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Ar. Qsosi I 300O H H 4, N ^\= E 200 - 100 O - 250 300 350 400 450 500 550 Wavelength (Nm) US 8,557,595 B2 Page 2 US008557595 B2 (12) United States Patent (10) Patent No.: US 8,557,595 B2 Trogler et al. (45) Date of Patent: Oct. 15, 2013 (54) FLUORESCENCE DETECTION OF (56) References Cited NITROGEN-CONTAINING EXPLOSIVES AND BLUE ORGANIC LED U.S. PATENT DOCUMENTS (75) Inventors: William C. Trogler, Del Mar, CA (US); 5,063,297 A 1 1/1991 Hardenbrook Jason Sanchez, The Woodlands, TX 5,115,459 A 5/1992 Bertozzi (US) (Continued) (73) Assignee: The Regents of the University of FOREIGN PATENT DOCUMENTS California, Oakland, CA (US) WO WOO2.38653 A1 5, 2002 WO WO 2005-047363 5, 2005 *) NotOt1Ce: Subjubject to anyy d1Sclaimer,disclai theh term off thisthi patent is extended or adjusted under 35 OTHER PUBLICATIONS U.S.C. 154(b) by 320 days. Korshak, V. V. et al., Russian Chemical Bulletin 1962, 11, 2153 (21) Appl. No.: 12/523,104 2155.* (22) PCT Filed: Jan. 29, 2008 (Continued) (86). PCT No.: PCT/US2O08/OO1193 Primary Examiner — Arlen Soderquist S371 (c)(1) (74) Attorney, Agent, or Firm — Greer, Burns & Crain Ltd. C s (2), (4) Date: Mar. 11, 2010 (57) ABSTRACT (87) PCT Pub. No.: WO2008/140635 The invention provides a sensor for detecting nitrogen con taining high explosives. The sensor includes a Substrate and a PCT Pub. Date: Nov. 20, 2008 blue-photoluminescent metallofluorene copolymer to be car O O ried on said Substrate during testing for nitrogen containing (65) Prior Publication Data high explosives. The copolymer is preferably a blue-photo US 2010/0173420 A1 Jul. 8, 2010 luminescent metallofluorene copolymer, and preferably is a Related U.S. Application Data vinyl bridged silafluorene copolymer. A method for detecting nitrogen containing high explosives involves exposing a (60) Provisional application No. 60/897.988, filed on Jan. copolymer to an analyte, preferably by spraying the copoly 29, 2007. mer or otherwise coating the substrate after it has been exposed to analyte and then exciting the copolymer to lumi (51) Int. Cl. nesce. The copolymer is observed for fluorescence quench GOIN 33/22 (2006.01) ing, which can be through human or electronic observation. GOIN 2L/64 (2006.01) The invention also provides for synthesis of a vinyl bridged (52) U.S. Cl. silafluorene polymer by providing diethynylmetallofluorene USPC ..... 436/106; 422/425; 422/82.06; 422/82.07; and dihydrosilafluorene as precursors and conducting cata 422/82.08: 436/107:436/166; 436/167; 436/172 lytic hydrosilation of the precursors. In a blue emitting (58) Field of Classification Search organic light emitting diode of the invention, an emitting USPC .......... 436/106-107,166-167, 172: 422/400, layer is blue-photoluminescent metallofluorene copolymer. 422/425, 82.05-82.08 See application file for complete search history. 24 Claims, 4 Drawing Sheets 800 700 - 12 O 14 600 l l l talyti s 500 - Si -- Si --ar. QSOSi i 300o H H 4, N ^\= E 200 - 100 O - 250 300 350 400 450 500 550 Wavelength (nm) US 8,557,595 B2 Page 2 (56) References Cited Chen, J. et al, Macromolecules 2003, 36,4319-4327.* Lam, J. W.Y. et al. Macromolecular Symposia 2003, 196, 29-89 U.S. PATENT DOCUMENTS 3OO.* Yamashita, H. etal, Polymer 2003, 44, 7089-7093.