pH-Induced Protonation of Lysine in Aqueous Solution Causes Chemical Shifts in X-ray Photoelectron Spectroscopy

We demonstrate the applicability of X-ray photoelectron spectroscopy to obtain charge- and
site-specific electronic structural information of biomolecules in aqueous solution. Changing the pH of an
aqueous solution of lysine from basic to acidic results in nitrogen 1s and carbon 1s chemical shifts to
higher binding energies. These shifts are associated with the sequential protonation of the two amino groups,
which affects both charge state and hydrogen bonding to the surrounding water molecules. The N1s chemical
shift is 2.2 eV, and for carbon atoms directly neighboring a nitrogen the shift for C1s is ∼0.4 eV. The
experimental binding energies agree reasonably with our calculated energies of lysine(aq) for different pH
values.