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Electron Spin Resonance John R. Wasson SYNTHECO, Inc., 1920 Industrial Pike Road, Gastonia, North Carolina 28052
This review covers the published literature from July 1981 to July 1983 although a few citations of other work are also included. The volume of literature to be covered in so short a space has led to considerations and limitations discussed in earlier reviews (1,2).
Although the applications of computers in ESR spectroscopy have been present for many years, it is evident that there is an explosion of usage brought about by the presence of affordable instrumentation. The amount of software being developed is very impressive. Coincident with this increased
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Table I. Reviews ref
topic general review theoretical aspects matrix effects radicals trapped in rare-gas matrices magnetic resonance and relaxation in structurally incommensurate systems superoperators computer simulation of spectra matching up of NMR and ESR spectrometers ESR at zero magnetic field laser magnetic resonance spectroscopy ultrasonically modulated paramagnetic resonance EPR in one and two dimensions time-resolved ESR transient methods detection of transient paramagnetic intermediates slow dynamics and central peak phenomenon near phase transitionsESR and ENDOR electron-beam interactions in the solid state paramagnetic properties of zinc oxide semiconductors-impurities and defects defects in 111-V semiconductors tetrahedrally bonded amorphous semiconductors, H and F defects semimagnetic semiconductors impurities in magnetic insulators semiinsulating gallium arsenide neutron-irradiated silicon amorphous silicon and germanium amorphous semiconductors transition-metal ions lowsymmetry effects rare earth hydrides exchange reactions of coordination compounds, in solution Mn(I1) in polycrystalline and amorphous materials copper complexes-role of microwave frequency paramagnetic ions in paramagnetic hosts spin glasses theory of ESR of magnetic ions in metals graphite intercalated compounds distinguishing synthetic from natural gem stones surface chemistry Q-band ESR in catalysis research
1 2 3 4 5
6 7 8 9 10 11
12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35, 36
37 38 39 40 41
computer usage J. Wiley and Sons has announced the appearance of a new journal Computer Enhanced Spectroscopy. While these developments are greeted enthusiastically, one tries not to become cynical and to maintain hope that those being trained in the art are not slighted when it comes to grounding in the fundamentals.
BOOKS AND REVIEWS The books on ESR (3-15) continue to emphasize the growing number of biological applications as well as the utility of spin-label and probe techniques. Reviews are cited in Table I; for convenience, the references for Table I are collected separately in the biblography.
APPARATUS AND SPECTRAL ANALYSIS A useful formula for the number and relative intensities of the lines in an ESR spectrum due to first-orFr coupling with a group of equivalent nuclei with spin I > has been developed (16) which enables the generation of ascal-type triangles. An ESR experiment for an advanced laboratory course which employs oxovanadium(1V) compounds has been detailed (17). The combination of a helium-3/helium-4 dilution refrigerator and an ESR spectrometer has been described (18). A high-temperature ESR (K-band) system has been reported (19) which allows uniaxial stress single crystal work. An HP-85 microcomputer can be used to control the magnetic field of a Varian E-109 spectrometer via the IEEE-488 interface (20). Details have been described of the
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topic ruthenium in zeolites clay minerals flame retardant mechanisms polymer chemistry polymers in bulk state polymers-spin labels organic radicals in solids organic radicals-structure organic radicals-kinetics and mechanisms triplets and biradicals radicals in solution by ENDOR and triple resonance spectroscopy CF,-group effects nitroxides and chemical physics inorganic and organometallic radicals or ganosilicon radical cations metallocenes and diarene complexes hemoglobin hemoproteins metalloproteins Cr and Co nucleotides-interactions with enzymes bimetalloenzymes mitochondrial respiratory chain B,,-dependent enzyme reactions and related systems active sites in enzymatic complexes ribosomesspin labeling medicine spin labeling in disease biological problems biomembranesspin labels membranes-rotational dynamics; saturation transfer EPR studies biopolymersspin labels water in biopolymers resolution of flavin ESR spectra using Fourier transforms boundary lipids lipid-protein interactions in membranes lipid and membrane systems-spin label probes spin label studies of liposomes spin-labeled muscle proteins-rotational dynamics vertebrate rod outer segments photochemistry of protein and nucleic acid constituents primary reactants in photosynthesisESR and ENDOR humic acid research
