Molecular fluorescence, phosphorescence, and ... - ACS Publications

Anal. Chem. 1980, (154) J . Radioanal. Chem., 44, No. 2 (1978). (155) J . Radioanal. Chem., 48, No. 1 and 2 (1979). (156) Radiochem. Radioanal. Lett., 36, No. 4 and 5 (1978). (157) Fried, S., Ed., "Radioactive Waste in Geologic Storage". ACS Symposium Series 100, American Chemical Society, Washington, D.C., 1979. (158) Pinta, M., "Modern Methods for Trace Element Analysis", Ann Arbor Science, Ann Arbor, Mich., 1978. (159) Faure, G., "Principles of Isotope Geology", Wiley, New York, 1977. (160) "Monitoring of Airborne and Liquid Radioactive Releases fom Nuclear Facllities to the Environment", International Atomic Energy Agency, Vienna, 1978. (161) Jenkins, E. N., "Radioactivity", Wykeham Publications, London, 1979. (162) Morse, J. G., Ed., Nuclear Methods in Mineral Exploration and Production", Elsevier, Amsterdam, 1977. (163) Deconninck, G., "Introduction to Radioanaiytical Physics", Elsevier, Amsterdam, 1978. (164) Dzubay, T. G.. Ed., "X-ray Fluorescence Analysis of Environmental Samples", Ann Arbor Science Press, Ann Arbor, Mich., 1977. (165) Karr, C., Jr.. Ed., "Analytical Methods for Coal and Coal Products", Vol. 1. Academic Press, New York, 1978. (166) Crook, M. A,, Johnson, P., Ed., "Liquid Scintillation Counting", Vol. IV, Heyden and Son Ltd., New York, 1977. (167) Herglotz, H. K., Birks, L. S., Ed., "X-ray Spectrometry", Marcel Dekker, Inc., New York. 1978. (168) Valyi. L., "Atom and Ion Sources", Wiley, New York, 1977. (169) Wuilleumier, F., Farge, Y., "Synchrotron Radiation Instruments and Developments", North-Holland Publishing, Amsterdam, 1978. (170) Nucl. Instrum. Methods. 162, No. 1-3, part I,1979. (171) Nucl. Instrum. Methods, 162, No. 1-3, part 11, 1979. (172) Roberts, T. R., "Radiochromatography", Elsevier, Amsterdam, 1978. (173) Chard, T., "Introduction to Radioimmunoassay and Related Techniques" North-Holland Publishing, Amsterdam, 1978. (174) Cindro, N., Ed., "Nuclear Molecular Phenomena", North-Holland, Amsterdam, 1978. (175) Nucl. Instrum. Methods, 150, No. 1 (1978). (176) "Proceedings of the Meeting on Fission Product Nuclear Data", Petten, Netherlands, 1977, NTIS. (177) "Proceedings of the Nuclear Science Symposium", San Francisco, IEEE Trans. Nucl. Sci., No. 1, 1978. (178) "Proceedings of the Symposium on Radioimmunoassay and Related Procedures in Medicine", IAEA, Vienna, 1978. (179) "Proceedings of the International Symposium on Food Preservation by Irradiation", IAEA, Vienna, 1978. (180) "Proceedings of the Seminar on Radioactive Affluents from Nuclear Fuel Reprocessing Plants", Karlsruhe, Germany, 1977. (181) "Proceedings of the International Symposium on National and International Standardization of Radiation Dosimetry", IAEA, Vienna, 1978. (182) "Proceedings of the IAEA Symposium on Natural Fission Reactors", Paris, 1977, NTIS. (183) "Proceedings of the Symposium on Radiation Instrumentation", San . . Diego, 1978, NTIS. (184) "Proceedings of the Symposium Commemorating the 25th Anniversary of the Discoverv of Elements 99 and 100". Berkelev. 1978. NTIS. (185) Nucl. Instrim. Methods, 156, No. 1 and 2 (19f8). (186) "Proceedings of the Symposium on Superheavy Elements", Lubbock, Texas, 1978, NTIS. (187) Parr, R. M., Ryabukhin, Yu, S.,A t . Energy Rev., 16, 547 (1978). (188) "Proceedings of the International Symposium on Isotope Hydrology", IAEA, Vienna, 1979. (189) "Proceedings of the Conference on Effluent and Environmental Radiation Surveillance", Johnson, Vt., 1978, NTIS. (190) J . Radioanal. Chem., 51, No. 1 (1979).

52, 75 R-90 R (191) "Proceedings of the Symposium on Neutron Capture of Gamma Ray Spectroscopy", Upton, N.Y., 1978, NTIS. (192) "Proceedings of the Symposium on the Behavior of Tritium in the Environment", IAEA, Vienna, 1979. (193) "Proceedings of the IAEA Symposium on Nuclear Material Safeguards", IAEA, Vienna, 1978. (194) "Proceedings of the International Symposium on Radiopharmaceuticals", Seattle, 1979, NTIS. (195) Osterhage, W. W., J . Radioanal. Chem., 52, 203 (1979). (196) Osterhage, W. W., J . Radioanal. Chem., 49, No. 1, 131 (1979). J . Radioanal. Chem., 46, 159 (1978). (197) Gryntakis, E. M., Kim, J. I., (198) Greenwood, R. C., Heimer, R . G., Gahrke, R. J.. Nucl. Instrum. Methods, 153, 465 (1979). (199) Hnatowicz, V.. Nucl. Instrum. Methods, 161, 151 (1979). (200) Helmer, R. G., Greenwood, R. C., Gehrke, R. J., Nucl. Instrum. Methods, 155, 189 (1978). (201) Masumoto. K., Kato, T., Suzuki, N., Nucl. Instrum. Methods, 157, 567 (1978). (202) Mori, C., Noguchi, H., Ishigure. N.. Watanabe, T., Nucl. Instrum. Methods. 155, 435 (1978). (203) Mannhart, W., Vonach, H., Nucl. Instrum. Methods, 151, 157 (1978). (204) Zikovsky, L., Radiochem. Radioanal. Lett., 32, 63 (1978). (205) Goldstein, N. P., Health Phys.. 36, 505 (1979). (206) Davydov, M. G . . Dobrynina, N. P., Mantoptin. V. A,, Naumov, A. P.. Radiochem. Radioanal. Lett., 35, 67 (1978). (207) Murayama, H., Tanaka, E., Nohara. N., Nucl. Instrum. Methods, 164, 447 (1979). (208) Kocher, D. C.. Oak Ridge National Laboratory, Oak Ridge, Tenn., ORNL/NUREG/TM-102 (1977). (209) Maeck, W. J., Emel, W. A., Duce, F. A., Tromp, R. L., Meteer, J. W., Allied Chemical Corp., Idaho Falls, ICP-1142 (1978). (210) Browne, E., Dairiki, J. M., Doebler, R. E., Shihab-Eldin. A. A,, Jardine, L. J., Tuli, J. K., Buyrn, A. B.. "Table of Isotopes", Wiley, New York. (1978). (211) Wainerdi, R. E., Pure Appl. Chem., 51, 1185 (1979). (212) Hoit, P. D., Phys. Med. Biol., 24, 1 (1979). (213) Lakshmanan. A., Bhatt, R. C., Int. J . Appl. Radist. Isot., 29, 353 (1978). (214) Prokic, M., Nucl. Instrum. Methods, 151, 603 (1978). (215) Aypar, A,, Int. J . Appl. Radiat. Isot., 29. 369 (1978). (216) Shastry, S. S.,Kher, R. K., Nucl. Instrum. Methods. 159, 593 (1979). (217) Oliveri, E., Fiorella, O., Mangia, M., Nucl. Instrum. Methods, 163, 569 (1979). (218)Srivastava, J. K., Supe. S. J., Nucl. Instrum. Methds, 155, 233 (1978). (219) Srivastava, J. K., Supe, S. J., Nucl. Instrum. Methods, 160, 529 (1979). (220) Ramanathan. G. NaaDal. -. J. S.,Ganoadharan. P., Nucl. Instrum. Methods, 164, 601 (1979). (221) Pradhan, A. S.. Kher, R. K., Dere. A., Bhatt. R. C., Int. J. Appl. Radiat. Isot.. 29, 243 (1978). (222) Shinde, S. S., Shastry. S. S., Int. J . Appl. Radiat. Isot., 30, 501 (1979). (223) Pradhan, A. S.,Bhatt, R. C., Nucl. Instrum. Methods, 161, 243 (1979). (224) Nagpal, J. S., Pendurkar, H. K., Nucl. Instrum. Methods, 159, 581 (1979). (225) Lakshrnanan, A. R., Chandra, B., Bhatt, R. C.. Nucl. Instrum. Methods, 153, 581 (1978). (226) Shinde, S. S., Shastry, S. S., Int. J. Appl. Radiat. Isot., 30, 75, (1979). (227) Gordon, A. M. P. L., Muccillo, R., I n t . J . Appl. Radiat. Isot., 30, 571 (1979). (228) Lakshmanan, A., Bhatt, R. C., Int. J. Appl. Radiat. Isot., 30, 571 (1979). (229) Lakshmanan, A. R., Vohra, K. G., Nuci. Instrum. Methods, 159, 585 (1979). (230) Mohammadi, H., Zlemer, P. L., Nucl. Instrum. Methods, 155, 503 (1978). (231) MOSS,A. L., McKlveen, J. W., Health Phys.. 34, 137 (1978). (232) Lyon, W. S.,Ed., "Radioelement Analysis: Progress and Problems", Ann Arbor Science Press, Ann Arbor, Mich. (Feb 1980).

Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry E. L. Wehry Department of Chemistty, University of Tennessee, Knoxville, Tennessee 379 16

INTRODUCTION This review, the first under the present authorship, covers literature indexed by Chemical Abstracts from mid-November 1977 (Vol. 87, issue 21) through the end of November 1979 (Vol. 91, issue 22). Because chemiluminescence increasingly is assuming an important role in practical analytical measurements, it is incorporated explicitly in the title of this review for the first time. The present review, which does not purport to be comprehensive, was prepared with the assistance of a computer 0003-2700/80/0352-75R$05.00/0

search profile of Chemical Abstracts titles and identifiers prepared locally. As in the previous review in this series ( A I ) , certain topics are excluded; for example, virtually all publications concerning atomic fluorescence, molecular luminescence in flames, X-ray fluorescence, solid-state phosphor luminescence (both organic and inorganic), radioluminescence, liquid scintillation counting, and photosynthesis and solar energy conversion have been excluded. Papers dealing with luminescence detection in liquid, thin-layer, or paper chromatography are cited only when they appear to be of ap-

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preciable spectroscopic interest. Certain other subject matter areas, noted explicitly in the appropriate sections of the review, are covered in a highly selective and biased manner. The ritual apologies are sincerely extended to those investigators whose work is omitted (advertently or otherwise) from the review. In the reviewer’sjudgment, especially noteworthy progress was made in the followin general areas of analytical luminescence spectrometry iuring the 1978-79 biennium. (a) The meaningful use of lasers as sources for photoluminescence measurements under conditions in which high incident photon flux is not the only reason for turning to laser excitation. (b) The continued development of a number of worthwhile approaches to complex mixture analysis by luminescence methods. (c) Continued development and use of fluoroimmunoassay, microspectrofluorometry, and fluorescence flow cytometry (and related procedures) and their intelligent application to a variety of biochemical and bioanalytical problems. (d) Increased sophistication in the applications of fluorescent probe techniques and increasing circumspection in the interpretation of the results of such experiments. (e) T h e vastly increased use of chemiluminescence as a measurement procedure in a variety of complex real samples. (0 Increasing use of electronic array detectors in a variety of luminescence measurements. (g) The widespread (virtually routine) use of fluorescence for liquid chromatographic detection.

