Infrared spectrometry - ACS Publications - American Chemical Society

Anal. Chem. 1990, 62, 223R-255R (U20) Mller, J. B.; Garroway, A. N. J . Magn. Reson. 1989, 82, 529-538.

SOLVENT SUPPRESSION (MM) (MMI) Monis, 0. A,; Sllveston, A. C. T.; Waterton, J. C. J . Magn. Reson.

. 1080, 82, 97-108. (MM2) Monis, Q.A.; Sllveston, A. C. T.; Waterton, J. C. J . Magn. Reson. 1888, 81, 641-645. (MM3) Amr, J. R.; Brunettl, A.; Nagashima, 0.; Hossmann, K. A. Magn. asson. M . isen. 11. 73-84. ( M M 4 ) - D a ~ , - A . L;Wlmberis, S. J . M a p . Reson. 1989. 84, 620-626. (W5) Starcuk, 2.; Flak, R.; Bertusek, K.; Starcuk, 2.. Jr. J . Magn. Reson. 1880, 82, 265-269. (MM6) Takegoshi, K.; Tsuda, S.; Hlkichl, K. J . Magn. Reson. 1989, 8 5 , 198-202. ( M 7 ) Markn, D.; Ikwa, M.; Bax, A. J . Magn. Reson. 1989, 84, 425-430. ( M 8 ) Kwoda, Y.; Wada, A.; Yamazaki, T.; Nagayama, K. J . Magn. Reson. 1989, 84, 604-610.

SPIN-SPIN CWPLINa (NN) ("1) Jones, C. Nucl. Map. Reson. 1989, 18. 289-309. Undon, J. C.; Wlllams, J. M. Nucl. klegn. Reson. 1989, 18, 69-133. ("2) W s h e d e , J. Nucl. Mgn.R e m . 1989, 18, 73-88. ("3) (31, V. M. S.; Van Phlllpsbom, W. Magn. Reson. Chem. 1989, 27, ("4) 409-430. ("5) Kay, L. E.; Brooks, B.; Sparks, S. W.; Torchia, D. A.; Bax, A. J . Am. them. SOC. 1989, 17 1, 5486-5490. ("6) Uhrin, D.; Upta]. T. J . Magn. Reson. 1989, 81, 82-91. ("7) Bermel, W.; Wagner, K.; Griesinger, C. J . Magn. Reson. IS89, 83, 223-232. ("6) Zlh, K. W.; Helnekey, D. M.; Mlllar, J. M.; Payne, N. G.; Neshyba, S. P.; Duchamp, J. C.; Szczyrba, J. J . Am. Chem. Soc. 1990, 112, 920-929.

WATER STRUCTURE (00) (001) Ottlng, G.; Wijthrlch, K. J . Am. Chem. SOC.1989, 111, 1871-1875. ZEOLITES AND CATALYSTS (PP) (PPI) Bell, A. T. ACS Symp. SW.1089. NO. 398, 68-82. (W2) Thomas, J. M.; Vaughan. D. E. W. J . Phys. Chem. SOWS1989, 50, 449-467. (PP3) Engeihardt, 0. TrAC, Trends Anal. Chem. (Pers. Ed.) 1989, 8 . 343-347. (PP4) Klinowskl. J. CollOMs Surf. 1989, 36, 133-154. (PP5) Pfeifer, H. Co/&ids Surf. 1988, 36, 169-177. (PP6) Fyfe, C. A.; &s, H.; Feng, Y.; Kokotallo. 0. T. Nature (London) 1989, 34 1 , 223-225. (PP7) Meiler, W.; Wutscherk, T. Isotopenjraxis 1989, 25, 41-47. (PP8) Anderson, M. W.; Kllnowskl, J. NahKe (Lonobn) 1989, 339, 200-203. (W9) Lechert, H.; Basler, W. D. J . Phys. Chem. SoMs 1989, 50, 497-521. (PPlO) Hayashi, S.; Suzuki, K.; Hayamizu, K. J . Chem. Soc., Faracby Trans. 1 1989, 85, 2973-2982. (PPll) Karger, J.; Ruthven, D. M. Z&s 1989, 9,267-281. (PP12) Fraissard, J.; Kaerger, J. Zedltes 1989, 9 , 351. (PP13) Foerste, C.; Helnk, W.; Kaerger, J.; Pfeifer, H.; Feokistova, N. N.; Zhdanov, S. P. Zeo/ites 1989, 9 , 299-302. (PPl4) Grandjean, J.; Laszlo, P. ACS Symp. Ser.1989, No. 415,398-406. (PPl5) Bucher, J. P.; Buttet, J.; Van der Klink, J. J.; Graetzel, M.; Newson, E.; Truong, T. B. Co/bidsSurf. 1989, 36, 155-167. (PP16) Duncan. T. M.; Zlim, K. W.; Hamilton, D. M.; Root, T. W. J . Phys. Chem. 1989, 93, 2563-2590. ZERO FIELD NMR (OQ)

(QQl) Pines, A. in Roc. of 100th S c W of Physics "Enrico Fermi"; Maravlglla, B., Ed.; North-Holland: Amsterdam, 1988; pp 43-120. (QQ2) Pines, A. Chem. Eng. News 1988, 41. ((243) Tycko, R. Phys. Rev. Left. 1988, 60, 2734.

Infrared Spectrometry Richard A. Nyquist,* M. Anne Leugers, Marianne L. McKelvy, Richard R. Papenfuss, Curt L. Putzig, and Lori Yurga Analytical Sciences Laboratory, 1897 Building, The Dow Chemical Company, Michigan Division, Midland, Michigan 48667

INTRODUCTION This review covers the published literature for the period late 1985to late 1989 on aspecta of infrared spectrometry that are relevant to chemical analysis. Our review has a strong bias toward papers published in English, or in certain aspects of IR spectrometry that are of particular interest to one or more of the coauthors. In addition, a few selected references to FT-Raman spectrometry are included for reasons given below.

OVERVIEW OF ANALYTICAL INFRARED SPECTROMETRY Infrared radiation is usually defined as that electromagnetic radiation whose fre uency is between -14 300 and 20 cm-' (-0.7 and 500 pm). (tyithin this region of the electromagnetic spectrum, chemical compounds absorb IR radiation providing

there is a dipole moment change during a normal molecular vibration, molecular rotation, molecular rotation-vibration, or a lattice mode or from combination, difference, and overtones of the normal molecular vibrations. The frequencies and intensities of the IR bands exhibited by a chemical compound uni uely characterize the material, and its IR spectrum can be use% to identify and quantify the particular substance in an unknown sample. Different classes of chemical compounds contain chemical groups which absorb IR radiation at essentially identical frequency(ies) and have essentially the same band intensity(ies) within each class of compound, and these bands are termed "group frequencies". Group frequencies are predictable and allow the anal st to elucidate and identify molecular structures without avairable IR standard reference spectra for comparison. In addition IR spectra can be recorded rapidly

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of materials in the solid, liquid, solution, and vapor phases over a wide range of temperature. Such studies aid in elucidating the molecular structure of materials in different physical phases. Today modern IR instrumentation allows spectra to be recorded of samples available in only low nanogram quantities using IR microscopy techniques or as low as high picogram quantities using matrix isolation (MI)-IR techniques. No other technique allows examination and identification of materials under such a wide variety of physical conditions, and it is this versatility that has allowed IR spectrometry to develop into the "work horse" of analytical science. One should be aware of the fact that Raman spectrometry is a complementary technique to IR spectrometry. In cases where a chemical compound has a center of symmetry, certain normal vibrations will only be active in the Raman and certain normal vibrations will only be active in the IR. Thus, one needs both techniques to record the complete vibrational spectrum of many chemical compounds. Moreover, bands that are strong in the Raman are usually weak in the IR, and vice versa in cases where the normal modes are allowed in both vibrational techniques. With the recent development of Fourier transform Raman (FT-Raman), it is now possible to rapidly record Raman s ectra of most materials by using the FT-IR system equippeg with the FT-Raman option. The FT-Raman technique has distinct advan es over the traditional dispersive Raman technique in that uorescence and thermal decomposition have been essentially eliminated. This is possible since FT-Raman usually uses a NdYAG laser for excitation, and the excitation is in the near-IR region. FT-Raman is commercially available from several manufacturers, and we predict that in the future both IR and Raman

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INFRARED SPECTROMETRY Curtls L. Putzb is a Research Leader in the Instrumental Methods Group 01 the AnalytF c d Sciences Laboratories. Dow Chemical U.S.A. He received his B.S. degree from Wayne State University in 1971 and his M.S. degree in analytical chemistry from Purdue Universiiy in 1973. He joined The Daw Chemical Company in 1973. and his career has been mainly in the fields 01 I R and Raman spectroscopy and m a s spectrometry. He is the author or coauthor ot 14 pubiicalions. Hi5 research l n t e r e ~ include t~ the elucidation of molecular structure. polymer characterization. separation sciences, and the computer analysis of spectroscopic data.

Rkhard A. Nyqul.1 is a Senior ASsoCiate Sckntist in the Instrumental Methods Group 01 the AnaMical ScIBnoes Laboratories. The DOW chekicai Company U.S.A. H i mceived his B.A. degree in chemistry from Augustans College. Rock Island, IL. and hls M.S. from Oklahoma State Unlversiiy. He joined the The OOW Chemical Company in 1953. and his career has been mainly in the

molecular ~tructure.and tor qualitative and

ertcahChemi& Sbciety. The Society ;Or Appiied Spectroscopy. and ASTM E t 3 on mOleCUlar spectroscopy. In 1985 he received the Williams-Wright Award for his Contributions to industria infrared spectroscopy from the Cobientz Soclety. and in 1989 he received an ASTM Award of Appreciation for his leadership and work with ASTM E13. Nyquist was a National Tour Speaker for The Society of Appiied Spechoscopy in 1989. Anne Lewers is a Project Leader in Ib Instrumental Methods Group of the Analytical Sciences Laboratory at Dow Chemical U.S. A.. Midland, MI. Anne received a B.S. degree in chemistry from Xavier Univerriiy in Cincinnati. OH. and a Ph.D. degree in physk cal chemistry from the University of Cincinnati in 1981. She performed postdoctarai research at Syracuse University and University 01 Arizona before taking a research position in the paper industry studying the $ material science of paper. She joined Dow in 1984 where she began working in the area of liber-aptic and Raman spectroscopy and detection. Anne's research interests in- I clude application of Raman and fiberqtic 5peclroscopy to the chemicai and morphological characterization of synthetic polymers. Anne has received two U.S. patents and has several disclosures filed She has also aulhored six publications in the area of high-resolution and laser spectroscopy ~

Msrlanne L. McKeIvy Is a Fmlect Leader in the Polvmerlc Meteroak Research Center 01 the Analytical Sciences LabDralwbs of Dow Chemical. USA. Midland. MI. She received I the B.S. degree from the University of Detroit. OeWOit, M I (1979). the M.S. degree 119821 and the FhD. (1985) from Poiytechnlc Universtty. Brooklyn, NY Subsequently. she joined the Analvical Sciences Laboralories where she is involved in solving polymer problems wing infrared spectroscopy. Her research interests involve the characterizatiin of pdymers using Vibmtion- I ai specho~copyand inhared microspectras copy. She is a member of the Society fm ': Applied Spectroscopy and the Cobientz Society.

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Rlchard R. Papmluu is a Re-rcn ASP cmte w th the Po ymeric Mater a h Research Center. D a w Cnemica U S A he received h 5 B S dear88 tiom Wisconsin Slate Cd. leqe at La6rors He lolned Daw m 1963. a i d has worked in the Inorganic. Organic. and Agricultural Products Groups. For the last 12 years he has concentrated in applyinq both qualiative and quantitative infrared

meric and Other relatd materials.

s ctra will he recorded of materials on a routine hasis for the eKcidation and idrntification of molecular structure. Thrretore, we have included a few selerted references to FT-R;iman spectrometry fur your convenirnce.

