Theoretical Study of Silver-Ion-Mediated Base Pairs: The Case of C–Ag–C and C–Ag–A Systems

Silver-mediated base pairs applied to DNA represent a new biomacromolecular nanomaterial useful for generating nanodevices as ion sensors. Reported herein is a full quantum chemical study devoted to give further knowledge on the electronic and energetic properties of C-Ag-C and mixed C-Ag-A mismatched base pairs. The B3LYP functional in conjunction with the dispersion effects (D3) has been applied. Single-point calculations have been also performed by using the M06-L functional. The investigation of their behavior has been extended to the duplex DNA modeled by the (dC-Ag-dC)2 and (dC-Ag-dA)2 more complex systems. The solvent effect has been taken into account by the conductor-like screening model, COSMO. In the case of mixed C-Ag-A and (dC-Ag-dA)2 systems, both the Watson-Crick and Hoogsteen arrangements have been taken into account. Results show that for (dC-Ag-dA)2 systems, the binding energies are almost double that of the corresponding values of C-Ag-A ones.