ref 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
72 73 74 75 76 77 78 79 80 81
82 83
interface between a DEC PDP I1 V03 microcomputer and a Varian Century Series ESR spectrometer (21). A microprocessor-based g-value controlled device has been described for ESR amplitude measurements (22). A g-value processor can be constructed for use with an ESR spectrometer to calculate and display g values and place g markers on the chart recorder (23). A low-cost microprocessor-based data collection and analysis system for an EPR spectrometer has been detailed (24). A microcomputer system for the digital acquisition and analysis of ESR spectra has been described (25). The use of a computer-assisted two-circle goniometer to assess hyperfine interaction and g2tensors in the crystallographic axis system has been described (26). A new method determining direction cosines in ESR crystallography with limited data has been presented (27). A technique has been described which allows selective suppression of overlapping single-crystal spectra of anisotropic paramagnetic species (28). A computer program for simulation of powder spectra with axial symmetry has been described (29). A BASIC program for simulation of isotropic spectra has been detailed (30). Time dependence of transient magnetization can be sampled by using a single microwave pulse and observing the intensity of free induction decay (FID) (31). A detailed systematic study of the dependence of saturation transfer ESR spectral parameters on instrument setting has been reported (32). A balanced cavity scheme for saturation transfer dispersion ESR (33) has been described as a technique called “orientation modulated ESR” (34) which facilitates single
ELECTRON SPIN RESONANCE Jh.l R. W a n m * p d d m l I o t s m , 1%. m WM ban h si. w,MO. and ro. C e W d Na Sducamn at ma unlvasny Of Mlssourt-Colurnbla (13,s.. 1963 M.A.. 1966) and lMnda Insmute of T W (RI.0.. 1970). He Is mS aumDT or w U m Q Of ma0 ma" 100 reMarch papers. revltrws. and technical arl!4es. Hls plbllcatbns and hlerests a,* h me arms 01 magnetic rex. nance spectropcCQy. lranahlomtal and orgsnmtallic chernlstry. cstalysts. and b a n q materials. He Is a member Of me A w n Chermcsl Socletv. T k chsrmcslSccbty. AAAS. he Royal soclehr tile ChernlstS and C o l o ~ l s phi . lam&
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crystal work. Theory of ESR parallel-ed e lines of slowly tumbling molecules has been elucidated (357.A simple direct method has been proposed for characterizing the extent of slow-tumblin molecular motions of nitroxide spin labels in amorphous su!xtances (3s). Simulations of slow-motion ESR, ELDOR, and saturation-transfer ESR spectra from solutions of the stochastic Lionville equation with Pade approximants have been discussed (37). Modification of hyperfine coupling of radicals by changes of temperature or pressure can be employed to aid determination of the relative signs of hyperfine tensor components from powder spectra (38). The use of the Fourier method to deconvolute the hyperfine splittings and the line shape function from observed ESR spectra has been discussed (39) as has a microprocessor-based interface for an ESR spectrometer (40). A Fourier transform logarithm approach has been reported for Voigt profile analysis of ESR lines (41) and an expression derived for the discrete Fourier transform of an ESR line (42). Occurrences of abnormal divergence peaks in axially symmetric ESR hyperfine powder spectra have been discussed (43). A method has been described (44) for the investigation of the spatial distribution of paramagnetic centers in a sample. Measurement of spinapin distances from the intensity of the half-field transition (45)has been described as has simulation of spectra of powders by analytical functions (46). A nonlinear least-squares analysis of ESR powder patterns with noncoincident principal axes of the g and hyperfine tensors has been outlined (47). The problem of the determination of parameter errors in a rigorous least-squaresfitting procedure used for estimating spin-Hamiltonian parameters from EPR data has been explicitly considered (48). Coupled transitions and higher-order effects in isotropic spectra of a two-nucleus radical have been dismissed theoretically (49) and compared to previous treatments of higher-order effects. Solution of the spin Hamiltonian with orthorhombic hf and g tensors (I = S = '13 has been presented theoretically (50) and practically (51). An analytical expression for the powder pattern of axially symmetric systems with simultaneous anisotropy in principal-axes-coincidentg and A tensors has been derived (52). An efficient approach to computer simulation of ESR spectra of high-spin iron(II1) in rhombic ligand fields has been tested (53). The simulation of powder spectra of systems with S > in the absence of hyperfine interactions has been described and applied to a number of materiala (54).
