Adsorption and two-dimensional condensation of 5-methylcytosine

Purine and pyrimidine derivatives occurring in nucleic acids posses an extraordinary high ability of self-association at the electrode surface and can form there by a two-dimensional (2D) condensation a monomolecular compact film (self-assembled monolayer-SAM). The effects of methyl substituent on the 2D condensation were studied using the 5-methylcytosine molecule which is involved in gene silencing and has a great biological impact. At acid pHs, 5-methylcytosine forms at the mercury electrode a physisorbed self-assembled 2D layer at potentials close to the potential of electrocapillary maximum. From the temperature dependence of the electrode double layer capacitance, the standard Gibbs energy of adsorption (Delta G(m) = -12.7 kJ mol(-1)), lateral interaction coefficient of the Frumkin adsorption isotherm (a(c) = 2.05) and area occupied by one molecule (A = 1.31 nm(2)) in the 2D layer were determined. Measurements performed on a single-crystal Au(111) surface show that the 2D condensation can take place on other substrates as well. (C) 2009 Elsevier B.V. All rights reserved.