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 AJAC  Vol.5 No.13 , September 2014
Identification of N-Methyl Bis(2-(Alkyloxy-Alkylphosphoryloxy)Ethyl) Amines by LC-HRMS/MS
Abstract: N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are important markers of chemical warfare agents because they are structurally relative to both nerve agents and N-mustards. In this study, fragmentation pathways of the most characteristic fragment ions in Q-TOF mass spectrometry were proposed based on the information from accurate mass and secondary fragmentations of product ions scan experiments. Results indicated that the base ion in LC/HRMS was the quasi-molecular ion [M+H]+. In LC-HRMS/MS, it was [M+H-CnH2n+1P(O)(OH)CmH2m+1O]+ fragment ion which was formed by losing an alkyloxy alkylphosphoryloxy group from the quasi-molecular ion. The diagnostic ion m/z84.0814 was identified as [C5H10N]+, which was the group of (CH2=CH)2N+(H)CH3. PNPs have two protonated centers. One is on the N atom, the other is on the O atom (P=O). O-n-propyl PNPs generally exhibited two fragmentation pathways. Firstly, the quasi-molecular ion [M+H]+ lost a propoxy alkylphosphoryloxy group to produce [R1P(OH+)(O-n-C3H7)OCH2CH2N(CH3)CH=CH2]+, which could be fragmented further to produce [C5H10N]+ ion. Secondly, [R1P(OH+)(O-n-C3H7) OCH=CH2]+ ions were produced from [M+H]+ and fragmented further to produce the abundant ions [R1P(OH+)(OH)OCH =CH2]. However, O-isopropyl PNPs characteristically produced weak fragment ions [M+H-C3H6]+, which were presumably formed via loss of CH3CH=CH2 from [M+H]+. Other PNPs showed similar fragmentation pathways as O-n-propyl PNPs. On the summarization of the MS fragmentation pathways of PNPs, LC-HRMS/MS quantitative and qualitative methods were developed and applied to analyze N-Methyl bis(2-(butoxy-methylphosphoryloxy)ethyl]amine in high background organic samples. The analytical results had successfully supported the sample preparation for the 33rd official proficiency test of Organization for Prohibition of Chemical Weapons (OPCW).
Cite this paper: Yu, H. , Liu, S. , Sun, D. , Pei, C. and Xiang, Y. (2014) Identification of N-Methyl Bis(2-(Alkyloxy-Alkylphosphoryloxy)Ethyl) Amines by LC-HRMS/MS. American Journal of Analytical Chemistry, 5, 820-827. doi: 10.4236/ajac.2014.513091.
References

[1]   Mesilaakso, M. (2004) Chemical Weapons Convention Chemical Analysis: Sample Collection. Preparation and Analytical Methods.

[2]   Timonthy, C.M., Robert, L.M. and Frederick, R.S. (2007) Chemical Warfare Agents: Toxicology and Treatment. 2nd Edition, John Wiley & Sons Ltd., England.

[3]   Wils, E.R.J. and Hulst, A.G. (1992) The Use of Thermospray-Liquid Chromatography/Mass Spectrometry for the Verification of Chemical Warfare Agents. Fresenius Journal of Analytical Chemistry, 342, 749-758.
http://dx.doi.org/10.1007/BF00321871

[4]   Wils, E.R.J. and Hulst, A.G. (1998) Determination of Organophosphorus Acids by Thermospray Liquid Chromatography-Mass Spectrometry. Journal of Chromatography, 454, 261-272.
http://dx.doi.org/10.1016/S0021-9673(00)88619-7

[5]   Mercietal, J.P. (1999) Liquild Chromatography Analysis of Phosphonic Acids on Porous Graphitic Carbon Stationary Phase with Evaporative Light-Scattering and Mass Spectrometry Detection. Journal of Chromatography A, 849, 197-207.
http://dx.doi.org/10.1016/S0021-9673(99)00556-7

[6]   D’Agostin, P.A. and Hancock, J.R. (1999) Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry Analysis of Organosphosphorus Chemical Warfare Agents. Journal of Chromatography A, 840, 289-294.
http://dx.doi.org/10.1016/S0021-9673(99)00264-2

[7]   D’Agostin, P.A. and Hancock, J.R. (1999) Analysis of OethylS-2-(diisopropylamino)ethyl Methylphosphonothioate (VX) and Its Degradation Products by Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry. Journal of Chromatography A, 837, 93-105.
http://dx.doi.org/10.1016/S0021-9673(99)00102-8

[8]   D’Agostin, P.A. and Hancock, J.R. (2000) Determination of Organophosphorus Chemical Warfare Agents and Their Hydrolysis Products in Soil by Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry. Technical Report, Canada.

