Anal. Chem. 1986, 58,13R-33R (340)Chang, R. K.; Laube, B. L. CRC Grit. Rev. Solid State Mater. Sci. 1984. 12 (1)1-73. (341)Creighton, J. A. Springer Ser. Chem. fhys. 1983, 33, 55-63. (342)Kerkar, M. Acc. Chem. Res. 1084, 17 (8),271-277. (343)Kerker, M. Pure Appl. Chem. 1984, 56 (lo),1429-1437. (344)Higuchi, S.;Zheng, 2.; Tanaka, S. Bunseki Kagaku 1984, 33 (l), 6568;Chem. Abstr. 1984, 100, 174126. (345)Thaoi, P. V. Raman Spectrosc. R o c . Int. Conf. 8th 1982, 743-744. (346)Clark, R. J. H. J. Mol. Struct. 1984, 113, 117-128. (347)Ivanov, I. E.; Naumova, T. M. Opt. Spekstrosk 1985, 58 (5),10231028; Chem. Abstr. 1985, 103, 29461. (348)Takenaka, T.; Umemura, J.; Takahashi, H. Raman Spectrosc. R o c . Int. Conf. 8th 1982, 131-132. (349)Imae, T.; Ikeda, S.; Itoh, K. J . Chem. SOC., Faraday Trans. 11983, 79 (12),2843-2851. (350)Scharf, B. Chem. fhys. Lett. 1983, 102(2-3),184-188. (351)Gurinovich. I. F.; Ivashin, N. V.; Terekhov, S. N.J. Mol. Struct. 1984, 114, 463-466. (352)Ivanara, T. M.; Berdyugln, V. V. J. Mol. Struct. 1984, 117 (3-4), 287-294. (353)Anderson, L. A.; Loehr, T. M.; Chank, C. K.; Mauk, A. G. J. Am. Chem. SOC.1985. 107(1),182-191. (354)Mitchell, M. L.; Campbell, D. H.; Taylor, T. G.; Spiro, T. G. Inorg. Chem. 1985, 24 (6),967-971, (355)Jones, C. M.; Naim, T. A,; Ludwig, M.; Murtaugh, J.; Flaugh, P. L.; Dudik, J. M.; Johnson, C. R.; Asher, S. A. Tr. AC Trends Anal. Chem. (fers. Ed.) 1985, 4 (3),75-80. (356)Asher, S. A.; Johnson, C. R. Science (Washington, D.C., 1883-) 1984, 225 (4659),311-313. (357)Johnson, C. R.; Asher, S. A. Anal. Chem. 1984, 56(12), 2258-2261. (358)Asher, S.A. Anal. Chem. 1984, 56 (4),720-724. (359)Ziegler, L. D.; Hudson, B.; Strommen, D. P.; Peticolas, W. L. Biopolymers 1984, 23 (lo),2067-2081. (360)Furtak, T. E. J. Electroanal. Chem. Interfacial Nectrochem. 1983, 150 (1-2),374-388. (361)Seki, H.; Chuang, T. J. Chem. fhys. Lett. 1983, 100 (5),393-396. (362)Otto, A. Vacuum 1983, 33 (10-12),797-802. (383)Sliman, 0.; Bumm, L. A.; Callaghan, R.; Kerker, M. Time-Resolved Vib. Spectrosc. (Proc. Int. Conf. TRVS) 1982. 387-390. (364)Creighton, J. A.; Alvarez, M. S.; Weitz, D. A.; Garoff, S.; Kim, M. W. J. Phys. Chem. 1983, 87 (24),4793-4799. (365)Miller, S.K.; Baiker, A.; Meier, M.; Wokaun, A. J. Chem. Soc., Faraday Trans. 1 1984, 80 (5), 1305-1312. (366)Wokaun, A.; Baiker, A.; Miller, S. K.; Fluhr, W. J . fhys. Chem. 1985, 89 (lo),1910-1914. (367)Dorain, P. 6.; Cheu, T. T.; Chang, R. K. f r o c . SPIE-Int. SOC. Opt. Eng. 1984, 482, 116-124. (368)Garoff, S.;Sandroff, C. J. J. fhys. Colloq. 1983, C10, 483-486. (369)Saad, E.; Lippitsch, M. E.; Leither, A.; Aussenegg, F. R. Springer Ser. Chem. Phys. 1984, 39, 486-490.
(370)Yamada, H.; Yamamoto, Y. Surf. Sci. 1983, 134 (l), 71-90. (371)Loo, B. H.; Lee, Y. G. J . fhys. Chem. 1984, 88 (4),706-709. (372)Marinyk, V. V.; Lazorenko-Manevich, R. M.; Kolotyrkin, Ya. M. Dokl. Akad. Nauk SSSR 1983, 272(5), 1161-1165:Chem. Abstr. 1984, 100, 58948. (373)Sanchez, L. A.; Lombard4 J. R.; Birke, R. L. Chem. Phys. Lett. 1984, 108 (1)45-50. (374)Vo-Dinh, T.; Hiramoto, M. Y. K.; Begun, G. M.: Moody, R. L. Anal. Chem. 1984, 56 (9),1867-1670. (375)Patterson, M. L.; Allen, C. S. Appl. Surf. Sci. 1984, 18 (4),377-388. (376)Keifer, W.; Beckmann, A. J . Mol. Struct. 1984. 13, 83-99. (377)Takahashi, H. Kagaku no Ryoiki Zokan 1983, 139, 31-50; Chem. Abstr. 1984, 100, 164395. (378)Keifer, W. Tangungsber Wiss. Tag-Tech Hochsch Karl Marx-Stadi 1984, 151-178;Chem. Abstr. 1985, 102, 69404. (379)Maeda, S.;Kataoka, H.; Kamisuki, T. Oyo Butsuri 1983, 52 (6),477484;Chem. Abstr. 1983, 99, 113023. (380)Maeda, S. Gendai Kagaku 1983, 151, 56-65; Chem. Abstr. 1984, 100, 41852. (381)Attal, 6.; Paelat, M.; Taran, J. P. J . fhys. Colloq. 1983, C7, 287-298. (382)Brandt, D.;Langllaar, J.; Van Voorst, J. D. W. Ned. Tfdschr. Natuurkd. A I984! A50 (I), 23-28; Chem. Abstr. 1984, 101, 100274. (383)Baldis, H. A. Plasma fhys. 1983, 25 (12),1297-1310. (384)Goss, L. P.; Switzer, G. L.; Trump, D. D.; Schreiber, P. W. J. Energy 1983, 7 (5),403-409. (385)Hall, R. J.; Eckbreth, A. C. Laser Appl. 1984, 5 , 213-309. (386) Inoue, T.; Iguchi, S. Kagaku no Ryoiki Zokan 1983, 140, 17-23; Chem. Abstr. 1984, 100, 88218. (387)Stufflebeam, J. H.; Hall, R. J.; Verdieck, J. F. Prog. Astronaut. Aeronaut. 1984, 92, 3-23. (388)England, W. A.; Greenhalgh, D. A.; Jenny, S. N.; Milne, J. A.; Porter, F. M. Raman Spectrosc. R o c . Int. Conf. 8th 1982, 165-166. (389)England, W. A.; Milne, J. M.; Jenny, S. N.; Greenhalgh, D. A. Appl. Spectrosc. 1984, 38 (e),867-876. (390)England, W. A,; Greenhalgh, D. A. Inst. Chem. Eng. Symp. Ser. 1984, 87, 263-270. (391)Ferrario, A.; Garbi, M.; Maivicini, C. Report 1983, C18E-2042,Avail. NTIS from Sci. Tech. Aerosp. Rep. 1983, 21 (21),Abstr. No. N8332903. (392)Apanasevich, P. A. J . Mol. Struct. 1984, 115, 233-236. (393)Van Hare, D. R.; Carreira, L. A.; Rogers, L. B.; Azarraga, L. Appl. Spectrosc. 1984, 38 (4),543-552. (394)Van Hare, D. R.; Carreira, L. A,; Rogers, L. B. Appl. Spectrosc. 1985, 39 (2),347-352. (395)Dreler, T. Report 1983 Avail NTIS from Sci. Tech. Aerosp. Rep. 1984, 22 (20),Abstr. No. N48-30008. (396)Hartford, A. Laser Focus Electro-Opt. Mag. 1984, 20 (4).63-4,66, 68,70, 72. (397)Chew, H.; Wang, D. S.; Kerker, M. J . Opt. SOC.Am. B , Opt. fhys. 1984, 7 (l), 56-66.
Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry E. L. Wehry Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996
A. INTRODUCTION This review emphasizes advances in the experimental techniques of luminescence spectrometry and instrumentation relevant (or potentially relevant) to analytical utilization of molecular luminescence phenomena. Applications (especially of well-established techniques) are cited only when they seem unusually novel or of especially broad interest. The review was prepared with the help of a computer search profile of Chemical Abstracts titles and identifiers. It covers literature indexed by Chemical Abstracts from November 1983 (Vol. 99, issue 21) through October 1985 (Vol. 103, issue 20). In addition, journals scanned manually by the author are covered up through issues received by November 30, 1985. As in the previous review in this series ( A l ) ,certain topics are excluded from coverage. They include the following: atomic fluorescence; molecular luminescence in flames, plasmas, or discharges; infrared fluorescence; solid-state phosphor and semiconductor luminescence; radioluminescence; liquid scintillation counting; and X-ray induced luminescence, The huge literature on fluorescent probing of biological and macromolecular systems has been excluded, 0003-2700/86/0358-13R$06.50f0
except for citation of a few reviews. Many other subject matter areas are covered in a seemingly arbitrary manner, in order to keep the size of the review and the number of citations from becoming totally preposterous. As the field of molecular luminescence continues to develop, it becomes progressively harder to pigeonhole publications into the categories traditionally used in this review. Some browsing may therefore be required for one to find those citations of greatest relevance to one’s specific interests. Because this is the last of these reviews that I shall be preparing, I would like to thank most sincerely those persons who have kept me informed of their most recent results and apologize to those authors whose work may appear to have been slighted.
B. BOOKS AND REVIEWS OF GENERAL INTEREST The first volume of a multiauthor monograph on molecular luminescence spectrometry edited by Schulman ( B I )includes (among other chapters) an overview of luminescence principles (B2)and lengthy, detailed reviews of the luminescence of 0 1986 American
Chemical Society
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MOLECULAR FLUORESCENCE, PHOSPHORESCENCE, AND CHEMILUMINESCENCE SPECTROMETRY
pharmaceuticals (B3); the fluorescence of amino acids, proteins, vitamins, nucleic acids, alkaloids, porphyrins, and other organic natural products (with 1417 literature citations!) (B4); luminescence methods for the determination of inorganic analytes (with 1444 literature citations) (B5); and the luminescence of complexes of metal ions with ligands of biological significance (B6). Other chapters in this book dealing with more specific topics are cited in subsequent sections of this review. A new book by Lakowicz on fluorescence stresses applications to biochemical systems (especially proteins and membranes) and also contains useful treatments of instrumentation for steady-state and time-resolved fluorometry, solvent effects on fluorescence, fluorescence quenching phenomena, and the principles and practice of polarized fluorescence measurements
(B7). An ASTM publication entitled “New Directions in Molecular Luminescence”, edited by Eastwood, consists of eight chapters by different authors. Several of the individual chapters in this compilation are cited in appropriate specific sections of this review (B8). Warner and co-workers have reviewed the analytical utility of “multidimensional luminescence measurements”, wherein several luminescence parameters (spectra, polarization, decay time, quenching phenomena, etc.) are used in various combinations to enhance the information content and selectivity of fluorometric analysis (B9). A brief, very readable, survey of recent developments in fluorescence and chemiluminescence analysis by Miller stresses improvements in selectivity (BIO). The same author has reviewed photo- and chemiluminescence techniques for drug determinations (B29). The most recent volume of the Chemical Society’s Specialist Periodical Report series on “Photochemistry” includes a useful review of recent progress in the study of photophysical processes (including luminescence) in solid and liquid media (B11). A review of inter- and intramolecular electronic energy transfer in liquid solution stresses recent studies and novel aspects of the phenomena (BIZ). A book chapter by Wehry reviews the fundamentals and experimental techniques of photoluminescence and chemiluminescence and surveys their application to the determination of inorganic constituents of natural water samples (BI3). Fluorometric techniques for determination of Cu(I1) have been reviewed (B14). Environmental applications of fluorescence spectrometry are reviewed oil pollution analysis receives particular emphasis (B15). Review chapters on spectrometric techniques for determination of polycyclic aromatic hydrocarbons include discussions of the many fluorescence and phosphorescence techniques that have been applied to this important problem (B16, B17). Guilbault has surveyed the principles and applications of fluorescence and phosphorescence, with special reference to enzyme assay and the use of immobilized enzymes in fluorometric analysis (B18). The luminescence characteristics of nucleic acids have been reviewed (BI9). The use of fluorescence to study the structure and function of proteins has been reviewed (B20). A review by Jameson stresses the use of fluorescence in immunoassay and the study of protein-ligand interactions (B21). The luminescence of tryptophan, tyrosine, and cystine and their derivatives has been reviewed (BZZ-S24). The principles of “fluorescence correlation spectroscopy” and “fluorescence photobleaching recovery” experiments are reviewed, and applications of the techniques to measure rates of molecular transport (e.g., lateral diffusion of fluorophorelabeled molecules on the surfaces of biological cells; fundamental studies of diffusion phenomena in solution) have been discussed by Elson (B25). The principles and practice of “hematofluorometry” for determinations of such analytes as bilirubin, hemoglobin, and zinc protoporphyrin in clinical samples have been reviewed (B26). Fluorogenic reagents for primary and secondary amines and thiols have been reviewed (B27). The use of fluorescence techniques in the study of polymer colloids has been reviewed by Winnik (B28). Other books and reviews, dealing with specific topics, are cited in subsequent sections.
C. LAMP SOURCES A grand total of one citation on this topic, albeit one of 14R
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significant interest. Warner and co-workers have reported a technique for stabilizing the output of a dc xenon arc lamp, by superimposing an ac wave form on the dc source voltage. This apparently has the effect of modulating the lamp output in a virtually reproducible manner dependent upon the ac frequency. Use of detection with an appropriate time window (dependent on the ac frequency) is necessary. The possibility that this procedure will increase the useful lifetime of xenon arc lamps also is noteworthy ( C I ) .
