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.

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.

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.

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.

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.

Adsorption and Assembly of Cellulosic and Lignin Colloids at Oil/Water Interfaces.

The surface chemistry and adsorption behavior of submicrometer cellulosic and lignin particles have drawn wide-ranging interest in the scientific community. Here, we introduce their assembly at fluid/fluid interfaces in Pickering systems and discuss their role in reducing the oil/water interfacial tension, limiting flocculation and coalescence, and endowing given functional properties. We discuss the stabilization of multiphase systems by cellulosic and lignin colloids and the opportunities for their adoption. They can be used alone, as dual components, or in combination with amphiphilic molecules for the design of multiphase systems relevant to household products, paints, coatings, pharmaceutical, foodstuff, and cosmetic formulations. This invited feature article summarizes some of our work and that of colleagues to introduce the readers to this fascinating and topical area.

Accounting for Substrate Interactions in the Measurement of the Dimensions of Cellulose Nanofibrils.

Mechanically fibrillated cellulose nanofibrils (CNFs) have attracted special attention as building blocks for the development of advanced materials and composites. A correlation exists between CNF morphology and the properties of the materials they form. However, this correlation is often evaluated indirectly by process-centered approaches or by accessing a single dimensionality of CNFs adsorbed on solid supports. High-resolution imaging is currently the best approach to describe the morphological features of nanocelluloses; nevertheless, adsorption effects need to be accounted for. For instance, possible deformations of the CNFs arising from capillary forces and interactions with the substrate need to be considered in the determination of their cross-sectional dimensions. By considering soft matter imaging and adsorption effects, we provide evidence of the deformation of CNFs upon casting and drying. We determine a substantial flattening associated with the affinity of CNFs with the substrate corresponding to a highly anisotropic cross-sectional geometry (ellipsoidal) in the dried state. Negative-contrast scanning electron microscopy is also introduced as a new method to assess the dimensions of the CNFs. The images obtained by the latter, a faster imaging method, were correlated with those from atomic force microscopy. The cross-sectional area of the CNF is reconstructed by cross-correlating the widths and heights obtained by the two techniques.

How Cellulose Nanofibrils Affect Bulk, Surface, and Foam Properties of Anionic Surfactant Solutions.

We study the generation and decay of aqueous foams stabilized by sodium dodecyl sulfate (SDS) in the presence of unmodified cellulose nanofibrils (CNF). Together with the rheology of aqueous suspensions containing CNF and SDS, the interfacial/colloidal interactions are determined by quartz crystal microgravimetry with dissipation monitoring, surface plasmon resonance, and isothermal titration calorimetry. The results are used to explain the properties of the air/water interface (interfacial activity and dilatational moduli determined from oscillating air bubbles) and of the bulk (steady-state flow, oscillatory shear, and capillary thinning). These properties are finally correlated to the foamability and to the foam stability. The latter was studied as a function of time by monitoring the foam volume, the liquid fraction, and the bubble size distribution. The shear-thinning effect of CNF is found to facilitate foam formation at SDS concentrations above the critical micelle concentration (cSDS ≥ cmc). Compared with foams stabilized by pure SDS, the presence of CNF enhances the viscosity and elasticity of the continuous phase as well as of the air/water interface. The CNF-containing foams have higher liquid fractions, larger initial bubble sizes, and better stability. Due to charge screening effects caused by sodium counter ions and depletion attraction caused by SDS micelles, especially at high SDS concentrations, CNF forms aggregates in the Plateau borders and nodes of the foam, thus slowing down liquid drainage and bubble growth and improving foam stability. Overall, our findings advance the understanding of the role of CNF in foam generation and stabilization.

Surface Activity and Foaming Capacity of Aggregates Formed between an Anionic Surfactant and Non-Cellulosics Leached from Wood Fibers.

This study relates to the release of non-cellulosic components (cell wall heteropolysaccharides, lignin, and extractives) from swollen wood fibers in the presence of an anionic surfactant (sodium dodecyl sulfate, SDS) at submicellar concentrations. Highly surface-active aggregates form between SDS and the leached, non-cellulosic components, which otherwise do not occur in the presence of cationic or nonionic surfactants. The in situ and efficient generation of liquid foams in the presence of the leached species is demonstrated. The foaming capacity and foam stability, as well as the foam's structure, are determined as a function of the composition of the aqueous suspension. The results indicate that naturally occurring components bound to wood fibers are extractable solely with aqueous solutions of the anionic surfactant. Moreover, they can form surface-active aggregates that have a high foaming capacity. The results further our understanding of residual cell wall components and their role in the generation of foams.

