Chemiluminescence in Analytical Chemistry

tion while minimizing any interference from the NO O3 reaction, which occurs in the red and near-IR spectral regions [151]. The fully optimized reaction cell is evacuated to approximately 300 torr with an ozone partial pressure of approximately 22 torr. Under these conditions, and with a 5.4 s integration time, the detection limit was found to be 400 pptv, but 5 ppbv could be measured as fast as 1 Hz. Although it might be expected that other common biogenic compounds such as pinene, limonene, and various other monoterpenes would chemiluminesce under the same conditions, investigations indicated that the light produced from their reactions with ozone was virtually nondetectable. It is known that these compounds readily react with ozone in the atmosphere, but the exact nature of their failure to chemiluminesce in the isoprene detector is not understood. Significant interferences include propene, and to a lesser extent, ethene, dimethyl sulfide, 3-butene-2-one, and 2-methylpropenal. The instrument is able to measure isoprene emissions from a single leaf and to measure eddy correlation fluxes at frequencies up to 1 Hz.

6.4 Dimethyl Sulfide Detector

The chemiluminescent reaction with F2 was demonstrated to be sufficiently sensitive and selective to measure dimethyl sulfide, emitted by oceanic phytoplankton, in the marine boundary layer without a prior chromatographic separation [69] and with a detector response fast enough to measure DMS fluxes using the eddy covariance technique [142]. Limits of detection (S/N 1) of 39, 12, and 4 pptv DMS were demonstrated for 0.1-, 1-, and 10-s integration times, respectively. Whereas all organosulfur compounds produce vibrational overtone emission from HF†, only methylated sulfur compounds produce HCF* [6]. Emission of HCF* occurs in the wavelength range 500–700 nm, which is blue-shifted from HF† emission at 670–900 nm (Fig. 7). Therefore, selectivity for HCF* is achieved by using a blue-sensitive PMT.

7. CONCLUDING REMARKS AND FUTURE TRENDS

Gas-phase chemiluminescence has been demonstrated to provide highly sensitive detection for a wide range of compound classes with selectivities ranging from very specific, as in the detection of only H2S and CH3SH with OClO, to nearly universal, as in the reactions of active nitrogen at atmospheric pressure. The use of a combustion chamber to achieve element selectivity by converting all compounds containing that element to a single surrogate analyte (e.g., NO for nitrogen compounds and SO for sulfur compounds) has proven especially beneficial in gas chromatography. There are a number of highly efficient chemiluminescence reactions that have yet to be fully exploited in analytical chemistry. Chemilumi-

nescence of NO and SO with O atoms, for example, holds the potential of greater sensitivity than the corresponding reactions with ozone, provided contributions from background emissions can be minimized.

The chemical characterization of aerosol particles currently is of great interest in the field of atmospheric chemistry. A major goal is the development of a method for continuous elemental analysis of aerosols, especially for the elements C, N, and S. Chemiluminescence reactions described in this chapter have adequate sensitivity and selectivity for such analyses. In fact, considering that a 1- m-diameter particle has a mass of 0.5–1.0 pg, online analysis of single aerosol particles should be achievable, especially for larger particles.

During the past decade, single fluorescent molecules have been detected by repeatedly exciting them to fluorescence within a high-intensity laser beam, and the method has been applied to problems ranging from studies of the dynamics of single molecules to rapid sequencing of DNA. Although the concept of single-molecule detection is now well established, it has not yet been applied to atmospheric chemistry. Few, if any, atmospheric molecules have large enough extinction coefficients and fluorescence quantum yields to be detected as single molecules by laser-induced fluorescence. Although highly speculative at this point, it may be possible to detect single molecules in the gas phase based on initiation of chain reactions, such as the F2 H2 reaction, that produce chemiluminescence. If successful, this would, of course, provide the ultimate sensitivity for gas-phase detection.

REFERENCES

1.A Fontijn, AJ Sabadell, RJ Ronco. Anal Chem 42:575–579, 1970.

2.DW Joseph, CW Spicer. Anal Chem 50:1400–1403, 1978.

3.DW Fahey, G Hubler, DD Parrish, EJ Williams, RB Norton, BA Ridley, HB Singh, SC Liu, FC Fehsenfeld. J Geophys Res 91:9781–9793, 1986.

4.BA Ridley, FE Grahek. J Atmos Ocean Technol 7:307–311, 1990.

5.RJ Glinski, JN Getty, JW Birks. Chem Phys Lett 117:359–364, 1985.

6.RJ Glinski, EA Mishalanie, JW Birks. J Photochem 37:217–231, 1987.