GENERAL B-OOKS AND REVIEWS Lumb ( B I ) has edited a multiauthor volume on luminescence spectroscopy;of particular interest are excellent chapters surveying luminescence instrumentation and the luminescence of organic molecules. The annual Chemical Society Specialist Periodical Report on Photochemistry, the most recent volume of which covers the literature published between July 1976 and June 1977, includes the usual thorough and highly authoritative chapter on “Photophysical Processes in Condensed Phases”, within which is subsumed much useful fundamental information on photo- and chemiluminescence (B2). Regrettably, this series now is to include coverage on “Instrumentation and Experimental Techniques” only in alternate years, and the present year is an “off year” for that topic. Guilbault (B3) has contributed a chapter to “Comprehensive Analytical Chemistry” which provides an introductory view of luminescence fundamentals and instrumentation and a very useful survey of classes of applications (with many examples). The new edition of Turro’s organic photochemistry text (B4) provides a superb introduction to fluorescence and phosphorescence fundamentals. Schenk has contributed a chapter on molecular fluorescence and phosphorescence to a new instrumental analysis textbook (B5). O’Haver has presented an interesting historical survey of the development of luminescence as an analytical method (B13). From among the plethora of reviews dealing with chemiluminescence, those of greatest general interest include a very extensive survey of chemiluminescence and bioluminescence a relatively brief review of analysis by Seitz and Neary (B6), a brief biochemical microanalysis via chemiluminescence (B7), survey of clinical ap,plications (BB),an exceedingly readable a review review of redox chemiluminescence by Faulkner (B9), of gas-phase chemiluminescence (BIO),an entry, written by Rauhut, on the subject in the Kirk-Othmer encyclopedia (BII),and an audio tape cassette review of analytical applications (2312).

INSTRUMENTATION AND EXPERIMENTAL TECHNIQUES Reviews. Hamilton, Munro, and Walker have reviewed instrumentation for fluorescence and phosphorescence in detail ( C l ) . Not only are the customary “classical” topics treated nicely, but this review also incorporates some relatively new instrumental procedures (including wavelength modulation, time resolution, and excitation by synchrotron radiation); S / N enhancement techniques also receive careful discussion. Klinkenberg has movided a useful and detailed review of experimentd methods for spectroscopy in the near IR, visible, and UV (C2). 76R

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Sources. Lamps are rather prosaic nowadays, but they are still the most important sources for photoluminescence spectrometry; therefore, a review of incoherent light sources by Eby and Levin is very welcome (C3). The spectral output and noise power spectrum of the Eimac pre-focused xenon lamp have been discussed (C4). The production of instabilities in the output of a compact xenon arc lamp when the dc current through the lamp is modulated has been considered (C5). The UV continuum radiation produced by a metallic wire exploded in a capacitive discharge (C6) may have applications in fluorescence or phosphorescence, though none has yet been reported. The literature on lasers is burgeoning and only the most general items can be cited here. An introductory text describes laser action and provides example applications of lasers (C7). The principles of lasers, and a brief survey of the various types of lasers, have been examined (C8). A second edition of Schiifer’s monograph on dye lasers has appeared (C9). General reviews of dye lasers which are both comprehensive and readable have been presented by Peterson ( C I O ) and Latz ( C l l ) . Solid-state lasers (particularly Nd:YAG, Nd:glass, and ruby) are reviewed by Weber (C12). Bridges has reviewed atomic and ionic gas lasers, including helium-neon and argon and krypton ion lasers (C13). A revised and expanded table of wavelengths of lines which can be obtained from the various gas lasers has been published (C14). Rare-gas excimer lasers offer interesting possibilities for excitation of fluorescence in the deep UV; Rhodes has edited a monograph which considers principles and applications of excimer lasers ( C 1 5 ) . A laser safety handbook will be useful to those investigators who are unfamiliar with the electrical and optical hazards associated with careless use of lasers (C16). A high-efficiency CW ring dye laser, which has some very attractive features as a source for fluorometry, has been developed (C17) and is commercially available. Many analytes do not cooperate by absorbing in the visible, so the problem of obtaining adequate, continuously tunable, output from dye lasers in the UV continues to attract attention. Among the techniques used are second-harmonic generation (“frequency doubling”) (C18, C19) and sum-frequency mixing in nonlinear materials (C19-C21). Pumping the dyes p-terphenyl or “PBD” (or a mixture of the two) with a KrF* excimer laser produces pulsed UV output tunable over the wavelength range 326-378 nm with peak power approaching 2 mW (C22). Use of the excimer laser as a high-power UV source encounters practical difficulties, due principally to degradation of the laser gas mixture; experimental techniques for maximizing the lifetime of operation of an excimer laser system have been described (C23). A pulsed dye laser with output in the near IR (7W900 nm tuning range), pumped by a flashlamp-driven dye laser, has been described (C24). Scanning of a dye laser in such a way that the theoretical resolution of the output is actually achieved requires constant optimization of cavity parameters throughout the scan. A technique for accomplishing this, wherein the laser output frequency is locked to the setting of a high-resolution monochromator via closed-loop microprocessor control, has .been described (C2.5). A technique for measuring the wavelength stability and bandwidth of the output from a dye laser, using a diode array detector, has been reported (C26). Considerable effort has been devoted to analysis of the problem of pulse-to-pulse amplitude variations and their effects on analytical measurements performed with pulsed dye lasers (C27, C28). A microcomputer-controlled gated integration system for pulse amplitude normalization has been described (C29). Richardson and George have compared the relative merits of nitrogen-pumped dye lasers and pulsed argon ion lasers for analytical molecular fluorescence spectrometry, and have concluded that either laser system is suitable for trace detection but the N pumped dye laser is the more flexible and generally applicaiie source for analytical applications (C30). In addition to lamps and lasers, other sources are occasionally used in molecular photoluminescence spectrometry. While not everyone can have his or her own personal synchrotron, the optical radiation therefrom has unique characteristics (C31) which are certain to be exploited for fluorescence studies, especially those requiring time resolution (q.v.) (C32, C33). The possibility of using Cherenkov radiation for excitation in analytical fluorometry has been discussed


Earl L. Wehry is professor of chemistry at the University of Tennessee. He received the B.S. degree from Juniata College in 1962 and the Ph.D. from Purdue University in 1965. After serving on the faculty of Indiana University, he joined the Chemistry Department at Tennessee in 1970. Dr. Wehry’s current research interests include fluorescence, phosphorescence, and FTIR spectroscopy; trace organic analysis by spectroscopic methods: low-temperature techniques in analytical spectroscopy; analytical applications of laser spectroscopy; and the chemical degradation of environmental pollutants. He is editor of the monograph Modern Fhorescence Spectroscopy, and currently serves on the editorial boards of Analytical Letters and the monograph series Contemporary Instrumentation and Analysis. He is a member of the American Chemical Society, Society for Applied Spectroscopy, Optical Society of Imerica, American Association for the Advancement of Science, and Inter-American Photochemical Society.

(C34). Pulsed electron beams have been used, particularly in physicochemical studies, to excite luminescence from organic molecules (C35). Monochromators. Hamilton, Munro, and Walker have provided a useful survey of the operating principles of dispersive monochromators ( C l ) . A filter, continuously variable over the 460-750 nm range with a 1-nm bandpass (C36),may find use in fluorescence spectrometry. S a m p l e Illumination. Unger has prepared a monograph dealing extensively with both the principles and practice of fiber optics (C37). The ways in which fiber optics can be used effectively for illumination of difficult samples are exemplified by a study of the fluorescence of tissue samples (C38). The advantages of front-surface illumination for strongly absorbing samples have once again been stressed (C80). Harrick and Loeb (C39) have reviewed the use of internal reflection techniques in fluorescence. A detailed description of apparatus for total internal reflection fluorescence, and applications to studies of protein adsorption a t solid-liquid interfaces, has appeared (C40). A theoretical and experinental study of the angular distribution of fluorescence from strongly absorbing layers of fluorescent species, under internal reflection conditions, has been reported ( C 4 l ) . Hirschfeld has predicted the inner-filter effect in strongly absorbing solutions to be much less severe for internal reflection fluorometry than in the usual case of front-surface illumination (C42). Mathematical techniques to correct for inner-filter effects under a variety of illumination conditions have been described (C43, (244, C294).

Detectors. The operating principles, design, and performance of photomultiplier tubes (PMTs) have been reviewed by Zwicker (C45). A feedback technique which can be used to extend the linear range of a P M T and reduce base-line drift in P M T circuits has been described (C46). Optimization of measxement parameters in photon counting using PMTs has been discussed in considerable detail ((247C49). A high-speed dc-coupled counting system, suitable for high-performance photon-counting measurements but much less expensive than commercial hardware, has been described (C50). Ni.emczyk and Ettinger have described a computercontrolled photon-counting spectrometer which automatically alters the scan rate as a function of S / N within a resolution element (C51). The occurrence of abrupt pulse-height changes and varying steady-state pulse heights as a function of count rate in PMTs commonly used for photon counting has been discussed (C52). Hayes et al. have provided a detailed discussion of the effective deadtime of pulse-counting systems and its relationship to discriminator thresholds (C53). Microchannel plate (MCP) detectors have been reviewed by Leskovar (C54) and Lecomte and Perez-Mendez (C55); though these devices are not yet widely used for fluorescence detection, except for time resolution (q.v.), they have interesting possibilities. A gain model for the microchannel plate indicates a tendency for the MCP to act in a manner analogous to a discrete-state electron multiplier; specific band areas along the channel walls serving the functions of dynodes appear to exist ((2%).Prototype high-gain (>lo6) MCPs have been reported and their operating Characteristics (including single photoelectron pulse height, pulse height resolution, quantum

