Remote regulation on the hydration sites of adenine molecules via derivatization

Hydration, as a ubiquitous and vital phenomenon in nature, has attracted great attention in the field of surface science concerning the fundamental interactions between water and organic molecules. However, the role of functional group derivatization is still elusive in terms of its potential impact on hydration. By the combination of high-resolution scanning tunneling microscopy imaging and density functional theory calculations, the hydration of 9mA molecules was realized on Au(111) in real space, forming 9mA–H2O–9mA structures. In comparison with the hydration of adenine molecules, methyl derivatization is experimentally found to remotely regulate the hydration sites from the imidazole ring to the pyrimidine ring and is further theoretically revealed to allow intramolecular electron redistribution and, therefore, steer the priority of the hydration sites. These results provide sub-molecular understandings of the relationship between derivatization and hydration, which would shed light on the regulation of hydration processes in chemically and biologically related systems.