( A ) ROOKS An extensive collection of vapor-phase IR group frequencies 224R

lyticalbciencer Labdrataies. bow Chemical :! U.S.A. She received a B.S. degree In chemistry and biology from Central Michlgan Universlty and joined the DOW Chemical Company in t983. She Spent two years in methods development in the Organic Products Group prior to her assisnment 10 Me Instrumental Methods Group where her expertise was concentrated in problem soMng using infrared and Raman Spectroscopy. Her research interests are in the develop ment and utilization 01 hyphenated techn i q m combining chranatqraphy and infrared SpeCtrOSCOpy. She recently transferred lo her current IIIVOIY~S wpewision 01 the lnsecllcldes Group

ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990

have been developed by Nyquist and these data are useful in the interpretation of GC/IR data ( A I ) . Vapor-phase IR spectra illustrating data discussed in ref A1 are shown in ref A 2 The 9200 vapor-phase IR spectra published by Sadtler have been edited by Nyquist (A3). Infrared spectrastructure correlations for compounds containing carhon-carbon double and triple bonds are presented as well as their IR spectra. These spectra are useful in identifying materials used in the manufacture of polymeric materials (A4). In the past few years Sadtler has increased their standard IR spectral collection to 15000 (A5). Spectra-structure correlations have been developed between carbonyl stretching frequencies and NMR carbon-13 chemical shifts for the carbonyl group for a variety of compounds (A@. Nakamoto has updated his treatise on IR and Raman spectra of inorganic and mrdination compounds ( A n . Ishida has edited nine hooks pertaining to the characterization of polymers hy application of IR (A8). Craver has edited a hook on polymer characterization which includes the application of IR (A9). Messerschmidt and Harthcock edited a comprehensive treatise on the instrumentation and applications of IR..micmsnecf.rnsconv A 10,. ...~ .......-... ....-,(~ . ~ ~ . , ~ ~

Griffiths and de Haseth have authored a comprehensive treatise on the theory and applications of FT-IR (AIZ). Yates and Madey have edited a hook on the characterization of molecules on surfaces, and it includes the application of 1R (AZZ). McClure has edited a hook on the application of computers in quantitative IR analysis (AI3). Mackenzie has edited a treatise which includes IR techniques for microsampling, external and internal (ATR) reflection spectroscopy, diffuse reflectance, photoacoustic, and emission Spectroscopy (A14). Clark and Herter edited a book on matrix-isolated species (A15). Willis edited a book on recent developments and applications of IR analytical instrumentation (A16). Osborne and Fearn wrote a hook on the applications of near-IR spectroscopy for food analysis (AZ7). Williams and Norris coedited a hook on the applications of near-IR in the agricultural and food industries (A18).

(B) REVIEWS Wehry and Mamantov reviewed the literature on matrix isolation molecular spectrometry in analysis including GC/ MI/IR (SI).Jinno (E?), Taylor and Calvey (S3),andLater et al. (B4) reviewed the literature on supercritical fluid IR.

INFRARED SPECTROMETRY

the eluate on 'a small area. Griffiths and Henry reviewed the literature on GC/IR. He emDhasizes GC/MI/IR and states that detection limits are in the mid-pi am'range for polar analytes. They state that real time G C T can be achieved by trapping at 77 K in the absence of an inert gas matrix (B6). Hurrell has reviewed the literature on chromatographic considerations in the optimization of GC/IRperformance (B7).Slack and Heim (B8)and Wikns (B9)rewewed the literature on GC/MS, GC/IR, and GC/IR/MS. The identification of substances in multicomponent mixtures is discussed. White reviewed the literature on the basic instrumentation (hardware and software) used in GC/IR together with ap lications @IO). Harrington et al. reviewed the literature on b / I R with emphasis on reducing noise rather than increasing the signal as a method of increasing sensitivity (B11). Crummett et al. have reviewed the literature on applications of multidimensionaltechniques including GC/IR and LC/IR (B12). Griffiths and Conroy reviewed the literature on the measurements with flow cells in size-exclusionchromatography, normal-phase chromato aphy, and microbore HPLC/IR with emphasis on earl an recent works for solvent elimination techniques in I-#LC/IR (B13). Griffiths et al. reviewed the literature on GC/IR, LC/IR, SFC/IR with emphasis on the interfaces between the chromato raphs and the IR spectrometers (B14). Hellgeth and TaJor reviewed the literature on interfacing desi ns, FT-IR instrumentation, and data manipulation for LC/fR (B15).Jinno has reviewed the literature on recent approaches in LC/IR (B16).Green has reviewed the literature on absor tion detectors for highrformance LC including IR (BI 7f De Haseth has reviewed cbridized techniques including LC/IR (B18). Fredericks has reviewed the literature on reflectance IR methods, micro techniques, and hyphenated techniques (B19). Hellmann reviewed the literature and discusses his twenty years experience using thin-layer chromatography/IR in the solution of chemical problems (B20). Golovnya has reviewed the literature on headspace GC in conjunction with IR and MS data (B21). Hanst has reviewed the progress of utilizin IR for the detection of ~ollutantsin the atmomhere. Pohtants that have been measured by IR in ambient air have included "OB, HN02, NH3, 03,CO, C02, SO ,NO, NO2,H2C0,hydrocarbons, Deroxvnitrates. HC1, and k F (B22). Dhvse et al. have reviewed the literature on the analysis of com lex multicomponent mixtures such as found in the flue gas #om waste incinerators by application of IR (B23). Amoto has reviewed remote-sensing instrumentation and included the airborne IR imaging spectrometer (B24). Belton et al. reviewed the literature on the princi les of hotoacoustic IR spectroscopy and demonstrate ita utfity by po!ymorphs (B25). king able to distinguish between two Brown and Beauchemin have reviewed t e literature on the a plications of thin-layer chromatography and diffuse re&ctance/IR (B26). PNSSet al. have reviewed the literature on the ap lications of IR fibers in remote gas sensing usin IR. EmpRasis has been given to fluorozirconate fibers. Fiker requirements reggeometrical data, spectral attenuation, and mechanical as we as durabilit for future applications have been summarized (B27). Bogra has reviewed the development of vehicle-portable systems based on com uter-controlled IR and other techni ues (B28). Hewitt et a! have reviewed the evolution of d - I R from the laboratory to the production environment with emphasis on the intrinsic and extrinsic properties of FT-IR which make the instrument capable of yielding real time analytical data (B29). Wilks has written a review on the application of FT-IR uersus filter IR for on stream process monitoring (B30). Roth and ODonnell-Leach have reviewed the advantages, obstacles, and the design of FT-IR analyzers for application of real time multicomponent analysis of process streams (B31). Coates et al. reviewed the use of novel samplin devices recently introduced for liquid sampling, diffuse reffectance analysis of solids, and ATR reflectance analysis of pastes, semisolids, and films (B32).

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Hirschfeld has reviewed and criticized the throughput advantage obtainable by FT-IR with the use of a Michelson interferometer. Advantages obtained by the reduction of detector and instrument sizes with no nearb limit to match them to state-of-the-art re uirements in a sorption spectroscopy sampling are also iscussed (B33). Smith has reviewed the instrumental considerations, the techni ues of trace analysis, and applications of IR to the atmos&ere, environment, soil,water, polymer, semiconductor, surface, and interface analyses (B34). Reffner et al. reviewed the use of light microscopy combined with FT-IR (B35). Griffith reviewed the use of IR and Raman for the analysis and characterization of minerals (B36). Wilks reviewed the use of the ATR/IR technique for aqueous systems (B37). Brill reviewed the principles of fast thermolysis/FT-IR spectroscopy and examples from the rocket propellant and explosive field are discussed (B38). Korzeniewski and Pons have reviewed the experimental details involved in obtainin IR spectra of electrochemical systems. A description of t e electrochemical cell and the surface selection rule is given. The commonly used spectroelectrochemical techniques for the analysis and characterization of the electrode surface are also discussed (B39). Zerbi reviewed the new developments in vibrational spectroscopy, the intensity of an IR band, molecular electrical parameters from IR intensities, and the difficulties in using the IR band intensity data (B40). S ra g reviewed the advantages and limitations of direct anJindiirect approaches to quantitative analysis by a plication of IR based on Beer's law (B41). Bowater reviewefthe use of microprocessors in dispersive spectrometers, data stations, and FT-IRspectrometers (B42). Miller reviewed the use of photoacoustic and photothermal techniques for infrared spectroscopy (B43). Suzuki et al. have prepared a IR and Raman literature bibliography covering the period June 1986-May 1988 (B44, B45). Haller has reviewed far-IR applications for semiconductors (B46). Gramaccioli reviewed the calculations of vibrational frequencies in molecular crystals with regard to the possibility of evaluating thermodynamic functions and temperature factors (B47). Davidson reviewed the literature on IR and Raman spectra of compounds containing group I-VI11 elements (B48). Gendreau et al. wrote a review on the application of IR for biological applications (B49). Porter reviewed external reflection IR and its effects and parameters in the study of surfaces after chemical modifcation (B50). Chabal reviewed the theoretical and experimental foundation of surfaces using IR and its applications (B51). Rose reviewed the application of IR in the analysis of antibiotics (B52). Wong reviewed the field of vibrational spectroscopy using high pressure (B53). Harris and Chapman reviewed IR applications for the analysis of biochemistry and medicine (B54). Mink reviewed IR for the analysis of catalysis (B55). Nafie and Freedman reviewed vibrational circular dichroism spectroscopy in which the measurement of the differential absorbance of an optically active molecule, with respect to left and right circularly polarized IR radiation, provides information concerning its molecular stereoconformation (B56). Miller reviewed IR reflectance techniques (B57). Brian et al. reviewed applications of s ectroscopic techniques in soil analysis (B58). Reviews on iochemical applications appear in section I. Mantz reviewed the application of tunable diode lasers in the detection of trace gases in air and in the manufacturin processes in the semiconductor industry (B59). Kochhar and Rossell reviewed the potential and capabilities of microprocessor-controlled IR spectrometers in the analysis of food (B60). Nunziante and Torracca reported on the history of early a plications of IR spectroscopy in chemistry during the 18008 $61). Sheppard et al. have ublished the definitions and recommended names and sym\ols for the quantities used in IR, UV, and visible spectrometry (B62). Brill has reviewed fast thermolysis/IR s ectrosco y and applications in the rocket propellant and expgsive fielf(B63). Sibila et al. have reviewed the principles, limitations, and anal ical a lications of IR, Raman, UV, visible near-IR, N M Z and &$R (B64). Grasselli has reviewed the use of IR and Raman spectroscopy in examination of catalysts, poly-

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mers, chemical reaction studies, and process control in an industrial laboratory (B65). Smith et al. have reviewed the literature for the analysis of synthetic pol ers for the period 1984-1988 and have included the re erences to polymer analysis using IR and Raman spectroscop (B66, B67). Wilson and Childers reviewed the field of h / F T - I R (B68).

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NEAR-IR SPECTROSCOPY The absorptions that occur in the near-IR region of the electromagnetic spectrum are due to overtones and combination bands of the fundamental vibrations found in the mid-IR. (The absorptions that are due to transitions to lowlying electronic states will not be treated in this article.) Furthermore, vibrations involving hydrogen (CH, OH, and NH stretches in particular) will predominate in the near-IR. The appearance of combinations and overtones results only because of anharmonicity, and the hydrogen stretching modes are enerally quite anharmonic due to the large displacement of t e hydrogen atom during a vibration. Overtones and combinations have weaker absorbances than the constituent fundamentals, and there is ro My a factor of 10 decrease in intensity in hi her vibration3 levels with each additional fundamental. h a n exceptions exist to this last statement, especially when d&g with molecules of high symmetry, but it 18 still a good rule of thumb for most analytical applications. From a spectroscopic viewpoint, analytical applications can be based e ually well on fundamental, overtone, or combination ban% All of these vibrational levels are well-defined quantum mechanical states of the molecule and all reflect and are affected by molecular structure. In general, the mid-IR will contain the eatest amount of spectral information while the near-IR will limited principa~yto information involving hydrogen stretching vibrations. Since the fundamentals are much stronger than the overtones and combinations, a very short path length is required in the mid-IR. In the near-IR, path lenghs in the r a n g of 0.5-10 mm are enerally used to obtain a orbances in e range of 0.1-0.7 A$. The absolute strength of the bands is generally of no consequence unless only small amounts of material are available for the analysis. Longer path lengths are an advantage for on-line liquid analyses since the material must flow readily through the sampling area. Current1 fiber-optic a plications are best performed in the near-& region since ighly transparent, mechanically stable optical fibers are not yet available for the mid-IR region. The applications of near-infrared spectroscopy have increased dramatically in recent years due to a number of factors. Mathematical data treatments such as partial least uares (PLS)or multiple linear regression (MLR) have been significant help in modeling the spectra obtained in this spectral region where spectra are frequently quite complex and bands may be difficult to assign. In addition, the path length required to obtain good signal to noise is quite long (0.5-10 mm). This factor enables the measurement of samples containing small to moderate concentrations of water by transmission or diffuse reflectance measurements. This factor also allows quantitation on samples where the path length could vary by a few hundreths of a millimeter. Moreover this path length is a reasonably large gap through which even viscous material may flow.

