Real-Time Investigation of the H/D Exchange Kinetics of Porphyrins and Oligopeptides by Means of Neutral Cluster-Induced Desorption/Ionization Mass Spectrometry.

The kinetics of the H/D exchange reaction in angiotensin II, hexaglycine (Gly6 ), Co(II)tetra(3-carboxyphenyl)porphyrin, and tetra(4-carboxyphenyl)porphyrin were followed in real time by mass spectrometry employing desorption/ionization induced by neutral SO2 clusters. The change of the isotope patterns with increasing degree of deuteration was recorded as a function of D2 O exposure and the underlying H/D exchange kinetics, i.e., the dependence of the different degrees of deuteration on time, were deduced. The results were modeled by means of Monte Carlo simulations taking into account different reaction constants for the H/D exchange reaction at different functional groups. In the case of the investigated porphyrins, the rate constants were directly assigned to the functional groups involved; in the case of the peptides, reaction at the explicit functional groups and the backbone chain of the molecules could be discriminated.