Detection of multiple nitroaromatic explosives via formation of a Janowsky complex and SERS

Research output: Contribution to journalArticle

Abstract

Military grade explosives such as 2,4,6-trinitroluene (TNT) are still a major worldwide concern in terms of terror threat and environmental impact. The most common methods currently employed for the detection of explosives involve colourimetric tests, which are known to be rapid and portable, however often display false positives and lack sensitivity. Other methods used include ion mobility mass spectrometry, gas chromatography – mass spectrometry (GC-MS) and liquid chromatography – mass spectrometry (LC-MS), which despite producing more reliable results; often require large, expensive instrumentation and specially trained staff. Here we demonstrate an alternative approach that utilises the formation of a coloured Janowsky complex with nitroaromatic explosives through reaction of the enolate ion of 3-mercapto-2-butanone. The coloured complex is formed rapidly and can then be detected sensitively using surface enhanced Raman scattering (SERS). We demonstrate that SERS can be used as a quick, sensitive and selective technique for the detection of 2,4,6-trinitrotoluene (TNT), hexanitrostillbene (HNS) and 2,4,6- trinitrophenylmethylnitramine (tetryl) with a detection limit of 6.81 ng mL-1 achieved for TNT, 17.2 ng mL-1 for tetryl and 135.1 ng mL-1 for HNS. This method of detection also requires minimal sample preparation, can be done in a solution based format and utilises the same pre-cursor reagents for complex formation with each of the explosives which can then be identified due to the specificity of the unique SERS response obtained. We demonstrate the ability to simultaneously identify three explosive compounds within a total analysis time of 10 minutes. This method of detection shows promise for the development of rapid and portable SERS based assays which can be utilised in the field in order to achieve reliable and quantitative detection.
Original languageEnglish
Number of pages10
JournalAnalytical Chemistry
Early online date13 Jan 2020
DOIs
Publication statusE-pub ahead of print - 13 Jan 2020

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Raman scattering
Mass spectrometry
Trinitrotoluene
Ions
Liquid chromatography
Gas chromatography
Environmental impact
Assays
nitramine

Keywords

  • surface enhance Raman spectroscopy (SERS)
  • explosives
  • chemical detection

Cite this

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title = "Detection of multiple nitroaromatic explosives via formation of a Janowsky complex and SERS",
abstract = "Military grade explosives such as 2,4,6-trinitroluene (TNT) are still a major worldwide concern in terms of terror threat and environmental impact. The most common methods currently employed for the detection of explosives involve colourimetric tests, which are known to be rapid and portable, however often display false positives and lack sensitivity. Other methods used include ion mobility mass spectrometry, gas chromatography – mass spectrometry (GC-MS) and liquid chromatography – mass spectrometry (LC-MS), which despite producing more reliable results; often require large, expensive instrumentation and specially trained staff. Here we demonstrate an alternative approach that utilises the formation of a coloured Janowsky complex with nitroaromatic explosives through reaction of the enolate ion of 3-mercapto-2-butanone. The coloured complex is formed rapidly and can then be detected sensitively using surface enhanced Raman scattering (SERS). We demonstrate that SERS can be used as a quick, sensitive and selective technique for the detection of 2,4,6-trinitrotoluene (TNT), hexanitrostillbene (HNS) and 2,4,6- trinitrophenylmethylnitramine (tetryl) with a detection limit of 6.81 ng mL-1 achieved for TNT, 17.2 ng mL-1 for tetryl and 135.1 ng mL-1 for HNS. This method of detection also requires minimal sample preparation, can be done in a solution based format and utilises the same pre-cursor reagents for complex formation with each of the explosives which can then be identified due to the specificity of the unique SERS response obtained. We demonstrate the ability to simultaneously identify three explosive compounds within a total analysis time of 10 minutes. This method of detection shows promise for the development of rapid and portable SERS based assays which can be utilised in the field in order to achieve reliable and quantitative detection.",
keywords = "surface enhance Raman spectroscopy (SERS), explosives, chemical detection",
author = "Kirsty Milligan and Shand, {Neil C.} and Duncan Graham and Karen Faulds",
year = "2020",
month = "1",
day = "13",
doi = "10.1021/acs.analchem.9b05062",
language = "English",
journal = "Analytical Chemistry",
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AU - Milligan, Kirsty

AU - Shand, Neil C.

AU - Graham, Duncan

AU - Faulds, Karen

PY - 2020/1/13

Y1 - 2020/1/13

N2 - Military grade explosives such as 2,4,6-trinitroluene (TNT) are still a major worldwide concern in terms of terror threat and environmental impact. The most common methods currently employed for the detection of explosives involve colourimetric tests, which are known to be rapid and portable, however often display false positives and lack sensitivity. Other methods used include ion mobility mass spectrometry, gas chromatography – mass spectrometry (GC-MS) and liquid chromatography – mass spectrometry (LC-MS), which despite producing more reliable results; often require large, expensive instrumentation and specially trained staff. Here we demonstrate an alternative approach that utilises the formation of a coloured Janowsky complex with nitroaromatic explosives through reaction of the enolate ion of 3-mercapto-2-butanone. The coloured complex is formed rapidly and can then be detected sensitively using surface enhanced Raman scattering (SERS). We demonstrate that SERS can be used as a quick, sensitive and selective technique for the detection of 2,4,6-trinitrotoluene (TNT), hexanitrostillbene (HNS) and 2,4,6- trinitrophenylmethylnitramine (tetryl) with a detection limit of 6.81 ng mL-1 achieved for TNT, 17.2 ng mL-1 for tetryl and 135.1 ng mL-1 for HNS. This method of detection also requires minimal sample preparation, can be done in a solution based format and utilises the same pre-cursor reagents for complex formation with each of the explosives which can then be identified due to the specificity of the unique SERS response obtained. We demonstrate the ability to simultaneously identify three explosive compounds within a total analysis time of 10 minutes. This method of detection shows promise for the development of rapid and portable SERS based assays which can be utilised in the field in order to achieve reliable and quantitative detection.

AB - Military grade explosives such as 2,4,6-trinitroluene (TNT) are still a major worldwide concern in terms of terror threat and environmental impact. The most common methods currently employed for the detection of explosives involve colourimetric tests, which are known to be rapid and portable, however often display false positives and lack sensitivity. Other methods used include ion mobility mass spectrometry, gas chromatography – mass spectrometry (GC-MS) and liquid chromatography – mass spectrometry (LC-MS), which despite producing more reliable results; often require large, expensive instrumentation and specially trained staff. Here we demonstrate an alternative approach that utilises the formation of a coloured Janowsky complex with nitroaromatic explosives through reaction of the enolate ion of 3-mercapto-2-butanone. The coloured complex is formed rapidly and can then be detected sensitively using surface enhanced Raman scattering (SERS). We demonstrate that SERS can be used as a quick, sensitive and selective technique for the detection of 2,4,6-trinitrotoluene (TNT), hexanitrostillbene (HNS) and 2,4,6- trinitrophenylmethylnitramine (tetryl) with a detection limit of 6.81 ng mL-1 achieved for TNT, 17.2 ng mL-1 for tetryl and 135.1 ng mL-1 for HNS. This method of detection also requires minimal sample preparation, can be done in a solution based format and utilises the same pre-cursor reagents for complex formation with each of the explosives which can then be identified due to the specificity of the unique SERS response obtained. We demonstrate the ability to simultaneously identify three explosive compounds within a total analysis time of 10 minutes. This method of detection shows promise for the development of rapid and portable SERS based assays which can be utilised in the field in order to achieve reliable and quantitative detection.

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