Molecular fluorescence, phosphorescence, and chemiluminescence

Anal. Chem. 1988, 60, 162R-175R (126)Hambitzer, G.; Hellbaum, J. Anal. Chem. 1988, 5 8 , 1067-70. J. INSTRUMENTATION

(JI)Jayaweera, P.; Rarnaley, L. Anal. Instrum. 1988, 15, 259-77. (J2)Gabrlelll, D.;Huet, F.: Keddarn, M. Electrochlm. Acta 1988, 3 1 , 1025-39. (J3)Svestka, M.; Bond, A. M. J. Electroanal. Chem. 1888, 200, 35-46. (J4)Blxler, J. L.; Bond, A. M.; Lay, P. A.; Thormann, W.; Fleischmann, J.; Pons, S.;Van den Bosch. P. Anal. Chim. Acta 1988, 187, 67-77. (J5)Hlnsberg, W. D.; Willson, C. G.; Kanazawa, K. K. J. Electrochem. SOC. 1986, 133, 1448-51. (J6)Baker, C. K.; Reynolds, J. R . Polym. Prepr. 1987, 2 8 , 284-5.

(J7) Cornpton, R. G.; Waller, A. M. J. Elechoanal. Chem. 1985, 795, 289-97. (JB) Hambitzer, G.;Hekbaum, J. Anal. Chem. 1888, 5 8 , 1067-70. (J9) Fanelli, N.; Fuoco, R.;Guidarinl, D.;Papoll, P. Anal. Chim. Acta 1988, 185. 33-48. (JIO) Hagan, D.; Splvey, J.; Niculescu, V. A. Rev. Scl. Inshum. 1987, 58,

468-74. (J11)Nagaoka, T.; Fukunaga, T.; Yoshlno, T. Anal. Sci. 1987, 2 , 301-4. (J12)Rarnaley, L. Anal. Instrum. 1986, 15, 101-25. (J13)Stefani, S.;Seeber, R. Anal. Chim. Acta 1988, 787, 213-22. (J14)Tacussel, J.; Leclerc, P.; Fornbon, J. J. J. Electroanal. Chem. 1988, 214, 79-94. (J15) Yarnagishi, H. J. Electroanal. Chem. 1987, 235, 117-29.

Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry Isiah M. Warner* Department of Chemistry, Emory University, Atlanta, Georgia 30322

Linda B. McGown Department of Chemistry, Duke University, Durham, North Carolina 27706

A. INTRODUCTION As you may have already noted, this year introduces a new set of authors for this fundamental review. As new authors, we hope that we can do as accurate a job as did our predecessor, Professor Earl Wehry, of the University of Tennessee. The format for this review follows the basic outline used by Professor Wehry ( A I ) ,with some modifications. We have condensed several sections and eliminated the section on gas-phase chemiluminescence. The primary areas of emphasis including advances in experimental techniques, developments in instrumentation, and applications for chemical analysis, remain the same. To keep the review at a reasonable length, we have not included articles that are only peripherallyrelated to analytical chemistry or those that represent straightforward extensions or demonstrations of previously published research. In this first issue, it is likely that we have made some errors of omission, and we request your assistance in identifying any obvious errors. We have tried to be conscientious in surveying the literature and have also surveyed individual researchers in the field. This review covers literature indexed by Chemical Abstracts from January, 1985, Vol. 102, issue 1,through October 1987, Vol. 107, issue 16. Accordingly, there will be some overlap between this review and Professor Wehry’s last review (AI).

B. BOOKS, REVIEWS, AND CHAPTERS OF GENERAL INTEREST Introductions to luminescence spectroscopy that are di-

rected toward a general audience include chapters on the fundamental nature of luminescenceprocesses by Demas and Demas ( B I ) and on the practical aspects of molecular fluorescencefor materials characterization by McGown (B2). Two instructional books on spectrophotometry and fluorometry have been written (B3,B4). One of these presents a series of undergraduate-levelexperiments (B3),while the other (B4) is written as a guide for biochemical researchers and includes introductory material on basic and practical aspects, as well as chapters on “assays”, ligand binding, stopped-flow techniques, and other areas of application. Several general reviews have been written, including a review of luminescence spectroscopy for trace analysis (with 392 references) by Hurtubise (B5) and a review by Froehlich (B6) on the fluorescence of organic compounds that focuses on 162 R

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structure-property relationships and substituent effects in relation to fluorescence analysis. A review by Kasa on chemical aspects of luminescence (B7) includes discussions of luminescenceprocesses, chemiluminescence,instrumentation, acid-base interactions, effects due to solvent, heavy atoms, and Shpol’skii matrices. Books and reviews on topics related to luminescence analysis include a compilation of various types of spectra, including fluorescence, phosphorescence, and Shpol’skii spectra as well as other types, of polycyclic aromatic compounds (Bs).A proceedings contributionby Gerard0 on recent advances in optical measurement methods (B9)discusses laser-excited fluorescence diagnostics and optical-based sensors. Dittrich has ’ven a critical review (with 458 references) of the analysis of #atomic molecules in the gaseous phase by UV-visible emission, absorption, and fluorescence spectroscopies (B10).Warner et al. have reported on multidimensional luminescence measurements, including advances in instrumentation and data analysis for multiparametric techniques (BII). Mirabella has reviewed internal reflection spectroscopy (B12) and includes a section on total internal reflection fluorescence spectroscopy. The application of luminescencemethods to specific areas of analysis has been reviewed. Sanville has discussed the use of luminescence for the detection and determination of biological compounds, including the use of luminescent labels for immunoassays (B13). Fluorescence techniques in biotechnology are reviewed by Schneckenburger et al. (B14). Guilbault has reviewed luminescence analysis of pharmaceutical compounds, including discussions of various immunoassay techniques (B15)and of clinical and agricultural samples (B16).The latter review emphasizes enzyme reactions and discusses front-surface fluorescence and chemiluminescence techniques. Oestgaard has reviewed the determination of environmental pollutants by direct fluorescence spectroscopy (BIT), with over 100 references on applications to oil pollution and air, soil and water analysis. Cline Love and Eastwood edited an ASTM publication on advances in luminescence spectroscopy (B18)with eight chapters on topics such as the probing of chemical microenvironments, the coupling of phenomena, including photoacoustic studies and metal ion sensors, to luminescence spectroscopy, synchronous excitation fluorescence, and pattern recognition of low-temperature fluorescence spectra. Some

0 1988 American Chemical Society

MOLECULAR FLUORESCENCE

Idah Mmwl Wnrnr is Sa& CandLK Dobbs Professor of ChsWsby at EUnlwrshy. He r e c e w hls B.S. m c e e h m Smnhm University at Baton Rouge In 1968. From 1988 to 1973. he waked fw hnei1o N & W ~ S I in ~ichiand.WA. as B Research Chemist. He entered graduate schwl at the Univerony of WashlngIon In 1973 and received his Ph.0. in 1977. He was on lhe chemisby tacuhy a1 Texas A8M 1 Univerohy for 5 yean from 1977 10 1982 and Pined lhe chemistry department at Emory Unkersny in 1982. In 1984. he was one 01 200 scbnusts awarded wesidemiai Young InvePtisata' awards. His current r e search inter& include (1) IumineSCenCe SpOCbOSMpy. (2) SpSCbWCOplC app~~cetlons 01 munichannei detectors. (3) anaigcal chemism in organized media. and (4) chemometriw. He holds two ptenta related lo these areas of research. ne IS aim c&nw wlth Professor Unda McOOwn of an UDCOI~F ing mnqlraph on MuHWInmnrlonal Lumlwscence MBBsuremdnlS. tie is a m m k Of lhe American Chemical Soclaly. Soclety lor Applied Speetrmcopy, Nallonsl Cwganizalion 01 Black ChemiSta and Chemlcai Engineers. and slgma xi.

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tivity and selectivity of this instrument was demonstrated by using light-induced absorbance and fluorescence quantum yield changes in redox state of electron carriers. Thomas et al. have recently reported the design and development of a novel fluorometer for measurement of fluorescence-detected circular dichroism (Cn.This system employs a linear photodiode array for detection. Photodiode array detection was also used to obtain high-resolution molecular luminescence, allowing resolution of 0.2 nm for a 10-nm spectral range for structurally similar compounds (CS). A sample arrangement has been described for the measurement of luminescenceand scattered light (CS).A method for enhancing fluorescence signals by using a double-pass cell configuration has also been discussed (CIO)and was shown to increase fluorescence sensitivity by a factor of 2.0-2.5. An improved method for determining Stern-Volmer constants has been reported ( C l I ) . In this approach, a ternary-gradient solvent-delivery system is used to combine varying amounts of a dilute solution of the fluorophore with a dilute solution of the quencher and a dilute solution of a nonquenching salt, which is used to maintain constant ionic strength.

D. LASER-BASED TECHNIQUES M a Bah. McaOm Is an Asmiate Rp fasor of Chmlsby at h l k e Univnshy. she recelvsd her B.S. degree horn the Skate Univershy of New Y a k at Butfalo In 1975 and her Ph.D. from the univnsny Of washIngIon in 1979. She served as a predocb ral i n m o r at Texas AhM Vnivershy m n g lhe 1978-1979 academic year. followed by three yean as an A~soclateProfessor at CSlilDmia State University. Long Beach. She Pined lhe tacuky of Olthhoma Slate Univnrny in 1982 and was p~omoled10 ASsmbte Protesso~in 1985. Her research ICtneots center on luminescence analysis. Including inetime techniques. immumchemical methcds. analysis of munidimensional data 8Brrays. on-line fluOreSCenCe lifeUme delemlnallons in HFiC. micellar svsterns. and the characterization and Rngerprinling of complex samples.

of these chapters are individually referenced in later sections of this review.

C. GENERAL INSTRUMENTATION In this section, we cover general considerations related to improvements in luminescence instrumentation such as new detectors, improvements in calibration, and novel instrumentation. Scattering in solution a t low light levels bas always been a serious problem in luminescence measurements, particularly for biological samples. Tbeisen ( C I ) has recently described a procedure for minimizing the effects of scattered and stray light on the measurement of luminescence. This procedure involves a combination of improved optical path, filtering, and computer processing. A novel method has been described for absolute calibration of the detection efficiency of fluorescence collection systems (CZ). This approach is employed over the wavelength range of 1%2-OOO nm, using the spontaneous Raman scattering in H, to derive an expression for the scattering cross section that is averaged over the solid angle of the fluorescence collection system. Improvements in photon countin for measuring of fluorescencedecay have been reported (83). Reduction of the time increments required for such measurements were made posihle by using shift registers and random access memories (RAM) as buffer memories in conventional multichannel analyzers. Lakowicz and co-workers have also described a frequency domain fluorometer that operates from 4 to 2000 MHz (C4). This system was precise enough to measure differences of 20 ps for decay times of 500 ps. Phase-sensitive resolution of emission and Raman scattering signals has also been described (CS). The utility of the approach is demonstrated by the separation of Raman scattering from the fluorescence signal. A versatile spectrometer for measnring circular dichroism, linear dichroism, and light-induced changes in absorbance and fluorescence yield has been described (C6). The high sensi-

