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 -