SignificanceEvery folded protein presents an interface with water that is composed of domains of varying hydrophilicity/-phobicity. Many simulation studies have highlighted the nonadditivity in the wetting of such nanostructured surfaces in contrast with the accepted theoretical formula that is additive. We present here an experimental study on surfaces of identical composition but different organization of hydrophobic and hydrophilic domains. We prove that the interfacial energy of such surfaces differs by ∼20% and that a significant difference in the interfacial water H-bonding structure can be measured. As a result, in combination with molecular-dynamics simulations, we propose a model that captures the wetting of molecularly heterogeneous surfaces, showing the importance of local structure (first-nearest neighbors) in determining the wetting properties.
Morphological and gel-to-liquid phase transitions of lipid membranes are generally considered to primarily depend on the structural motifs in the hydrophobic core of the bilayer. Structural changes in the aqueous headgroup phase are typically not considered, primarily because they are difficult to quantify. Here, we investigate structural changes of the hydration shells around large unilamellar vesicles (LUVs) in aqueous solution, using differential scanning calorimetry (DSC), and temperature-dependent ζ-potential and high-throughput angle-resolved second harmonic scattering measurements (AR-SHS). Varying the lipid composition from 1,2-dimyristoyl- sn -glycero-3-phosphocholine(DMPC) to 1,2-dimyristoyl- sn -glycero-3-phosphate (DMPA), to 1,2-dimyristoyl- sn -glycero-3-phospho- l -serine (DMPS), we observe surprisingly distinct behavior for the different systems that depend on the chemical composition of the hydrated headgroups. These differences involve changes in hydration following temperature-induced counterion redistribution, or changes in hydration following headgroup reorientation and Stern layer compression.
Interfacial phase transitions are of fundamental importance for climate, industry, and biological processes. In this work, we observe a hydration mediated surface transition in supercooled oil nanodroplets in aqueous solutions using second harmonic and sum frequency scattering techniques. Hexadecane nanodroplets dispersed in water freeze at a temperature of ∼15 °C below the melting point of the bulk alkane liquid. Addition of a trimethylammonium bromide (CXTA+) type surfactant with chain length equal to or longer than that of the alkane causes the bulk oil droplet freezing transition to be preceded by a structural interfacial transition that involves water, oil, and the surfactant. Upon cooling, the water loses some of its orientational order with respect to the surface normal, presumably by reorienting more parallel to the oil interface. This is followed by the surface oil and surfactant alkyl chains losing some of their flexibility, and this chain stretching induces alkyl chain ordering in the bulk of the alkane phase, which is then followed by the bulk transition occurring at a 3 °C lower temperature. This behavior is reminiscent of surface freezing observed in planar tertiary alkane/surfactant/water systems but differs distinctively in that it appears to be induced by the interfacial water and requires only a very small amount of surfactant.
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