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(C) NEAR-IR REVIEWS Hirschfeld has reviewed the effect of sample nonuniformity on error in diffuse-reflectance near-IR spectrometric analysis of particulate samples. The o timum conditions call for d current practice sample areas larger than most of Zose ~ a e in and the use of a variable-size detector ( C l ) . Weyer has reviewed the use of derivative nodes in near-IR spectroscopy. This technique is useful in the analysis of mixtures of components. Crossover points in the derivative spectra minimize spectral interferences. He emphasizes that it is important to examine the neat spectra of all components in a system to determine what the data treatment and measuring wavelengths chosen by regressions actually represent (CZ). Stark et al. have made an extensive review of near-IR instrumentation techno1 ,calibration and calculation procedures, and Buchanan and Honigs have reviewed the a plications tleory and instrumentation of near-IR analysis and pro se future trends using this technique (C4). Davies revieweEhe

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progress of near-IR spectrometric analysis, the reasons why it is theoretically complex but simple in ractice, and the recent developments in instrumentation wiich make it user friendly (C5). Mark reviewed the studies of rincipal components as a analysis. Principal calibration method for near-IR rel-ce component analysis provides a means of generatin calibrations for near-IR instruments that reduce the need for trial and error methods of determining the proper set of variables to use in the analytical method ((76). Wetzel has reviewed the field of chemical sensing using near-IR reflectance (C7). Bruce and Turnbull have reviewed the advantages of using near-IR spectrometry for on-line process monitoring (C8). Tunnell has reviewed the use of near-IR for product identification. He emphasizes that re ular performance checks of the instrument must be includA in any routine rocedure in order to ensure reliability of the method (C9). %itch and Gargus have reviewed remote UV-VIS-near-IR spectroscopy using fiber optical chemical sensing (C10).Williams has reviewed applications of FT-IR in the near-IR, UV, and visible (C11). A very thorough review on the subject of quantitative and qualitative analysis in the near-IR was repared by Stark, Luchter, and Margoshes (C12). The autiors discuss instrumentation, calibration methods, calculations, and ap lications. A review of vibrational s ectroscopy in the near- R region written by Salzer (C13) iscusses the features encountered in this spectral region and the utility of the re ion for nondestructive evaluation and measurements on highy scattering samples. The use of near-IR s ectroscopy in the analysis of pharmaceuticals was reviewe by Ciurczak (C14). Numerous reviews on the application of NIR spectroscopy to food and agricultural analysis have been presented. Wetzel reviewed the potential for chemical sensing using near-IR reflectance spectroscopy and postprocessing techniques for quantitation (C15).Davies et al. reviewed the use of near-IR to detect protein, starch, and oil in flour and a wide variety of other constituents in foods as well as the recent advances in data treatments (C16). Davies and Grant (C17) reviewed the major absorption bands observed in near-IR spectroscopy for the analysis of foods and wine. In a review on the application of near-IR spectroscopy to food and agriculture in Hungary, Kaffka (C18)discussed the equipment used and its application. Law (C19) reviewed the application of near-IR reflectance techniques to the determination of malting quality of barley. Ronalds and Miskelly reviewed the methods of calibration of near-IR refledance spectroscopy for applications in food analysis (C20). The possibilities, limitations, and experiences of near-IR spectroscopic analysis to cereals in the Federal Republic of Germany were reviewed by Bolling and Gerstenkorn (C21). McDermott reviewed the potential a plications of near-IR spectroscopy to food snaly~is( ~ 2 2 )d. e principles of near-IR reflectance measurements and the application to hay, straw, grass, and silage were reviewed by Murray (C23). A review of the application of near-IR analysis in the tobacco industry as well as some specific testin results were presented by McClure (C24). McClure and Wdiamson ((225)also reviewed the status of near-IR analysis in the tobacco industry. Applications of near-IR methods in a wide variety of agricultural products was reviewed by Stark (C26).

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(D) TECHNIQUES Using unmodified commercially available instrumentation, Smith and Carl reported some applications of microspectroscopy in the near-IR ( 0 1 ) . Masterson et al. ( 0 2 )reported the design and characterization of an integrating s here spectrometer for high-temperature applications. A wile variety of postprocessing software has been evaluated (03-020) to enable quantitative determination of samples using complex near-IR spectra. A wavelength standard based on the near-IR reflectance spectra of a mixture of three rare-earth oxides was proposed by workers at the National Bureau of Standards, Weidner, Barnes, and Eckerle (021). Lodder and Hieftje (022)describe a near-IR-based method for the reconstruction of surface layers concealed by layers of overcoatin s Chemicals and Polymers. A near-IR study ofthe hydrogen bond uilibrium constants was performed by Buchet and Dion on the complexes of benzotriazole and some nucleoside derivatives. Davies et al. (024) re orted a study of food packaging laminates by near-IR reiectance spec-

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troscopy to detect the absence of any of the layers in a multilayer film. Silicone coating weights on paper were accurately determined by near-IR reflectance methods in an investigation by Paralusz (025). Wallin and Dabney (026, 027) reported the application of near-I reflectance spectroscopy to the successful determination of active detergent, solids, moisture, benzoic acid, and pH with no sample reparation for quality assurance of shampoos. Miller ant! Yin (0%) found that poly(octadecy1methacrylate) adsorption on alumina particles could be followed b analysis of the near-IR reflectance s ectra. Using near-18 reflectance methods, Chalmers a n i Campbell (029) found the hydroxyl value in block or random ethylene oxide-propylene oxide copolymers prepared from a wide variety of initiators. Miller and Honigs investigated the otential of using the near-IR reflectance spectroaco y for tEe discrimination of the differing crystalline forms of gyycine (030). Food and Agriculture. Grain Beverages. Near-IR reflectance spectroscopy was used to predict quality, theaflavin content, and moisture content of black tea in a study by Hall, Robertson, and Scotter (031). Another study of tea constituents was performed by Ikegaya et al. where the near-IR reflectance spectra of caffeine and related com ounds were measured (032). A discriminant analysis of blac! tea by NIR reflectance methods was erformed by Osborne and Fearn (033). Gardfam reportet?(D34) the application of near-IR to the determination of sucrose, moisture, and fat content during the processing of chocolate. Grains and Cereals. Bertrand et al. (035) reported the assi nment of near-IR absor tion bands in durum wheat profucts by multidimensionJanalyses of spectral data and its a plication to the estimation of purity. Finney, Kinney, and bonelson (036)studied the near-IR reflectance spectra of whole wheat Sam les to predict the quantity of damaged starch. Near-IR reRectance spectroscopy was found to be applicable to the determination of protein content in rice and wheat (037). The determination of fat in a variety of cereal foods was investigated by application of near-IR spectroscopy . also employed near-IR reflectance by Osborne (038)&borne techniques to monitor the rotein content of flour to optimize milling conditions (039). kear-IR reflectance measurements were performed by Rubenthaler and Pomeranz (040) to determine the feasibilit of the technique in predicting protein content and breadmdng potential of hard red winter wheats. Kemeny and Wetzel (041) investigated the use of spectral reconstruction in near-IR spectra to account for the problems associated with variation in particle size in the analysis of moisture and protein in hard wheat. Weustink discussed near-IR reflectance measurements of enzyme-induced degradation of wheat starch to glucose (042). The effect of nitrogen fertilizers on the near-IR and Kjeldahl protein measurements were investigated by McDonald and Bruns (043). The anal is of rapeseed by near-IR spectrosco y has been investigatedrsby a number of authors. Renard et (044)and Yan et al. (045) used near-IR reflectance measurements to pre8ct the glucosinate content in whole rapeseed. Panford et al. used near-IR spectroscopy to measure oil, protein, moisture, and fiber contents in a wide range of oil-bearing crops, including rapeseed (046). The concentration of oil in rapeseed usin near-IR spectroscopy was also inveatigated by Cowe et al. 647). Dairy Products. The protein and moisture content of soy milk was rapidly determined in a study by Akiyama et al. using near-IR transmission and reflectance spectroscopy (048).The application of near-IR reflectance spectroscopy to the determination of contituents in butter was reported by Sato et al. (049). Near-IR reflectance spectroscopy was used by Wehling and Pierce (050) to determine the fat content in cheese. A study of the mathematical treatments of near-IR s ectra of milk was erformed b Robert et al. to minimize $e li h6 scatting robem in the letermination of fat content in m k! by near-fik spectroscopy (051). Sat0 et al. (052) reported the analysis of the ma’or constituents in milk by near-IR spectroscopy and multipfe linear regression. Another study on the analysis of major contituents in milk owders and cheese was reported by Frankhuizen and Van Veen (053). Fruit and Vegetables. Using near-IR reflectance Meurens et al. were able to determine the concentrations of amino acids

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in an orange juice model mixture (054). A nondestructive method for the determination of sugars and soluble solids in ripening cantaloupe using near-IR reflectance spectroscop was investigated by Dull et al. (055). Giangiacomo and D d (056) employed near-IR spectroscopy to determine glucose and fructose in aqueous sugar solutions ranging up to 40%. Beer and Wine. Halsey (057) reported the application of near-IR transmission and transflectance to the determination of ethanol and gravity in the analysis of beer. Halsey also evaluated the use of near-IR reflectance spectroscopy to the determination of moisture and total nitrogen in whole malt (058). Bouvier (059) reported the development and application of a continuous, automated near-IR technique for the determination of total sugars in the fermentation of grape musts. Meat. Near-IR reflectance spectroscopy was investigated as a tool for the determination of fat and moisture in the analysis of mutton by Bartholomew and Osuala ( B O ) . Valdes and Summers reported the determination of crude protein and fat in poultry samples by near-IR reflectance measurements (061). Grasses, Silage, Forage, Feedstock. Near-IR spectroscopy was applied to the measurement of carbohydrate concentration determination by Brown, Piacitelli, and Mislevy in tropical rasses (062) and in subtropical grasses by De Ruiter et al. fD63). Analysis of forage research samples was performed by Brown and Moore (064) utilizing a combination of wet chemistry and near-IR reflectance spectroscopy. Reeves (OSS) applied near-IR reflectance spectroscopy to the analysis of sodium chlorite treated forages and other lant materials. Near-IR reflectance spectroscopy was use by Jones et al. (066) to determine the concentration of fiber, protein, and mineral in forages and compared with results by wet chemical methods. A collaborative study reported by Barton and Windham (067) evaluated the reproducibility of near-IR reflectance techniques performed at collaboratinglaboratories to determine fiber and protein contents of forage. The study demonstrated that near-IR could be reliabl used as a standard method. Abrams et al. ( B 8 )evaluateithe efficacy of broad-based calibration equations in the determination of forage quality. The total alkaloid concentration in larkspur and lupine forages was determined by wet chemical techniquies and found to correlate with near-IR reflectance methods in a study by Clark et al. (069). Clark et al. (070) also measured the mineral content in forages by near-IR reflectance techniques. In a study by Coelho et al. (0711, the methods of microbial, enzymic, chemical, and near-IR reflectance were compared in the evaluation of forages. Clark et al. (072) performed a study to determine the applicability of near-IR spectroscopy to the determination of trace elements in forages. Reeves (073) performed chemical assays on forages for the determination of fiber, lignin, and lignin component concentrations to aid in the understanding of their interrelationships in the near-IR reflectance spectra. Usin near-IR reflectance measurements, Kaffka (074) found relia%lepredictions could be made regarding the concentrations of amino acids. Bertrand et al. applied principal com onent analysis to the prediction of lucerne protein contenty! near-IR spectroscopy (075). Blosser and Reeves (076) collected samples over a 3-year period and evaluated the factors affecting wet chemical testing methods versus near-IR reflectance spectroscopy. In a study involving testing at collaborating labs, the Karl-Fischer method was evaluated and compared to the near-IR reflectance method for moisture determination on forage samples. The study, reported by Windham, Barton, and Robertson (077) found near-IR analysis to accurately and precisely predict the moisture content of forages. Abrams, Shenk, and Harpster (078) evaluated the technique of NIR spectroscopy for the determination of silage composition in ensiled forages. NIR reflectance spectroscopy on whole field peas followed by multiple linear regression technques was found to accurately predict the protein content in a study performed by Tkachuk, Kuzina, and Reichert (079). Cho et al. found that the determination of 7s and 11s globulins in whole ground soybeans by NIR spectroscopy could be correlated with the values measured by ultracentrifugation (080). A methodology study was performed by Frankel, Nash, and Snyder (081) comparing results of various techniques in the evaluaton of the soybean quality. NIR reflectance spectroscopy was also

