Polarographic Reduction of Polynitrate Esters

Whitnack, Gerald C.; Nielsen, Julien M.; Gantz, E. St. Clair

doi:10.1021/ja01647a064

Cited by 40 publications

(11 citation statements)

References 1 publication

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“…Analogous polarographic measurements in an ethanol-water system yielded increasing diffusion current with the number of ONO 2 groups. 11 Adding an organic co-solvent (such as acetonitrile or ethanol) to the running buffer led to an increased PETN signal but led to a concomitant loss of resolution for the EGDN, PGDN and NG peaks (not shown).…”

Section: Resultsmentioning

confidence: 97%

“…The electrochemical reduction of various nitrate ester explosives at mercury and silver electrodes was evaluated in early studies. 11,12 These studies indicated that nitrate ester compounds undergo a two-electron reduction process (which releases nitrite ion and alcohol), 11 making them ideal candidates for amperometric detection. Such cathodic detection was demonstrated previously following conventional liquid-chromatographic Scheme 1 Structures and abbreviations of the nitrate ester explosives.…”

Section: Introductionmentioning

confidence: 99%

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Rapid and sensitive measurements of nitrate ester explosives using microchip electrophoresis with electrochemical detection

Piccin

Dossi

Cagan

et al. 2009

Analyst

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This article describes an effective microchip protocol based on electrophoretic-separation and electrochemical detection for highly sensitive and rapid measurements of nitrate ester explosives, including ethylene glycol dinitrate (EGDN), pentaerythritol tetranitrate (PETN), propylene glycol dinitrate (PGDN) and glyceryl trinitrate (nitroglycerin, NG). Factors influencing the separation and detection processes were examined and optimized. Under the optimal separation conditions obtained using a 15 mM borate buffer (pH 9.2) containing 20 mM SDS, and applying a separation voltage of 1500 V, the four nitrate ester explosives were separated within less than 3 min. The glassy-carbon amperometric detector (operated at -0.9 V vs. Ag/AgCl) offers convenient cathodic detection down to the picogram level, with detection limits of 0.5 ppm and 0.3 ppm for PGDN and for NG, respectively, along with good repeatability (RSD of 1.8-2.3%; n = 6) and linearity (over the 10-60 ppm range). Such effective microchip operation offers great promise for field screening of nitrate ester explosives and for supporting various counter-terrorism surveillance activities.

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Rapid and sensitive measurements of nitrate ester explosives using microchip electrophoresis with electrochemical detection

Piccin

Dossi

Cagan

et al. 2009

Analyst

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“…It is thought that this reduction event corresponds to the conversion of the nitrate ester group to the corresponding alcohol with release of a nitrite anion. 16 The reductions all occur at approximately the same potential (-1.52 to -1.60 V vs fc). The irreversible anodic events may correspond to the oxidation of the species formed during the irreversible reduction of 6, 7, and 10.…”

Section: Electrochemical Behaviourmentioning

confidence: 91%

Synthesis and Electrochemical Behavior of Electron‐Rich s‐Tetrazine and Triazolo‐tetrazine Nitrate Esters

Myers

Snyder

Chávez

et al. 2016

Chemistry A European J

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We have prepared energetic nitrate ester derivatives of 1,2,4,5-tetrazine and 1,2,4-triazolo[4,3-b]-[1,2,4,5]-tetrazine ring systems as model compounds to study the electrochemical behavior of tetrazines in the presence of explosive groups. The model compounds showed lower thermal stabilities relative to PETN (pentaerythritol tetranitrate), but slightly improved mechanical sensitivities. The presence of electron-rich amine donors leads to a cathodic shift of the tetrazine redox potentials relative to those of previously reported tetrazine explosives. At these potentials, electron-rich tetrazines with either covalently bound or co-dissolved nitrate ester groups are irreversibly reduced. Effectively, changes in the electronic structure of tetrazines affect their electrochemical response to the presence of nitrate ester groups. Thus, it may be possible to develop tetrazine-based electrochemical sensors for the detection of specific explosives and electrocatalysts for their disposal.

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“…According to the same author, PETN is irreducible a t the dropping-mercury cathode. Polarographic methods for the determination of PETN have not been recorded in literature, although this substance has been investigated by Whitnack (6). In the early stages of investigation, acetone was used as the solvent.…”

Section: Discussionmentioning

confidence: 99%

Simultaneous Polarographic Determination of Pentaerythritol Tetranitrate and Cyclotrimethylenetrinitramine

Hetman¹

1960

Anal. Chem.

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Polarographic Reduction of Polynitrate Esters

Cited by 40 publications

References 1 publication

Rapid and sensitive measurements of nitrate ester explosives using microchip electrophoresis with electrochemical detection

Rapid and sensitive measurements of nitrate ester explosives using microchip electrophoresis with electrochemical detection

Synthesis and Electrochemical Behavior of Electron‐Rich s‐Tetrazine and Triazolo‐tetrazine Nitrate Esters

Simultaneous Polarographic Determination of Pentaerythritol Tetranitrate and Cyclotrimethylenetrinitramine

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