Continued improvements and developments in laser technology have made lasers more viable excitation sources for molecular luminescence. Some of the major developments in the application of lasers to luminescence measurements are reviewed in this section. Reviews. Over the past 2 years, several reviews in the area of laser applications and analytical chemistry have appeared. Sepaniak has reviewed the clinical uses of laser-excited fluorometry ( D l ) ,with approximately 75 references. Applications of lasers in biology have also been reviewed with particular emphasis on laser-induced fluorescence methods for studying DNA in biological systems (DZ). Several reviews have been done by the Hieftje group ( 0 3 - 0 5 ) . One of these papers discusses recent applications of lasers in chemistry, including both molecular and atomic applications (D3). With regard to molecular systems, the review covers applications of frequency and time domain fluorescencemeasurements for determination of radiative lifetimes, as well as some pertinent references on fiber optic based sensors. The second reference is an invited lecture by Professor Hieftje, the Theophilus Redwood Lecture, which was presented a t the Royal Society of Chemistry Annual Chemical Congress a t the University of Warwick on April 9,1966. In this lecture, Professor Hieftje discussed models, measurements, methods, and machines in analytical chemistry as well as laser-based measurements in analytical chemistry ( 0 4 ) . The third reference, from ICP Information Newsletter, is a reference on new laser-based methods for atomic and molecular fluorescence ( 0 5 ) . Techniques based on laser-induced fluorescencefor studying reactive flows, such as combustion zones, have also been reviewed (D6). This review includes 40 references on the possibilities of performing imaging measurements with high temporal resolution. Amanetto and Rossi (D7) have reviewed laser-induced fluorescence and ionization techniques for analysis, with particular emphasis on the activity a t the Joint Research Center in Ispra, Italy. The advantages of the high spatial, temporal, and spectral resolution properties of lasers for use in monitoring chemical and physical phenomena have been reviewed (D6). In this review, special emphasis was placed on the detection of high-temperature species for measurement of the temperature dependence of elementary rate constants. Zare has recently reviewed the use of lasers in chemical analysis (D9). Several examples are cited from the general research areas of multiphoton ionization and laser fluorescence analysis, and the conclusion is that recent experiments are approaching the ultimate limit of single-atom or single-molecule detection. New laser techniques that are capable of achieving this ultimate limit of detection (DlO)are cited in another review with six references. Laser measurement techniques in the semiconductor industry, including a number of experimental techniques for measuring time-dependent luminescence and laser-excitation spectra, have also been reviewed ( D l l ) . The use of bighresolution, highly sensitive techniques such as laser-induced fluorescence line narrowing, spectral hole burning, and coherent optical transients for probing microscopic structures ANALYTICAL CHEMISTRY. VOL. 60. NO. 12. JUNE 15,

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of glasses are summarized in a recent review with 54 references (012). Applications. A commercial dye laser system has been modified to measure excitation spectra for phosphor emission under dye laser excitation (013). This was accomplished by designing and building a system for driving the cavity grating of the dye laser. A new technique has been described in which the frequency and line width of a laser is controlled through optical feedback from a holographic pattern in a barium titanium oxide crystal (014). Applications of this system were demonstrated by measurement of excitation spectra in a supersonic expansion. Site-selective spectroscopyhas been demonstrated for both parametric and nonparametric four-wave nonlinear mixing in a pentacene:p-terphenyl system (015). The existence of pressure-induced resonances in four-wave mixing has been reported (016). Time-resolved fluorescence detection has been used to quantify three polynuclear aromatic compounds by using the preexponential factor of the fluorescence decay curve rather than the integrated fluorescenceintensity as is normally used (017). The calibration curves were predicted and found to be independent of the zero concentration in the solvent. The acquisition of picosecond time-resolved emission spectra at high signal-to-noise ratio by using a laser spectrometer has been reported (018). It has been demonstrated that aromatic hydrocarbons can be deteded at subpicogram levels under the conditions of high spectral resolution when the sample is placed in an aromatic crystal that has approximatelythe same molecular dimensions as the analyte (019). The authors evaluated the analytical utility of their approach (020)using a prototype system of chloronaphthalenes in a naphthalene matrix. A new technique has been described that allows Dopplerfree and background-free fluorescencespectra to be recorded without using intermodulation techniques (021). This method is based on a new approach using Doppler free laser spectroscopy in which the position of a laser beam is modulated, rather than the more commonly used modulation of the intensity of polarization. The application of laser-excited fluorescence to the identification of bacterial pathogens has also been described (022). The method relies on the extent of aminopeptidase hydrolysis of a series of nonfluorescent L-amino acid @-naphthylamides to produce the highly fluorescent @-naphthylamine. Fingerprinting of polynuclear aromatic hydrocarbons (PAHs)in particulate matter and other environmentalsamples by laser-induced fluorescence with an electrothermal vaporization technique has been reported (023). A new sampling technique has been developed for this approach, and the advantages and limitations of this screening technique are discussed. The multiphoton infrared dissociation of SFe by using a pulsed COz laser has been used for selective determination of hydrocarbons (024). The emissions from C2,CH, and HF fragments that are produced by hydrocarbons in the presence of fluorine atoms after laser excitation are monitored in this approach. The chemiluminescence emission shows a characteristic delay time before reaching its maximum. Laser luminescence and excitation spectroscopies have been used to discriminate between similar inks in questioned documents (025)when conventional methods were not successful. This forensic application shows considerable utility for measurements of inks. A new pump/probe technique called asynchronous optical sampling has been described (026). This technique involves the use of the 10-kHz beat frequency produced by the frequency difference between two lasers. This produces a repetitive, relative phase walk-out of the pump and probe pulses, which replaces the optical delay line used in conventional instruments. A new technique for ultrasensitive, laser-induced fluorescence detection for use in hydrodynamically focused flows has been described. The detection of a sin le molecule by using this approach has been reported ( 0 2 8 . A relatively simple and highly sensitive system for ultratrace fluorometric analysis has been described (028). This system uses a continuous-wave argon ion laser excitation source and a fiber optic coupler to direct the laser output to an optical fiber that is positioned to illuminate the area under the objective of a microscope. 164R

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Determination of mixed polynuclear aromatic hydocarbons in the vapor phase by using laser-induced fluorescence spectrometry has also been described (029). Mixtures of anthracene, fluoranthene, and phenanthrene were analyzed in a vapor cell at temperatures ranging from 50 to 90 "C. Photofragment fluorescence continues to be a useful analytical technique. The photodissociation of gas-phase compounds by using a laser at suitably short UV wavelengths to produce electronically excited photofragments has been described (030). The use of molecular fragmentation for fluorometric detection and quantification of nonfluorescent organic and organometalliccompounds has also been described (031). These measurements are based on the emissive characteristics of many small fragments, such as OH, CNH, etc., produced by bombardment with high-energy electrons and photons. In addition, a pulsed laser beam has been used to photofragment molecules of a gaseous sample that is introduced into a vacuum chamber (032).

E. FIBER OPTICS BASED TECHNIQUES Application of fiber optics continues to expand and has become an important area of luminescence analysis. It is apparent that this trend is likely to continue in the near future. For this reason, we have designated this section for the discussion of fiber optics applications in luminescence. Reviews. Wolfbeis has recently reviewed the applications of fluorescence fiber optic sensors in analytical chemistry (El). This review of 14 references covers recent advances in optical fiber technology and optoelectronics as applied to the relatively new analytical technique of fiber optical fluorosensing. Other reviews have focused on biomedical sensing using fiber optics (E2, E3) and metal ion sensors based on immobilized fluorogenic ligands (E4). Applications. A mathematical calculation has been recently described that accounts for modulation of the fluorescence signal due to energy transfer and inner filter effects (E5). The derived results provide a theoretical basis for analyzing an increased number of species by using optical fiber fluorescence measurements. A number of general applications of fiber optic based fluorescence measuremenk can be cited. Vo-Dinh and White have described the development of luminescence techniques to evaluate the permeability of protective clothing material to large polyaromatic compounds (E6). In this study, roomtemperature phosphorescence and fluorescence measurements were made on a portable fiber optic based luminoscope. Determination of chloroorganics in ground waters by using fiber optic based chemical sensors has been recently reported (E7). A dedicated fiber optic based fluorometer for determination of such species has been described by the same group. The determination of several priority pollutants in ground water by using UV lasers and fiber optics has been reported in a similar study (E9). The use of fiber optics based fluorescence and absorbance measurements to probe combustion products has also been described (EIO). The use of fiber optics for the determination of selected chemical species continues to be an active area of analysis. The most recent example involves measurement of the hydrogen ion (or pH). The preparation and performance of two types of fiber optic based sensors for pH measurements have been recently described ( E l l ) . The same research group has evaluated the fluorescence versus pH profile of a new series of pH indicators (E12). The larger Stokes shift of these new indicators makes them less susceptible to interference form scattered light. A combination of sensors has been used to measure both pH and ionic strength by determinations at two different pH values (E13). In another study, covalently bonded fluorescein isothiocyanate (FITC) was used as a fiber optic probe for pH measurements (E14). A fiber optic based technique for measuring ammonia (E15) has been described. This system is based on the change in fluorescence intensity of an indicator solution in silicon rubber upon exposure to ammonia. The determination of halothane and or oxygen by using fiber optics employing a method based on ynamic fluorescencequenching has been reported (E16). Improvementsin oxygen determination by measuring the ratio of two luminescence bands with fiber optics have also been reported (E17). The measurement of sodium ion has been achieved by using a reagent phase that responds to sodium ion (E18).

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A series of titrations has been monitored using a fiber optic based instrument that uses fluorescent indicators for detection of the end point. The instrument has been applied to the precise determination of the end points for various acid-base titrations, by using l-hydrox pyrene-3,6,8-trisulfonateand fluorescein as indicators (E197. The direct determination of A13+ has been accomplished by using the instrument to monitor the fluorescence intensity of the aluminum-morin complex (E20). The same system has also been used to monitor kinetic titrations of sulfide with heavy-metal ions (E21). In this case, the fluorescence quenching of an acridine derivative by hydrogen sulfide was used as an indicator for the titration. Clinical measurements continue to be a fertile area for selective, fiber optic based fluorescence measurements. VoDinh and co-workers have recently described a portable fiber optic instrument for fluorimetric bioassays (E22). The instrument is readily adapted for use with commercially available biotesting wells on microplates. Another fiber optic probe, that has a substrate immobilized on the tip of the fiber optic, has been used to determine enzyme activities (E23). A commercial gas analyzer has been interfaced with a fiber optics COz, and pH in coupled fluorescence sensor to monitor 02, the extracorporeal circuit during mitral valve replacement surgery (E24). A fiber optic based system for similar measurements has also been described by Milanovich and coworkers (E25). Vo-Dinh has recently described an improved fiber optics instrument for monitoring luminescent organic contaminants on skin (E26). The improved system compensates for various skin backgrounds by electronically nulling the background. Fiber optic based luminescence lifetime measurements are also of interest. A new fluorescence lifetime instrument, which rapidly ac uires the fluorescence frequency response spectrum, has been 8escribed (E27). The fluorescence lifetime may be easily calculated from the acquired data. Calculated lifetimes in the nanosecond and subnanosecond range were found to agree with literature values. Hieftje and co-workers have also reported the fluorescence emission spectra and lifetimes of several fluorophores adsorbed on nonionic resins (E28). The systems were evaluated for their utility as fiber optic based sensors. The feasibility of time domain luminescence spectroscopy has been evaluated (E29,E30). This fiber optic based approach has been found to be sensitive, reproducible, and rapid. The possible applications in the field of medicine have also been discussed (E30).

F. SAMPLE PREPARATION AND RELATED TOPICS Sample Deoxygenation. Current methods of solution deoxygenation have been reviewed, with particular emphasis on fluorescence measurements (FI).An automated method for sample deoxygenation in luminescence measurements has also been described (F.2). The automated apparatus combines a multiple sampling valve and a membrane barrier to generate a concentration gradient for sample deoxygenation. Inner-Filter Effects. Two articles have been published by the same researcher in this area. The first deals with derivation of relationships for primary inner filtering in double-pass cells, including a comparison of the derived results with experimentallyobserved inner filtering (F3). The second article involves a consideration of two additional assumptions: beam. collimation and the treatment of fluorescenceemission as emanating from a point source (F4). Theoretical relationships produced as a result of these assumptions agreed better with experimental results.