D. LASER SOURCES AND THEIR APPLICATIONS As laser technology continues to develop, the use of laser sources in analytical fluorometry becomes increasingly realistic. The following developments in laser science (especially that pertaining to dye lasers) seem especially relevant. Dye Lasers. A 335-page book by Maeda is a compendium of the properties of about 445 (!) laser dyes (01). For many applications of laser-induced fluorescence tunable laser output in the 217-260 nm region is needed. A comparison of the characteristics and operating costs of three possible solutions to this problem (flashlamp-, excimer-, and Nd:YAG-pumped dye lasers) has been offered by a presumably neutral observer (i.e., one not employed by a laser manufacturer) (02). In dye lasers using separate oscillator and amplifier cells, the optimal solvents for oscillator and amplifier may occasionally be different for a particular dye ( 0 3 ) The efficiencies with which 17 common laser dyes and dye mixtures can be pumped by a XeF excimer laser (351 nm) have been measured (04).Dyes and dye mixtures reportedly suitable for generation of UV (260-330 nm) via frequency doubling of a flashlamp-pumped dye laser are discussed (05). A conical dye cell is claimed to offer significant advantages over more conventional designs as an amplifier for high-power excimer- and YAG-pumped dye laser systems ( 0 6 ) . An arrangement consisting of a cylindrical dye cell and two 90” mirrors is reported to improve substantially the beam quality from an excimerpumped dye laser (07). Decreasing the spacing of the cavity modes in a CW laser can be achieved by increasing the cavity length. An Ar+pumped CW dye laser having an effective cavity length of 17 m (!) has been constructed (08).New “jet-stream”techniques may offer advantages in CW dye laser systems ( 0 9 ) . A “self-scanning”CW Ar+-pumped dye laser is fitted with a BaTi03 single crystal as the sole tuning element. The frequency and line width of laser output are controlled by optical feedback from a holographic pattern in the phase-conjugate reflecting crystal. The laser exhibits a scan range of ca. 500 cm-’ at a resolution that could be achieved (in a conventional dye laser) only via use of one or more intracavity etalons. Application of this laser to high-resolution fluorometry in a supersonic expansion is described (DIO, Dl I ) . Synchronization of the scan action of the etalon and grating to achieve expanded wavelength tuning intervals in the etalon-narrowed output of a N2-pumped dye laser has been described (012). Techniques to stabilize the output of a pulsed NdYAGpumped ring dye laser so as to compensate for pulse-to-pulse amplitude fluctuations of the pump laser have been described (013). A computer-based instrument serving a number of control functions in pulsed-laser experiments (e.g., correction for pulse-to-pulse laser intensity fluctuations) is described (014).Use of a diode array detector and monochromator as the basis for an optical spectrum analyzer to measure bandwidths of dye laser output has been described (015). Perylene tetracarboxylic acid derivatives, which lase in the 565-600 nm region, reportedly may be more resistant to degradation under YAG pumping than is the perennially popular rhodamine 6G (D16).Benzoxazine derivatives have interesting possibilities as N2-pumpable dyes lasing in the 500-675 nm region (017). The search for alternatives to liquid-solution media for laser dyes continues. The use of microporous quartz as a medium for incorporation of laser Xanthene dyes incorporated dyes has been described (D18). into poly(methy1 methacrylate) are claimed to exhibit useful characteristics for laser use, if additives are used to increase the damage threshold for the polymer (019). An unexpectedly large second-harmonic generation (SHG) efficiency was observed when a broad-band (1.4 nm) N?pumped dye laser (590 nm) was doubled using KDP. It 1s
MOLECULAR FLUORESCENCE, P H O S W R E S C E N C E . AND CHEMILUMINESCENCE SPECTROMETRY
Earl L. W.h*
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concluded that both SHG and frequency-mixing phenomena are involved. The bandwidth of the doubled beam was a factor of I smaller than that of the fundamental, sug esting use of the phenomenon for both enhancing apparent 8HG efficiencies and decreasing the effective bandwidth of a dye laser (020). The use of KNhO, as a nonlinear material for frequency-doubling the output of a CW dye laser to generate CW radiation in the blue has been described (021). The problem of amplitude modulating the radiation produced by frequency doubling without introducing undesired Fourier components in the frequency spectrum is a tricky one which has been tackled by appropriate use of a Bragg cell cavity dumper (022).
Other Laser Systems. The second edition of a monograph . use of an excimer on excimer lasers ban appeared (023)The (ArF, 193 nm) as pump laser for generation of vacuum UV down to 156 nm by stimulated Raman scattering in H, is reported to produce kW peak powers (024). Generation of tunable vacuum UV down to 136.2 nm is achieved by antiStokes Raman shifting in H, of the output of a commercial excimer-pumped dye laser (025).The very important practical matter of minimizing contamination of the gases used in excimer lasers has been addressed (026). The design and performance of a fluorescence spectrometer using a near-IR emitting semiconductor laser source has been described. Principal advantages of this laser include its relatively small size, high reliability, and low cost. Its major disadvantage is the fact that its emission range (>I500 nm) does not correspond to wavelengths absorbed by many fluorophores. Circumventing this problem by development of fluorescence labeling reagents that absorb in the near-IR, or by using nonlinear techniques to generate visible or UV photons, is discussed (D27). Applications of Lasers. Laser-excited fluorescence methods in analytical chemistry have been surveyed by Wright (DZ?). Zare has surveyed the use of lasersin chemical analysis; laser-induced fluorescence and its future prospects are discussed authoritatively (029). If the absorption transition leading to fluorescence is saturated, the fluorescence signal no longer is linear in source power. Then, fluorescence can be differentiated from Raman and Rayleigh scattering background by amplitude modulation of the laser output. Since the 'saturated" fluorescence signal is a nonlinear function of the source power, a signal will he generated at harmonics of the modulation frequency; such is not the case for the scatter background, which should be linear in source power. Thus,second (or higher) harmonic detection of fluorescence using amplitude-modulated excitation at sufficiently high source power to achieve saturation should improve limits of detection by decreasing contributions from scatter background. This principle has been demonstrated in atomic fluorescence hy several groups. Given that molecular absorption transitions tend to he more difficult to saturate than those of atoms, the question arises as to whether this technique can have practical use in molecular fluorometry. This question is discussed in detail, with appropriate data (030). Various types of two-color pump-and-prohe experiments (and the required instrumentation) are described in consid-
erable detail by Lytle and co-workers. Ground- and excited-state absorption spectra, stimulated emission spectra, y d excited singlet decays can he measured. Example cases In fluorometric analysis in which such techniques could have significant advantages over more mundane measurement approaches are discussed ( 0 3 1 ) . A study of limits of detection in 'aminopeptidase profiling" represents an excellent example of how laser excitation can he used to improve limits of detection in complex biological eamples via decreasing the intensity of interfering background luminescence (032). The prohe-ion solid-state laser-induced luminescence technique is applied to determination of Re'+; the selectivity of the method and the nature of possible interferences are discussed carefully. Potential applications to geological samples are discussed ( 0 3 3 ) . Applications of laser-induced fluorescence in clinical chemistry (and the advantages of laser excitation in such The use of lasersystems) are reviewed hy Sepaniak (034). induced fluorescence imaging to study distributions of fluorescent species in single living biological cells has been reviewed (D3.5). The possibility of using N,-laser induced fluorescence of hematoporphyrin derivatives in tissues to distinguish normal from tumor tissue has been discussed (036).
Techniques for coal characterization hy laser-induced fluorescence microscopy are described. Both spectral and decay-time data are used to characterize fluorescent maceral coal domains (037). Remote laser fluorescence techniques for detecting oil spills on water, identifying the oil, and estimating the thickness of oil layers continue to he refined (0381. ' The use of laser-induced fluorescence in flow injection analysis is described (039). Utilization of vapor-phase laser-induced fluorescence for identification of chemical species released in simulated nuclear reactor accidents has been discussed (040). Determination of anthracene, fluoranthene, and henanthrene in mixtures of the three polycyclic aromatic hyd)rocarbons by laser-induced fluorometry in the gas phase has been reported ( 0 4 1 ) . The principles of the laser-induced fluorescence technique for hydroxyl radical determination in the atmosphere are discussed (D42). A laser fluorescence method for OH in the troposphere is claimed to be limited by the shot noise of the solar background. Techniques for suppressing interference due to laser photodissociation of 0,are discussed ( 0 4 3 ) . A two-photon fluorescence procedure for OH proceeds via IR laser population of a vihrationally excited state of the ground electronic state, followed by UV laser production of an emissive electronically excited state. It is contended that this scheme circumvents background problems encountered in other laser-induced fluorometric determinations of OH (044). Decreases in background contributions in dye-laser-induced fluorometric determinations of OH and HO, in urban air can be achieved by expanding the gas sample through a nozzle prior to excitation of fluorescence (045). Applications of laser sources in such diverse areas as detection in liquid chromatography, low-temperature and time-resolved fluorometry, and fluoroimmunoassay are cited in subsequent sections.
E. S A M P L E I L L U M I N A T I O N TECHNIQUES I n t e r n a l Reflection. The use of internal reflection methods in fluorescence s ctrometry is now attracting substantial interest. AxelrXBurghardt, and Thompson have reviewed the principles and techniques of total internal reflection fluorescence and the use of this technique to examine molecular phenomena at liquid-solid interfaces (El, E2). A review of internal reflection spectr~scopyincludes a discussion of internal reflection techniques in fluorescence spectrometry; numerous examples are cited (E3). The performance of total internal reflection fluorometry, using a pulsed laser source, is reported. I t is suggested that the technique (which is capable of providing both depth and time resolution) could he very useful in surface characterization (e+, of polymer films) ( E 4 ) . Measurement of the fluorescence intensity (via total internal reflection fluorescence) as a function of the direction of polarization of the beam from a laser source is described. Use of the data to measure orientation distributions of fluorescent molecules constituting ANALYTICAL CHEMISTRY. VOL. 58. NO. 5. APRIL 1986
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an adsorbed layer is discussed (E5,E6). An internal reflection technique for fluoroimmunoassay employs an antibody immobilized on an internal reflection element that is then contacted with a solution containing the antigen. The idea is that the beam propogated through the internal reflection element will detect antigen-antibody complexes formed a t the element-solution interface, but not in bulk solution (E7, E8). A probe comprising a single optical fiber is capped with an opaque end cap. When a laser beam is passed through the fiber, the evanescent field a t the interface between the fiber walls and a medium into which the fiber is immersed produces fluorescence if the medium contains fluorescent components. Such a probe may be useful for detection of species that adsorb onto the fiber (E9). Fiber Optics. Interest in the use of fiber optics in conjunction with fluorescence measurement is an exceedingly active area, with the development of miniaturized sensors of particular interest. Reviews of fiber optic sensors for industrial use (E10)and applications to the life sciences ( E l l )describe a broad array of phenomena, including some based on fluorescence. Fiber optic fluorometric sensor techniques and applications are surveyed by Wolfbeis (E12). The design and use of fiber optic probes for measurement of fluorescence from very small-volume liquid samples (including in vivo biological fluids) is described (E13). The use of fiber optics for analysis of remote samples via laser-induced fluorescence has been surveyed (E14),and application to determination of uranium in very radioactive samples has been outlined (E15). A useful survey of fiber-optical sensors wherein a reagent is immobilized on a fiber-optic probe and a reaction of that reagent with an analyte is detected by an optical signal (e.g., fluorescence or chemiluminescence), propagated through the probe to a detector, is presented by Seitz. Comparisons of the performance of such “optrodes” with electrode sensors are offered (E16).Metal ion sensors, based on interactions of metal ions with fluorescent ligands immobilized on fiber optic probes, are discussed (E17). Fiber optic sensors for Be(I1) (E18)and Al(III), Mg(II), Zn(II), and Cd(I1) via immobilized 8-hydroxyquinolinesulfonate (E19) are described. Fluorescence “optrodes” for continuous determination of such species as 02,C02, and H+in biological systems are discussed in detail (E20, E21). A fiber-optic fluorometric probe for pH measurement in the pH 6.5-8.5range is reported to exhibit a precision of better than fO.10 pH unit for serum samples (E.22). Fiber optic fluorometric sensors for C02have been developed (E23, E24). Fiber optic probes for measurement of O2partial pressure in blood or biological tissues employ immobilized pyrene dibutyrate or pyrenebutyric acid, the fluorescence of which is quenched by O2 (E25, E26). Comparisons of oxygen “optrodes” based on fluorescence quenching with O2electrodes, for use in bioreactors, have been set forth (E27). “Boundary layer” effects influencing the sensitivity of this type of optrode are discussed (E.28). A fiber-optic sensor for the anesthetic 2-bromo-2-chlorol,l,l-trifluoroethane in the presence of O2 in the gas phase is based on quenching, by the analyte, of immobilized polycyclic aromatic hydrocarbons. A second sensing layer is used a notorious fluorescence to correct for interference by 02, quencher (E29). A glucose “optrode” is based on quenching of pyrenebutyric acid fluorescence by O2 consumed in the glucose oxidase catalyzed oxidation of the analyte. An outer membrane containing the enzyme is separated from an internal solution of pyrenebutyric acid (in a viscous organic solvent) by a fluorocarbon membrane (E30). The possibility of direct in vivo detection of atherosclerosis, by use of a catheter employing an optical fiber, is based on differences in fluorescence between normal arterial walls and fibrous plaque (E31). A submersible fiber-optic probe for analysis of phytoplankton in situ (via chlorophyll fluorescence) in marine waters can be towed by a ship (E32). A fiber-optic temperature sensor is based on the temperature dependence of the decay time for the luminescence of Nd3+ in glass (E33). 16R