efficiency, and transit time) have been specified (C57). Activity in the use of electronic array detectors continues to intensify. The proceedings of an ACS symposium on image detectors have been published (C58). Talmi has given an overview of array detectors and their chemical applications (C59). A useful general discussion of the vidicon as a fluorescence detector has been presented (C60). A brief general discussion of the characteristics of vidicons serves as a useful introduction to the subject (031). Christian’s group continues their high level of activity in vidicon fluorometry. A detailed description of their SIT vidicon fluorometer is now available (C62). The use of “excitation-emission matrices” for fluorometric analysis of mixtures has been discussed (C63, C64); the feasibility of this technique for “fingerprinting” specific fluorescent constituents in complex mixtures represents one of the most important reasons for considering the use of an array detector in molecular luminescence spectrometry. Warner and co-workers have described the optical layout (with an especially detailed description of the lensing system) for a two-dimensionalvidicon fluorometer (C65). The inherent tradeoff between spectral resolution and wavelength coverage always has been a significant shortcoming of array detectors. Hoffman and Pardue have described a modified CzernyTurner spectrometer providing for the display of six different 100-nm chunks of a spectrum along the second dimension of a vidicon; each individual spectral segment can be scanned independently (C66). A multiple entrance slit vidicon spectrometer designed by Busch et al. attacks this same problem in a somewhat different way (C67); this instrumental configuration may be useful for molecular luminescence. Use of a S I T vidicon to detect chemiluminescence produced by chemical reactions in low-temperature matrices has been demonstrated ((268). A time-resolved phosphorescence spectrometer using a SIT vidicon detector has been designed by Goeringer and Pardue (C69). Use of a S I T vidicon as a liquid chromatography detector, by both absorption and fluorescence, has been described in detail (C70). Kohen and co-workers have presented a detailed discussion of an elegant SIT vidicon microfluorometer for detection and topogra hic mapping of fluorescent materials in living biological cells (871). Both SIT and ISIT vidicons have been interfaced to a flow cytometer; this mode of detection promises to be especially useful for following time-dependent processes via spectral changes (C72). The image intensifier and silicon vidicon have been compared by Felkel and Pardue, who determined the former to be about a factor of 25 more sensitive than the latter (C73). Whether or not the image dissector achieves widespread use in molecular luminescence remains to be seen; a fluorescence microfluorometer for quantitative cytochemistry, which uses an image dissector, indicates some interesting possibilities (C74). Photodiode arrays are the subject of a detailed review by Horlick and Codding (C75). As yet, Ingle’s group appears to

be the only one to have reported appreciable use of these detectors in molecular luminescence; both fluorescence (including kinetic analyses) and chemiluminescence studies have been described (C76). At present, the SIT vidicon seems more generally useful than the diode array for most types of molecular luminescencespectrometry. One must, however, attach the caveat that solid-state diode-array technology is still improving; for example, the new, lar er (2.5-mm height) arrays offer a substantial practical S/N ajvantage in most situations over previously-availablearrays (C77). While electronic array detectors certainly will not supplant PMTs any time soon, if ever, their use certainly will continue to expand. Computers and Automation. Wampler (C78) has reviewed the use of on-line computers in molecular luminescence spectrometry. Fitzgerald (C79) has compared digital and analog measurement techniques in fluorescence spectroscopy. Tiffany has described the design and application of a centrifugal fast analyzer system modified for performance of fluorescence and chemiluminescence measurements (C81). A computer-controlled syringe-drive titration assembly coupled to a commercial fluorometer, useful for binding studies in biological systems, has been described (C82). Interfacing of a Gilford 3500 computerized analyzer system with a commercial fluorescence spectrometer has been described (C83). Automated systems for fluorometric amino acid analyses have ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

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been designed (‘284, C85, C293). Procedures for automation of fluoroimmunoassay procedures have been reported (C86(288).

P h o s p h o r e s c e n c e Techniques. A cryostat having the capability of continuously variable temperature over the range 77-300 K may be useful for phosphorescence spectrometry (C89). Time-resolved phosphorimeters using pulsed nitrogen or nitrogen-pumped dye laser excitation (C90) or SIT vidicon detection (C69) have been described. Use of heavy-atom solvents to improve detection limits in time-resolved phosphorimetry has been discussed (C90). An extensive compilation of glass transition temperatures for organic liquids and binary mixtures thereof may assist in choosing solvent media for phosphorimetry (C91). Though room-tem erature phosphorescence normally is regarded as a solixsurface technique (see next section), Turro et al. (C92) have noted that phosphorescence often can be observed in fluid solution, using various combinations of nitrogen purging, heavy-atom solvents, and addition of surfactants; the analytical implications of these results merit consideration. Room-Temperature Phosphorescence a n d O t h e r Soli d - S u r f a c e T e c h n i q u e s . Solid-surface luminescence techniques-especially room-temperature phosphorescence (RTP)-have received considerable attention. Guilbault has reviewed solid-surface fluorometric analysis, with emphasis on the silicone rubber pad technique developed by his group (C93, C94). A review of R T P by Vo-Dinh and Winefordner includes a discussion of methodology and apparatus (C95). Modifications of a spectrodensitometer (C96) and commercial fluorometers (C97, C98) for R T P measurements on filter paper or thin-layer chromatography (TLC) plates have been described. Vo-Dinh and Gammage have discussed the application of synchronous scanning to RTP; the operative parameter in this case is the triplet-ground state energy separation (C99). The use of second-derivative techniques in R T P to achieve improved selectivity has been reported (C100). Hurtubise has compared experimental analytical calibration curves for solid-surface luminescence with those calculated via a modified Kubelka-Munk model (C101). The use of heavy-atom matrices for R T P continues to be reported (C102, C103). In certain cases, the heavy-atom effect operates in such a way as to increase the phosphorescence efficiency only for some components of a complex sample; Vo-Dinh and Hooyman have presented a n extensive tabulation of such results for R T P analysis of polycyclic aromatic compounds (C104). Solid sodium acetate has been used as a substrate for R T P of organic compounds (C105). A flow-through cell packed with a permeable adsorbent (which allows the same surface to be used for every sample) has been reported (C137). Techniques for fluorometric or phosphorometric detection in thin-layer chromatography continue to be developed and refined. Miller has reviewed techniques for measuring luminescence from TLC plates (C106). Techniques for and advantages of scannin fluorescence simultaneously from both sides of a TLC plate f a v e been described; the principal advantage over conventional procedures appears to be expansion of the linear dynamic range for quantitation (C107). A clever technique, useful for volatile analytes separated by TLC, is to remove them (one spot at a time) from the plate by vacuum sublimation onto a cold finger which is then washed with a suitable solvent, such as a Shpol’skii solvent for low-temperature fluorometry (C108). Reagents for producing or enhancing luminescence from compounds on TLC plates continue to be developed (C97, C109, C110). Limits of detection for fluorimetry of compounds on TLC plates often are improved if, after sam le application but prior to illumination, the plates are placex in an electric discharge for a short time (C111).

Q u a n t i t a t i v e Relationships, Calibration, Q u a n t u m Yields, a n d SIN Considerations. Winefordner and coworkers have presented a detailed mathematical treatment of luminescence radiance expressions for narrow band excitation; for sufficiently high source irradiance, the observed luminescence radiance is predicted to vary with the analyte concentration but to be independent of both the source irradiance and fluorescence quantum yield of the analyte. The conditions under which saturation can be achieved by laser excitation of molecular fluorescence also are discussed (C112). The relationship between measured fluorescence radiance and 78 R

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analyte concentration is, of course, linear only under certain limiting conditions. The errors associated with linear and higher-order approximations in the fluorescence vs. concentration relation have been treated (C113). An analysis of the errors made by assuming a linear relationship between fluorescence and concentration, particularly as regards the determination of fluorescence quantum yield ( aF)by the comparative procedure, has been presented (C114). Photoacoustic spectroscopy has been used for absolute @F measurements by a number of groups (C115-C120). Calorimetric techniques (C121, C122) and thermal blooming (C123) also have been utilized for absolute @F measurements. Upton and Love (C124) have developed a technique for comparative aF determinations based on pulged-source photon counting measurements. An approach to the comparative method for @F measurement, wherein a separate measurement of the absorbances of the “unknown” and “standard” solutions need not be made, has been reported (C125). The relative luminescence quantum efficiencies of several quantum counters (rhodamine B, rhodamine 6G, methylene blue, nile blue A, and azure B) have been measured by Taylor and Demas as a function of wavelengths, using a “quantum counter comparator” apparatus designed specifically for the purpose (C126). Absolute calibration of rhodamine B as a uantum counter has been achieved by use of a bolometer evice (C127). Rhodamine B, which has been used as a quantum yield standard, exhibits a @F which is strongly temperature-dependent; it must therefore be used for this purpose only with considerable care (C128). Cresyl violet has been suggested as a standard for determinations by the comparative method requiring excitation in the red (540-640 nm) region of the spectrum (C129). The effect of excitation bandwidth on apparent values of aF determined by the comparative technique has been discussed (C130). Refractive index effects on luminescence quantum yield determinations have been considered (C131). A set of deuterium lamps calibrated for use as irradiance standards in the 200-350 nm range has been described (C132). T h e spectral response of a hydrogen-stabilized plasma arc has been calibrated over the 60-360 nm wavelength range (C133). New “spectrum separation” parameters, for measuring the extent to which the absorption and fluorescence spectra of a molecule overlap, have been proposed as more meaningful for practical use than the simple Stokes shift (C134). Mathematical procedures to correct for inner-filter effects in fluorescence measurements have been described (C43, C44, C294). Computer methods for “decomposing” overlappin fluorescence spectra in liquid solution for identification and quantitative determination of specific sample constituents have been described (C138, C139). Computer techniques applied to deconvolution of overlapping bands in X-ray (C140) and photoelectron (C141) spectroscopy should be useful in fluorescence spectrometry as well. Cova and Longoni (C174) have provided a detailed discussion of signal-to-noise (S/N) considerations in spectroscopic measurements. Winefordner et al. have presented a two-part review of S/N considerations in spectroscopy, which considers in detail the origins of noise in spectroscopic measurement systems and presents equations for S/N under various conditions (C135. C136). Wavelengt’h Modulation a n d Derivative Techniques. O’Haver has reviewed the methodology and applications of wavelen h modulation and derivative spectrometry (C142(2144). pwavelength modulation technique useful for resolution of overlapping peaks and measurement of small shifts in fluorescence band maxima has been described by Burtnick and Steinberg (C145). In this procedure, a photoelastic modulator plus two polarizing filters permits light from alternating halves of the emission monochromator exit slit to reach the detector; thus, the wavelength moddation interval can be altered by changing the slit width. Wavelength modulation of the output of a dye laser can be achieved by mechanically vibrating the tuning element a t a known frequency (C146) or by using an electro-optic birefringent filter tuning element and modulatin the voltage applied to it (C147, C148). O’Haver has presentecfa discussion of possible clinical applications of derivative and wavelength modulation techniques (C149). An analog computer system for producing successive derivatives of spectra has been described; for UV-visible ab-

