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Diabetes is a group of metabolic conditions resulting in high blood sugar levels over prolonged periods that affects hundreds of millions of patients worldwide. Measuring glucose concentration enables patient-specific insulin...

Self-assembled monolayers (SAMs) of alkanethiols on gold are a commonly used platform for nanotechnology owing to their ease of preparation and high surface coverage. Unfortunately, the gold–sulfur bond is oxidized at ambient conditions which alters the stability and structure of the monolayer. We show using scanning tunneling microscopy and X-ray photoelectron spectroscopy that decanethiolate molecules oxidize into decanesulfonates that organize into a hitherto unknown striped phase. Air-exposed SAMs oxidize, as can be determined by a shift of the S 2p peak and the appearance of O 1s photoelectrons as part of the decanethiol monolayer transforms into a lamellae-like decanesulfonate structure when exposed to air. The herringbone structure of the Au(111) surface is preserved, indicating that the interaction between the molecules and the surface is rather weak as these findings are substantiated by density functional theory calculations.

Polymer brush layers are responsive materials that swell in contact with good solvents and their vapors. We deposit drops of an almost completely wetting volatile oil onto an oleophilic polymer brush layer and follow the response of the system upon simultaneous exposure to both liquid and vapor. Interferometric imaging shows that a halo of partly swollen polymer brush layer forms ahead of the moving contact line. The swelling dynamics of this halo is controlled by a subtle balance of direct imbibition from the drop into the brush layer and vapor phase transport and can lead to very long-lived transient swelling profiles as well as nonequilibrium configurations involving thickness gradients in a stationary state. A gradient dynamics model based on a free energy functional with three coupled fields is developed and numerically solved. It describes experimental observations and reveals how local evaporation and condensation conspire to stabilize the inhomogeneous nonequilibrium stationary swelling profiles. A quantitative comparison of experiments and calculations provides access to the solvent diffusion coefficient within the brush layer. Overall, the results highlight the—presumably generally applicable—crucial role of vapor phase transport in dynamic wetting phenomena involving volatile liquids on swelling functional surfaces.

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We have studied the dynamic behavior of decanethiol and air-oxidized decanethiol self-assembled monolayers (SAMs) on Au(111) using time-resolved scanning tunneling microscopy at room temperature. The air-oxidized decanethiols arrange in a lamellae-like structure leaving the herringbone reconstruction of the Au(111) surface intact, indicating a rather weak interaction between the molecules and the surface. Successive STM images show that the air-oxidized molecules are structurally more stable as compared to the nonoxidized decanethiol molecules. This is further confirmed by performing current–time traces with the feedback loop disabled at different locations and at different molecular phases. Density function theory calculations reveal that the diffusion barrier of the physisorbed oxidized decanethiol molecule on Au(111) is about 100 meV higher than the diffusion barrier of a chemisorbed Au-decanethiol complex on Au(111). A two-dimensional activity map of individual current–time traces performed on the air-oxidized decanethiol phase reveals that all the dynamic events take place within the vacancy lines between the air-oxidized decanethiols. These results reveal that the oxidation of thiols provides a pathway to produce more robust and stable self-assembled monolayers at ambient conditions.

Self-assembled monolayers have been formed of semithio-bambusurils that undergo conformational changes to direct all S atoms to the gold surface.

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