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

Autor: Portz A; Institut für Angewandte Physik, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 16, D-35392 Giessen, Germany., Gebhardt CR; Bruker Daltonik GmbH , Fahrenheitstr. 4, D-28359 Bremen, Germany., Dürr M; Institut für Angewandte Physik, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 16, D-35392 Giessen, Germany.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. B [J Phys Chem B] 2017 Dec 14; Vol. 121 (49), pp. 11031-11036. Date of Electronic Publication: 2017 Dec 04.
DOI: 10.1021/acs.jpcb.7b06897
Abstrakt: The kinetics of the H/D exchange reaction in angiotensin II, hexaglycine (Gly 6 ), 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 SO 2 clusters. The change of the isotope patterns with increasing degree of deuteration was recorded as a function of D 2 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.
Databáze: MEDLINE