Nanoscale Chemical Imaging of Coadsorbed Thiolate Self-assembled Monolayers on Au(111) by Tip-Enhanced Raman Spectroscopy

Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p’-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of ~9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus –NH2, show different adsorption energy on Au(111) in vacuum and methanol, and thus the solvation effect on adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).

Methyl(—CH3)-terminated ZnO Nanowires for Selective Acetone Detection: Novel Approach Toward the Sensing Performance Enhancement Via Self-Assembly Molecules

The inspiration behind this work is to show the importance to tailor metal oxides (MOX’s) nanowires with suitable self-assembled monolayers (SAM’s) for the development of highly efficient, selective, and low...

Bioactive Coatings on Titanium: A Review on Hydroxylation, Self-Assembled Monolayers (SAMs) and Surface Modification Strategies

Titanium (Ti) and its alloys have been demonstrated over the last decades to play an important role as inert materials in the field of orthopedic and dental implants. Nevertheless, with the widespread use of Ti, implant-associated rejection issues have arisen. To overcome these problems, antibacterial properties, fast and adequate osseointegration and long-term stability are essential features. Indeed, surface modification is currently presented as a versatile strategy for developing Ti coatings with all these challenging requirements and achieve a successful performance of the implant. Numerous approaches have been investigated to obtain stable and well-organized Ti coatings that promote the tailoring of surface chemical functionalization regardless of the geometry and shape of the implant. However, among all the approaches available in the literature to functionalize the Ti surface, a promising strategy is the combination of surface pre-activation treatments typically followed by the development of intermediate anchoring layers (self-assembled monolayers, SAMs) that serve as the supporting linkage of a final active layer. Therefore, this paper aims to review the latest approaches in the biomedical area to obtain bioactive coatings onto Ti surfaces with a special focus on (i) the most employed methods for Ti surface hydroxylation, (ii) SAMs-mediated active coatings development, and (iii) the latest advances in active agent immobilization and polymeric coatings for controlled release on Ti surfaces.

Self-Localized Liquid Crystal Micro-Droplet Arrays on Chemically Patterned Surfaces

Liquid crystal (LC) micro-droplet arrays are elegant systems that have a range of applications, such as chemical and biological sensing, due to a sensitivity to changes in surface properties and strong optical activity. In this work, we utilize self-assembled monolayers (SAMs) to chemically micro-pattern surfaces with preferred regions for LC occupation. Exploiting discontinuous dewetting, dragging a drop of fluid over the patterned surfaces demonstrates a novel, high-yield method of confining LC in chemically defined regions. The broad applicability of this method is demonstrated by varying the size and LC phase of the droplets. Although the optical textures of the droplets are dictated by topological constraints, the additional SAM interface is shown to lock in inhomogeneous alignment. The surface effects are highly dependent on size, where larger droplets exhibit asymmetric director configurations in nematic droplets and highly knotted structures in cholesteric droplets.