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sorption spectra, optimum resolution of overlapping peaks in mixture spectra seems often to be achieved by taking the fourth derivative (C150). Applications of derivative methods to room-temperature phosphorescence have been described (C100). S y n c h r o n o u s S c a n n i n g a n d Related Luminescence Techniques. That a fluorescence or phosphorescence measurement actually involves two spectra (excitation and emission) has long been recognized as offering potential selectivity advantages over absorption techniques, but only recently has this fact been exploited effectively for photoluminescence analysis in multicomponent samples. In the simplest “synchronous” technique, the excitation and emission monochromators in a fluorimeter are scanned at the same rate, but the two wavelengths differ by an amount A i (C151-Cl53). If Ax is roughly equal to the Stokes shift for a particular compound, considerable spectral simplification for that compound occurs. A somewhat more complex experiment consists of generating “total luminescence contour maps” or “excitation-emission matrices”, wherein a plot of emission vs. excitation wavelengths is pre ared in which contours (lines of constant emission intensity7 are indicated. Such contours can be prepared by serial scanning of the emission wavelength a t a series of different excitation wavelengths (C154, C155) or by spatially dispersing the exciting light across the sample as a function of wavelength and recording the emission with an array detector (C62,C65). The interrelationships between these techniques have been discussed by Weiner (C156). Use of synchronous scanning to reduce Rayleigh and Raman scattering interferences for fluorometric trace analyses in aqueous solutions has been discussed (C157). The use of the relative intensities of fluorescence vs. Raman bands in synchronously-excited spectra of solvents has been suggested by Lloyd as a useful criterion for solvent purity (C158). Application of synchronous scanning to phosphorescence, wherein the relevant parameter is the singlet-triplet energy splitting, has been reported (C99). Qualitative applications of the various synchronous luminescence techniques, such as oil-spill fingerprinting (C154, C159) and identification of specific polycyclic aromatic compounds in mixtures (C1.51, C152),have been reported. Interest also is intensifying in quantitative use of these techniques. Christian and co-workers have discussed techniques for the acquisition of quantitative data from contour-map methods (C63, C64, C160). While the synchronous scan and contour map techniques certainly will receive greatly increased utilization for fluorometric analysis in multicomponent samples, they are not devoid of drawbacks; possible sources of qualitative and quantitative errors in synchronous scanning fluorometry have recently been described (C161). Polarized Luminescence a n d Related Techniques. A fluorescence polarization spectrometer, using photon counting for detection of weak signals and a reference compensation system for accurate subtraction of solvent background, has been described in detail by Weber and co-workers (C162). A fluorescence polarization detector which can be fitted to a commercial fluorometer has been designed (C163). A fluorescence polarization spectrometer suitable for simultaneous measurement of all quantities required for determination of orientation and mobility of moving molecules (e.g., in polymers) has been described (C164). An apparatus for measuring changes in fluorescence polarization brought about by changes in applied pressure has been constructed (C165). A device for flow cytometry based on fluorescencepolarization measurements has been developed (C166). Mathematical techniques to correct fluorescence anisotropies for finite detector apertures have been presented (C167). The use of nematic liquid crystals as orienting matrices for polarized fluorescence spectroscopy has been discussed (C168). Dale has reviewed the theor and experimental methods of time-resolved fluorescence cikpolarization measurements (C169). A dye-laser spectrometer for time-de endent fluorescence depolarization measurements has been &scribed (C170). The measurement of fluorescence anisotropy decay by time-correlated photon counting has been discussed (C171-CI73). Fluorescence Decay Times a n d Time Resolution. The literature pertaining to experimental procedures in nanosecond and subnanosecond luminescence spectrometry has grown to

mind-boggling proportions; since a boggled mind is of no use to anyone (C175),considerable (and arbitrary) selectivity of citation is exercised in this section. A number of relevant reviews have appeared. Topp has given a comprehensive review of pulsed laser spectroscopy (Cl76). Gauthier and Delpech have reviewed the techniques and applications of time-resolved laser-excited fluorometry (C177). Ippen and Shank have provided a readable general review on techniques in subpicosecond spectroscopy (C178). A monograph edited by Shapiro provides a useful compilation of experimental techniques and applications of ultrafast electronic spectroscopy (CI 79). Techniques and applications of fast spectroscopy in biological samples have been reviewed by Holten and Windsor (C180). Proceedings of two conferences dealing with subnanosecond processes include a number of papers dealing with experimental techniques (C181, C182). Detailed descriptions of a number of instruments for fluorescence decay-time measurements and/or time-resolved fluorometry have appeared (C183-C189). Reviews on techniques used to enerate subnanosecond pulses from lasers have been giventy Bradley (C190, C191). Mode locking of dye lasers has been discussed in detail by Shank and Ippen (C192). Among the techniques employed to obtain short pulses from dye lasers are active (C183)and passive (C193)mode locking; cavity dum ing (C183, C194); synchronous pumping using a mode-lockecfpump laser (C184, C187, C195-C200); combined mode-locked and cavity-dumped operation (C183);“double mode locking” (C202);and “pulsed Q-modulation” (C202). A mode-locked krypton ion laser (C203) and a laser functioning via three-photon amplification in nonlinear media (C204) also have interesting possibilities as sources for fast fluorometry. Techniques for shaping of pulses from a Q-switched laser via a Pockels cell to produce pulse widths of ca. 250 ps have been described (C205). Increasing the time separation between pulses produced by a mode-locked laser is essential whenever it is shorter than the phenomenon being studied. This objective often is accomplished by using a Bragg cell acousto-optic deflector which serves as a “cavity dumper” or “pulse picker” (depending upon the laser confi ation). Sidebands normally produced in this operation can geliminated spatially under certain conditions ((2245). The use of synchrotron radiation for time-resolved fluorescence measurements has been discussed (C32, C33, C206-C208). The use of the accurately known pulse width of synchrotron radiation (and the independence thereof of the wavelength) has been employed to calibrate the time-response characteristics of photomultiplier tubes and the pulse shapes of laboratory pulsed sources (C209). Various approaches for ultrafast gating of optical signals relevant to subnanosecond fluorescence spectroscopy have been discussed (C210-C212). General approaches for detecting very fast optical signals have been reviewed by Ippen and Shank (C211)and Bradley (C191). Green has described techniques for evaluating the performance of high-speed detectors (C213). A brief survey of the various designs for high-speed photomultiplier tubes (PMTs) has been given (‘2214). The use of a static crossedfield P M T for subnanosecond time-resolved measurements has been described (C215). The use of microchannel plates for fast detection in time-resolved fluorometry has been discussed (C216, C217). A constant-fraction discriminator for use with channel plates has been described (C218). The timing capabilities of crossed-field PMTs and microchannel plates has been compared (C219). A general discussion of time-correlated photon counting procedures for fluorescence-decay measurements has been given by Spears (C220). Detailed descriptions of apparatus and techniques for time-correlated photon counting in the nanosecond and subnanosecond regimes have been presented (C183, C185, C187, C221). Lytle and co-workers have compared different operating configurationsof a time-to-amplitude converter (TAC) for their suitability in time-correlated photon counting; the “inverted” configuration (wherein the fluorescence photon produces the “start” pulse) with the “busy” output of the TAC used to control the laser (such that the sample is never excited while the TAC is processing data) has been described as optimal (C222). Mathematical corrections for the fraction of TAC start pulses lost in the system “busy ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

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time” have been proposed (C223). Lytle and co-workers have discussed a sampled photon counting system for fluorescence decay measurements (C224). A multilevel discriminator circuit employed to increase the maximum count rate which can be used in photon counting via a sampling oscilloscope has been described (C225). T h e transit times of photoelectrons between the photocathode and first dynode depend upon the energy of the photon incident upon the photocathode; this time difference can be as much as several ns over the UV-visible spectral range (C226, C227). The problem can be especially irksome in deconvolution of the experimental luminescence decay curve from the decay function for the source, because the wavelengths of the somce radiation and sample fluorescence usually are quite different. A technique using a “wavelength shifter” having a broad-band emission spectrum, an accurately known (or exceedingly rapid) luminescence decay time, and an accurately known (or very rapid) rise time, has been described; the idea here is to obtain the source decay function by deconvolution from the (known) luminescence decay function of the “shifter” measured a t the same wavelength as that of the luminescence of the substance whose decay time is to be determined (C228). Mathematical procedures for eliminating or correcting for this problem also have been published (C227). Various electronic gating techniques suitable for use of vidicons as detectors in time-resolved fluorometry have been described (C229-C231). The design and application of streak cameras a8 detectors in the ps time domain have been discussed (C232-C235). Commercial diode chips have been used to fabricate a detector suitable for laser pulse diagnosis using ps lasers emitting anywhere from 257 nm out to the near IR ((2236). T h e phase-shift method continues to be utilized and refined. Phase-shift methods using modulated CW lasers as sources have been shown capable of decay-time determinations in the ps regime (C226, C237). Modulation of the output of a CW argon-ion laser over a wide frequency range, suitable for phase-shift decay-time measurements, has been achieved by use of a cavity dumper (C238). A number of new techniques for fluorescence decay-time measurement have been proposed. Barnes and Lytle have described the measurement of decay times by “modulated gain spectroscopy” (C239). In this technique, a mode-locked ion laser is used to excite molecules to the first excited singlet state. A beam from a dye laser (synchronously umped by the ion laser) stimulates emission from the excitecfstate, thus effecting a gain in intensity of the dye laser beam, which is measured. The manner in which the gain of the dye laser beam changes as a function of the time interval between incidence of the ion and dye laser beams upon the sample depends in a predictable way on the excited-state lifetime. The beauty of this procedure is that spontaneous fluorescence of the sample is not measured; hence, the method should be applicable to weak fluorescers or to systems in which efficient excited-state quenching is taking place. Harris and Hieftje and their respective groups have applied correlation methods to decay-time measurement; these methods basically involve cross-correlation of the exciting light with the fluorescence emitted by the sample (C240, C241). These methods appear to require less elaborate apparatus than most “conventional” decay-time measurement schemes; for example, a CW laser can be used if the technique is implemented in a certain way (C241). The use of an optical delay system to achieve the time delay required for the cross-correlation operation is especially ingenious (C240). In another novel procedure, Hieftje and co-workers have used a CW laser source, with its associated “mode noise” producing time-dependent fluctuations in the excited-state concentration within the sample. Because the excited state has a finite lifetime, its concentration cannot fluctuate at the highest frequencies encountered in the mode noise. Therefore, the extent to which the power spectra of the laser output and the fluorescence differ depends upon the excited-state lifetime (C242, C243). This technique does require an (expensive) high-frequency spectrum analyzer for implementation, but avoids the need for a short-pulse laser. Techniques for, and advantages of, two-photon-induced fluorescence of higher excited singlet states for studying rate rocesses involving the second (or higher) excited singlet have een discussed by Lin and Topp (C244).