ANALYTICAL A P P L I C A T I O N S Quantitative multimode cavity ESR spectrometry hy twostep spectral integration has been detailed (55). Quantitative spin determination (56) and the use of spectral simulations for the assay of radical concentrations hy ESR (57) have been reported. An airborne sampling system using a spin trapping method has been developed (58)to determine the concentration of OH radical in the trophosphere. A technique has been developed (59) which distinguishes surfactant deposition from penetration into a material; this technique also allows classification of surfactant films as packed or expanded. Determination of Cr(III), Mn(II), Cu(II), VO(IV), and Fe(111) in aqueous solutions of low pH and effects of instrumentation parameters has been reported (60). The determination of iron in aqueous media (buffer solutions, wine) by using EDTA and standard additions has been described (61). Determination of Cu(I1) and V O W ) by ESR following thinlayer chromatographic separation of the metals as acetyl-
acetone chelates has been reported (62). An ESR method for 5 x 10" to 2 x lod M Cu(I1) using partition of a spin-labeled enamino ketone between organic solvents and water has been reported (63). Determination of Re based on Re(V1) oxide halide complexes has been described (64). The isotopic compoeition of g m u s oxygen at -0.5 torr can be determined by measurinf the relative intensities of the distinct ESR signals from 602,'WSO, and lSO2and converting the intensities to amounts of the isotopic species by means of intensity factors derived from the transition moments and Boltzmann factors (65). The thermal histories of archaeological cereal grains have been examined (66)by ESR. ESR has been employed to characterize marble samples from Mediterranean quarries of archaeological interest (67) and its applications to foasil dating discussed (68-70). A model of linear uranium accumulation of Heidelberg and Tautavel bones for ESR dating has been presented (71). ESR measurements have been employed to date the calcite encrustation and bone of the Petralona hominid cranium (72). The principles of ESR dating of stalactites have been illustrated (73). Spectra of both organic and inorganic radicals in petrified woods have been studied (74) for assessment of age and burial condition.
SELECTED PARAMAGNETIC M A T E R I A L S Information from spin-probe ESR spectra can be supplemented by the application of paramagnetic ions (75). 2,2Bis(4-tert-oetylphenyl)-l-picrylhydrazylhas been synthesized and used as an alkane-soluble standard (76). A reversible thiol-specific spin label was synthesized and applied to papain active site labeling (77). 2,2-Disuhstituted-4,4-dimethylimidazolidinyl-3-oxy nitroxides can be used as indicators of aqueous acidity through variation of .N with pH (78). 1Methyl-4-acetylpyridinyl free radical can be employed as an ESR probe of solvent polarity (79). 4-Phenyl-4H-1,2,4-triazoline-3.5-dione is an effecient spin trap for a variety of carbon-and m e t a l e n t e r e d radicals (80). Difunctionalized tron.-2,5-disubstituted-pyrrolidine(azethoxy1)nitroxidespin labels (81)and azethoxyl nitroxide spin-labeled crown ethers and rryptands with the N 4 . group positioned near the cavity have been described (82). The non-Kekule tetraradical, 3 , 6 - d i m e t h y l e n e a n t h n e diyl-1,'l-dioxy (83) and the disjoint biradical, 2.6-dimethylanthracenediyl-4,&dioxy (84) have been characterized as has the [12]-annuleneanion radical (85). ?-Irradiation of methane encapsulated in zeolite 3A at 17 K forms methyl radicals which are stable in air up to -195 K (86). The use of liquid xenon as an inert solvent for reactive free radicals has been examined (87) and it noted that g values in xenon and normal solvents may differ. X-ray and laser UV irradiation have been employed to generate radicals in single crystals of L-ascorbic acid and partially deuterated basmrbic acid (88).ESR mwurements of a human erythrocyte suspension incubated with a fatty acid spin label were performed (89) with a narrow gap flat ESR sample cell under various flow stresses which evaluated erythrocyte deformability. Vegetative cells of Colstridium botulinum have been shown to contain ironaulfur proteins that react with added nitrite to form iron-nitric oxide complexes with resultant destruction of the iron-ulfur cluster (90).Four different types of paramagnetic species have been identified in cigarette smoke (91). Potassium peroxyhine dsulfonatehas been employed (92) as the basis for a physical chemistry experiment. Conduction ESR has been investigated in alkaline earth hexaamines (93). The decomposition of W(CO), adsorbed in the supercages of HY and NaY zeolites has been reported (94). The electronic structure of V(CO), in frozen cyclohexane and Cr(CO), hosts has been probed by using ESR spectroscopy (9.5). ESR studies of Tc(I1) complexes (96)and of Ni(II1) in methanogenic bacteria (97) have been reported. ACKNOWLEDGMENT The author is grateful to C. B. Stuhblefield and JoAnn T N I I , Lithium Corporation of America, fer use of library facilities. LITERANRE CITED ( 1 ) Wasson. J. R.; Sathns. J. E. Anal.
