Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal

Wong, Camille Hing; Edgar, Alexander Steven; Yang, Dali

doi:10.1002/prep.202100189

Title: Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal

Abstract

Abstract This study is the first attempt to document methodology development undergone using liquid chromatography tandem quadrupole time of flight mass spectrometry (LC‐QTOF) to investigate degradation products of eutectic bis(2,2‐dinitropropyl) acetal/formal nitroplasticizer (called NP here). Method properties investigated are: desolvation temperature (°C) and spray voltage (V) of the electrospray ionization source, and the development of an acetone system rinse to prevent any residual contamination between sample injections. Details are given on why it is essential to investigate method optimization with changes shown in MS/MS analysis in addition to MS results. Trends in MS/MS analytic results reveal important relationships between baseline and aged materials. In addition to verification of previously proposed fragments, insights offered by this newly developed methodology will also identify new degradation products and shed light on the complexity of NP degradation chemistry.

Authors:

Wong, Camille Hing ^[1];

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Wed Dec 01 00:00:00 EST 2021

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1872345

Alternate Identifier(s):: OSTI ID: 1826818

Report Number(s):: LA-UR-21-25350
Journal ID: ISSN 0721-3115

Grant/Contract Number:: 89233218CNA000001

Resource Type:: Accepted Manuscript

Journal Name:: Propellants, Explosives, Pyrotechnics

Additional Journal Information:: Journal Volume: 46; Journal Issue: 12; Journal ID: ISSN 0721-3115

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 42 ENGINEERING; 36 MATERIALS SCIENCE; Nitroplasticizer; LC-QTOF; BDNPA/F; Degradation

Citation Formats


                    Wong, Camille Hing, Edgar, Alexander Steven, and Yang, Dali. Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal.  United States: N. p., 2021. 
Web.  doi:10.1002/prep.202100189.

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                    Wong, Camille Hing, Edgar, Alexander Steven, & Yang, Dali. Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal.  United States.  https://doi.org/10.1002/prep.202100189

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                    Wong, Camille Hing, Edgar, Alexander Steven, and Yang, Dali. Wed .  
"Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal".  United States.  https://doi.org/10.1002/prep.202100189.  https://www.osti.gov/servlets/purl/1872345.

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@article{osti_1872345,

  title        = {Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal},

  author       = {Wong, Camille Hing and Edgar, Alexander Steven and Yang, Dali},

  abstractNote = {Abstract This study is the first attempt to document methodology development undergone using liquid chromatography tandem quadrupole time of flight mass spectrometry (LC‐QTOF) to investigate degradation products of eutectic bis(2,2‐dinitropropyl) acetal/formal nitroplasticizer (called NP here). Method properties investigated are: desolvation temperature (°C) and spray voltage (V) of the electrospray ionization source, and the development of an acetone system rinse to prevent any residual contamination between sample injections. Details are given on why it is essential to investigate method optimization with changes shown in MS/MS analysis in addition to MS results. Trends in MS/MS analytic results reveal important relationships between baseline and aged materials. In addition to verification of previously proposed fragments, insights offered by this newly developed methodology will also identify new degradation products and shed light on the complexity of NP degradation chemistry.},

  doi          = {10.1002/prep.202100189},

  journal      = {Propellants, Explosives, Pyrotechnics},

  number       = 12,

  volume       = 46,

  place        = {United States},

  year         = {Wed Dec 01 00:00:00 EST 2021},

  month        = {Wed Dec 01 00:00:00 EST 2021}

}

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Works referenced in this record:

Degradation of a poly(ester urethane) elastomer. III. Estane 5703 hydrolysis: Experiments and modeling
journal, March 2003

Salazar, Michael R.; Lightfoot, J. Michael; Russell, Bobby G.
Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 8
DOI: 10.1002/pola.10656

Thermal stability of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal: Part B. Degradation mechanisms under water and high humidity environments
journal, August 2016

