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(180) Muelier, F.; Moonen, C. T. W. Dev. Biochem. 1882, 27, 517-27. (181) Agrawal, P. K.; Rastogi, R. P. Heterocycles 1981, 78, 2181-236. (182) Englert, G. Carotenoid Chem. Blochem., Proc. Int. Symp. Caroteno i d ~6th 1981, 1982, 107-34. (183) Jardetzky, 0. Membr. Transp. 1882, 1, 109-13. (184) Westerhoff, H. V. Trends Blochem. Scl. (Pers. Ed.) 1982, 7 , 232. (185) Brown, C. E. Blomembranes 1983, 7 7 , 439-62. (186) Cullis, P. R.; Farren, S. 6.; Hope, M. J. Can. J. Spectrosc. 1981, 26, 89-95. (187) Davis, J. H. Biochlm. Biophys. Acta 1983, 737, 117-71. (188) Oldfield, E. Tech. Life Sci.; Biochem. 6 4 / 2 (B427), 23 pp. (189) Browning, J. L. Res. Monogr. Cell Tissue Physiol. 1981, 7 , 189-242. (190) Grlffln, R. G. Methods Enzymol. 1981, 72, 108-74. (191) Seellg, J.; Seelig, A.; Tamm, L. Lipid-Protein Interact. 1982, 2, 127-48. (192) Davies, D. B. Nucl. Magn. Reson. 1982, 7 1 , 179-204. (193) Cohen, J. S.; Wiodawer, A. Trends Biochem Sci. (Pers. Ed.) 1982, 7 , 369-9 1. (194) Wuethrich, K. NATO Adv. Study Inst. Ser., Ser. A 1992, 45, 215-35. (195) Sykes, 8. D. Can. J. Biochem. Cell Bioi. 1983, 67,155-64. (196) Oklfleld, E.; Janes, N.; et al. Blochem. SOC.Symp. 1981, 46, 155-81. (197) Conard, J.; Estrade-Szwarckopf, H.; Lauginie, P.; Hermann, G. Springer Ser. Solid-state Sci. 1981, 38, 264-73. (198) Ganesh, K. N. Curr. Scl. 1982, 51, 866-74. (199) Dobson, C. M. Jerusalem Symp. Quantum Chem. Biochem. 1982, 15, 461-95. (200) Wuethrich, K. Biochem. SOC.Symp. 1981, 46, 17-37. )I (201) Williams, R. J. P. Blochem. SOC.Symp. 1981, 46, 57-72. (202) Wuethrlch, K.; Wagner, G. Ciba Found. Symp. 1983, 93, 310-20. (203) Dobson, C. M. “Struct. Dyn.: Nucleic Acids Proteins, Proc. Int. Symp. 1982”; Clementi, E., Sarma, R. H., Eds.; Adenine Press: Guilderland, NY, 1963; pp 451-61. (204) Inagaki, F.; Miyazawa, T.; Wllllams, R. J. P. Biosci. Rep. 1981, 7 , 743-55. (205) Sarma, R. H.; Dhingra, M. M. Top. Nucleic Acid Struct. 1981, 33-63. (206) Krugh, T. R. Top. Nuclelc Acid Struct., 1981, 197-217. (207) Fiat, D.; Burgar, M. I.; et al. Dev. Endocrinol. 1981, 73, 239-50. (208) Kessler, H.; Ziessow, D. Nachr. Chem. Tech. Lab 1982, 30, 488-92, 494, 497; Chem. Abstr. 1982, 97, 1280171. (209) London, R. E., ACS Symp. Ser. 1982, No. 797, 119-55. (210) Deslauriers, R.; Smith, I. C. P. Dev. Endocrlnol. 1981, 73, 201-10. (211) Kricheldorf, H. R. Pure Appl. Chem. 1982, 54, 467-81. (212) Gierasch, L. M.; Frey, M. H.; Hexem, J. G.; Opella, S. J. ACS Symp. Ser. 1982, No. 797, 233-47. (213) ARona, C. NATO Adv Study. Inst. Ser. A 1982, 45, 161-214. (214) Delbarre, A.; Gaugain, 6.; et ai. Jerusalem Symp. Quantum Chem. Biochem. 1981, 74, 273-83. (215) Gorenstein, D. G.; Goldfield, E. M. Mol. Cell. Biochem. 1982, 46, 97- 120. (216) Perkins, S. J. Biol. Magn. Reson. 1982, 4, 193-336. (217) Reid, B. R. Top. Nucleic Acid Struct. 1981, 113-39. (218) Patel, D. J.; Pardi, A.; Itakura, K. Science 1982, 276,581-590. (219) Fritzsche, H. Stud. Biophys. 1981, 85, 141-58. (220) Hilliard, P. R.; Rill, R. L.; Levy, G. C.; Levy L. F. ACS Symp. Ser. 1982, NO. 191, 269-83. (221) Fritzsche, H. Comments Mol. Cell. Biophys. 1982, 1, 325-36.