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successfully ap lied to the determination of components in s ar cane by gerzut et al. (082).The analysis of cell-wall &hydrates and starch in alfalfa was performed by Albrecht et al. ( 0 8 3 ) using NIR reflectance. Pharmaceutical and Biological Applications. In a study by Ciurczak et al. ( 0 8 4 )pharmaceutical raw materials were analyzed by low angle laser light scattering and by near-IR reflectance to determine whether the mean particle size could be determined by near-IR spectroscopy for quality assurance. Near-IR reflectance spectroscopy was performed by Chasseur (085) on cimetidine granules to determine the feasibility of near-IR reflectance as an on-line method for cimetidine assay. Ranter et al, evaluated several chemometric techniques for the analysis of near-IR spectral data of pharmaceuticals (OSS). A ketoprofen assay was performed by Corti et al. (087)using near-IR spectroscopy to determine its suitability for quality control in pharmaceutical formulations. Aspirin, caffeine, and butalbital were identified by using computer-assisted processin of near-IR s ectral data i n measurements performed by biurczak and Jaldacker (088). The successful determination of water content and active in redient concentration in antibiotic powders by near-IR refiectance spectroscopy was reported by Lonardi et al. (089). Dubois et al. (090determined ) five com onents in a liquid pharmaceutical formulation using near-& reflectance measurements. By use of near-IR reflectance and MLR, the polymorphic forms of an active i ient in a harmaceutical were quantitatively determined y Gimet an Luong ( 0 9 1 ) . A method for the analysis of intact tablets b near-IR reflectance was reported by Lodder and Hieftje (892). Further work by Hieftje and co-workers ( 0 9 3 ) reported efforts to devise a method using near-IR spectroscopy to determine whether capsule tampering had occurred. Hieftje and coworkers ( 0 9 4 ) also assessed the feasibility of determining cholesterol and other blood constituents by near-IR analysis. Measurement of total serum protein was successfully erformed b using near-IR reflectance techniques by Fan ToorenenLrgen et al. (095). Montalvo et al. (096, 097) investi ated the use of near-IR s ctroscopy to the compositionafanalysis of cotton dust anKhe relation of cotton dust exposure to acute ulmonary response. Geology and d n e r a l s . Near-IR reflectance measurements in the field as well as in the lab were performed by Townsend (098) to estimate iron alteration materials in rock and soil samples. A study of the near-IR reflectance spectra of iron ores was reported by Fredericks et al. for the purpose of rapid characterization of mineral samples (099). Krohn (0100)invea ' ated the spectral propertiea (from 0.4 to 25 pm) of selected roc associated with disseminated gold and silver deposits. Near-IR spectrosco y was evaluated b Crowley and Vergo for the analysis of kaoin clay minerals (6101). Gaffer (0102)studied the near-IR reflectance spectra of anhydrous carbonate minerals to aid in the identification of the minerals. Textiles. Efforts to investigate the optimum heat-setting temperatures of carpet yams by analysis of near-IR reflectance s ectroscopy were reported by Ghosh and Rodgers (0103). #-her work in the area of heat-set optimization by near-IR spectrosco y was performed by Tincher et al. (0204). Tincher and Luk a$so reported the successful application of near-IR spectroscopy to the analysis of cotton-polyester yarns (0105). A near-IR reflectance method was developed to rapidly determine the degree of sizing required for polyester, cotton samples by Lemere (0106).

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(E) IN SITU A review on the subject of infrared spectroscopy of the electrode surface was presented by Korzeniewski and Pons ( E l ) . The design and implementation of an optically transparent thin layer electrochemical cell with a gold mini id electrode for IR transmission studies was reported by B&k et ai. (E2). The paper discusses the application to in situ spectroelectrochemistry studies of ferrocene. Another study (E31 by Bockris and Yang discuses the design and application of a thin layer flow cell for reflection-absorption measurements in the IR spectroscopy of electrode/electrolyte interphase. Adsor tion and oxidation of methanol on platinum and platinize$ glassy carbon electrodes in sulfuric acid solution was investigated by Christensen, Hamnett, and Weeks (E4). Anal sis of the oxidation of ethanol at a platinum electrode by I reflection absorption spectroscopy was reported by

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Iwasita et al. (E5). In situ surface measurements of isoquinoline adsorption at a mercury electrode by IR spectroscopy were performed by Blackwood et al. (Es).Us' multiple internal reflection IR spectroscopy, Pham et al. (E!detected the phenoxy radical during the anodic oxidation of phenol derivatives on iron. The reaction of calcium carbonate with sulfur dioxide was studied b Thompson and Palmer using in situ diffuse reflectance an photoacoustic IR spectroscopy (Es).The IR investigation of coke formation on dealuminated mordenite catalysts in situ was reported by Karge and Boldingh (E9).

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(F) NEAR-IR FIBER OPTIC SPECTROSCOPY General discussions of the applicabilit of fiber optics to remote spectroscopy and sensi may be round in articles by Heiman et al. (FI) and Fitch Gargus (F2). Development of a Fourier transform spectrometer configured to measure near-IR transmission spectra using 80 m of o tical fiber are discussed by Honigs and co-workers (F3, F4f A plications of near-IR fiber optic spectroscopy to particukr problems are discussed by category below. Near-IR spectroscopy is being widely a plied in the food industr for many types of evaluations. #elion and Boisde studidthe near-IR spectra of fruit to determine sugar content and the near-IR region of flour to determine the moisture in flour (F5). An application of near-IR fiber optic detection of methane as is discussed by Alarcon et al. (F6). Using InGaAsP lght-emitting diodes, the system was found to be capable of detecting approximately 1Torr of CHa in air or 2.6% of the lower explosive limit.

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IR FIBER OPTIC SPECTROSCOPY AND DETECTION Applications of fiber optic remote sensing and laser delivery in the mid-infrared are currently hindered by the inherent problems of producing highly IR-transparent optical fibers with good mechanical properties. A review of the research in IR materials development for optical fibers is beyond the scope of this review; however recent articles on the subject (F7-F9) may provide a starting point for obtaining current information on the subject. Pruss, Dreyer, and Koch (FIO,F11) d i m w the development work in the area of as-sensing devices based on mid-IR optical fibers with particdar emphasis on fluorozirconate materials. Application of an IR fiber made of As2S3glass to the remote analysis of hydrocarbon gases was performed by Saito et al. (F12)where a detection limit of 300 ppm for CHI was found using the 3.39-rm laser line. Saggese et al. investigated the application of fluoride glass fibers to the analysis of methane gas in nitrogen, alcohol concentration in water, and water concentration in 1,4-dioxane (F13). The flexibility and limitations of these applications are discussed. Several successful applications of fiber optic spectroscopy in the mid-IR were accomplished by mechmically stabilizing the fiber whose cladding had been stripped. The stripped portions were embedded in epoxy and the fiber was then used as both the ATR element and the li ht conduit. Two recent applications of this technique are iiscussed by Druy et al. (F14) and Young et al. (F15). Temperature measuring devices utilizing optical fibers operating in the near-IR and mid-IR are commercially available and citations to such applications should be found in engineering journals. A recent application of this technology is found in work by Amory et al. (F16) where the authors describe the measurement of the strand temperature in the spray chamber in continuous casting of steel.

(G) ON-LINE A general discussion of the use of on-line IR anal zers for analysis of process streams is given by Willrs (GI)an8McIvor (G2). Another paper by Wilks (G3)reports the development of a cylindrical internal reflection cell that allows the measurement of IR spectra on aqueous process streams. A reaction analysis s stem develo ed to monitor chemical reactions ww developedrby usin d - I R technology and reported by Rein (G4). Niemela (G8reported the development of an industrial process analyzer that incorporated the use of a four-channel Pb-salt detector to replace the traditional tilting filter wheel construction.


The analysis of fausti): steams by neqIR-methods is compared mth flow injection analysis and titration methods in a paper by Watson and Baughman (G6). Kunikawa et al. report the use of near-IR spectroscopy to monitor the continuous sulfation of organic hydroxy compounds (G7). The analysis of moisture content of many products and raw materials is very important in many industries and is widely applied. Recent measurements using IR detection schemes are discussed by Brown (G8), Van den Hauten (G9), and Hanebeck et al. (G10). IR detection methods are also widely applied to the determination of film thickness. Recent applications include the determination of polymer film thickness by Bang ( C l l ) , the measurement of coating thickness by Fukui (G12), and the measurement of thin organic films on metallic sheets by Sturm (G13). In a study reported by Izcue and Krafft (G14) IR spectroscopy was used to monitor relative concentrations of reactants and products in the manufacture of lubricating eases. The in-line measurement of COz in beer roduction IR measurements is discussed by Wilks (C15). &e process and a paratus for the control of aerobic fermentation using cytoc rome IR absorption was described in a patent application by Hess (G16). Remote measurement of gases by IR s ectroscopy has been widely investigated for atmospheric anfindustrial gas monitoring. Recent applications were reported by Dhyse et al. (G17) and Hawley et al. (G18). A new solid-state acoustmptic tunable filter anal zer operating in the IR for simultaneous analysis of CO, Cd., SOz, NO, NOz was reported by Nelson (G19).

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(H) FAR-IR SPECTROSCOPY By use of a simple model, the wavelength de endence on the far-IR of the extinction of crystalline ancfamorphous carbon grains was investigated theoretically and experimentally by Wirisch (HI). Far-IR s ectroscopy was employed by W ner, Seelewind, and Koidp (H2) to study the residual s d o w acceptors in as-grownsemiinsulatinggallium arsenide. A theoretical study of the line shape and intensity of far-IR bands in liauid carbon tetrachloride was reported bv Joslin and Gray 013). In an application of far-IR spectroscopy to biochemistry, Wittlin et al. (H4) studied the far-IR spectroscopy of oriented films of dry and hydrated DNA. Single crystal Raman and far-IR spectra of N-M-Uracil were measured by Columbo, Kirin. and Schrader to determine the hvdroaen bond force constkts from the lattice mode calculbioG (H5). Using eigenvectors from a dynamical model refined to include the latest neutron scatterin data the far-IR absorption of the 0 form of pol (dA)-poly$dT) was calculated by Young and Prohofsky ($6). These neutron data have allowed refinement of the model to account for long range nonbonded interactions in DNA. The reaction rates of m oglobin at low temperatures were enhanced with irradiation a far-IR laser at 50.5 cm-' in studies reported by Austin et al. (Ha.The authors found that simple solvent heating could not account for the observed changes.

