We report the energy-dependent fragmentation patterns upon protonation of eight sulfides (organosulfur compounds) in Proton Transfer Reaction-Mass Spectrometry (PTR-MS). Studies were carried out, both, experimentally with PTR-MS, and with theoretical quantum-chemical methods. Charge retention usually occurred at the sulfur-containing fragment for short chain sulfides. An exception to this is found in the unsaturated monosulfide allylmethyl sulfide (AMS), which preferentially fragmented to a carbo-cation at m/z 41, C3H5+. Quantum chemical calculations (DFT with the M062X functional 6-31G(d,p) basis sets) for the fragmentation reaction pathways of AMS indicated that the most stable protonated AMS cation at m/z 89 is a protonated (cyclic) thiirane, and that the fragmentation reaction pathways of AMS in the drift tube are kinetically controlled. The protonated parent ion MH+ is the predominant product in PTR-MS, except for diethyl disulfide at high collisional energies. The saturated monosulfides R-S-R' (with R

Sulfides: Chemical ionization induced fragmentation studied with Proton Transfer Reaction-Mass Spectrometry and density functional calculations / Schuhfried, E.; Probst, M.; Limtrakul, J.; Wannakao, S.; Aprea, E.; Cappellin, L.; Mark, T. D.; Gasperi, F.; Biasioli, F.. - In: ENVIRONMENTAL SCIENCE & TECHNOLOGY. - ISSN 0013-936X. - ELETTRONICO. - 48:3(2013), pp. 367-378. [10.1002/jms.3153]

Sulfides: Chemical ionization induced fragmentation studied with Proton Transfer Reaction-Mass Spectrometry and density functional calculations

Aprea E.;Gasperi F.;
2013-01-01

Abstract

We report the energy-dependent fragmentation patterns upon protonation of eight sulfides (organosulfur compounds) in Proton Transfer Reaction-Mass Spectrometry (PTR-MS). Studies were carried out, both, experimentally with PTR-MS, and with theoretical quantum-chemical methods. Charge retention usually occurred at the sulfur-containing fragment for short chain sulfides. An exception to this is found in the unsaturated monosulfide allylmethyl sulfide (AMS), which preferentially fragmented to a carbo-cation at m/z 41, C3H5+. Quantum chemical calculations (DFT with the M062X functional 6-31G(d,p) basis sets) for the fragmentation reaction pathways of AMS indicated that the most stable protonated AMS cation at m/z 89 is a protonated (cyclic) thiirane, and that the fragmentation reaction pathways of AMS in the drift tube are kinetically controlled. The protonated parent ion MH+ is the predominant product in PTR-MS, except for diethyl disulfide at high collisional energies. The saturated monosulfides R-S-R' (with R
3
Schuhfried, E.; Probst, M.; Limtrakul, J.; Wannakao, S.; Aprea, E.; Cappellin, L.; Mark, T. D.; Gasperi, F.; Biasioli, F.
Sulfides: Chemical ionization induced fragmentation studied with Proton Transfer Reaction-Mass Spectrometry and density functional calculations / Schuhfried, E.; Probst, M.; Limtrakul, J.; Wannakao, S.; Aprea, E.; Cappellin, L.; Mark, T. D.; Gasperi, F.; Biasioli, F.. - In: ENVIRONMENTAL SCIENCE & TECHNOLOGY. - ISSN 0013-936X. - ELETTRONICO. - 48:3(2013), pp. 367-378. [10.1002/jms.3153]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11572/247026
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