Fluorescent signaling based on sulfoxide profluorophores: Application to the visual detection of the explosive TATP

Journal of the American Chemical Society

Volumn 130, Issue 39, 2008, Pages 12846-12847

  Malashikhin, Sergey ^a   Finney, Nathaniel S ^a  

^a UNIVERSITY OF ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMOSENSING; FLUORESCENCE SIGNALING; FLUORESCENT PROBES; TRIACETONE TRIPEROXIDE; VISUAL DETECTION; VISUAL RESPONSE;

SIGNALING;

FLUORESCENCE;

EID: 67650292728     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja802989v     Document Type: Article

References (34)

1. Wolffenstein, R. Chem. Ber. 1895, 28, 2265-2269.
2. (a) Yeager, K. Dangerous innovations. In Trace Chemical Sensing of Explosives; Woodfin, R. L., Ed.; John Wiley & Sons: Hoboken, NJ, 2007.
3. For a discussion of entropic factors in TATP explosions, see: (b) Dubnikova, F.; Kosloff, R.; Almog, J.; Zeiri, Y.; Boese, R.; Itzhaky, H.; Alt, A.; Keinan, E. J. Am. Chem. Soc. 2005, 127, 1146-1159.
4. For a recent review on the detection of peroxide-based explosives, see: Schulte-Labeck, R.; Vogel, M.; Karst, U. Anal. Bioanal. Chem. 2006, 386, 559-565.
5. For an overview of explosive detection methods, see: (a) Trace Chemical Sensing of Explosives; Woodfin, R. L., Ed.; John Wiley & Sons: Hoboken, NJ, 2007.
6. (b) Moore, D. S. Sens. Imaging 2007, 8, 9-38.
7. Itzhaky, H.; Keinan, E. Chem. Abstr. 1999, 131, 172322. Method and kit for the detection of explosives. U.S. Pat. 6,767,717, Jul 7, 2004.
8. A peroxidase-based method for the instrumental fluorescence detection of trace (≤ng) TATP has been reported: Schulte-Labeck, R.; Kolla, P.; Karst, U. Analyst 2002, 127, 1152-1154.
9. For representative reviews of fluorescent chemosensors, see: (a) Callan, J. F.; de Silva, A. P.; Magri, D. C. Tetrahedron 2005, 61, 8551-8588.
10. (b) Bell, T. W.; Hext, N. M. Chem. Soc. Rev. 2004, 33, 589-598.
11. (c) Rurack, K.; Resch-Genger, U. Chem. Soc. Rev. 2002, 31, 116-127.
12. 2, see: (a) Miller, E. V.; Chang, C. J. Curr. Opin. Chem. Biol. 2007, 11, 620-625.
13. (b) Soh, N. Anal. Bioanal. Chem. 2006, 386, 532-543.
14. Phosphines reagents have been developed for the quantification of, e.g., lipid peroxides. As an archetypal example, diphenyl(1-pyrenyl)phosphine, which is nonfluorescent as the result of electron transfer quenching by phosphorus(III), is readily oxidized to the corresponding phosphine oxide, which is strongly fluorescent. See: (a) Akasaki, K.; Ohrui, H. J. Chromatogr., A 2000, 881, 159-170.
15. (b) Akasaki, K. Tohoku J. Ag. Res. 1995, 45, 111-119.
16. (c) Akasaka, K.; Suzuki, T.; Ohrui, H.; Meguro, H. Anal. Lett. 1987, 20, 731745.
17. For other examples, see ref 8. (For conceptually related work coupling the "Staudinger ligation" to a fluorescent signal, see: (f) Lemieux, G. A.; de Graffenried, C. L.; Bertozzi, C. R. J. Am. Chem. Soc. 2003, 125, 4708.)
18. The use of phosphines for the detection of TATP encounters two significant limitations. First, even triphenyl phosphine does not react directly with TATP (Bellamy, A. J. J. Forensic Sci. 1999, 44, 603-608) and, second, in our experience, many phosphine profluorophores are susceptible to rapid aerial oxidation, complicating their isolation and handling (Fang, A. G. Development of novel fluorescent chemosensors. Ph.D. Thesis, University of California, San Diego, La Jolla, CA, 2003).
19. Of particular importance to the present work are fundamental studies on the photochemistry of aryl sulfoxides: (a) Vos, B. W.; Jencks, W. S. J. Am. Chem. Soc. 2002, 124, 2544-2547.
20. (b) Cubbage, J. W.; Jencks, W. S. J. Phys. Chem. A 2001, 105, 10588-10595.
21. (c) Lee, W.; Jencks, W. S. J. Org. Chem. 2001, 66, 474-480.
22. (d) Guo, Y.; Jencks, W. J. J. Org. Chem. 1997, 62, 857-864, and references therein.
23. In support of an R-cleavage pathway in quenching fluorescence from 3b and 4b, we find that broad-spectrum UV irradiation leads to complete decomposition within 30 min, in analogy to the results described in ref 11d. The products formed are consistent with radical fragmentation/ recombination; see Supporting Information.
24. For leading studies on intramolecular electron transfer involving sulfides, see: (a) Görner, H.; Griesbeck, A. G.; Heinrich, T.; Kramer, W.; Oelgemöller, M. Chem. - Eur. J. 2001, 7, 1530-1538.
25. (b) Griesbeck, A. G.; Schieffer, S. Photochem. Photobiol. Sci. 2003, 2, 113-117. To our knowledge, there is no precedent for electron transfer quenching of fluorescence by sulfoxides.
26. See Supporting Information for experimental and spectroscopic details.
27. The C-S bond dissociation energy of dimethyl sulfoxide is estimated as 55 kcal/mol, compared to 68 kcal/mol for dimethyl sulfone. See : Benson, S. W. Chem. Rev. 1978, 78, 23-35.
28. Berlman, I. B. Handbook of Fluorescence Spectra. Academic Press: New York, 1965.
29. 2: (a) Vassell, K. A.; Espenson, J. H. Inorg. Chem. 1994, 33, 5491-5498.
30. (b) Yamazaki, S. Bull. Chem. Soc. Jpn. 1996, 69, 2955-2959.
31. 2) in a quartz cuvette. Fluorescence spectra were recorded over a 90 minute period. A similar procedure was used for the inset picture, but with 10 μL of TATP solution.
32. Similarly, we note that while 3b and 4b are prone to acid-catalyzed hydrolysis, 2b is stable in the presence of acid.
33. The reported colorimetric assay (ref 5) is applicable to mg-quantities of TATP. The method described here is thus more sensitive, and comparable in terms of ease-of-use, although slightly slower. The reported instrument-based fluorescence method (ref 6) for TATP detection is ca. 100-fold more sensitive than the method described here.
34. For a review of sulfoxide coordination chemistry, see: Calligaris, M.; Carugo, O. Coord. Chem. Rev. 1996, 153, 83-154.