7.AA Turnipseed, JW Birks. J Phys Chem 95:6569–6574, 1991.

8.JW Birks. In: JW Birks, ed. Chemiluminescence and Photochemical Reaction Detection in Chromatography. New York: VCH Publishers, 1989, pp 1–37.

9.DM Steffenson, DH Stedman. Anal Chem 46:1704–1709, 1974.

10.PN Clough, BA Thrush. Chem Commun 783–784, 1966.

11.WB DeMore, SP Sander, DM Golden, RF Hampson, MJ Kurylo, CJ Howard, AR Ravishankara, CE Kolb, MJ Molina. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, JPL Publication 97-4. Pasadena: NASA JPL, 1997.

12.AA Mehrabzadeh, RJ O’Brien, TM Hard. Anal Chem 55:1660–1665, 1983.

13.AA Mehrabzadeh, RJ O’Brien, TM Hard. Rev Sci Instrum 54:1712–1718, 1983.

14.S Toby. Chem Rev 84:277–285, 1984.

15.JC Greaves, DJ Garvin. J Chem Phys 30:348–349, 1959.

16.H Harrison, DM Scattergood. Upper Limits for Chemiluminescence from Single Collisions of O3 with NO, CO, H2S, and CS2, Boeing Scientific Research Laboratories Document D1-82-0480. Seattle: Boeing Scientific Research Laboratories, 1966.

17.RD Kenner, EA Ogryzlo. In: JG Burr, ed. Chemiand Bioluminescence. New York: Marcel Dekker, 1985, pp 45–185.

18.AE Douglas. J Chem Phys 45:1007–1015, 1966.

19.VM Donelly, F Kaufman. J Chem Phys 66:4100–4110, 1977.

20.VM Donelly, F Kaufman. J Chem Phys 68:5671, 1978.

21.VM Donelly, DG Keil, F Kaufman. J Chem Phys 71:659–673, 1979.

22.DG Keil, VM Donelly, F Kaufman. J Chem Phys 73:1514–1520, 1980.

23.RL Benner, DH Stedman. Appl Spectrosc 48:848–851, 1994.

24.CJ Halstead, BA Thrush. Photochem Photobiol 4:1007–1013, 1965.

25.H Akimoto, JJ Finlayson, JN Pitts. Chem Phys Lett 12:199–202, 1971.

26.A Kaldor, W Braun, MJ Kurylo. J Chem Phys 61:2496–2499, 1974.

27.RJ Glinski, JA Sedarski, DA Dixon. J Phys Chem 85:2440–2443, 1981.

28.MAA Clyne, CJ Halstead, BA Thrush. Proc Roy Soc Lond A 295:355–362, 1966.

29.CJ Halstead, BA Thrush. Proc Roy Soc Lond A 295:363–379, 1966.

30.CJ Halstead, BA Thrush. Proc Roy Soc Lond A 295:380–398, 1966.

31.A McKenzie, BA Thrush. Proc Roy Soc Lond A 308:133–140, 1968.

32.EKC Lee, GL Lopin. In: SH Lin, Ed. Radiationless Transitions. New York: Academic Press, 1980, pp 1–425.

33.S Glavas, S Toby. J Phys Chem 79:779–782, 1975.

34.JS Gaffney, DJ Spandau, TJ Kelly, RL Tanner. J Chromatogr 347:121–127, 1985.

35.W Bruening, FJM Concha. J Chromatogr 112:253–265, 1975.

36.BJ Finlayson, JN Pitts, R Atkinson. J Am Chem Soc 96:5356–5367, 1974.

37.U Schurath, H Gusten, R-D Penzhorn. J Photochem 5:33–40, 1976.

38.JT Herron, RE Huie. J Am Chem Soc 99:5430–5435, 1977.

39.AA Turnipseed. In: JW Birks, Ed. Chemiluminescence and Photochemical Reaction Detection in Chromatography. New York: VCH Publishers, 1989, pp 39–69.

40.ME Fraser, DH Stedman, MJ Henderson. Anal Chem 54:1200–1201, 1982.

41.ME Fraser, DH Stedman. J Chem Soc Faraday Trans I 79:527–542, 1983.

42.DH Stedman, DA Tammaro. Anal Lett 9:81–89, 1976.

43.DH Stedman, DA Tammaro, DK Branch, R Pearson. Anal Chem 51:2340–2342, 1979.

44.K Fujiwara, Y Watanabe, K Fuwa, JD Winefordner. Anal Chem 54:125–128, 1982.

