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(12) Patent Application Publication (10) Pub. No.: US 2005/0101026A1 Sailor Et Al US 2005O101026A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0101026A1 Sailor et al. (43) Pub. Date: May 12, 2005 (54) PHOTOLUMINESCENT POLYMETALLOLES Publication Classification AS CHEMICAL SENSORS (76) Inventors: Michael J. Sailor, La Jolla, CA (US); (51) Int. Cl." ..................................................... G01N 21/64 William C. Trogler, Del Mar, CA (52) U.S. Cl. ............................................ 436/106; 436/172 (US); Honglae Sohn, Gwangiu (KR); Rebecca M. Calhoun, Austin, TX (US) Correspondence Address: (57) ABSTRACT Steven P. Fallon GREER, BURNS,& CRAIN, LTD. A method to develop inexpensive inorganic polymeric Sen Suite 2500 Sors that can provide a Sensitivity and Selectivity for explo 300 South Wacker Drive Sive nitroaromatic compounds. Selectivity is provided by the Chicago, IL 60606 (US) arrays of 12 different reactive fluorescent Sensors to mimic the human olfactory System. The Sensors are based on (21) Appl. No.: 10/244,053 photoluminescence quenching of polymers containing met alloid-metalloid backbones Such as Si-Si, Si-Ge, or Ge-Ge. (22) Filed: Sep. 14, 2002 The Sensor employs a thin film of photoluminescent copoly Related U.S. Application Data mers, which is Stable in air, water, acids, common organic Solvents, and even Seawater containing bioorganisms. The (60) Provisional application No. 60/322.908, filed on Sep. detection method involves measurement of the quenching of 15, 2001. photoluminescence of the polysilole by the analyte. Patent Application Publication May 12, 2005 Sheet 1 of 23 US 2005/0101026A1 Figure 1 Patent Application Publication May 12, 2005 Sheet 2 of 23 US 2005/0101026A1 o o'-it' Figure 2 Patent Application Publication May 12, 2005 Sheet 3 of 23 US 2005/0101026 A1 it is is sis Wavelength Figure 3 Patent Application Publication May 12, 2005 Sheet 4 of 23 US 2005/0101026A1 Figure 4 Figure 5 Patent Application Publication May 12, 2005 Sheet 5 of 23 US 2005/0101026 A1 350 400 450 500 550 600 650 Wavelength (nm) Figure 6 Patent Application Publication May 12, 2005 Sheet 6 of 23 US 2005/0101026A1 350 400 450 500 550 600 650 Wavelength (nm) Patent Application Publication May 12, 2005 Sheet 7 of 23 US 2005/0101026 A1 3 2 O 000E-00 100E-04 200-04 Conc ( O.OOE-00 SOOE-05 OOE-04 1 SOE-04 200-04 Conc, (M 0.00E+00 1 00-04 200-04 Conc (f b Figure 8 0.00+00 200E-05 4 00-05 600E-05 800-05 100E-04 Conc (M 0 00E-00 1,00E-04 200E-04 Conc (h C 0.00E--00 20OE-05 4 OOE-05 8 OOE-05 8 OOE-05 1 OOE-04 Conc. (M Patent Application Publication May 12, 2005 Sheet 8 of 23 US 2005/0101026 A1 0.8 0.6 - 0.4 0 u -1 0.3 - u: .-1 ux -6 -x O.2 - to:- u-x -31 ul-K -- 0.1 - () - so --- -- O 2- --- - -- 0.00E+00 4.00E-05 8.OOE-05 1.20E-04 16OE-04 TNT (M) Figure 9 Patent Application Publication May 12, 2005 Sheet 9 of 23 US 2005/0101026A1 Figure 10 S Figure 11 polymers Patent Application Publication May 12, 2005 Sheet 10 of 23 US 2005/0101026A1 Figure 12 Patent Application Publication May 12, 2005 Sheet 11 of 23 US 2005/0101026 A1 Reduction Potential (V vs NHE) Figure 13 Patent Application Publication May 12, 2005 Sheet 12 of 23 US 2005/0101026A1 0.7 0.6 0.5 0.4 0.3 0.2 0.1 ppm Figure 14 Green light out hy A y y Polymetalioles TN y y --TN S/N-NY,O c CB -- Quenching PL R (M. SSV VBuse N LUM CH -a HOMO hy A hy A UV light in Figure 15 Patent Application Publication May 12, 2005 Sheet 13 of 23 US 2005/0101026 A1 400 450 500 550 600 650 Wavelength (nm) Figure 16 Patent Application Publication May 12, 2005 Sheet 14 of 23 US 2005/0101026A1 Patent Application Publication May 12, 2005 Sheet 15 of 23 US 2005/0101026A1 øº|øº ZON~~~~OºH ?ON ZOZO SSSOºHSSS LNG-?y'zgNG-C'?, !No.rsN?OZON euqueu??uuoIÂu?ºL ZONZON 1^ON|Z 8IºInáH ZO Patent Application Publication May 12, 2005 Sheet 16 of 23 US 2005/0101026A1 Patent Application Publication May 12, 2005 Sheet 17 of 23 US 2005/0101026A1 N Patent Application Publication May 12, 2005 Sheet 18 of 23 US 2005/0101026A1 2. 5. { 2 A.2. , i Patent Application Publication May 12, 2005 Sheet 19 of 23 US 2005/0101026 A1 O r O N er WO C O E. -- o & Se &CN 9 dCn as C -- NX en S e 2 D s bu Patent Application Publication May 12, 2005 Sheet 20 of 23 US 2005/0101026A1 N Kai-stay ºmejisqnSIS 9.InáH12QçZ Patent Application Publication May 12, 2005 Sheet 21 of 23 US 2005/0101026A1 & O Or) ed O - O C, SN ORC ?h N + OCN 2 fr 15 Y N () CM) &o vs.N S 1. C 2 e t O L- S. g s t OCVS CS2 & lf) CMO l a? O- N. SNO 2 or vu 1. Patent Application Publication May 12, 2005 Sheet 22 of 23 US 2005/0101026A1 i Patent Application Publication May 12, 2005 Sheet 23 of 23 US 2005/0101026 A1 US 2005/0101026 A1 May 12, 2005 PHOTOLUMNESCENT POLYMETALLOLES AS diffraction (Luggar, R. D., Farquharson, M. J.; Horrocks, J. CHEMICAL SENSORS A.; Lacey, R. J. J. X-ray Spectrotm. 