Biological noncovalent N/O⋯V interactions: insights from theory and protein data bank analyses.

Computations at the PBE0-D3/def2-TZVP level of theory in conjunction with a Protein Data Bank (PDB) survey have provided first time evidence of favorable noncovalent interactions between ADP metavanadate (VO 4 ) and ADP orthovanadate (VO 5 ) and electron rich atoms. These involve a σ-hole present in the V atom and the lone pairs belonging to (i) protein residues ( e.g. , serine (SER), glutamate (GLU) or histidine (HIS)), (ii) backbone carbonyl groups and (iii) water molecules. A computational study has been carried out to rationalize the physical nature and directionality of the interaction in addition to its plausible biological role. The results reported herein are expected to have an impact in the fields of medicinal chemistry, bioinorganic chemistry and chemical biology.