* 5,162,478 A * 1 1/1992 Barton et al. ................... 528/15 Law, C. C. W. et al. Journal of Inorganic and Organometallic Poly 5,498,736 A * 3/1996 Tamao et al. ................. 556,406 mers 2004, 14, 39-51.* 6,169,193 B1 1/2001 West et al. Saxena, A. etal, Chemistry of Materials 2005, 17, 2181-2185.* 6,376,694 B1 4/2002 Uchida et al. Chan, K. L. et al. Journal of the American Chemicall Society 2005, 2003/01OO123 A1 5, 2003 Schanzeet al. 127, 7662-7663.* 2003/01786O7 A1 9/2003 Swager et al. 2004/O1552O2 A1 8, 2004 Poteet Lee, S. H. et al. Journal of the American Chemicall Society 2005, 2005/0101026 A1 5, 2005 Sailor et al. 127,907 1-9078.* 2007/0248839 A1 * 10, 2007 Towns et al. .................. 428,690 Chen, R.-F. et al. Synthetic Metals 2006, 156, 1161-1167.* 2009/O137059 A1 5/2009 Trogler et al. Albizane, A., et al., Organolithium Route to Poly(arylsilane)s, Poly 2010/0291698 A1* 1 1/2010 Trogler et al. ................ 436,110 mer International 26 (1991), pp. 93-96. Benfarimo, N., et al., Synthesis and Characterization of Luminescent OTHER PUBLICATIONS Polymers of Distyryibenzenes with Oligo(ethylene glycol) Spacers, Macromolecules, vol. 31, No. 11 (1998), pp. 3595-3599. Luneva, L. K. etal, Russian Chemical Bulletin 1968, 17, 160-163. Carre, M.C., et. al. “Fluorimetric nitrite analysis using 2. Corriu, R. J. P. et al. Journal of Polymer Science: Part C: Polymer 3-diaminonapthalene: an improvement of the method'. Analusis, Letters 1990, 28,431-437.* 1999, 27, p. 835-838. Pang, Y. etal, Macromolecules 1993, 26, 5671-5675.* Damiani, P., et. al. "Fluorimetric Determination of Nitrite', Talainta, Chauhan, B. P. S. et al., Chemistry Letters 1997, 785-786.* vol. 33, No. 8, pp. 649-652; 1986. Ohshita, J. et al. Acta Polymerica 1998, 49, 379-403.* Sohn, H., et al., “Detection of Nitroaromatic Explosives Based on Toal, S.J. et al. Organometallics 2005, 24, 3081-3087.* Photoluminescent Polymers Containing Metalloles”. J. Am. Chem. Toal, S.J. et al., Chemical Communications 2005, 465-467. Soc., vol. 125, No. 13 (2003), pp. 3821-3830. Kim, J. H. et al. Bulletin of the Korean Chemical Society 2006, 27. Sohn, H. et al., “Detection of TNT and Picrick Acid on Surfaces and 869-874. in Seawater by Using Photoluminescent Polysiloles'. Angew Chem. Wang, E. etal, Journal of Materials Chemistry 2006, 16,4133-4140.* Int. Ed., vol. 40, No. 11 (2001), pp. 2104-2105. Toal, S.J. et al. Journal of Forensic Science 2007, 52, 79-83.* Yang, J., et al., “Fluorescent Porous Polymer Films as TNT Chang, L. S. et al. Organometallics 1989, 8, 1885-1893.* Chemosensors: Electronic and Structural Effects', J. Am. Chem. Takahashi, T. etal, Journao of the American Chemical Society 1991, Soc., vol. 120 (1998), pp. 11864-11873. 113, 8564-8566.* Yang.J., et al., “Porous Shape Persistent Fluorescent Polymer Films: Corriu, R. J.-P. etal, Journal of Organometallic Chemistry 1993, 456, An Approach to TNT Sensory Materials”. J. Am. Chem. Soc., vol. 120 35-39.* (1998), pp. 5321-5322. Rushkin, I. L. et al, Macromolecules 1996, 29, 5784-5787.* Toal. Sarah J., et al. Polymer Sensors for Nitroaromatic Explosives Kim. D. S. et al. Journal of Polymer Science A: Polymer Chemistry Destection, Journal of Materials Chemistry, 2006, pp. 2871-2883. 