Controlling the Nematic Liquid Crystallinity of Cellulose Nanocrystals with an Alcohol Ethoxy Sulfonate Surfactant.

Cellulose nanocrystals (CNCs) are biobased colloidal nanorods that have unlocked new opportunities in the area of sustainable functional nanomaterials including structural films and coatings, biomedical devices, energy, sensing, and composite materials. While selective light reflection and sensing develop from the typical chiral nematic (cholesteric, Nem*) liquid crystallinity exhibited by CNCs, a wealth of technologies would benefit from a nematic liquid crystal (LC) with CNC uniaxial alignment. Therefore, this study answers the central question of whether surfactant complexation suppresses CNC chirality in favor of nematic lyotropic and thermotropic liquid crystallinity. Therein, we use a common surfactant having both nonionic and anionic blocks, namely, oligo(ethylene glycol) alkyl-3-sulfopropyl diether potassium salt (an alcohol ethoxy sulfonate (AES)). AES forms complexes with CNCs in toluene (a representative for nonpolar organic solvent) via hydrogen bonding with an AES' oligo(ethylene glycol) block. A sufficiently high AES weight fraction endows the dispersibility of CNC in toluene. Lyotropic liquid crystallinity with Schlieren textures containing two- and four-point brush defects is observed in polarized optical microscopy (POM), along with the suppression of the cholesteric fingerprint textures. The results suggest a nematic (Nem) phase in toluene. Moreover, thermotropic liquid crystallinity is observed by incorporating an excess of AES, in the absence of an additional solvent and upon mild heating. The Schlieren textures suggest a nematic system that undergoes uniaxial alignment under mild shear. Importantly, replacing AES with a corresponding nonionic surfactant does not lead to liquid crystalline properties, suggesting electrostatic structural control of the charged end group of AES. Overall, we introduce a new avenue to suppress CNC chirality to achieve nematic structures, which resolves the long-sought uniaxial alignment of CNCs in filaments, composite materials, and optical devices.

Stereochemistry-dependent thermotropic liquid crystalline phases of monosaccharide-based amphiphiles.

Conformational rigidity controls the bulk self-assembly and liquid crystallinity from amphiphilic block molecules to copolymers. The effects of block stereochemistry on the self-assembly have, however, been less explored. Here, we have investigated amphiphilic block molecules involving eight open-chain monosaccharide-based polyol units possessing different stereochemistries, derived from D-glucose, D-galactose, L-arabinose, D-mannose and L-rhamnose (allylated monosaccharides t-Glc*, e-Glc*, t-Gal*, e-Gal*, t-Ara*, e-Ara*, t-Man*, and t-Rha*), end-functionalized with repulsive tetradecyl alkyl chain blocks to form well-defined amphiphiles with block molecule structures. All compounds studied showed low temperature crystalline phases due to polyol crystallization, and smectic (lamellar) and isotropic phases upon heating in bulk. Hexagonal cylindrical phase was additionally observed for the composition involving t-Man*. Cubic phases were observed for e-Glc*, e-Gal*, e-Ara*, and t-Rha* derived compounds. Therein, the rich array of WAXS-reflections suggested that the crystalline polyol domains are not ultra-confined in spheres as in classic cubic phases but instead show network-like phase continuity, which is rare in bulk liquid crystals. Importantly, the transition temperatures of the self-assemblies were observed to depend strongly on the polyol stereochemistry. The findings underpin that the stereochemistry in carbohydrate-based assemblies involves complexity, which is an important parameter to be considered in material design when developing self-assemblies for different functions.

Stable glycosylamines at the reducing ends of cellulose nanocrystals.

The reaction of reducing end groups in cellulose nanocrystals with dodecylamine was examined. Using a direct-dissolution solution-state NMR protocol, the regioselective formation of glucosylamines was shown. This provides an elegant approach to sustainably functionalize these bio-based nanomaterials, that may not require further reduction to more stable secondary amines.

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.

Unidirectional Perpendicularly Aligned Lamella-Structured Oligosaccharide (A) ABA Triblock Elastomer (B) Thin Films Utilizing Triazolium+/TFSI- Ionic Nanochannels.

We designed and synthesized high χ-low N-maltoheptaose-(triazolium+/N(SO2CF3)2-)-polyisoprene-(triazolium+/N(SO2CF3)2-)-maltoheptaose ABA triblock elastomers featuring triazolium+/N(SO2CF3)2- (TFSI-) counteranion ionic interfaces separating their constituting polymeric sub-blocks. Spin-coated and solvent-vapor-annealed (SVA) MH1.2k-(T+/TFSI-)-PI4.3k-(T+/TFSI-)-MH1.2k thin films demonstrate interface-induced charge cohesion through ca. 1 nm "thick" ionic nanochannels which facilitate the self-assembly of a perpendicularly aligned lamellar structure. Atomic force microscopy (AFM) and (grazing-incidence) small-angle X-ray scattering ((GI)SAXS) characterizations of MH1.2k-(T+/TFSI-)-PI4.3k-(T+/TFSI-)-MH1.2k and pristine triBCP analogous thin films revealed sub-10 nm block copolymer (BCP) self-assembly and unidirectionally aligned nanostructures developed over several µm2 areas. Solvated TFSI- counterions enhance the oligosaccharide sub-block packing during SVA. The overall BCP phase behavior was mapped through SAXS characterizations comparing di- vs triblock polymeric architectures, a middle PI sub-block with two different molecular masses, and TFSI- or I- counteranion effects. This work highlights the benefits of inducing single-point electrostatic interactions within chemical structures of block copolymers to master the long-range self-assembly of prescribed morphologies.