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T h e problem of deconvolution of the experimental fluorescence decay from the source decay function, to yield a “true” decay curve, can be counted upon to rear its head. Ware and co-workers have made a detailed comparison of the most common deconvolution procedures; most of the published methods work for a single exponential decay but closely-spaced multiple exponentials or nonexponential single-component decays cause trouble. Careful study of this paper is strongly recommended to anyone forced to grapple with the deconvolution problem (C246). Techniques based on Fourier transforms (‘2185, C247) or modulating functions (C248),which purportedly do not require a priori assumptions regarding the mathematical form of the decay law, have been described for deconvolution. Cooper emphasizes that caution always should be exercised in deconvolution procedures (C249). Eisenfeld and Ford have discussed the perennial problem of extracting accurate decay constants from multiple exponential decay curves; multiple decay-curve measurements (at different excitation and emission wavelengths) and use of the method of moments for data analysis are advocated (C250). A procedure for correcting measured fluorescence decay curves for errors produced by scattered source light has been described (C251). Dale has reviewed the experimental techniques in timeresolved fluorescence depolarization studies (‘2169). Various instruments for time-resolved polarized fluorescence spectroscopy have been described (C170-Cl73). Chemiluminescence. Only instrumentation and techniques which appear to be of reasonable general applicability are considered here; applications of chemiluminescence (CL) and bioluminescence (BL) to specific analyses are considered in the appropriate section. Standardization, calibration, and quantum efficiency measurement techniques for solution CL have been reviewed by Seliger; this review also contains an authoritative discussion of photometric measurement units, fluorescence quantum yield determination, and photomultiplier calibration (C252). Seitz has provided useful reviews of CL in analytical chemistry which include general discussions of instrumentation and measurement techniques (B6,C253). Wampler et al. have provided detailed descriptions of instrumentation constructed in their laboratory for CL and BL measurements (C254);also described is a portable photometer for field use and a computer-controlled CL instrument for laboratory use (C255). The characteristics of several commercial instruments for CL measurements have been compared (C256). Freeman and Seitz have described a CL measurement device employing a fiber optic probe, the surface of which is coated with an immobilized enzyme preparation. When this probe is inserted into a solution containing a substrate for the enzyme, CL is generated (e.g., in the luminol reaction) and conveyed to a detector by the fiber optic probe. Under appropriate conditions, the CL signal can be related to the substrate concentration (C257). The immobilization of bacterial luciferase and NADH:FMN oxidoreductase on lass beads has been reported by DeLuca and co-workers, a n i the advantages of this system over solution techniques for CL analyses have been discussed (C258-CZSO). CL measurements often are well suited to flow cell, rather than static solution, measurements; useful discussions of flow cell design parameters have appeared (C261, C262). Use of a microporous (“poroplastic”) membrane to separate a reagent reservoir from the analyte stream in a CL flow apparatus is shown to produce measurements of high sensitivity (C263). Apparatus for chemiluminescence detection in flow-injection analysis has been described (C264). The use of self-scanned solid-state diode arrays (‘276) and vidicon tubes (C68) as detectors for CL measurements has been discussed; the ability to observe spectral chan es as a function of time is a useful characteristic of array fetector measurement systems. CL and BL devices for water quality monitoring and measuring microbiological populations in water have been described (C265). An automated instrument for clinical applications of CL has been designed (C266). Comparisons of luminol with various other phthalic hydrazides as reagents for CL assays have been reported (C267). Techniques in gas-phase CL measurement have been reviewed by Fontijn (C268). Design details for a chemiluminescence monitor for aliphatic hydrocarbons in air samples


(using a microwave discharge to generate oxygen atoms as “reagent”) have been described (C269). A CL apparatus suitable for upper-atmosphere measurements from rockets has been described (C270). A CL detector for GC, selective for iodinated hydrocarbons, has been described (C271). GC detectors for aliphatic hydrocarbons are based upon CL generated when the eluant is passed into a microwave discharge containing Nz(C272) (the emitting species is the CN radical) or upon reactions of hydrocarbons with O3 (C273). Luminescence i n Liquid a n d Gas Chromatographic Detection. The use of fluorescence as a detection technique in LC has been reviewed by DiCesare (C274). Porro has discussed the design parameters of detector cells suitable for sensitive LC detection by fluorescence (C275). A laminar flow cell for fluorometric LC detection with an effective detection volume of ca. 50 nL is capable of yielding detection limits in the nanomolar region when laser excitation of fluorescence is used; a particular advantage of the design is that the sample does not come into contact with the cell windows, thus decreasing contamination of the windows by dirty samples (C276). Detailed comparisons of the performance of several commercial fluorometric LC detectors have been reported (C277). Cut-off filters have been compared with dispersive monochromators as energy selectors for fluorometric LC detection; not surprisingly, use of a cut-off filter enhances sensitivity a t the expense of selectivity. Only if the chromatographic system produces “complete” separations is use of a cut-off filter really satisfactory (C281). A German patent describes a system wherein the LC effluent is passed through a flow cell packed with a solid adsorbent; fluorescence of the adsorbed solute(s) is measured. This device is purportedly more sensitive than conventional liquid flow cells (C284). While most fluorometric LC detection is performed using lamp sources, the advantages of laser excitation are becoming increasingly evident. The combination of high photon flux, low scattered light intensity (because the position of the beam can be located in a precise manner with respect to the detection optics), and small required active volume signify that very low detection limits can be achieved by laser fluorometry coupled with LC; e.g., g for aflatoxins (C278-CZ80) and mesoporphyrin IX dimethyl ester (C276). The use of a suspended droplet of LC eluant as a “windowless cell” (C278C B O ) and a laminar micro flow cell (C276)in conjunction with laser excitation have been described in detail. Derivatization to form fluorescent compounds for detection by fluorescence in LC has been reviewed by Frei (C282) and Seiler and Demisch (‘2283). A reaction system for fluorometric detection of organic nitrogen com ounds in GC effluents, wherein the compounds are convertel to NH3 by reaction with high-pressure H2 and the ammonia then is converted into a fluorescent product by reaction with o-phthaldehyde, has been designed (C285): Miscellaneous. Construction details of an inexpensive filter fluorometer designed for use in titrimetric procedures have been reported (C286). A laser fluorescence spectrometer designed for topographic examination of solid samples has been described (C287). A fluorometric detection system for coulometric titrations has been constructed (C288). Design details for a vacuum UV fluorometer have been reported; the instrument uses a pulsed capacitive discharge source, and methods used for pulse-to-pulse intensity variation corrections are described (C289). A technique named “metastable transfer emission spectroscopy”, wherein energy transfer from metastable excited nitrogen to analyte species in a gas flow roduces fluorescence from the analyte, has been demonstratef for both atomic and molecular analytes (C290). “Photoselected fluorescence detected circular dichroism”, wherein the optical activity of a chromophore is obtained by measuring the difference in its fluorescence intensity for excitation by left and right circularly polarized light, has been discussed (C291). The reaction between N-bromosuccinimide and N-acetyltryptophanamide is suggested as a suitable chemical system for measuring the dead time of a fluorescence stopped-flow spectrometer (C292).

ANALYTICAL APPLICATIONS In this section, only applications of relatively new or unconventional techniques, or those more conventional types of applications which (in the reviewer’s judgment) appear to

have especially broad general interest, are discussed. Laser-Induced Fluorescence. Applications of laser excitation, to obtain enhanced selectivity or detectivity (or both), are appearing in greatly increasing numbers. Omenetto has edited a monograph on analytical laser spectroscopy which contains several chapters relevant to the subject matter of this review ( 0 1 ) . Demtroder has given a detailed review of the laser-induced absorption and fluorescence of molecular systems (02). Some recent advances in analytical laser spectroscopy have been surveyed by Keller and Travis (03). The proceedings of an ACS symposium on new laser applications contain several papers related to laser fluorescence measurements ( 0 4 ) . Richardson and Ishibashi and their respective co-workers have demonstrated detection limits in favorable cases of less than 1 part per trillion (with a linear dynamic range as large as 7 decades) for fluorescent analytes in aqueous solution by use of a nitrogen-pumped dye laser as excitation source (05, 0 6 ) . Zare and co-workers (C278-C280,07) and Christian et al. (C276) have achieved detection limits in the pg (or lower) region for laser-induced fluorometric detection in LC. Imasaka and Zare have coupled the Lowry “enzyme amplification” chemical system with excitation of fluorescence by a He-Cd laser to achieve detection limits for NADP at the lo-’ M level (08). At such low analyte concentrations, luminescence and scattering from the solvent become a very significant problem; Matthews and Lytle have noted that purification of reagent-grade solvents generally produces material inferior in purity to the best commercial high-purity solvents ( 0 9 ) . The opportunities for increased selectivity afforded by laser excitation are beginning to be exploited in an effective manner. Wright and co-workers have reviewed laser techniques for selective excitation of fluorescence in ionic solids (010,0 1 1 ) . The selective excitation of probe ion luminescence (“SEPIL”) method has been applied to the determination of nine lanthanides in mixtures, by quantitative coprecipitation in CaF, and selective excitation of their 4f electron line luminescence spectra with a nitrogen-pumped dye laser (012). The technique has been extended to determination of nonluminescent ions by exploiting the fact that a luminescent “probe ion” (e.g., Er3+)in a CaFz precipitate which has some other guest ion as a nearest neighbor will absorb and emit a t a slightly different energy from the unperturbed probe ion; thus, the probe ions which occupy specific types of lattice sites can be selectively excited by a dye laser ( 0 1 3 ) . A different type of “site-selective’’ excitation of fluorescence in solid media has been utilized by Small e t al. in studies of polycyclic aromatic hydrocarbons in low-temperature organic solvent glasses. Though the solute molecules in such matrices exist in a variety of sites (with consequent “inhomogeneous broadening” of their spectra), selective laser excitation of fluorescence from molecules of a compound occupying specific sites produces substantial band narrowing in their fluorescence spectra (014). Wirth and Lytle have discussed techniques and applications of two-photon-excited fluorescence; the technique is especially suited to strongly absorbing solutions (wherein the measured fluorescence intensity is not linear in analyte concentration for single-photon excitation); this problem does not arise for two-photon excitation because of the very small molar absorptivity for two-photon absorption processes. Inner-filter effects also can be suppressed by use of two-photon excitation (027). Laser-induced fluorescence is receiving increased attention for environmental monitoring and remote sensing. Measures has reviewed the analytical applications of laser spectroscopy in remote sensin ; fluorescence methods are compared with other laser-base3 spectroscopic techniques in terms of applicability to remote sensing (015). Birnbaum has reviewed the use of laser-induced fluorescence for air pollution monitoring ( 0 1 6 ) . A comparison of the utility of lasers vs. flash lamps for NOz fluorescence monitoring has been reported ( 0 1 7 ) . A laser fluorometric system for remote sensing of atmospheric polycyclic aromatic hydrocarbons near coal conversion plants has been described (D18). A detailed description of an airborne laser remote sensing fluorometer for surface water pollutant detection and its use in the measurement of oil spills and paper mill effluents has appeared (019). A laser radar fluorometric system for Raman and fluorescence detection of oil spills, using a Nd:YAG laser ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

