Graphene research and technology development requires to reveal adsorption processes and understand how the defects change the physicochemical properties of the graphene-based systems. In this study, shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and graphene-enhanced Raman spectroscopy (GERS) coupled with density functional theory (DFT) modeling were applied for probing the structure of riboflavin adsorbed on single-layer graphene substrate grown on copper. Intense and detailed vibrational signatures of the adsorbed riboflavin were revealed by SHINERS method. Based on DFT modeling and detected downshift of prominent riboflavin band at 1349 cm-1 comparing with the solution Raman spectrum, π-stacking interaction between the adsorbate and graphene was confirmed. Different spectral patterns from graphene-riboflavin surface were revealed by SHINERS and GERS techniques. Contrary to GERS method, SHINERS spectra revealed not only ring stretching bands but also vibrational features associated with ribityl group of riboflavin and D-band of graphene. Based on DFT modeling it was suggested that activation of D-band took place due to riboflavin induced tilt and distortion of graphene plane. The ability to explore local perturbations by the SHINERS method was highlighted. We demonstrated that SHINERS spectroscopy has a great potential to probe adsorbed molecules at graphene.
Keywords: DFT; GERS; Raman; SHINERS; graphene; ribityl; riboflavin.