Gas Chromatography Electron Ionization Mass Spectrometric Analysis of Trimethylsilyl Derivatives of Bis(2-Hydroxyethylthio)Alkanes and Bis(2-Hydroxyethylsulfonyl)Alkanes
Restricted accessResearch articleFirst published online August, 2006
Gas Chromatography Electron Ionization Mass Spectrometric Analysis of Trimethylsilyl Derivatives of Bis(2-Hydroxyethylthio)Alkanes and Bis(2-Hydroxyethylsulfonyl)Alkanes
This communication describes the GC/MS analysis of the bis(trimethylsilyl) (bis-TMS) derivatives of bis(2-hydroxyethylthio)alkanes (BHETAs) and bis(2-hydroxyethylsulfonyl)alkanes (BHESAs) which are important markers of sulfur mustard class of chemical warfare agents. The study was undertaken with a view to develop a spectral database of these compounds for verification analysis of the Chemical Weapons Convention (CWC). Based on the obtained mass spectra of bis-TMS derivatives of BHETAs and BHESAs, the fragmentation routes are proposed, which explain most of the characteristic ions.
ReddyT. J.PrabhakarS.KumarR.M.SaradhiVijaya U.V.R. and VairamaniM., “Mass spectral studies of a series of N,N-dialkyl aminoethyl-2-chlorides and trimethylsilyl ethers of N,N-dialkyl aminoethyl-2-ols under electron impact conditions”, J. Mass Spectrom.41, 59 (2006). doi: 10.1002/jms.946
2.
GuptaA.K.ShakyaP.D.PardasaniD.PalitM. and DubeyD.K., “Mass spectral analysis of synthones of nerve agents for verification of the Chemical Weapons Convention”, Rapid Commun. Mass Spectrom.19, 975 (2005). doi: 10.1002/rcm.1876
3.
DubeyD.K.PalitM.GuptaA.K.PardasaniD.ShakyaP.D. and SrivastavaR.K., “Study of electron ionization mass spectra of bis(trimethylsilyl) esters of alkylphosphonic and alkylthiophosphonic acid”, Rapid Commun. Mass Spectrom.19, 1763 (2005). doi: 10.1002/rcm.1966
4.
PardasaniD.GuptaA.K.PalitM.ShakyaP.D.KanaujiaP.K.SekharK. and DubeyD.K., “Gas chromatography/mass spectrometric analysis of methyl esters of N,N-dialkyl aminoethane-2-sulfonic acids for the verification of the Chemical Weapons Convention”, Rapid Commun. Mass Spectrom.19, 3015 (2005). doi: 10.1002/rcm.2165
5.
GuptaA.K.PalitM.ShakyaP.D.PardasaniD.SrivastavaR.K. and DubeyD.K., “Micro-synthesis and electron ionization mass spectral analysis of O-alkyl N,N-dialkylphosphoramidocyanidates”, Eur. J. Mass Spectrom.11, 309 (2005). doi: 10.1255/ejms.741
6.
PalitM.PardasaniD.GuptaA.K. and DubeyD.K., “Microsynthesis and electron ionisation mass spectrometric analysis of chemical weapons convention (CWC)-related O,O-dialkyl-N,N-dialkylphosphoramidates”, Anal. Bioanal. Chem.381, 477 (2005). doi: 10.1007/s00216-004-2873-x
7.
Central OPCW Analytical Database, Version 6, Released on December (2004), Technical Secretariat of OPCW, The Hague, The Netherlands.
8.
Convention on the Prohibition of the Development, Production, Stockpiling and use of Chemical Weapons and their Destruction, Technical Secretariat of the Organization for Prohibition of Chemical Weapons. The Hague, The Netherlands (1997). Available: http://www.opcw.nl
9.
MesilaaksoM., “Analysis Strategy for Analysis of Chemicals Related to the Chemicals Weapons Convention in an Off-site Laboratory”, in Chemical Weapons Convention Chemical Analysis; Sample Collection, Preparation and Analytical Methods, Ed by MesilaaksoM.John Wiley & Sons, Chichester, UK, p. 151 (2004).
10.
KostiainenO., “Analysis of Chemicals related to the Chemicals Weapons Conventions”, in Forensic Science, Handbook of Analytical Separations, Vol. 2, Ed by BoguszM.J.Elsevier Science, Amsterdam, The Netherlands, p. 405 (2000).
11.
HooijshuurE.W.J.HulstA.G.De JongAd.L.ReuverL.P.De Van KrimpenS.H.Van BaarB.L.M.WilsE.R.J.KientzC.E. and BrinkmanU.A.Th., “Identification of chemicals related to the chemical weapons convention during an inter laboratory proficiency test”, Trends Anal. Chem.21, 116 (2002). doi: doi:10.1016/S0165-9936(01)00140-6
12.
Criteria for Acceptable Performance of Laboratories in Proficiency Testing, Conference of the State Parties. OPCW, The Hague, C-I/DEC.62, 22 May 1997.
13.
HooijschuurE.W.J.KientzC.E. and BrinkmanU.A. Th., “Analytical separation techniques for the determination of chemical warfare agents”, J. Chromatogr. A982, 177 (2002). doi: 10.1016/S0021-9673(02)01426-7
14.
WilsE.R.J., “Gas chromatography / Mass Spectrometry in Analysis of Chemicals Related to the Chemicals Weapons Convention”, in Chemical Weapons Convention Chemical Analysis; Sample Collection, Preparation and Analytical Methods, Ed by MesilaaksoM.John Wiley & Sons, Chichester, UK, p. 249 (2004).
15.
FrankeS., “Chemistry of chemical warfare agents,”Manual of military chemistry, Vol. 1. National Technical Information Service (NTIS), US Department of Commerce, Springfield VA, USA, pp. 134–135 (1967).
16.
MunroN.B.TalmageS.S.GriffinG.D.WatersL.C.WatsonA.P.KingJ.F. and HauschildV., “The sources, fate and toxicity of chemical warfare agent degradation product”, Environ. Health Perspect.107, 933 (1999).
17.
BlackR.M. and MuirB., “Derivatization reactions in the chromatographic analysis of chemical warfare agents and their degradation products”, J. Chromatogr. A1000, 253 (2003). doi: 10.1016/S0021-9673(03)00183-3
18.
HooijschuurE.W.J.KientzC.E. and HulstA.G., “Determination of Hydrolysis Products of Sulfur Mustards by Reversed-Phase Microcolumn Liquid Chromatography Coupled On-Line with Sulfur Flame Photometric Detection and Electrospray Ionization Mass Spectrometry Using Large-Volume Injections and Peak Compression”, Anal. Chem.72, 1199 (2000). doi: 10.1021/ac991035o
19.
TimperleyC.M.BlackR.M.BirdM.HoldenI.MundyJ.L. and ReadR.W., “Hydrolysis and oxidation products of the chemical warfare agents 1,2-bis(2-chloroethylthio)ethane Q and 2,2-bis(2-chloroethylthio)diethyl ether T”, Phosphorus, Sulfur and Silicon178, 2027 (2003). doi: 10.1080/10426500390228710
20.
HalketJ.M. and ZaikinV.G., “Derivatization in mass spectrometry-1, Silylation”, Eur. J. Mass Spectrom.9, 1 (2003). doi: 10.1255/ejms.527