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and SIT vidicon detector, has been described ( 0 2 0 ) . Laserbased remote sensing fluorometric techniques for oil spill characterization and identification (021) and oil film thickness measurement ( 0 2 2 )have been designed. Calculations of the influence of wave action on the signal strengths observed by airborne fluorescence sensors have appeared ( 0 2 3 ) . Laser excitation also can be very useful when the sample is extremely small and/or it is desired to perform topographic mapping of the fluorescence of a sample. A laser fluorometer for topographic mapping of impurities on semiconductor surfaces has been described (C287). Flow cytometry and related techniques for fluorescent characterization of single cells (q.v.) represents an important application of lasers to fluorescence measurement (C72, 024-026). Lasers are also used in most analytical applications of time-resolved fluorescence (see following section). Time-Resolved Fluorescence Spectrometry. T o date, few applications of time-resolved fluorometry to strictly “analytical” problems have been reported. The fact that fluorescence spectra of metal chelates with organic ligands, such as 8-hydroxyquinoline, tend to be extremely similar has hampered applications of fluorometry to metal-ion determination in mixtures using such reagents. However, heavy-atom effects may be operative in such a way that chelates of the same ligand with different metals have fluorescence decay times which are sufficiently different that time-resolved analysis of mixtures may be practical ( 0 2 8 , 0 2 9 ) . However, this approach is unlikely to be universally applicable ( 0 3 0 ) . Heavy-atom substitution in organic molecules may also shorten the fluorescence decay time such that substituted aromatics may be time resolved from the parent in solution under conditions in which spectral resolution is impossible (031). Dickinson and Wehry (C186) have used time resolution to distinguish between compounds whose low-temperature matrix-isolation fluorescence spectra overlap. Rayner and Szabo have discussed the use of fluorescence decay profiles as an additional parameter useful for oil-spill characterization (021). The possibility of using differences in fluorescencedecay times to determine individual compounds in mixtures of atabrine and its homologues has been discussed (032). The use of time resolution to distinguish between fluorescence and scattering in fluorometric studies of biological samples has been discussed ( 0 3 5 ) . Hirschfeld has discussed the use of time resolution for fluorescent staining experiments in biological systems (e.g., in histochemistry); the idea is to distinguish between the fluorescence of the bound dye and background emission (from excess, unbound, dye or intrinsic sample fluorescence) ( 0 3 3 , 0 3 4 ) . Time discrimination also can be effected for this purpose in a relatively inexpensive manner by time-gated photobleaching ( 0 3 4 ) . Use of time resolution to achieve discrimination of signal from background in fluoroimmunoassay techniques has been discussed ( 0 112). Many more applications of time-resolved fluorometry have appeared in the application of fluorescent probe techniques to biological systems (not covered in the present review). Low-Temperature Luminescence Techniques. Considerable interest currently exists in the use of low-temperature media for the purpose of obtaining narrow-band fluorescence spectra suitable for analysis of multicomponent samples. Wehry and Mamantov have reviewed the techniques and advantages of matrix isolation as a low-temperature sampling procedure ( 0 3 6 ) . Use of time resolution in conjuction with matrix isolation has been shown useful for characterization of mixtures of fluorophores whose low-temperature fluorescence spectra overlap (C186). Use of matrix isolation fluorescence spectrometry for distinguishing between isomeric polycyclic aromatic hydrocarbons ( 0 3 7 , 0 3 8 ) and characterizing coal liquids and shale oils ( 0 3 9 ) has been discussed. Small and co-workers have described the use of “line narrowing” or “site selection” low-temperature fluorometry, wherein quasilinear fluorescence spectra are obtained from molecules in organic solvent glasses by use of narrow-line laser excitation; unlike the “Shpol’skii effect”, this phenomenon should be observable in virtually any solvent system which exhibits reasonable optical properties ( 0 1 4 ) . The Shpol’skii frozen-solution fluorescence technique has been applied to characterization of coal macerals and coal-tar pitch ( 0 4 0 ) , identification of polycyclic aromatic hydrocarbons in air and automobile exhaust samples (Cl08, 0 4 1 ) , identification of 82R


polycyclic aromatic hydrocarbons in fresh water sediments (042),and identification of thiophene derivatives in mixtures (043). D’Silva and Fassel and their co-workers have re orted the use of X-ray excited Shpol’skii fluorescence to i&ntify polycyclic aromatic hydrocarbons extracted from raw coal (045). That Shpol’skii fluorescence spectra can be obtained by vapor deposition (i.e., matrix isolation) as well as by the conventional frozen-solution procedure has been shown (046). A brief review of the analytical utility of phosphorescence has been presented by Miller and Bridges ( 0 4 4 ) . Though room-temperature phosphorescence is gaining the lion’s share of the attention these days, applications of more conventional phosphorescence techniques continue to appear. The use of phosphorescence techniques in the study of protein structure has been reviewed ( 0 4 8 ) . Phosphorometric determinations of beryllium ( 0 4 7 ) and antiinflammatory and antipyretic drugs ( 0 4 9 ) have been reported. Supersonic expansion of a gas stream through a nozzle into a vacuum can be used to produce cooling of polyatomic molecules to rotational temperatures of 0.5 K or less ( 0 5 0 ) . The resulting electronic spectra often are characterized by extraordinarily high resolution of fine structure and therefore are of potential analytical interest. Though no analytical applications of this procedure have yet been reported, the phenomenon has been observed for molecules as large as free base phthalocyanine ( 0 5 1 ) ; notwithstanding some experimental complexities, it is reasonable to anticipate analytical exploitation of the supersonic jet principle. Chemiluminescence. Reviews of applications of solution chemiluminescence (CL) have been presented by Seitz and Neary (B6),Paul ( 0 5 2 ) ,and Seitz (C253). Wettermark et al. have reviewed the use of CL in biochemical microanalyses (B7). Gorus and Schram have reviewed applications of CL and bioluminescence (BL) in clinical analysis (B8). Solution CL continues to be applied frequently to determinations of inorganic analytes. Among noteworthy examples are the following. The luminol system continues to experience applications to determinations of metal ions, including Cu(II), Cr(III), Fe(II1) ( 0 5 3 ) ,Ir(IV), Pt(I1) (054),Ge(1V) ( 0 5 5 ) ,and Co(I1) (C263,053). Detection limits for Cr(II1) via luminol CL can be improved by addition of C1- or Br- to the sample; determination of Cr(II1) in seawater by luminol CL also has been described (056). Trace metals determined by lucigenin CL (057) include Co(I1) ( 0 5 8 ) ,V(1V) and Mo(V) (059). The lophine CL system has been used to determine Co(II), Cr(III), Cu(II), and OC1- ( 0 6 0 , 0 6 1 ) . Trace metal and H 2 0 2determinations using the peroxyoxalate CL system have been reported (062). Zn(I1) is determined by an indirect technique wherein a deactivated enzyme (pyruvate oxidase) is activated by Zn(I1) in a concentration-dependent manner; the oxidation of pyruvate acid by O2 (catalyzed by the enzyme) produces H 2 0 2which is determined by a CL reaction with bis(3,4,6trichloropheny1)oxalate ( 0 6 3 ) . Solution CL applications to organic analysis include the following. Determination of aromatic hydrocarbons via peroxyoxalate CL has been reported (062). Interferences in the CL determination of nitrosamines via pyrolysis to NO have been studied ( 0 6 4 , 0 6 5 ) . GC/CL and GC/MS procedures for N-nitrosodimethylamine have been compared ( 0 6 6 ) . CL induced by reaction with O3has been proposed as an analytical technique for organic contaminants in water (067). CL has been discussed as a possible approach to the detection of explosives (068). A luminol CL method for amines has been described ( 0 6 9 ) . Mannitol, sorbitol, and related substances have been determined by a luminol CL quenching method (070). Numerous applications of solution CL in clinical and biochemical analysis have appeared. Use of CL measurements in immunoassay procedures has been discussed ( 0 7 1 , 0 7 2 ) . Systems for the CL determination of enzymatically-generated H202,and applications of this analytical system to a variety of enzyme-catalyzed reaction systems, are discussed in detail by Seitz ( 0 7 3 ) . Use of the earthworm BL system for HzOz assay is described by Mulkerrin and Wampler ( 0 7 4 ) . Enzyme-catalyzed reaction systems which produce HzOz detectable by CL have been used for determinations of cholesterol ( 0 9 9 ) ,lactose, and glucose ( 0 7 5 ) . The luminol CL system has been used to determine amino acids (076),penicillin ( 0 7 3 , and serum lucose (C264). The utility of luminol CL for monitoring oxifative metabolism in


phagocytic cells has been discussed (078). The lucigenin CL system has been employed for determination of several clinically important reducing agents, including ascorbic and uric acids, glucose, and glutathione ( 0 7 9 ) . Luciferase BL techniques for a number of analytes, including NADH, NADPH (C258-C260, 0 8 0 ) , F M N (D80),aldehydes and fatty acids ( 0 8 1 ) , guanine nucleotides ( 0 8 7 ) , and glycerol and triglycerides ( 0 8 2 ) have been described. Use of various BL and CL systems for studying protein binding reactions has been discussed ( 0 8 3 , 0 8 4 ) . Proteinprotein interactions have been studied via BL energy transfer (085). The use of gas-phase chemiluminescence for air pollutant monitoring has been reviewed by Fontijn (C268). Gas-phase CL processes have been reviewed by Campbell and Baulch (B10). The use of CL in the study of adsorption of gaseous species on solid surfaces, and catalytic phenomena involving such species, has been reviewed ( 0 8 6 ) . Process industry applications of CL air pollutant analyzers have been reviewed (088).

CL methods for atmospheric H20z(D89),aliphatic hydrocarbons (C269), oxides of nitrogen (090-093), nitric acid ( 0 9 1 ) ,ozone ( 0 9 2 , 0 9 4 ) ,and SOz ( 0 7 7 , 0 9 5 ) have been reported. Improvements in sensitivity of a CL olefin analyzer by addition of H2S or CS2 to the reaction mixture have been demonstrated (096). Interferences by various species in CL measurements of nitrogen oxides have been discussed ( 0 9 7 , 0 9 8 ) . The intercalibration of CL monitors for nitrogen oxides and ozone has been discussed (092). Studies of NO mixing ratios in the upper atmosphere using a rocket-borne CL detector have been reported (C270). Solid-Surface Luminescence. Room-temperature phosphorescence (RTP) on solid surfaces has been applied to determinations of polycyclic aromatic hydrocarbons (Cl02, C104), nitrogen heterocycles (C96, 0100, 0101), aromatic carboxylic acids ( 0 1 0 2 ) ,pharmaceuticals (DI03),and pesticides (0104). The reagentless rubber-pad technique has been used in an enzymatic determination of serum creatinine (0105). Polarized Fluorescence and Related Techniques. The use of fluorescence polarization for quantitative analyses in binary mixtures of fluorophores whose fluorescence spectra overlap has been discussed (0106-0109). This procedure is in many ways precisely analogous to the measurement of changes in fluorescence polarization upon binding of a fluorophore to a macromolecule, which is widely used in biochemical systems. A fluorescence polarization method for proteolytic enzymes, in which fluorescein isothiocyanate conjugates of proteins are used as substrates, has been reported (0110). A determination of blood-coagulation “factor XIII”, wherein the decrease in rotational Brownian motion (measured by fluorescence polarization) which occurs when monodansyl cadaverine is reacted with casein in the presence of factor XI11 to form monodansyl casein is related to the factor XI11 concentration in the original sample, has been described (0111). Many fluoroimmunoassay techniques (q.v.) make use of changes of fluorescence polarization occurring in antigen-antibody reactions. Other Applications-Organic. Described in this section are those applications of luminescence spectrometry to organic analysis, not mentioned in preceding sections of this review, which appear to be of particular interest. Lumb has provided a useful review of the fluorescence and phosphorescence of organic molecules (0113). The luminescence of organic solids has been reviewed by Williams (0114).

