\u3csup\u3e13\u3c/sup\u3eC NMR Reveals No Evidence of n–π* Interactions in Proteins

An n ‒ Π* interaction between neighboring carbonyl groups has been postulated to stabilize protein structures. Such an interaction would affect the 13C chemical shielding of the carbonyl groups, whose paramagnetic component is dominated by n ‒ Π* and Π ‒ Π* excitations. Model compound calculations indicate that both the interaction energetics and the chemical shielding of the carbonyl group are instead dominated by a classical dipole-dipole interaction. A set of high resolution protein structures with associated carbonyl 13C chemical shift assignments verifies this correlation and provides no evidence for an inter-carbonyl n ‒ Π* interaction