1999, 37, 2933-2940.* Sanchez, Jason C. et al., “Synthesis, Luminescence Properties and Buriak, J. M. etal, Journal of the American Chemical Society 1999, Explosives with 1,1-Tetraphenylsilole- and 1,1-Silafluorene 121, 11491-11502.* vinylene Polymers”, Chem. Mater. 2007, 19, 6459-6470. Tamao, K. et al. Journal of Organometallic Chemistry 2000, 611, 5-11.* * cited by examiner U.S. Patent Oct. 15, 2013 Sheet 1 of 4 US 8,557,595 B2 V C r v Na *\. g C S. S 3 s O 4. o- NaC.Y. f -- CN t ve CfO U.S. Patent Oct. 15, 2013 Sheet 2 of 4 US 8,557,595 B2 U.S. Patent Oct. 15, 2013 Sheet 3 of 4 US 8,557,595 B2 U.S. Patent Oct. 15, 2013 Sheet 4 of 4 US 8,557,595 B2 5 s : 3 US 8,557,595 B2 1. 2 FLUORESCIENCE DETECTION OF Many conventional chemical sensors are not amenable to NITROGEN-CONTAINING EXPLOSIVES AND manufacture as inexpensive, low-power portable devices. BLUE ORGANIC LED Typical chemical sensing methods are limited to vapor phase detection, which is disadvantageous given the low volatility of many explosives. Nitroaromatic explosives such as TNT PRIORITY CLAIMAND REFERENCE TO 5 have moderate vapor pressures (7x10. Torrat room tempera RELATED APPLICATION ture), but at low surface concentrations, the vapor concentra tion of TNT molecules is significantly lower than its equilib The application claims priority under 35 U.S.C. S 119 from rium vapor pressure. Nitramine high explosives, such as RDX prior provisional application Ser. No. 60/897.988, which was (cyclotrimethylenetrinitramine, also known as cyclonite, filed on Jan. 29, 2007. 10 hexogen, and T4) and HMX (cyclotetramethylene-tetranitra mine) have substantially lower vapor pressures (5x10 and STATEMENT OF GOVERNMENT INTEREST 8x10' Torr, respectively) than TNT, which makes vapor detection of these compounds very difficult. Vapor concen This invention was made with government Support under trations can be up to six times lower than TNT when these F49620-02-1-0288 awarded by Air Force Office of Scientific 15 compounds are enclosed in a bomb or mine casing, or when Research. The government has certain rights in the invention. they are present in a mixture with other explosives. The broad array of nitrogen-based explosives has rendered it difficult to FIELD provide a single method whereby multiple types of explosives may be detected. A field of the invention is analyte detection. Another field While efficient explosives detection has always been a of the invention is light emitting diodes. Example applica predominating concern, there exists a renewed urgency for tions of the invention include safety Screenings, such as development of rapid and highly sensitive detection of screenings of cargo, facilities or people, and forensic inves organic, nitrogen-based explosives, including nitroaromatic tigations. compounds, nitramine-based explosives and nitrate ester 25 based explosives. In addition to detecting TNT, for example, BACKGROUND detection of the nitrogen-based plastic explosives compounds associated with improvised explosives devices (IEDs), namely RDX and PETN (pentaerythritol tetranitrate), has Chemical sensors can be used to detect ultra-trace explo life-saving applications in a vastarray of applications, such as sive analytes.
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