45.RJ Strutt. Proc Phys Soc 23:66, 1910.

46.FC Fehsenfeld, KM Evenson, HP Broida. Rev Sci Instrum 36:294–298, 1965.

47.JW Carnahan. Am Lab 31–36, 1983.

48.A Khan, M Kasha. J Am Chem Soc 92:3293–3300, 1970.

49.JW Birks, B Shoemaker, TJ Leck, DM Hinton. J Chem Phys 65:5181–5185, 1976.

50.AP Ongstad, JW Birks. J Chem Phys 81:3922–3930, 1984.

51.AP Ongstad, JW Birks. J Chem Phys 85:3359–3368, 1986.

52.KH Becker, W Groth, D Thran. Chem Phys Lett 6:583–586, 1970.

53.A Sharma, JP Padur, P Warneck. J Phys Chem 71:1602, 1967.

54.EP Lewis. Phys Rev 18:125–128, 1904.

55.AN Wright, CA Winkler. Active Nitrogen. New York: Academic Press, 1968, pp 1–602.

56.JE Melzer, DG Sutton. Appl Spectrosc 34:434–437, 1980.

57.GW Rice, JJ Richard, AP D’Silva, VA Fassel. Anal Chem 53:1519–1522, 1981.

58.DG Sutton, KR Westburg, JE Melzer. Anal Chem 51:1399–1401, 1979.

59.JT Clay, TM Niemczyk. Spectroscopy 2:36, 1987.

60.RH Getty, JW Birks. Anal Lett 12:469–476, 1979.

61.SR Spurlin, ES Yeung. Anal Chem 57:1223–1227, 1985.

62.DE Mann, BA Thrush, DR Lide, JJ Ball, N Acquista. J Chem Phys 34:420–431, 1961.

63.WH Duewer, DW Setser. J Chem Phys 58:2310–2320, 1973.

64.M VanPee, KD Cashin, RJ Mainiero. Combust Flame 31:187–196, 1978.

65.JK Nelson, RH Getty, JW Birks. Anal Chem 55:1767–1770, 1983.

66.RJ Glinski, EA Mishalanie, JW Birks. J Am Chem Soc 108:531–532, 1986.

67.TG Chasteen, GM Silver, JW Birks, R Fall. Chromatographia 30:181–185, 1990.

68.TG Chasteen, R Fall, JW Birks, HR Martin, RJ Glinski. Chromatographia 31:342– 346, 1991.

69.AJ Hills, DH Lenschow, JW Birks. Anal Chem 70:1735–1742, 1998.

70.RI Patel, GW Stewart, K Castleton, JL Gole, JR Lombardi. Chem Phys 52:461– 468, 1980.

71.K Shobatake, JM Parson, YT Yee, SA Rice. J Chem Phys 59:1416–1426, 1973.

72.JM Parson, YT Lee. J Chem Phys 56:4658–4666, 1972.

73.RJ Glinski, CD Taylor. Chem Phys Lett 155:511–512, 1989.

74.JW Birks, SD Gabelnick, HS Johnston. J Mol Spectrosc 57:23–46, 1975.

75.JJ Valentini, MJ Coggiola, YT Lee. J Am Chem Soc 98:853–854, 1976.

76.JJ Valentini, MS Coggiola, YT Lee. Disc Faraday Soc 62:232–245, 1977.

77.CC Kahler, YT Lee. J Chem Phys 73:5122–5130, 1980.

78.JM Farrar, YT Lee. J Am Chem Soc 96:7570–7572, 1974.

79.M Yamada, A Ishiwada, T Hobo, S Suzuki, S Araki. J Chromatogr 238:347–356, 1982.

80.S Araki, S Suzuki, M Yamada, H Suzuki, T Hobo. J Chromatogr Sci 16:249–253, 1978.

81.SR Spurlin, ES Yeung. Anal Chem 54:318–320, 1982.

82.SS Brody, JE Chaney. J Gas Chromatogr 4:42–46, 1966.

83.PT Gilbert. Anal Chem 38:1920–1922, 1966.

84.WL Crider. Anal Chem 41:534–537, 1969.

85.T Sugiyama, Y Suzuki, T Takeuchi. J Chromatogr 77:309–316, 1973.

86.S Sass, GA Parker. J Chromatogr 189:331–349, 1980.

87.SO Farwell, CJ Barinaga. J Chromatogr Sci 24:483–494, 1988.

88.DA Ferguson, LA Luck. Chromatographia 12:197–203, 1979.

89.AR Baig, CJ Cowper, PA Gibbons. Chromatographia 16:297–300, 1982.

