Melt-functionalization of cellulose nanocrystals using dynamic hindered ureas

Cellulose nanocrystal (CNC)-reinforced composites are gaining commercial attention on account of their high strength and sustainable sourcing. Grafting polymers to the CNCs in these composites has the potential to improve their properties, but current solution-based synthesis methods limit their production at scale. Utilizing dynamic hindered urea chemistry, a new method for the melt-functionalization of cellulose nanocrystals has been developed. This method does not require toxic solvents during the grafting step and can achieve grafting densities competitive with state-of-the-art solution-based grafting methods. Using cotton-sourced, TEMPO-oxidized CNCs, multiple molecular weights of poly(ethylene glycol) (PEG) as well as dodecane, polycaprolactone, and poly(butyl acrylate) were grafted to the CNC surface. With PEG-grafted nanoparticles, grafting densities of 0.47 chains nm−2 and 0.10 chains nm−2 were achieved with 2000 and 10,000 g mol−1 polymer chains respectively, both of which represent significant improvements over previous reports for solution-based PEG grafting onto CNCs

Physicochemical Properties and Bio-Interfacial Interactions of Surface Modified PDLLA-PAMAM Linear Dendritic Block Copolymers

Here, we demonstrate the applicability of self-assembling linear-dendritic block copolymers (LDBCs) and their nanoaggregates possessing varied surfaces as therapeutic nanocarriers. These LDBCs are comprised of a hydrophobic, linear polyester chemically coupled to a hydrophilic dendron polyamidoamine (PAMAM)—the latter of which acts as the surface of the self-assembled nanoaggregate in aqueous media. To better understand how surface charge density affects the overall operability of these nanomaterials, we modified the nanoaggregate surface to yield cationic (NH3+), neutral (OH), and anionic (COO−) surfaces. The effect of these modifications on the physicochemical properties (i.e., size, morphology, and surface charge density), colloidal stability, and cellular uptake mechanism of the polymeric nanocarrier were investigated. This comparative study demonstrates the viability of nanoaggregates formed from PDLLA-PAMAM LDBCs to serve as nanocarriers for applications in drug delivery