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ELECTRON SPIN RESONANCE (2) Wasson, J. R.; Corvan, P. J. Anal. Chem. 1980. 50,92R-100R. (3) Rogers, M. A. J., Powers, E. L., Eds. “Oxygen and Oxy-Radicals in Chemistry and Biology”; Academic Press: New York, 1981. (4) Marshall, A. G., Ed. “Fourler, Hadamard, and Hilbert Transforms in Chemistry”; Plenum Press: New York, 1982. (5) Pryor, W. A., Ed. “Free Radicals in Biology”; Academic Press: New York, 1982. (6) Kaufmann, E. N., Shenoy, G. K., Eds. “Nuclear and Electron Resonance Spectroscopies Applied to Materials Science”; Elsevler: New York, 198 1; Vol. 3. (7) Poole, C. P., Jr. “Electron Spin Resonance”, 2nd ed.; Wiley: New York, 1983. (8) Clarke, R. H., Ed. “Triplet State ODMR Spectroscopy Techniques and Applications to Biophyslcal Systems”; Wlley: New York, 1982. (9) Weltner, W., Jr. “Magnetic Atoms and Molecules”; Scientific and Academic Editions: New York, 1983. (10) Waugh, J. S., Ed., “Advances In Magnetic Resonance”; Academic Press: New York, 1983 Vol. 10. (1 1) Berliner, L., Reuben, J., Eds. “Biological Magnetic Resonance”; Plenum Press: New York, 1982; Vol. 4. (12) McBrien, D. C. H., Slater, T. F., Eds. “Free Radicals, Lipid Peroxidation and Cancer”; Academic Press: New York, 1982. (13) Cohen, J. S., Ed. ”Magnetic Resonance In Blology”; Wiiey: New York, 1983; Vol. 2. (14) Molin, Yu. N. “Spin Polarization and Magnetic Effects in Radical Reactlons”; Elsevier: New York, 1983. (15) Carrlngton, A.; Hudson, A.; MacLachkn, A. D. “Introduction to Magnetic Resonance”, 2nd ed.; Chapman & Hall: New York, 1983. (18) Koster, D. F.; Jones, W. J. Chem. Educ. 1982, 59,289. (17) Borer, L. L. J. Chem. Educ. 1982, 59, 1065. (18) Von Spalden, Y., Baberschke, Physica B+C (Amsterdam) 1981, 707, 599-600. (19) Berlinger, W. Rev. Sci. Instrum. 1982, 53, 338-41. (20) Rich, E. S.; Wampier, J. E. Am. Lab. (Fairfield, Conn.) 1982, 74, 17-21, 23-24, 26, 28. (21) O’Conner, S. E.; SDraaginas. . -- - T. A,: Grisham, C. M. Comwt. Chem. . 1981, 5, 181-4. Wormald, D. J. 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ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(64) Borisova, L. V.; Ermakov, A. N.; et al., Analyst (London) 1982, 107, 500-4. (65) Bjerre, N.; Larsen, E. Anal. Chem. 1983, 55,2236-8. (86) Hillman, G. C.; Robins, G. V.; et al. Science 1983, 222, 1235-6. (67) Cordlschi, D.; Monna, D.; Segre, A. L. Archaeometry 1983, 25,88-76. (68) Yokoyama, Y.; Nguyen, H. V.; et al. PACT (Rixensart, Belgium), 1982, 6, 103-15. (69) Symons, M. C. R. PACT (Rixensart, Belgium) 1982, 6 , 302-13. (70) Robins, G. V.; et ai. PACT(Rixensart, Belgium) 1982, 6 , 322-32. (71) Ikeya, M. Jpn. J. Appl. Phys., Part 2 1982, 21,690-2. (72) Hennlg, G. J.; Herr, W.; Weber, E.; Xirotlris, N. I. Nature (London) 1981, 292,533-6. (73) Ikeya, M. Gypsum Lime 1982, 777,81-7; Chem. Abstr. 