Applications of luminescence analysis to problems relevant in environmental science and energy production are appearing in increasing numbers. Frank (0115) and Bentz (0116) have reviewed analytical techniques (including fluorescence) for oil spill characterization. A remote sensing fluorescence procedure for determining the thickness of oil films on bodies of water has been described (0147). Various fluorescence procedures for characterization of coal liquids and shale oils have been reported ( 0 3 9 , 0 4 0 , 0117-0119). Fluorometric determinations of polycyclic aromatic hydrocarbons in sampled airborne particulate matter have been reported (0120). The use of fluorescence sensitization (0122) and quenching (0121) phenomena in determinations of polycyclic aromatic

hydrocarbons has been reported. Phillips et al. have provided a thorough review of the uses of photoluminescence methods in polymer science (0123). Morawetz has presented a brief survey of advances in fluorometry as applied to polymer systems (0124). The use of intramolecular excimer fluorescence as a probe of polymer blend compatibility has been suggested (0125). The identity of substances responsible for the observed phosphorescence of Nylon 66 has been discussed (0126). The use of fluorescence depolarization to study segmental motions in poly(methyl methacrylate) has been reported (0127). A quarternary ammonium anion-exchange resin dyed with a fluorophore whose emission is suppressed by an inner-filter effect when contacted with colored analytes can be used for determination of T N T in water samples (0128). Hydroxylation of pyridines with a reagent consisting of catechol, iron(II1) perchlorate, and HzOzproduces fluorescent products suitable for analytical purposes (0129). The compound 2(4’-isocyanatophenyl)-6-methylbenzthiazole is recommended as a reagent for fluorometric determination of amines, amino acids, alcohols, and phenols (0130). New fluorogenic reagents for amines (0131),aromatic aldehydes (0132),nitrosamines (0133),aliphatic isocyanates (0134),and thiols (0135) have been reported. Other Applications-Inorganic. In addition to the applications of luminescence techniques to inorganic systems cited in preceding sections, the following items are noteworthy. Imbusch (0136)has reviewed the luminescence of inorganic solids. The efficiency of quenching of uranium fluorescence (in the classical flux method for U determinations) by other metal ions has been studied, and improvements in the flux procedure have been suggested (0137). A kinetic fluorometric procedure for Al(III), based on its reaction with 8-hydroxyquinoline-5-sulfonic acid, has been developed (0138). Kinetic fluorometric techniques, based on enzyme-catalyzed reactions, for Mn(I1) ( 0 1 3 9 ) and As(V) (0140)have been described. A determination of Cu(I1) based on its ability to quench fluorescence of t-ADP has been reported (0141). Improvements in the 2-hydroxy-3-naphthoic acid fluorometric method for Be(I1) have been reported (0142). The use of Schiff bases as fluorogenic reagents for Al, Ga, Sc, and Be has been discussed (0143). Fluorescence reagents for Cr(V1) (0144) and (0145) have been reported. A fluorescence technique for determining the vertical distribution of water vapor in the stratosphere, by photolyzing the H 2 0 and measuring fluorescence of the resulting OH radicals, has been reported (0146). The identification of asbestos minerals in ambient air by a fluorescence staining procedure has been described (0148).

BIOCHEMICAL A N D CLINICAL APPLICATIONS This section deals with techniques and applications of luminescence spectrometry of special relevance to problems in the life sciences. Coverage is highly selective, limited to those publications which describe relatively new or emerging techniques or which appear to have especially broad general interest. Of course, many of the techniques covered in previous sections of this review also have important biochemical applications, some of which are cited in those sections. Microfluorometry, Flow Cytometry, and Histochemistry. One of the most exciting developments of recent years is the emergence of sophisticated new fluorometric techniques for the examination of very small biological samples, down to and including living cells. The use of flow cytometry for cell sorting and analysis is the subject of a book ( E l ) and several reviews (024-026). A review of fluorescence techniques in histochemistry has appeared (E2). Microspectrofluorometers for measuring fluorescence spectra of single living cells and for topographic mapping of fluorophore distributions in cells have been described (C71,E3, E4). Chance et al. have described a fiber-optic fluorometer for the examination of tissue samples (C38). Improvements in a dual-laser flow cytometric instrument have been described (E5). The use of a vidicon detector in flow cytometric instrumentation has been reported (C72). A flow polarimeter, for use in performing fluorescence polarization measurements in single cells, has been described and the uses of polarized fluorescence spectrometry in flow cytometry have been discussed (Cl66, E6). ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

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Computer data collection and analysis procedures and computer graphics for flow microfluorometry have been described (E15). A fluorometer using a CW He-Cd laser (A = 325 nm) for studies of cultured cells still attached to the growth surface has been described (E7). Experimental techniques for measuring fluorescence decay curves for substances adsorbed on isolated living cells have been described (E8). The use of energy transfer in a flow system to estimate proximities of cell surface receptors has been discussed (E9). A “virometer”, which is a device for detecting and sizing viruses which have been treated with a fluorescent stain, by measuring fluctuations in fluorescence intensity produced by time-dependent fluctuations in the number of stained viruses as they drift by Brownian motion through a small illuminated volume, has been described (E19). Techniques in the fluorometric examination of chromosomes have been discussed by Berns ( E l l ) . Several papers describing new labeling techniques and/or new stains for cytofluorometry have appeared (E12-El4). A useful discussion of pitfalls in staining and data analysis in cellular DNA determinations by rapid hypotonic staining has been presented (E16). Mathematical techniques for decomposing fluorescence histograms of cell populations into components corresponding to designated phases of the cell cycle have been outlined (E17, E18). The significance of the bimodal distribution of DNA fluorescence often observed in flow cytometric analyses has been discussed (E10). The advantages of using both static and flow cytometry to study growth parameters of complex cell populations, and to assess the effects of various procedures for cell pretreatment, have been considered (E20). Kohen and co-workers have described microfluorometric studies of rates of intercellular transfer of molecules and rates of metabolism (with topographic analysis of metabolic transients) in single cells and cell cultures (E21-EZ3). Quantitative fluorescence probe methods for measuring the pH in living cells have been described (E24, E25). The use of pyrenebutyric acid as a fluorescent probe for intracellular O2 analyses has been reported (E26). Dolbeare has described a technique termed “flow cytoenzymology” for identification of enzymes and measurement of enzyme activities in intact cells (E31, E32). The use of collisional fluorescence quenchers to selectively quench certain cellular components, and the use of such measurements to probe fluorophore locations in cells, has been discussed (E27). Use of a fluorescence cell sorter to assay benzo[a]pyrene metabolites in single cells has been reported (E28). Procedures for microfluorometric determinations of NAD(P)H (E29) and glycolipids (E30) in brain tissue sam les have been reported. The use of fluoresceinsubstitutealectins to determine fluorometrically the number of receptor sites and binding constants for cell surfaces has been discussed (E33). Methods for assay of intracellular calcium, including fluorescence techniques, have been reviewed by Caswell ( E X ) . Procedures for the use of chlorotetracycline as a fluorescent probe for Ca2+in cells have been reported (E35). Fluoroimmunoassay. The development of immunofluorescence as an analytical technique continues to show impressive progress. An introductory survey of fluoroimmunoassay principles and techniques has been presented by O’Donnell and Suffin (E36). A review of the present status and important problems in fluoroimmunoassay has been presented by Soini and Hemmila (E37). Parker has reviewed the use of fluorescence methods in the study of antigen-antibody and hapten-antibody reactions (E38). Nairn has presented an exhaustive review of the use of immunofluorescence for tracing of native components and foreign materials in tissues, and for tracing of antibodies in tissues and biological fluids (E39). Dandliker has reviewed the use of fluorescence polarization measurements in the study of immunochemical reactions (E40). Zare and co-workers have described a laser fluorescence immunoassay procedure, wherein the bound and free fluorophore-labeled antigen are separated by a liquid chromatograph equipped with a laser fluorescence detector; the technique has been applied to determination of insulin (E41). The use of time-resolution techniques to achieve background rejection in fluoroimmunoassay has been discussed by Wieder. In this approach, an antigen to be detected is tagged with a fluorophore having a fluorescence decay time which is long 84R


compared with those of other sample constituents; specific fluorophores and instrumentation for time-resolved fluoroimmunoassay are described (0112). Immunoassay procedures in which chemiluminescence, rather than fluorescence, is measured have been described ( 0 7 1 , 0 7 2 , E42, E43). Apparatus and techniques for automated quantitative fluoroimmunoassays have been described (E44).An automated continuous flow instrument suitable both for fluoroimmunoassay and radioimmunoassay procedures has been designed (E45). The use of a poly(methy1 methacrylate) film with a plane surface as a solid phase for antigen binding is claimed to offer significant advantages over conventional procedures for quantitative fluoroimmunoassay (E46). The use of a flow cytometer for immunoassay procedures has been described with particular reference to cytotoxicity assays (E47). A procedure for preparation of fluorescamine-labeled antibodies has been described (E51). The principles of “fluorescence protection immunoassay”, wherein formation of an immune complex of a fluorophorelabeled antigen protects the fluorescent species from binding by antibodies to it, have been described. This technique serves as the basis of homogeneous assay procedures which require no separation step and do not require pure preparations of labeled IgG conjugates (E48). Silver and co-workers have reviewed the use of immunofluorescence techniques in the analysis of chromosomal proteins (E52). Quantitative fluoroimmunoassay procedures for microorganisms or of antibodies directed to surface constitutents thereof have been reported (E49). Techniques in quantitative fluoroimmunoassay for antibodies to, and surface antigens of, human lymphoblastoid cells have been described (E50). A technique for detecting simultaneously the presence of two antigens in the same tissue section has been described (E53). A nonlinear regression analysis procedure for analyzing fluorescencequenching data in the characterization of heterogeneous antibody-hapten interactions has been developed (E54). Quantitation of C-reactive protein in serum can be achieved by fluoroimmunoassay ( E 5 5 ) . Fluoroimmunoassays for steroids (E56, E57), cortisol (E43,E58), testosterone derivatives (E42),insulin (E41,E43), neocarzinostatin (E43),gonadotropin (E59),thyroxine (072,E60), phenytoin (E61,E62), and prostatic acid phosphatase (E63)have been reported. The use of fluoroimmunoassay procedures for the detection of low levels of wild yeasts in brewery products has been discussed (E64). A fluorescence antibody procedure for studying nitrifying microbial populations in soil samples has been described (E65). O t h e r Clinical a n d Biochemical Applications. In addition to the applications of molecular luminescence to biochemical and clinical systems described in preceding sections of this review, the following applications appear of particular interest. The use of fluorometry in drug analysis has been reviewed by Schulman and Naik (E66)and Terhaar and Porro (E67). Froehlich has reviewed the use of luminescence methods for analysis in clinical and biological samples (E123). The potential of luminescence spectrometry in clinical applications has been discussed by Whitehead et al. (E68). Fluorometric procedures for mandelic and phenylglyoxylic acids, useful as a routine monitoring procedure for persons exposed to styrene, have been described (E69). Fluorescence methods for total serotonin serum cholesterol (E70),urinary estrogens (E71), (E72),plasminogen (E73),a -plasmin inhibitor (E74),cefoxitin (E75),and bilirubin (E76) 2ave appeared. Determination of total and free serum bilirubin via its static quenching of dansyl bovine serum albumin fluorescence has been reported (E77). Interference by formaldehyde in the fluorometric determination of morphine has been discussed (E78). LC-fluorescence (E79) and TLC-fluorescence (E80)techniques for LSD assay have been described. Fluorescence-LCmethods for adrenaline and noradrenaline (E81),prostaglandins (E82),and reserpine (E83) have been reported. Comparisons of the reliabilities of quinidine determinations in plasma by fluorometric and LC methods have been made (E84). TLC-fluorescence techniques for disopyramide (E85),am hetamine (E86),and adriamycin (E87) have been describe1 Williams has reviewed applications of spectroscopy (including fluorescence) in forensic science (E88). The use of phosphorescence to distinguish between different glass samples (which cannot be distinguished by refractive index


