TY - JOUR
T1 - Elucidating H/D-Exchange Mechanism of Active Hydrogen in Aniline and Benzene-1,2-dithiol
AU - Ahmed, Arif
AU - Islam, Syful
AU - Kim, Sunghwan
N1 - Publisher Copyright:
© 2021, Korean Society for Mass Spectrometry. All rights reserved.
PY - 2021/12
Y1 - 2021/12
N2 - In this study, the hydrogen/deuterium (HDX) exchange mechanism of active hydrogen, nitrogen, and sulfur-containing polycyclic aromatic hydrocarbon (PAH) dissolved in toluene and deuterated methanol by atmospheric pressure photoionization (APPI) is investigated. The comparison of the data obtained using APPI suggests that aniline and benzene-1,2-dithiol contain two exchanging hydrogens. The APPI HDX that best explains the experimental findings was investigated with the use of quantum mechanical calculations. The HDX mechanism is composed of a two-step reaction: in the first step, analyte radical ion gets deuterated, and in the second step, the hydrogen transfer occurs from deuterated analyte to de-deuterated methanol to complete the exchange reaction. The suggested mechanism provides fundamentals for the HDX technique that is important for structural identification with mass spectrometry. This paper is dedicated to Professor Seung Koo Shin for his outstanding contributions in chemistry and mass spectrometry.
AB - In this study, the hydrogen/deuterium (HDX) exchange mechanism of active hydrogen, nitrogen, and sulfur-containing polycyclic aromatic hydrocarbon (PAH) dissolved in toluene and deuterated methanol by atmospheric pressure photoionization (APPI) is investigated. The comparison of the data obtained using APPI suggests that aniline and benzene-1,2-dithiol contain two exchanging hydrogens. The APPI HDX that best explains the experimental findings was investigated with the use of quantum mechanical calculations. The HDX mechanism is composed of a two-step reaction: in the first step, analyte radical ion gets deuterated, and in the second step, the hydrogen transfer occurs from deuterated analyte to de-deuterated methanol to complete the exchange reaction. The suggested mechanism provides fundamentals for the HDX technique that is important for structural identification with mass spectrometry. This paper is dedicated to Professor Seung Koo Shin for his outstanding contributions in chemistry and mass spectrometry.
KW - Atmospheric pressure photoionization (APPI)
KW - Hydrogen/deuterium exchange (HDX)
KW - Potential energy surface
KW - Quantum mechanical calculation
UR - http://www.scopus.com/inward/record.url?scp=85126350344&partnerID=8YFLogxK
U2 - 10.5478/MSL.2021.12.4.146
DO - 10.5478/MSL.2021.12.4.146
M3 - Article
AN - SCOPUS:85126350344
SN - 2233-4203
VL - 12
SP - 146
EP - 151
JO - Mass Spectrometry Letters
JF - Mass Spectrometry Letters
IS - 4
ER -