilities of lignin in the fields of flame retardancy, food packaging, plant protection, electroactive materials, energy storage and health sciences. The most recent outcomes are evaluated given the importance of lignin extraction, within established and emerging biorefineries. We consider the benefit of lignin compared to synthetic counterparts. Bridging the gap between fundamental and application-driven research, this account offers critical insights as far as the potential of lignin as one of the frontrunners in the uptake of bioeconomy concepts and its application in value-added products.

Assembling Native Elementary Cellulose Nanofibrils via a Reversible and Regioselective Surface Functionalization.

Selective surface modification of biobased fibers affords effective individualization and functionalization into nanomaterials, as exemplified by the TEMPO-mediated oxidation. However, such a route leads to changes of the native surface chemistry, affecting interparticle interactions and limiting the development of potential supermaterials. Here we introduce a methodology to extract elementary cellulose fibrils by treatment of biomass with N-succinylimidazole, achieving regioselective surface modification of C6-OH, which can be reverted using mild post-treatments. No polymer degradation, cross-linking, nor changes in crystallinity occur under the mild processing conditions, yielding cellulose nanofibrils bearing carboxyl moieties, which can be removed by saponification. The latter offers a significant opportunity in the reconstitution of the chemical and structural interfaces associated with the native states. Consequently, 3D structuring of native elementary cellulose nanofibrils is made possible with the same supramolecular features as the biosynthesized fibers, which is required to unlock the full potential of cellulose as a sustainable building block.

Chitin-amyloid synergism and their use as sustainable structural adhesives.

Structural adhesives are relevant to many engineering applications, especially those requiring load-bearing joints with high lap shear strength. Typical adhesives are synthesized from acrylics, epoxies, or urethanes, which may pose a burden to sustainability and the environment. In nature, the interfacial interactions between chitin and proteins are used for structural purposes and as a bio-cement, resulting in materials with properties unmatched by their man-made counterparts. Herein, we show that related supramolecular interactions can be harnessed to develop high strength green adhesives based on chitin nanocrystals (ChNCs), isolated from shrimp shells, and hen egg white lysozyme (HEWL) used in its monomeric or amyloid forms. Consolidation of the bicomponent suspensions, placed between glass substrates, results in long-range ordered superstructures. The formation of these structures is evaluated by surface energy considerations, followed by scanning electron, atomic force, and polarized microscopies of the consolidated materials. For 0.8 mg of bio-adhesive (lysozyme, ChNCs or their composites), lap shear loads of over 300 N are reached. Such remarkable adhesion reaches maximum values at protein-to-ChNC ratios below 1 : 4, reflecting the synergy established between the components (ca. 25% higher load compared to ChNCs, the strongest single component). We put the observed adhesive performance in perspective by comparing the lap-shear performance with current research on green supramolecular adhesives using natural biopolymers. The results are discussed in the context of current efforts to standardize the measurement of adhesive strength and bond preparation. The latter is key to formalizing the metrology and materials chemistry of bio-based adhesives. The proposed all-green system is expected to expand current developments in the design of bio-based adhesives.

Superstructured mesocrystals through multiple inherent molecular interactions for highly reversible sodium ion batteries.

Soft structures in nature, such as supercoiled DNA and proteins, can organize into complex hierarchical architectures through multiple noncovalent molecular interactions. Identifying new classes of natural building blocks capable of facilitating long-range hierarchical structuring has remained an elusive goal. We report the bottom-up synthesis of a hierarchical metal-phenolic mesocrystal where self-assembly proceeds on different length scales in a spatiotemporally controlled manner. Phenolic-based coordination complexes organize into supramolecular threads that assemble into tertiary nanoscale filaments, lastly packing into quaternary mesocrystals. The hierarchically ordered structures are preserved after thermal conversion into a metal-carbon hybrid framework and can impart outstanding performance to sodium ion batteries, which affords a capability of 72.5 milliampere hours per gram at an ultrahigh rate of 200 amperes per gram and a 90% capacity retention over 15,000 cycles at a current density of 5.0 amperes per gram. This hierarchical structuring of natural polyphenols is expected to find widespread applications.

Deconstruction and Reassembly of Renewable Polymers and Biocolloids into Next Generation Structured Materials.

