Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines
The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of th...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2012
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| Online Access: | http://hdl.handle.net/1721.1/74230 |
| _version_ | 1826214074498678784 |
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| author | Swager, Timothy Manning Andrew, Trisha Lionel |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Swager, Timothy Manning Andrew, Trisha Lionel |
| author_sort | Swager, Timothy Manning |
| collection | MIT |
| description | The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of this photofragmentation are reactive, electrophilic NO[subscript x] species, such as nitrous and nitric acid, nitric oxide, and nitrogen dioxide. N,N-Dimethylaniline is capable of being nitrated by the reactive, electrophilic NO[subscript x] photofragmentation products of RDX and PETN. A series of 9,9-disubstituted 9,10-dihydroacridines (DHAs) are synthesized from either N-phenylanthranilic acid methyl ester or a diphenylamine derivative and are similarly shown to be rapidly nitrated by the photofragmentation products of RDX and PETN. A new (turn-on) emission signal at 550 nm is observed upon nitration of DHAs due to the generation of fluorescent donor−acceptor chromophores. Using fluorescence spectroscopy, the presence of ca. 1.2 ng of RDX and 320 pg of PETN can be detected by DHA indicators in the solid state upon exposure to sunlight. The nitration of aromatic amines by the photofragmentation products of RDX and PETN is presented as a unique, highly selective detection mechanism for nitroester- and nitramine-containing explosives and DHAs are presented as inexpensive and impermanent fluorogenic indicators for the selective, standoff/remote identification of RDX and PETN. |
| first_indexed | 2024-09-23T15:59:24Z |
| format | Article |
| id | mit-1721.1/74230 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:59:24Z |
| publishDate | 2012 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/742302022-10-02T05:33:44Z Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines Swager, Timothy Manning Andrew, Trisha Lionel Massachusetts Institute of Technology. Department of Chemistry Swager, Timothy Manning Swager, Timothy Manning Andrew, Trisha Lionel The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of this photofragmentation are reactive, electrophilic NO[subscript x] species, such as nitrous and nitric acid, nitric oxide, and nitrogen dioxide. N,N-Dimethylaniline is capable of being nitrated by the reactive, electrophilic NO[subscript x] photofragmentation products of RDX and PETN. A series of 9,9-disubstituted 9,10-dihydroacridines (DHAs) are synthesized from either N-phenylanthranilic acid methyl ester or a diphenylamine derivative and are similarly shown to be rapidly nitrated by the photofragmentation products of RDX and PETN. A new (turn-on) emission signal at 550 nm is observed upon nitration of DHAs due to the generation of fluorescent donor−acceptor chromophores. Using fluorescence spectroscopy, the presence of ca. 1.2 ng of RDX and 320 pg of PETN can be detected by DHA indicators in the solid state upon exposure to sunlight. The nitration of aromatic amines by the photofragmentation products of RDX and PETN is presented as a unique, highly selective detection mechanism for nitroester- and nitramine-containing explosives and DHAs are presented as inexpensive and impermanent fluorogenic indicators for the selective, standoff/remote identification of RDX and PETN. United States. Army Research Office National Science Foundation (U.S.) (ECCS-0731100) 2012-10-24T17:49:58Z 2012-10-24T17:49:58Z 2011-03 2011-02 Article http://purl.org/eprint/type/JournalArticle 0022-3263 1520-6904 http://hdl.handle.net/1721.1/74230 Andrew, Trisha L., and Timothy M. Swager. “Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines.” The Journal of Organic Chemistry 76.9 (2011): 2976–2993. en_US http://dx.doi.org/ 10.1021/jo200280c Journal of Organic Chemistry Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Swager via Erja Kajosalo |
| spellingShingle | Swager, Timothy Manning Andrew, Trisha Lionel Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title | Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title_full | Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title_fullStr | Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title_full_unstemmed | Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title_short | Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines |
| title_sort | detection of explosives via photolytic cleavage of nitroesters and nitramines |
| url | http://hdl.handle.net/1721.1/74230 |
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