1982, 97, 41895a. (74) Ikeya, M. Jpn. J. Appi. Phys. 1982, 21,L28-L30. (75) Pecar, S.;Schara, M.; Nemec, M.; Sentjurc, M. Period. Blol. 1982, 8 4 , 173-5. (76) Dziobak, M. P.; Mendenhali, G. D. J. Magn. Reson. 1982, 50,274-80. (77) Berliner, L. J.; Grunwald, J.; Hankovszky, H. 0.; Hideg, K. Anal. Biochem. 1982, 779,450-5. (78) Keana, J. F.; Acarregui, M. J.; Boyle, S. L. M. J. Am. Chem. SOC. 1982, 704, 827-30. (79) Kolling, V. W. Anal. Chem. 1983, 55. 145-6. (80) Alberti, A.; Pedulli, G. F. J. Org. Chem. 1983, 4 8 , 2544-9. (81) Keana, J. F. W.; Seyedrezal, S. E.; Gaughan, G. J. Org. Chem. 1983, 48, 2644-7. (82) Keana, J. F. W.; Cuomo, J.; Laszlo, L.; Seyedrezai, S. J. Org. Chem. 1983, 48, 2647-54. (83) Seeger, D. E.; Berson, J. A. J. Am. Chem. SOC.1983, 705,5144-6. (84) Seeger, D. E.; Berson, J. A. J. Am. Chem. SOC. 1983, 705,5146-7. (85) Stevenson, G. R.; Concepcion, R.; Reiter, R. C. J. Org. Chem. 1983, 48, 2777-8. (86) Lemire, A. E.; Gesser, H. D. J. Chem. SOC.,Chem. Commun. 1983, 1175-7. (87) Cook, M. D.; Roberts, B. P. J. Chem. SOC.,Chem. Commun. 1983, 264-6. (88) McDearmon, G. F.; Mouiton, G. C. Radiat. Res. 1982, 89, 468-80. (89) NoJI, S.;Inoue, F.; Kon, H. Blood Cells 1981, I , 401-1 1. (90) Reddy, D.; Lancaster, J. R., Jr.; Cornforth, D. P. Science 1983, 227, 789-70. (91) Pryor, W. A.; Hales, B. J.; Premovic, P. I.; Church, D. F. Science 1983, 220,425-7. (92) Eastman, M. P. J. Chem. Educ. 1982, 59,677-9. (93) Robb, F. Y.; Glaunsinger, W. S. J. Magn. Res. 1982, 4 6 , 98-109. (94) Abdo, S.; Gosbee, J.; Howe, R. F. J. Chim. Phys.-Chim. Biol. 1981, 78,885-9. (95) Bran, S. W.; Kassyk, A.; Perutz, R. N.; Symons, M. C. R. J. Am. Chem. SOC. 1982, 704, 490-4. (96) Yang, G. C.; Heitzmann, M. W.; Ford, L. A,; Benson, W. R. Inorg. Chem. 1982, 27, 3242-3. (97) Clarkson, A. 8.; Amole, B. 0. Science 1982, 276, 1324. LITERATURE FOR TABLE I
Symons, M. C. R. Annu. Rep. Prog. Chem., Sect. C. 1982, 7 8 , 15 1-200. (2) Hudson, A. Eiectron Spin Reson. 1982, 7 , 41-55. (3) Symons, M. C. R. NATO Adv. Study Inst. Ser., Ser. C . 1981, C76, 369-95. (4) Symons, M. C. R. NATO Adv. Study Inst. Ser., Ser. C . 1981, C76, 69-89. (5) Bllnc, R. Phys. Rep. 1981, 79,332-98. (6) Jeener, J. Adv. Magn. Reson. 1982, 10, 1-51. (7) Brumby, S. Magn. Reson. Rev. 1983, 8, 1-32. (8) Buckmaster, H. A.; Hansen, C. H. J. Magn. Res. 1982, 4 6 , 521-4. (9) Bramley, R.; Strach, S. J. Chem. Rev. 1983, 8 3 , 49-82. (10) Davies. P. 8.: Hack, W.: TemDs, F. Ber. Max-Plank Inst. Stroemungs’ forsch. 