Fluorescent-Dye Doped Thin-Film Sensors for the Detection of Alcohol Vapors

Jonathan K. Fong, Royce N. Dansby-Sparks, Adam C. Lamb, Thomas W. Owen, Mohammad Mushfiq, Uma Sampathkumaran, Kisholoy Goswami, Scott L. Jensen, Zi-Ling Xue

Department of Chemistry, University of Tennessee, Knoxville, USA.
InnoSense LLC, Torrance, USA.
NASA John C. Stennis Space Center, Stennis Space Center, USA.

DOI: 10.4236/ajac.2014.59064                

Abstract

Fluorescence sensors based on a trifluoroacetophone compound doped in ethyl cellulose (EC) thin films have been developed for the detection of methanol, ethanol, and 2-propanol (isopropanol, PriOH) vapors. Thin-film sensors are prepared with 4-dibutylamino-4’-(trifluoroacetyl)stilbene (Chromoionophore IX or CIX) as the fluorescent dye and its solution in EC was spin-coated onto glass slides. The luminescence intensity of the dye (555 nm) is quenched when exposed to alcohol vapor. Tested in the range of ca. 0 - 1.5 × 10⁴ ppm (wt) for MeOH and EtOH, and ca. 0 - 2.3 × 10⁴ ppm for PrⁱOH, the sensors gave detection limits of 9, 13, 21 ppm and quantification limits of 32, 43, and 70 ppm, respectively. To enhance the sensitivity of the sensors, TiO₂ particles have been added to the films to induce Mie scattering, which increases the incident light interaction with the sensing films. The sensors in this work have been designed to work in a multianalyte platform for the simultaneous detection of multiple gas analytes.

