Nickel Adatoms Induced Tautomeric Dehydrogenation of Thymine Molecules on Au(111)

Tautomerization of nucleobases may induce base mismatches resulting in the abnormal disturbance of gene replication and expression, which has therefore attracted widespread interests in many disciplines. Metal atoms participating in a variety of important biological processes are found to be able to affect the nucleobase tautomerization as evidenced by many theoretical and spectroscopic studies. To get the real-space evidence and to unravel the underlying mechanism for the metal-induced tautomerization, especially from the keto form to the enol one, the interplay of high-resolution scanning tunneling microscopy imaging/manipulation and density functional theory (DFT) calculations has been employed. We present a process showing the Ni adatom-induced keto–enol tautomeric dehydrogenation of thymine molecules on Au(111). The key to making such a process feasible is the Ni atoms which greatly lower the energy barrier for the tautomerization from keto to enol form, which is rationalized by extensive DFT-based transition-state search calculations.