1981, No. 75. (11) Devine, S.D.; Robinson, W. H. Adv. Magn. Reson. 1982, 10,53-117. (12) Drumheller, J. E. Magn. Reson. Rev. 1982, 7,123-45. (13) Venkatataraman, B. Curr. Sci. 1982, 57,397-400. (14) Weissman, S. I. Annu. Rev. Phys. Chem. 1982, 33, 301-18. (15) Trifunac, A. D.; Lawier, R. G. Magn. Reson. Rev. 1982, 7 , 147-74. (16) Daial, N. S. Adv. Magn. Reson. 1982, 10, 119-215. (17) Symons, M. C. R. Ultramicroscopy 1982, 10, 15-24. (18) Neumann, G. Curr. Top. Mater. Sci. 1981, 7 ,269-78. (19) , I Corbett. J. W.: Kieinhenz. R. L.: You, 2. P. Lect. Note Phys. 1983, 775, 11-49. (20) Schneider, J.; Kaufmann, U. Conf. Set‘.-Inst. Phys. 1981, 59,55-67. (21) Shimizu, T.; Kumeda, M.; Ueda, S. Oyo Butsuri 1981, 50 (12), 1266-61; Chem. Abstr. 1982, 96,95494h. (22) Galazka, R. R. Lect. Notes Phys. 1982, 752,294-301. (23) Mehran, F.; Stevens, K. W. H. Phys. Rep. 1982, 8 5 , 123-60. (24) Goltzene, A,; Schwab, C. Mlcroelectron. J . 1982, 13, 23-8. (25) Corbett, J. W.; Klelnhenz, R. L.; Wm, E.; You, 2.J. Nucl. Mater, 1982, 108-109, 617-26. (26) Bourgoin, J. C. “Electron, Struct, Cryst. Defects Dlsord. Syst., Summer Sch. 1980”; Gantler, F., Geri, M., Guyot, P., Eds.; Les Ulis, Fr., 1981; pp 405-34. (27) Yonezawa, F. Jpn . Annu. Rev. Electron ., Comput. Teiecommun .: Amorphous Semicond. Techno/. Devices 1982, 9-31. (28) Porte, A. L. Electron Spin Reson. 1982, 7, 69-123. (29) Piibrow, J. R.; Lowrey, M. R. Rep. Progr. Phys. 1980, 4 3 , 433-95. (30) Druiis, H. Cryst. Electr. FieldEff. f-Electron Magn., 4th, 7981 1982, 112-23. (31) Marov, I. N. Pure Appi. Chem. i983, 55, 115-24. (32) Nicula, A.; Peteanu, M. Rev. Roum. Phys. 1981, 26, 1047-54. (1)
Anal. Chem. 1084, 56, 133R-156R (59) Palmer, G. fhys. Biolnorg. Chem. Ser. 1983, 2,43-88. (60) Blackburn, N. J. Electron Spln Reson. 1982, 7 , 340-81. (61) Villafranca, J. J. Methods Enzymol. 1982, 87, 180-97. (62) Villafranca, J. J.; Raushel, F. M., Adv. Inorg. Biochem. 1982, 4 , 289-319. (63) Beinert, H. Membr. Transp 1982, 1, 389-98. (64) Plbrow, J. R., B,,(twelve) 1982, l q 431-62. (65) Cohn, M.; Reed, G. H., Annu Rev. Blophys. Bloeng. 1982, 51, 365-94. (66) Dugas, H.;Rodrlguez, A. Can. J . Chem. 1982, 6 0 , 1421-31. (87) Dodd, N. J. F. Electron Spin Reson. 1982, 7 , 382-405. (68) Butterfleld, D. A. Biol. Magn. Reson. 1982, 4 , 1-78. (69) Symons, M. C. R. "Free Radicals, Lipid Peroxidation Cancer, (Proc. N.F.C.R. Cancer Symp.) 1st 1981"; McBrien, D. C. H., Slater, T. F., Eds.; Acadernlc Press, New York, 1982; pp 75-99. (70) Lai, C. S. Electron Spin Reson. 