Surface‐enhanced Raman spectroscopy of DNA bases

Abstract A Raman microprobe has been used to measure the surface‐enhanced Raman spectra of adenine, guanine, cytosine and thymine. Comparison of the SERS spectrum with solution spectra shows that some line positions are not influenced by the adsorption process while others show large shifts. In the SERS spectrum new lines, not visible in the solution spectrum, appear while some lines visible in the solution spectrum are not enhanced to a detectable level and are therefore not seen in SERS. The relative intensities are changed owing to an apparently vibration‐dependent enhancement factor. A line‐broadening effect occurs for most lines except carbonyl stretching vibrations in cytosine and thymine. All SERS spectra show increased contributions of bending vibrations and side‐chain groups. In particular, amino group vibrations in adenine and cytosine are clearly visible. Comparison of the shape and intensity of the carbonyl stretching vibrations in cytosine, thymine and guanine show important differences. It is hypothesized that these differences indicate differences in the orientation of these groups with respect to the surface.