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The difficulties associated with remote fiber-optic fluorometry using UV laser sources are discussed, and the use of a Nz laser or the fourth harmonic of a Nd:YAG laser for fiber-optic fluorometric detection of various UV-absorbing organic compounds (e.g., phenols) is evaluated. The potential use of such measurements for monitoring groundwater contamination is considered (E34). The possibility of damage to optical fibers through which laser beams are propagated should not be ignored (E35). The use of light-emitting diodes as sources for fiber-optic fluorosensors is described (E23). A fiber optics based apparatus for measuring fluorescence or phosphorescence from samples immersed in liquid helium or nitrogen is described (E36). Microfluorometric Techniques and Flow Cells. The illumination of samples of very small volume is a practical problem of importance (e.g., in liquid chromatography detection; see section L), and also represents an approach to achievement of very low absolute limits of detection. Fluorometric techniques for examination of liquid samples of submicroliter volume are described (E37). Extension of “Raman microprobe” instrumentation and techniques to fluorescence measurement is discussed ( E a ) . The factors that must be considered in the design of very small volume systems for achievement of very low mass detection limits are outlined, and the advantages of sheath flow cuvettes for this purpose are discussed (E39) Techniques for achieving extremely low limits of detection by solution fluorometry, using dye laser excitation in a sheath flow cell, are described. The problem of reducing the background contributions from cell window fluorescence scattering, and impurity fluorescence is discussed with particular care (E40). A sheath flow cell, when illuminated properly with a focused laser beam, exhibits an illuminated volume as small as 50 fL.The illuminated volume can be changed by changing the flow rate of the sample solution and/or sheath stream. Uses of this device for fluorometric detection in samples of small volume are considered (E41). A fluorescence microscope, using an Ar+ laser source, is used to detect a fluorescent species adsorbed onto 10-pm diameter silica spheres. For the molecule studied (rhodamine 6G), a limit of detection of ca. 8000 analyte molecules is reported (E42). Instrumentation for, and applications of, laser microfluorometry and imaging of constituents of single living biological cells have been reviewed ( 0 3 5 ) . Such techniques are considered further in section T. Winefordner and Voigtman report that, in the laser-fluorometric detection of various polycyclic aromatic hydrocarbons and drugs, better limits of detection were achieved by using a static cuvette than when a flow cell was used (E43). The suitability of various flow cells for constant-wavenumber difference synchronous fluorometry is discussed (E44). The quenching, by halide ions, of acridinium or quinolinium fluorophores immobilized on chemically modified glass plates is used to determine C1-, Br-, or I- in solution. The samples are pumped through a flow cell, one wall of which contains the immobilized fluorophore (E45). Flow Injection and Related Techniques. The use of a “nested loop” valve system in fluorescence derivatization reactions via flow injection is claimed to be advantageous (E46). Flow-injection fluorometric methods for determination of Hz02 in water (E47),rapid screening of blood serum for ochratoxin A (E48),determination of pyridoxal and pyridoxal 5-phosphate in serum (E49),and determination of CN- (E50)have been reported. Apparatus and techniques for stopped-flow fluorometric determinations of metal ions via kinetic methods have been described (E51). Automated continuous-flow fluorometric methods for H20zin rain or snow (E52),furfurals in beverages and foodstuffs (E53),P-deoxy-~-glucose(E53), and DNA via labeling with Hoechst 33258 (E54)are described. Centrifugal Analyzers. An evaluation of a commercial centrifugal analyzer designed for fluorescence and scattering measurements in fluoroimmunoassay has been performed (E55). Use of centrifugal analyzers for fluorometric determinations of NH, in plasma (E56)and angiotensin-converting enzyme in serum (E57) is described. Inner-Filter Effects. A thin-layer front-surface fluorescence cell has been described (E58). A thin-layer cell (thickness variable from 2.5 to 10 pm) for measuring fluorescence from very concentrated solutions with minimal inner-filter error is described (E59). A fiber optic coupled I
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3 2 - ~ Lflow cell suitable for front-surface illumination permits on-line computer corrections for inner-filter effects (E60). A general intensity expression for molecular luminescence incorporating all forms of inner-filter effects as well as the possibility that more than one “inner-filter species” may be present in a sample has been presented. The influences of the various inner-filter artifacts on the shapes of analytical calibration curves also are considered (E61). Correction for the effects of inner-filter absorption of both incident source radiation and analyk fluorescence is discussed in detail, with specific reference to the “cell-rotation” automated correction procedure (E62).Corrections for inner-filter absorption of incident source radiation under conditions in which a mirror is placed behind the cuvette to reflect unabsorbed incident light back through the sample are discussed (E63). Corrections for inner-filter effects, using a small volume flow cell in which excitation and front-surface collection of fluorescence are achieved by fiber optics, are discussed in detail (E60).Calculations indicate that self-absorption errors are minimized in front-surface fluorometry if the cell is illuminated at an angle of 45-50’ to the cell surface and the Errors fluorescenceis observed at 90’ to the cell surface (EM). in “hematofluorometry” (measurement of fluorescence from blood samples via front-surface illumination) are discussed (E65). Removal of Oxygen. The problem of O2 removal from samples containing analytes sensitive to fluorescence quenching is a perennial one. A novel approach to alleviating it is based on circulating the sample solution throu h tubing which is permeable to O2 (but, obviously, impermea le to the anal e or solvent) and then chemically scavenging the O2 in a Crg-Zn(Hg) reactor (E66). Mirrored Cells. A variant of the classical ploy of increasing observed fluorescence signals by using mirrors in the cell compartment to increase the fraction of emitted photons which eventually reach the detector consists of evaporative deposition of a film of highly reflective aluminum or silver on two adjacent walls of a conventional rectangular cuvette (E67,E68). Fluorescence Spectroelectrochemistry. Most optically transparent thin-layer electrode spectroelectrochemical cells are designed for absorbance measurements. Such a cell (using a gold minigrid electrode) has been devised for fluorescence measurements (E69).
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F. DETECTORS Photomultipliers. A useful review of nonideal photomultiplier tube (PMT) characteristics (dark pulses, dynode inhomogeneities, backscattered electrons, afterpulses, etc.) and their influence on photon-counting measurements is available (FI). The origins and alleviation of afterpulse effects in PMTs have been discussed (F2). Circuit designs for photon counting at low light levels and short dead-time applications have been described (F3).Techniques for computer acquisition and processing of spectral data obtained by photon counting are presented (F4). The use of sodium salicylate as a fluorescent coating on (or in front of) a PMT to extend its response into the vacuum-UV is moderately common. It is suggested that the high reflectivity of sodium salicylate films can also be exploited to extend the response of a PMT into the red, and optical designs for detection over the 125-940 nm range using a single PMT are suggested (F5). Array Detectors. The characteristics of photodiode arrays (F6)and silicon intensified target (SIT) vidicons (F7)as spectroscopic detectors have been reviewed. The proceedings of a symposium on multichannel image detectors (consisting of 15 chapters) have appeared (FB).Chapters of particular relevance to this review include the following: comparisons, for low light-level applications, of the performance of SIT and intensified SIT vidicons and intensified and nonintensified a discussion of the characteristics silicon diode arrays (F9); of charge-injection and charge-coupled device array detectors (FIO); the use of an intensified diode array as a detector in fluorometry ( F I I ) ; and the use of multichannel detector techniques for spatial localization of analytes in samples (FIZ). The techniques and uses of fluorescence imaging microscopic measurements in cell biology, using array detectors, are reviewed (FI3).
A miniature diode-array fluorescence detector for liquid chromatography has been described. The description of procedures employed for successful use of the diode array detector in conjunction with a very small illuminated volume is of general interest (F14). The use of an intensified diode array detector for imaging of the laser-induced fluorescence produced by hematoporphyrin derivatives localized in cancer tissues is stated to achieve considerable improvement in the specificity with which cancerous tumors can be located in tissue samples (FI5). Instrumentation for digitization of fluorescent images produced by SIT vidicon detection of fluorescence from individual biological cells is described (FI6). Instrumentation for quantitative fluorescence image analysis using a SIT vidicon is described (F17). A portable multichannel fluorometer, using a diode array detector, and its use for determination of chlorophyll in seawater is described (FIB).
G. QUANTITATIVE RELATIONSHIPS, CORRECTED SPECTRA, QUANTUM-YIELD MEASUREMENTS, AND CHEMOMETRIC TECHNIQUES Quantification. An evaluation of the factors that contribute to quantitative imprecision in fluorescence intensity measurements with a commercial fluorometer indicates the primary problem to be fluctuations in the intensity of the source. The possibility that thermal lensing in solution samples (even when lamp sources are used) may occasionally be a significant factor adversely affecting the precision of fluorometry also is considered (GI).Use of the Stokes Raman scatter signal from H20 as an internal standard for quantifying the fluorescent compounds in aqueous solution samples is discussed (GZ). Theoretical limits of detection for a variety of spectrometric methods, including molecular luminescence, have been calculated. It is concluded that a detection limit of ca. l molecule cm-3 by fluorometry is theoretically achievable (G3). Mathematical corrections of fluorescence intensity and polarization data for absorption and scattering of incident and emitted light are presented (G4).A mathematical method for subtracting Rayleigh scatter contributions from measured fluorescence spectra, based on assumptions regarding the wavelength distribution of the scattering and fluorescence, is automated and applied to alleviation of scatter artifacts in the fluorescence spectra of proteins (G5).Corrections for inner-filter effects are discussed in section E. Corrected Spectra. The acquisition and uses of corrected spectra have been surveyed (BIO). A useful tabular survey of procedures for correcting emission and/or excitation spectra has been assembled, and the impact on spectral correction of very accurate radiometry via the use of silicon photodiodes is discussed (G6). A computerized system for comparing and calibrating quantum counters has been developed (G7).A detailed investigation of the use of phenazoxonium dyes as quantum counters is reported. One such dye reportedly can serve as a quantum counter over the very broad wavelength range 240-700 nm (GB).Some of the results in this paper subsequently were challenged by other investigators (G7).The possibility that certain laser dyes may find use as quantum counters in the 600-800 nm region is discussed (G9). Quantum Yields. The IUPAC Photochemistry Commission has suggested six liquid-solution fluorescence quantum yield (a,) standards covering the 270-600 nm emission wavelength range (GIO).The question as to the correct value of for 9,lO-diphenylanthracene (a widely used “standard for determinations via the comparative method) is ad= 0.93 -+ 0.03 for 9,lO-didressed. It is concluded that aPF phenylanthracene in room-temperature hexane, cyclohexane, decalin, and benzene solutions ( G I I ) . In a comparative procedure for measuring fluorescence and phosphorescence quantum yields in frozen solutions at 77 K, 9,lO-diphenylanthracene is used as a standard with an assumed a, of 1.00 in methylcyclohexane at 77 K ( G I 2 ) . The possible use of 2-aminopyridine (aF= 0.66 in 1 M H2S04)as a quantum-yield standard is discussed ( G I I ) . The validity of the “n2” correction for GF values mrasured in different solvents is discussed ( G I I ) . ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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Use of photoacoustic spectroscopy (PAS) for absolute aF measurements in solids continues to attract interest (G13). In a comparison of @F measurements for a series of solid organic compounds by the comparative method and PAS, the values obtained by PAS were consistently greater. Possible reasons for this discrepancy are considered (G14). Chemometrics. Molecular complexes of a variety of organic compounds with indanedione derivatives are fluorescent. A “decision tree” chemometric analysis of the influence of the molecular structure of the complexing reagent on the fluorescence intensity of the adduct is illustrative of the use of computer techniques to “tailor” intensely luminescent derivatives of nonluminescent molecules and to design analytical methods based on such chemical derivatization procedures (G15). A pattern-recognition algorithm for spectral matching of Fourier-transformed excitation-emission matrices, to be used for comparison of data for unknown samples with those of standards, is described (G16). Possible use of the excitation-emission matrix of human blood serum for fingerprinting of blood samples (e.g., for disease diagnosis) by pattern recognition is discussed (G17).
H. LUMINESCENCE IN ORGANIZED MEDIA Molecular luminescence measurements in “organized” media (principally surfactant micelles or cyclodextrin cavities) are currently receiving much attention, as indicated by a spate of recent reviews. A review of analytical implications of micelle chemistry by Cline Love and co-workers includes consideration of the effects of micellar environments on the luminescence of organic molecules and analytical exploitation of these phenomena ( H I ) . A useful review of the use of micelles and cyclodextrin inclusion complexes by Cline Love and Weinberger has appeared (H2). A monograph on room-temperature phosphorescence (RTP) by Vo-Dinh includes discussions of the principles and practice of RTP in micellar solutions (H3). The analytical utility of R T P produced by micellar stabilization, cyclodextrin inclusion, and sensitization (or quenching) using biacetyl or another species that phosphoresces in liquid solution is compared ( H 4 ) . Micelle-enhanced fluorescence and its analytical implicaA review tions are surveyed by Hinze and co-workers (H5). of “analytical applications of organized molecular assemblies” includes a discussion of micelle-enhanced fluorescence and phosphorescence (H6). Incorporation of phosphorescent molecules and heavy-atom perturbers into inclusion complexes with cyclodextrins is discussed as a technique for generation of R T P in liquid-solution media. Selectivity results from the steric constraint that the phosphorescent analyte must fit into the interior of the cyclodextrin cavity for the phenomenon to be observed. The measurement is less susceptible to oxygen quenching than other reported liquid-solution RTP techniques (H7-HIO). The enhancement of phosphorescence is increased by using heavy-atom-substituted cyclodextrins (H11). Enhancements of fluorescence quantum efficiencies for molecules in the presence of cyclodextrins also are reported (H12-H14) and the origins of such enhancements have been discussed (H14, H15). The use of micellar systems in fluorescence immunoassay is reported. Sodium dodecyl sulfate micelles quench the emission of fluorescein bound to gentamicin when the gentamicin is free but not when it is bound to antibody. Hence, the fluorescence of the antibody-bound labeled analyte can be distinguished from that of the free labeled analyte, making it feasible to determine gentamicin without separation of the bound and free compound (H16). The question as to whether fluorescence enhancements observed in the presence of micelles or cyclodextrins result from increases in the fluorescence quantum yield of the analyte or from solubilization of a fluorophore that is sparingly soluble in “conventional” solution media is of interest, though not necessarily easy to resolve. Some ideas regarding samplepreparation methodology in such studies have been given (HI?). Enhancement by micellar media of the observed fluorescence efficiencies for a variety of phenols is reported, and implications of the observations for drug detection are conOther fluorescent compounds or systems for sidered (H18). which use of surfactants is reported to effect increases in 18R
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analytical sensitivity include the morin metal chelation system for determinations of A1 (H19)and Nb (H20)and various Nb and T a chelates (H21). Limits of detection for “sensitized biacetyl phosphorescence”, wherein an analyte molecule in a photoproduced triplet state sensitizes the well-known solution phosphorescence of biacetyl, reportedly are improved substantially in the presence of sodium dodecyl sulfate micelles or 0-cyclodextrin. In general, the micellar medium leads to better detection limits than the cyclodextrin (H22). The effect of cyclodextrin cavity size on the efficiency of sensitized biacetyl phosphorescence has been examined (H23). The use of heavy atom-substituted micelle-forming reagents to effect additional phosphorescence enhancement in micellar RTP has been described (H13). Improvements in the selectivity of micellar RTP by use of synchronous-scan and second-derivative techniques are described (H24). The performance of liquid chromatographic separations using micellar mobile phases, with RTP detection, is described (H25). The possibility of achieving luminescence enhancement for fluorescence of compounds on thin-layer chromatography plates by using surfactant or cyclodextrin spray reagents has been investigated (H26). Use of micellar media to enhance chemiluminescence (CL) signals is also beginning to attract interest (H27,H28). An interesting application of micellar enhancement in CL is a procedure for SO2 in air, wherein a nebulized aqueous Mn04solution is sprayed into a flowing air sample. The reaction of Mn0,- and HS03- produces CL, which is enhanced if a separate solution containing a micelle-forming surfactant also is aspirated into the air stream (H29). Background fluorescence from the surfactant “Triton X” can be suppressed by catalytic hydrogenation of its benzene ring (H30). A fluorescence microscope system for examining surfactant monolayers at airlwater interfaces (via added fluorescent probe dyes) has been described (H31).