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(I) BIOCHEMICAL APPLICATIONS A tremendous amount of work has been published regarding the application of infrared spectroscopy to investigation of biological systems. The area has been well researched and re orted by several reviewers. The various features of the viEratiod sy.ctrum used to characterize DNA structure were reviewed by suboi et al. (11).The use of vibrational circular dichroism and its role in characterizing biopolymers was detailed b Keider!ing et al. (12). Mantsch and Casal(13) explored d e use of h a r e d s ometry to study structure and quantitation of proteins, p"t.' ipids, carbohydrates, and nucleic acids. Infrared studies of conformational analysis and conformational transitions of DNA were reviewed by Taillandier et al. (14). Temperature-dependent conformational changes in membrane proteins were reviewed by Muga et al. (15). Vibrational spectrosco ic studies of enzyme structure and function were c a ~ o g u ebyl Wharton (16). The use of infrared linear dichroism and X-ray diffraction to study DNA conformation was detailed by Pohle et al. (17). The role of resolution-enhancedIR spectra in determining protein secondary structure was reviewed by Surewicz and Mantsch (18).

Resolution enhancement in biolo ical infrared spectrometry was explored by Mantsch et al. b9). Applications and specialized techniques, such as ATR, vibrational circular dichroism and infrared microspedroscopy to biological systems were reviewed by Dluh and Mendelsohn (110). Studies of biomembranes and modermembranes were reported by Lee and Chapman ( I l l ) ,Braiman and Rothschild (112), and Chapman et al. (113). Second-derivative spectroscopy and its application to biomembranes was discussed by Lee and Chapman (114). The bulk of the literature in the field of biochemistry refers to structural investigations of lipids and proteins. The structure of phosphatidylethanolamine was studied by Sen et al. (115). In situ FTIR studies of Langmuir-Blod ett monolayers were performed by Mitchell and Dluhy (116). "he use of phospholipids as biomarkers for sulfate-reducin bacteria was studied by Dowling, Nichols, and White (117). b?ng and Huang (118) observed the effect of pressure on the infrared spectra of phosphatidylcholine in deuterium oxide, while Wong and Mantsch studied the effect of ressure on the spectrum of dioleoyl phosphatidylcholine (fig). Interactions between ascorbyl palmitate and phospholipids were characterized by Koehler, Mantsch, and Casal(120). The main phase transition in phosphatidylcholine/ water was investigated by Mellier and Abdallah (121). Wong and Mantsch (122) examined water binding sites in phospholipids under high ressure. Conformations of lipids and proteins were studied By Carmona, Ramos, and DeCozar (123, 124). Interactions between melittin and lipids were investigated by Akyoz and Severcan (125). Phase transitions of phospholipids were studied by Mitchell and Dluhy (126). The interaction of doxorubicin with phospholipids was investi ated by Giuliani et al. (127). Casal et al. characterized the dermal phase behavior of phosphatidylserine with lithium and calcium (128-130). McClure et al. developed a quantitative procedure to determine lipids in blood serum (131). An IR detector to detect lipids in HPLC was demonstrated by Hamilton et al. (132). Interactions between lipids and acids were studied by Casal et al. (133).Siminovitch et al. measured spectra of ether- and ester-linked phos hatidylcholine at high pressure (134). Thermotro ic phase Behavior in phosphatidylcholines was studied by bantsch et al. (135). The IR and UV spectra of various lipids were measured by Ahmed et al. (136). Interactions of water and carbohydrates with phospholipids were observed by Crowe and Crowe (137). Anderle studied lipid-protein interactions in membrane systems (138). Ondarroa and Quinn investigated the interactions of phos hatidylcholine and ubiquinone-10 (139,140). Conformatiodactivities of lipid-A were discussed in a revlew article by Labischinski et al. (141). Myelin membranes were studied by Ramos et al. (142). Interactions between membranes and surfactants were investigated by Valpuesta et al. (143). Small molecule incorporation in phospholipid membranes was studied by Hadzi and Kidric (144). Structure and dynamics of lipid model membranes were reviewed by Blume et al. (145). Lipid rotein interactions in pulmonary surfactant were monitorec& y Reilly et al. (146). Areas et al. studied the conformation of phospholipases (147). Cis and trans unsaturation in phospholipid bilayers was studied at high pressure by Siminovitch et al. (148). Brumfeld et al. (149) used fluorescent labeling to study IR spectra of proteins. The interaction of transition-metal ions with purine bases was studied by Adam et al. (150). The extent of base pairing and base stacking in RNA was estimated by Fabian et al. (151). Crisma et al. (152) characterized the structures of long, chiral pol eptide 310-helixes. Infrared spectrmpy was used to d e s c r x protein dynamics by Bialek and Goldstein (153). Nabedryk et al. characterized protein secondary structures in purple membrane (154). Cytochrome c oxidase was studied by Grahn et al. (155). Conformationalstudies of bacterial cell wall analogues were performed by Labischinski et al. (156). Protein conformation and dynamics of membranes were discussed by Chapman and Haris (157,158) and Chapman et al. (159). Crystalline phase transitions in micellar calcium phosphate preparations were investigated by Nelson et al. (160). Interactions between carbohydrates and dried roteins were investigated by Carpenter and Crowe (161). 8usi and Byler reviewed the use of infrared spectroscopy to study protein conformation (162). Cluster analysis was used to examine protein infrared spectra ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990

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by Chittur et al. (163). DNA and RNA conformational transitions at low tem ratures were studied by Tajmir-Riahi and Theophanides Casal et aL (165)examined low-tem rature conformational Banb)eassignmentsfor the IR

(a).

phases of phosphocholines were studied by Dluhy et al. (168). The effect of ionic environment on DNA structures was investigated b Keller and Hartman (169). A procedure for the synthesis oTa new Edman-type reagent and its characterization was reported by Jin et al. (170). The amide I bandwidth of albumin and its relationship to bound water was investigated by Jakobsen et al. (171). The structure of gramicidin was assigned by Naik and Krimm (172). Walters et al. (173) studied the nature of amide ligation to the metal sites of iron-molybdenum cofactor. Conformational enalyais of the A, B, C, and D forms of DNA was made by Premilat and Albiser (174). Secondary structures of proteins in properdin were studied by Perkins et al. (175). Cytochrome P was characterizedby Schappacher et al. (1%). Bolbukh et al7177) investigated hydration of double-helical olynucleotide films. Oriented second structure in mem!ran, proteins was studied by Bazzi 3 W o o d y (178). Hydration roperties of ten proteins were determined by Poole and Barrow (179). Interaction of tocopherol with phospholipids was investigated by Villalain et al. (180). Letellier et al. (181) used normal coordinate analysis to predict the vibrational spectra of guanosine and c idine residues. Bandekar and Krimm (182)calculated n o d m o d e s for x-turn structures. Quantitative subtraction of water from aqueous protein solutions was discussed by Dousseau et al. (183). Oriented films of the A and B forms of DNA were studied by Flemming et al. (184). The stereochemistry of proton exchange in acetoin was investigated b Drake et al. (185). Pande et al. (186) studied the infrareispectrum of rabbit liver metallothioein. A harmonics dynamics calculation was used by Ghomi et al. (187) to investigate the structure of DNA. Theoretical studies of a pe tide crystal were compared to s ectral data by Kitson anSHagler (188). Studies of the con ormers of gl coaldehyde in low temperature matrixes were performed %y Aspiala et al. (189). Protein-surface interactions were studied by Houska et al. (190). Interactions between DNA and histone were monitored b Yuan et al. (191). Synthesis and characterization of three ofigonucleotides were performed by Adam et al. (192). Smulevich et al. (193) investigated spectra of cytochrome c peroxidase-carbon monoxide adducts. Metastable and stable forms of hydrated cerebroside bilayers were studied by Lee et al. (194). Interactions between Ni2+and polynucleotides were studied by Bourtayre et al. (195). Thermal properties and spectra of water in myoglobin crystals of subzero temperatures were obtained by Doster et al. (196). Fedoreev et al. (197) identified the structure of dibromoisophakelin from marine sponges. The effect of Cs+ on protein secondary structure was determined by Adam et al. (198). Conformational studies of solutions of chemotactic pe tides were performed by Valensin et al. (199). Trudelle et a! examined the conformations of linear gramicidins (1100). Self-deconvolution and difference spectroscopy were used to study thermally induced conformational changes in ribonuclease A by Yamamoto and Tasumi (1101). The structure of diphtheria toxin was studied by Cabiaux et al. (1102). Kirsch and Koenig (1103) investigated secondary structures in proteins at variable temperatures. Bertoluzza et al. (1104) investigated the structure of elastin. Tyrosinase activity was monitored by Sugumaran et al. (1105). Glassy behavior in proteins was investigated by Iben et al. (1106). The influence of protein adsorption on substrate surface free ene was described b Schakenraad et al. (1107). The structure a p h o s t a t i n was Jetermined by Kojiri et al.

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The structure of nitrimyoglobin was characterized by Bondoc and Timkovich (1109). Mechanisms of interactions between salivary proteins and hydroxyapatite were studied by Embery et al. (1110). The secondary structure of 8-galactosidase was determined by Arrondo et al. (1111). Photoisomerization of all-trans-retinal was analyzed by Baron et al. (1112). The effect of DMSO on the spectral properties of 230R


melanin was studied by Cooper et al. (1112). Valensin et al. (1114) investigated biologically active peptides in solution. Structures of hydrated poly(dG-dC) were determined by Keller and Hartman (1115). Properties of photoactive nucleotides were studied by Evans and Hale (1116). Proton transfer in histidine-phosphate hydrogen gonds was investigated by Burget and Zundel (1117). Conformations of nucleotides at high humidities and in solution were studied by Taillandier et al. (1118). Interaction between Ni2+and adenine in DNA was observed by Liquier and Taillandier (1119). Pohle and Flemming (1120) studied interactions between adriamycin and daunom cin and DNA. Interactions of the histadine residue in Pro-his dipeptides were investi ated by Boussard et al. (1121). The0 hanides and Tajmir-kiahi (1122) studied the structure and tfynamics of metals as they interact with nucleic acids. The relationship between protein hydration and conformation in lysozyme, lactalbumin, and crystallin was studied by Poole et al. (1123). Gow et al. (1124) used IR and X-ray diffraction to probe structures of chitins. Carbon dioxide evolved during growth was used to profile microorganisms in a study by Perks et al. (1125).

The isolation and structural characterization of the photoadducts of 5,7-dimethoxycoumarin and adenosine were described by Cho et al. (1126). The membrane structure of bombesin was characterized by Erne and Schwyzer (1127). Low-temperature matrix isolation was used by Blagoi et al. (1128) to obtain spectra of nucleic acid bases, their deutero and Me derivatives, and some amino acids. Letellier et al. used valence force field calculations to predict vibrational modes for adenine and guanine (1129)and uracil and cytosine (1130). After exposure of plant plasma membranes to 2,4-D growth hormone analogue, Morre et al. (1131)used IR to reveal changes in membrane conformation. Erne at al. (1132) characterized the membrane structure of the neuropeptide substance P. Conformational behavior of N-acetyl(glycine, L-alanine, L-leucine)-”-methylamides in chloroform was measured by Jose et al. (1133). Characterization of mixedligand Pt2+complexes of 2,2’-bipyridine and amino acids was performed by Jain et al. (1134). Spectral studies revealing &pleated sheet conformations in eggshell proteins of the fish S. gairdneri were performed by Hamodrakas et al. (1135). Liquier et al. (1136) studied the induction of the 2 conformation in DNA. High-pressure IR spectra of live bacteria were measured for the first time by Wong et al. (1137) as part of studies of human roinsulin gene expression in E. coli. Wong (1138) investigatetf the structural and dynamic properties of biomembranes at high pressure. Naumann et al. (1139) analyzed m-sequential bacterial cell wall pe tides. The interaction of poly(2-amino-8-methyldeoxyacfenylic acid) with pyrimidine nucleotides was studied by Kanaya et al. (1140). Analyses of alkylated DNA purine bases used to determine DNA alkylation rates in mammalian embryonic tissue were performed by Platzek et al. (1141). Conformational properties of atriopeptin I11 were investigated by Surewicz et al. (1142). The thermal behavior of a dihydrate guanosine film was studied by Bertoluzza et al. (1143). Reactions of cis-Pt(ino)zClzwith various amino acids in methanolic solutions were investigated by Garoufis et al. (1144). Acetylcholine receptor structure and its role in of cations through syna tic membranes was studiec!bTF Konski et al. (1145). fhree pseudopolymorphic forms of testosterone were characterized by Fletton et al. (1146). Semenov et al. (1147) analyzed the secondary structure of transfer RNA. Solution and membrane structures of enkephalins were studied by Surewicz et al. (1148). The tetramethylammonium salt of guanylyl(3’-5’)guanosine was characterized by Toth et al. (1149). Proton polarizability as a function of cations resent in glutamic acid-dihydrogen phosphate hydrogen L n d e d networks was measured by Burget and Zundel (1150). Spectroscopic evidence for solvent accessibility to peptide NH groups of dynorphin A(1-13) was obtained by Renugopalakrishnan et al. (1151). Spectroscopic evidence to determine the structure of valilactone produced by actinomycetes are reaented by Kitahara et al. (1152). The solution structure of g e ATP-bindin peptide of adenylate kinase was characterized by Fry et a f (1153). Concanavalin A in solution was characterized by Arrondo et al. (1154). The influence ofwater on the spectrum of a liposoluble magnesium porphyrin was


