Non-enzymatic lipid peroxidation may change biomembrane structure and function. Here, we employed molecular dynamics simulations to study the effects of either phospholipid or cholesterol peroxidation individually, as well as the combined peroxidation of both components. When lipids were peroxidized, the generated OOH groups migrated to the membrane surface and engaged in H-bonds with each other and the phospholipid carbonyl ester groups. It caused the sn-2 acyl chains of phospholipid hydroperoxides to bend and the whole sterol backbone of cholesterol hydroperoxides to tilt. When phospholipids were kept intact, peroxidation of the sterol backbone led to a partial degradation of its condensing and ordering properties, independently of the position and isomerism of the OOH substitution. However, even in massively peroxidized membranes in which all phospholipids and cholesterol were peroxidized, the condensing and ordering properties of the sterol backbone were still significant. The possible implications for the formation of membrane lateral domains were discussed. Cholesterol peroxyl radicals were also investigated and we found that the OO groups did not migrate to the headgroups region.

Graphene oxide (GO)-based materials have been considered for potential energy storage applications, in particular supercapacitors. Here, for the first time, we present a detailed analysis of the properties of GO-based supercapacitors as a function of both chemical composition and charge density on the electrodes. Differential capacitance was determined and the effect of the degree of oxidation of the electrodes was taken into account. Also, structural and energetic details on the electrode–electrolyte interaction and, consequently, the double-layer electric structure were analyzed. The differential capacitance value for all supercapacitors is within the range of 1.5–5.4 μF cm–2 in the ±3 V window for the electrode potential and presents the highest value for the R20 system, which also had the highest mean integral capacitance. One important result is the gradual transition from bell-shaped to camel-shaped as the degree of oxidation increases. The results presented here provide the missing complement for a detailed and complete description of the properties of GO supercapacitors, indicating how they behave with the variation of charge density and degree of oxidation.

We report here density functional theory calculations and molecular dynamics atomistic simulations to determine the total capacitance of graphene-modified supercapacitors.

The amphiphilic character of graphene oxide was analysed in terms of its interfacial activities, using atomistic molecular dynamics. Graphene oxides at four different degrees of oxygenation were investigated considering both the effects of oxidation and carboxyl edge-functionalization. Solvation free energies are strongly negative and of increasing magnitude with the concentration for all systems, even in the toluene phase, indicating that GO presents a favourable solvation in both pure liquids as well as interfaces. The PMF results indicate that only the R20 system is slightly active at the water/vacuum interface, with a PMF minimum of about -2.6 kJ mol-1. Both analyses, free energy and PMF, indicate that all systems with higher oxygen concentrations have lower free energy in water than in toluene, while the R20 system opposes this tendency. Comparison between the reduced GOs (20%) shows that edge-functionalised systems were more active than basal-functionalized systems, indicating that oxygen concentration plays a more relevant role than the distribution of functional groups.