TY - JOUR
T1 - L -Cysteine Modified by S-Sulfation
T2 - Consequence on Fragmentation Processes Elucidated by Tandem Mass Spectrometry and Chemical Dynamics Simulations
AU - Macaluso, Veronica
AU - Scuderi, Debora
AU - Crestoni, Maria Elisa
AU - Fornarini, Simonetta
AU - Corinti, Davide
AU - Dalloz, Enzo
AU - Martinez-Nunez, Emilio
AU - Hase, William L.
AU - Spezia, Riccardo
N1 - Publisher Copyright:
© 2019 American Chemical Society.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/5/2
Y1 - 2019/5/2
N2 - Low-energy collision-induced dissociation (CID) of deprotonated l-cysteine S-sulfate, [cysS-SO 3 ] - , delivered in the gas phase by electrospray ionization, has been found to provide a means to form deprotonated l-cysteine sulfenic acid, which is a fleeting intermediate in biological media. The reaction mechanism underlying this process is the focus of the present contribution. At the same time, other novel species are formed, which were not observed in previous experiments. To understand fragmentation pathways of [cysS-SO 3 ] - , reactive chemical dynamics simulations coupled with a novel algorithm for automatic determination of intermediates and transition states were performed. This approach has allowed the identification of the mechanisms involved and explained the experimental fragmentation pathways. Chemical dynamics simulations have shown that a roaming-like mechanism can be at the origin of l-cysteine sulfenic acid.
AB - Low-energy collision-induced dissociation (CID) of deprotonated l-cysteine S-sulfate, [cysS-SO 3 ] - , delivered in the gas phase by electrospray ionization, has been found to provide a means to form deprotonated l-cysteine sulfenic acid, which is a fleeting intermediate in biological media. The reaction mechanism underlying this process is the focus of the present contribution. At the same time, other novel species are formed, which were not observed in previous experiments. To understand fragmentation pathways of [cysS-SO 3 ] - , reactive chemical dynamics simulations coupled with a novel algorithm for automatic determination of intermediates and transition states were performed. This approach has allowed the identification of the mechanisms involved and explained the experimental fragmentation pathways. Chemical dynamics simulations have shown that a roaming-like mechanism can be at the origin of l-cysteine sulfenic acid.
UR - http://www.scopus.com/inward/record.url?scp=85065099209&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.9b01779
DO - 10.1021/acs.jpca.9b01779
M3 - Article
C2 - 30945861
AN - SCOPUS:85065099209
VL - 123
SP - 3685
EP - 3696
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 17
ER -