G. DATA REDUCTION AND PRESENTATION Corrected Spectra. An absorption correction procedure, based on a cell rotation method, has been reported for molecular fluorescence (GI). Different path lengths of the measured solution are used to obtain an absorption-corrected fluorescence intensity that is linear with concentration for absorbances as high as 2.5. Quantum counters continue to be important for spectral correction. A recent comparison of front and rear viewing configurations for quantum counters has been reported (G2). A discussion is provided for avoiding quantum counter errors in different configurations. Quantum Yields. The photoacoustic measurement of quantum yields in solids has been described (G3). The results

compare favorably with those obtained by other procedures. A pulsed optoacoustic detection system has been used to measure quantum yields of several dyes in methanol solution (G4). A similar procedure that employs fluorescence quenchers and photoacoustic spectroscopy has also been described (G5). A photocalorimetric technique for determining the excited-state absorption cross section of fluorescent materials and their quantum efficiencies has been reported (G6). O’Neal and Schulman have described the determination of fluorescence quantum yields in highly absorbing solutions (G7). In their procedure, fluorescence intensities of unknowns and standards are measured at high absorbance. Some distinct advantages over measurement under weakly absorbing conditions are cited. Chemometrics. Data analysis procedures for multidimensional luminescence measurements have been reviewed (G8). Quantitative analysis of fluorescent mixtures that do not obey Beer’s law has been achieved by using standards that are mixtures of the individual components (G9). The structural and physicochemical descriptors for the solid-state fluorescence enhancement of 2-(diphenylacetyl)-l,3-indamdione-l-(p-(dimethy1amino)benzaldazine)in the presence of a variety of compounds have been described by using chemometrics (G10). A structure-fluorescence enhancement model for predicting the fluorescence activity of the fluorophore is presented. A method using orthogonal functions has been applied to the correction of interferences in fluorometric analysis (G11). The preliminary results were encouraging and further utility of this approach is likely. Menu-driven software has been described for computer-assistedfluorescence analysis of benzopyrene in the presence of other fluorophores (G12). Gerow and Rutan have reported a background subtraction procedure for fluorescence detection in thin-layer chromatography (G13). The procedure combines derivative spectrometry with the adaptive Kalman filter and was demonstrated to give eightfold lower detection limits for anthracene as compared to conventional background-subtraction procedures. An expert system for identifying environmentally important polynuclear aromatic hydrocarbons has been reported (G14). A recent study has shown that the selection of the spectral coefficients of pure components can be improved by imposing additional constraints (G15). A pattern recognition procedure for studying low-temperature luminescence spectra of hazardous chemicals has been reported (G16).

H. LUMINESCENCE IN ORGANIZED MEDIA The use of organized media in luminescence spectroscopy has continued to grow at a phenomenal rate. Applications have included uses of luminescent molecules to probe organized media as well as the enhancement of luminescence through measurementsin organized media. Zana has reviewed luminescent probes of surfactant solutions (HI). Several important areas of micellar chemistry such as micropolarity, microviscosity, surface aggregation, solution dynamics, and partition coefficients are covered in this review of 185 references. In another study, four different techniques for inducing room temperature phosphorescence in fluid solution for analytical measurements were compared (H2). The general analytical utility of each of the methods is discussed. Cyclodextrins are finding increased utility for analytical measurements. For example, the inclusion complex of &cyclodextrin ((3-CD)with indole has been reported (H3). The factors that affect the stability of the complex were evaluated by using absorption and fluorescence spectroscopies. Quantification of selected hallucinogenic drugs in the presence of a- and (3- cyclodextrins has been evaluated (H4). Calibration curves were found to be linear over 2-3 orders of magnitude. A spectrofluorimetricprocedure for estimating the association constant of pyrene inclusion complexes with (3-cyclodextrin and methylated (3-cyclodextrinshas been described (H5). The variation in pyrene vibronic-band-intensityratios is exploited in this procedure for determining association constants. The effect of cyclodextrin complexation on sensitized room-temperature phosphorescencehas been evaluated (H6). The rate of triplet-triplet energy transfer was found to correlate with cavity size. Bello and Hurtubise have investigated the use of a-cyclodextrin-NaC1 mixtures as substrates for solid-surface room-temperature fluorescence and phosphorescence measurements (H7). ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988

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Many of the recent studiea in organized media have involved micelles rather than cyclodextrins. Removal of oxygen in micellar solution has continued to be a problem. A procedure employing NazSOsas an oxygen scavenger has been used in micellar media for micelle-stabilized room-temperature phosphorescence analysis (H8). Micelles have been used to stabilize and enhance chemiluminescence. Recent studies have involved the use of membrane mimetic agents to amplify the chemiluminescenceof the lucigenin-hydr en peroxide system (H9) and to determine hydrogen peroxi e by using luminol (H10). Ultratrace determinations of niobium and tantalum in micellar media have been evaluated by us’ various organic Best results werextained by using chelating reagents (H12). morin and quercetin as chelating agents. Another study by the same group focuses on determination of niobium with morin enhanced by cetyltrimethylammoniumbromide micelles (H13). The method was found to be highly selective with a niobium detection limit of 1 L-l. In a later paper, the fluorescence study of A13+,Nb k+,and Ta5+complexes with flavonols, 8-hydroxyquinoline derivatives, azo dyes, and anthracene derivatives in micellar media is reported (H14). A flow injection procedure for the determination of Tb(II1) based on solubilizing the ternary complex with pivaloyltrifluoroacetone and trioctylphosphine oxide in micellar solution has been described (H15).The phosphorescence state of naphthalene solubilized in trimethyl-n-alkylammonium bromide micelles has been studied and compared to results for similar systems in sodium n-alkyl sulfate micelles (H15). The use of microemulsions in combination with flow injection analysis for the spectrofluorometricdetermination of primary amines has been reported (HI7). The lifetime characteristics of fluorescein-labeled phenobarbital have been evaluated in micellar media (H18).

7

I. LOW-TEMPERATURE LUMINESCENCE Measurement of luminescence under cryogenic conditions continues to be an important area of investigation due to the increased selectivity of such measurements. Wehry has discussed the general principles of cryogenic measurements in - a recent book chapter (1i). The utilitv of ShDol’skii fluorescencefor the identification of sulfur-coktainin’g polynuclear aromatic compounds was described in a recent study (12). The general application of Shpol’skii measurements for determination of polycyclic aromatic hydrocarbons in environmental samples has been evaluated (13). The results of the high-resolution Shpol’skii measurements were compared to other analytical methodologies for these compounds. A fiber optics based system for measurement of fluorescence at low temperatures has been demonstrated (14) and applied to the measurement of photoluminescence from cadmium and manganese telluride. The utility of combining low-temperature sample preparation with measurement by two-photon excitation was recently examined (15). The selectivity of this approach allowed detection of femtogram quantities of some methylnaphthalene derivatives. Fluorescence line-narrowing spectrometryhas been explored for the identification of polycyclic aromatic hydrocarbon metabolites (16). The same research group has extended this approach to include DNA adducts of benzo(a)pyrene (17). Vo-Dinh and co-workers have examined the utility of fluorescence line-narrowing spectrometry for examining polycyclic aromatic compounds on filter paper substrates (18). The feasibility of detecting benzo(a)pyrene, chrysene, and pyrene in unfractionated coal liquid samples was demonstrated in this study. Sample cooling in supersonic jets continues to be explored for low-temperature measurements. A recent review with 38 references discussed the technique of supersonic jet spectroscopy (19). The utility of supercritical fluids for sample introduction in supersonic jet spectrometry has been examined (110). Supersonic jet spectroscopy has also been explored for detection of capillary gas chromatographyeffluents (111).The supersonic jet spectroscopy of anthracene in the presence of n-alkanes has been studied (112). A reduced description of molecular line shapes in the fluorescence of polyatomic molecules has been achieved by using a Green function correlation approach (113). This algorithm was then examined by using anthracene in a supersonic jet expansion. Low-temperaturephosphorescence analysis of mebendazole and related imidazoles has been reported (114). Low-teml00R

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perature phosphorescenceof pharmaceutical compounds has also been studied (115).

J. TOTAL LUMINESCENCE AND SYNCHRONOUS EXCITATION SPECTROSCOPIES Synchronous Excitation Spectroscopy. There have been several new developments in techniques used for synchonous excitation spectroscopy. Kerkhoff et al. have described a rapid-scanning fluorometer for constant-energy synchronous scanning (J1).The instrument, which processes spectral information in real time, uses PMT detection to achieve signal-to-noise ratios that are superior to those obtained with silicon-intensified target vidicon detection. The apparent increase in sensitivity obtained with constant-energy scanning relative to synchronous-wavelength scanning has been dwussed (J2),and the former technique is recommended for cases in which the difference between the emission and excitation wavelengths exceeds the difference between the Rayleigh and Raman peaks. The theoretical optimization of parameter selection in constant-energy synchronous luminescence has been described by Inman et al. (J3). Nithipatikom and McGown described the suppression of scattered light in synchronous-excitation spectra by phase resolution (J4). Improvements in detection limits were observed for several compounds relative to steady-state synchronous spectral determinations made with blank correction. The same authors investigated the use of synchronous excitation for phase-resolved fluorimetric determinations in multicomponent systems (J5) and applied the use of fluorescence-lifetime-dependentintensities to the analysis of five- and six-component mixtures (J6). Rubio et al. have reviewed the analytical applications of synchronous fluorescence spectroscopy ( J n ,with 72 references on synchronous-excitation, constant-energy, and variableseparation techniques. Synchronous-excitationspectroscopy has been applied to the characterization of phenolic species (J8),the evaluation of the excited states of 7-hydroxycoumarin (J9),the simultaneous determination of umbelliferone and scopoletine (J10),the measurement of benzo(a)pyrene metabolites in urine ( A I ) , the determination of benzo(a)pyrenediol epoxide-DNA adducts (J12),and the determination of cochromatographing metabolites of 7-methylbenz(c)acridine (J13). Constant-energy synchronous fluorescence spectrometry has been used for the identification of polyaromatic hydrocarbons in mixtures at low temperature (J14) and for the determination of pesticides (J15). Variable-angle synchronous excitation has been applied to pharmaceutical analysis (J16). Derivative synchronous-excitation spectrometry for multicomponent analysis has been discussed by Garcia-Sanchez et aL (J17).Numerous applications of the technique have been described (J18J26). Bright and McGown have described the use of first-derivative synchronous excitation to minimize bilirubin interference in the determinationof fluorescein (J.27). Total Luminescence Spectroscopy. The use of total luminescence spectroscopy for the study of excitation-dependent emission processes is emphasized in a review with 33 references by Kallir et al. (J28). Studies in this research area were also described by Suter et al. (529). Nithipatikom and McGown demonstrated the phase-resolved suppression of scattered light in totalluminescence spectra (J30) and were able to eliminate the scattered light contribution in the spectrum of a fivefold dilution of pooled serum. Recent advances in data analysis for multidimensional luminescence analysis including work in the areas of linear analysis, Fourier methods, and optimization have been reviewed by Neal et al. (G8). Rossi and Warner have described the use of pattern recognition for spectral matching of total luminescence spectra (J31). The spectra of standard components and mixtures of the componentsare first transformed into the frequency domain by Fourier transform, followed by eigenvector deconvolution and pattern recognition analysis to identify the individual components in the mixtures. In another paper, the same authors described the use of frequency analysis of eigenvectors to estimate the rank of total luminescence spectra (J32). Burns et al. have developed a generalized approach to rank annihilation with incomplete information (J33),and Sanchez and Kowalski have discussed generalized rank annihilation factor analysis (J34).