measurements) has forensic applications (E89). Recent progress in fluorescence techniques for the study of amino acids, peptides, and proteins has been reviewed by Hoggett (Ego). A review of the carbonyl compound-induced fluorescence of biogenic amines and its use in histochemical analyses has been presented by Partanen (E91). Optimum reaction conditions for the fluorogenic reaction of amines and amino acids with o-phthaldehyde have been discussed (E92E X ) . Use of the native fluorescence of catecholamines in LC detection has been discussed (El02). The possible competition of other nucleophiles (especially secondary amines and thiols) with primary amines in the fluorescamine reaction, and the influence of pH thereon, has been studied (E97). The use of o-phthaldehyde and fluorescamine in peptide analyses has been reviewed by Lai (E98). Fluorescamine and 2-methoxy2,4-diphenyl-3(2H)furanone as fluorescence reagents for peptides have been reviewed by Stein and Udenfriend (E99, E100). TLC followed by fluorescent mapping with fluorescamine has been used for peptide mapping in proteins (EIOI). Competitive inhibition of the fluorescamine reaction with primary amines by proline and hydroxyproline is the basis of a procedure for determination of the latter compounds ( E l 03). Procedures for dansyl chloride derivatization of amines have been described (E105). A modification of the lyoxylic acid method for amines in tissues has been described fElO6). Udenfriend has reviewed fluorescence methods for isolation, characterization, and assay of peptides and proteins ( E l 04). The use of phosphorescence methods in the investigation of protein structure has been reviewed ( 0 4 8 ) . Labeling techniques and apparatus for quantitating proteins and DNA in electrophoresis gels are dwcribed in detail (E107,E108). The use of bioluminescence energy transfer to study proteinprotein interactions has been discussed (085). Protein binding reactions have been studied by various chemiluminescence and bioluminescence approaches ( 0 8 3 , 0 8 4 ) . The use of injected serum proteins which have been labeled with fluorophores, and their localization by photometric and histochemical techniques, has been reviewed by Nairn (E109). A kinetic fluorometric method for tryptophan in feed and food samples has been described ( E l 1 0 ) . The design and application of "intramolecularly quenched fluorogenic substrates" in the fluorometric analysis of hydrolytic enzymes has been described. These substrates contain both a fluorophore and a quencher; cleavage of the substrate eliminates the intramolecular quenching interaction and produces a significant increase in fluorescence intensity (El 11, E112). A procedure termed "incremental analysis", for use in determining both enzyme and inhibitor activities in cell cytoplasmic fractions, has been described. This technique uses an insoluble fluorescein-labeled polymeric collagen fibril as substrate (E113). A fluorescence polarization procedure for proteolytic enzymes, using fluorescein isothiocyanate-conjugated proteins as substrates, has been reported ( 0 1 1 0 ) . Fluorescent staining procedures for transamidating enzymes, wherein the enzyme-catalyzed incorporation of fluorescent monodansylcadaverine into casein is measured, have been described (E114, E115). The use of 4-methylumbelliferyl sulfate as a fluorogenic substrate to locate enzymes in chromatographic fractions has been discussed ( E l 16). Eight stains useful for simultaneous staining of DNA and proteins have been compared (E117). The enhancement, via com lexation with DNA, of the fluorescence of 4,6'-diamid?lno-2-phenylindole or bisbenzimidazole can be used to detect DNA a t nanogram levels in cellular homogenates (El18). Comparisons of the ethidium bromide fluorescence and hydroxyapatite chromatography procedures for DNA structural analysis have been discussed ( E l 19). A technique for structural analysis of oligosaccharides (including sugar unit sequences and linkage points) in which the reducing and sugars are tagged with a fluorophore (2aminopyridine) has been reported (E120). Enhancement of the fluorescence of an aqueous solution of 1,6-diphenyl1,3,5-hexatriene by phospholipid vesicles is the basis of a method for determination of the latter (E121). A technique for mapping Zr and A1 distributions in lung tissue samples, using morin as the fluorogenic reagent, has been described (E122). A procedure for fluorometric determination of inorganic phosphate in renal tubular fluid has been reported (0145).

The use of fluorescent probes to make inferences regarding molecular microenvironments, dynamics, binding, and molecular organization in biological systems continues to increase in sophistication. While space precludes a detailed survey of the enormous literature in this area, several reviews pertaining to fluorescent probe techniques merit citation. Badley has provided a thorough review of the use of fluorescence techniques to probe the dynamic and molecular organization of biological membranes (E124). Fluorometric and magnetic resonance studies of membranes have been reviewed by Lee (E125). DePetris has reviewed the applications of immunofluorescence in membrane biology (23126). The fluorometric study of drug-membrane interactions has been reviewed by Hoss (E127). The use of fluorometric techniques to study the diffusional transport of toxic substances in membranes has been reviewed by Lakowicz and Hogan (E128). The use of cyanine dyes as fluorescent probes of membrane potential has been discussed by Waggoner (E129). The use of fluorescence techniques in the study of energy-linked processes in mitochondria has been reviewed by Azzi (E130). The use of Forster resonance ("long-range") intermolecular electronic energy transfer to estimate distances between chromophoric groups in biological macromolecules has been reviewed by Stryer (E131). Kalyanasundaram (E132) and Gratzel and Thomas (E133) have reviewed the use of luminescence techniques to probe molecular organization and dynamics in micelle-forming surfactant systems. Churchich has discussed the fluorescent probing of binding sites in proteins and enzymes (E134).

ACKNOWLEDGMENT The assistance of Reddy R. Rodda, of the University of Tennessee Science and Engineering Library, in preparing the Chemical Abstracts literature search profile used in preparation of this review is gratefully acknowledged. LITERATURE CITED INTRODUCTION ( A l ) O'Donnell, C. M.; Solie, T. N. Anal. Chem. 1979, 5 0 , 189R-205R. GENERAL BOOKS AND REVIEWS ( E l ) Lumb, M. D. "Luminescence Spectroscopy"; Academic Press: London, 1978. (82) Cundall, R. B.; Wyn-Jones, M. I n "Specialist Periodical Report Series: Photochemistry", Voi. 9. Bryce-Smith, D., Ed.; The Chemical Society: London, 1978; pp 92-139. (B3) Guilbault, G. G. I n "Wilson and Wilson's Comprehensive Analytical Chemistry", Svehla, G., Ed.; Elsevier: Amsterdam, 1977, pp 71-205. (84) Turro, N. J. "Modern Molecular Photochemistry"; Benjamin-Cummings: Menlo Park, Calif., 1978. (85) Schenk, G. H. I n "Instrumental Analysis", Bauer, H. H., Christian, G. D., O'Reillv. J. H..Eds.: Allvn and Bacon: Boston. Mass.. 1978: DD 728-55. (E61 Seiti'W. R.: N e a j , M: P. Contemp. Top. Anal. Chem. Clin, ' C k m . 1977, 1 , 49-125. (87) Wettermark, G.; Broiin, S. E.; Hjerten, S. Cell. Mol. Biol. 1977, 22, 329-39. (88) Gorus, F.; Schram, E. Clin. Chem. 1979, 25, 512-19. (89) Faulkner, L. R. Methods Enzymol. 1978. 5 7 , 494-526. (B10) Campbell, I.M.; Baulch, D. L. Gas Kinet. Energy Transfer 1978, 3 , 42-81; Chem. Absb. 1979, 9 0 , 194749. (E1 1) Rauhut, M. M. Kirk-Othmer Encycl. Chem. Techno/.,3rdEd. 1979, 5 , 416-50. (812) Nathan, R. A. Cassette tape; American Chemical Society, 1976. (813) O'Haver, T. C. J . Chem. Educ. 1978, 55. 423-33. INSTRUMENTATION AND EXPERIMENTAL TECHNlQUES ( C I ) Hamilton, T. D. S.; Munro, I. H.; Walker, G. I n "Luminescence Spectroscopy", Lumb, M. D., Ed.; Academic Press: London, 1978, pp 149-238. (C2) Klinkenberg, P. F. A. I n "Methods of Experimental Physics", Williams, D., Ed.; Academic Press: New York, 1976; Vol. 13A. pp 253-346. (C3) Eby, J. B.; Levin, R . E. I n "Applied Optics and Optical Engineering", Shannon, R. R., Wyant, J. C., Eds.; Academic Press: New York, 1979. (C4) Cochran, R. L.; Hieftje, G. M. Anal. Chem. 1977, 4 9 , 2040. (C5) Gallo, C. F.; Lama, W. C. Appl. Opt. 1977, 16, 819. ((26) Thomas, P.; Sacks, R . D. Anal. Chem. 1978, 50, 1084-88. (C7) Beesley, M. J. "Lasers and their Applications", Halsted Press: New Yo&, 1978. (C8) Sacchi. C. A.; Sveko, 0. I n "Analytical Laser Spectroscopy", Omenetto, N.. Ed.; John Wiiey: New York, 1979, pp 1-46. (C9) Schafer, F. P. "Dye Lasers"; Springer-Verlag: Berlin; 2nd ed., 1977. (C10) Peterson, 0. G. I n "Methods of Experimental Physics", Tang, C. L., Ed.; Academic Press: New York, 1979; Vol. 15A, pp 251-359. (C11) Latz, H. W. I n "Modern Fluorescence Spectroscopy", Wehry, E. L., Ed.; Plenum Press: New York, 1976; Vol. 1, pp 83-119. (C12) Weber, M. J. I n "Methods of Experimental Physics", Tang, C. L., Ed.; Academic Press: New York, 1979; Vol. 15A, pp 167-208. ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

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Nuclear Magnetic Resonance Spectrometry John R. Wasson"' and Jorge E. Salinas Ellestad Research Laboratories, Lithium Corporation of America, P.O. Box 795, Bessemer City, North Carolina 280 16

This review covers the published literature from July 1977 to July 1979 although a few references to other work are also included. As noted previously ( I ) , thousands of papers containing information on NMR spectrometry are published in the two-year period covered by this review and space limitations preclude citing more than a few of the publications. Comments on the literature of NMR spectrometry and its usage have been made in previous review ( I , 2). The Chemical Society (London) Specialist Reports on NMR spectrometry are the best continuing series of comprehensive reviews on the subject and are recommended for literature searching a topic of recent vintage or finding applications to particular systems. In addition to sources mentioned earlier ( I , 2), a new source of current computer searches of the magnetic resonance For biographical material, see the review on Electron Spin Res-

onance. 90 R

0003-2700/80/0352-90R$O 1.OO/O

literature has become available from the Institute for Scientific Information, 325 Chestnut Street, Philadelphia, Pa. 19106. Such computer searched current awareness services have become almost obligatory for the NMR practioner who must keep abreast of the subject. To summarize the recent NMR literature in a short space is clearly an impossibility. However, it is hoped that where this review fails as a review, it succeeds in capturing the flavor of this dynamic research area and serves as a useful guide to the current literature on NMR spectrometry.

BOOKS AND REVIEWS The books (3-25) on NMR spectrometry emphasize the growth of other-than-proton spectroscopy. In particular, the increasing number of books dealing with carbon-13 NMR underscore the activity in that area. The book by Levy and Lichter on nitrogen-15 NMR (20) affords a significant starting

0 1980 American Chemical Society

Molecular fluorescence, phosphorescence, and ... - ACS Publications

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