investigated by Chapados et al. (1155). Melanin-iron comlexes and melanoproteins were studied by Bilinska et al. 1156,1157). The antisymmetric stretching vibration of the PO - groups in DNA and ita chan es on hydration were stuiied by Pohle and Bohl(1158). dutant strains of bakers' yeast cytochrome c peroxidase were studied by Smulevich et al. (1159). Evidence for two nonequivalently bound cyanides in half-methemocyanin cyanide was obtained by Pavlovsky and Larrabee (1160). Keller (1161)used infrared spectroscopy to study structural and conformational chan ea of DNA and DNA complexes. Secondary structure of bfack-eyed ea trypsin and chymotrypsin inhibitor was investi ated gy Aragao and Ventura (1162).Muga et al. (1163)stuged the interaction of detergent with &galactosidase. The infrared spectrum of one cell was obtained by using infrared microspectroscopy. Dong et al. (1164)characterized the protein structure of a single erythrocyte and were able to detect differences among individual red blood cells. Conformational isomers of sodium d(m5CG-T-A-m5C-G)at various hydrations were characterized by Taillandier et al. (1165).The secondary structure of Neurospora crassa cell membrane was characterized by Goormaghtigh et al. (1166).Metal ion interactions with a glutamate-containing tetrapeptide were studied by Zineddine et al. (1167). Holloway et al. (1168)used the side chain carboxyl group in the glutamate residues of cytochrome b5 and cytochrome c to study interactions between these two proteins. The orientation of CO and the relationship between spectra and structural/functional parameters in carbonmonoxmyoglobin were studied by Ormos et al. (1169).Substituent effects in benzenesulfonamide inhibitors of carbonic anhydrase were investigated by DeBenedetti et al. (I170). DeNiro and Weiner (1171)characterized collagen in prehistoric bones by using infrared spectroscopy. The temperature dependence on the IR s ctra of various proteins in aqueous solution was studied b Y asumi P and Yamamoto (1172).The influence of water on the infrared spectra of mucin was studied in vitro by Liu et al. (1173). Solubilization of sarco lasmic reticulum by a nonionic detergent was investigatediy Arrondo et al. (1174). Tselepi-Kalouli and Katsaros characterized complexes of Ru3+with nucleic acid bases and nucleosides (1175). Structures of a ar extracted from Chinese red seaweeds were determined l y Ji et al. (1176).The effect of pH and tem rature on the structure of @Aoglobulin B was investigated Casal et al. (1177). Infrared s ectra of bacteriochlorophylra and b cations and bacterio &tin a and b anions were obtained by Maentele et al. (11787,Metabolites of 1,8cineole in rabbits were characterized by Miyazawa et al. (1179). Short DNA duplexes containing a no-base residue were studied by Adam et al. (1180). Zundel(1181)proposed mechanisms for roton transfer and olarizabilit of hydro en bonds in bior)ogical systems. The knding m e c L m of jycophos hate adsorbed onto clay was studied by McConnell and d!ossner (1182). Structures of 3,5-dimethoxy-p-hydroxyphenylproane comounds were established by Khan et al. (1183).Easa1 et al. r.184) measyred the spectra of several globular proteins at low temperatures. The secondary structure of 11S globulin in aqueous solution was studied by Dev et al. (1185). The gel to liquid crystal phase transition in intact cells was com ared to that for isolated membranes of Acholeplasma laidawii by Mantsch et al. (1186).Spectral differences in the uridine residues in rat liver RNA indicated the presence of U.U mispairs in a study by Fabian et al. (1187). The binding and photodissociation of CO in cytochrome b from the bacterium Thermus therrnophilus was studied by%narsdottir et al. (Z188). Letellier et al. (1189)calculated the vibrational modes for the phosphate-background contributions to the vibrational spectrum of an infiiite helicoidal polymeric chain. Cabiaux et al. (Z190)studied the secondary structure of diphtheria toxin in the presence of phospholipid vesicles. The chromatographic and spectroscopic pro erties of hemiacetals of aflatoxin and steri atocystin metatolites were investigated by Orti et al. ( 1 1 9 1 ~ T hrole e of C19+ derivatives in lucose metabolism was explored by Govindaraju et al. (11927. The effect of hydrocarbon chain unsaturation on the interaction of magnesium with phos hatidylserines was studied b Casal, Mantsch, and Hauser 8193). Hydration in hos piolipids was measured by Mellier (1194). PetersReim

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Blodnieks, and Halladay investigated the use of trivalent lanthanides to probe cation binding sites formed by membrane lipids (1195). Thermotropic phase behavior of phosphatidylcholines containing fatty acyl chains was studied by Mantsch et al. (1196). Wong, C a m , and Mantsch investigated hydrogen bonding between cholesterol and phosphatidylcholines (1197).Hydrogen bondin in phosphatidylserine was examined by Leberle, Kempf, and%undel(1198).Interactions between proteolipid apoprotein and various lipids were studied by Nedelec, Alfsen, and Lavialle (1199). The use of infrared spectroscopy to study conformation and protonation of bacteriorhodopsin was reviewed by Rothschild (1200,1201).The effect of acids on the infrared spectra of Schiff bases was used as a model for rotonation in rhodopsins in a study by Lussier et al. (1202),Eerwert et al. (1203),and Badilescu et aL (1204).Selective tyrosine nitration and isotopic labeling were used by Roepe et al. (1205,1206) to investigate carboxyl protonation changes in the bacteriorhodopsin photocycle. Tyrosine-185 protonates and deprotonates were studied by Braiman et al. (1207). Comparison of spectra at low and normal temperatures suggested a mechanism for tyrosine rotonation during the primar phototransition of bacterioriodopsin in an investigation i y Rothschild et al. (1208).Secondary structures of baderiorhodopsin and bovine rhodopsin in their native membranes were characterized by Downer et al. (1209).Bagley et al. (1210)compared s ectra of octopus and bovine rhodopsins and their bathorhdopsin intermediates. A mechanism for the transformation of light energy into proton transfers was proposed by Gerwert and Siebert (1211),based on an investigation of isomerization in bacteriorhodopsin. Protonation changes of aspartic acid residues and their role in light-driven proton transport were studied b Braiman et al. (1212). The low-temperature photoproc$ucta of rhodopsin were investigated by Bagley et al. (1213). Water-induced conformational changes in bacteriorhodopsin were studied by Varo and Eisenstein (1214). Evidence for light-induced lysine conformational chan es in the bacteriorhodopsin photocycle was presented by Mcdaster and Lewis (1215).Attenuated total reflection was used by Marrero and Rothschild (1216)to study conformational changes in bacteriorhodopsin and by Marrero (1217) to obtain infrared spectra of bacteriorhodopsin in different aqueous environments. The chemistry of hemoglobin and heme proteins was extensively investigated by infrared spectroscopy. Abe (1218) reviewed applications of normal coordinate analyses to the study of metalloporphyrins as model compounds for heme. Stephens (1219)reviewed the application of near-IR magnetic circular dichroism in the characterization of heme proteins. The application of this technique to study heme in cytochromes was reported by Simpkin et al. (1220). Moh et al. (1221)used infrared spectroscopy to study the conformational sensitivity of 0-93 cysteine sulfh dry1 to ligation of hemoglobin. Evidence for the presence of Jstorted FeCO units in heme proteins was presented by Li and Spiro (1222). Infrared spectra of pooled monomeric Hb carbonyl and the major component carbonyl in the monomeric Hb from Glycera dibranchiata were reported by DiFeo and Addison (1223).The effect of metal ions on the frequencies of dibound oxygen in model heme proteins was investigated by Nakamoto et al. (1224).Lactonization and inversion of vicinal diols in heme d-type chlorins were studied by Andersson et al. (1225). Oxy en binding in aqueous synthetic porphinatoiron was studief by Yuasa et al. (1226).Fe-CO stretch vibrations in synthetic iron-porphyrin complexes were measured by Tsuchida et al. (1227).Evidence for two liganded oxygen strucested in the oxygen IR spectra of oxyhemoglobin tures and oxymyog was obin obtained by Potter et al. (1228).Photolyzed carboxymyoglobin was characterized by Fiamingo and Alben (1229).Infrared spectra of sulfonated heparins were reported by Grant et al. (1230).Grant et al. (1231)suggested a model for two conformational forms of heparins/heparans. Heparin-cation complexes were investigated by Grant et al. (1232). A traditional application of infrared spectroscopy in the biochemical field is the characterization of kidney stones. Pinon et al. (1233)reported a simple method to determine the qualitative and quantitative composition of urinary calculi. Identification of uroliths in domestic animals by infrared spectroscopy was reported by Manning and Blaney (1234). Iatrogenic urinary calculi were characterized by Asper and

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Schmucki (1235).Oka et al. (1236)used IR spectrometry to estimate the calcium oxylate dihydrate to monohydrate ratio in kidney stones. The a plication of infrared s ectrosco y to biochemistry and meicine was reviewed by t a r i s a n i Chapman (1237). The role of uanidines in medicinal chemistry was reviewed by Greenhilf (1238).The use of near-IR to indicate oxy enation changes in cerebral tissue in vivo was demonstrate8 by Thorniley et al. (1239).The structure of the bacterial virus Pfl was investigated by Fritzsche et al. (1240). Four ichthyotoxins were isolated and characterized by Whitefleet-Smith et al. (1241).Skeletal muscle sarcoplasmic reticulum was studied by Borchman (1242).The role of hyaluronic acid and dermatan sulfate in aging human skin was investigated b Longas et al. (1243).Cairns et al. (1244)used in vivo near-& to assess brain metabolism in cats during periods of increased intracranial pressure. Five neurotoxic chemicals were synthesized and characterized by Nomeir and Abou-Donia (1245).Nuclei isolated from patients with chronic lymphatic leukemia were compared with those of a control group in a study by Benedetti et al. (1246,1247).Secondary structures of human claas I and class I1 histocompatability antigens were investiqated by Gorga et al. (1248).Van der Mei et al. (1249)obtained the infrared s ectra of oral streptococci. Melanins isolated from Haring-Passey mouse melanoma were characterized by GarciaBorron et al. (1250). The relationship of gramicidin channels to the mechanism of anesthesia was investigated by Buchet et al. (1251). Spectra of toxin from the venom of the sco ion Tityus serrulatus were presented b Areas et al. (1258. Pharmacological applications of inJared spectrosco y were reviewed by several authors. Applications of infraref; linear dichroism to DNA, DNA-drug complexes, and filamentous bacteriophages were discussed by Fritzsche et al. (1253)and Pohle and Raim (1254).Steroid biochemistry, as studied by spectro hotometry, was reviewed by Kochakian (1255). Butler et al. ( 256) reviewed the use of transition-metal carbonyl complexes as infrared markers for hormonal steroid activity. The identification of fentanyl derivatives was discussed by Cooper et al. (1257). Hydrogen bonding in halogen-containing solvents and the relationship to anesthetic potency was reviewed by Sandorfy et al. (1258). The use of transition-metal carbonyl clusters as markers for estradiol rece tor site detection was investigated by Jaouen et al. (1259f:Synthesis and characterization of organometallic estrogens were discussed by Vessieres et al. (1260). Toniolo et al. (1261)studied conformations of pe taibol antibiotics. The effect of procaine based drugs on erytEocyte membranes was studied by Stinga (1262).Several steroids were identified by Acuna-Johnson and Oehlschlager (1263).cis-Cinnamoylcocaine was characterized by By et al. (1264).S ectroscopic identification of nitromethaqualone was re rk$ by Clark (1265).Angel- and Meyers (1266)reported tR", identification of precursors and

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characterization of the analgesic system 3,3'-dit l,&thiazolidin-Cone] was described by Vigorita et al. (1268). In vitro investigations of antimicrobial activity of ternary complexes of Zn2+with &hydroxyquinoline and salycylic acids were conducted by Anjaneyulu et al. (1269). Characterization of structure of several cardiotonic ents and the role of structure on drug activity were discuss% by Moos et al. (1270). Binding of metal salts to the anticonvulsant drug val roate was investieated by Healy and Aslam (1271).A senes opdrugs used to inhibit microtubular polymerization was characterized by Bouchaour et al. (1272). Hi h-pressure infrared spectroscopy was used to study the ekect of the local anesthetic tetracaine on li id membranes by Auger et al. (1273).The relationship of Eydrogen bonding in halocarbon anesthetics to anesthetic potency was discussed by Buchet and Sandorfy (1274).

