Functional cellulose nanocrystals containing cationic and thermo-responsive polymer brushes.

Cationic and thermo-responsive polymer brushes were grafted from the surface of cellulose nanocrystals. Di(ethylene glycol) methyl ether methacrylate (MEO2MA) and poly(oligoethylene glycol) methyl ether acrylate (OEGMA300) and (2-methacryloyloxyethyl) trimethylammonium chloride (DMC) were grafted from cellulose nanocrystals (CNCs) via free radical polymerization. The CNC-g-POEGMA (CP) possessed a tunable lower critical solution temperature (LCST) of about 50 °C, and cloud point measurements confirmed that the LCST of the nanoparticles could be manipulated within the range of 40-47 °C by adjusting the DMC content. The salt effect was also investigated, and the results revealed a typical salting-out effect for the CNC-g-POEGMA after the introduction of KCl. On the other hand, the CNC-g-POEGMA-g-DMC (CPD) copolymers displayed two salt-responsive characteristics; polyelectrolyte effect at lower salt concentrations, followed by the salting-out effect at higher salt concentrations, which is dependent on the DMC content.

Self-Healable Conductive Nanocellulose Nanocomposites for Biocompatible Electronic Skin Sensor Systems.

Electronic skins are developed for applications such as biomedical sensors, robotic prosthetics, and human-machine interactions, which raise the interest in composite materials that possess both flexibility and sensing properties. Polypyrrole-coated cellulose nanocrystals and cellulose nanofibers were prepared using iron(III) chloride (FeCl3) oxidant, which were used to reinforce polyvinyl alcohol (PVA). The combination of weak H-bonds and iron coordination bonds and the synergistic effect of these components yielded self-healing nanocomposite films with robust mechanical strength (409% increase compared to pure PVA and high toughness up to 407.1%) and excellent adhesion (9670 times greater than its own weight) to various substrates in air and water. When damaged, the nanocomposite films displayed good mechanical (72.0-76.3%) and conductive (54.9-91.2%) recovery after a healing time of 30 min. More importantly, the flexible nanocomposites possessed high strain sensitivity under subtle strains (<48.5%) with a gauge factor (GF) of 2.52, which was relatively larger than the GF of ionic hydrogel-based skin sensors. These nanocomposite films possessed superior sensing performance for real-time monitoring of large and subtle human motions (finger bending motions, swallowing, and wrist pulse); thus, they have great potentials in health monitoring, smart flexible skin sensors. and wearable electronic devices.

CO2-Responsive Cellulose Nanofibers Aerogels for Switchable Oil-Water Separation.

Cellulose nanofibers (CNFs) aerogels with controllable surface wettability were prepared by grafting poly( N, N-dimethylamino-2-ethyl methacrylate) (PDMAEMA) polymer brushes via surface-initiated atom-transfer radical polymerization. After grafting PDMAEMA polymer, the surface of the aerogel was hydrophobic. However, in the presence of CO2, the surface of the aerogel gradually changes from hydrophobic to hydrophilic. The porous structure and CO2-responsiveness of PDMAEMA brushes within the CNFs aerogels allowed for the on-off switching of the oil-water mixture separation process. These CNFs aerogels were recyclable and displayed attractive separation efficiency for oil-water mixture and surfactant-stabilized emulsions. Furthermore, the switchable surface wettability holds an advantage of avoiding oil-fouling, which will greatly improve its recyclability.

Functionalization of cellulose nanocrystals for advanced applications.

Replacing the widespread use of petroleum-derived non-biodegradable materials with green and sustainable materials is a pressing challenge that is gaining increasing attention by the scientific community. One such system is cellulose nanocrystal (CNC) derived from acid hydrolysis of cellulosic materials, such as plants, tunicates and agriculture biomass. The utilization of colloidal CNCs can aid in the reduction of carbon dioxide that is responsible for global warming and climate change. CNCs are excellent candidates for the design and development of functional nanomaterials in many applications due to several attractive features, such as high surface area, hydroxyl groups for functionalization, colloidal stability, low toxicity, chirality and mechanical strength. Several large scale manufacturing facilities have been commissioned to produce CNCs of up to 1000kg/day, and this has generated increasing interests in both academic and industrial laboratories. In this feature article, we will describe the recent development of functionalized cellulose nanocrystals for several important applications in ours and other laboratories. We will highlight some challenges and offer perspectives on the potentials of these sustainable nanomaterials.

Cellulose nanocrystal-poly(oligo(ethylene glycol) methacrylate) brushes with tunable LCSTs.

This paper reports on the synthesis of poly(oligoethylene glycol) methyl ether acrylate (POEGMA) grafted cellulose nanocrystals (CNCs) via surface initiated atom transfer radical polymerization (ATRP). An ATRP initiator (α-Bromoisobutyryl bromide) was covalently bonded to the surface of CNCs, followed by copolymerizing di(ethylene glycol) methyl ether methacrylate (MEO2MA) and oligoethylene glycol methyl ether methacrylate (OEGMA300) monomers from the surface using Cu(I)Br/2,2-dipyridal. Multiple POEGMA-g-CNC systems with varying MEO2MA/OEGMA300 content were synthesized, and they displayed a range of lower critical solution temperatures (LCSTs) in aqueous medium. µDSC endotherms and microstructural analysis indicated the collapse of POEGMA chains, followed by the aggregation of nanoparticles above their LCSTs. Cloud point measurements demonstrated a hysteresis in the heating and cooling of the POEGMA-g-CNC systems. It was found that the LCST of the nanoparticles could be tuned to between 23.8 to 63.8°C by adjusting the OEGMA300 content of the POEGMA brushes.

Continuous flow adsorption of methylene blue by cellulose nanocrystal-alginate hydrogel beads in fixed bed columns.

The adsorption behavior of methylene blue by cellulose nanocrystal-alginate (CNC-ALG) hydrogel beads in a fixed bed column was studied by varying the initial dye concentrations, bed depths and flow rates. An unusual phenomenon was observed in the early phase of the adsorption, and the phenomenon was elucidated by varying other critical design parameters, such as the flow direction, diameter of column and composition of adsorbent. The swelling and shrinkage of hydrogel beads during the adsorption was responsible for the anomalous concentration versus time profile of the adsorption process. The maximum adsorption capacity of the column was 255.5mg/g, which is in agreement with the batch study determined from the Langmuir adsorption isotherm. A comprehensive understanding on the adsorption mechanism of CNC-ALG hydrogel beads during the early stages of adsorption was derived from this study.

Self-Assembly Behavior of Thermoresponsive Oligo(ethylene glycol) Methacrylates Random Copolymer.

A well-defined random copolymer containing 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA, Mn = 188 g/mol) and poly(ethylene glycol) methyl ether methacrylate (PEGMA, Mn = 2080 g/mol) (poly(MEO2MA-co-PEGMA2080)), Mn = 17300 g/mol) was synthesized using the atom transfer radical polymerization (ATRP) process, and its thermoresponsive behaviors in aqueous solution were investigated. In comparison to other temperature-sensitive random copolymers based on oligo(ethylene glycol) methacrylates, this copolymer exhibited an unusual thermally induced two-stage aggregation process. The copolymer chains associate at the first thermal transition followed by a rearrangement process at the second thermal transition to produce a stable core-shell micellar structure. The morphology of the micelle comprises of a methacrylate core stabilized by the longer ethylene glycol segments (Mn = 2080 g/mol) shell.