Computational characterisation of dried and hydrated graphene oxide membranes.

A multi-step molecular dynamics procedure was developed to construct fully flexible atomistic models of graphene oxide (GO) membranes. The method of preparation replicates the experimental synthesis of the material; i.e. the flow-directed self-assembly of individual flakes onto a substrate or filter. A total of 180 GO membrane models were prepared with water contents varying between 0 and 20%, providing an insight into changes in the membrane's interlayer distance with swelling. Membranes with 15% water content have an average interlayer distance (0.80 nm), bulk density (1.77 g cm-3) and tensile modulus (18.1 GPa) in excellent agreement with the experimental literature, demonstrating that air-dried membranes have 15% water content. The models reveal the intrinsic structural heterogeneity and complex morphology of GO membranes. This feature has previously been unaccounted for in both experimental interpretations and GO nanopore models, which often use pre-defined and idealised 2D geometries. Completely dried membranes have considerable free pore volume. This observation explains the modest change in interlayer distance (0.02 nm) as the membrane's water content is increased from 0% to 10% compared to a much more significant change (0.12 nm) as the water content is increased from 10% to 20%. Combined with this new understanding of membrane swelling, the availability of such representative models opens the possibility of the molecular-level design of GO membranes for a variety of applications, such as gaseous and aqueous separations.

Micelle response to changes in solvent properties.

The dynamics of co-polymer systems play an important role in the preparation and stability of formulations, as well as on their capability to function in drug delivery systems. Micelle inversion can occur as a result of a change in concentration when a solvent is very volatile and evaporates, or as a result of a change in solvent quality upon addition of another solvent to the original solution, or upon changes in pH. In this work, dissipative particle dynamics (DPD) is used to examine the dynamics of micelle inversion in concentrated systems of diblock and triblock amphiphiles, where interactions between neighboring aggregates are observed. Significant differences were observed in the inversion process of different amphiphilic molecules, with a large amount of co-polymer exchange between inverting aggregates made of diblock amphiphiles, and practically no exchange of molecules between aggregates during the inversion of triblock copolymer aggregates. Fundamental mechanisms of inversion are revealed that provide information which can be used to help design micelles for targeted drug release and allow understanding of history dependant formulations.