Analysis of Complex Samples and Spectral Fingerprinting. The use of total luminescence and synchronous excitation spectroscopies for the characterization of fluorescent samples such as fossil fuels, environmental samples, and biological samples has been the subject of numerous studies. Applications to the area of petroleum products include a discussion by Soutar of the use of luminescence techniques for the characterization of oil samples (J35). Three-dimensional spectra have been used in the analysis of motor oils and lubricants (J36) and gasoline (J37). The fingerprinting of gasoline and crude oil by constant-energy synchronous luthe analysis of fuel oil by excitation resolved minescence (J38), synchronous fluorescence (J39), and the identification of mineral oils by synchronous excitation fluorescence (J40)have also been discussed. Von der Dick and Kalkreuth have described the application of synchronous excitation and threedimensional fluorescencetechniques to organic geochemistry (J41) and for the ranking of coal samples (J42). The use of synchronous excitation for the ranking of tential carcinogens in synfuel products has been describefiy Vo-Dinh (J43). Applications of fingerprinting in environmental analysis include the use of synchronous excitation for the rapid screening of air samples (J44),anal sis of aqueous and solid analysis , of gasoline wastes from a coal gasification unit &4) engine exhaust (J46), and spectral fingerprinting of highvolume ambient air samples (J47).Forensic applications of total luminescence spectroscopy have been discussed in a report by Siege1 (J48),and an automated system for oil spill identification by usin total luminescence has been described (549). Investigationst y Wolfbeis and co-workers of biological samples include total luminescence spectral characterization of human urine (J50) and human blood serum (J51),as well as total luminescence studies of human plasma low-density lipoproteins (J52)and serum tryptophan (553). Warner and co-workers have used pattern recognition techniques to study the fluorescence characteristics of bacteria (J54-J56) and phytoplankton populations (J57, J58).

K. S O L I D S U R F A C E LUMINESCENCE The use of solid surface luminescencefor chemical analysis has been discussed by Su et al. ( K l ) . Miller has reviewed (with 56 references) applications of solid surface techniques in areas such as cryogenic and room-temperature phosphorescence, fluorescence immunoassay, and thin-layer chromatography ( K 2 ) . Areas of research activity have included studies of substrates and reagents, instrumentation, techniques, and applications, with emphasis on room-temperature luminescence spectroscopy including room-temperature phosphorescence (RTP) and mom temperature fluorescence (RTF). Substrates, Reagents, a n d Spectral Effects. Andino et al. used X-ray photoelectron spectroscopy to study the surfaces of filter paper substrates before and after spotting with a luminescent compound and/or heavy-atom solution ( K 3 ) . Suter et al. studied the luminescence of heterocyclic compounds adsorbed on a cellulose filter paper substrate and found that the substrate provides a very polar environment with hi h hydrogen-bonding activity for the adsorbed probe molecufes (K4).Fidanza and Aaron evaluated several filter paper substrates, including an anion-exchange filter paper, for use in solid surface RTF analysis (K5). Burrell and Hurtubise compared calibration curves for solid surface fluorescence with those for solid surface phosphorescence and determined that fluorescence can occur both from molecules in the surface and in multilayers of molecules, whereas phosphorescenceoccurs only from the adsorbed molecules on the surface ( K 6 ) . Various reagents have been studied for use in solid surface luminescence. Long and Su evaluated fluorescamine as a derivatizing agent for the RTP analysis of amino acids (K7). Vo-Dinh and White used anthracene as a sensitizer for the determination of polynuclear aromatic compounds (K8). Excitation energy is absorbed by anthracene that has been adsorbed on treated filter paper and transferred to the adsorbed analyte molecules. Cyclodextrins have been used in several ways to enhance or induce room-temperature luminescence. Bello and Hurtubise described the use of an a-cyclodextrin-NaC1 matrix as a solid surface substrate for organic compounds and reported analytical figures of merit for the induced luminescence (K9,KIO).Ofthe 55 compounds studied, 42 showed RTF and/or RTP (K9). Vo-Dinhand Alak

reported the enhancement of the RTP of anthracene on filter paper that was treated with 0-cyclodextrin (K11). Less enhancement was observed with y-cyclodextrin, and none with a-cyclodextrin. Heavy-atom effects in RTP have been investigated, including studies of filter paper substrates that were treated with heavy-atom-containing surfactants (K12) and of external heavy-atom perturbers (K13). Su and Winefordner described a model for the induction of RTP on filter paper substrates Other by the heavy atom/analyte substrate interaction (K14). effects have also been stu led, such as the effects of pH and substrate on the RTP of indolecarboxylic acids (K15) and the effects of temperature on the solid surface luminescence of p-aminobenzoic acid adsorbed on sodium acetate (K16). Analytes, Methods, and Applications. The room-temperature luminescence properties of p-aminobenzoic acid adsorbed on sodium acetate-sodium chloride mixtures (K17) and of aromatic carbonyl compounds adsorbed on several different solid surfaces (K18)have been described. A method for the determination of RTF and RTP quantum yields was described by Ramasamy et al. and used to determine the quantum yields for compounds adsorbed on substrates including sodium acetate, a polyacrylic acid-sodium bromide mixture, and filter paper (K19). Vo-Dinh et al. described line narrowing in the phosphorescence spectra of coronene and phenanthrene adsorbed on filter paper substrates that had been impregnated with thallium acetate to enhance the triplet-singlet transition probability (K20). In another paper by the same authors, a fluorescence line-narrowing technique for the characterization of polycyclic compounds adsorbed on filter paper and measured at 4 K is described (18). The technique was used for the detection of the compounds in an unfractionated coal liquid sample. New developments in procedures and instrumentation include a sample-dryingtechnique for RTP (K21)and a sample compartment assembly for both low-temperature and roomtemperature measurements of phosphorescence on solid substrates (K22). A luminescence sampling system that was used in the measurement of RTP of pesticides (K23) and a personnel dosimeter in which vapors of polynuclear aromatic pollutants are directly detected by RTP (K24)have also been described. Room-temperature luminescence has been applied to the determination of pharmaceutical compounds (K25, K26), detection of benzo(a)pyrene-DNA adducts by laser excitation (K27), the selective detection of nitrogen-containing compounds ( K B ) ,and the determination of benzoquinoline isomers in complex samples such as coal tar fractions (K29). Room-temperature phosphorescence spectrometry has also been applied to the analysis of multicomponent samples (K30, K31).

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L. LUMINESCENCE IN CHROMATOGRAPHY AND FLOW SYSTEMS Luminescence detection for HPLC has been reviewed (60 references) by Brinkman et al. (LI), with emphasis on on-line postcolumn derivatization, laser fluorescence detection, and on-line chemiluminescence detection. Frei et al. have reviewed (152)and discussed (L3) the use of intermolecular energy transfer for room-temperature phosphorescence detection in liquid chromatography, including both sensitization and quenching techniques. Applications for flow injection analysis were also considered (L3). Weinberger has reviewed the use of liquid chromatography with luminescence detection (L4) including 120 references on fundamental concepts in luminescence, instrumental techniques, pre- and postcolumn derivitization, and detection by chemiluminescence and room-temperature phosphorescence. Although the primary use of luminescence techniques in chromatography has been for detection, fluorescence spectroscopy has also become an important tool for the study of chromatographic stationary phases. Staahlberg and Almgren used fluorescence measurements of adsorbed pyrene to determine the polarity of chemically modified silica surfaces (W). Experimental variables that were considered included the effects of mobile-phase composition. In another study, a spectrofluorimetricmethod was developed for the quantitation of amino groups on several different solid support materials (L6). This procedure was used to optimize conditions for the ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988

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immobilization of ligands on the support surfaces. Luminescence Detection for Liquid Chromatography. Experimental aspects of luminescence detection have been studied, including the use of anthracene as a standard for fluorescence detection in HPLC (L7) and sources of baseline shifta and detector response variations that occur in gradient elution chromatography with spectrometric detection (L8). Fluorogenic reagents have been described for liquid chromatographic detection of various analytes such as primary amines and amino acids (L9,LIO),thiols in biological sam les (L11),and carboxylic-containing compounds (L12). Fributyltin has been determined in estuarine waters by chelation with morin in micellar solution (L13). On-line electrochemical generation of Br oxidant was used for the fluorescence detection of phenothiazines (L14). Solid-state reagent addition was used for peroxyoxalate chemiluminescence detection (L15, L16),and electrochemiluminescencedetection was described for reversed-phase HPLC (L17). Jurkiewicz and Dasgupta described an indirect detection method for ion chromatography (LIB)in which self-quenching eluent ions are diluted by sample ions, resulting in positive signals. Takeuchi and Yeung reported signal enhancement for on-line fluorimetric detection in open-tubular capillary liquid chromatography due to effects of the stationary-phase environment (L19). Shellum and Birks used singlet oxygen sensitization as a photochemical amplifier for both UV absorption and fluorescence detection in liquid chromatography (L20)* Multiwavelengthdetection capabilities have been achieved in several different ways. Kerkhoff and Winefordner described a rapid-scanning constant-energy synchronous fluorescence detector that scans 200 nm/s and processes data in real time (L21). Several multiwavelength detectors have been developed, including a detector containing four interference filter-photomultiplier tube detector channels that are used to simultaneously monitor four wavelengths (L22), a video fluorometer system with laser excitation, and a microchannel plate-intensified diode array detector (L23). Laser-based detectors have been the subject of a number of studies. In the area of microcolumn liquid chromatography, Wilson and Yeung have developed a laser-based detector with simultaneous absorbance, fluorescence, and refractive index measurements (L24),and Yeung has described a flow optical cell with a 1-pL volume for use with this detection system (L25). McGuffin and Zare described a laser-inducedfluorescence detector with a continuous-wave HeCd laser source for microcolumn systems (L26) and evaluated three types of flow cells (flowing droplet, ensheathed effluent stream, and a fused silica capillary) for use with the detection system (L27). Zarrin and Dovichi described a subpicoliter sheath flow cuvet that when probed with a well-focused laser source had an adjustable volume in the range of 50 fL to 100 pL (L28). The ultimate lower volume limit was estimated to be approximately 5 fL. Other HPLC detection systems include a supersonic jet/laser fluorescence detector by Imasaka et al. (L29)and a low-volume, fiber optic fluorescence system by Berthod et al. (L30). The optimization and use of scanning densitometry with both absorption and fluorescence measurements for HPLC detection have been discussed (L31). Several time-domain detection systems have been described, including the use of time-resolved sensitized fluorescence for the detection of biacetyl in reversed-phase HPLC (L32) and time-resolved fluorescencedetection of polynuclear aromatic hydrocarbons ( 0 17). Desilets et al. used pulsed-laser excitation for the measurement of fluorescence lifetimes of eluting compounds on-the-fly in liquid chromato aphy (L33). Cobb and McGown used on-line phase-modu%tion fluorescence lifetime measurements and heterogeneity analysis to spectrally resolve overlapping chromatographic peaks in a two-component system (L34). Retention times, fractional intensity contributions, and fluorescence lifetimes were calculated for the two components from the on-line phase-modulation data collected at three modulation frequencies. Other Chromatographic a n d Flow Systems. A longpathlength detedor for gas chromatography with concurrent absorption and fluorescence measurements was described by Van Engelen et al. (L35). Detectors for capillary gas chromatography including a laser-excited fluorescence detector with a pulsed supersonicjet interface (L36)and a vapor-phase fluorescence detector (L37) have been described. 168R

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Multidimensionaldetection and data analysis for thin-layer chromatography (TLC), using multichannel detectors (L38) and a robust method for quantitative analysis of two-dimensional chromatographic/spectral data sets (L39),have been explored by Burns et al. Fluorescence line-narrowing spectroscopy using laser excitation a t low temperatures has been applied to detection in TLC (L40,L41). Fluorescence techniques have been used for the off-line detection of compounds that have been separated on narrow-bore liquid chromatographic columns and subsequently immobilized on TLC plates (L42). Rutan and Motley used several different mathematical approaches,which were based on factor analysis and Kalman filtering, for the quantitation of componentsthat have severe chromatographic and spectral overlap in TLC/ fluorescence analysis (L43). Patterson has reported the development of a fluorescence method for the measurement of local concentrations of chemical components in turbulent liquid mixing systems (L44). The development of a fluorescence derivatization method for the flow-injection determination of tertiary amines in nonaqueous media has been described by Whiteside et al. (L45).

