Sensitivity and selectivity of switchable reagent ion soft chemical ionization mass spectrometry for the detection of picric acid

Bishu Agarwal, Ramón González-Méndez, Matteo Lanza, Philipp Sulzer, Tilmann D. Märk, Neil Thomas, Chris A. Mayhew

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

We have investigated the reactions of NO+, H3O+, O2 +, and Kr+ with picric acid (2,4,6 trinitrophenol, C6H3N3O7, PiA) using a time-of-flight mass spectrometer with a switchable reagent ion source. NO+ forms a simple adduct ion PiA·NO+, while H3O+ reacts with PiA via nondissociative proton transfer to form PiAH+. In contrast, both O2 + and Kr+ react with PiA by nondissociative charge transfer to produce PiA+. For Kr+, we also observe dissociation of PiA, producing NO2 + with a branching percentage of approximately 40%. For the reagent ions H3O+ and O2 + (and operating the drift tube with normal laboratory air), we find that the intensities of the PiAH+ and PiA+ ions both exhibit a peak at a given drift-tube voltage (which is humidity dependent). This unusual behavior implies a peak in the detection sensitivity of PiA as a function of the drift-tube voltage (and hence E/N). Aided by electronic-structure calculations and our previous studies of trinitrotoluene and trinitrobenzene, we provide a possible explanation for the observed peak in the detection sensitivity of PiA.

Original languageEnglish
Pages (from-to)8229-8236
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume118
Issue number37
DOIs
Publication statusPublished - 18 Sep 2014
Externally publishedYes

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Ionization
Mass spectrometry
reagents
Mass Spectrometry
mass spectroscopy
selectivity
Ions
tubes
ionization
acids
sensitivity
Trinitrotoluene
Trinitrobenzenes
ions
trinitrotoluene
Proton transfer
Electric potential
electric potential
Mass spectrometers
Ion sources

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Sensitivity and selectivity of switchable reagent ion soft chemical ionization mass spectrometry for the detection of picric acid. / Agarwal, Bishu; González-Méndez, Ramón; Lanza, Matteo; Sulzer, Philipp; Märk, Tilmann D.; Thomas, Neil; Mayhew, Chris A.

In: Journal of Physical Chemistry Letters, Vol. 118, No. 37, 18.09.2014, p. 8229-8236.

Research output: Contribution to journalArticle

Agarwal, Bishu ; González-Méndez, Ramón ; Lanza, Matteo ; Sulzer, Philipp ; Märk, Tilmann D. ; Thomas, Neil ; Mayhew, Chris A. / Sensitivity and selectivity of switchable reagent ion soft chemical ionization mass spectrometry for the detection of picric acid. In: Journal of Physical Chemistry Letters. 2014 ; Vol. 118, No. 37. pp. 8229-8236.
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abstract = "We have investigated the reactions of NO+, H3O+, O2 +, and Kr+ with picric acid (2,4,6 trinitrophenol, C6H3N3O7, PiA) using a time-of-flight mass spectrometer with a switchable reagent ion source. NO+ forms a simple adduct ion PiA·NO+, while H3O+ reacts with PiA via nondissociative proton transfer to form PiAH+. In contrast, both O2 + and Kr+ react with PiA by nondissociative charge transfer to produce PiA+. For Kr+, we also observe dissociation of PiA, producing NO2 + with a branching percentage of approximately 40{\%}. For the reagent ions H3O+ and O2 + (and operating the drift tube with normal laboratory air), we find that the intensities of the PiAH+ and PiA+ ions both exhibit a peak at a given drift-tube voltage (which is humidity dependent). This unusual behavior implies a peak in the detection sensitivity of PiA as a function of the drift-tube voltage (and hence E/N). Aided by electronic-structure calculations and our previous studies of trinitrotoluene and trinitrobenzene, we provide a possible explanation for the observed peak in the detection sensitivity of PiA.",
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AU - González-Méndez, Ramón

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AU - Märk, Tilmann D.

AU - Thomas, Neil

AU - Mayhew, Chris A.

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AB - We have investigated the reactions of NO+, H3O+, O2 +, and Kr+ with picric acid (2,4,6 trinitrophenol, C6H3N3O7, PiA) using a time-of-flight mass spectrometer with a switchable reagent ion source. NO+ forms a simple adduct ion PiA·NO+, while H3O+ reacts with PiA via nondissociative proton transfer to form PiAH+. In contrast, both O2 + and Kr+ react with PiA by nondissociative charge transfer to produce PiA+. For Kr+, we also observe dissociation of PiA, producing NO2 + with a branching percentage of approximately 40%. For the reagent ions H3O+ and O2 + (and operating the drift tube with normal laboratory air), we find that the intensities of the PiAH+ and PiA+ ions both exhibit a peak at a given drift-tube voltage (which is humidity dependent). This unusual behavior implies a peak in the detection sensitivity of PiA as a function of the drift-tube voltage (and hence E/N). Aided by electronic-structure calculations and our previous studies of trinitrotoluene and trinitrobenzene, we provide a possible explanation for the observed peak in the detection sensitivity of PiA.

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