Details
Original language | English |
---|---|
Article number | 117235 |
Journal | International Journal of Mass Spectrometry |
Volume | 500 |
Early online date | 26 Mar 2024 |
Publication status | Published - Jun 2024 |
Abstract
Nitrate adducts of nitroglycerin (NG) and 1,3-dinitroglycerin (1,3-DNG) were produced from atmospheric pressure chemical ionization with chloride reagent ions and in-source decomposition of M·Cl−. The nitrate adducts subsequently dissociated in the drift region with enthalpies of 109 ± 9 kJ mol −1 at 142–150 °C for NG·NO3− and 101 ± 8 kJ mol−1 at 161–173 °C for 1,3-DNG·NO3−. Similar behavior was not observed generally for other explosives although nitrate adducts of each explosive could be formed using electrospray ionization with a nitrate salt solution. Ion abundances were measured over a range of ion energies with collision induced dissociation in tandem mass spectrometry and models from Density Functional Theory were used to correlate the experimental findings to structural motifs and other adduct properties. The computational modeling showed that adduct stability is dominated by the electrostatic interaction between the nitrate ion and the dipole moment of the neutral explosive. Specifically, explosives having the ability to adapt a conformer with a large dipole moment showed the most stable adducts. Other binding contributions are possible yet were found to be minor in the explosive adducts studied here.
Keywords
- Collision induced dissociation, Density functional theory, Enthalpy of dissociation, Explosives, Ion mobility spectrometry, Mass spectrometry, Nitrate adducts
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Instrumentation
- Physics and Astronomy(all)
- Condensed Matter Physics
- Chemistry(all)
- Spectroscopy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: International Journal of Mass Spectrometry, Vol. 500, 117235, 06.2024.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - NO3− loss from nitrate adducts of explosives by thermal decomposition in tandem Ion mobility spectrometry and by collision induced dissociation in tandem mass spectrometry
AU - Haack, Alexander
AU - Gurung, Bhupendra K.
AU - Eiceman, Gary A.
N1 - Funding Information: We acknowledge the gift from Sciex of the Model 4000 tandem mass spectrometer and discussions with Dr. John Stone, Prof. Emeritus, Queens Univ. Kingston, Ontario. The authors would like to acknowledge the LUH Compute Cluster located at and funded by the Leibniz University Hannover, Germany, on which the computations of this works were conducted. Alexander Haack gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – 526357638.
PY - 2024/6
Y1 - 2024/6
N2 - Nitrate adducts of nitroglycerin (NG) and 1,3-dinitroglycerin (1,3-DNG) were produced from atmospheric pressure chemical ionization with chloride reagent ions and in-source decomposition of M·Cl−. The nitrate adducts subsequently dissociated in the drift region with enthalpies of 109 ± 9 kJ mol −1 at 142–150 °C for NG·NO3− and 101 ± 8 kJ mol−1 at 161–173 °C for 1,3-DNG·NO3−. Similar behavior was not observed generally for other explosives although nitrate adducts of each explosive could be formed using electrospray ionization with a nitrate salt solution. Ion abundances were measured over a range of ion energies with collision induced dissociation in tandem mass spectrometry and models from Density Functional Theory were used to correlate the experimental findings to structural motifs and other adduct properties. The computational modeling showed that adduct stability is dominated by the electrostatic interaction between the nitrate ion and the dipole moment of the neutral explosive. Specifically, explosives having the ability to adapt a conformer with a large dipole moment showed the most stable adducts. Other binding contributions are possible yet were found to be minor in the explosive adducts studied here.
AB - Nitrate adducts of nitroglycerin (NG) and 1,3-dinitroglycerin (1,3-DNG) were produced from atmospheric pressure chemical ionization with chloride reagent ions and in-source decomposition of M·Cl−. The nitrate adducts subsequently dissociated in the drift region with enthalpies of 109 ± 9 kJ mol −1 at 142–150 °C for NG·NO3− and 101 ± 8 kJ mol−1 at 161–173 °C for 1,3-DNG·NO3−. Similar behavior was not observed generally for other explosives although nitrate adducts of each explosive could be formed using electrospray ionization with a nitrate salt solution. Ion abundances were measured over a range of ion energies with collision induced dissociation in tandem mass spectrometry and models from Density Functional Theory were used to correlate the experimental findings to structural motifs and other adduct properties. The computational modeling showed that adduct stability is dominated by the electrostatic interaction between the nitrate ion and the dipole moment of the neutral explosive. Specifically, explosives having the ability to adapt a conformer with a large dipole moment showed the most stable adducts. Other binding contributions are possible yet were found to be minor in the explosive adducts studied here.
KW - Collision induced dissociation
KW - Density functional theory
KW - Enthalpy of dissociation
KW - Explosives
KW - Ion mobility spectrometry
KW - Mass spectrometry
KW - Nitrate adducts
UR - http://www.scopus.com/inward/record.url?scp=85189033077&partnerID=8YFLogxK
U2 - 10.1016/j.ijms.2024.117235
DO - 10.1016/j.ijms.2024.117235
M3 - Article
AN - SCOPUS:85189033077
VL - 500
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
SN - 1387-3806
M1 - 117235
ER -