Keywords

Optical Thin Film Sensors, Chromoionophore IX Dye, Alcohol Vapor Detection

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Costantini, M.G. (1993) Health Effects of Oxygenated Fuels. Environmental Health Perspectives, 101, 151-160. http://dx.doi.org/10.1289/ehp.93101s6151
[2]	Flipsen, B. (2010) Designing Microfuel Cells for Portable Electronics. Journal of Fuel Cell Science and Technology, 7, Article ID: 061014. http://dx.doi.org/10.1115/1.4001352
[3]	http://www.epa.gov/ttn/atw/187polls.html
[4]	Young, J.A. (2006) Methanol. Journal of Chemical Education, 83, 1131. http://dx.doi.org/10.1021/ed083p1131
[5]	http://www.osha.gov/dts/chemicalsampling/data/CH_251600.html
[6]	Finkelstein, Y. and Vardi, J. (2002) Progressive Parkinsonism in a Young Experimental Physicist Following Long-Term Exposure to Methanol. NeuroToxicology, 23, 521-525. http://dx.doi.org/10.1016/S0161-813X(02)00033-5
[7]	Federal Register (2010) Environmental Protection Agency, 68094-68150.
[8]	Torsner, E. (2010) Solving Corrosion Problems in Biofuels Industry. Corrosion Engineering Science and Technology, 45, 42-48. http://dx.doi.org/10.1179/147842209X12579401586726
[9]	Oliverio, N., Jiang, L., Yilmaz, H. and Stefanopoulou, A. (2009) Ethanol Detection in Flex-Fuel Direct Injection Engines Using In-Cylinder Pressure Measurements. SAE International Journal of Fuels and Lubricants, 2, 229-241.
[10]	Zhang, Y., Zhi, Z. and Yang, F. (2010) Highly Sensitive and Selective Alcohol Sensor Based on Ag-Doped In2O3 Coating. Industrial & Engineering Chemistry Research, 49, 3539-3543. http://dx.doi.org/10.1021/ie100197b
[11]	Bangalore, A.S., Small, G.W., Combs, R.J., Knapp, R.B. and Kroutil, R.T. (1994) Automated Detection of Methanol Vapor by Open Path Fourier Transform Infrared Spectrometry. Analytica Chimica Acta, 297, 387-403. http://dx.doi.org/10.1016/0003-2670(94)00241-X
[12]	Criddle, W.J., Parry, K.W. and Jones, T.P. (1987) On-Line Determination of Ethanol during Fermentation Process Using a Fuel Cell Sensor. Analyst, 112, 615-618. http://dx.doi.org/10.1039/an9871200615
[13]	Win, D.T. (2006) Breath Alcohol Testers—Prevents Road Accidents. AU Journal of Technology, 10, 75-80. http://www.journal.au.edu/au_techno/2006/oct06/journalTechV10N2_aticle01.pdf
[14]	Monblanc, P. and Lacan, B. (2005) US Patent No. 6942835 B2.
[15]	Gonzalez, M.H., Araujo, G.C.L., Pelizaro, C.B., Menezes, E.A., Lemos, S.G., Batista de Sousaa, G. and Nogueira, A.R.A. (2008) Coconut Coir as Biosorbent for Cr(VI) Removal from Laboratory Wastewater. Journal of Hazardous Material, 159, 252-256. http://dx.doi.org/10.1016/j.jhazmat.2008.02.014
[16]	Morey, T.E., Booth, M.M., Prather, R.A., Nixon, S.J., Boissoneault, J., Melker, R.J., Goldberger, B.A., Wohltjen, H. and Dennis, D.M. (2011) Measurement of Ethanol in Gaseous Breath Using a Miniature Gas Chromatograph. Journal of Analytical Toxicology, 35, 134-142. http://dx.doi.org/10.1093/anatox/35.3.134
[17]	Gessei, T., Sato, H., Kazawa, E., Kudo, H., Saito, H. and Mitsubayashi, K. (2009) Bio-Sniffers for Ethanol and Acetaldehyde Using Carbon and Ag/AgCl Coated Electrodes. Microchimica Acta, 165, 179-186. http://dx.doi.org/10.1007/s00604-008-0117-z
[18]	NASA Stennis Space Center (2007) Environmental Assessment for the Construction and Operation of the Constellation Program A-3 Test Stand. http://www.ssc.nasa.gov/environmental/docforms/eas/eas.html
[19]	Tejwani, G.D., McVay, G.P., Langford, L.A. and St. Cyr, W.W. (2006) Planning for Plume Diagnostics for Ground Testing J-2X Engines at the SSC. Stennis Space Center, NASA. http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20100003145_2010002997.pdf
[20]	http://www.osha.gov/dts/chemicalsampling/data/CH_248400.html
[21]	Dhillon, S. and von Burg, R. (1995) Isopropyl Alcohol. Journal of Applied Toxicology, 15, 501-506. http://dx.doi.org/10.1002/jat.2550150612