M. DYNAMIC M E A S U R E M E N T S OF LUMINESCENCE Reviews. A special journal issue on time-resolved fluorescence spectroscopy, edited by Visser ( M I ) ,includes papers on pulse methods, phase-modulation methods, data analysis, and other topics. A review by Rentzepis on picosecond spectroscopy (MZ)includes discussions of fluorescence techniques. In other articles, single-photon counting techniques (M3, M4) and the use of synchrotron radiation (M5, M6) for time-resolved fluorescence spectroscopy were reviewed. Lakowicz has discussed photon-counting and phase-modulationmeasurements (M7) and frequency domain fluorometry (M8,M9).Applications of dynamic information in fluorescence analysis have been discussed by Fugate (M10). Biological applications of time-resolved fluorescence microsA critical review (with copy have also been reviewed (M11). 71 references) of phase-resolvedfluorescence spectroscopyin chemical analysis by McGown and Bright (M12) includes discussions of theory, instrumentation, and applications. Time-Resolved Luminescence. Nithipatikom and Pollard described a room-temperature phosphorescence lifetime spectrometer that is capable of resolving multicomponent decay curves into the individual lifetime components (M13). A technique in which a two-channel sampling oscilloscope is used to simultaneously acquire two values of the decay curve generated by pulsed-laser excitation for measuring fluorescence lifetimes on-the-fly has been described (M14). A single-photon-countingtechnique with a synchrotron excitation source in which the difference between the barycenters of the exciting pulse and the fluorescence response is measured at several wavelengths and coupled to the analysis of the fluorescence decay c w e at a single wavelength (015)has been developed. This configuration resulted in faster numerical analysis and elimination of spectral distortions due to the lamp profile. A system for subpicosecond luminescence spectroscopy based on sum frequency generation has been described (M16),and a picosecond time-resolved system, based on single-photon detection with multichannel plate detectors that have short transient time jitter, was developed for studying nucleic acid fluorescence (MI 7). Vickers et al. used an optical fiber probe for time-resolved measurements (MIB) and calculated that fibers approaching l km could be used for lifetime measurementswithout signifcant loss of accuracy or precision. Coveleskie et al. described a method for chemical timing in which oxygen quenching is used to reduce fluorescence lifetimes into the picosecond range for studies of intramolecular vibrational relaxation (M19). Chen has explored the resolution of complex decays by using fluorescence difference decay curves that are obtained from time-correlated singlephoton experiments by subtracting a reference decay curve from a sample decay curve (M20). A paper by Carraway et al. describes the elimination of wavelength-dependent phototube time shifts in fluorescence lifetime measurements by the phase plane method of deconvolution (M21). Theory has been described by Knoell et al. for time-resolved and the phenomenon of racorrelation spectroscopy (M22), diation imprisonment has been applied by Wiorkowski and Hartmann to time-resolved fluorescence spectroscopy with


pulsed excitation (M23). Braun et al. conducted a comparison of exDerimenta and theory in time-resolved fluorescence spectioscopy (M24). Phase-Modulation/Frequency Domain Techniques. Much of the research activity in phasemodulation fluorometry centers on the development of multifrequency instruments, as discussed by Lakowicz et al. (M25). Gratton and Barbieri reported the theory and applications of multifrequency phase fluorometry with pulsed sources (M26),and several multifrequency instruments based on the use of the harmonic content of a mode-locked laser have been described, including a cross-correlation instrument develo ed by Alcala, et al. (M27). A fiber optic fluorometer, for fetermination of subnanosecond fluorescence lifetimes, has been developed by Bright et al. (E27). An instrument incorporating a UHF television tuner has been discussed by Wilson et al. (M28). Nithipatikom and McGown have discussed the effects of several experimental and instrumental factors on phasemodulation fluorescence lifetime determinations (M29). Applications of frequency domain techniques include the resolution of individual decay curves and or spectral contributions of individual components in comp ex samples (M30, M31), studies of fluorescence quenching (M32, M33), and the measurement and resolution of anisotropy decays (M34-M37). Alcala et al., reported the frequency domain analysis of protein fluorescence in which a continuous distribution of lifetime values is used instead of an exponential model (M38). A general method for the correction of contaminant fluorescence in frequency domain fluorometry based on the approximation of the decay law of the background by using phase and modulation measurements a t a sufficient number of modulation frequencies has been described (M39). Phase-Resolved Techniques. A growing interest in phase-resolved techniques is evident from the variety of aplications that have appeared in the literature. Phase-resoh i o n is generally accomplished through the use of a lock-in amplifier to convert a time-dependent ac intensity signal into a time-independent intensity that is a function of fluorescence spectral and lifetime properties. An alternative, softwarebased approach has also been described, in which phase-resolved spectra are obtained directly from the time-dependent signals for components with known lifetimes (M40). McGown and Bright have demonstrated the use of phaseresolved intensity measurements a t several combinations of wavelengths, detector phase angle, and modulation frequency for the quantitative analysis of a mixtures of as many as four polycyclic aromatic hydrocarbons with highly overlapping spectra. Neither the spectra nor the lifetimes of the components are required, and simple least-squares fits are used for data analysis (M41-M43). The approach has also been successfully applied to the simultaneous two-component determination of metals with 5-sulfo-8-quinolinol (M44) and lumogallion (M45) chelating agents. Keating-Nakamoto et al. have described techniques for obtaining the phase-resolved spectra of components in two- and three-component mixtures by using combinations of modulation frequency and detector phase angle along with nonlinear least-squares analysis (M46, M47). A generalized multidimensional data format in which phase-resolved fluorescence intensities are plotted as a function of detector phase angle and synchronously scanned wavelength at one or more modulation frequencies has been described by Nithipatikom and McGown (J5). This data format has also been applied to the determination of mixtures containing as many as six fluorescent components (J6). Demas has discussed the use of error analysis for phase-resolved fluorimetric analysis to determine a priory the optimum detector phase angles and modulation frequencies to use for a given set of fluorescence lifetime components (M48). Other applications of phase-resolved fluorescence spectroscopy include the determination of thermodynamic binding parameters (M49),the determination of fluorescence lifetimes and heterogeneity analysis (M50),the elimination of quenching effects ( M 5 I ) , and the elimination of Raman signals in fluorescence measurements and vice versa (M52-M54).

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N. FLUORESCENCE POLARIZATION, MOLECULAR DYNAMICS, AND RELATED PHENOMENA Books and Reviews. Polarized optical spectroscopy of

partially oriented solutions has been discussed in a recent book

( N I ) . A number of examples are given to demostrate the utility of this measurement approach. Chen and Scott have discussed fluorescence polarization detection of global and nonglobal rotations in proteins (N2). The use of polarized optical spectroscopy to obtain information on transition moment directions and hidden transitions of molecules aligned in stretched polyethylene has been reviewed (N3). Circularly polarized luminescence has also been reviewed (N4, N5). Instrumentation and Techniques. The use of Mueller matrices to determine optical artifacts in circularly polarized luminescence has been discussed (N6). In another study, the artifacts in circularly polarized luminescence have been examined (N7). A computerized polarization spectrometerfor measurements of both polarized emission and excitation has been reported (N8). A new fluorescence polarization method for measuring phospholipids in amniotic fluid has been described (N9). Time-resolvedanisotropy of absorption and phosphorescence has been used to study the submicrosecond and microsecond rotational motions of eosin-labeled myosin (N10). Time-dependent fluorescence depolarizationhas been used to measure conformational changes in soil fulvic acid as a function of solution pH, ionic strength, and sample concentration (N1I). The fluorescence intensity cross-correlation functions for different polarizations of excitation and detection have been used to separate nonorientational and orientational contributions in fluorescence correlation spectroscopy (N12). Polarization a t low signal-to-noise ratios has been achieved by a microcomputer-controlledpolarization spectrometer (NI3). The excitation polarization spectra of phosphorescence and fluorescence from a rigid glass solution of 0.05 mM tryptophan at 1.0-nm resolution was one of several systems used to evaluate this instrument. Bright and McGown have reported a three-component determination using fluorescence anisotropy measurements and wavelength selectivity (NI4). Results were then compared with those obtained by nonpolarization techniques. The measurement of fluorescence anisotropy measurements is one of several techniques recently evaluated for studying molecular dynamics of biological molecules (N15). A fluorescence correlation procedure for measurement of the rotational diffusion of bovine carbonic anhydrase B has been described (N16). In a recent study, it was demonstrated that pump and probe techniques can be used to follow slow rotational motions of fluorophores bound to macromolecules in solution (NI 7). A general theory of this new technique, termed fluorescence recovery spectroscopy, has been described. The rotational constants and geometries of large molecules have been evaluated by using Doppler-free, time-resolved polarization spectroscopy (NIB). The stationary fluorescence depolarization of two fluorescent derivatives of human fibrinogen has been described (NI9). It was determined that reorientational processes in the subnanosecond and microsecond time ranges account for the observed depolarization. A second study on the same system has been reported by the same research group (N20). The utility of time-resolvedfluroescence spectroscopy for studies of protein dynamics has been discussed (N21).

0. CHEMILUMINESCENCE Reviews. Topics in chemiluminescence that have been

reviewed include chemiluminescence techniques in research and clinical laboratories ( O I ) , photographic detection of chemiluminescence and bioluminescence ( 0 2 ) ,a thermodynamic view of chemiluminescence that emphasizes thermodynamic limits to quantum yield (03),chemiluminescenceas a tool in the clinical laboratory ( 0 4 ) ,and the development of gas chromatographic detectors based on chemiluminescence

(05). Instrumentation and Techniques. A laboratory-built automatic injection device has been used to study various factors affecting the reproducibility of chemiluminescence analysis (06). A chemiluminescence procedure for determination of 8-lactam antibiotics has been reported (07). Detection of polynuclear aromatic hydrocarbons of active nitrogen-induced chemiluminescence has been described (OB). The utility of the approach was demonstrated by multichannel detection of a hydrocarbon/polynucleararomatic hydrocarbon mixture separated on a gas chromatograph. Hinze has discussed the effects of organized assemblies on chemiluminescence reactions ( 0 9 , 010). The influence of ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988

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hydroxylamine on the chemiluminescence that is generated during the oxidation of pyrogallol with periodate has been evaluated (011).A 4-&fold increase in yield is observed in the presence of hydroxylamine. Poulsen et al. have recently reported the first solid-state chemiluminescence detector for high-performance liquid chromatography (012). The luminol/H202 chemiluminescence reaction has been used in a flow injection analysis system for the determination of sucrose (013). The precision of the measurement was determined to be 2-3%. Quantitative measurement of iron(I1) in ferrioxalate chemical actinometry has been achieved via luminol chemiluminescence measurement (014). Luminol, immobilized on silica and controlledpore glass, has been used for chemiluminescence analysis in flowing streams (015). A cyclic flow-injectionprocedure, based on fluorescein-sensitized chemilumescence detection, has been reported for determination of copper(I1) in the 0.1-10 ng range (016). The regenerative chemiluminescence of autooscillating reactions has been used to measure ruthenium complexes with 2,2’-bipyrine over a wide dynamic range (017). Chemiluminescent additives have been used to detect phase transitions (018). The approach is demonstrated by using the phase transitions in glasses of aqueous NaOH solutions a t low temperature. Chemiluminescence has also been used as a tool to study oxidative stress and prostaglandin release from hearts of male rats (019). The use of nitrogen compounds to prolong chemiluminescence reactions has been reported (020). The chemiluminescence of luminol-potassium persulfate has been examined in the presence of 32 metal ions (021). Sixteen of the metal ions were found to enhance the chemiluminescence of the system.

