PMID- 19744863
OWN - NLM
STAT- MEDLINE
DCOM- 20100118
LR  - 20211020
IS  - 1879-1123 (Electronic)
IS  - 1044-0305 (Linking)
VI  - 20
IP  - 11
DP  - 2009 Nov
TI  - Nucleophile addition of reduced glutathione on 2-methyl-2-nitroso compound: a 
      combined electron paramagnetic resonance spectroscopy and electrospray tandem 
      mass spectrometry study.
PG  - 2013-20
LID - 10.1016/j.jasms.2009.07.018 [doi]
AB  - Mass spectrometry (MS) was used in conjunction with electron paramagnetic 
      resonance (EPR) to characterize products arising from reactions between reduced 
      glutathione (GSH) and 2-methyl 2-nitroso propane (MNP) in an oxidative medium, to 
      evaluate the reactivity of this tripeptide as a nucleophile toward a nitroso 
      compound. Depending on the experimental conditions, different radical species 
      could be detected by EPR, which allowed some structural assumptions. These 
      samples were then submitted to electrospray ionization, in both positive and 
      negative ion modes, for structural elucidation in tandem mass spectrometry. 
      Although the primary nitroxide products could not be detected in MS, structurally 
      related compounds such as hydroxylamine and O-methyl hydroxylamine could be fully 
      characterized. In the absence of light, a S-adduct was formed via a 
      Forrester-Hepburn reaction, that is, a nucleophile addition of MNP onto the thiol 
      function in reduced glutathione to yield a hydroxylamine intermediate, further 
      oxidized into nitroxide. In contrast, irradiating the reaction medium with 
      visible light could allow an inverted spin trapping reaction to take place, 
      involving the oxidation of both MNP and GSH before the nucleophilic addition of 
      the sulfenic acid function onto the nitrogen of MNP, yielding a so-called 
      O-adduct. It was also found that dilution of the reaction medium with methanol 
      for the purpose of electrospray ionization could allow nitroxides to be 
      indirectly observed either as hydroxylamine or O-methyl hydroxylamine species.
FAU - Triquigneaux, Mathilde
AU  - Triquigneaux M
AD  - Universites Aix-Marseille I, II & III-CNRS, UMR 6264: Laboratoire Chimie 
      Provence, Spectrometries Appliquees a la Chimie Structurale, Marseille, France.
FAU - Tuccio, Beatrice
AU  - Tuccio B
FAU - Lauricella, Robert
AU  - Lauricella R
FAU - Charles, Laurence
AU  - Charles L
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20090807
PL  - United States
TA  - J Am Soc Mass Spectrom
JT  - Journal of the American Society for Mass Spectrometry
JID - 9010412
RN  - 0 (Hydroxylamines)
RN  - 0 (Nitroso Compounds)
RN  - 2FP81O2L9Z (Hydroxylamine)
RN  - 9TZH4WY30J (methoxyamine)
RN  - GAN16C9B8O (Glutathione)
RN  - JGX6N17V2U (tert-nitrosobutane)
SB  - IM
MH  - Electron Spin Resonance Spectroscopy/*methods
MH  - Glutathione/*chemistry/*metabolism
MH  - Hydroxylamine/chemistry
MH  - Hydroxylamines/chemistry
MH  - Molecular Structure
MH  - Nitroso Compounds/*chemistry/*metabolism
MH  - Oxidation-Reduction
MH  - Spectrometry, Mass, Electrospray Ionization/methods
MH  - Tandem Mass Spectrometry/methods
EDAT- 2009/09/12 06:00
MHDA- 2010/01/19 06:00
CRDT- 2009/09/12 06:00
PHST- 2009/04/10 00:00 [received]
PHST- 2009/07/15 00:00 [revised]
PHST- 2009/07/15 00:00 [accepted]
PHST- 2009/09/12 06:00 [entrez]
PHST- 2009/09/12 06:00 [pubmed]
PHST- 2010/01/19 06:00 [medline]
AID - S1044-0305(09)00582-0 [pii]
AID - 10.1016/j.jasms.2009.07.018 [doi]
PST - ppublish
SO  - J Am Soc Mass Spectrom. 2009 Nov;20(11):2013-20. doi: 
      10.1016/j.jasms.2009.07.018. Epub 2009 Aug 7.