[9]   D’Agostin, P.A., Hancock, J.R. and Provost, L.R. (2001) Determination of Sarin, Soman and Their Hydrolysis Products in Soil by Packed Capillary Liquild Chromatography-Electrospray Mass Spectrometry. Journal of Chromatography A, 912, 291-299.
http://dx.doi.org/10.1016/S0021-9673(00)01275-9

[10]   D’Agostin, P.A., Chenier, C.L. and Hancock, J.R. (2002) Packed Capillary Liquid Chromatography-Electrospray Mass Spectrometry of Snow Contaminated with Sarin. Journal of Chromatography A, 950, 149-156.
http://dx.doi.org/10.1016/S0021-9673(02)00050-X

[11]   Liu, Q., Hu, X.Y. and Xie, J.W. (2004) Determination of Nerve Agent Degradation Products in Environmental Samples by Liquid Chromatography-Time-of-Flight Mass Spectrometry with Electrospray Ionization. Analytica Chimica Acta, 512, 93-101.
http://dx.doi.org/10.1016/j.aca.2004.02.023

[12]   Wils, E.R.J. and Hulst, A.G. (1990) Determination of O-ethylS-2-diisopropylaminoethyl Methylphosphonothioate (VX) by Thermospray Liquid Chromatography-Mass Spectrometry. Journal of Chromatography A, 523, 151-161.
http://dx.doi.org/10.1016/0021-9673(90)85019-R

[13]   Creasy, W.R., Stuff, J.R., Williams, B., Morrissey, K., Mays, J., Duevel, R. and Durst, H.D. (1997) Identification of Chemical-Weapons-Related Compounds in Decontamination Solutions and Other Matrices by Multiple Chromatographic Techniques. Journal of Chromatography A, 774, 253-263.
http://dx.doi.org/10.1016/S0021-9673(97)00155-6

[14]   Black, R.M. and Read, R.W. (1997) Application of Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry and Tandem Mass Spectrometry to the Analysis and Identification of Degradation Products of Chemical Warfare Agents. Journal of Chromatography A, 759, 79-92.
http://dx.doi.org/10.1016/S0021-9673(96)00763-7

[15]   Black, R.M. and Read, R.W. (1998) Analysis of Degradation Products of Organophosphorus Chemical Warfare Agents and Related Compounds by Liquid Chromatography Using Electrospray and Atmospheric Pressure Chemical Ionisation. Journal of Chromatography A, 794, 233-244.
http://dx.doi.org/10.1016/S0021-9673(97)00611-0

[16]   Read, R.W. and Black, R.M. (1999) Rapid Screening Procedures for the Hydrolysis Products of Chemical Warfare Agents Using Positive and Negative Ion Liquid Chromatography-Mass Spectrometry with Atmospheric Pressure Chemical Ionization. Journal of Chromatography A, 862, 169-177.
http://dx.doi.org/10.1016/S0021-9673(99)00944-9

[17]   Asbury, G.R., Wu, C., Siems, W.F. and Hill Jr., H.H. (2000) Separation and Identification of Some Chemical Warfare Degradation Products Using Electrospray High Resolution Ion Mobility Spectrometry with Mass Selected Detection. Analytica Chimica Acta, 404, 273-283.
http://dx.doi.org/10.1016/S0003-2670(99)00726-6

[18]   Van Baar, B.L.M., Hulst, A.G. and Wils, E.R.J. (1998) Identification of the C3H7 Moiety of Isopropyl- and Propylphosphonates by Electrospray Tandem Mass Spectrometry. Journal of Mass Spectrometry, 33, 1104-1108.
http://dx.doi.org/10.1002/(SICI)1096-9888(1998110)33:11<1104::AID-JMS727>3.0.CO;2-B

[19]   Palit, M., Pardasani, D., Gupta, A.K., Shakya, P. and Dubey, D.K. (2005) Microsynthesis and Electron Ionisation Mass Spectrometric Analysis of Chemical Weapons Convention (CWC)-Related O,O-dialkyl-N,N-dialkylphosphoramidates. Analytical and Bioanalytical Chemistry, 381, 477-486.
http://dx.doi.org/10.1007/s00216-004-2873-x

 
 
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