1982, 7 , 313-39. (71) Thomas, D. D. Membr. Transp. 1982, 1, 135-9. (72) Robinson, B. H. Electron Spin Reson. 1982, 7 , 293-312. (73) Ebert, B.; Elmgren, H.; Hanke, T. Stud. Biophys. 1982, 91, 19-22. (74) Dunham, W. R.; Harding, L. T.; et al. Dev. Biochem. 1982, 21,568-72. (75) Devaux, P. F.; Davoust. J. Membr. Transp. 1982, 1 , 125-33. (76) Devaux, P. F.; Davoust, J.; Rousselet, A. Blochem. SOC.Symp. 1981, 46,207-22. (77) Marsh, D. Tech. Llfe Scl.: Blochem 1982, 6 4 / 2 (B426), 44 pp. (78) Marsh, D.; Watts. A. Res. Monogr. Cell Tissue Physiol. 1981, 7 , 139-88. (79) Thomas, D. D. Clba Found. Symp. 1983, 93, 189-85. (80) Watts, A. frog. RetinalRes. 1982, 1 , 153-78. (81) Riesz, P.; Rosenthal, I.Can. J . Chem. 1982, 6 0 , 1474-9. (82) Hoff, A. J. Biophys. Strucf. Mech. 1982, 8 , 107-50. (83) Schritzer, M. R o c . Int. feat Symp. 1981, 17-44.
(33) Hyde, J. S.; Froncisz, W. Annu. Rev. Biophys. Bioeng. 1982, 1 1 , 39 1-41 7. (34) Upreti, G. C.; Saraswat, R. S. Magn. Reson. Rev. 1982, 7 , 215-37. (35) Mydosh, J. A. Lecf. Notes fhys. 1981, 149,87-106. (36) Ford, P. J. Confemp. fhys. 1982, 23, 141-88. (37) Barnes, S. E. Adv. fhys. 1981, 36,599-610. (38) Conard, J.; Estrade-Szwarckopf, H.;Lauginie, P.; Hermann, G. Sprlnger Ser. SolM-State Sci. 1981, 38,264-73. (39) Troup, G. J.; Hunon, D. R. J. Gemmol. 1983, 18, 421-31. (40) Howe, R. F. Adv. Colloid Interface Scl. 1982, 18, 1-55. (41) Clarkson, R. B. V I A , Varlan Instrum Appl. 1981, 15, 17. (42) Lunsford, J. H. Stud. Surf. Scl. Cafal. 1982, 12, 1-13. (43) Pinnavaia, T. J. Dev. Sedimenfol. 1982. 34, 139-81. (44) Tkac, A. Dev. Polym. Stab. 1982, 5, 153-231. (45) Hik D. J. T.; O'Donnell, J. H.; Pomery, P. J. Electron Spln Reson. 1982, 7, 1-40. (46) Cameron, G. G., Pure Appl. Chem. 1982, 5 4 , 483-92. (47) Bullock, A. T. Electron Spin Reson. 1982, 7 , 280-92. (48) Kemp, T. J. Electron Spin Reson. 1982, 7 , 252-79. (49) Gilbert, B. C. Electron Spin Reson. 1982, 7 , 174-215. (50) Ayscough, P. 8. Electron Spin Reson. 1982, 7, 216-51. (51) Hudson, A. Electron Spln Reson. 1982, 7 , 58-68. (52) Moebius, K.; Plato, M.; Lubitz, W. fhys. Rep. 1982, 8 7 , 171-208. (53) Stock, L.; Wasielski. M. I n "Progress In Physical Organic Chemistry"; Tan, R. W., Ed.; Why: New York, 1981; Vol. 13, Chapter 4. (54) Freed, J. S. Kern.-Keml 1982, 9 ,50-1. (55) Symons, M. C. R. Electron Spln Reson. 1982, 7 , 124-73. (56) Bock, H.; Kaim, W. Acc. Chem. Res. 1982, 15,9-17. (57) Solodovnikov, S. P. Usp. Khim. 1982, 51, 1874-97; Chem. Ab&. 1983, 98,4584q. (58) Blumberg, W. E. Methods Enzymol. 1981, 76, 312-29.