I. LOW-TEMPERATURE LUMINESCENCE Crystalline Hosts. Thornberg and Maple report that use of crystalline durene as a host for low-temperature fluorometry of methylnaphthalenes produces selectivity far superior to that reported for these analytes in other low-temperature solid media. The general characteristics of the use of aromatic crystals as host materials for low-temperature fluorometric determination of aromatic compounds are discussed, as is the applicability of the technique to complex real samples (11). Two-photon excitation of methylnaphthalene fluorescence in durene crystals also is described; identification of individual constituents in mixtures of isomeric methylnaphthalenes has been achieved, and subpicogram limits of detection are reported for some compounds despite the relatively low efficiency of two photon-excited fluorescence (12). Pace and Maple have reported that preparation of samples in aromatic crystal hosts by vapor deposition (i.e., matrix isolation) offers significant advantages over other samplepreparation methods. They have reported high-resolution fluorescence spectra of a number of naphthalene derivatives using naphthalene as the host in a matrix isolation experiment (13,14). This approach appears very promising, especially for analytes that do not yield highly resolved spectra in Shpol’skii media or “conventional” rare gas solids. Shpol’skii Frozen Solutions. D’Silva and Fassel have reviewed the principles and analytical utility of laser-induced fluorescence in Shpol’skii matrices (15). Validation of the quantitative reliability of Shpol’skii fluorometry in mixtures is afforded by comparison of determinations of the relative quantities of five monomethylphenanthrenes in crude oil and GCIMS; good agreement of the results obtained by the two methods is reported (16). Use of scattered source radiation as a reference signal for empirical standardization of fluorescence intensity measurements is advocated as a simpler alternative to combined internal standard-standard addition quantitative fluorometry in Shpol’skii frozen solutions (17). Laser-excited Shpol’skii fluorometry following solvent extraction at elevated temperature (ca. 240 “C) is used to detect polycyclic aromatic hydrocarbons adsorbed on particulate matter sampled from a power plant (18). The Shpol’skii frozen-solution fluorescence spectra of 36 polycyclic aromatic derivatives of thiophene are presented (19). Shpol’skii fluorometry is used to identify polycyclic aromatic hydrocarbons
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(with isomer specificity) in extracts from petroleum, coal, rocks, and sediment samples (110,111). Matrix Isolation. The analytical characteristics of laser-induced matrix-isolation fluorescence spectrometry are surveyed, and use of the technique for selective quantification of individual constituents of complex samples is stressed (112). Fluorescence Line Narrowing. It is reported that pyrene and its derivatives exhibit fluorescence line narrowing as adsorbates on thin-layer chromatography plates cooled to 20 K. Analytical implications of the phenomenon are discussed (113,114). The phosphorescence of polycyclic aromatic hydrocarbons adsorbed on filter paper has been line-narrowed by direct So T1*excitation using an intense lamp source (115). Optical site-selection fluorometry of fluorene and naphthalene in 3-methylpentane frozen solutions a t 5-10 K is achieved by use of the extracavity frequency-doubled radiation from an Ar+-pumped CW dye laser for excitation. Advantages of this approach for analytical applications of fluorescence line narrowing are discussed (116). An exchange of comments regarding the analytical utility of fluorescence line-narrowing spectrometry in glassy frozen solutions has occurred (117-119). The use of fluorescence line narrowing in glassy frozen solutions to obtain high-resolution fluorescence spectra of adducts of polycyclic aromatic hydrocarbon (PAH) metabolites with DNA, and to identify individual PAH metabolites in mixtures, is reported by Small and co-workers (120-122). Supersonic Expansions. The characteristics and advantages of supersonic jet expansions for analytical spectroscopy have been surveyed (123). Apparatus for performance of quantitative supersonic expansion fluorometric measurements has been described (124). The possibility of using lamp, rather than laser, excitation in supersonic jet fluorometry is discussed (125-127). Lamps are simpler to use (and less expensive) than lasers, but their use appears to diminish both the sensitivity and selectivity of fluorometric determinations using supersonic expansions. A major advantage of lamp over laser excitation may materialize whenever very high-energy photons (e.g., vacuum-UV) are needed for excitation. The trade-offs involved in choice of source for this form of high-resolution fluorometry are considered in some detail (125). A supersonic-jet fluorometer using a xenon lamp as source has been constructed and evaluated (126). Quantitative fluorometry of perylene and benzo[a]pyrene in argon supersonic expansions is reported. The spectral resolution is extremely impressive; the reported limits of detection are less exciting. Some comparisons of the analytical utility of supersonic jet fluorometry with that of solid-state cryogenic fluorometric techniques are presented (124). Synchronous Low-TemperatureFluorescence. The use of synchronous scanning in conjunction with frozen-solution fluorometry at 77 K is described and applied to the identification of individual polycyclic aromatic hydrocarbons in mixtures (128). Experimental Techniques. A fiber-optic apparatus for measuring fluorescence or phosphorescence from samples immersed in liquid nitrogen or helium does not necessitate use of a Dewar equipped with optical windows (E36). A conduction-cooling cell for low-temperature luminescence at 77 K, in which samples cool down within 30-45 s after insertion, is described (G12).
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J. SYNCHRONOUS AND “MULTIDIMENSIONAL” LUMINESCENCE Excitation-Emission Matrices and Related Matters. Multidimensional and contour-map luminescence methods are reviewed lucidly by Suter, Kallir, and Wild (JI). A review of multiparameter luminescence measurements by Warner and co-workers includes a discussion of video fluorometry and contour-map methods (B9).Miller has surveyed the use of synchronous and contour fluorescence methods for enhancement of analytical selectivity (B10). Forensic applications of the three-dimensional fluorescence spectra of petroleum and refined petroleum products are reviewed (J2). Pattern-recognition techniques for matching excitationemission matrices (EEMs) of unknown materials with those of reference compounds are reported (G16). The possible use of the EEM profile of human serum for fingerprinting of blood samples for disease diagnosis by pattern recognition is dis-
cussed (G17). The use of Fourier transform filtering as a data smoothing method for EEMs obtained near the limit of detection is discussed (53). Synchronous Luminescence. Vo-Dinh has surveyed the principles of synchronous luminescence and its application for rapid screening of fluorescent constituents of complex samples (J4). “Variable-angle” synchronous fluorometry consists of scanning the excitation and emission monochromators at different rates (under computer control), so that Ak (or AD) varies during the scan. In effect, one scans through the EEM at some angle other than 4 5 O in this approach. In some cases, doing so reportedly results in substantially enhanced selectivity. Implementation of the technique and application to pharmaceutical samples are discussed (J5). Performance of constant-wavenumber synchronous fluorometry at rapid scan rates (20 nm s-l) is compared with conventional fluorometry for the determination of polycyclic aromatic hydrocarbons in liquid solutions using flow cells of various designs (E44). Instrumentation for constant-wavenumber synchronous scanning has been developed; the monochromators are scanned at rates up to 200 nm s-l (J6). Applications to detection in liquid chromatography are discussed (J7). The combination of synchronous scanning at constant wavenumber interval with measurement of fluorescence at 77 K is described and applied to identification of polycyclic aromatic hydrocarbons in mixtures (128). The use of first-derivative synchronous fluorescence is compared with conventional fluorometry for determination of Mg2+ (58) and Cd2+ (J9) via formation of fluorescent chelates. The use of second-derivative synchronous fluorometry for determination of epinephrine and norepinephrine in urine is reported (J10). Second-derivative synchronous fluorometry is applied to determination of Ti4+,Zr4+, and HP+ in mixtures (as their biacetyl monoxime nicotinylhydrazone chelates) (J11). Determination of adducts of DNA with a benzo[a]pyrene diol epoxide in DNA isolated from human lymphoblasts, using synchronous fluorometry, may be useful for monitoring occupational exposure to benzo[a]pyrene (512). Use of synchronous fluorometry for rapid screening of the polycyclic aromatic hydrocarbon content of indoor and outdoor air samples is discussed (513). Use of constant-wavenumber synchronous fluorometry to obtain “spectral fingerprints” of atmospheric particulate matter is described (J14). Synchronous and second-derivative techniques are applied to determination of isomeric benzoquinolines in coal tar via room-temperature phosphorescence on filter-paper substrates (J15). Application of synchronous and three-dimensional fluorescence measurements to assignment of rank parameters to coal (J16) and characterization of edible oils (J17) are reported. Use of three-dimensional fluorescence to identify oils is described (J18).
K. SOLID-SURFACE LUMINESCENCE Reviews and Fundamental Developments. A monograph by Vo-Dinh includes detailed discussions of the principles and practice of room-temperature phosphorescence (RTP) of molecules adsorbed on solid substrates (H3). Miller has reviewed the analytical use of the photoluminescence of species on solid surfaces, including RTP and solid-phase immunoassays (K1). Vo-Dinh has surveyed the principles of R T P and its application to rapid screening detection of individual fluorescent constituents of complex samples (&). The process(es) by which adsorption of organic molecules on solid supports lead to observation of RTP have never been satisfactorily elucidated. It is suggested that, for paper supports, substantial swelling of the paper upon contact with polar solvents enables solute molecules to penetrate into fiber pores. When the paper is dried, this pore structure is thought to collapse, and the solute molecules can then be envisioned as trapped inside the interior structure of the cellulosic material, relatively inaccessible to potential quenchers. It is contended that this phenomenon may be thought of as a form of matrix isolation ( K 2 ) . The fluorescence of rhodamine B deposited on the surface of a three-layer optical waveguide (the center layer of which is a silver film) is reported to be a factor of ca. 100 more intense ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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than that of the same compound deposited on an ordinary microscope slide (K3). The generation of highly resolved luminescence spectra by “line narrowing” or “optical site selection” has in the past been restricted to glassy or crystalline frozen solutions or vapordeposited matrices. Recently, examples of luminescence line narrowing of organic fluorophores adsorbed on solid surfaces have been noted. Line narrowing of the phosphorescence of polycyclic aromatic hydrocarbons adsorbed on filter paper is achieved via direct So TI* excitation (115). When adsorbed on thin-layer chromatography plates cooled to 20 K, pyrene and substituted pyrenes are reported to exhibit fluorescence line narrowing (113); implications of the observation for mixture analysis are interesting (114). Instrumentation and Techniques. A sample compartment for performing luminescence measurements of compounds adsorbed on solid substrates a t room or low temperature (down to 208 K) is designed to be compatible with the sample-chamber optics of a commercial fluorometer. Background spectra (at 298 and 208 K) for a variety of substrates and dopants (e.g., heavy-atom additives) are given (K4). Apparatus for preparation of large numbers of samples for R T P on filter paper is described (K5). That both the precision and sensitivity of R T P on paper substrates are improved by illuminating the entire sample, rather than just part of it, is stressed. Modifications of a commercial fluorometer to achieve full illumination of such samples are described (K6). Techniques for quantification of individual constituents in mixtures by RTP on paper have been described (K7). The background emission of cellulose filter paper supports is reportedly diminished by drying followed by illumination a t 285 nm prior to use (K8). The precision of determinations via RTP reportedly is improved by use of a glovebag drying chamber to isolate samples from moisture during measurement of phosphorescence (K9). Limits of detection for polar analytesby RTP on filter paper or silica gel can reportedly be improved by addition of polyacrylic acid to sample solutions prior to spotting them on the substrate or by use of salts of polyacrylic acid as binders when silica gel is used as substrate (KIO).Techniques for derivatizing nonluminescent analytes on paper supports for R T P are described (K11). The determination of individual phosphorescent compounds in mixtures without separation, via use of different substrates and heavy-atom additives, continues to progress (K5). The use of first- and second-derivative techniques to improve the selectivity of analyses of mixtures by RTP (and fluorescence) of organic compounds on filter paper is discussed by Hurtubise and co-workers (K12-K14). Instrumentation and computational methods for measuring simple and complex solid-substrate phosphorescence decay curves have been developed (K15). Use of both the room-temperature fluorescence and phosphorescence emissions of luminophores on silica or cellulose solid surfaces is discussed (K16). Applications. RTP on filter-paper substrates i s the basis of a dosimeter for measurement of exposure of personnel to polycyclic aromatic hydrocarbons in occupational settings (K17). Use of R T P on paper for rapid screening of the polycyclic aromatic hydrocarbon content of indoor and outdoor air samples (J13) and quantification of isomeric benzoquinolines in coal tar (J15)are reported. On paper substrates, HgClz quenches the phosphorescence of aromatic hydrocarbons but enhances the RTP of nitrogen heteroaromatics, thus facilitating determination of the latter in the presence of the former (K18). Applications of R T P to assay of p-aminobenzoic acid in urine for assessment of pancreatic function (K19) and to determination of pesticides (K5,K20) are of interest. Fluorometric detection in thin-layer chromatography is considered in the following section.