.
Raman Spectroscopy Donald L. Gerrard
BP Research Centre, Sunbury-on- Thames, Middlesex, England The period of this review is from late 1981 to late 1983. During this time over 4000 papers have appeared in the scientific literature dealing with many applications of Raman spectroscopy and extending its use to several new areas of study. This large number of publications includes the proceedings of the 8th International Conference on Raman Spectroscopy held in Bordeaux, France, in 1982 ( I ) . It is necessary to be highly selective in collecting material which has direct relevance to analytical chemistry for this review. Where a topic has produced a considerable number of‘papers with a relatively low proportion of analytical interest, the appropriate reviews have been included to which the reader is referred for a more complete background. It is particularly interesting to note that Raman spectroscopy is becoming more widely used as an industrial analytical technique ( 2 , 3 )and reviews have also appeared on chemical applications (4) and recent developments (5,6). Other reviews have covered the evaluation of Raman spectral data (7)and 0003-2700/84/0356-2 19R$O1.50/0
vibrational band intensities of hydrocarbons (8). Time-resolved Raman spectroscopy is becoming more widely used (9, 10) and picosecond laser pulses have been used in studied of photoinduced reaction intermediates, the separation of Raman scattering from luminescence, and Raman gain spectroscopy (11).
The topics to which Raman spectroscopy is applicable continue to expand and reviews have covered single-crystal studies (12), polysaccharides (13),molecular crystals (14), glasses (15-13, environmental problems (I&?),metal cluster compounds (19),iron corrosion (20), and inorganic and organometallic compounds (21-25). As in the previous review in this series (26), a separate section dealing with solids has not been included as many of the references in this area are more properly considered as solid-state physics. The development of surface-enhanced Raman spectroscopy has been so rapid that this is now more conveniently considered in conjunction with resonance-enhanced Raman studies. A 0 1984 American Chemical Society
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separate section on polymers has been included together with one on high-temperature and high-pressure studies which is another area of ra id progress. Most of the app ications relevant to solids are covered in one or other of the ten separate sections, but those which have not been discussed elsewhere include the characterization of (27) and resonance interactions in (28,29) semiconductors and Raman studies of roup 5 amorphous semiconductors (30). Carbon has also gee, studied extensively in many different forms and papers have been published concerning coals (31), soot in the Arctic (32), diamond growth from methane/hydrogen gas mixtures (331, graphitization rocesses (34), and ordering in benzene-derived graphitic fiters (35).
P
troscopy as a tool for the detection and identification of pollutants in water (65). Information has been obtained on the structure of supercooled water (66433, and spectroscopic data relating to amorphouswater and its relationship to liquid water have been reviewed (69). Studies of the structure of water in microemulsions have shown evidence for the existence of a layer of water whose structural properties differ from those of bulk water (70). Picosecond light pulses have been used to record highresolution spectra of polyatomic molecules in the liquid state (71-73) and to evaluate the dynamics and structures of liquids (74). An apparatus has been described for monitoring the concentration of a mixed acid bath and can be used to adjust concentrations for surface treatment processes (75). Conformational studies on alkanes continue to provide interesting results. The trans-gauche equilibriumof n-butane in dichloromethane and carbon tetrachloride solutions has been reported (76). Conformationalorder in liquid n-alkanes has been studied (77) and reorientational relaxation of cyclohexane in the liquid state has been determined from the analysis of the totally symmetrical vibrations (78). The structures of cyclobutane (79), n-alkanes and perfluoro-nalkanes (80), all in the liquid state, have been evaluated from studies of their low-frequency Raman spectra. Reviews have been published on vibrational dynamics in ionic liquids (81) and on solute-solute interactions in liquid ammonia (82). Other reviews have been concerned with band contours of infrared and Raman bands in liquids (83) and on the spectroscopy of molecular interactions in dense fluids (84).
