Anal. Chem. 1980, 52, 5 0 R - 5 3 R (348) Stevens, M. D.; MacKenzie, W. F.; Anand, V. D. Biochem. Med. 1977, 18, 158. (349) Butrimovitz, G. P.; Purdy, W. C. Anal. Chlm. Acta 1977, 94, 63. (350) Johnson, D. J.; Djuh, Y. Y.; Bruton, J.; Williams, H. L. Clin. Chem. 1977, 23, 1321. (351) Lopez Fonseca, J. M.; Sanz Pedrero, P.; Otero, S.; Bugeiro, M. T. An. Qulm. 1978. 74, 398. (352) Mosescu, N.; Kalrnutchi, G.; Badea, S. Rev. Chim. (Bucharest),1977, 28. 373. (353) Jombik, J.; Solcova, M.; Fuchsova, 0. Farm. Obz. 1977, 32, 397. (354) Beavin, P., Jr. J . Assoc. Off. Anal. Chem. 1977, 60, 663. (355) Miyagi, H.; Kawazoe, K.; Kamo, T.; Takata, Y.; Nakajima, F.; Arikawa, Y. Jpn. Anal. 1978. 27. 561. 1356) Lazeeva. G. S.: Petorv. A. A,: Khomvakov. R. V. Zh. Prikl. Soektrosk. ' 1977, 2 6 , 1112. (357) Gacs, I.; Vargay, Z.; Dombi, S. J. Radioanal. Chem. 1978, 4 5 , 15. (358) Kozlowski, E.; Biziuk, M. Mikrochlm. Acta 1979 11, 19. (359) Abramyan, A. A.; Khanzadyan, A. K. Arm. Khim. Zh. 1978, 31, 790. 13601 Zheleznvakov. N. S.: Tatarinskii. V. S.: M. M. Z h . Anal. . Fedvachkin. , ' Khim. 1978:~33,'1401. ' (361) Mazzeo-Farina, A.; Mazzeo. P. Microchem. J . 1978, 23, 137. (362) Anisimova, G. F.; Klimova, V. A. Zh. Anal. Khim. 1978, 33, 538. (363) Kobylinska-Mazurek, B.; Kozlowski, E. Mikrochim. Acta 1978 I , 137. (364) Abramyan, A. A.; Kocharyan, A. A. Arm. Khim. Zh. 1977, 3 0 , 45. (365) Futekov, L.; Kuetschukov, D.; Specker. H. fresenius' Z . Anal. Chem. 1977, 284, 197. (366) Kozlowski, E.; Biziuk, M. Mikrochim. Acta 1979 11, 1. (367) Khanzadyan, A. K.; Abramyan. A. A. Arm. Khim. Zh. 1978, 37, 793. (368) Tsuji, K.; Fujinaga, K.; Hara, T. Bull. Chem. SOC.Jpn. 1977, 5 0 , 2292; 1978, 57, 2951. (369) Pella, E.; Colombo, B. Mikrochlm. Acta 1978 1, 271. (370) Skoroboaatova. V. I.: Balashenko, L. V.; Grornkova, R. A. Zh. Anal. Khim. 1977,-32, 327. (371) Sakla, A. B.; Rashid, M.; Karirn, 0.: Barsoum, B. N. Anal. Chim. Acta 4978. ... ., 98. .., 121. .- .. (372) Glazov, V. M. Zh. Anal. Khim. 1978, 3 3 , 1590. (373) Henningsen, W. P.; Schaetzier, H. P.; Kuehn, W. Atomkernenergie 1978, 31, 131. (374) Lisovskii, I.P.; Smakhtin. L. A. Zh. Anal. Khlm. 1977, 32, 1214. (375) Shand, J. H.; Noble, R . C. Clin. Scl. Mol. Med. 1976, 51, 511. (376) Windsor, D. L.; Denton, M. B. Appl. Spectrosc. 1978, 32, 366. (377) Bhattacharya, S. K. Anal. Lett. 1977, 10, 817. (378) Tatro, M. E.; Raynolds, W. L.; Costa, F. M. At. Absorpt. News/. 1977, 16, (6), 143. (379) Ishino, F.; Matsumae, H.; Shibata. K.; Ariga, N.; Goshima, F. Jpn. Anal. 1978, 2 7 , 232. (380) Del Castilho, P.; Herber, R. F. M. Anal. Chim. Acta 1977, 9 4 , 269. (381) Pozzoli, L.; Minoia, C. Ann. 1st. Super. Sanita 1977, 13, 377. (382) Boiteau, H. L.; Metayer, C. Analusis 1978. 6 , 350. (383) Wawschinek, 0. Mlkrochim. Acta 1979 11, 111. (384) Arpadyan, S.; Kachov, I. Zentralbl. Pharm. Pharmakother. Laboratoriumdiagn. 