P. FLUORESCENCE IN IMMUNOCHEMICAL TECHNIQUES A chapter on competitive luminescence immunoassay by Karnes et al. (PI)includes discussions of luminescent labels, homogeneous (nonseparation) and heterogeneous (requiring separation of bound and free fractions) fluorescence techniques, and other luminescence approaches including the use of phosphorescent, chemiluminescent, and bioluminescent reagents. Hemmila has reviewed competitive, antigen-labeled fluoroimmunoassay (FIA) and antibody-labeled immunofluorimetric (IMFA) techniques (P2). Two steady-state (non-time-resolved) FIA methods have been described for the determination of cannabinoids in urine (P3),one employing fluorescence polarization measurements and the other based on the use of antibodies that are covalently coupled to magnetizable particles. Fluoroimmunoassay techni ues for phenytoin including a homogeneous, double antibo y technique (P4) and a substrate-labeled, enzymatic approach (P5)have also been described. Fiber optic chemical sensors have been developed for FIA determinations of anti-rabbit immunoglobulin G (PS)and benzo(a)pyrene (P7). The sensors have the reagent (rabbit immunoglobulin G and anti-benzo(a)pyrene antibodies, respectively, for the above studies) covalently immobilized at the sensor surface and are employed in combination with laser excitation for either benchtop or in situ applications. Fluorescence-lifetime based techniques include both time-resolved and phase-resolved approaches. The time-resolved techniques are generally based on the use of a long-lived fluorescent label that is measured after the much shorter-lived background signal has been reduced to a negligible level. Ekins and Dakabu discussed the use of lanthanide chelate labels for time-resolved techniques (P8). Bailey et al. have described the fluorescence spectral and lifetime properties of some aminoaromatic terbium chelates that can be used as A terbium chelate label has long-lived fluorescent labels (B). been used for the competitive, time-resolved FIA of immuand europium chelate labels have been noglobulin G (PIO), used in several applications, including ”sandwich” IMFA techniques for human a-fetoprotein (PI 1) and thyrotropin (P12), and a solid-phase IMFA for cortisol (P13). Homogeneous, phase-resolved FIA techniques in which fluorescence lifetime is used to distinguish between free and antibody-bound fluorescent-labeled antigen have been described for phenobarbital ( P I 4 ) and human serum albumin (PI5). Nithipatikom and McGown described a homogeneous IMFA technique for human lactoferrin that is based on energy transfer from fluorescein-labeled antibody to rhodamine-la-

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beled antibody that is assumed to be bound to the same multivalent lactoferrin molecule (P16).The energy-transfer process causes a decrease in the phase-resolved fluorescence intensity, reflecting a decrease in both the fluorescence intensity and lifetime of the fluorescein label.

Q. FLUORESCENCE TECHNIQUES IN BIOLOGICAL SYSTEMS Reviews. The applications of fluorescence spectroscopy in the biomedical sciences (81)and in molecular cytogenetics (Q2) have been reviewed. Other areas that have been reviewed include picosecond coherent Raman and fluorescence spectroscopy of biological objects (Q3), the real-time spectroscopic analysis of ligand-receptor dynamics (with 127 references) (Q4),and the fluorometric measurement of ligand-protein binding (Q5). Reviews of microspectrofluorometry include discussions of modifications and optical requirements (86) and biological applications (67, Q8). The principles, instrumentation, experimental considerations, and applications of laser flow cytometry have been discussed by Hein and Thomas (89). Applications of flow cytometry to cell biology have been discussed in a book (&IO), and applications to the measurement of the mitotic cycle of cells have been reviewed (Q11). Fluorescence correlation spectroscopy and photobleaching recovery were reviewed in two papers by Elson (Q12, Q13). One review (with 143 references) emphasizes biochemical applications (QIP), and the other focuses on studies of membrane dynamics (Q13). Techniques a n d Applications. A microfluorimetric cell detection method has been described in which a silicon intensifier target video camera is used with a fluorescence microscope for image processing (Q14). Fluorescence correlation spectroscopy has been applied to the study of molecular aggregation (Q15, Q16). One of these studies included the development of a scanning technique for the measurement of molecular aggregation in systems such as biological membranes that have slow diffusion or flow (Q15). Articles describing research in flow cytofluorometry are far too numerous to be fuUy reviewed here, so only a few examples are discussed. The fluorescent dyes nile red (Q17)and thiazole orange (Q18) have been used as selective stains, and a technique for slowing the fading of fluorescent dyes has been described (819).Experimental considerations that have been studied include the dependence on excitation intensity of the fluorescence intensity ratios used for quantitation in flow cytometry (QZO), a cell-by-cellautofluorescence correction for low signal-to-noise systems (Q21), and the use of on-line reagent addition to minimize imprecision due to variations in the time between reagent addition and measurement (Q22). Two-parameter data acquisition systems have been described (Q23)and applied to the quantitative determination of cell subpopulations (Q24). Fluorescence polarization measurements of intracellular fluorescein have been used to study and flow cytometry subtle physiological changes in cells (Q25), has been compared with fluorescence microscopy for the determination of surface membrane immunoglobulin (Q26). Other studies of luminescence spectroscopy for biological systems include the evaluation of lanthanide-sensitized luminescence for the determination of tetracycline in serum (Q27), the development of an enzymatic method for the fluorimetric determination of branched-chain L-amino acids in microliter volumes of plasma (Q28), and a study of relative spectral response as a function of sequential ligand binding for macromolecular and biopolymeric systems (Q29). A noninvasive technique for in vivo acquisition of fluorescence emission and excitation spectra using an intensified photodiode array has been described (Q30).

R. OTHER TECHNIQUES AND APPLICATIONS Inorganic Analysis a n d Complexation. This topic has been an active area, and numerous applications have been reported. Buenzli and Pradervand used Eu(II1) as a luminescent probe for the laser spectroscopic studies of crown ether complexes (R1). The use of high-intensity monochromatic excitation and quasilinear radiation spectra of organoluminophores in metal complexes has been explored for the analysis of inorganic samples in nonaqueous media (R2). Luminescence properties of various metal complexes have


been studied, including metal complexes of 8-hydroxyquinoline-5-sulfonic acid (R3) and aluminum-quinizarin complex (R4). Luminescent complex formation has been applied to the determination of inorganic analytes including terbium and dysprosium (with tetramethylbicyclozinc and cadmium (with pyridil nonanedionecarboxylate) (R5), bis(quinoly1hydrazone)) (R6), aluminum (with N-phenylbenzohydroxamic acid and morin) (R7),gallium (with hydroxycarboxyanthraquinone)(R8), gallium in nickel alloy and aluminum (with N-oxalylamine(salicy1aldehydehydrazone)) (R9),and zinc (with dibromoquinolinol) (RIO). The use of phase-resolved fluorescence spectroscopy for the fluorescence-lifetime-based determination of metal chelates has been described (M44, M45). The use of immobilized fluorogenic ligands for metal ion sensors has been reviewed (E4). Fluorescence in Thin Liquid Films. The fluorescence properties of rhodamine B in thin liquid films formed from various surfactants, including anionic, nonionic, and cationic representatives, have been studied by von Wandruszka and Winefordner (RII). Studies of other fluorescent molecules in thin films formed from the cationic detergent cetyltrimethylammonium bromide were conducted by Jones and Winefordner (RI2). A model for fluorescence in thin li uid films based on the results of these studies was propose%by von Wandruszka and Winefordner (RI3). Miscellaneous Studies and Applications. The use of thermally activated delayed fluorescence for the determination of porphyrins and xanthene dyes has been reviewed (R14). In the area of inorganic analysis, Radspinner and Wehry have described the use of electron-impact-inducedfluorescence for the determination of molecular nitrogen in the gas phase (RI5),and a luminescence microprobe was developed for the identification of fission product CsI (R16). Applications to organic analysis include the use of complexation with bovine serum albumin to enhance the fluorescence of carboxy-substituted anthracenes (R17) and the use of fluorescence quenching to determine the equilibrium constants for the binding of polycyclic aromatic hydrocarbons to dissolved humic materials (RI8). Ayah et al. developed a computerized spectrofluorometric titrator, which they applied to studies of bimolecular luminescence quenching and the binding of luminescent metal complexes to micelles (R19). Hite et al. described the use of aminopyrene as a fluorescence probe to study polar surfaces (R20).

ACKNOWLEDGMENT The authors gratefully acknowledge the assistance of Ms. Patricia ONeill, Ms. Lorna Clarke, Mr. Mark P. Thomas, and Dr. Steve Fuh during the preparation of this manuscript. LITERATURE CITED A. IMROWCTION

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(MI) Visser, A. J. W. G., Ed. Time Resolved Fluorescence Spectroscopy; Marcel Dekker: New York, 1986; 372 pp. (M2) Rentzepls, P. M. R o c . S f I E - I n t . SOC. Opt. Eng. 1987, 742, 72. (M3) Leskover, B. I€€€ Pans. Nucl. Scl. 1985,NS-32(3), 1232. (M4) Klnoshite, S.; Kushlda, T. Anal. Instrum. 1985, 14(3-4), 503. (M5) Munro, I.H.; Shaw, D.; Jones, G. R.; Martin, M. M. Anal. Instrum. 1085, 14(3-4), 465. (M6) Moeller, T.; Zimmerer, G. fhys. Scr. 1987, T17, 177. (M7) Lakowicz, J. R. I n Applications of Fluorescence in Slomedicai Sciences; Alan R. Llss: 1986; pp 29-67. (M8) Lakowlcz, J. R. Laser Focus 1985,21(5), 156, 158, 160. (M9) Lakowicz, J. R. I n Applications of Fluorescence in Biomedical Sciences; Alan R. Liss: 1986; pp 225-244. (M10) Fugate, R. D. Res. Dev. 1085,27(4), 120. (M11) Docchio, F.; Ramponi, R.; Sacchi, C. A.; Bottiroll, G.; Freltas, I.Ettore Majorana Int. S c . Ser.: fhys. Scl. 1085,22, 85. (M12) McGown, L. B.; Bright, F. V. CRC Crit. Rev. Anal. Chem. 1987, 18(3), 245. (M13) Nlthipatlkom, K.; Pollard, B. D. Appi. Spectrosc. 1085, 39(1), 109. (M14) Desilets, D. J.; Coburn, J. T.; Lantrip. D. A,; Kissinger, P. T.; Lytle, F. E. Anal. Chem. 1988,58, 1123. (M15) Prhrat, J. P.; Wahl, P.; Brochon, J. C. Slochimie 1085. 67(9), 949. (M16) Shah, J.; Damen, T. C.; Deveaud, B.; Block, D. Appi. fhys. Lett. 1987,50(19), 1307. (M17) Rigler, R.; Claesens, F.; Lomakka, G. Springer Ser. Chem. fhys. 1084. 38, 472. (M18) Vickers, G. H.; Miller, R. M.; Hieftje, G. M. Anal. Chim. Acta 192, 145. (Ml9) Coveleskle, R. A.; Dolson, D. A.; Parmenter, C. S. J. fhys. Chem. 1085. 89(4), 645. (M20) Chen, R. Anal. Lett. 1084, 17(A11), 1225. (M21) Carraway, E. R.; Hauensteln, B. L., Jr.; Demas, J. N.; DeGraff, B. A. Anal. Chem. 1985,57, 2304. (M22) Knoell, L.; Weber, 0.; Schaefer, T. J. fhys. 6 1084, 17(24), 4861. (M23) Wiorkowski, P.; Hartmann. W. Opt. Commun. 1985,53(4), 217. (M24) Braun, M.; Liming, H.; Storr, 8.; Wiorkowski, P. Opt. Commun. 1985, 53(4), 221. (M25) Lakowlcz, J. R.; Mallwal, B. P.; Gratton, E. Anal. Instrum. 1086, 14(3-4), 193. (M26) Gratton, E.; Barblerl, B. Spectroscopy 1088, 1(6), 28. (M27) Alcala, J. R.; Gratton, E.: Jameson, D. M. Anal. Instrum. 1985. 14(3-4), 225. (M26) Wilson, D. A.; Vickers, 0. H.; Hieftje, 0. M. Anal. Instrum. 1985, 14(3-4), 483. (M29) Nithipatikom, K.; McOown, L. B. Appl. Spectrosc. 1088,40(4), 549. (M30) Lakowlcz, J. R.; Gryczynskl, I.; Cherek, H.; Laczko, G.; Joshi, N. TrAC. Trends Anal. Chem. 1086. 5(10), 257. (M31) Alcala, J. R.; Gratton, E.; Prendergast, F. G. Siophys. J . 1987, 51, 567. (M32) Lakowlcz, J. R.; Johnson, M. L.; Gryczynski, I.; Joshi, N.; Laczko, G. J. fhys. Chem. 1987,91(12), 3277. ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15. 1988