INSTRUMENTATION AND SAMPLING The instrumentation and sample handling methods used in Raman spectroscopy are continually modified and developed to improve the capability of the technique. A fourchannel photon counter has been developed (36, 37) which can perform simultaneous measurements of four different Raman signals, and an optically reflecting bulb has been designed which maximizes the collection of scattered light from a sample located a t its center (38). Several new instrumental design features have appeared during the period covered by this review including an apparatus which can be used for luminescence, time-resolved phosphorescence, and Raman measurements (39), a simple homemade microprobe (40), and a commercial microprobe (41). A new spectrograph has been produced with a multichannel optical detector for the h a n characterization of microparticles(42) and the use of multichannel detectors is expanding rapidly (43-47). New LIDAR systems have been described for environmental and atmospheric probing (48). Developments in laser technology are often of interest to Raman spectroscopists and reviews have been published which discuss tunable infrared lasers (49), the use of lasers in Raman spectroscopy (50), and tunable lasers and resonance Raman spectroscopy (51). The development of ultraviolet and tunable ultraviolet lasers promises to extend the applicability of Raman spectroscopy. Various ultraviolet sources have been used, mostly based on excimer lasers (52) and work reported has included trace detection of small molecules (53)and spatially resolved concentration determinations of silane in a chemical vapor deposition reactor (54). Computer control and data handling are also important areas of expansion and an inexpensive computer system has been described which allows the acquisition of Raman data and the control of the spectrometer operation modes (55). A computer has also been used to evaluate the parameters of complex bands in the spectra of polymers (56). A diagnostic and control system has been described for combustion measurements (57) and a simple computer method has been used successfully to discriminate against background luminescence (58). Another method designed to reduce luminescence problems is based on time-resolved rejection via high repetition rate gated photon counting (59). Sample handling is of particular importance and cell design is often a very relevant feature of Raman experiments. A glass anvil cell has been described which can be used as a substitute for diamond anvil cells for pressures up to 12.6 kbar (60), and a diamond anvil cell has been constructed which enables Raman and X-ray diffraction measurements to be made on the same sample (61). A cell with a very high optical efficiency which uses a multilayered ZnS/MgF, reflecting layer has been reported (62) and a spinning cell for low-temperature resonance work has been used to monitor the temperature-dependent ligation of ferrous tetraphenylporphine by 1,2-dimethylimidazole (63). Finally, a paper has been published describing a fiber optic probe for remote Raman spectroscopy (64). This provides the facility for sampling, distant from both laser and spectrometer. It can be used for sampling in hostile environments and is easily used by an unskilled operator.
GASES AND MATRIX ISOLATION The technique of matrix isolation continues to be a valuable aid to spectral interpretation. Reviews have been published concerning the technique in general (85-87) and the spectra of transition-metal compounds (88). A high-resolutionstudy of the coherent anti-Stokes Raman spectrum of carbon monoxide in a nitrogen matrix has been reported (89) and useful information has been obtained on the vibrational modes of small antimony clusters by matrix isolation spectroscopy (90). Spectra of mixtures of halogens with ethene or 2,3-dimethylbut-2-ene in argon and nitrogen matrices have been interpreted in terms of the structure of the complexes (91). A high-pressure cell has been described for matrix isolation Raman spectroscopy and the data obtained considered in terms of anharmonic effects (92). A wide range of gas-phase studies has been reported and this is an area of application which is proving to be of considerable practical use. Reviews have been published on the photoacoustic Raman spectroscopy of gases (93) and the hyper-Raman effect in molecular gases (94). Other reviews have concerned the chemical applications of gas phase linear Raman spectroscopy (951, the Raman intensity of gases (96), and resonance-enhanced scattering (97). The use of gas-phase spectroscopy in environmental studies has been the subject of reviews concerning the remote sensing of atmospheric properties of meteorological significance (98) and the determination of atmospheric pollutants (99). In the area of environmental studies Raman resonant diffusion measurements have been used to monitor the movement of polluted masses of air (loo),Raman scattering has been used in the analysis of ambient air in the lower portion of the atmosphere (101), and Lidar h a n techniques have been used to measure the gas composition of the atmosphere (102). Lidar has also been used to measure tropospheric ozone using excimer lasers (103) and to measure the temperature of atmosphericgases (104).Temperature and concentrationmeasurements in methane/nitrous oxide flames have shown good agreement with thermochemical equilibrium calculations (105). Multichannel detection has been used to analyze perturbations caused by a flame propagating through a gas mixture (106) and gases produced from model flames have been analyzed for oxygen, carbon dioxide, and carbon monoxide contents (107).
