Characterization of a 1,4-dithiane gold self-assembled monolayer: an electrochemical sensor for the cyt-c redox process

Electrochemical desorption and spectroscopic investigations of the gold electrode surface modified with 1,4-dithiane (1,4-dt) organothiol species were performed. The wave observed at −0.87 V versus Ag ∣ AgCl in the LSV (linear sweep voltammetry) reductive curve of the 1,4-dt compared to that for a similar 4-mercaptopyridine (pyS) system (−0.56 V) is indicative of a most effectively chemisorbed monolayer. The evaluation of the capability of the 1,4-dt self-assembled monolayer (SAM) in assessing the direct electron transfer (ET) of cytochrome c (cyt c) metalloprotein was investigated by cyclic voltammetry. The electrochemical response of the cyt c (E1/2 ≈0.0 V vs. Ag ∣ AgCl, ΔEp ≈50 mV) showed the characteristics of a reversible redox process. The cyt c voltammetric parameters acquired with the 24-h air exposure modified electrode, and after 100 cycles suggest a considerable improvement of the 1,4-dt electrode performance. The surface enhanced Raman spectroscopy (SERS) spectra revealed that 1,4-dt species is in a mixed gauche and trans orientation on the gold surface. The shift for higher wavenumbers observed for the C–S stretching modes in the SERS spectra, comparatively to the normal Raman spectrum, is assigned to the 1,4-dt coordination to surface gold atoms via a π interaction with the sulfur p-orbitals. The data collected suggest that this π interaction plays an important role on the stability of the 1,4-dt adlayer, improving the assessment of the cyt c heterogeneous electron transfer reaction.