Nanocomposite hydrogels are prepared combining polymer brush‐modified ‘hard’ cellulose nanocrystals (CNC) and ‘soft’ polymeric domains, and bound together by cucurbit[8]uril (CB[8]) supramolecular crosslinks, which allow dynamic host–guest interactions as well as selective and simultaneous binding of two guests, i.e., methyl viologen (the first guest) and naphthyl units (the second guest). CNCs are mechanically strong colloidal rods with nanometer‐scale lateral dimensions, which are functionalized by surface‐initiated atom transfer radical polymerization to yield a dense set of methacrylate polymer brushes bearing naphthyl units. They can then be non‐covalently cross‐linked through simple addition of poly(vinyl alcohol) polymers containing pendant viologen units as well as CB[8]s in aqueous media. The resulting supramolecular nanocomposite hydrogels combine three important criteria: high storage modulus (G′ > 10 kPa), rapid sol–gel transition (<6 s), and rapid self‐healing even upon aging for several months, as driven by balanced colloidal reinforcement as well as the selectivity and dynamics of the CB[8] three‐component supramolecular interactions. Such a new combination of properties for stiff and self‐healing hydrogel materials suggests new approaches for advanced dynamic materials from renewable sources.

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.

Cellulose microfibrils physically bound together by soft hemicellulose chains form the scaffolding that makes plant cell walls strong. Inspired by this architecture, we designed biomimetic thermoreversible hydrogel networks based on reinforcing cellulose nanocrystals (CNC) and thermoresponsive methylcellulose (MC). Upon dissolving MC powder in CNC aqueous dispersions, viscoelastic dispersions were formed at 20 °C, where the storage modulus (G′) is tunable from 1.0 to 75 Pa upon increasing the CNC concentration from 0 to 3.5 wt % with 1.0 wt % MC. By contrast, at 60 °C a distinct gel state is obtained with G′ ≫ G″, G′ ∼ ω 0 , with an order of magnitude larger G′ values from 110 to 900 Pa upon increasing the CNC concentration from 0 to 3.5 wt % with constant 1.0 wt % MC, due to the physical cross-links between MC and CNCs. Therefore, simply mixing two sustainable components leads to the first all-cellulose thermoreversible and tunable nanocellulose-based hydrogels.

Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications.

We show that composite hydrogels comprising methyl cellulose (MC) and cellulose nanocrystal (CNC) colloidal rods display a reversible and enhanced rheological storage modulus and optical birefringence upon heating, i.e., inverse thermoreversibility. Dynamic rheology, quantitative polarized optical microscopy, isothermal titration calorimetry (ITC), circular dichroism (CD), and scanning and transmission electron microscopy (SEM and TEM) were used for characterization. The concentration of CNCs in aqueous media was varied up to 3.5 wt % (i.e, keeping the concentration below the critical aq concentration) while maintaining the MC aq concentration at 1.0 wt %. At 20 °C, MC/CNC underwent gelation upon passing the CNC concentration of 1.5 wt %. At this point, the storage modulus (G′) reached a plateau, and the birefringence underwent a stepwise increase, thus suggesting a percolative phenomenon. The storage modulus (G′) of the composite gels was an order of magnitude higher at 60 °C compared to that at 20 °C. ITC results suggested that, at 60 °C, the CNC rods were entropically driven to interact with MC chains, which according to recent studies collapse at this temperature into ring-like, colloidal-scale persistent fibrils with hollow cross-sections. Consequently, the tendency of the MC to form more persistent aggregates promotes the interactions between the CNC chiral aggregates towards enhanced storage modulus and birefringence. At room temperature, ITC shows enthalpic binding between CNCs and MC with the latter comprising aqueous, molecularly dispersed polymer chains that lead to looser and less birefringent material. TEM, SEM, and CD indicate CNC chiral fragments within a MC/CNC composite gel. Thus, MC/CNC hybrid networks offer materials with tunable rheological properties and access to liquid crystalline properties at low CNC concentrations.

No abstract

A series of well-defined thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) macromonomers was prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization followed by aminolysis and nucleophilic Michael addition. 2-(Dodecylthiocarbonothioylthio)-2-methylpropanoic-2-phenoxyethyl ester (CTA) was used as the RAFT chain transfer agent to prepare six PNIPAM-CTA precursors with target degrees of polymerization of 20, 30, 40, 50, 60, and 75. These NIPAM polymerizations were conducted in 1,4-dioxane and proceeded with good control and low polydispersities (M w/M n < 1.10) up to more than 90% conversion. The PNIPAM trithiocarbonate end-groups were then converted to methacrylate end-groups by combining (i) aminolysis and (ii) nucleophilic Michael addition using the bifunctional reagent, 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHPMA), in a one-pot reaction. The resulting PNIPAM macromonomers were evaluated as reactive steric stabilizers for latex syntheses. Near-monodisperse submicrometer-sized latexes were obtained by alcoholic dispersion polymerization of styrene in methanol, as judged by scanning electron microscopy (SEM) and dynamic light scattering (DLS). In contrast, a latex synthesized in the presence of a PNIPAM-CTA had a bimodal size distribution, while thiol-capped PNIPAM chains produced ill-defined nonspherical particles and styrene polymerization conducted in the absence of any stabilizer led to macroscopic precipitation. These control experiments confirm that using the methacrylate-capped macromonomers is essential for successful latex syntheses. 1H NMR analysis confirm the presence of PNIPAM chains in the latex particles and XPS measurements indicate that the stabilizer is located on the particle surface, as expected. The well-known thermo-responsive nature of the stabilizer was successfully transferred to these latexes, which exhibit reversible flocculation upon heating above the LCST of the PNIPAM chains.

Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supramolecular hydrogels, displaying enhanced rheological yield strain and a synergistic improvement in storage modulus. The supramolecular hydrogel consists of naphthyl-functionalized hydroxyethyl cellulose and a cationic polystyrene derivative decorated with methylviologen moieties, physically cross-linked with cucurbit[8]uril macrocyclic hosts. Fast exchange kinetics within the supramolecular system are enabled by reversible cross-linking through the binding of the naphthyl and viologen guests. The colloidal hydrogel consists of nanofibrillated cellulose that combines a mechanically strong nanofiber skeleton with a lateral fibrillar diameter of a few nanometers. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces. This work shows methods to bridge the length scales of molecular and colloidal hybrid hydrogels, resulting in synergy between reinforcement and dynamics.