Swelling Effects on the Conductivity of Graphene/PSS/PAH Composites

Graphene/poly-(sodium-4-styrene sulfonate)(PSS)/poly-(allylamine hydrochloride) (PAH) composite is a frequently adopted system for fabricating polyelectrolyte multilayer films. Swelling is the bottleneck limiting its applications, and its effects on the conductivity is still controversial. Herein, we report successful swelling of a graphene/PSS/PAH composite in a vapor atmosphere, and the relation with the mass fraction of water is uncovered. The composite was prepared via a layer-by-layer assembly technique and systematically characterized. The results indicated that the average thickness for each bilayer was about 0.95 nm. The hardness and modulus were 2.5 ± 0.2 and 68 ± 5 GPa, respectively, and both were independent of thickness. The sheet resistance decreased slightly with the prolongation of immersion time, but was distinct from that of the water mass fraction. It reduced from 2.44 × 105 to 2.34 × 105 ohm/sq, and the change accelerated as the water mass fraction rose, especially when it was larger than 5%. This could be attributing to the lubrication effect of the water molecules, which sped up the migration of charged groups in the polyelectrolytes. Moreover, molecular dynamics simulations confirmed that a microphase separation occurred when the fraction reached an extreme value owing to the dominated interaction between PSS and PAH. These results provide support for the structural stability of this composite material and its applications in devices.

Polyelectrolyte Multi-Layered Griseofulvin Nanoparticles: Conventional versus Continuous In-Situ Layer-by-Layer Fabrication

Polyelectrolyte multilayers are promising drug carriers with potential applications in the delivery of poorly soluble drugs. Furthermore, the polyelectrolyte multilayer contributes towards electrostatic interactions, which enhances the physical and chemical stability of colloids when compared to those prepared by other approaches. The aim of this work was to generate a polyelectrolyte multilayer on well characterised nanoparticles of the poorly water-soluble drug, griseofulvin. Griseofulvin (GF) nanoparticles (300 nm) were produced by wet bead milling, bearing a negative surface charge due to the use of poly(sodium 4-styrenesulfonate) (PSS) as a stabiliser. Six further layers of alternating chitosan and PSS polyelectrolyte multilayer were successfully generated at the particle surface either via use of: (1) the conventional method of adding excess coating polymer followed by centrifugation, or (2) the continuous in situ approach of adding sufficient amount of coating polymer. The continuous in situ method was designed de novo by the consecutive addition of polymers under high shear rate mixing. In comparison to the continuous in situ method, the conventional method yielded nanoparticles of smaller size (282 ±9 nm vs. 497 ±34 nm) and higher stability by maintaining its size for 6 months. In conclusion, the parent griseofulvin nanosuspension proved to be a suitable candidate for the polyelectrolyte multilayer fabrication providing an avenue for a bespoke formulation with versatile and potentially enhanced drug delivery properties.