(J) QUALITATIVE APPLICATIONS Bowen et al. have studied the sample preparation methods for IR analysis of organophosphonate on clay mineral substrates (&). Khorami and Lemieux have analyzed attapulgites from different sources using IR and TGlDTG (J2).Hurst et al. have used IR to identify the chemical composition of 232R


urinary calculi obtained from laboratory animals (J3). Davidson et al. have measured the IR spectrum of ClONO at 295 and 233 K and stated that the spectrum can be used to determine stratospheric C10N02 concentrations (J4). Zander and Demoulin have used IR to detect CIONOl in the stratosphere (J5). Xia has identified a white mass for the metal-to-metal bonding of the gap between the axel pin and sleeve of a (J6). Paterson has Chinese Q in chariot as Ca5(P0 described IR experiments for t i e identification of some minerals (J7).Nandagopal et al. have recorded IR s ectra of pigments used in automobile paints and suggest tfat IR can be used to identify these materials in forensic cases (J8). Belton et al. have discussed the otential for using IR s ectroscopy for the analysis of con ectionery products (J97. Zieba utilized IR to study the rate of oil degradation during automobile usage (JIO),and for the differentiation of lubricatin oil stains on textiles (JI1). Mosini and Cesaro studied the Ik spectrum of aged P. halepensis resin and stated the data indicate the presence of a methylene oup in a terminal position, and this is characteristic of B a g c amber (J12). T e d IR to help identify two unusual pipe bomb fillers (J13) ans et al. utilized IR to identify an unusual explosive, triacetone triperoxide (J14).Sheina et al. used low-temperature IR to prove the existence of keto-enol tautomerism of purine bases in an Ar matrix (J15). Srinivasan et al. used IR for the examination of 18 petroleum products collected from different locations and showed differences in absorption of some typical absorption bands (J16). Belton and Sullivan utilized IR and LC to characterize epoxy cresol novolac-phenol formaldehyde novolac-tertiary amine resin systems (J17).Standt used extraction,preparative high-performance LC, and IR to characterize low-molecular-weight compounds of dashboard plastic foils in automobiles (J18).

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(K) ENVIRONMENTAL ANALYSIS A number of applications of IR in determining or monitoring air pollutants are the direct result of either the development of new instrumentation or modification of existing instruments. Because of this, the section on environmental will include both instrument development and applications. Nelson (KI)reports that an acoustooptic tunable filter built with T1 Assea gives a tuned IR source that can be directed across t i e stack of any combustion rocess to simultaneously NO, NO2,CHI, C2%, measure the concentration of CO, and water. Janatuinen and Byckling (K2)also report using IR for continuous measurement of stack gas concentrations. Draghi et al. (K3)stated that CH in air can be determined by using an IR spectrometer, a ddYag laser, a Li NbOs parametric oscillator, a receivi telescope, and an electronic system. Walker and Phillips 3 4 ) studied the feasibility of using a high-resolution diode laser spectroscopy to measure CHI in turbine engine exhausts. The range of path lengths and concentrations over which the technique is feasible was established. Bierman et al. (K5)determined nitrogen s ecies in urban ambient air using long path length IR and &-vis multiple reflection optical systems. Saperstein et al. (K6)used IR to measure low concentrations of aromatic hydrocarbons removed from air by activated carbon. Cueto et al. (K7)used a continuous flow gas cell to monitor NO and NO2 concentrations in cigarette smoke with time. Kogelschaatz and Baessler (KB)determined nitro en oxide in the output of air-fed Osgenerators. Groves a n f Ellwood (K9)determined respirable quartz in air free of minerals that interfere in the IR. Pickard et al. (K10)compared X-ray diffraction and IR as a means of determining quartz in air and concluded IR is less costly but less specific than X-ray diffraction. Zahniser et al. (K11)describe an open path IR absorption instrument for eddy correlation measurements of fluxes of trace atmos heric asea which impact on the greenhouseeffect. McRae et (K127developed a remotely operable four-band differential IR absorption mstrument to measure HCl vapors from rocket launches. Bishop et al. (K13)develo ed a long-path IR photometry instrument that measures C8/CO ratio in the exhaust from an automobile passing down a singfe-lane highway. Stedman

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(KI4)used remote IR s ectrometry to monitor CO emissions by individual automobfes. Cha et al. (KI5,KI6) developed and used a gas-filter correlation spectrometer to measure MeOH concentrations from methanol-fueled vehicles. McClenny et al. (KI 7) used transmission spectroscopy to determine NH4+and SO 2- in ambient aerosol particles collected on Teflon filters. Smith et d. (KI8)studied the effect of solar radiation and various particulates on the oxidation of sop Liberatori et al. (KI9)determined the concentrations of organic and inorganic thiocyanates in aqueous solution. Organic thiocyanates require an extraction with CC14,while inorganic thiocyanates are derivatized with Me2S04and determined as methylthiocyanates. Shakar et al. (K20)determined D in water using gas-phase IR spectrophotometr . Response was linear with concentration from natural agundance (150 ppm) to 11.8atm % D. Morra et al. (K21)used cylindrical internal reflectance to analyze Aldrich humic acid in water. Ah0 et al. (K22) studied the yrolysis of peat by therm avimetry and FT-IR. Spectra of c am were recorded usin YBr pellets, DRIFT, and PAS. COP,CO, NO, NO2, and hyfrocarbons were measured in the p 01 is gases using IR spectrometry. Majid and Ripmeester (G3Yused IR, elemental analysis, proton, and 13CNMR to characterize unextractable or anic matter associated with heavy minerals from oil sand. benesi et al. (K24) studied the interaction mechanisms between humic acids of different and nature and electron donor herbicides us? IR,WR, ~ ~ ~ l e m e nanalysis. tal Calvert et al. (K25)use both pyrolpis-GC/IR/FID and pyrolysis-GC/MS/FID in an attempt to correlate particle size fractions to chemical composition. The fates in individual compounds and classes of compounds were also determined. Piccolo et al. (K26)recorded the spectra of humic substances extracted with dipolar aprotic solvents and found that DMSO and acetone extracts were particularly rich in aliphatics and proteinaceous components. Singhal and Soni (K27) examined soil humic acids from Garhwal Himalayas and identified functional and atomic groups. Fruend et al. (K28)used IR and '9c NMR to determine structural differences between humic fractions from different soil types. Chandler et al. (K29)studied the water-soluble organics extracted from under beech and spruce trees in NE Baveria. Gupta et al. (K30)studied humic acids in municipal wastes during four stages of composting. Yang and Lui (K31) studied the infrared s ectra of agar-agar extracted from Gracilaria cultivated in baiwan. Durig et al. (K32) investigated the chemical variability of woody peats from Indonesia and Macharacterized humic and fulvic laysia. Roletto and Luda (K33) acids extracted from poplar bark after 12 and 30 months of compostin Kim and:Shin (K34)studied the characteristics of humic acids extracted from decom osing plant residues. Zech et al. (K35)used 13CNMR and Ik to study spruce and ine litter at two different sta es of decomposition. Hempiing et al. (K36)used chemic3 degradation, IR, NMR, and yrolysis field ionization mass spectrometry to study litter ecomposition and humification in acidic forest soils. Senesi et al. (K37)investigated the role of humic substances in the environmental chemistry of chlorinated phenoxyused IR and ESR alkanoic acids and esters. Senesi et al. (K38) to study Cu2+ and Fe3+ complexation by soil humic acids. Adhikari et al. (K39)obtained IR spectra of humic substances synthesized under different conditions in the laboratory. Perkins and Ridge (K40)used infrared s ectroscop in permeation tests for selecting protective clot ing and g ove material.

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(L) COAL ANALYSIS Infrared spectroscopy continues to be a valuable tool in the characterization of coal and charcoal. Development and improvement of techniques to analyze surface layers of coal were reported by McClelland (LI). Data reduction methods to characterize humic substances in coal were described by Ibarra (L2). Philip and Anthony (L3) analyzed the nondistillable portion of coal liquids by size exclusion chromato raphy/ Fourier transform IR spectrometry. Diffuse reffectance Fourier transform IR spectrometry was used by Wood (L4) to characterize charcoals and by Pakdel et al. (L5)to identify solid residues from wood vacuum pyrolysis.

(M) FOOD SCIENCE The use of both mid- and near-infrared spectroscopy to characterize foods and agricultural products was extensively reported in the literature. Wilson et al. (MI) reviewed the use of infrared spectroscopy in the study of food biopolymers, with emphasis on phase transitions of starches. The vibrational spectroscopy of carbohydrates was discussed b Mathlouthi and Koenig (M2). Applications of on-line near-d methods were evaluated by Davies and Grant (M3). A review of vibrational spectroscopy of chlorophylls was presented by Tasumi and Fujiwara (M4). Qualitative and quantitative analysis of milk usin infrared spectroscopy was reviewed by Barbano and Clark &M5)and by Biggs et al. (M6). Conformational studies of casein and other food proteins were discussed by Byler and Susi (M7). Analysis by infrared spectroscopy is an important tool in the dairy industry. Calcium ion interaction with the carboxylate groups of casein was studied by Byler and Farrell (M8). The effect of heat on ice cream constituents was investigated by Bhanderi et al. (M9). Quantitative methods to determine casein content of milk were described by Karman et al. (MIO), Van de Voort et al. ( M I I ) ,and Sjaunja and Andersson (MI2). Differences in the mechanisms of photosynthesis in various plants were monitored with IR spectroscopy by Daley et al. (MI3). Spectra of chlorophyll in its various forms were characterized by Chapados ( M I 4 ) . Daley and Jahn (MI5) studied photosynthesis and chloro hyll content in leaves of clones of Frageria. Photochemic$products obtained from jasmone were analyzed by Tateba and Mihari (MI6). Residues of beet root pulp after partial digestion in the rumens of fistulated goats were analyzed by Robert et al. (MI7). Rapeseed glucosinolates were analyzed with near-IR reflectance in a study b Biston et al. (M18).Wheat straw lignin was isolated a n B characterized by Jung and HimButa and Galletti (M20) investigated the melsbach (MI9). lignin components in eight lignocellulosic byproducts.

