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Fragmentations and reactions of three isotopically labelled dimethyl methylphosphonate ions produced by electrospray ionisation in an ion trap mass spectrometer

Fragmentations and reactions of three isotopically labelled dimethyl methylphosphonate ions produced by electrospray ionisation in an ion trap mass spectrometer
Fragmentations and reactions of three isotopically labelled dimethyl methylphosphonate ions produced by electrospray ionisation in an ion trap mass spectrometer
In an initial investigation into the electrospray ionisation ion trap mass spectrometry (ESI/ITMS) of simple organophosphate esters we reported that in one of the collision induced fragmentation steps of protonated dimethyl methylphosphonate (DMMP), formaldehyde was eliminated with a concomitant partial scrambling of the methyl group attached to the phosphorus and a methoxy group. The present paper describes a further investigation of this reaction. Three novel isotopomers of DMMP were used for this study and their synthesis and properties are reported. A mechanism for the formaldehyde elimination and scrambling of the methyl groups is proposed and supported by a kinetic analysis of a limiting case. During this study black holes were found to occur in one of the ITMS instruments used and it is shown that these could lead to severe distortions in the amounts of product ions observed. A brief analysis of this observation is presented.
black holes
1463-9076
2200-2205
Barr, J.D.
c54182e7-c4d4-4161-a42f-1898fd5f8aff
Bell, A.J.
a3daf8c9-3047-4f42-8038-b839ff6ec575
Konn, D.O.
500145d8-6516-4d01-88e7-43b96678b278
Murrell, J.
9479f5f5-d41c-4a26-88ca-83379dfe57f3
Timperley, C.M.
edc8d723-7947-45ad-9de8-65474e0f4d15
Waters, M.J.
bd9823a5-3220-460b-b5cb-91fb904512fb
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb
Barr, J.D.
c54182e7-c4d4-4161-a42f-1898fd5f8aff
Bell, A.J.
a3daf8c9-3047-4f42-8038-b839ff6ec575
Konn, D.O.
500145d8-6516-4d01-88e7-43b96678b278
Murrell, J.
9479f5f5-d41c-4a26-88ca-83379dfe57f3
Timperley, C.M.
edc8d723-7947-45ad-9de8-65474e0f4d15
Waters, M.J.
bd9823a5-3220-460b-b5cb-91fb904512fb
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb

Barr, J.D., Bell, A.J., Konn, D.O., Murrell, J., Timperley, C.M., Waters, M.J. and Watts, P. (2002) Fragmentations and reactions of three isotopically labelled dimethyl methylphosphonate ions produced by electrospray ionisation in an ion trap mass spectrometer. Physical Chemistry Chemical Physics, 4 (11), 2200-2205. (doi:10.1039/b111192m).

Record type: Article

Abstract

In an initial investigation into the electrospray ionisation ion trap mass spectrometry (ESI/ITMS) of simple organophosphate esters we reported that in one of the collision induced fragmentation steps of protonated dimethyl methylphosphonate (DMMP), formaldehyde was eliminated with a concomitant partial scrambling of the methyl group attached to the phosphorus and a methoxy group. The present paper describes a further investigation of this reaction. Three novel isotopomers of DMMP were used for this study and their synthesis and properties are reported. A mechanism for the formaldehyde elimination and scrambling of the methyl groups is proposed and supported by a kinetic analysis of a limiting case. During this study black holes were found to occur in one of the ITMS instruments used and it is shown that these could lead to severe distortions in the amounts of product ions observed. A brief analysis of this observation is presented.

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More information

Published date: 2002
Keywords: black holes

Identifiers

Local EPrints ID: 19662
URI: http://eprints.soton.ac.uk/id/eprint/19662
ISSN: 1463-9076
PURE UUID: 070e6681-3b12-40cf-91ea-bd9bd375d105

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Date deposited: 16 Feb 2006
Last modified: 15 Jul 2019 19:26

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