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L. LUMINESCENCE I N CHROMATOGRAPHIC DETECTION Liquid Chromatography. Hulshoff and Lingeman have reviewed the principles and practice of fluorescence detection in liquid and thin-layer chromatography (L1). Lingeman et al. have also presented an exhaustive review (672 literature citations) of fluorescence detection in liquid chromatography (LC) (L2).Derivatizing reagents are dealt with in particular detail. Tables summarizing reported procedures for detection 20R
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of drugs and drug metabolites in biological fluids are presented in both reviews, which contain an enormous amount of information. A general survey of the principles of fluorescence detection in LC has been presented (L3). A review of LC fluorescence principles and techniques stresses the determination of drugs in biological fluids; chemiluminescence and room-temperature phosphorescence detection also are considered (L4). A review of optical and electrochemical LC detectors includes a useful discussion of fluorescence and chemiluminescence detection (L5). A review of lasers in chemical analysis includes a useful discussion of laser-induced fluorescence in LC detection (029). Three laser fluorescence detection systems for microcolumn LC, using He-Cd lasers (A = 325 or 442 nm) for excitation, are described. All are reported to exhibit wide linear dynamic ranges (L648). Two of the detectors use flow cells compatible with microcolumn LC (L7,L8);the third employs on-column excitation (L6). An on-column fluorescence detection system for open-tubular LC, using a mercury lamp source and reference detector to compensate for lamp intensity fluctuations, is described (L9). A flow cell for LC having a volume of ca. 1 FL can be used for laser fluorometric detection, absorption, and/or refractive index detection in microcolumn LC (LIO). A fluorescence detector for microcolumn LC, with a detection volume of ca. 150 nL, uses a diode array detector (F14). A LC detector capable of simultaneous measurement of fluorescence (254-nm excitation), absorbance (254 nm), and electrical conductivity has been developed (L11). The use of pulsed dye-laser time-resolved fluorometry in LC detection continues to attract interest (L12, L13). Instrumentation for rapid-scanning constant-wavenumber synchronous fluorescence spectrometric detection in LC has been described (J7). An “indirect” fluorescence detector for ion chromatography operates by use of a luminescent eluant ion (e.g., salicylate). Whenever another type of ion emerges from the column, the concentration of salicylate in the eluant decreases, producing a corresponding diminution in fluorescence signal. Signalto-noise considerations in the use of such detectors are discussed, and a double-beam optical arrangement with a He-Cd laser source is described (L14). The influence of inner-filter and self-absorption phenomena in the use of a “spiked mobile phase” LC detector have been considered. In this detector, an eluting compound attenuates the fluorescence of a luminescent additive to the mobile phase (L15). Use of room-temperature biacetyl phosphorescence for LC detection is discussed. The biacetyl phosphorescence may be used in the “sensitized” mode, wherein the analyte is photoexcited as it emerges from the column and then transfers energy to the biacetyl to form the emissive triplet state. Alternatively, biacetyl may be excited directly, and quenching of its phosphorescence by an eluant is measured. The latter approach is believed to represent a useful approach to detection in ion chromatography (L16, L17). The use of quenched and sensitized room-temperature liquid-solution phosphorescence for LC detection of polychlorinated biphenyls and naphthalenes in complex samples is described (L18). The use of micellar mobile phases in LC with room-temperature phosphorescence detection is discussed (H25). A scrubber column packed with zinc is used to scavenge dissolved O2in LC solvents. The result is an improvement in limits of detection for compounds whose fluorescence is susceptible to oxygen quenching (~5.29). Conversion of nonluminescent analytes to fluorescent products for detection continues at its usual lively pace. The various reagents used to convert primary and secondary amines and thiols to fluorescent species, and use of these reagents in LC detection, is reviewed (B27). Postcolumn photodecomposition of nonfluorescent analytes to form fluorescent products continues to attract attention (L17, ,520). A postcolumn photochemical detector for various oxygen-containing compounds operates via measurement of the change in fluorescence intensity that occurs when anthraquinone-2,6-disulfonate(very weakly fluorescent) is photoreduced to an intensely fluorescent product. The photolysis occurs at an appreciable rate only in the presence of compounds capable of hydrogen atom donation to the anthraquinone; thus, such species can be detected via the
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increase in fluorescence that occurs in their presence (L21). The use of postcolumn electrochemical production of fluorescent species may- represent a useful approach to LC de._ tection (L22). One of the most popular derivatizing reagents for fluorescence detection in LC is o-ohthalaldehvde. The svnthesis and properties of relatives of 6-phthalaldihyde for derivatization of amines are discussed; it is hoped that some of these materials may produce derivatives more stable than those formed by o-phthalaldehyde (L23). Automated apparatus for derivatization of amino acids with o-phthalaldehyde, which then injects the derivatized compounds onto an LC column, has been developed (L24). Interference of metal ions with derivatizing reagents for amino acids (e.g., fluorescamine, 0phthalaldehyde, and NBD-F) is reported (L25). Changes in the composition or concentration ratio of the reagents may be used to increase the stabilities of reaction products of primary amines with o-phthalaldehyde (1526). A postcolumn reactor is used to adjust the pH of LC column eluents to maximize the fluorescence intensities of compounds having pH-dependent fluorescence characteristics (L27). A hollow membrane fiber reactor system for LC postcolumn derivatization has been described and applied to fluorescence derivatization reactions (1528). Mixing apparatus for precolumn fluorescence derivatization continues to be refined (L29). Sources of base line drift in gradient-elution LC detection via fluorescence and chemiluminescence are discussed, and remedies are recommended (L30). The use of fluorescence to investigate interactions of solute molecules with chromatographic stationary phases continues to produce interesting results ( L 3 1 4 3 4 ) . Fluorescence techniques for measuring the void volume of an LC column have been described and compared (L35). LC Chemiluminescence, The design of postcolumn chemiluminescence (CL) reactors suitable for use with microbore LC columns is discussed (L36). The use of aryl oxalate CL for LC detection is surveyed (L37). Postcolumn reaction systems for polycyclic aromatic hydrocarbons and other compounds that produce CL in the peroxyoxalate CL system, suitable for use with microbore columns, have been developed (L38). The influence of solvent and pH upon the CL characteristics of peroxyoxalate systems is examined with reference to LC detection via postcolumn reaction (L39). Sources of noise in this system are due principally to pump pulsations and reagent mixing (L40). The requirement for very small cells in this system (to avoid unacceptable chromatographic broadening) is alleviated to some extent by the short lifetime of the CL signal (L41). A scheme for detection of amino acids separated by LC exploits suppression of CL in the Coz+-luminol-HzOz system by amino acids; advantages of this method over ninhydrin or o-phthalaldehyde derivatizations are discussed (L42). CL detection of proteins proceeds via their inhibition of Cu2+ catalysis of luminol CL (L43). Amino acids can be detected via bis(2,4,6-trichlorophenyl)oxalate CL (L36). A scheme for detection of amino acids separated by LC exploits suppression of CL in the Co2+-luminol-HZO2system by amino acids; advantages of this method over ninhydrin or o-phthalaldehyde derivatizations are discussed (L42). CL detection of proteins proceeds via their inhibition of Cuz+ catalysis of luminol CL (L43). Amino acids can be detected via bis(2,4,6-trichlorophenyl)oxalate CL (L36). Peroxyoxalate CL is used for LC detection of steroids in plasma (L44) and amino (L45)and nitro (L46) derivatives of polycyclic aromatic hydrocarbons. Thin-Layer Chromatography. Fluorescence detection in thin-layer chromatography (TLC) is reviewed (LI). Instrumentation for laser-induced fluorescence detection in TLC is discussed (L47). If a silica TLC plate on which pyrene (or a substituted pyrene) has been spotted is cooled to 20 K using a closed-cycle cryostat, the laser-induced fluorescence spectrum of the compund exhibits line narrowing. The potential use of this interesting phenomenon for identifying and quantifying constituents of complex samples is outlined (113,114). The possibility that luminescence signals of compounds on TLC plates may be enhanced by surfactant or cyclodextrin spray reagents has been examined; enhancements are observed on some, but not all, TLC stationary phases (H26).
Gas Chromatography. A He-Cd laser fluorescence GC detector has been developed and used for detection of polycyclic aromatic hydrocarbons in complex samples (L48). An apparatus for GC detection via simultaneous measurement of UV absorbance and fluorescence is described; a fiber-optic flow cell for such measurements has been devised (L49). Use of the fluorescence of small molecular fragments formed by the electron impact dissociation of large nonfluorescent molecules has been suggested for GC detection (L50). A CL detector suitable for GC detection of reducing agents operates via reduction, by the analyte, of NOz to NO in a postcolumn reactor. The NO is then detected by the CL reaction with 0 A variety of classes of organic compounds can be detected in this way (L51).The detection of GCseparated nitro derivatives of polycyclic aromatic hydrocarbons via combustion followed by NO O3CL is reported
.
+
(L52). Electrophoresis. A two-dimensional computer-controlled scanner for quantifying the fluorescence of fluorophore-stained DNA samples in agarose gels (gel electrophoresis)is described (L53). The use of fluorescence to monitor transfer of proteins from gels to nitrocellulose or other membrane supports (“Western blotting”) has been described (L54). Fluorescence detection in isotachophoresis is discussed. Experimental methods for simultaneous measurement of fluorescence and UV absorption are described, detection limit and linear dynamic range considerations are addressed, and the use of fluorescence quenching procedures to detect nonfluorescent compounds is described (L55). M. TIME-RESOLVED LUMINESCENCE General Reviews. Techniques and applications of fluorescence decay measurements in studies of biological systems are reviewed by Meech et al. ( M I ) . Phase and pulse techniques (using flashlamps) in time-resolved fluorometry are surveyed, and computational methods for acquiring accurate decay times are discussed (M2). The proceedings of a NATO Advanced Study Institute on time-resolved fluorescence in the biological sciences have been edited by Cundall and Dale (M3). Fluorescence Decay Time Standards. The IUPAC Photochemistry Commission has suggested 1 2 fluorescence decay time standards, spanning the T F range from 66 ps to 410 ns, for the calibration of decay-time instrumentation (G10). The fluorescence decay kinetics of 9,lO-diphenylanthracene, quinine, and 2-aminopyridine (all of which have been suggested, at one time or another, as T F standards) have beren scrutinized (G11). Use of quinine as a T F standard has fallen into disfavor because of the proclivity of quinine to exhibit a complex decay. This problem reportedly is alleviated by restricting the detected fluorescence to that occurring within a narrow wavelength window at ca. 480 nm. This also is reported to be true for C1--quenched quinine fluorescence, which would permit quinine to serve as a standard of variable decay time under carefully controlled conditions (M4). Phase and Modulation Methods. This is now an area of substantial activity. The use of phase and modulation techniques in time-resolved fluorometry has been reviewed by Teale (M5)and Lakowicz (M6). McGown and Bright have reviewed the principles and techniques of decay-time measurement via phase fluorometry and have discussed the use of phase-resolved fluorometry for the determination of individual constituents in mixtures (M7). In a mixture containing two or more fluorophores whose fluorescence spectra overlap but which exhibit different decay times, each emitter produces a different phase shift in a properly designed experiment. Advantage can be taken of this fact to obtain steady-state fluorescence spectra of each of the individual fluorophores via use of a phase-sensitive detector readout system (M8). dhase fluorometry at modulation frequencies as high as 875 MHz, with time resolution in the 20-ps region, is performed using a gain-modulated silicon avalanche photodiode, rather than a PMT, as detector (M9). Techniques for resolution of two- and three-component mixtures via phase resolution at a single modulation frequency is discussed. This application is suited to commercially available fixed-frequency phase fluorometers (M10). The techniques and applications of phase fluorometry using ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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multiple modulation frequencies, to deal with complex fluorescence decays, have been reviewed in detail (M11,M12). Instrumental and computational aspects of multiple modulation frequency phase fluorometry are discussed clearly and in depth (M13-MI5). The problem also is considered from a general perspective (M16). Example applications of the technique to resolve two- and three-component mixtures of fluorophores are described (MI 7-M19). Ramsey and Hieftje have considered several schemes for extracting T F information from the frequency response of a fluorophore subjected to excitation with an intensity-modulated source. Detailed S/N considerations for these methods (most of which have yet to be experimentally evaluated) are set forth in a thought-provoking way (M20). Improvements in instrumentation for T~ measurements via cross-correlation of the sample emission intensity with the “mode noise” of a CW laser are based on signal processing by a “sampling correlator”, the operation of which is described. Sources of noise and limitations of the time-resolution capabilities of the technique are discussed (M21). Use of phase-resolved spectrometry to suppress Raman interference in fluorescence measurement (and vice versa) has been examined (M22,M23). Demas and Keller provide an especially useful comparison of phase resolution with other (time-resolution and non-time-resolution) methods for distinguishing fluorescence from background (M23). Apparatus for double-beam phase fluorometry is described, criteria for choice of modulation frequency are promulgated, and the origin and alleviation of systematic errors in T~ values measured by the technique are discussed (M24). P u l s e Fluorometry a n d Time-Correlated Photon Counting. Instrumentation and techniques of pulse timeresolved fluorometry are reviewed by Ware (M25) and McDermid (M26). A monograph on time-correlated photon counting by 0’Connor and Phillips deals with fundamental principles, instrumentation, and data analysis (pulse pile-up corrections, deconvolution, etc.). An authoritative discussion of the strengths and limitations of commercial instrumentation is especially valuable (M27). The design of a pulse fluorometer, using time-correlated photon counting via two simultaneous detection channels (i.e., two PM tubes) with matched impulse response characteristics, is described. This instrument, which uses a flashlamp source, allows one detector to observe at the excitation wavelength while the other observes at a wavelength at which the analyte emits. This setup is intended to provide automatic normalization for variations in the temporal profile in the source output. Alternatively, the two monochromators can be set to two different fluorescence wavelengths, a particularly useful arrangement in a photochemically reacting system (M28). Conventional pulse-fluorometric techniques measure the sample’s fluorescence decay and the source decay function using different pulses from the source. This can cause serious problems if the pulse profile of the source varies from one shot to the next. A differential pulse fluorometer has been designed to eliminate this problem, by measuring the source decay and fluorescence decay pulses simultaneously. In this instrument, two PMTs having matched response in time-correlated photon counting are used in a dual-detection channel arrangement (M29). Possible difficulties with use of this approach to measure very fast fluorescence decays are noted (M30). The problem of obtaining accurate decay curves via pulse fluorometry for molecules that photodecompose is important whenever the molecule in question must be exposed to many source pulses. Techniques for dealing with the problem are described (M3I). The influence of self-absorption followed by re-emission on the measured value of T F (and on the dependence of 7F on the emission wavelength) is scrutinized both theoretically and experimentally (M32). The time-resolution performance of inexpensive PMTs (e.g., RCA 931A) can reportedly be improved dramatically if one takes care to illuminate only a small fraction of the photocathode area. Applicability of this approach to time-correlated photon counting is discussed (M33). Two commercial microchannel-plate PMTs have been examined for their applicability to time-correlated photon counting. One of these tubes reportedly exhibits a transit-time spread of only 60 ps (M34). A silicon avalanche photodiode is reportedly capable 22R