LIQUIDS AND SOLUTIONS Liquid phase studies account for much of the published work on Raman spectroscopy but this section is mainly restricted to aqueous systems, technique innovations, and conformational studies. Reviews have been published on water analysis (64) and the application of resonance Raman spec-
BIOLOGICAL MOLECULES The application of Raman spectroscopy, and particularly resonance-enhancedmeasurements, to the study of biological species in still growing rapidly and represents, in terms of publications, the major single application of the technique. It is not possible in this review to deal with more than a few
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RAMAN SF'ECTROSCoPY
Doluld L. (i.nud ia h charge ol he Faman Spactroscopy unn at me British PswLnm R-rd) W e at Sunbwym W ~ ban S ~n~ v h a m ~ l a m s EWW. ~. and remhwd hb B.Sc. d a p e homThs Cny unkasny. Loodon. In 1967. Then as a r e mrh s w n t he worked on barwbansle, complexes. recsMng hb Ph.D. w e e In 1970. He Men pined 8mlsh Petroleum where he worked In the absorption spectroscopy group. and In 1872 he begs" to develoo his Interest In Raman
I
representative examplea and some of those which have a novel aspect. The material which has been omitted has been ad+ quately covered in the large number of reviews which are Listed in this section. Two books have been published covering the biochemical (108) and biological (109) applications of Raman and resonance Raman spectroscopy. Reviews have covered such topics as the appliration of spontaneous ( 1 10, I 1 1 ) and resonance (112) Raman spertroscopy, structural determinations (113. 1/41, phou,isomerization of pigments ( 1 1 5 ) , inverse Raman and Raman gain spectroscopy (116).coherent antiStukes Raman spertroscopy ( 1 1 7 ) . and pirosecond spectroscopy ( 1 181. More specialized reviews have been concerned with rwnance (119,120)and timeresolved resonancestudies (121) of hemoglobin. nucleic acids (122). resonance studies of heme protein structure 1/23, 124J, protein structure determination (1255).enzyme studies (126,127).carotenecontaining hiomolecdes (1%). products isolated from rat liver (129).and carotenes in bacterial reaction centers (130). Low-frequencyh e s observed in the Raman spectra of living cells have been interpreted and comparisons made between malignant and normal cells (131). Surface-enhanced Raman spectroscopy has proved useful in stud~esof biological molecules in general (132) and nucleic acids in panicular (133). Techniques have been descrihed for studying isolated cell populations (13441 and the examination of microsamples (1.35). Results have been r e p o d for airborne (136) and remote (137) sensing of pigments. including chlorophyll, in seawater.
POLYMERS Raman spectroscopic studies on polymers continue to provide valuable information on composition and structure for both academic and industrial workers. Reviews have been published on the resonance Raman spectrum of polyacetylene (138), the Raman spectrum of poly(methy1 methacrylate) (139), probing the real structure of polymeric materials in terms of chain disorder and micrmtructure (140).and Raman studies of the polymeric solid state ( 1 4 1 ) . The polymer which is currently attracting most attention in terms of Raman studies is polyacetylene. which exhihita very intense resonance enhancement. Polyacetylene and related polymers are of considerable interest because of their unusual elertriral properties. Structural studies have been b e d out on the polymer itself (142-150) and on doping with electron donors or accepmrs (151 -15fi). Useful information has also been ohtained concerning the c i s p isqmerization n studied m some process (157-161). Polyethylene has alw detail, particularly the strurtural significance of the low-frequency longitudinal acoustic modes (162-167). Other aspect8 of polyethylene analysis have been the cross-linking of low density polyethylene (168). changes in crystallite size distribution during rrystallization (169,. high-pressure studies (170. 171). and crystallinity measurements (172-174). Other Raman studies which have produced useful information relate to the orientation (17,5) and degradation (176) of poly(viny1chloride). surfaceenhanced Raman spectroscopy of polymers (/77), and crystallization studies on polypropylene (178, 1791.
HIGH-TEMPERATURE A N D HIGH-PRESSURE STUDIES The value of Raman spectroscopy for noninvasive analysis in hostile environmenta is reflected by the publication of an
increasing number of papers relatin to high-pressure-temperature work Reviews have been pu%lishedon high-pressure studies (180)and on conformational equilibrium and hydrogen bonding effects at high presaures (181). A micrrmptic system has been described for the study of small samples (