[22]	Jones, A.W. (1992) Driving under the Influence of Isopropyl. Clinical Toxicology, 30, 153-155. http://dx.doi.org/10.3109/15563659208994457
[23]	Stevens, N. and Akins, D.L. (2007) Dye-Doped Inorganic/Organic Composite Films as Fluorescence Sensors for Methanol Vapor. Sensors and Actuators B, 123, 59-64. http://dx.doi.org/10.1016/j.snb.2006.07.021
[24]	Pang, F., Han, X., Chu, F., Geng, J., Cai, H., Qu, R. and Fang, Z. (2007) Sensitivity to Alcohols of a Planar Waveguide Ring Resonator Fabricated by a Sol-Gel Method. Sensors and Actuators B, 120, 610-614. http://dx.doi.org/10.1016/j.snb.2006.03.031
[25]	McCorkle, D.L., Warmack, R.J., Patel, S.V., Mlsna, T., Hunter, S.R. and Ferrell, T.L. (2005) Ethanol Vapor Detection in Aqueous Environments Using Micro-Capacitors and Dielectric Polymers. Sensors and Actuators B, 107, 892-903. http://dx.doi.org/10.1016/j.snb.2004.12.051
[26]	Stich, M.I.J., Fischer, L.H. and Wolfbeis, O.S. (2010) Multiple Fluorescent Chemical Sensing and Imaging. Chemical Society Reviews, 39, 3102-3114. http://dx.doi.org/10.1039/b909635n
[27]	Holthoff, E.L. and Bright, F.V. (2007) Molecularly Imprinted Xerogels as Platforms for Sensing. Accounts of Chemical Research, 40, 756-767. http://dx.doi.org/10.1021/ar700087t
[28]	Maffei, F., Betti, P., Genovese, D., Montalti, M., Prodi, L., Zorzi, R.D., Geremia, S. and Dalcanale, E. (2011) Highly Selective Chemical Vapor Sensing by Molecular Recognition: Specific Detection of C1-C4 Alcohols with a Fluorescent Phosphonate Cavitand. Angewandte Chemie International Edition, 50, 4654-4657.
[29]	Tonezzer, M., Quaranta, A., Maggioni, G., Carturan, S. and Mea, G.D. (2007) Optical Sensing Responses of Tetraphenyl Porphyrins toward Alcohol Vapours: A Comparison between Vacuum Evaporated and Spin-Coated Thin Films. Sensors and Actuators B: Chemical, 122, 620-626. http://dx.doi.org/10.1016/j.snb.2006.07.009
[30]	Zhang, Z.H., Lockwood, R., Veinot, J.G.C. and Meldrum, A. (2013) Detection of Ethanol and Water Vapor with Silicon Quantum Dots Coupled to an Optical Fiber. Sensors and Actuators B: Chemical, 181, 523-528. http://dx.doi.org/10.1016/j.snb.2013.01.070
[31]	Mohr, G.J., Citterio, D. and Spichiger-Keller, U.E. (1998) Development of Chromogenic Reactands for Optical Sensing of Alcohols. Sensors and Actuators B, 49, 226-234. http://dx.doi.org/10.1016/S0925-4005(98)00132-4
[32]	Mohr, G.J. and Spichiger-Keller, U.E. (1997) Novel Fluorescent Sensor Membranes for Alcohols Based on p-N,N-di- octylamino-4’-Trifluoroacetylstilbene. Analytica Chimica Acta, 351, 189-196. http://dx.doi.org/10.1016/S0003-2670(97)00365-6
[33]	Mohr, G.J., Lehmann, F., Grummt, U. and Spichiger-Keller, U.E. (1997) Fluorescent Ligands for Optical Sensing of Alcohols: Synthesis and Characterisation of p-N,N-dialkylamino-Trifluoroacetylstilbenes. Analytica Chimica Acta, 344, 215-225. http://dx.doi.org/10.1016/S0003-2670(97)00113-X
[34]	Wriedt, T. (1998) A Review of Elastic Light Scattering Theories. Particle & Particle Systems Characterization, 15, 67-74. http://dx.doi.org/10.1002/(SICI)1521-4117(199804)15:2<67::AID-PPSC67>3.0.CO;2-F
[35]	Carrington, N.A., Thomas, G.H., Rodman, D.L., Beach, D.B. and Xue, Z.L. (2007) Optical Determination of Cr(VI) Using Regenerable, Functionalized Sol-Gel Monoliths. Analytica Chimica Acta, 581, 232-240. http://dx.doi.org/10.1016/j.aca.2006.08.032
[36]	Allain, L.R. and Xue, Z.L. (2000) Optical Sensors for the Determination of Concentrated Hydroxide. Analytical Chemistry, 72, 1078-1083. http://dx.doi.org/10.1021/ac990908b
[37]	Canada, T.A. and Xue, Z.L. (2002) High-Basicity Determination in Mixed Water-Alcohol Solutions by a Dual Optical Sensor Approach. Analytical Chemistry, 74, 6073-6079. http://dx.doi.org/10.1021/ac0202987
[38]	Fong, J.K. and Xue, Z.L. (2013) A Dye-Doped Optical Sensor for the Detection of Biodiesel in Diesel. Chemical Communications, 49, 9015-9017. http://dx.doi.org/10.1039/c3cc43958e