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(M33)Joshi, N.; Johnson, M. L.; Gryczynski, I.; Lakowicz, J. R. Chem. phys. Len. 1987, 135(3),200. (M34) Lakowicz, J. R.; Laczko, G.; Gryczynski, I.; Cherek, H. J. Blol. Chem. . . 1988, 261(5),2240. (M35) Maliwal, B. P.; Lakowicz, J. R. Blochim. Biophys. Acta 1988, 873, 161 (M36) Gryczynski, I.; Cherek, H.; Laczko, G.; Lakowicz, J. R. Chem. Phys. Lett. 1987. 135131. 193. (M37) Lakowicz, J: R.; Laczko, G.; Gryczynski. I . Blochemistry 1987, 2 6 , 82. (M38) Aicala, J. R.; Gratton, E.; Prendergast, F. G. J. Siophys. 1987, 5 1 , 925. (M39) Lakowicz, J. R.; Jayaweera, R.; Joshi, N.; Gryczynski, I. Anal. Biochem. 1987, 160, 471. (M40) Gratton, E.; Jameson, D. M. Anal. Chem. 1985, 57(8),1694. (M41) McGown, L. B.; Bright, F. V. Anal. Chim. Acta 1985, 169,117. (M42) Bright, F. V.; McGown, L. B. Anal. Chem. 1985, 57(1),55. (M43) Bright, F. V.; McGown, L. 8. Anal. Chem. 1985, 57(14),2877. (M44) Vitense, K. R.; McGown, L. B. Anal. Chlm. Acta 1987, 193, 119. (M45) Vitense, K. R.; McGown, L. B. Analyst 1987, 112, 1273. (M461 Keatino-Nakamoto.. S.: . Cherek.. H.:. Lakowicz. J. R. Ana/. Biochem. ' 1985, 349. (M47) Keating-Nakamoto, S.;Cherek, H.; Lakowicz, J. R. Anal. Chem. 1987, 59, 271. (M48) Demas, J. N. Proc. SPIE-Int. SOC.Opt. Eng. 1987, 743,9. (M49) Bright, F. V.: Keimig, T. L.; McGown, L. B. Anal. Chlm. Acta W85, 175, 189. (M50) McGown. L. B. Anal. Instrum. 1985, 14(3-4),251. (M51) Demas, J. N.; Jones, W. M.; Keller, R. A. Anal. Chem. 1988,58(8), 1717. (M52) Demas, J. N.; Keller, R. A. Anal. Chem. 1985, 57(2),538. (M53) Berndt, K. Opt. Commun. 1985, 56(1),30-5. (M54) Genack, A. 2 . Sprlnger Ser. Chem. Phys. 1984, 38,72.

Ma,

N. FLUORESCENCE POLARIZATION, MOLECULAR DYNAMICS, AND RELATEDPHENOMENA (NI) Michi, J.; Thulstrup. E. W. Spectroscopy wlth Poladzed Llght: Solute Allgnment by Photoselection, in LlquM Crystals, Polymers, and Membranes; VCH Publishers: New York, 1987;573 pp. (N2) Chen, R. F.: Scott, C. H. I n Advances In Luminescence Spectroscopy: Cline Love, L. J., Eastwood, D., Eds.; ASTM: Philadelphia, PA, 1985;p 26-39. Rembish, K.; Cline Love, L. J. I n Advances In Luminescence Spectroscopy; Cline Love, L. J., Eastwood, D., Eds.; ASTM: Philadelphia, PA, 1965;p-40-54. (N3) Thulstrup, E. W.; Michl, J. Acta Phys. Pol. 1987, A 7 1 ( 5 ) , 839. (N4) Riehl, J. P.; Richardson, F. S. Chem. Rev. 1988, 86(1). (N5) Brlttain, H. G. Spectroscopy 1986, 1(4),38. (N6) Dekkers, H. P. J. M.; Moraal, P. F.; Timper, J. M.; Riehl, J. P. Appl. Spectrosc. 1985, 39(5). (N7) Shindo, Y.; Nakagawa, M. Appl. Spectrosc. 1985, 39(1),32. (NE) Shimizu, 0.; Watanabe, J. Rev. Sci. Instrum. 1987, 56(3).346. (N9) Russell, J. C. Clln. Chem. 1987, 33(7),1177. (N10) Eads, T. M.; Thomas, D. D.; Austin, R. H. J. Mol. Blol. 1984, 179(1). 66

-I.

(N11) Lochmuiier, C. H.; Saavedra, S. S. Anal. Chem. 1988, 58, 1976. (N12) Kask, P. €est/ NSV Tead. Akad. Tolm.. Fuus., Mat. 1988, 35(4), 443. (N13) Shimizu, 0.; Watanabe, J. Kiyo-Nagoya -shlritsu Daigaku Kyoyobu, Shlzen Kagaku-hen 1985, 3 1 , 11. (N14) Bright, F. V.; McGown, L. B. Anal. Chem. 1988, 58(7),1424. (N15) Rigler. R. Springer Ser. Blophys. 1987, 1 , 136. (N16) Kask, P.; Plksarv. P.; Mets, U.; Pooga, M.; Lippmaa, E. Eur. Blophys. J . 1987, 14(4),257. (N17) Wegener, W. A. Blophys. J. 1984, 46(6), 795. (NIB) Baskin, J. S.:Felker, P. M.; Zewail. A. H. J. Chem. Phys. 1988, 84(8), 4708. (N19) Acuna, A. U.; Gonzalez-Rodriguez. J.; Lillo, M. P.; Naqvi, K. R. Blophys. Chem. 1987, 26(1),55. (N20) Acuna, A. U.; Gonzalez-Rodriguez, J.; Lillo, M. P.; Naqvi, K. R. Blophys. Chem. 1987, 26(1),63. (N21) Gratton, E.; Alcala, R.; Marriott, G.; Prendergast, F. Proc. Intl. Symp. Comp. Anal. Life Scl.; Kawabata, C., Bishop. A. R.; Eds.: Hayashibara Forum 1985,Tokyo, Japan, 1986:pp 1-11. 0. CHEMILUMINESCENCE

(01) Campbell, A. K. Trends Biochem. Scl. (Pers. Ed.) 1988, 11(3),104. (02) Kricka, L. J.; Thorpe, 0. H. 0. Methods Enzymol. 1988, 133, 404. (03) Chukova, Y. P. Izv. Akad. Nauk. SSSR,Ser. Flz. 1987. 51(3),531. (04) TsuJi, A. Kensa to GUutsu 1988, 14(10), 1051.

(05) Hutte, R. S.; Sievers, R . E.; Birks, J. W. J. Chromatogr. Sci. 1988, 2 4 ,

499. (06) Taniguchi, A.; Hayashi, Y.; Yuki. H. Chem. Pharm. Bull. 1988, 34(8). 3475. (07) Milbrath. D. S.Eur. Patent Appl. EP 157629 A2, 1985;33 pp. (08)Jurgensen, H. A.; Yu, T.; Winefordner. J. D. Can. J. Spectrosc. 1984, 29(5), 113. (09) Hinze, W. L. Contrlb. Cient. Techno/. 1985. (Numero €spec.), 20. (010) Malehorn, C. L.: Riehl, T. E.; Hinze, W. L. Analyst 1988, 111, 941. (011) Evmirldis, N. P. Analyst 1887, 112(6),625. (012) Poulsen, J. R.; Blrks, J. W.; GUbitz, 0.; Van Zoonen, P.; Gooijer, C.; Velthorst, N. H.; Frei, R. W. J . Chromatogr. 1986, 360, 371. (013) Koerner, C. A.; Nieman, T. A. Anal. Chem. 1986, 58, 116. (014)Nussbaum, M. A.; Nekimken, H. L.; Nieman, T. A. Anal. Chem. 1987. 59,211. (015) Hool, K.; Nieman, T. A. Anal. Chem. 1987, 59,569 174R


(018) Yamada, M.; Suzuki. S. Anal. Chlm. Acta 1987, 193,337. (017) Karavaev, A. D.; Kazakov. V. P.; Tokstikbv, G. A.; Yakshin, V. V.; Khokhlova, N. L. Zh. Anal. Khlm. 1988, 4 1(I), 42. (018)

Kaplan, A. M.; Shvedchikov. A. P.; Lotnik, S. V.; Kazakov, V. P.

Therm. Anal., Proc. ICTA, 8th 1905, 2 , 303. (019)Barsacchi, R.; Camici, P.; Pelosi, G.; Nanni, N.; Benassi, A,; Glannessi,

D.; Ursini, F. I n Chemllumlnescence: A Tool to Investbate the Oxidative Stress in the Heart; Novelli, G. P., Ursini, F. K., Eds.; Karger: Basil, Switzerland, 1986 pp 175-179. (020) Dattagupta, N.; Clemens, A. H. Eur. Patent Appl. EP 210449 A2, 4 Feb 1987; 100 pp. (021) Zhang, X.; Zhang, 2. Huaxue Xuebao 1987, 45(2), 195. P. FLUORESCENCE IN IMMUNOCHEMICAL TECHNIQUES (PI) Karnes, H. T.; O'Neai, J. S.; Schulman, S. G.; I n Molecubr Lumlnescence Spectroscopy: Methods and Appllcatlons; Schulman, S. G., Ed.; Wiley: New York, 1985;part 1, pp 717-779. (P2) HBmmili, I.Clln. Chem. 1985, 31(3),359. (P3) Colbert, D. L.; Sidki, A. M.; Gailacher, G.; Landon, J. Analyst 1987, 112,

1483. (P4) O'Neal, J. S.; Schulman, S. G. Anal. Chim. Acta 1985, 170, 143. (P5) O'Neal, J. S.; Sloan, K. 6.; Schulman, S. G. J. Pharm. Blomed. Anal. 1988, #(I), 103. (P6) Tromberg, B. J.; Sepanlak, M. J.; Vo-Dinh, T.; Griffin, G. D. Anal. Chem. 1987, 59, 1226. (P7) Vo-Dinh, T.; Tromberg. B. J.; Griffin, G. D.; Ambrose, K. R.; Sepaniak, M. J.; Gardenhire. E. M. Appl. Spectrosc. 1987, 41(5),735. (P8) Ekins, R. P.; Dakabu, S. Pure Appl. Chem. 1985, 57(3),473. (P9) Bailey, M. P.; Rocks, 8. F.; Riley, C. Analyst 1985, 110, 603. (PIO) Kuo, J. E.; Milby, K. H.; Hinsberg, W. D.; Poole, P. R.; McGuffin, V. L.; Zare, R. N. Clln. Chem. 1985, 31(1),50. (P11) Suonpaa, M. U.; Lavi, J. T.; Hemmila, I.V.; Lovgren, T. N.-E. Clln. Chlm. Acta 1985, 145,341. (P12) Kaihola, H.-L.; Irjala, K.; Viikari, J.; Nanto, V. Clin. Chem. 1985,

31(10), 1706.