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of 10-ps time resolution; its use in an instrument for T F measurements is described (M35). To decrease the time required to measure fluorescence decays by time-correlated photon counting, a modified “vernier chronotron” is used in place of a time-to-pulse height converter. Reportedly, this instrument can obtain a decay curve a factor of 20 more rapidly than can a conventional photoncounting instrument. Details of electronic design and performance of this instrument are promulgated (M36). Instrumentation for time-correlated photon counting at high source repetition rates (50 MHz) operates by decreasing the rate of time-to-pulse height converter “stop” signals (from the source) to that of “start” signals (emitted photons) (M37). Correction techniques for the dependence of the temporal response of a P M T on wavelength have been set forth (M38-M41). One way to deal with the problem is to use “reference compounds” that emit a t approximately the same wavelength as the analyte (M39, M42). These reference compounds must have accurately known decay times and profiles (preferably single exponentials). Techniques for relating the decay behavior of reference compounds to that of a single “master reference compound” (p-terphenyl) are described (M42). The nature of, and remedies for, the “pulse pile-up” problem in time-resolved photon counting has been reviewed (M43). Calculations indicate that the optimum source repetition rate ~ 1/11~, in time-correlated photon counting lies between 1 / and in which case there will be some overlap of successive fluorescence decay pulses (M44). A widely used PMT reportedly exhibits a background luminescence due to the glass end window at wavelengths less than 320 nm. The net effect is to “contaminate” the excitation pulse with PMT luminescence at such wavelengths. This background is sufficiently weak to have little effect except in the already difficult case of resolving two or more closely spaced fluorescence decays. Computational techniques for dealing with this problem are presented (M45). A gating circuit for a PMT runs the tube in the “on” state except for a brief interval during the firing of the excitation source. Advantages of this unconventional PMT gating technique are discussed (M46). Resolution of two-, three-, and four-component fluorescence decays via time-correlated photon counting is demonstrated (M47). Pulsed Sources. Eccentricities in the temporal profiles from commercial nitrogen-pumped dye lasers could complicate time-resolved fluorescence measurements (M48). Modifications to a commercial cavity dumper, to reduce or eliminate leakage of radiation from the laser between pulses, are described (M49). Techniques for obtaining subnanosecond pulses from excimer-pumped dye lasers are described (M50M52). The use of a pulsed semiconductor laser as a source for fluorescence decay time measurements is advocated as an inexpensive alternative to the more conventional lasers (M53). A review chapter by Fleming describes the design, mode of operation, and applications of synchronously pumped dye lasers (M54). Useful analyses of pulse energy and pulse width fluctuations, with random variations in the repetition rate, for synchronously pumped dye lasers have appeared (M55, M56). The deleterious effects on stable mode-locked operation of diffuse-reflectance feedback of laser radiation into the resonator in mode-locked Ar’ lasers and synchronously pumped dye lasers are discussed and remedies are recommended (M57). Variation of the output pulse duration of a svnchronouslv pumped dve laser with the -pump-pulse width - ii studied (n/is8). Techniques for obtaining virtually transform-limited pulses (ca. 4 ps) from synchronously pumped dye lasers are described (M594461). Colliding-pulse synchronously pumped dye lasers have been described and their advantages for use in timeresolved spectroscopy are discussed (M62-M64). The use of synchrotron radiation in time-resolved fluorometry is reviewed (M65). Use of a synchrotron as a high repetition-rate source for phase fluorometry (using multiple modulation frequencies to deal with complex decays and employing cross-correlation techniques) is described; tests of the instrumentation in a variety of chemical systems are reported (M66). Deconvolution a n d Related Travails. Ware has given an overview of the problems inherent in extracting fluoresA
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cence decay rate data from experimental decay curves (M67). Data-analysis techniques are discussed in a monograph on time-correlated photon counting (M27). Least-squares convolution techniques have been reviewed (M68). “Global” nonlinear least-squares analysis is applied to the analysis of complex decay curves. A set of decay curves is obtained by varying some parameter that affects the observed fluorescence decay of the system (e.g., excitation or emission wavelength, pH, solvent composition). A simultaneous mathematical analysis of the family of experimental decays is then performed. It is contended that the method is applicable both to pulse and phase fluorometry (M69). The important question of how to assess the accuracy of a mathematical model for an observed fluorescence decay curve is discussed, and deficiencies in the x2 test for goodness of fit in nonlinear least squares analysis is considered (M70). Application of a “A-invariance test” for selecting the proper number of exponential functions to be used for proper description of a complex decay curve is discussed (M71). The use of “modulating functions“ to deconvolute fluorescence decav curves for one- and two-component decays is described, and advantages of this techniqueover others are suggested (M72. - , M73). -- , Fourier transform techniques for deconvolving fluorescence decays from the source temporal profile have been discussed (M74). For single exponential decays measured by timecorrelated photon counting, it is concluded that Fourier transform and iterative convolution techniques yield virtually identical results, provided that the number of channels in the photon-counting measurement is large. The Fourier transform method requires less computer time. Different “Fourier transform” methods described by different investigators are not necessary identical (M75). A comparative study of T F values obtained by iterative deconvolution and a faster, approximate, procedure omitting reconvolution is reported. For decays 2 5 times the source decay time, the approximate procedure seems to generate acceptable results, but (not surprisingly) shorter decays require full deconvolution (M76). To deal with multiple-component decay curves obtained via time-correlated photon counting, Chen discusses “difference decay spectroscopy”,wherein computer subtraction of individual components from the decay curve is used to determine decay constants for the remainder of the experimental curve. The rather stringent experimental conditions that must be satisfied for this method to produce accurate results are compiled, and example systems (including a three-component mixture) are treated by the technique (M77). “Linear programming” (M78) and iterative reconvolution (M79) methods for treating complex decays are discussed. Applications of a “phase plane” computational procedure to data perturbed by Forster energy transfer (M80) or scattered source radiation (M81) are reported. The method of moments and its application to analysis of fluorescence decay curves has been reviewed (M82, M83). Laplace transform deconvolution techniques have been reviewed (M84). The resolution of two- and three-exponential decays by “2 transformation with spike recovery” is described (M85). Mathematical relationships for the observed phosphorescence response as a function of the temporal characteristics of a pulsed source and the phosphorescence decay time (Q) of a molecule are derived. Experimental data bearing on the matter also are presented. The goal is optimization of temporal resolution of a single constituent in a mixture (M86). The analysis of fluorescence anisotropy decays by timecorrelated photon counting is discussed, with special emphasis devoted to the relative susceptibilities of different computational techniques for dealing with the problem to systematic error (M87). The deconvolution problem is especially nasty for measurements of time-resolved fluorescence polarization data of molecules in partially ordered environments, such as membranes or liquid crystals. General aspects of the problem are discussed, and a modified iterative deconvolution method for dealing with it is set forth (M88). Analytical Applications. Probably the most common present-day application of time resolution to fluorometry is in fluoroimmunoassay (see Section Q). The use of phase-resolved fluorometry to determine the individual constituents of mixtures is discussed (M89). The combination of phase resolution with selective excitation im\
proves the selectivity of each approach to mixture analysis (M90). The question as to how to distinguish between compounds having very similar fluorescence spectra and decay times by phase resolution is addressed (M91). Use of phase resolution to suppress interfering luminescence by bilirubin in the determination of fluorescein is described (M92),as is the determination of each compound in a four-component mixture of anthracene derivatives (M93). Improvements in limits of detection of “aminopeptidase profiling” by pulsed-laser time-resolved fluorometry are reported. For the various sources of background emission, time resolution is very useful in eliminating some but nugatory for others. This study is an excellent example of how laser excitation and time resolution can improve limits of detection in complex biological samples wherein interfering luminescence is the principal analytical problem (032). Use of time-resolved luminescence to correct for quenching in liquid solution is applied to determination of UOZ2+in aqueous samples (M94)and polycyclic aromatic hydrocarbons in liquid solution without prior removal of 02,an effective quencher for many of these compounds (M95). Combination of time resolution with total internal reflection optics enables achievement both of temporal and depth resolution of fluorescence. The potential of such measurements for surface characterization (e.g., of polymer films) is discussed (E4). The uses of time-resolved fluorescence microscopy in biomedical analysis are discussed (M96, M97). A time-resolved luminescence determination of enzymes proceeds by labeling a substrate of the enzyme with Eu3+. Enz me catalyzed destruction of the substrate liberates the Eu3Y, which - can be detected by its luminescence. Because this luminescence has a much longer decay time than that of most biological macromolecules, interference from the latter can be alleviated by time resolution (M98). The possible use of fluorescence decay times (along with conventional steady-state excitation and emission spectra) for identification of bacteria is discussed (M99). N. P O L A R I Z E D F L U O R E S C E N C E A N D RELATED PHENOMENA Reviews. Lakowicz has reviewed the principles, practice, and applications of polarized fluorescence measurements in detail. The measurement both of steady-state and time-resolved fluorescence anisotropies also is discussed ( N l ) . A review of multiparameter methods in luminescence spectrometry includes a discussion of the principles and techniques of luminescence polarization and fluorescence-detectedcircular dichroism (B9). Brittan has reviewed the applications of circularly polarized luminescence spectrometry and fluorescence-detected circular dichroism (N2). Instrumentation and Techniques. Descriptions of instrumentation for polarized fluorescence measurements by flow cytometry have appeared (N3,N4). Applications of such measurements to cellular immunology have been reviewed (N4). A description of an instrument using a quartz elastooptic modulator to produce circularly polarized light has appeared, and use of this instrument for various types of luminescence measurements (linearly or circularly polarized fluorescence; delayed luminescence) is discussed (N5). Applications. A fluorescence polarization assay for urinary lysozyme activity is based on a decrease in fluorescence polarization brought about by reaction of the enzyme with a fluorescein-labeledsubstrate (N6). Fluorescence polarization techniques for detecting the production of fetal lung surfactant are described (N7). Applications of fluorescence polarization in immunoassay are considered in section Q.
0. S O L U T I O N C H E M I L U M I N E S C E N C E Reviews. A 100-page review with over 200 literature citations, by Campbell, Hallett, and Weeks, discusses thoroughly the applications of chemiluminescence (CL) and bioluminescence (BL) in cell biology and medicine. CL principles and experimental techniques are also treated in this wideranging review ( 0 1 ) . Kricka and Thorpe have reviewed thoroughly the principles, techniques, and applications of CL and BL in analytical chemistry (02). The use of CL and BL in clinical analytical chemistry and medical diagnosis is reviewed (03). The proceedings of the Third Annual Symposium on Analytical Applications of Bioluminescence and Chemiluminescence have been published (04). ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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The use of flow-injection techniques in solution CL has been reviewed (05). Faulkner and Glass have reviewed the principles and experimental methods of electrochemically generated CL (06). Schuster and Schmidt have reviewed the state of current knowledge of the mechanisms of organic CL systems, including the analytically popular luminol and peroxyoxalate systems (07). Mechanisms in BL have been reviewed by Shimomura (08). Instrumentation and Techniques. The use of micellar media (H27,H28) and cyclodextrin-containing solutions (09) for enhancement of CL signals has been studied. Solubilization of a water-insoluble product of the lucigenin CL system by addition of a surfactant to lucigenin solutions increases the practical utility of lucigenin CL (010). That the optimum pH for generation of luminol CL is alkaline can be a nuisance whenever one is dealing with clinical samples. The use of luminol-protein conjugates is reported to assist in performing CL assays a t neutral pH (011). Techniques for coimmobilizing luciferase and flavin mononucleotide oxidoreductase on collagen strips are described, and use of this immobilized enzyme system for NADH determination i s demonstrated (012). A continuous-flow BL method for bile acids in serum uses a nylon tube support for immobilization of three enzymes, including luciferase. The light detection apparatus used in conjunction with this chemical system is described in detail (013). Immobilization of luciferase and NAD(P)H:FMN oxidoreductase on coils on Nylon 6, and use of this system for BL determinations of NADH, is described (014). A sensor consisting of immobilized peroxidase and a photodiode is applied to HzOzdetermination via luminol CL. A similar system employing two immobilized enzymes (peroxidase and glucose oxidase) is used to determine glucose (015). Use of an immobilized fluorophore (3-aminofluoranthene, bound to silica, cellulose, or glass beads) in conjunction with peroxyoxalate CL is asserted to simplify the application of this CL system to determination of HzOz (016). The use of a solid bed reactor packed with bis(2,4,6-trichlorophenyl)oxalate is advocated as an approach to overcoming reagent solubility limitations in peroxyoxalate CL. A reactor design is presented and use of the apparatus for HzOzdeterminath is described (017. 018). A flow cell design suitable for use in two-phase solution CL systems (e.g., contact of a liquid solution sample with an immobilized enzyme or other reagent on a solid substrate) is reported (019). A two-compartment cell for CL determination of 02-and HzOz in insoluble biological materials (e.g., tissue homogenates) separates the sample from a luminol solution by a dialysis membrane (020). An immersible flow apparatus for CL measurements of seawater samples has been developed (021). Various flow and flow injection apparatus for solution CL and BL have been described (022-026). BL and CL measurements using instant photographic film as the detector are reported to be fast and especially useful for rapid screening applications; no electricity is needed and a permanent record of the results is produced (027, 028). Applications of this approach to determinations of ethanol, ATP, NADH, and cholyl glycine (029) and to CL immunoassay procedures (030) are described. Smoothing of CL data by a Fourier transform algorithm is described and used to improve the speed and precision of CL measurements (031). Applications. A CL technique for reducing agents measures the effect of the analyte on the time period required to achieve measurable CL in the ferriheme-catalyzed luminolHzOzsystem. The idea is that the reducing agent reduces an intermediate Fe(II1) species, and CL is not observed until this “scavenging” action by the analyte ceases-that is, until the analyte is consumed. The time required to accomplish consumption of the analyte depends on its concentration. Thus, the measurement is one of time, rather than light intensity. Application to automated clinical analysis is discussed (032). The famous complex Ru(bpy)32+can be detected a t conM by electrogenerated CL. It is centrations as low as suggested that Ru(bpy)3z+may be useful as a CL label for competitive protein binding reactions involving biologically important compounds. For example, the specificity of Ru(bpy)?+ appears significantly greater than that observed for luminol as a CL label (033). Enhancement of electrogenerated CL of luminol by Co2+reportedly yields a limit of detection 24R
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for Co2+of ca. M (034). The use of electrogenerated CL in homogeneous immunoassay is discussed (035). The use of CL to indicate the possible presence of singlet oxygen in biological samples is reviewed (036). A pyrene derivative is reported to serve as a specific CL probe for singlet oxygen (037). A determination of OH radicals (or of species which react to form OH radical) in solution proceeds by reaction with weakly luminescent phthalic hydrazide to form much more strongly luminescent hydroxylated compounds which are then detected by conventional CL methods (038). Techniques for estimating the stability of polymers, by measuring the CL produced during thermal oxidation of the samples, are described (039). Use of CL to estimate the extent of degradation of polymers subjected to exposure to ionizing radiation is discussed (040). Determination of HzOz in polymers via luminol CL is described (041). The CL generated when oils and lubricants are autoxidized a t elevated temperature may be used as a measure of the oxidative stabilities of these materials and may also encounter application in the identification of liquid hydrocarbon samples (042). An extensive review of CL procedures for determination of N-nitrosamines in foods has appeared (043). Enzymecatalyzed conversion of urinary glucuronides to glucuronic acid is followed by determination of the latter via lucigenin CL. A flow system incorporating a column containing immobilized enzyme is used in this determination (024). Another flow CL method using an immobilized enzyme column is used to determine glucose and uric acid in serum via luminol CL (044). A CL method for heparin involves acid hydrolysis of the analyte to disaccharide products which are then determined by lucigenin CL (045). Clinical uses of luminol CL measured in whole blood (e.g., for possible diagnosis of peritonitis) are discussed (046). A determination of total polyamines in cells or serum proceeds by enzymatic conversion to aldehydes + Hz02followed by assay for the latter by luminol CL (047). Luminol CL methods for cholesterol (048)and superoxide dismutase (049) are reported. The use of luminol CL to measure rates of ligand-exchange reactions of Cr(II1) species and to study the rate of adsorption of Cr(II1) from aqueous solution onto solid iron oxide may signify useful applications of CL techniques for examining dynamics of environmental phenomena (050). CL determination of Cu(I1) via its catalysis of the oxidation of flavin mononucleotide by HzOzis described (051). Hydrogen peroxide, in the presence of Fe(I1) or Cr(III), undergoes decomposition to singlet oxygen which sensitizes luminescence of brilliant sulfoflavine. This solution CL system is applied to determination of the two metal ions. A thorough investigation of the effects of interfering ions is presented (052). CL resulting from the Co(I1)-catalyzed oxidation of hematine by HzOzis applied to determination of cobalt in steel and natural water samples (053). CL determinations of Os, Ru, and Ir (by luminol or lucigenin) in real samples (slags, ore tailings, etc.) are reported (054). A luminol procedure for C10, in water uses a membrane flow cell technique (055). Applications of CL in liquid chromatography detection are considered in section L; applications to immunoassay are discussed in section Q.