Protein Adsorption and Coordination-Based End-Tethering of Functional Polymers on Metal-Phenolic Network Films.

Metal-phenolic network (MPN) coatings have generated increasing interest owing to their biologically inspired nature, facile fabrication, and near-universal adherence, especially for biomedical applications. However, a key issue in biomedicine is protein fouling, and the adsorption of proteins on tannic acid-based MPNs remains to be comprehensively studied. Herein, we investigate the interaction of specific biomedically relevant proteins in solution (e.g., bovine serum albumin (BSA), immunoglobulin G (IgG), fibrinogen) and complex biological media (serum) using layer-by-layer-assembled tannic acid/FeIII MPN films. When FeIII was the outermost layer, galloyl-modified poly(2-ethyl-2-oxazoline) (P(EtOx)-Gal) could be grafted to the films through coordination bonds. Protein fouling and bacterial adhesion were greatly suppressed after functionalization with P(EtOx)-Gal and the mass of adsorbed protein was reduced by 79%. Interestingly, larger proteins adsorbed more on both the MPNs and P(EtOx)-functionalized MPNs. This study provides fundamental information on the interactions of MPNs with single proteins, mixtures of proteins as encountered in serum, and the noncovalent, coordination-based, functionalization of MPN films.

Green Formation of Robust Supraparticles for Cargo Protection and Hazards Control in Natural Environments.

In parallel with important technological advances, nanoparticles have brought numerous environmental and toxicological challenges due to their high mobility and nonspecific surface activity. The hazards associated with nanoparticles can be significantly reduced while simultaneously keeping their inherent benefits by superstructuring. In this study, a low-temperature and versatile methodology is employed to structure nanoparticles into controlled morphologies from biogenic silica, used as a main building block, together with cellulose nanofibrils, which promote cohesion. The resultant superstructures are evaluated for cargo loading/unloading of a model, green biomolecule (thymol), and for photo-accessibility and mobility in soil. The bio-based superstructures resist extremely high mechanical loading without catastrophic failure, even after severe chemical and heat treatments. Additionally, the process allows pre and in situ loading, and reutilization, achieving remarkable dynamic payloads as high as 90 mg g-1 . The proposed new and facile methodology is expected to offer a wide range of opportunities for the application of superstructures in sensitive and natural environments.

Particulate Coatings via Evaporation-Induced Self-Assembly of Polydisperse Colloidal Lignin on Solid Interfaces.

Polydisperse smooth and spherical biocolloidal particles were suspended in aqueous media and allowed to consolidate via evaporation-induced self-assembly. The stratification of the particles at the solid-air interface was markedly influenced, but not monotonically, by the drying rate. Cross-sectional imaging via electron microscopy indicated a structured coating morphology that was distinctive from that obtained by using particles with a mono- or bimodal distribution. Segregation patterns were found to derive from the interplay of particle diffusion, interparticle forces, and settling dynamics. Supporting our experimental findings, computer simulations showed an optimal drying rate for achieving maximum segregation. Overall, stratified coatings comprising nano- and microparticles derived from lignin are expected to open opportunities for multifunctional structures that can be designed and predicted on the basis of experimental Péclet numbers and computational order.

Effect of Anisotropy of Cellulose Nanocrystal Suspensions on Stratification, Domain Structure Formation, and Structural Colors.

Outstanding optical and mechanical properties can be obtained from hierarchical assemblies of nanoparticles. Herein, the formation of helically ordered, chiral nematic films obtained from aqueous suspensions of cellulose nanocrystals (CNCs) were studied as a function of the initial suspension state. Specifically, nanoparticle organization and the structural colors displayed by the resultant dry films were investigated as a function of the anisotropic volume fraction (AVF), which depended on the initial CNC concentration and equilibration time. The development of structural color and the extent of macroscopic stratification were studied by optical and scanning electron microscopy as well as UV-vis spectroscopy. Overall, suspensions above the critical threshold required for formation of liquid crystals resulted in CNC films assembled with longer ranged order, more homogeneous pitches along the cross sections, and narrower specific absorption bands. This effect was more pronounced for the suspensions that were closer to equilibrium prior to drying. Thus, we show that high AVF and more extensive phase separation in CNC suspensions resulted in large, long-range ordered chiral nematic domains in dried films. Additionally, the average CNC aspect ratio and size distribution in the two separated phases were measured and correlated to the formation of structured domains in the dried assemblies.

Optical Properties of Self-Assembled Cellulose Nanocrystals Films Suspended at Planar-Symmetrical Interfaces.

