Self-Healing Composite Coating Fabricated with a Cystamine Cross-Linked Cellulose Nanocrystal-Stabilized Pickering Emulsion.

A gelled Pickering emulsion system was fabricated by first stabilizing linseed oil droplets in water with dialdehyde cellulose nanocrystals (DACNCs) and then cross-linking with cystamine. Cross-linking of the DACNCs was shown to occur by a reaction between the amine groups on cystamine and the aldehyde groups on the CNCs, causing gelation of the nanocellulose suspension. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the cystamine-cross-linked CNCs (cysCNCs), demonstrating their presence. Transmission electron microscopy images evidenced that cross-linking between cysCNCs took place. This cross-linking was utilized in a linseed oil-in-water Pickering emulsion system, creating a novel gelled Pickering emulsion system. The rheological properties of both DACNC suspensions and nanocellulose-stabilized Pickering emulsions were monitored during the cross-linking reaction. Dynamic light scattering and confocal laser scanning microscopy (CLSM) of the Pickering emulsion before gelling imaged CNC-stabilized oil droplets along with isolated CNC rods and CNC clusters, which had not been adsorbed to the oil droplet surfaces. Atomic force microscopy imaging of the air-dried gelled Pickering emulsion also demonstrated the presence of free CNCs alongside the oil droplets and the cross-linked CNC network directly at the oil-water interface on the oil droplet surfaces. Finally, these gelled Pickering emulsions were mixed with poly(vinyl alcohol) solutions and fabricated into self-healing composite coating systems. These self-healing composite coatings were then scratched and viewed under both an optical microscope and a scanning electron microscope before and after self-healing. The linseed oil was demonstrated to leak into the scratches, healing the gap automatically and giving a practical approach for a variety of potential applications.

Amphiphilic Cellulose Nanocrystals for Aqueous Processing of Thermoplastics.

Conventional composite formulation of cellulose nanocrystals (CNCs) with thermoplastics involves melt compounding or in situ polymerisation. In this rather unconventional approach, polypropylene (PP) microparticles were finely suspended and stabilized, at varying weight loadings, in aqueous suspensions of amphiphilic CNCs to enable adsorption of the nanoparticles onto the thermoplastic. In order to achieve these suspensions, CNCs were modified with either octyl or hexadecyl groups. These modifications imparted hydrophobic properties to the CNCs, hence increasing interfacial adhesion to the PP microparticles. The modification, however, also retained the sulfate half ester groups that ensured dispersibility in aqueous media. The CNCs were evidently coated on the PP microparticles as revealed by confocal microscope imaging and had no detrimental effect on the melt properties of the PP-based composites. The approach is demonstrated to increase the Young's moduli of CNC-thermoplastic composites prepared in optimum suspension loadings of 0.5 wt. % octyl-modified and 0.1 wt % hexadecyl-modified CNCs. This procedure can be extended to other thermoplastics as the ability to aqueously process these composites is a major step forward in the drive for more sustainable manufacturing.

Starch hydrogels as targeted colonic drug delivery vehicles.

Targeted colonic drug delivery systems are needed for the treatment of endemic colorectal pathologies, such as Crohn's disease, ulcerative colitis, and colorectal cancer. These drug delivery vehicles are difficult to formulate, as they need to remain structurally intact whilst navigating a wide range of physiological conditions across the upper gastrointestinal tract. In this work we show how starch hydrogel bulk structural and molecular level parameters influence their properties as drug delivery platforms. The in vitro protocols mimic in vivo conditions, accounting for physiological concentrations of gastrointestinal hydrolytic enzymes and salts. The structural changes starch gels undergo along the entire length of the human gastrointestinal tract have been quantified, and related to the materials' drug release kinetics for three different drug molecules, and interactions with the large intestinal microbiota. It has been demonstrated how one can modify their choice of starch in order to fine tune its corresponding hydrogel's pharmacokinetic profile.

Octylamine-Modified Cellulose Nanocrystal-Enhanced Stabilization of Pickering Emulsions for Self-Healing Composite Coatings.

Linseed oil-in-water Pickering emulsions are stabilized by both sulfated CNCs (sCNCs) and octylamine-modified CNCs (oCNCs). oCNCs with hydrophobic moieties grafted on the surfaces of otherwise intact nanocrystals provided emulsions exhibiting stronger resistance to creaming of oil droplets, compared with unmodified sCNCs. sCNCs were not able to completely stabilize linseed oil in water at low CNC concentrations while oCNCs provided emulsions with no unemulsified oil residue at the same concentrations. Oil droplets in oCNC emulsions were smaller than those in samples stabilized by sCNCs, corresponding with an increased hydrophobicity of oCNCs. Cryo-SEM imaging of stabilized droplets demonstrated the formation of a CNC network at the oil-water interface, protecting the oil droplets from coalescence even after compaction under centrifugal force. These oil droplets, protected by a stabilized CNC network, were dispersed in a water-based commercial varnish, to generate a composite coating. Scratches made on these coatings self-healed as a result of the reaction of the linseed oil bled from the damaged droplets with oxygen. The leakage and drying of the linseed oil at the location of the scratches happened without intervention and was accelerated by the application of heat.

Structural heterogeneities in starch hydrogels.

Hydrogels have a complex, heterogeneous structure and organisation, making them promising candidates for advanced structural and cosmetics applications. Starch is an attractive material for producing hydrogels due to its low cost and biocompatibility, but the structural dynamics of polymer chains within starch hydrogels are not well understood, limiting their development and utilisation. We employed a range of NMR methodologies (CPSP/MAS, HR-MAS, HPDEC and WPT-CP) to probe the molecular mobility and water dynamics within starch hydrogels featuring a wide range of physical properties. The insights from these methods were related to bulk rheological, thermal (DSC) and crystalline (PXRD) properties. We have reported for the first time the presence of highly dynamic starch chains, behaving as solvated moieties existing in the liquid component of hydrogel systems. We have correlated the chains' degree of structural mobility with macroscopic properties of the bulk systems, providing new insights into the structure-function relationships governing hydrogel assemblies.