Tunable Sieving of Ions Using Graphene Oxide: Swelling Peculiarities in Free-Standing and Confined States.

The paper describes a comparative study of swelling processes in free-standing graphene oxide (GO) membranes and GO laminates encapsulated with epoxy glue. For free-standing graphene oxide membranes, a huge variation in d-spacing in the range of 8-12 Å depending on the ambient humidity and from 12 to >30 Å depending on the electrolyte type and its concentration was revealed using direct in situ and in operando XRD studies. Limited swelling at various humidity levels as well as in electrolyte solution with low constriction/expansion of epoxy-encapsulated GO is counterposed to that of free-standing graphene oxides. The swelling suppression was explained by both physical constriction and the intercalation of amines into GO laminates, which was proved by local EDX studies. This results in ion diffusivity variation for over 2 orders of magnitude in free-standing and constrained graphene oxide membranes and provides factual evidence for tunable sieving of ions with confined graphene oxides.

Oxidized Carbon-Based Spacers for Pressure-Resistant Graphene Oxide Membranes.

In this study, we report the influence of carbon-based spacer-oxidized derivatives of fullerenes (fullerenols) C60(OH)26−32 and graphene oxide nanoribbons on the performance and pressure stability of graphene-oxide-based composite membranes. The impact of the intercalant shape and composition on the permeance of the selective layers for water vapors has been studied under pressure gradients. It is shown that the insertion of ball-shaped fullerenols between graphene oxide nanoflakes allows a suppression in irreversible permeance loss to 2−4.5% and reversible permeance loss to <25% (at 0.1 MPa), while retaining large H2O/N2 selectivities of up to ~30,000. The demonstrated approach opens avenues for the highly effective stabilization of GO membranes at elevated pressures for industrial-scale dehumidification.

The Effects of Cholesterol Oxidation on Erythrocyte Plasma Membranes: A Monolayer Study.

Cholesterol plays a key role in the molecular and mesoscopic organisation of lipid membranes and it is expected that changes in its molecular structure (e.g., through environmental factors such as oxidative stress) may affect adversely membrane properties and function. In this study, we present evidence that oxidation of cholesterol has significant effects on the mechanical properties, molecular and mesoscopic organisation and lipid-sterol interactions in condensed monolayers composed of the main species found in the inner leaflet of the erythrocyte membrane. Using a combination of experimental methods (static area compressibility, surface dilatational rheology, fluorescence microscopy, and surface sensitive X-ray techniques) and atomistic molecular dynamics simulations, we show that oxidation of cholesterol to 7-ketocholesterol leads to stiffening of the monolayer (under both static and dynamic conditions), significant changes in the monolayer microdomain organisation, disruption in the van der Waals, electrostatic and hydrophobic interactions between the sterol and the other lipid species, and the lipid membrane hydration. Surface sensitive X-ray techniques reveal that, whilst the molecular packing mode is not significantly affected by cholesterol oxidation in these condensed phases, there are subtle changes in membrane thickness and a significant decrease in the coherence length in monolayers containing 7-ketocholesterol.