Rapid degradation of alkanethiol-based self-assembled monolayers on gold in ambient laboratory conditions

Self-assembled monolayers (SAMs) consisting of alkanethiols and similar sulfur-containing molecules on noble metal substrates are extensively used and explored for various chemical and biological surface-functionalization in the scientific community. SAMs consisting of thiol- or disulfide-containing molecules adsorbed on gold are commonly used due to their ease of preparation and stability. However, the gold-thiolate bond is easily and rapidly oxidized under ambient conditions, adversely affecting SAM quality and structure. Here, the oxidation of dodecanethiol on gold is explored for various 12-h exposures to ambient laboratory air and light. SAM samples are freshly prepared, air-exposed, and stored in small, capped vials. X-ray photoelectron spectroscopy (XPS) reveals nearly complete oxidation of the thiolate in air-exposed samples, and a decrease in carbon signal on the surface. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the carbon K-edge shows a loss of upright orientational order upon air exposure. Alternatively, the oxidation of the thiolate is minor when SAMs are stored in limited-air-containing small 15 ml vials. Thus, care must be taken to avoid SAM degradation by ensuring alkanethiolates on gold have sufficient durability for each intended environment and application.