RESUMEN
This study focuses on how the mesophase transition behaviour of the phospholipid dioleoyl phosphatidylethanolamine (DOPE) is altered by the presence of 10 nm hydrophobic and 14 nm hydrophilic silica nanoparticles (NPs) at different concentrations. The lamellar to inverted hexagonal phase transition (Lα-HII) of phospholipids is energetically analogous to the membrane fusion process, therefore understanding the Lα-HII transition with nanoparticulate additives is relevant to how membrane fusion may be affected by these additives, in this case the silica NPs. The overriding observation is that the HII/Lα boundaries in the DOPE p-T phase diagram were shifted by the presence of NPs: the hydrophobic NPs enlarged the HII phase region and thus encouraged the inverted hexagonal (HII) phase to occur at lower temperatures, whilst hydrophilic NPs appeared to stabilise the Lα phase region. This effect was also NP-concentration dependent, with a more pronounced effect for higher concentration of the hydrophobic NPs, but the trend was less clear cut for the hydrophilic NPs. There was no evidence that the NPs were intercalated into the mesophases, and as such it was likely that they might have undergone microphase separation and resided at the mesophase domain boundaries. Whilst the loci and exact roles of the NPs invite further investigation, we tentatively discuss these results in terms of both the surface chemistry of the NPs and the effect of their curvature on the elastic bending energy considerations during the mesophase transition.
RESUMEN
Understanding the frictional properties of nanostructured surfaces is important because of their increasing application in modern miniaturized devices. In this work, lateral force microscopy was used to study the frictional properties between an AFM nanotip and surfaces bearing well-defined nanodomes comprising densely packed prolate spheroids, of diameters ranging from tens to hundreds of nanometers. Our results show that the average lateral force varied linearly with applied load, as described by Amontons' first law of friction, although no direct correlation between the sample topographic properties and their measured friction coefficients was identified. Furthermore, all the nanodomed textures exhibited pronounced oscillations in the shear traces, similar to the classic stick-slip behavior, under all the shear velocities and load regimes studied. That is, the nanotextured topography led to sustained frictional instabilities, effectively with no contact frictional sliding. The amplitude of the stick-slip oscillations, σf, was found to correlate with the topographic properties of the surfaces and scale linearly with the applied load. In line with the friction coefficient, we define the slope of this linear plot as the stick-slip amplitude coefficient (SSAC). We suggest that such stick-slip behaviors are characteristics of surfaces with nanotextures and that such local frictional instabilities have important implications to surface damage and wear. We thus propose that the shear characteristics of the nanodomed surfaces cannot be fully described by the framework of Amontons' laws of friction and that additional parameters (e.g., σf and SSAC) are required, when their friction, lubrication, and wear properties are important considerations in related nanodevices.