(N) POLYMERS Infrared spectroscopy is often the technique of choice for the analysis of a wide variety of polymeric materials. Pyrolysis-IR spectroscopy was used by Brueck (NI) to determine com osition of an EPDM/nitrile rubber/carbon black tire treaimaterial. Microstructure of hydrogenated nitrile rubber was investigated using IR, NMR, and pyrolysis gas chromatography in a study by Kondo et al. (N2). Changes in the infrared s ectrum of natural rubber after modification by zinc oxide anfzinc sulfide were monitored by Kronstein (N3). Orientation in high cis-1,4-polybutadiene using infrared dichroism was investigated by Amram et al. (N4). Janssen et al. (N5)characterized ABA block copolymers of styrene and y-benzyl-bglutamate. Orientation in uniaxially stretched poly (2,6-dimeth 1-1,Cphenylene oxide)-atactic polystyrene blends was s t u i e d by Bouton et al. (N6). Orientation-relaxation in 6-armpolystyrene stars was measured by Lantman et al. (N7). The development of a gel permeation chromatography/ FT-IR system and its application to measurement of short chain branching in linear low-density polyethylene was demeasured scribed by Housaki et al. (N8). Batra et al. (N9) infrared spectra of polypropylene sheets from six different manufacturers. Differences in the spectra due to the additive packages used by the manufacturers were used for forensic characterization of these materials. Infrared spectroscopy, combined with microscopy and X-ray techniques, was used to identify and characterizemodified ac lic fibers from eight different manufacturers in a study by Zrieve and Cabiness (NIO). Bond rearran ement during the gelation, setting, and hardening of zinc pogyacrylate cement was investigated by Nicholson et al. (NII).Hydrogen bonding in polybenzimidazole/ polyimide systems using low molecular wei ht model compounds was studied by Musto et al. (NI2). $he characterization of epoxy lues and hardeners was discussed by Allen and Sanderson (5713).

(0)ATTENUATED TOTAL REFLECTANCE DeBlase has designed a nanosampling internal reflection prism which acts as a waveguide optical funnel. The device ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990

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is particularly suited to the study of contaminants, aqueous Von Maltzan and microdrops, and inorganic powders (01). Naumann have developed a new multisample ATR-accessory for the analysis of very similar complex biological material (02). Sellitti et al. have characterized the functional oups arising from oxidation of pitch-based graphitized c a r g n fibers by ATR (03). Diacikova and Durcova have employed ATR IR s ectroscopy and electron microscopy techniques to con irm e!t existence of a skin-core structure in polypropylene fibers containin a high-molecular-wei ht modifying agent (04). Mirabefla et al. employed A!I’R/IR spectroscopy and wide-angle X-ray diffraction to determine the macromolecular orientation of a series of six uniaxially oriented polypropylene sheets (05). Scheuing utilized a cylindrical internal reflection element (IRE) as a support for a hydrocarbon-aqueous nonionic surfactant interface. Time-resolved FT-IR spectra of the interface during the removal of the hydrocarbon from the IRE surface by the detergency action of the flowing surfactant solutions were recorded (06). Schernau investigated the defects in an acrylic glaze coat damaged by contact with gasketing material by ATR/IR Lotta et al. characterized the organization spectroscopy (07). of several Langmuir-Blodgett assemblies with ATR/IR spectroscopy (08). Ishitani et al. studied oxygen-implanted pol ethylene by various analytical techniques including A T ~ / I Rspectroscopy. The ATR measurements indicate generation of various functional groups like hydroxy, carbonyl, and carboxyl groups in a depth distribution similar to that of the oxygen depth penetration into the polyethylene film

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(09).

Schoepflin et al. studied the mechanism of local anesthetic action with phospholipid model membranes by infrared ATR/IR spectroscopy. IR spectra revealed unambi uously that all the local anesthetics investigated tend to atsorb in multilayers to the membrane already at pharmacological relevant concentrations (010). Brandenburg and Seydel studied the orientation behavior of hydrated membrane systems made from lipopol saccharide and its lipid component, free lipid A, using F4-IR spectroscopy (011). Goormaghtigh et al. studied the adriamycin-cardiolipin complex structure using ATR/IR spectroscop (012). Keto describes an improved proce&re for the separation and identification of the major components of the military plastic explosive compound (2-4. Analysis is by ATR/IR spectrosco y (013).Iordanov and Schrader describe an attempt to o tain circular dichroic IR spectra using a conventional attenuated total reflectance attachment. A theoretical treatment is resented (014). Ozaki et a f recorded in situ the infrared spectra for an albino rabbit lens capsule. Direct evidence for the existence of collagen helix structure in the lens capsule was detected (015). Ozaki and Kaneuchi also em loyed ATR/IR spectroscopy to examine whole rat stomac , liver, and ancreas. These studies suggest that ATR spectrosco y couldge useful in clinical examinations and for studies of tEe internal organs (016). Quintard-Dorques et al. studied the conformation of bio1 ical molecules and the reactions between them in aqueous sgution (017,018). Badilescu and Sandorfy examined the hydration of gramicidin incorporated in lipid bilayers. The dependence of the stability of the system on the water environment of the olypeptide moiety and of the structural water of the lipid gilayer is discussed (019). Fringeli et al. examined the surfacing and membrane-penetrating ability of vinculin and of bovine serum albumin on a molecular level by ATR/IR spectroscopy (020). Fink et al. employed ATR/IR s ectroscopy to quantify surface-adsorbed and bulk proteins (821).

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(P) PHOTOACOUSTIC AND PHOTOTHERMAL SPECTROSCOPY Sigrist et al. reviewed the literature on the applications of IR-laser photoacoustics to trace-gas monitoring as well as to spectroscopic studies on absorbing liquids (PI). Belton et al. have reviewed the literature on the principles of PAS/IR s ectroscopy and ita analytical application (PZ).Yang and have reviewed the literature on the basic parameters and instrumentation of FT-IRphotoacoustic spectroscopy and its applications to polymer studies (P3).Miller reviewed pho-

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toacoustic and photothermal techniques for IR spectroscopy P4).

Hurdelbrink utilized photoacoustic IR laser spectroscopy for analyzing trace gaseous contaminents. Concentration in the ppb scale and even molecular parameters such as the line intensity can be measured with great precision (P5).Ryan and Feldman employed an acoustico-optical tunable filter placed between an IR radiation source and a photoacoustic detector for the selective detection and measurement of gases. Concentrations in the parts-per-million range are measured in a few seconds (P6). Urban and Koenig studied the effect of v temperature on the photoacoustic spectra of silicon d i o x m . Bertrand illustrated the advantages of phase analysis in FT-IR photoacoustic spectroscopy which include the correction of saturation effects, sample dilution, and optical scattering, even in heterogeneous samples, to give absorption coefficient real values (P8).Michaelian examined interfero am symmetrization and multiplicative phase correction offrapid-scan and step-scan photoacoustic FT-IR data and found that the two phase correction methods are generally in agreement, provided that a sufficient amount of information is used in either calculation (P9). Carter and Peck examine the experimental requirements to obtain photoacoustic s ectra from low-surface-areasolid samples. They concludetfthat cell volume, the background material, the interferometer mirror velocity, and the cell gas compression must be controlled (P10).Hauser and Oelichmann com ared solid sampling techniques (KBr pellet, ATR, DR& ,and PAS)in order to make roper use of their mutual advantages (P11).b u s h and Oelichann discuss the various types of analysis (sample identification,quantitation, and depth profiling) that can be reformed on industrial samples by usin a photoacoustic Ietector (P12). Gaboury and &ban found that PAS/FT-IR was an effective calorimetric method for monitoring radical cross-linking of unsaturated polyester resins with styrene (P13).PAS/ FT-IR measurements showed no sensitivity for monitoring cross-link formation of hydroxy-terminated dimethylsiloxane with tetraethoxysilane; however, the spectral changes could be correlated with viscosity change data (P14).Salazar-Rojas and Urban investi ated the curing of nonpigmented alkyd coatings detected %y PAS/FT-IR. Anal sis of IR spectra indicated that both film formation and iegradation of the coatin occurred almost simultaneously (P15). Chafmers and Wilson discussed the use of PAS/FT-IR spectroscopy for resin characterization in carbon-fiber-reinforced prepregs. Examples of its application to both thermoset and thermoplastic systems are Given (PIS).Grosse and Wynands give a matrix method which enables calculation of the surface temperature of a multilayer structure with any number of homogeneous lamellae of any optical and thermal properties. Photoacoustic spectra simulated by this method reproduce the measured spectra (Pl7).Zhang et al. successfully assigned the normal mode constructions by the internal coordinates and projection operator technique on poly(l,4phenylene sulfide) based upon PAS spectra (P18). Brunn et al. constructed a PAS cell with a spectral response down to 180 wavenumbers; more than one octave lower than previously reported useful broadband measurements (P19). Ramsey-Bell recorded photoacoustic measurements of atmospheric absorption coefficients at ultraviolet, visible, and infrared wavelengths (PZO). Zhou et al. stuhed the metalo hyrin complexea and their NO-surface ads ecies by PAff@?’he results showed that CoTPP and FefPP have stron er abilities of coordination than others (P21).Lynch et ak. characterized the surface functionality of coals by PAS. Distinct carbonyl peaks were discovered whose relative proportions differed for different coals (P22).Gordon presents a simple and efficient method to enhance the FT-IR photoacoustic signal from powdered samples of plant material. The method utilizes the increase in signal strength that a ears to be inversely related to the rate of absorption of ax&d water by the sample (P23).

(Q)DIFFUSE REFLECTANCE SPECTROSCOPY Leyden and Murthy reviewed the literature on diffuse reflectance Fourier transform spectroscopy (QI).Fredericks and Doolan describe an approach to quantitative analysis using reflectance spectra of solid materials in conjunction with


the computerized IR data processing technique CIRCOM, to correlate constituents or properties of the samples (82). Pattacini and Porro discuss the advanta es of using diffuse reflectance FT-IR s ectroscopy (DRIF'fS) for difficult-toanalyze materials ($3). Ilari et al. employed near-IR diffuse reflectance to determine the particle size of sorbitol owders by multiplicative scatter correction (84). Richter and!Erb developed an accurate sphere arrangement for directional-hemispherical reflectance measurements at 1-15 pm (85). Hembree and Smyrl investigated anomalous dispersion effects in diffuse reflection FT-IR.They concluded that specular reflection, whether in the form of regular Fresnel reflection or diffuse Fresnel reflection, is the major cause of s ctral distortion in typical diffuse reflectance measurements ($3). Griffiths et al. describe two techniques, diffuse reflectance and grazin incidence reflection-absorption spectrometry, for measuring t i e IR spectra of absorbed species on surfaces of different types (87). Suzuki et al. published several articles describing foresnic applications of diffuse reflectance IR spectroscopy for the direct analvsis of Dolvmeric foams (88). - . metallic Daints (89). .and metallic panels 1 10). Cole et al. em loye DRIFTS for the nondestructive determination of t i e degree of crvstallinitv at the surface of composite materials made frompolyphenylene sulfide reinforced with carbon fibers (Qll). Additional applications, which include the characterization of epoxy matrixes (compositions, cross-linking, and de adation) and the detection of surface contamination are iscussed in a second paper (Q12). Venter and Vannice u t i l i diffuse reflectance spectroscopy to characterize surface groups on hi h-surface-area carbons, metal carbonyls dispersed on car on black, and carbon monoxide adsorbed on reduced-carbon-supported metals. DRIFTS can provide a quantitative charactenzation technique to study C surface functional groups (Q13). Highfield and Bowen applied DRIFTS to monitor the degradation process that occurs when AlN ceramic powders are suspended in water at 25' (Q14). Venter charactenzed carbon-supported osmium, iron, ruthenium, and iron-manganese catalysts by DRIFTS (Q15). Savolahti studied the isothermal degradation of crude barley protein obtained as a side product of alcohol production. The main reactions observed in the DRIFTS s ectra were oxidation (816). Baes and Bloom studied the DflIFTSIIR spectra of humic and fulvic acid.s obtain from peat. Spectral comparisons were made with the KBr pellet transmission spectra of the acids ( 17). Siesler emp oyed DRIFTS to study the surface of glass powder coated with increasin amounts of a silane coupling ent (818). Fries and Mira%ella monitored the chemical asorption and polymerization of ropylene to form atactic poly ropylene on several Zie ler- atta Ti polymerization c a d s t s (819). Sagliano et .!a em loyed DRIFTS to characterize liquid chromatographic s i h a gels at three stages: before bonding of butyl groups, after bonding, and after exposure to hydrolytic conditions. The extent of hydrolysis dewnds umn the silica used and the initial deeree of coverwe of-the boGded phase (Q20). Ross and Byrne utilized DRIFTS to improve the analysis of nonvolatile hydrocarbon residues associated with critical surfaces of the NASA space shuttle main propulsion system (Q21). Gordon et al. characterized fine particle (

Infrared spectrometry - ACS Publications - American Chemical Society

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