Hierarchically structured materials comprising rod-like, chiral, nanoparticles are commonly encountered in nature as they can form assemblies with exceptional optical and mechanical characteristics. These include cellulose nanocrystals (CNCs), which have a large potential for the fabrication of bioinspired materials mimicking those advanced properties. Fine-tuning the optomechanical properties of assemblies obtained from CNCs hinges on the transformations from suspensions of liquid crystals to long-range order in the dry state. So far, associated transitions have been studied using trivial interfaces such as planar substrates. Such transitions are explored as they evolve onto meshed supports. The meshed substrate offers a complex topology, as is encountered in nature, for the formation of CNCs films. The CNCs self-assembly occurs under confinement and support of the framework bounding the mesh openings. This leads to coexisting suspended and supported nanoparticle layers exhibiting nematic and/or chiral nematic order. Optical microscopy combined with crossed polarizers indicate that the formation of the suspended films occurs via intermediate gelation or kinetic arrest of CNCs across the mesh's open areas. The formation of self-standing, ultrathin films of CNCs with tunable optical properties, such as selective reflections in the visible range (structural color), is demonstrated by using the presented simple and scalable approach.

Influence of Ionic Strength on the Deposition of Metal-Phenolic Networks.

Metal-phenolic networks (MPNs) are a versatile class of self-assembled materials that are able to form functional thin films on various substrates with potential applications in areas including drug delivery and catalysis. Different metal ions (e.g., FeIII, CuII) and phenols (e.g., tannic acid, gallic acid) have been investigated for MPN film assembly; however, a mechanistic understanding of the thermodynamics governing MPN formation remains largely unexplored. To date, MPNs have been deposited at low ionic strengths (<5 mM), resulting in films with typical thicknesses of ∼10 nm, and it is still unclear how a bulk complexation reaction results in homogeneous thin films when a substrate is present. Herein we explore the influence of ionic strength (0-2 M NaCl) on the conformation of MPN precursors in solution and how this determines the final thickness and morphology of MPN films. Specifically, the film thickness increases from 10 nm in 0 M NaCl to 12 nm in 0.5 M NaCl and 15 nm in 1 M NaCl, after which the films grow rougher rather than thicker. For example, the root-mean-square roughness values of the films are constant below 1 M NaCl at 1.5 nm; in contrast, the roughness is 3 nm at 1 M NaCl and increases to 5 nm at 2 M NaCl. Small-angle X-ray scattering and molecular dynamics simulations allow for comparisons to be made with chelated metals and polyelectrolyte thin films. For example, at a higher ionic strength (2 M NaCl), sodium ions shield the galloyl groups of tannic acid, allowing them to extend away from the FeIII center and interact with other MPN complexes in solution to form thicker and rougher films. As the properties of films determine their final performance and application, the ability to tune both thickness and roughness using salts may allow for new applications of MPNs.

Formation of Polyrotaxane Particles via Template Assembly.

In this study, we report a versatile method to assemble tunable poly(ethylene glycol) (PEG)-based polyrotaxane (PRX) particles and capsules. By threading α-cyclodextrins (αCDs) onto PEG chains physically adsorbed onto template particles and subsequently dissolving the templates, PRX replica particles and hollow capsules are formed. This approach overcomes issues related to CD steric hindrance, and also reduces the multiple processing steps often associated with PRX-based particle formation. By simple variation of the molecular weight and end-group functionality of the PEG, we show that the rate of particle degradation as well as the stability of the particles can be tuned. We also demonstrate the loading and release of model (drug) compounds, achieving burst and controlled release of the compounds. It is envisaged that this approach will provide a flexible platform for the engineering of a diverse range of PRX-based particles, enabling PRX materials to be further explored in various applications.

Self-assembled stimuli-responsive polyrotaxane core-shell particles.

Thermodynamically assembled core-shell nanocarriers are potential candidates for drug delivery applications due to their submicrometer size and the ability to load drugs into their hydrophobic core. Herein, we describe the formation of core-shell particles that consist of noncovalent polymers, that is, polyrotaxanes (PRXs), that form an α-cyclodextrin (αCD) core surrounded by a corona of low-fouling poly(ethylene glycol) (PEG). The PRX core-shell particles are able to sequester small organic molecules, such as pyrene and calcein, releasing these small molecules during degradation. The small, cellular peptide, glutathione, was used to degrade the particles through the reductive cleavage of disulfide bonds that stabilize the individual PRX polymers. Cleavage of a single bond allows for the degradation of the supramolecular-polymer, making these PRX core-shell particles highly responsive. Furthermore, these particles demonstrate negligible cytotoxicity in mammalian cells, making them promising carriers for future drug delivery research.

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.

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.

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.