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The co-adsorption of complementary DNA bases adenine and thymine on gold thin-film electrodes from 0.1 M HClO4 solutions in H2O and D2O is studied by surface-enhanced infrared absorption spectroscopy in the attenuated total reflection mode (ATR-SEIRAS). The comparison of the spectra in the range 1750–1550 cm− 1 for co-adsorbed adenine and thymine at controlled potentials to those of the individual adsorbed bases shows the enhancement of the signals associated to the vibration modes of adenine and the inhibition of those of thymine. The results can be explained by invoking the rearrangement of both molecules on the electrode surface in order to facilitate the Watson–Crick (W–C) and/or Hoogsteen (HG) interactions between the bases. The co-adsorption seems to be a cooperative process in which a low surface concentration of each base can induce the rearrangement of the complementary base molecules on the surface. Financial support from Ministerio de Educación y Ciencia (Spain) (Projects CTQ2010-19823 and CTQ2009-13142 and a FPU-grant to JA), Junta de Andalucía (Grupo FQM202) and Generalitat Valenciana (ACOMP/2011/200) are greatly acknowledged.

In situ Fourier transform infrared reflection absortion spectroscopy (FT-IRRAS) has been used in the external (SNIFTIRS method) and the internal (ATR-SEIRAS) reflection configurations to determine the pH influence, in the neutral and basic range, on the adsorption of adenine on Au(111) and gold nanofilm electrodes from D2O and H2O solutions. In D2O solutions, the main adsorbate band around 1640 cm−1,due to a ring stretching mode, shows different characteristics in the spectra collected at pH values at which the neutral and the basic adenine forms predominate in solution. The analysis of these differences, in comparison with the respective spectra of adenine in solution, permits us to conclude that both forms of adenine can adsorb chemically. The high sensitivity of the ATR-SEIRAS method has been used to analyze the contribution to the spectra of each form of adsorbed adenine as a function of the pH of the solution. The pKa2 obtained for the adsorbed species from this analysis is almost coincident with the pKa2 reported for adenine in solution, indicating that the coordination to the electrode and the second acid-base equilibrium involves different atoms of the adenine molecule. This result confirms the previously proposed adsorption model for adenine, implying the bonding of adenine to the electrode by the amine nitrogen (N10) and either the ring nitrogens N1 or N7, while the second acid-base equilibrium of adenine involves the ring nitrogen N9. Comparison of the 3400-3600 cm−1 region of the ATR-SEIRAS spectra of adenine obtained in H2O solutions at different pH values, which corresponds to the characteristic–OH stretching mode of the interfacial water molecules, permits us to discard the co-adsorption of water molecules in neutral and basic media, contrary to the case of adenine adsorption from acid media. Financial support from the Spanish Ministry of Science and Technology (CTQ2010-19823 and a FPU-grant to JAM), from the Junta de Andalucia (PAI FQM202) and University of Alicante.