Yang, Dali; Pacheco, Robin; Edwards, Stephanie
Polymer Degradation and Stability, Vol. 130
DOI: 10.1016/j.polymdegradstab.2016.06.007

RDX and HMX with Reduced Sensitivity Towards Shock Initiation–RS-RDX and RS-HMX
journal, February 2008

Hammer Johansen, Øyvind; Digre Kristiansen, Jørn; Gjersøe, Richard
Propellants, Explosives, Pyrotechnics, Vol. 33, Issue 1
DOI: 10.1002/prep.200800203

Low-temperature oxidative degradation of PBX 9501 and its components determined via molecular weight analysis of the Poly[ester urethane] binder
journal, December 2009

Salazar, Michael R.; Kress, Joel D.; Lightfoot, J. Michael
Polymer Degradation and Stability, Vol. 94, Issue 12
DOI: 10.1016/j.polymdegradstab.2009.08.011

Calibration of ion spray mass spectra using cluster ions
journal, June 1992

Anacleto, J. F.; Pleasance, S.; Boyd, R. K.
Organic Mass Spectrometry, Vol. 27, Issue 6
DOI: 10.1002/oms.1210270603

Degradation of a poly(ester urethane) elastomer. II. Kinetic modeling of the hydrolysis of a poly(butylene adipate)
journal, January 2002

Salazar, Michael R.; Pack, Russell T.
Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 2
DOI: 10.1002/polb.10080

Physical characterization of Bis(2,2-dinitropropyl) acetal and Bis(2,2-dinitropropyl) formal
journal, March 2020

Edgar, Alexander; Yang, Justine; Chavez, Manuel
Journal of Energetic Materials, Vol. 38, Issue 4
DOI: 10.1080/07370652.2020.1737987

Radical Cations in Electrospray Mass Spectrometry: Formation of Open‐Shell Species, Examination of the Fragmentation Behaviour in ESI‐MS ⁿ and Reaction Mechanism Studies by Detection of Transient Radical Cations
journal, October 2007

Schäfer, Mathias; Drayß, Miriam; Springer, Andreas
European Journal of Organic Chemistry, Vol. 2007, Issue 31
DOI: 10.1002/ejoc.200700199

Small molecule adduct formation with the components of the mobile phase as a way to analyse valproic acid in human serum with liquid chromatography-tandem mass spectrometry
journal, May 2014

Dziadosz, Marek; Klintschar, Michael; Teske, Jörg
Journal of Chromatography B, Vol. 959
DOI: 10.1016/j.jchromb.2014.03.033

Thermal stability of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal: Part A. Degradation mechanisms in air and under nitrogen atmosphere
journal, July 2016

Yang, Dali; Pacheco, Robin; Edwards, Stephanie
Polymer Degradation and Stability, Vol. 129
DOI: 10.1016/j.polymdegradstab.2016.05.017

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Similar Records

Title: Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal

Abstract

Citation Formats

Degradation of a poly(ester urethane) elastomer. III. Estane 5703 hydrolysis: Experiments and modeling journal, March 2003

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Calibration of ion spray mass spectra using cluster ions journal, June 1992

Degradation of a poly(ester urethane) elastomer. II. Kinetic modeling of the hydrolysis of a poly(butylene adipate) journal, January 2002

Physical characterization of Bis(2,2-dinitropropyl) acetal and Bis(2,2-dinitropropyl) formal journal, March 2020

Radical Cations in Electrospray Mass Spectrometry: Formation of Open‐Shell Species, Examination of the Fragmentation Behaviour in ESI‐MS n and Reaction Mechanism Studies by Detection of Transient Radical Cations journal, October 2007

Small molecule adduct formation with the components of the mobile phase as a way to analyse valproic acid in human serum with liquid chromatography-tandem mass spectrometry journal, May 2014

Thermal stability of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal: Part A. Degradation mechanisms in air and under nitrogen atmosphere journal, July 2016

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