.
Emission Spectrometry Peter N. Keliher,*' Walter J. Boyko, Joseph M. Patterson 111, and J. Wilson Hershey Chemistry Department, Villanova University, Villanova, Pennsylvania 19085
This is the 19th article in the series of biennial reviews in the field of emission spectrometry/spectroscopy and is the third written by the Villanova University author group. This year J. Wilson Hershey joins us as a new coauthor. This review article will survey selectively the emission spectrochemical literature of 1982 and 1983. By agreement, however, flame emission publications are reviewed in the section of this review issue entitled "Atomic Absorption, Atomic Fluorescence, and Flame Spectrometry" authored by Gary Horlick. This follows previous custom. Because of the late arrival of some journals appearing in December 1983, we may have missed some references of importance, and it is hoped that these will be discussed in the next biennial review. In general, we are following the format that we have used in the previous two reviews (18A, 19A), this is essentially the format that had been used by the previous author of this review, Ramon M. Barnes. Because of space considerations, however, we have had to be particularly selective and we have not attempted to provide an all-inclusive bibliography. In this fundamental review, the emphasis will be on developments in theory, methodology, and instrumentation. Applications will be cited only insofar as they advance the state of the art or have particular current relevance. References will be cited only if they are of particular importance to analytical chemists and spectroscopists; articles of primary interest to astronomers and/or physicists are not, in general (with some exceptions in Section B), cited. Readers should note that detailed and specific application information is available from Analytical Abstracts, Chemical Abstracts, and also the more specific
annual series Annual Reports on Analytical Atomic Spectroscopy (ARAAS)(%A,49A) published by the Royal Society of Chemistry, Burlington House, London, W1V OBN, United Kingdom. These annual reports provide detailed information on emission spectrometry and atomic absorption spectrometry and are absolutely highly recommended to those with an interest in the field. Whereas our biennial selective review provides several hundred references, each of the ARAAS annual reviews provides over 2000 references including a wealth of information on meeting presentations. Volume 12, reviewing 1982, has just appeared (49A) and the Editors, L. Ebdon and K. W. Jackson, are commended for their outstanding effort. In going thro h the 1982-1983 literature, we have selected the following p3lications as being most relevant and most emission spectrometry papers published in these journals are cited in this review: Analyst (London),Analytica Chimica
Acta, Analytical Chemistry, Analytical Letters, Applied Optics, Applied Spectroscopy, Applied Spectroscopy Reviews, Atomic Spectroscopy, Canadian Journal of Spectroscopy, CRC Critical Reviews in Analytical Chemistry, Environmental Science and Technology, Fresenius' Zeitschrift fur Analytische Chemie, ICP Information Newsletter, International Journal of Environmental Analytical Chemistry, Journal of Chemical Education, Journal o the Optical Society of America, Journal of Quantitative pectroscopy and Radiative Transfer, Microchemical Journal, Optica Acta, Progress i n Analytical Atomic Spectroscopy, Reviews i n Analytical Chemistry, Review of Scientific Instruments, Science, Spectrochimica Acta Part B, Spectroscopy Letter, and Talanta. Papers published in unreviewed magazines such as Americanllnternational Laboratory, Industrial Research and Development, Laboratory Practice, etc. are not generally
Q
Atomic Absorption and Emission Spectrometry Abstracts published by the PRM Science and Technology Agency (4A). In addition, the latest Application Reviews issue of Analytical Chemistry (3A) contains many recent spectrochemical application references. Readers should also note the excellent
cited. However, where we feel that a publication is of fundamental importance, it is cited whatever the source. A comment should be made regarding the citation of inductively coupled plasma mass spectrometry (ICP-MS) publications.
'Reprints of t h i s review are available o n request. OOO3-2700/84/0356- 133R$06.50/0-1
0
1984 American Chemical Society
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