90.WA Aue. J Chromatogr Sci 13:329–333, 1975.

91.R Greenhaigh, MA Wilson. J Chromatogr 128:157–162, 1976.

92.M Dressler. Selective Gas Chromatographic Detectors. Amsterdam: Elsevier, 1986, pp 1–319.

93.DH Stedman, ME Fraser. In: JG Burr, ed. Chemiand Bioluminescence. New York: Marcel Dekker, 1985, pp 439–468.

94.RS Braman, JM Ammons, JL Bricker. Anal Chem 50:992–994, 1978.

95.J Godin, J Cluet, C Boudene. Anal Chem 51:2100–2102, 1979.

96.RW Fair, BA Thrush. Trans Faraday Soc 65:1208, 1969.

97.WC Swope, YP Lee, HF Schaefer. J Chem Phys 70:947–953, 1979.

98.WL Crider, RW Slater. Anal Chem 41:531–533, 1969.

99.JM Zehner, RA Simonaitis. J Chromatogr Sci 14:348–350, 1976.

100.G Marcalin. J Chromatogr Sci 15:560–562, 1977.

101.S Fredriksson, A Cedergren. Anal Chim Acta 100:429–438, 1978.

102.S Cheskis, E Atar, A Amirav. Anal Chem 65:539–555, 1993.

103.EJ Sowinski, IH Suffet. J Chromatogr Sci 9:632–634, 1971.

104.R Belcher, SL Bogdanski, SA Ghonaim, A Townshend. Anal Chim Acta 109:229– 239, 1979.

105.PL Patterson. Anal Chem 50:345–348, 1978.

106.PL Patterson, RL Howe, A Abu-Shumays. Anal Chem 50:339–344, 1978.

107.E Atar, S Cheskis, A Amirav. Anal Chem 63:2061–2064, 1991.

108.A Amirav, H Jing. Anal Chem 67:3305–3318, 1995.

109.EA Mishalanie, JW Birks. Anal Chem 54:918–923, 1986.

110.WT Foreman, CL Shellum, JW Birks, RE Sievers. J Chromatogr 465:23–33, 1989.

111.U Brunner, TG Chasteen, P Ferloni, R Bachofen. Chromatographia 40:399–403, 1995.

112.V Stalder, N Bernard, KW Hanselmann, R Bachofen, TG Chasteen. Chromatographia 303: 91–97, 1995.

113.H Gu¨rleyu¨k, VV Fleet-Stalder, TG Chasteen. Appl Organomet Chem 11:471–483, 1997.

114.V VanFleet-Stalder. J Photochem Photobiol 43:193–203, 1998.

115.RL Benner, DH Stedman. Anal Chem 61:1268–1271, 1989.

116.RL Benner, DH Stedman. Environ Sci Technol 24:1592–1596, 1990.

117.NG Johansen, JW Birks. Am Lab 23:112–119, 1991.

118.RL Shearer. Anal Chem 64:2192–2196, 1992.

119.HR Martin, RJ Glinski. Appl Spectrosc 46:948–952, 1992.

120.PL Burrow, JW Birks. Anal Chem 69:1299–1306, 1997.

121.RL Shearer, RE Sievers. In: JW Birks, ed. Chemiluminescence and Photochemical Reaction Detection in Chromatography. New York: VCH Publishers, 1989, pp 71– 97.

122.J Jager. J Chromatogr 152:575–578, 1978.

123.JN Pitts, KAV Cauwenberghe, D Grosjean, JP Schmid, DR Fitz, WL Belser, GB Knudson, PM Hynds. Science 202:515–519, 1978.

124.CY Wang, M-S Lee, CM King, PO Warner. Chemosphere 9:83–87, 1980.

125.DH Fine, D Lieb, F Rufeh. J Chromatogr 107:351–357, 1975.

126.DH Fine, DP Roundbehler. J Chromatogr 109:271–279, 1975.

127.DH Fine, F Rufeh, D Lieb, DP Roundbehler. Anal Chem 47:1188–1191, 1975.

128.PE Oettinger, F Huffman, DH Fine, D Lieb. Anal Lett 8:411–414, 1975.

129.C Ruhl, J Reusch. J Chromatogr 328:362–366, 1985.

130.DH Fine, F Rufeh, B Gunther. Anal Lett 6:731–733, 1973.

131.DH Fine, F Rufeh, D Lieb. Nature (Lond) 247:309–310, 1974.

132.HV Drushel. Anal Chem 49:932–939, 1977.