P. GAS-PHASE CHEMILUMINESCENCE Instrumentation and Techniques. Mass flow and chemical rate equations for gas-phase CL measurements to predict the CL signal as a function of such parameters as the sample flow rate, gas pressure, and the volume of the reaction chamber have been presented (PI). Examples of CL resulting from reactions of “active nitrogen” (formed in discharges or afterglows) with various organic and organometallic compounds are tabulated, and comments regarding analytical applicability of the phenomenon are offered (P2). CL of gas-phase polycyclic aromatic hydrocarbons produced by energy transfer from active nitrogen can be used to detect subnanogram amounts of the compounds (P3). A CL method for continuous monitoring of SOz in air proceeds by spraying a nebulized aqueous solution into a flowing air sample. The reagent solution contains Mn04-, which oxidizes HSO; to excited SOz, which exhibits CL. The CL signal amplitude can be enhanced if a separate reagent solution, containing a sensitizer such as flavin mononucleotide
MOLECULAR FLUORESCENCE, PHOSPHORESCENCE, AND CHEMILUMINESCENCE SPECTROMETRY
and a micelle-forming surfactant, also is aspirated into the air sample (H29). A somewhat similar CL method for SOz involves formation of a mercury disulfite complex using a filter substrate; the complex is then decomposed by MnO,, whereupon CL results (P4). Clearly, such procedures incorporate elements both of gas-phase and solution CL techniques, as does a procedure for SOz wherein enhancement by SOz of the CL generated by reaction of luminol with NOz is measured
(Pa.
Fluorine can be produced for use as a CL reagent by infrared multiple-photon dissociation of SF, via a COz laser. The reaction of Fz so produced with aliphatic hydrocarbons, such as CzH4, generates CL (in which the emitting species appear to be C2, CH, and HF) (P6). A portable CL detector for Ni(C0I4, based on the reaction of Ni(C0)4 with O3 in the presence of CO, has been described. Parts-per-billion limits of detection for Ni(C0)4,Fe(CO)5,and NO are claimed (P7). Applications. Radicals such as HO and HOPoxidize NO to NOz in the presence of CO by a chain mechanism which recycles the radical. Thus, large numbers of NOz molecules can be produced by each radical present in an atmospheric sample. Measurement of the amount of NOz so produced by luminol CL leads to a method for which detection of radical concentrations in the parts-per-trillion range are reported (P8). A comparison of the results of determinations of NO, NOz, and HN03 (by NO O3 CL) with those obtained by diodelaser absorptiometry is reported. Diode laser IR absorption is free from the interference problems that can cause difficulties with the CL method, but CL produces much better limits of detection. The IR method may be useful for validating results obtained by CL and for indicating the presence of species that interfere in the CL technique (P9). A detailed description of a dual-channel CL photometer for simultaneous determination of NO and NOz is provided (PIO).Ballooncarried instrumentation for determination of stratospheric NO via the 0 reaction is described (P11). Methods for mathematically estimating errors in determination of nitrogen oxides by CL (due to quenching) are described (P12). Some organic nitrogen and sulfur compounds exhibit positive interference in CL “NO,” analyzers. Though the interferences often are small, there are specific situations in which they could lead to significant overestimates of atmospheric NOz levels (P13). Improved instrumentation and techniques for decreasing the extent of interference in CL determination of NOz in air are reported; use of the instrumentation in aircraft is discussed (P14). Interference by HNOz in the determination of HNO, by a “NO,” CL monitor is discussed (P15). The conditions under which a CL “NO,” analyzer can be used to obtain accurate results for atmospheric peroxyacetyl nitrate have been described (P16). The sensitivity of a commercial “NO,” CL analyzer may be degraded by formation of solid deposits on the glass filter disk separating the reaction chamber from the detector when ambient air samples are analyzed (PI 7). Modifications of commercial NO detectors to improve their sensitivities are described (P18). Gaseous reducing agents can be detected by bringing them into contact with NOz in a catalytic reactor. Reducing agents that convert NOz to NO can be detected via the NO O3CL reaction (L51). Modifications of a procedure for determination of NO, in solution by use of a commercial ”NO,” CL analyzer have been described (P19). A CL procedure for determination of nitrogen-containing compounds in oil-shale retort waters proceeds by combustion to NO followed by NO + O3CL (P20).
+
+
Q. FLUOROIMMUNOASSAY AND RELATED TECHNIQUES Fluoroimmunoassay (FIA) and related techniques now constitute a gigantic literature. This review stresses advances in technique; applications are reviewed in the binennial review on clinical chemistry (Q1). Reviews. Karnes, O’Neal, and Schulman have reviewed the principles and practice of luminescence immunoassay, with special emphasis on homogeneous and heterogeneous fluorolmmunoassays. Some interesting speculations on future trends in the area also are offered (Q2). A review by Jameson deals with fundamentals of fluorescence and applications to immunoassay (B21). Hemmila has reviewed the principles and practice of FIA and immunofluorometric assay (Q3). A survey of recent advances in fluorometric analysis includes
a general discussion of FIA (BIO). Surveys of the principles and practice of FIA and applications of fluorescence in immunology have appeared (Q4-Q6). The principles, techniques, and applications of heterogeneous and homogeneous FIA have been reviewed by Nakamura (Q7). The principles of homogeneous FIA have been reviewed (Q8). A survey of luminescence measurements on solid surfaces includes a useful overview of solid-phase FIA (K1). In 1983, fluorometric instruments had a 16% share of the immunoassay instrument market, but it is predicted that this share will rise to ca. 42% by 1988 (Q9). Not surprisingly, FIA is receiving increasing attention in the business community (&lo). Detailed discussions of prospects and problems in the definition and standardization of immunofluorescence are of considerable interest (Q11,Q12). A review on interference in immunoassay procedures includes examples, and their effects, in FIA (Q13). A review of quantitative immunofluorescence microscopy considers such matters as chemical techniques for labeling proteins with fluorophores and the influence of the experimental apparatus on fluorescence yields and image contrast. Applications are surveyed (Q14). The use of immunofluorescence for determination of serum antibodies to blood platelets or neutrophils is reviewed (Q15). Developments in Instrumentation and Technique. An internal-reflection homogeneous FIA technique is described. The antibody is covalently immobilized on an internal reflection element, which is then placed in contact with a solution containing an antigen. If the reaction of the immobilized antibody with an antigen in solution produces (or can be coupled to production of) fluorescence, the fluorescence generated at the waveguide-solution interface can be coupled to an external detedor. The evanescent light wave propagated through the internal reflection element is supposed to interact with antigen-antibody complexes formed at the interface, but not with the bulk solution, thereby decreasing the possibility of interference. Application of the principle to a two-site FIA for IgG is reported (E7, E8). “Particle concentration fluorescence immunoassay” is a two-site sandwich immunoassay method wherein immunoreactive species are bound to small polystyrene particles. Then, the particles are dispersed in the sample, to which the fluorophore-labeled reagent is added. After the analyte and labeled reagent bind to the particle surface, fluorescence is measured in a multiple-well assay plate. Use of this technique for rapid batch quantification of IgA, IgM, and IgG in serum is described (Q16, 817). The design of automated commercial instrumentation for the performance of enzyme-labeling FIA on filter-paper substrates is described in detail (Q18). Use of a laser to photolyze bilirubin and carotenoid compounds present in human serum prior to performance of FIA has the potential to improve the limits of detection via reduction in fluorescence background interference (Q19). Time-Resolved FIA. The use of time-resolved fluorescence in immunoassay has been reviewed (Q6,Q20-QZ2). Interest in the use of lanthanide chelates as labeles for time-resolved FIA continues. New chelates reportedly exhibiting very high formation constants (and thus less likely to dissociate when present in solution at low concentration) have been prepared (Q23). Studies of Eu3+ and Tb3+ luminescence intensities are directed at improved limits of detection for time-resolved FIA using chelates of these ions as labels (&24-Q26). The preparation and luminescence characteristics of a variety of Tb3+chelates of potential utility in time-resolved FIA are reported (Q27). A time-resolved FIA for phenobarbital proceeds by phase-resolved fluorescence, rather than the more conventional pulse technique, for distinguishing the fluorescence of fluorescein-labeled free antigen from that of the labeled antigen bound to the antibody (Q28). Applications of time-resolved FIA include determinations of chorionic gonadotropin in serum (Q29),testosterone in serum (&30),a-fetoprotein in amniotic fluid and serum (Q31),IgG in serum (Q32),thyrotropin in serum (Q33),and cortisol in serum (Q34). Fluorescence Polarization Immunoassay. Reviews of the use of polarization FIA in drug analysis (Q35) and applications of polarized fluorescence, measured via flow cytoANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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metry, to cellular immunology (N4) have appeared. The binding of a fluorescent compound to an analytespecific binding protein alters both the intensity and polarization characteristics of the fluorescent label. The utility of measuring the vertically and horizontally polarized fluorescence components, rather than the degree of polarization, is discussed with specific reference to homogeneous ligandbinding FIA (Q36). The use of commercial fluorescence polarization immunoassay instrumentation for several common assays is described, and the results are compared with those obtained by nonfluorescence immunoassay methods. Advantages of the commercial instrument are discussed (Q37).The results obtained by fluorescence polarization fluoroimmunoassay for tobramycin in whole blood or serum (Q38) and theophylline in serum (Q39)are concluded not to be significantly influenced by sample storage time or temperature, container material, or storage medium. Polarization FIA for phenobarbital may produce erroneous results for patients having renal disease (Q40). Interference by steroids and lipids may cast doubt on the accuracy both of polarization FIAs and radioimmunoassays for digoxin (Q41). Interference of serum proteins in polarization FIA for digoxin is discussed, as are procedures for surmounting the problem (642). Labels for FIA. The use of labels that undergo excitedstate proton transfer has the advantage that the wavelength difference between excitation and emission maxima usually is much larger than the Stokes shift for either prototropic form of the compound. Thus, background scattering interference may be diminished, as may interfering fluorescence from other sample constituents (Q43,Q44). Photobleacliing of fluorescein isothiocyanate (FITC) labeled entities is a significant headache (Q45, Q46). The ability of eight “antibleaching” reagents to suppress such photobleaching phenomena is evaluated; unfortunately, most of these reagents have minimal effect (Q47). Control of the quality of FITClabeled reagents for FIA is discussed (Q48). A technique for direct conjugation of antibodies with FITC is described, and its applicability to immunofluorescence microscopy is discussed (Q49). A procedure for rapid preparation of FITC conjugates of IgG and Fab from immune serum is described (Q50). The characteristics of phycofluors as orange and red emitters suitable for use in FIA have been surveyed (Q51). Reliability of FIA Results. Various assays are used to evaluate the performance of an automated commercial instrument for substrate-labeled FIA (Q52). An evaluation of the performance of a commercial centrifugal analyzer in FIA is presented (E55). Discrepancies between enzyme and fluoroimmuno assay results for tobramycin in serum are noted, with indications that the enzyme immunoassay may be more accurate (Q53).
