Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents

Read, Douglas H.; Achyuthan, Komandoor E.; Fix, Cory S.; Manginell, Ronald P.; Moorman, Matthew W.; Simonson, Robert J.; Wheeler, David R.; Whiting, Joshua J.

doi:10.2116/analsci.18P537

Title: Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents

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Abstract

We used for the first time hydrogen bonded acidic (HBA) polymer, poly{methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)phenyl]propylsiloxane } , (DKAP), as stationary phase for gas chromatography (GC) of chemical warfare agent (CWA) organophosphate (OP), surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high sensitivity and selectivity. Adsorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also performed for the first-time thermodynamic studies on the adsorption of OP vapors and obtained quantitative binding energy data for interactions with various stationary phases. These data help to identify the correct pair of hetero-polar columns for a two-dimensional system, employing nonpolar stationary phase as GC1, rejecting interfering molecules, and DKAP as GC2 stationary phase, for selective, sensitive, and rapid field detection of CWAs.

Authors:

Read, Douglas H. ^[1]; Achyuthan, Komandoor E. ^[1]; Fix, Cory S. ^[2]; Manginell, Ronald P. ^[1]; Moorman, Matthew W. ^[1]; Simonson, Robert J. ^[1]; Wheeler, David R. ^[1]; Whiting, Joshua J. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
CBRNE Defense, Battelle Memorial Institute, Columbus, OH (United States)

Publication Date:: Fri Feb 15 00:00:00 EST 2019

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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

OSTI Identifier:: 1498482

Report Number(s):: SAND-2018-11962J
Journal ID: ISSN 0910-6340; 668834

Grant/Contract Number:: AC04-94AL85000

Resource Type:: Accepted Manuscript

Journal Name:: Analytical Sciences

Additional Journal Information:: Journal Volume: 35; Journal Issue: 6; Journal ID: ISSN 0910-6340

Publisher:: Japan Society for Analytical Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Read, Douglas H., Achyuthan, Komandoor E., Fix, Cory S., Manginell, Ronald P., Moorman, Matthew W., Simonson, Robert J., Wheeler, David R., and Whiting, Joshua J. Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents.  United States: N. p., 2019. 
Web.  doi:10.2116/analsci.18P537.

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                    Read, Douglas H., Achyuthan, Komandoor E., Fix, Cory S., Manginell, Ronald P., Moorman, Matthew W., Simonson, Robert J., Wheeler, David R., & Whiting, Joshua J. Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents.  United States.  https://doi.org/10.2116/analsci.18P537

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                    Read, Douglas H., Achyuthan, Komandoor E., Fix, Cory S., Manginell, Ronald P., Moorman, Matthew W., Simonson, Robert J., Wheeler, David R., and Whiting, Joshua J. Fri .  
"Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents".  United States.  https://doi.org/10.2116/analsci.18P537.  https://www.osti.gov/servlets/purl/1498482.

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@article{osti_1498482,

  title        = {Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents},

  author       = {Read, Douglas H. and Achyuthan, Komandoor E. and Fix, Cory S. and Manginell, Ronald P. and Moorman, Matthew W. and Simonson, Robert J. and Wheeler, David R. and Whiting, Joshua J.},

  abstractNote = {We used for the first time hydrogen bonded acidic (HBA) polymer, poly{methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)phenyl]propylsiloxane } , (DKAP), as stationary phase for gas chromatography (GC) of chemical warfare agent (CWA) organophosphate (OP), surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high sensitivity and selectivity. Adsorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also performed for the first-time thermodynamic studies on the adsorption of OP vapors and obtained quantitative binding energy data for interactions with various stationary phases. These data help to identify the correct pair of hetero-polar columns for a two-dimensional system, employing nonpolar stationary phase as GC1, rejecting interfering molecules, and DKAP as GC2 stationary phase, for selective, sensitive, and rapid field detection of CWAs.},

  doi          = {10.2116/analsci.18P537},

  journal      = {Analytical Sciences},

  number       = 6,

  volume       = 35,

  place        = {United States},

  year         = {Fri Feb 15 00:00:00 EST 2019},

  month        = {Fri Feb 15 00:00:00 EST 2019}

}

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