Directional affinity of a spherical Gold nanoparticle for the adsorption of DNA bases

In this work, the adsorption activities of different facets of a spherical gold nanoparticle (Au(111), Au(100) and Au(110)) for adenine (ADE) and cytosine (CYT) in two different environments including gas phase and in the presence of solvent (water) have been investigated, separately. It has been found that the adsorption energy (E_ad) and geometry of the DNA bases depend strongly on the kind of nanoparticle facet. The Au (110) facet showed the highest adsorption affinity for the ADE and CYT in both gas phase and water compared to Au(111) and Au(100) facets. Comparison of the E_ads of bases calculated in the gas phase with those obtained in the presence of water showed that the electrostatic field of solvent decreases the E_ads of bases, especially, for the Au (110) facet. The adsorption geometry of the CYT showed strong dependency on the kind of nanoparticle facet compared to ADE. Also, it has been shown that the direction and amount of charge transfer (CT) between the molecule and nanoparticle strongly depends on the kind of nanoparticle facet and environment. The CT is from the Au (111) facet to the ADE while the CT direction is reversed when the ADE is adsorbed on the Au (110) and Au (100) facets in the gas phase. The CT is from the CYT to three facets in the gas phase while its direction for the ADE and CYT adsorbed on Au (100) facet is reversed. The atoms in molecules (AIM) analysis has been employed to determine the bond paths (BPs) and bond critical points (BCPs) between the bases and facets. The infrared (IR) spectra of the bases adsorbed on the selected facets were calculated and compared with each other and with the spectra of the isolated bases. It was found that the symmetric and unsymmetric stretching of the NH of NH₂ group, C-H stretching of the rings and CO stretching of bases can be used for the discrimination of the selected facets.