This review considers the most recent developments in supramolecular and supraparticle structures obtained from natural, renewable biopolymers as well as their disassembly and reassembly into engineered materials. We introduce the main interactions that control bottom-up synthesis and top-down design at different length scales, highlighting the promise of natural biopolymers and associated building blocks. The latter have become main actors in the recent surge of the scientific and patent literature related to the subject. Such developments make prominent use of multicomponent and hierarchical polymeric assemblies and structures that contain polysaccharides (cellulose, chitin, and others), polyphenols (lignins, tannins), and proteins (soy, whey, silk, and other proteins). We offer a comprehensive discussion about the interactions that exist in their native architectures (including multicomponent and composite forms), the chemical modification of polysaccharides and their deconstruction into high axial aspect nanofibers and nanorods. We reflect on the availability and suitability of the latter types of building blocks to enable superstructures and colloidal associations. As far as processing, we describe the most relevant transitions, from the solution to the gel state and the routes that can be used to arrive to consolidated materials with prescribed properties. We highlight the implementation of supramolecular and superstructures in different technological fields that exploit the synergies exhibited by renewable polymers and biocolloids integrated in structured materials.

Hybrid Living Capsules Autonomously Produced by Engineered Bacteria.

Bacterial cellulose (BC) has excellent material properties and can be produced sustainably through simple bacterial culture, but BC-producing bacteria lack the extensive genetic toolkits of model organisms such as Escherichia coli (E. coli). Here, a simple approach is reported for producing highly programmable BC materials through incorporation of engineered E. coli. The acetic acid bacterium Gluconacetobacter hansenii is cocultured with engineered E. coli in droplets of glucose-rich media to produce robust cellulose capsules, which are then colonized by the E. coli upon transfer to selective lysogeny broth media. It is shown that the encapsulated E. coli can produce engineered protein nanofibers within the cellulose matrix, yielding hybrid capsules capable of sequestering specific biomolecules from the environment and enzymatic catalysis. Furthermore, capsules are produced which can alter their own bulk physical properties through enzyme-induced biomineralization. This novel system uses a simple fabrication process, based on the autonomous activity of two bacteria, to significantly expand the functionality of BC-based living materials.

Infiltration of Proteins in Cholesteric Cellulose Structures.

Cellulose nanocrystals (CNCs) can spontaneously self-assemble into chiral nematic (cn) structures, similar to natural cholesteric organizations. The latter display highly dissipative fracture propagation mechanisms given their "brick" (particles) and "mortar" (soft matrix) architecture. Unfortunately, CNCs in liquid media have strong supramolecular interactions with most macromolecules, leading to aggregated suspensions. Herein, we describe a method to prepare nanocomposite materials from chiral nematic CNCs (cn-CNCs) with strongly interacting secondary components. Films of cn-CNCs were infiltrated at various loadings with strongly interacting silk proteins and bovine serum albumin. For comparison and to determine the molecular weight range of macromolecules that can infiltrate cn-CNC films, they were also infiltrated with a range of poly(ethylene glycol) polymers that do not interact strongly with CNCs. The extent and impact of infiltration were evaluated by studying the optical reflection properties of the resulting hybrid materials (UV-vis spectroscopy), while fracture dissipation mechanisms were observed via electron microscopy. We propose that infiltration of cn-CNCs enables the introduction of virtually any secondary phase for nanocomposite formation that is otherwise not possible using simple mixing or other conventional approaches.

Plant Nanomaterials and Inspiration from Nature: Water Interactions and Hierarchically Structured Hydrogels.

Recent developments in the area of plant-based hydrogels are introduced, especially those derived from wood as a widely available, multiscale, and hierarchical source of nanomaterials, as well as other cell wall elements. With water being fundamental in a hydrogel, water interactions, hydration, and swelling, all critically important in designing, processing, and achieving the desired properties of sustainable and functional hydrogels, are highlighted. A plant, by itself, is a form of a hydrogel, at least at given states of development, and for this reason phenomena such as fluid transport, diffusion, capillarity, and ionic effects are examined. These aspects are highly relevant not only to plants, especially lignified tissues, but also to the porous structures produced after removal of water (foams, sponges, cryogels, xerogels, and aerogels). Thus, a useful source of critical and comprehensive information is provided regarding the synthesis of hydrogels from plant materials (and especially wood nanostructures), and about the role of water, not only for processing but for developing hydrogel properties and uses.

Impact of incubation conditions and post-treatment on the properties of bacterial cellulose membranes for pressure-driven filtration.

Bacterial cellulose (BC) has shown potential as a separation material. Herein, the performance of BC in pressure-driven separation is investigated as a function of incubation conditions and post-culture treatment. The pure water flux of never-dried BC (NDBC), was found to be 9 to 16 times higher than that for dried BC (DBC), in a pressure range of 0.25 to 2.5 bar. The difference in pressure response of NDBC and DBC was observed both in cross-flow filtration and capillary flow porometry experiments. DBC and NDBC were permeable to polymers with a hydrodynamic radius of ∼60 nm while protein retention was possible by introducing anionic surface charges on BC. The results of this work are expected to expand the development of BC-based filtration membranes, for instance towards the processing of biological fluids.