1. Fast Qualitative Determination of Over-the-Counter Drugs and Cosmetics Roberto Fernandez-Maestre; Abu B. Kanu; Prabha Dwivedi; and Herbert H. Hill, Jr. Department of Chemistry, Washington State University, Pullman WA 99164-4630, USA Conclusions Introduction Results Ion mobility spectrometry (IMS) was used to determine mobility spectra’s of common over-the-counter drugs and cosmetics. The analysis was performed in a home-built µ-spray ionization IMS. Instrument conditions summary: µ-spray voltage 12,500 V; Ion drift voltage 8,480 V; Pullman atmospheric pressure 691-697 Torr; drift gas temperature, 189.5 0 C; drift length 17.4 cm. Successful implementation of µ-spray ionization IMS technology may lead to a simple and practical instrumentation that can be used for fast qualitative determination of over-the-counter drugs and cosmetics. Stand alone IMS was first introduced in 1970. Over the last couple of decades IMS has grown to become an important analytical separation technique. IMS has been found to be easy to use, and temporarily fast – it separates ions in the millisecond time-scale, compared to techniques like gas chromatography, liquid chromatography and capillary electrophoresis that separates compounds in the minutes time-scale. IMS is mechanically robust and very sensitive to a wide range of applications (explosive residue detection, illicit drug residue detection, chemical warfare agent detection, environmental monitoring, biological elucidation, industrial process control, space shuttle cabin monitoring, and workplace monitoring). The success of most of these applications was due to the development of high-resolution IMS mass spectrometry with resolving powers exceeding that of liquid chromatography and rivaling those of gas chromatography. The goal of this research was to develop a stand alone IMS that can be used for fast qualitative and quantitative determinations of a wide class of chemical compounds. This work describes the application of µ-spray IMS to the qualitative determination of over-the- counter drugs and cosmetics. Experimental Acknowledgements Figure 1: Photograph of the home built µ-spray IMS instrument. Figure 2: IMS spectra of µ-spray solvent and pain/fever relievers. Reduced mobilities (cm 2 V -1 s -1 ) of the major peaks are shown on the spectra. Sample preparation: Solid samples were ground into powder and dissolved in water. Oils, colognes, and creams were dissolved in methanol. All solutions were then prepared to achieve a µ-spray solvent composition of 49.5% methanol, 49.5% water, and 1% acetic acid. Analysis were performed in the positive ion mode IMS. Procedure: Mixtures of over- the-counter drugs and cosmetics were sprayed into the IMS to determine their mobility spectra. Table 1 is a summary of the instrumental conditions used in this investigation. This work demonstrated that µ-spray IMS may be a viable alternative for the fast qualitative determination of over-the-counter drugs and cosmetics. Analysis time excluding sample preparation was in the milliseconds time scale. Combination of a fast detection and low cost technique specific to IMS instrumentation makes this approach an attractive alternative to techniques like liquid chromatography for the determination of over- the-counter drugs and cosmetics. The work was supported partially by the EPA (Grant Number, X-97031101- 0). Further Work References Overview Identification of active ingredients responsible for the major reduced mobility peaks in each spectra. Use active ingredients standards to calibrate and determine concentrations of major reduced mobility peaks. ParameterSettings Reaction region length5.4cm Drift tube length17.4cm ESI voltage12500V Voltage at front of tube9500V Gate voltage8480V Potential closing gate±50V Aperture (last ring) voltage205V Drift tube pressure694 ± 3Torr Drift gas temperature189.5 0C0C ESI flow1µl min -1 Drift flow1000ml min -1 Gasnitrogen IMS gate pulse frequency40Hz IMS scan time35ms IMS gate pulse width150µs Table 1: Summary of instrumental condition for the home built µ-spray IMS instrument. Table 2: Summary of active ingredients and reduced mobilities for over-the-counter drugs and cosmetics. over-the-counter component Active IngredientsReduced mobility (cm 2 V -1 s -1 ) µ-spray solventmethanol, water, acetic acid2.56; 2.01; 1.68 Ibuprofenibuprofen2.04; 1.93; 1.69; 1.55; 1.47; 1.38; 1.22 Tylenol extra strengthacetaminophen1.40 Tylenol PMacetaminophen, diphenhydramine1.40; 1.15 Hydrocodonehydrocodone bitartate, acetaminophen1.92; 1.73; 1.55; 1.30; 1.09 Nyquil night timeacetaminophen, pseudoephedrine HCl etc.1.14; 1.01; 0.94; 0.88; 0.82; 0.78; 0.74 Fish oilfish oil concentrate, gelatin, glycerin0.97 Cephalexin antibioticcephalexin1.10 Sulphameth/trimeth antibioticsulphamethoxazole, trimethoprim2.38; 2.03; 1.76; 1.69; 1.56; 1.10 Echinacea Herbechinacea engustifoia, echinacea pallida1.95; 1.74; 1.37; 1.09 Mega men sportvitamins A, C, E, D, K, B-6, B-12, thiamin etc. 1.70; 1.51; 1.28; 1.16; 1.01 Jovan musk cologneSD alcohol 39-C, fragrance, benzophenone- 2 1.32; 1.13 Lavender cologneFragrance, lavender oil, rosewood oil etc.1.32 Vitamin Ed-alpha tocopheryl acetate, soybean oil etc.0.74  Cohen, M.J.; Karasek, F.W.; J. Chromatogr. Sci., 8: 1970; 330.  Eiceman, G.A.; Karpas, Z.; Ion Mobility Spectrometry, 2nd Ed., CRC Press, Boca Raton, FL, 2005.  Whitehouse, C.M.; Dreyer, R.N.; Yamashita, M.; Fenn, J.B.; Anal. Chem., 57(3): 1985; 675.  Fenn, J.B.; Man, M.; Meng, C.K.; Wong, S.F.; Whitehouse, C.M.; Science, 246: 1989; 64. Ion mobility fundamentals. Reduced mobility Figure 3: IMS spectra of hydrocodone pain reliever, nyquil cold/flu syrup and antibiotics. Reduced mobilities (cm 2 V -1 s -1 ) of the major peaks are shown on the spectra. Figure 4: IMS spectra of vitamins and pepto-bismol syrup. Reduced mobilities (cm 2 V -1 s -1 ) of the major peaks are shown on the spectra. Figure 5: IMS spectra of echinacea herb for cold/flu remedy, jovan musk cologne and lavender cologne. Reduced mobilities (cm 2 V -1 s -1 ) of the major peaks are shown on the spectra. Department of Chemistry Hill Research Group Ion Mobility Spectrometry