1998, 27, 87-94), neutron activation analysis, electron capture detection 0001. This work is supported by the National Science (Rouhi, A. M. Chem. Eng. News 1997, 75, 14-22), and Foundation (Grant CHE-0111376) and DARPA's Tactical cyclic voltammetry (Krausa, M.; Schorb, K. J. Electroanal. Sensors Program via a Space and Naval Warfare Systemns Chem. 1999, 461, 10-13). These techniques are highly Center Contract (>66001-98-C-8514). Selective, but Some are expensive and others not easily BACKGROUND OF THE INVENTION fielded in a Small, low-power package. 0008 Most detection methods for explosives are only 0002) 1. Field of the Invention applicable to air Samples due to interference problems 0003. The present invention relates, in general, chemical encountered in complex aqueous media. Sensing TNT and Sensing and, more particularly, to improved chemical Sen picric acid in groundwater or Seawater is important for the sors providing both selectivity and high sensitivity. Most detection of buried unexploded ordnance and for locating particularly, the present invention relates to polySole undenwater mines (Skiver-Lake, L. C.; Donner, B. L.; Ligler, F. S. Environ. Sci. Technol. 1997, 31, 837-841; Lu, J.; 0004 2. Description of Related Adt Zhang, Z. Analytica Chimica Acta 1996, 318, 175-179). 0005 Detecting hazardous chemicals in our environment There are also environmental applications for characterizing is fundamental to economic development, national Security soil and groundwater contaminated with toxic TNT at mili and the quality of life. The ever-increasing demand for better tary bases and munitions production and distribution facili Sensing or detection technologies to address needs in many ties (Approaches for the remediation of federal facility sites different areas, including but not limited to, Such as the contaminated with explosive or radioactive wastes. U. S. detection of concealed explosives in airports, land and water Environmental Protection Agency: Washington, D.C., mines, chemical agents that are extremely hazardous at trace 1993). Organic polymers and optical fibers (Albert, K. J.; levels, or industrial toxic waste produced by chemical Myrick, M. L.; Brown, S. B., James, D. L.; Milanovich, F. plants. To be effective, a chemical Sensing technology must P.; Walt, D. R. Environ. Sci. Technol. 2001, 35,3193-3200) provide a high degree of Sensitivity Selectivity, Stability, have been previously Studied to detect vapors of explosive robustneSS and portability. Significant advances in the cur analytes (McQuade, D. T.; Pullen, A. E.; Swager, T. M. rent chemical Sensing technology will be immeasurably Chem. Rev. 2000, 100, 2537-2574; Albert, K.J.; Lewvis, N. beneficial to national and global needs. S.; Schauer, C. L.; Sotzing, G. A.; Stitzel, S. E.; Vaid, T. P.; Walt, D. R. Chem. Rev. 2000, 100, 2595-2626). The trans 0006. Of the many transduction mechanisms existing for duction methods used include absorption, fluorescence, con chemical Sensing, optical absorption, in particular, is widely ductivity, etc. Such simple techniques are promising because used. Although the ultimate Sensitivity of an optical absorp they can be incorporated into inexpensive and portable tion measurement is limited by quantum noise arising from microelectronic devices. For example, a chemically Selective the discrete nature of light, this limit is rarely achieved in Silicone polymer layer on a SAW (Surface acoustic wave) practice. device has been shown to provide efficient detection for the 0007 Chenical sensors for nitroaromatics (NcOuade, D. nitroaromatic compounds (McGill, R. A.; Misna, T. E.; T; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000, 100, Mowery, R. In IEEE International Frequency Control Sym 2537-2574; Albert, K. J.; Lewis, N. S.; Schauer, C. L.; posium, 1998, pp 630-633). Recently, it was reported that Sotzing, G. A.; Stitzel, S. E.; Vaid, T. P.; Walt, D. R. Chem. the fluorescence of pentiptycene polymers (Yang, J. S.; Re: 2000, 100, 2595-2626), which offer new approaches to Swager, T. M. J. Am. Chem. Soc. 1998, 120, 5321-5322:; the rapid detection of ultra-trace analytes from explosives, Yang, J. S.; Swager, T. M. J. Am. Chem. Soc. 1998, 120, have attracted a great deal of attention in recent years, 11864-11873) and polyacetylene (Liu, Y.; Mills, R. C.; because explosives are important chemical Species to detect Boncella, J.
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