[39]	Dansby-Sparks, R.N., Jin, J., Mechery, S.J., Sampathkumaran, U., Owen, T.W., Yu, B.D., Goswami, K., Hong, K., Grant, J. and Xue, Z.L. (2010) Fluorescent-Dye-Doped Sol-Gel Sensor for Highly Sensitive Carbon Dioxide Gas Detection below Atmospheric Concentrations. Analytical Chemistry, 82, 593-600. http://dx.doi.org/10.1021/ac901890r
[40]	Dean, J.A. (1999) Lange’s Handbook of Chemistry. 15th Edition, McGraw-Hill, New York, 5.30.
[41]	Nakata, K., Sakai, M., Ochiai, T., Murakami, T., Takagi, K. and Fujishima, A. (2012) Fabrication and Characterization of Self-Organized Porous TiO2 Particle Layers. Materials Letters, 70, 160-162. http://dx.doi.org/10.1016/j.matlet.2011.12.016
[42]	You, J.H. and Hsu, K.Y. (2010) Preparation of Submicron-Sized Porous Titanium Oxide Particles by the Swelling Process. Chemical Engineering Research and Design, 88, 1049-1056. http://dx.doi.org/10.1016/j.cherd.2010.01.033
[43]	DuPont’s R706 Product Sheet.
[44]	AlcoMate AL-7000 Product Sheet. http://alcomate.net/prodmanuals/manual_Premium.pdf
[45]	AlcoHawk Precision Product Sheet. http://www.q3i.com/pdfs/AlcoHAWK-Precision-Datasheet.pdf
[46]	Bactrack S30 Product Sheet. http://www.bactrack.com/breathalyzer/images/s30-ownersmanual.pdf
[47]	Schmidt, E.W. and Wucherer, E.J. (2004) Hydrazine(s) vs. Nontoxic Propellants—Where Do We Stand Now? In: Wilson, A., Ed., Proceedings of the 2nd International Conference on Green Propellants for Space Propulsion (ESA SP-557), Chia Laguna (Cagliari), Sardinia, 7-8 June 2004. http://adsabs.harvard.edu/full/2004ESASP.557E...3S
[48]	Plemmons, D.H., Mehta, M., Clark, B.C., Kounaves, S.P., Peach Jr., L.L., Renno, N.O., Tamppari, L. and Young, S.M.M. (2008) Effects of the Phoenix Lander Descent Thruster Plume on the Martian Surface. Journal of Geophysical Research, 113, Article ID: E00A11. http://dx.doi.org/10.1029/2007JE003059
[49]	Taylor, L. and Oberman, S. (2006) Drunk Driving Defense. 6th Edition, Aspen, New York.
[50]	Mohr, G.J., Citterio, D., Demuth, C., Fehlmann, M., Jenny, L., Lohse, C., Moradian, A., Nezel, T., Rothmaier, M. and Spichiger, U.E. (1999) Reversible Chemical Reactions as the Basis for Optical Sensors Used to Detect Amines, Alcohols, and Humidity. Journal of Materials Chemistry, 9, 2259-2264. http://dx.doi.org/10.1039/a901961h
[51]	Federal Register (2008) National Highway Traffic Safety Administration, 16956-16960.
[52]	Jones, A.W. and Anderson, L. (2008) Determination of Ethanol in Breath for Legal Purposes Using a 5-Filter Infrared Analyzer: Studies on Response to Volatile Interfering Substances. Journal of Breath Research, 2, 7152-7155. http://dx.doi.org/10.1088/1752-7155/2/2/026006
[53]	Watterson, J.H. (2009) Assessment of Response of the Intoxilzyer 8000C to Volatiles of Forensic Relevance in Vitro, Part I: Acetone, Isopropanol, and Methanol. Journal of Analytical Toxicology, 33, 109-117. http://dx.doi.org/10.1093/jat/33.2.109
[54]	Conkle, J.P., Camp, B.J. and Welch, B.F. (1975) Trace Composition of Human Respiratory Gas. Archives of Environmental Health: An International Journal, 30, 290-295. http://dx.doi.org/10.1080/00039896.1975.10666702
[55]	Prest, L. (2011) Fundamental Investigation of Fuel Cell-Based Breath Alcohol Sensors and the Cause of Sensor Degradation in Low-Humidity Conditions. M.S. Thesis, University of Ontario Institute of Technology, Oshawa.
[56]	Jones, A.W. and Roessner, S. (2007) False-Positive Breath-Alcohol Test after a Ketogenic Diet. International Journal of Obesity, 31, 559-561. http://dx.doi.org/10.1038/sj.ijo.0803444
[57]	Loudon, G.M. (1995) Organic Chemistry. 3rd Edition, Benjamin/Cummins Publishing Company, San Francisco, 654.
[58]	Logan, B.K. and Distefano, S. (1998) Ethanol Content of Various Food and Soft Drinks and Their Potential for Interference with a Breath-Alcohol Test. Journal of Analytical Toxicology, 22, 181-183. http://dx.doi.org/10.1093/jat/22.3.181