(P13) Eskola, J. U.; Nanto, V.; Meuriing, L.; Lovgren, T. N.-E. Clln. Chem. 1985, 31(10), 1731. (P14) Bright, F. V.; McGown, L. B. Tabnta 1985, 32(1),15. (P15) Tahboub, Y. R.; McGown, L. B. Anal. Chlm. Acta 1988, 162, 165. (P16) Nithipatikom, K.; McGown, L. B. Anal. Chem. 1987, 59,423. Q. FLUORESCENCE TECHNIQUES I N BIOLOGICAL SYSTEMS

(Ql) Taylor, D. L.; Waggoner, A. S.; Murphy, R. F.; Lanni, F.; Birge, R. R.,

Eds. Appflcatlons of Fluorescence in the Blomedlcal Sciences; Alan R. Liss: New York, 1986;839 pp. (Q2).Latt, S. A.; Lalande, M.; Kunkel, L. M.; Schreck, R.; Tantravahi, U. Btopolymers 1985, 24(1),77. (Q3) Akhmanov, S.A.; Kamalov, V. F.; Koroteev, N. I.Stud. Phys. Theor. Chem. 1987, 45, 67. (44) Sklar, L. A. Annu. Rev. Blophys. Blophys. Chem. 1987, 16, 479. (Q5) Ward, L. D. Methods Enzymol. 1985, 117,400. ((26)Siegel, J. I.Am. Lab. 1986, 18(l),107. (Q7) Van der Ploeg, M.; Duijndam, W. A. L. NATO ASI Ser., Ser. A 1985,

83,55.

(Q8) Kohen, E.; Hirschberg, J. G.; Rabinovitch, A. Prog. Clin. Biol. Res.

1985, 196,45. (Q9) Hein, S.J.; Thomas, L. C. I n Analytlcal Appllcatlons of Lasers; Piepmeier, E. H., Ed.; Wiley: New York, 1986;p 521. (QIO) Flow Cyfometry in Cell Blology; Ratinaud, M. H., Julien, R., Ronot, X., Eds.; Elsevier: Paris, 1986;81 pp. (all)Keng, P. C. Int. J . Cell. Clonlng 1988, 4 ( 5 ) , 295. (Q12) Elson, E. L. Annu. Rev. Phys. Chem. 1985, 36,379. (Q13) Elson, E. L. SOC. Gen. Physiol. Ser. 1988, 4 0 , 367. 014) Suzuki, M.; Tamiya, E.; Karube, I.; Kataoka, T.; Tokunaga, T. Anal. Len. 1987, 20(2),337. ((215) Petersen, N. 0. Slophys. J. 1088, 49(4),809. (Q16) Palmer, A. G., 111, Thompson, N. L. Blophys. J. 1987, 52(2),257. (Q17)Greenspan, P.; Mayer, E. P.; Fowler, S. D. J. Cell. Blol. 1885, 100(3), 965. ((218) Lee, L. G.; Chen, C. H.; Chiu, L. A. Cytometry 1888. 7(6).508. (Q19) Franklin, A. L.; Filion, W. G. Stain Techno/. 1985, 60(3), 125. (Q20)Boehmer, R. M.; Papaioannou, J.; Ashcroft, R. G. J. Hlstochem. Cyfochem. 1985, 33(9),974. (Q21) Roederer, M.; Murphy, R. F. Cytometry lS88, 7(6),556. ((222) Pennings, A.; Speth, P.; Wessels, H.; Haanen, C. Cytometry 1987, 8(3),335. ((223) Weier, H. U.; Eisert. W. G. Rev. Sci. Instrum. 1988, 57(11),2902. ((224) Speth, P. A. J.; Linssen, P. C. M.; Boezeman, J. B. M.; Wessels, H. M. C.;Haanen, C. Cytometty 1085. 6(2), 143. (Q25)Dimkropoulos, K.; Roiland, J. M.; Nairn, R. C. Blochem. Blophys . Res. Commun. 1988, 136(3),1021. (Q26)Gebhard, D. F., Jr.; Mitteiman, A.; Cirrincione, C.; Thaler, H. T.; Koziner, B. J. Histochem. Cytochem. 1986, 34(4),475. (Q27) Files, L. A.; Hirschy, L.; Winefordner, J. D. J. Pharm. Biomed. Anal. 1085, 3(1),95. (Q28)Gleeson, M.; Maughan, R. J. Clln. Chem. Acta 1987, 166(2-3),163. ((229)Deerfield, D. W., 11; Hoke, R. A.; Pedersen, L. G.; Darden. T.; Hiskey. R. G. Slochem. Blophys. Res. Commun . 1986, 14 1(3),1207. (Q30)Pottier. R. H.; Chow, Y. F. A.; LaPlante, J. P.; Truscott, T. 0.; Kennedy, J. C.;Belner, L. A. Photochem. Photoblol. 1988, 4 4 ( 5 ) , 679.

R. OTHER TECHNIQUES AND APPLICATIONS (RI) Buenzli, J. C. 0.;Pradervand, G. 0. J. Chem. Phys. 1988, 85(5),2469. (R2) Zel'tser, I. E.; Tallpov, Sh.; Verechagina, N. G. Talanta 1987, 34(10),

873.

Anal. Chem. 1988. 60. 175R-181R (R3) Scmka. K.: Vlthanage. R. 5.; Phillps. D. A,: Walker. 6.: Dasguple. P. K. Anal. Chsm. 1987. 59(4). 829. (R4) Allen. N. 5.; Hayes. 0 ; Rlley. P. N. K.: Richards, A. M. J . phalochem. 1081 JQ .-. ., . ., 365 .. .. (R5) Egnova. A. V: Eel'lyukova. S. V.: Kravchenko. T. B.: Poleuklou. N. S. m. Anal. Khm. 1986, 41(2), 280. (RBI West. K. J.: m u m . R. T. Talanta 1988. 3.31101. 807. i R j j A&&I. Y.' K.: N&. A. K: J . m l a n C h e i . S ~ C1084, . 6 ~ ) 014. . (Re) Salinas Lopez. F.: Munoz de la P a . A,: Murllb. J. A. MIkrm+~fn.ACla 1984,311-2). 79. (R9) de Pablos. F.; Oalan. 0.: Ark% J. G. TaPlnta 1987, 34(10). 835. lR1OI Femander. P.: Perer-Conde.. C.:. Outiener. A. M.: Camara. C. J . Mol. ' sbuct. 1988. .1&. 549. p11) yon Wandruszka. R.: Winefordner. J. D. ralanta 1988. 33(11). 871.

(R12) Jones. B. T.; Winefordner. J. D. Anal. Chem. 1986. 58. 2870. (R13) M n Wandruszka. R.: Winslordner. J. D. Talanta 1987. 34181. 571. (R14) Nishlkawa. Y. BunJskiKagaku 1984. 33(10),E413. (R15) Radspinnsr. D. A,; Wehry. E. L. ralanta 1987. 34111). 963. (R16) AkareZ. J. L.; b y l e . T. E.: Deason. V. A. Microbeam Anal. 1985. ZOm. 65.

(Rl7) Schulman. S. 0.;Rutledge. J. M. Anal. Len. 1986. W21-22). 2141. (Rl8) Gaulhler. T. D.: Shane. E. C.; Guerin. W. F.; Seltr. W. R.; Grant. C. L. Enwon. Scl. Technol. 1988, ZO(11). 1182. (R19) Ayala. N. P.; Demas. J. N.; DeGratf. B. A. Anal. Chem. 1986. 58. 2488. (R20) Hie. P.; Krasnansky. R.; m s . J . K. J . mp. chem. 1886. 90(22). 5795.

Organic Elemental Analysis T.S. Ma Department of Chemistry, City Uniuersity of New York, Brooklyn, New York 11210

This review follows the previous one ( I ) and covers the period from October 1985to October 1987. During this period there were about 600 publications which deal with the analrjis of organic materials for the determination of the elements being present either as major components or as trace constituents.

CARBON, HYDROGEN, NITROGEN While commercial CHN analyzers have become standard equipment in organic analysis laboratories, workers are still constructing home-made apparatus or modifying purchased machines to suit special needs. Binkowski et al. (2) described an appratus for the automated analysis of 33 samples (0.3-3.5 mg) in 6 h; the CO,. H,O, and N, produced in a stream of He are separated by gas chromatography and measured by thermal conductivity. According to Honma et al. (31,in order to obtain a result within f0.3% of the theoretical by using the thermal conductivity technique, the sensitivity factors for C, H, and N should be within f0.062, f2.70,and f0.20 ~ c V / g , respectively. These workers analyzed volatile compounds by placing the sample in a silica capsule which is sealed with indium foil ( 4 ) and used an S-shaped reduction tube (5) for the Perkin-Elmer CHN analy7er. Sugawara et al. (6) modified the Hewlett-Packard operation procedure in order to determine low levels of C, H, and N. Saito et al. (7)analyzed coal and liquid fuel by pyrolyzing the sample under He, followed by oxidation of the volatile matter in heated C u O H,O and CO, are determined gravimetrically. For the removal of nitrogen oxides in C-H determination, Kent (8)recommended a new absorbent con-

chemlcal investigation of medicinal plants. wganic analysis and Synthesis in mlliigram lo microgram range. and the use 01 small-scale. Inexpensive equlpmem IO leach chemistry. Plolessar Ma receked me Benedenl-Pichler Award In Mlcrochemisby in 1978

me

sisting of finely dispersed Ag,O on CuO, this reagent, placed a t the end of the combustion tube, ala0 removes the oxidation produds of Hg, P, As, and halogens other than F. Gawargious e t al. (9) placed between the anhydrone and ascarite tubes a tube packed with La(NO& on silica gel to remove F, and used a plug of polyurethane foam at the end of the combustion tube to remove Sb (IO). For determining nitrogen only, Kirsten et al. (11) modified the Carlo Erba analyzer in order to handly large samples up to 100 mg. Chumachenkoet &. (12) heated 0.3-2 mg of sample with NiO in a closed silica tube filled with He; halogens and oxides of S, P, Si, and B are retained by the NiO; N, is measured by thermal conductivity after the removal of H,O and CO,: Breda (13)decomposed the organic compound by fusion with Na in a nickel micro-Parr bomb, whereupon nitrogen is converted to NaCN and the CN- is determined spectrophotometrically. Kimura et al. (14) applied low-temperature ashing under 0, for decomposition and recorded the emission spectrum of the combustion gases, using the N, 337.1-nm line for determination, preferably by measuring the intensity ratio of the N, 337.1-nm line to the CO 308-nm line to obtain the N-toC ratio in the sample. Griepink et al. (15) reported on the preparation of two reference materials for the analysis of fertilizers, while Kramer et al. (16) described a unified method for determining nitrogen in fertilizers. Kane (I 7) recommended CuSOsTi02 as Kjeldahl catalyst for the digestion of protein in animal feeds. Nevins et al. (18)described how to prepare small samples for nitrogen-isotope-ratio analysis hy in vacuo combustion with Cuprox reagent followed by molecular sieve trapping of the gaseous products.

OXYGEN, SULFUR, HALOGENS For the determination of oxygen, Borda (19) recommended pyrolysis a t 1080O in the presence of molybdenum carbide coated charcoal, the sample is placed in a silver capsule and the CO produced is separated by gas chromatography. Uhdeova (20) used aluminum capsules and reported that the retention of oxygen by the aluminum is reproducible. Schimmelmann et al. (21) described a method to determine oxygen-stable isotope ratios in organic matter containing C, H, 0,and N by pyrolyzing the sample at 550' in the presence of HgCI, in a vacuum-sealed Vycor ampule. A number of studies on the decomposition techniques for the determination of sulfur or halogens has been published. Patrick et al. (22) described an improved system for closedflask combustion: I t comprises a 500-mL conical flask with threaded neck, a screw cap, a silicone rubber ring, and Pyrex tube to which the platinum basket is attached: the flask in placed in a cabinet and ignition is effected by infrared radiation. Arutyunova et al. (23) utilized low-temperature plasma to decompose sulfur compounds, while Gimeno Adelantado et al. (24) investigated the feasibility of alkali fusion. Volodina et al. (25,261 described the decomposition of po-

0003-2700/88/0360-175R$O1.50/0 0 1988 American Chemical Society

175 R

Molecular fluorescence, phosphorescence, and chemiluminescence

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