TY - JOUR
T1 - Ketalization of phosphonium ions by 1,4-dioxane
T2 - Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions
AU - Chen, Hao
AU - Zheng, Xubin
AU - Cooks, R. Graham
N1 - Funding Information:
This work was supported by ONR funding from the Office of Navy Research and the Integrated Detection of Hazardous Materials (IDHM) Program, Center for Sensing Science and Technology (Purdue University), and the Naval Surface Warfare Center (Crane, Indiana). The authors acknowledge Marcos Eberlin, Zheng Ouyang, and Pengxiang Yang for constructive suggestions.
PY - 2003/3
Y1 - 2003/3
N2 - Phosphonium ions CH3P(O)OCH3+ (93 Th) and CH3OP(O)OCH3+ (109 Th) react with 1,4-dioxane to form unique cyclic ketalization products, 1,3,2-dioxaphospholanium ions. By contrast, a variety of other types of ions having multiple bonds, including the acylium ions CH3CO+ (43 Th), CH3OCO+ (59 Th), (CH3)2NCO+ (72 Th), and PhCO+ (105 Th), the iminium ion H2C=NHC2H5+ (58 Th) and the carbosulfonium ion H2C=SC2H5+ (75 Th) do not react with 1,4-dioxane under the same conditions. The characteristic ketalization reaction can also be observed when CH3P(OH)(OCH3)2+, viz. protonated dimethyl methylphosphonate (DMMP), collides with 1,4-dioxane, as a result of fragmentation to yield the reactive phosphonium ion CH3P(O)OCH3+ (93 Th). This novel ion/molecule reaction is highly selective to phosphonium ions and can be applied to identify DMMP selectively in the presence of ketone, ester, and amide compounds using a neutral gain MS/MS scan. This method of DMMP analysis can be applied to aqueous solutions using electrospray ionization; it shows a detection limit in the low ppb range and a linear response over the range 10 to 500 ppb.
AB - Phosphonium ions CH3P(O)OCH3+ (93 Th) and CH3OP(O)OCH3+ (109 Th) react with 1,4-dioxane to form unique cyclic ketalization products, 1,3,2-dioxaphospholanium ions. By contrast, a variety of other types of ions having multiple bonds, including the acylium ions CH3CO+ (43 Th), CH3OCO+ (59 Th), (CH3)2NCO+ (72 Th), and PhCO+ (105 Th), the iminium ion H2C=NHC2H5+ (58 Th) and the carbosulfonium ion H2C=SC2H5+ (75 Th) do not react with 1,4-dioxane under the same conditions. The characteristic ketalization reaction can also be observed when CH3P(OH)(OCH3)2+, viz. protonated dimethyl methylphosphonate (DMMP), collides with 1,4-dioxane, as a result of fragmentation to yield the reactive phosphonium ion CH3P(O)OCH3+ (93 Th). This novel ion/molecule reaction is highly selective to phosphonium ions and can be applied to identify DMMP selectively in the presence of ketone, ester, and amide compounds using a neutral gain MS/MS scan. This method of DMMP analysis can be applied to aqueous solutions using electrospray ionization; it shows a detection limit in the low ppb range and a linear response over the range 10 to 500 ppb.
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U2 - 10.1016/S1044-0305(02)00904-2
DO - 10.1016/S1044-0305(02)00904-2
M3 - Article
C2 - 12648924
AN - SCOPUS:0037805212
SN - 1044-0305
VL - 14
SP - 182
EP - 188
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
IS - 3
ER -