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.

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.

Lignin-Based Porous Supraparticles for Carbon Capture.

Multiscale carbon supraparticles (SPs) are synthesized by soft-templating lignin nano- and microbeads bound with cellulose nanofibrils (CNFs). The interparticle connectivity and nanoscale network in the SPs are studied after oxidative thermostabilization of the lignin/CNF constructs. The carbon SPs are formed by controlled sintering during carbonization and develop high mechanical strength (58 N·mm-3) and surface area (1152 m2·g-1). Given their features, the carbon SPs offer hierarchical access to adsorption sites that are well suited for CO2 capture (77 mg CO2·g-1), while presenting a relatively low pressure drop (∼33 kPa·m-1 calculated for a packed fixed-bed column). The introduced lignin-derived SPs address the limitations associated with mass transport (diffusion of adsorbates within channels) and kinetics of systems that are otherwise based on nanoparticles. Moreover, the carbon SPs do not require doping with heteroatoms (as tested for N) for effective CO2 uptake (at 1 bar CO2 and 40 °C) and are suitable for regeneration, following multiple adsorption/desorption cycles. Overall, we demonstrate porous SP carbon systems of low cost (precursor, fabrication, and processing) and superior activity (gas sorption and capture).

Chirality from Cryo-Electron Tomograms of Nanocrystals Obtained by Lateral Disassembly and Surface Etching of Never-Dried Chitin.

The complex nature of typical colloids and corresponding interparticle interactions pose a challenge in understanding their self-assembly. This specifically applies to biological nanoparticles, such as those obtained from chitin, which typically are hierarchical and multidimensional. In this study, we obtain chitin nanocrystals by one-step heterogeneous acid hydrolysis of never-dried crab residues. Partial deacetylation facilitates control over the balance of electrostatic charges (ζ-potential in the range between +58 and +75 mV) and therefore affords chitin nanocrystals (DE-ChNC) with axial aspect (170-350 nm in length), as determined by cryogenic transmission electron microscopy and atomic force microscopy. We find that the surface amines generated by deacetylation, prior to hydrolysis, play a critical role in the formation of individual chitin nanocrystals by the action of a dual mechanism. We directly access the twisting feature of chitin nanocrystals using electron tomography (ET) and uncover the distinctive morphological differences between chitin nanocrystals extracted from nondeacetylated chitin, ChNC, which are bundled and irregular, and DE-ChNC (single, straight nanocrystals). Whereas chitin nanocrystals obtained from dried chitin precursors are known to be twisted and form chiral nematic liquid crystals, our ET measurements indicate no dominant twisting or handedness for the nanocrystals obtained from the never-dried source. Moreover, no separation into typical isotropic and anisotropic phases occurs after 2 months at rest. Altogether, we highlight the critical role of drying the precursors or the nanopolysaccharides to develop chirality.

Chiral Plasmonics Using Twisting along Cellulose Nanocrystals as a Template for Gold Nanoparticles.

The right-handed twist along aqueous dispersed cellulose nanocrystals allows right-handed chiral plasmonics upon electrostatic binding of gold nanoparticles in dilute environment, through tuning the particle sizes and concentrations. Simulations using nanoparticle coordinates from cryo-electron tomography confirm the experimental results. The finding suggests generalization for other chiral and helical colloidal templates for nanoscale chiral plasmonics.

Rod-Like Nanoparticles with Striped and Helical Topography.

The behavior of nanoparticles in solution is largely dominated by their shape and interaction potential. Despite considerable progress in the preparation of patchy and compartmentalized particles, access to nanoparticles with complex surface patterns and topographies remains limited. Here, we show that polyanionic brushes tethered to rod-like cellulose nanocrystals (CNCs) spontaneously develop a striped or helical topography through interpolyelectrolyte complexation with polycationic diblock copolymers. Using cryogenic transmission electron microscopy (cryo-TEM) and tomography (cryo-ET), we follow the complexation process and analyze the delicate 3D topography on the CNC surface. The described approach is facile and modular and can be extended to other block chemistries, nanoparticles, and surfaces, thereby providing a versatile platform toward surface-patterned particles with complex topographies and spatially arranged functional groups.

Supracolloidal multivalent interactions and wrapping of dendronized glycopolymers on native cellulose nanocrystals.

Cellulose nanocrystals (CNCs) are high aspect ratio colloidal rods with nanoscale dimensions, attracting considerable interest recently due to their high mechanical properties, chirality, sustainability, and availability. In order to exploit them for advanced functions in new materials, novel supracolloidal concepts are needed to manipulate their self-assemblies. We report on exploring multivalent interactions to CNC surface and show that dendronized polymers (DenPols) with maltose-based sugar groups on the periphery of lysine dendrons and poly(ethylene-alt-maleimide) polymer backbone interact with CNCs. The interactions can be manipulated by the dendron generation suggesting multivalent interactions. The complexation of the third generation DenPol (G3) with CNCs allows aqueous colloidal stability and shows wrapping around CNCs, as directly visualized by cryo high-resolution transmission electron microscopy and electron tomography. More generally, as the dimensions of G3 are in the colloidal range due to their ~6 nm lateral size and mesoscale length, the concept also suggests supracolloidal multivalent interactions between other colloidal objects mediated by sugar-functionalized dendrons giving rise to novel colloidal level assemblies.

Polyelectrolyte brushes grafted from cellulose nanocrystals using Cu-mediated surface-initiated controlled radical polymerization.

Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.