133.SA Nyarady, RM Barkley, RE Sievers. Anal Chem 57:2074–2079, 1985.

134.JJ DeAngelis, RM Barkley, RE Sievers. J Chromatogr 441:125–134, 1988.

135.WT Foreman, RE Sievers, B Wenclawiak. Fres J Anal Chem 330:231–234, 1988.

136.WB Dodge, RO Allen. Anal Chem 53:1279–1286, 1981.

137.MJ Bollinger, RE Sievers, DW Fahey, FC Fehsenfeld. Anal Chem 55:1980–1986, 1983.

138.DW Fahey, CS Eubank, G Hubler, FC Fehsenfeld. J Atmos Chem 3:435–468, 1985.

139.LC Anderson, DW Fahey. J Phys Chem 94:644–652, 1990.

140.DAV Kliner, DC Daube, JD Burley, SC Wofsy. J Geophys Res 102:10,759–10,776, 1997.

141.DR Crosley. J Geophys Res 101:2049–2052, 1996.

142.DH Lenschow. In: PA Matson RC Harriss, Eds. Biogenic Trace Gases: Measuring Emissions from Soil and Water. American Chemical Society, Washington, D.C., 1995, pp 126–163.

143.GW Nederbragt, AVD Horst, JV Duijn. Nature (Lond) 206:87, 1965.

144.F Chisaka, S Yanagihara. Anal Chem 54:1015–1017, 1982.

145.RJ O’Brien, TM Hard, AA Mehrabzadeh. Environ Sci Technol 17:560–562, 1983.

146.DH Stedman, DL McElwee, GJ Wendel. In: A Fontijn, ed. Gas-Phase Chemiluminescence and Chemi-ionization. New York: Elsevier Science Publishing, 1985, pp 345–355.

147.E Hilsenrath, L Seiden, P Goodman. J Geophys Res 74:6873–6880, 1969.

148.JA Hodgeson, KJ Krost, AE O’Keeffe, RK Stevens. Anal Chem 42:1795–1797, 1970.

149.E Hilsenrath, PT Kirschner. Rev Sci Instrum 51:1381–1384, 1980.

150.JA Bognar, JW Birks. Anal Chem 68:3059–3062, 1996.

151.AJ Hills, PR Zimmerman. Anal Chem 62:1055–1060, 1990.

152.L Herman, J Akriche, H Grenat. J Quant Spectrosc Radiat Transfer 2:215–224, 1962.

153.W Worthy. Chem Eng News 63:42–44, 1985.

1. INTRODUCTION

For the analysis of biological and environmental samples, separation analyses have an important role in the determination of analytes in complex matrices. High-performance liquid chromatography (HPLC) has currently become dominant as a potential tool for the separation of a wide range of analytes in the diverse fields of analysis. As detection systems for HPLC, the ultraviolet-visi- ble light absorption and, to a lesser extent, refractive index (RI) detectors have been employed most commonly. Although these detection techniques are very universal and conveniently applicable, in general they lack sensitivity. In the case of trace analyses, fluorescence (FL) and electrochemical (EC) detections are utilized owing to their relatively high sensitivity and selectivity. When ultratrace quantities of an analyte in a complex sample matrix (e.g., biologically active compounds such as hormones in body fluids) are to be determined, highly sensitive chemiluminescence (CL) and laser-induced fluorescence (LIF) detections are often very powerful. CL-based techniques as a means of detection for HPLC have been developed since the 1980s. Although it is not as universal as FL detection, CL detection is rapidly growing owing to the very low detection limits, wide linear working ranges, and relatively simple instrumentations.

In this chapter, developments and applications of the CL detection methods in HPLC are reviewed.

2. FEATURES OF CL DETECTION IN HPLC

In the CL detection method, the excitation of a molecule is achieved via a chemical reaction that is generally an oxidation process. That is, an exciting light source is not required; thus, the CL is not accompanied by any scattering light and source instability. This permits a large signal-to-noise ratio (S/N), which finally provides an increase in sensitivity.

Most of the light emission in CL methods are in the visible region (the limiting factor for the occurrence of CL is that the energy required for luminescence in the visible region lies between 44 and 77 kcal/mol) [1]. To apply this CL emission to a detection system in HPLC, generation of CL by a postcolumn reaction of analytes in an eluent with reagent(s) is required. Therefore, excellent efficiency of the CL reaction is desired for HPLC. Although CL techniques permit sensitive detection of analytes owing to the reason described above, undesirable emission of CL derived from impurities in solvents and reagents sometimes interferes with the highly sensitive detection. When compared to FL detection, CL