R. CHEMILUMINESCENCE IN IMMUNOASSAY Reviews. A monograph on immunoassay includes a chapter dealing with chemiluminescence (CI.) in immunoassay (622). A review of the problems and future possibilities of bioluminescence (BL) and CL immunoassays stresses such matters as choice of label, solid-phase methods, and reagent stability considerations ( R I ) . Numerous surveys of CL and BL in immunoassay have appeared (01, Q2, R2-R6). Instrumentation and Techniques. Interfacing a microcomputer with a CL photometer enables the influence of experimental parameters in CL immunoassay to be ascertained (R7). Computer techniques for analyzing the data obtained in CI. immunoassays have been surveyed (R8). The use of instant photographic film as detector in CL and RL immunoassays, and its advantages, are discussed (030). The preparation of bacterial luciferase conjugates for BL immunoassays is discussed (R9). The use of reversibly inactivated luciferase as a BL label for an antigen in immunoassay is discussed, and an example assay based on this approach (for estriol) is described (RZO). The use of peroxyoxalate CL to determine compounds that have previously been labeled with a fluorophore (such as rhodamine B or a fluorescein derivative) is discussed. Possible application of this measurement system to homogeneous CIAimmunoassay is discussed ( R l l ) . 26R
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The use of aryl acridinium esters as CL labels for immunoassays for determination of polypeptides and proteins (e.g., ferritin) is discussed (R12). Labeling an antigen with a compound (e.g., 1-aminopyrene) that can produce CL upon electroreduction is proposed as a technique for homogeneous CL immunoassays (035). Many metal complexes catalyze the generation of CL in common systems (especially luminol). Competitive-binding CL immunoassays using analytes labeled with such metal chelates have been described (R13-R15). Enhancement of the CL signal produced in the peroxidase-catalyzed oxidation of luminol (or isoluminol) by 6-hydroxybenzothiazoles (R16,R17) or other aromatic hydroxyl compounds (R18)may enable more sensitive quantification of peroxidase conjugates in immunoassay. Such a method is applied to CL, enzyme immunoassay for serum progesterone (R19). A solid-phase BL assay for neuron-specific enolase in plasma uses antibodies immobilized on polystyrene tubes which can be reused (R20). A similar approach is used in CL immunoassays of urinary LH (R21),serum gentamicin and cortisol (R22),and various plasma proteins (R23). A homogeneous CL energy-transfer immunoassay for cyclic AMP is described, and the potential applicability of such procedures to the investigation of chemical events in intact cells is discussed (R24).
S. FLUORESCENCE FLOW CYTOMETRY Reviews. Instrumentation, technique, and applications of flow cytometry are reviewed in depth by Steinkamp ( S I ) . Parks and Herzenberg have reviewed the principles and experimental techniques of flow cytometry and applications of the technique to characterization of lymphoid cells (272). Cambier and Monroe have reviewed the methods and instrumental techniques of flow cytometry with special reference to the characterization of neurosecretory cells (S3). A brief but useful survey of techniques and applications of flow cytometry has appeared (S4). Applications of flow cytometry have been surveyed with reference to their potential utility in the emerging biotechnology industries (S5). A detailed description of instrumentation and techniques for polarized fluorescence measurements via flow cytometry has appeared (N3). The measurement of fluorescence polarization via flow cytometry, and applications of such measurements to cellular immunology, has been reviewed (N4). Instrumentation. The use of a modified flow cytometer to achieve very low limits of detection in solution fluorometry is described; the possibility of achieving the single-molecule limit of detection i s considered (E40). A slit-scan flow cytometer for simultaneous fluorescence and light scattering measurements has been described and applied to the characterization of chromosomes (S6). Flow cytometric techniques for measurement of efficiencies of energy transfer between species on cell surfaces, using a dualwavelength flow cytometer, are described (S7). Staining Techniques. Simultaneous staining of cell surface components and DNA (or RNA) makes it possible to detect changes in cell surface characteristics during various phases of the cell cycle by flow cytometry (S8). Double fluorescent label techniques for determining the base composition of bacterial DNA samples are described (S9). The results of flow-cytometric measurements of fluorescence intensity ratios between differently stained particles (e.g., via the use of two or more staining reagents) may depend strongly on the intensity of the exciting laser radiation; precautions t o alleviate this effect should be considered ( S l 0 ) . Techniques to retard the fading of Hoechst 33258-, acridine orange-, and mithramycin-stained erythrocytes are described (SI1). A comparison of the accessibility of DNA in Friend leukemia cells to nine common fluorescent DNA stains is reported (512). Fluorescent phycobiliprotein conjugates having huge Stokes shifts (ca. 115 nm), due to energy-transfer phenomena, offer the obvious advantage of minimal Rayleigh scatter interference and thus may be of use in fluorometric cell characterization and flow cytometry (S13). The advantages of 4,6‘-diamidino-2-phenylindole (“DAPI”) as a fluorescent DNA label are discussed (S14). Improvements in the procedure for staining DNA with “DAPI”, suitable for quantitative cytofluorometry, are reported (S15). The use of nile red as a fluorescent stain for intracellular lipid droplets by flow cy-
MOLECULAR FLUORESCENCE, PHOSPHORESCENCE, AND CHEMILUMINESCENCE SPECTROMETRY
tometry or fluorescence microscopy has been described (S16). The properties of new fluorescent nucleic acid labels have been reported ( S l 7 , S18). Modifications of DNA-staining methods for flow-cytometric cell cvcle txotzression analvses are described (S19). The compoundA7-aminoactinomycin D is recommended as a fluorescent DNA label for flow cytometry using an Ar+ laser source (S20). The characteristics of phycofluors as orange and red emitters suitable for use as probes in fluorescence-activated cell sorting are surveyed ( Q 5 l ) . Applications. The use of flow cytometry, involving a double-staining DNA label procedure, for characterization of bacteria is described (S21). Other interesting applications include methods for estimating the redox activity of single cells (S22),determination of intracellular lipid content (S23), assay of the estrogen receptor content of tumor cells (S24), and characterization of the distribution of insulin receptors in human lymphoblastoid cell lines (825).
T. FLUORESCENCE MICROSCOPY, SINGLE-CELL STUDIES, AND RELATED TECHNIQUES Reviews. Ploem has reviewed fluorescence microscopic techniques and their use to characterize biological surfaces ( T l ) . A useful review of instrumentation and techniques for laser-induced fluorescence imaging measurements for obtaining distributions and transport data of fluorescent-labeled constituents of single living cells has appeared (035). Fluorescence digital imaging microscope techniques and their applications to cell biology are reviewed (F13). Instrumentation. An imaging microfluorometer, for use in measuring fluorescence of cultured cell monolayers, uses a SIT vidicon detector (7'2). Instrumentation for digitizing fluorescent images obtained via SIT vidicon detection of fluorescence from individual biological cells is described (F16). Use of a diode-array detector for imaging of the laser-induced fluorescence of hematoporphyrin derivatives localized in cancer tissues is stated to achieve considerable improvement in the specificity with which cancerous tumors can be located in tissue samples (F15). Image analysis techniques (using a SIT vidicon detector), using thin-layer chromatography plates as matrices, are used to examine the complexation of prospective fluorescent labels with proteins, to distinguish "bound from "free" fluorescent compound, and to differentiate between covalently and noncovalently bound fluorophore. It is contended that this approach is useful for rapid production of optimally labeled protein-specific fluorescent probes (F17). A mechanically scanning fluorometer, capable of obtaining a fluorescence spectrum in 0.1 s at a claimed spectral resolution of 2.5 nm, is small enough to be used in conjunction with a microscope. Thus, photochemical changes accompanying excitation of fluorescence in histological samples can be detected ( S l 7 ) . The uses of pulsed laser time-resolved fluorescence microscopy in biomedical analysis are discussed (M96, M97). An automated device for achieving controlled transfer of thin molecular films from air-water interfaces to solid substrates includes an epifluorescence microscope that can be used to monitor the process (T3). Applications. An enzymatic technique for lactate in biological fluids, using a fluorescence microscope, can proceed with nanoliter sample volumes (T4). The techniques and applications of fluorescence photobleaching recovery experiments are surveyed (T5). Fluorescence and chemiluminescence techniques for the measurement of intracellular Ca2+ concentrations have been described (01,T6-T12). A nonfluorescent Ca2+ionophore and its use in calibrating fluorometric assays for cytoplasmic Ca2+have been described (2'13). Fluorescence techniques for estimation of intracellular pH values are reported (T2, T14). The use of fluorescence microscopy for the forensic analysis of colorless natural and synthetic fibers has been demonstrated (T15). The use of fluorescence microscopy to study carbohydrates and detect enzymes in cereals has been reviewed (T16). The use of membrane filtration followed by epifluorescence microscopy to measure bacterial contamination in intravenous fluids is described (T17). The possible use of chemiluminescence energy transfer immunoassay techniques to study chemical events in intact cells has been discussed (R24).
U. OTHER TECHNIQUES AND APPLICATIONS Cited in this section are techniques and applications of interest that cannot readily be subsumed in the preceding categories. Instrumentation and Techniques. When large molecules havine small fluorescence auantum vields are fragmented by electrYon impact, small fluorescent molecular fragments may be formed. Analytical implications of this phenomenon are considered (L50).A rather pessimistic prognosis for the future of X-ray induced luminescence of organic molecules as a viable analytical technique has been presented ( U l ) . Apparatus for photochemical conversion of nonfluorescent analytes to fluorescent products has been developed and applied to determination of the antimalarial drug primaquine (U2). Microanalysis by the ring-oven segment technique using fluorescence measurement is reviewed (U3). Applications. Determination of O2 by its quenching of the fluorescence of suitable organic fluorophores is a wellestablished method. Fluorophores suitable for this application which absorb in the 460-565 nm wavelength region are described (U4). Some cationic fluorescent dyes, when bound to anionic polyelectrolytes (e.g., those formed by dissolving "Nafion"), exhibit an increase in fluorescence quantum yield. Application of this fact to development of a fluorescence titration for anionic polyelectrolytes in solution has been discussed (U5). The luminescence characteristics of a molecule dissolved in solution may be quite different from those of the same compound in colloidal or suspension form. Use of these differences to ascertain whether a fluorescent compound is really dissolved or merely suspended in solution is discussed (U6). Fluorescence spectra and decay times for 26 different fluorescent labels bound to ovalbumin have been measured. Such a comparative listing may be useful in a general sense for evaluating the suitability of a particular fluorescent tag for other proteins (U7). LITERATURE CITED A. INTRODUCTION
(AI) Wehry, E. L. Anal. Chem. 1984, 5 6 , 156R-173R. B. BOOKS AND REVIEWS
(81) Schulman, S. G. "Molecular Luminescence Spectroscopy. Methods and Appllcations: Part 1"; Wiley: New York, 1985. (82) Schulman, S. G. I n "Molecular Luminescence Spectroscopy. Methods and Applications: Part 1"; Wiley: New York, 1985; pp 1-28. (83) Baeyens, W. R. G. I n "Molecular Luminescence Spectroscopy. Methods and Applications: Part 1"; Wiley: New York, 1985; pp 29-166. (84) Wolfbels, 0. S. I n "Molecular Luminescence Spectroscopy. Methods and Applications: Part 1"; Wiley: New York, 1985; pp 167-370. (85) Fernandez-Gutierrez, A.; Munoz de la Pena, A. I n "Molecular Luminescence Spectroscopy. Methods and Applications: Part 1"; Wiley: New York, 1985; pp 371-546. (86) Brittain, H. G. I n "Molecular Luminescence Spectroscopy. Methods and Applications: Part 1"; Wlley: New York, 1985; pp 547-82. (87) Lakowicz, J. R. "Principles of Fluorescence Spectroscopy"; Plenum: New York, 1983. (88) Eastwood, D. "New Directions in Molecular Luminescence" (ASTM Special Technical Publicatlon 822); ASTM: Philadelphia, PA, 1983. (B9) Warner, I . M.; Patonay, G.; Thomas, M. P. Anal. Chem. 1985, 5 7 , 463A-483A. (810) Miller, J. N. Analyst 1984, 109, 191-8. (B11) Cundaii, R. 8 . Photochemisfry (Chem. SOC.Specialist Periodical Report) 1984, 15, 3-54. (812) Speiser, S.J . Phofochem. 1983, 22, 195-211. (813) Wehry, E. L. I n "Water Analysis"; Minear, R. A., Keith, L. H., Eds.; Academic Press: New York, 1984; Vol. 2, pp 155-224. (814) Fernandez-Gutierrez, A.; Munoz de la Pena, A,; Roman, M. Ann. Chim. (Rome) 1984, 7 4 , 1-14. (815) Ostgaard, K. I n "Trace Analysis"; Lawrence, J. F., Ed.; Academic Press: Orlando, FL, 1984; Vol. 3, pp 163-212. (816) Wehry, E. L. I n "Handbook of Polycyclic Aromatic Compounos"; Bjarseth, A., Ed.: Marcel Dekker: New York, 1983: pp 323-96. (817) Howard, A. G.; Mills, G. A. I n "Trace Analysis"; Lawrence, J. F., Ed.; Academic Press: Orlando, FL, 1984; Voi. 3, pp 241-54. (818) Guilbault, G. G. Pure Appl. Chem. 1985, 57, 495-514. (819) Callis, P. R. Annu. Rev. Phys. Chem. 1983, 3 4 , 329-57. (820) Finazzi-Agro, A.; Avigliano, L. Life Chem. Rep. 1984, 2, 97-139; Chem. Abstr. 1984, 101, 166459. (821) Jameson, D. M. Fluorescein Hapten: Immunol. Probe 1984, 23-48; Chem. Absfr. 1984, 100, 153204. (822) Creed, D. Phofochem. Photobiol. 1985, 3 9 , 537-62. (823) Creed, D. Photochem. Photobiol. 1984, 3 9 , 563-75. (824) Creed. D. Photochem. Photobiol. 1984, 3 9 , 577-83. (825) Elson, E. L. Annu. Rev. Phys. Chem. 1985, 3 6 , 379-406. ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
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Dynamic Electrochemistry: Methodology and Application Dennis C. Johnson* Department of Chemistry, Iowa State University, Ames, Iowa 50011
Michael D. Ryan Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53233
George S. Wilson Department of Chemistry, University of Arizona, Tucson, Arizona 85721
This review covers the literature for the approximate period of December 1983 through November 1985 and gives emphasis to progress in the theory and methodology of quantitative electroanalytical chemistry. Cited also is literature describing auxiliary techniques for characterization of electrochemical phenomena. Three areas of high activity and significance for this review period are noteworthy at the outset: Microelectrodes received increased attention because of the virtual steady-state response that is obtained in unstirred solutions and the increased signal-to-background ratio. The study of chemically modified
solid electrodes continued to increase in popularity with much creativity shown for incorporation of electroactive functional groups into a variety of conductive films. Also apparent is the increased emphasis on the development of modified electrode surfaces for catalyzing bioselective and biospecific faradaic reactions.
A. BOOKS AND REVIEWS Newcomers as well as veterans in electroanalytical chemistry can benefit immensely from “Laboratory Techniques in Electroanalytical Chemistry”, edited by Kissinger and
QQQ3-27QQ/86/Q358-33R~Q6.50/0 0 1986 American Chemical Society
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