1978, 117, 237. (385) Menden, E. E.; Brockman, D.; Choudhury, H.; Petering, H. G. Anal. Chem. 1977, 4 9 , 1644. (386) Capar, S. G. J . Assoc. Off. Anal. Chem. 1977, 60, 1400. (387) Egaas, E.; Julshamn, K. At. Absorpt. News/. 1978, 77, (S), 135. (388) Agemian, H.; Chearn, V. Anal. Chim. Acta 1978, 101, 193. (389) Brzozowska, B. Rocz. Panstw. Zakl. Hlg. 1977, 28, 355, 441. (390) Moll, M. Brauwissenschaft 1977, 30, 347. (391) Evans, W. H.; Jackson, F. J.; Dellar, D. Analyst (London) 1979, 104, 16. (392) Rees, D. I. J . Assoc. Public Anal. 1978, 16, (3), 71. (393) Fudagawa, N.; Kawase, A. Jpn. Anal. 1978, 2 7 , 353. (394) Allenby, P.; Robertson, J. W.; Shenton, F. C. J . Assoc. Public Anal. 1977, 15(2), 61. (395) Pellerin, F.; Goulle, J. P. Ann. Pharm. f r . 1977, 3 5 , 189. (396) Kosonen, P. 0. Finn. Chem. Lett, 1978, 136. (397) Grizzle, P. L.; Wilson, C. A.; Ferrero, E. P.; Coleman, H. J. U.S. Energy Res. Dev. Adm.. Rep., No. BERC/RI-77/8, 1977. (398) Ure, A. M.; Hernandez-Artiga, M. P.; Mitchell, M. C. Anal. Chim. Acta 1978, 96. 37. (399) Hoenig, M.; Vanderstappen, R. Analusis 1978, 6, 312.
(400) Dalquist, R. Appl. Spectrosc. 1978, 3 2 , 1. (401) Jackson, C. J.; Porter, D. G.; Dennis, A. L.; Stockweli, P. B. Analyst (London) 1978, 103. 317. (402) Fischer, R. Erdol Kohle Erdgas Petrochem. Brennst.-Chem. 1978, 3 I , 200. (403) Jones, J. B., Jr. Commun. Soil Scl. Plant Anal. 1977, 8 , 349. (404) Holmberg, P.; Hyvonen. M.; Tarvainen. M. J . Radioanal. Chem. 1978, 42, 169. (405) Cesapa, A.; Nava, A.; Teatini, A.; Tenconi, T.; Terrani, M.; Terrani, S. J . Radioanal. Chem. 1978, 42, 435. (406) Buono, J. A,; Buono, J. C.; Fasching, J. L. J . Radioanal. Chem. 1977, 3 6 , 353. (407) Bando, S.; Imahashi, T. Jpn. Anal. 1977, 26, 138. (408) Piliay, K. K. S.;Kuis, R. L. J . Radioanal. Chem. 1978. 43, 461. (409) D'Hondt, P.; Lievens, P.; Versieck. J.; Hoste, J. Radlochem. Radloanal. Lett. 1977, 31, 231. (410) Behne, D.; Jurgensen, H. J . Radioanal. Chem. 1978, 4 2 , 447. (41 1) Versieck, J.; Hoste, J.; Barbier, F.; Michels, H.; De Rudder, J. Clln. Chem. 1977. 23. 1301. (412) Diksic: M.; Cole, T. F. Anal. Chim. Acta 1977, 93, 261. (413) Ritland, S.; Steinnes, E.; Skrede, A. Scand. J . Gastroenterol. 1977, 12, 81. (414) Versieck, J.; Hoste, J.; Barbier, F.; Steyaert, H.; De Rudder, J.; Michels, H. Clin. Chem. 1978, 2 4 , 303. (415) Lyengar, G. V.; Kasperek, K.; Feinendegen, L. E. Phys. M e d . Bid. 1978, 23, 66. (416) Kirzhner, M.A.; Kryzhenkova, N. A.; Kist, A. A. M e d . Radio/. 1977, 22, 85. (417) Anand, S. J. S. J . Radioanal. Chem. 1978, 4 4 , 101. (418) Kasrai, M.; Shoushtarian, M. J.; Bozorgzadeh, M. H. J . Radioanal. Chem. 1977, 4 1 , 73. (419) Tanner, J. T.; Friedman, M. H. J . Radioanal. Chem. 1977, 3 7 , 529. (420) Lo. J. G.; Yeh, S. J. Radioisotopes 1976, 25, 206. (421) Bergerioux, C.; Zikovsky. L. J . Radioanal. Chem. 1978. 46, 277. (422) Block. C.; Dams, R. Anal. Lett. 1977, IO, 1233. (423) Segebade, C. Fresenius' 2. Anal. Chem. 1977, 284, 23. (424) Srapenyants, R. A.; Saveliev, I. B. J . Radioanal. Chem. 1977, 38, 247. (425) Hattula, T.; Johanson, M. Radlochem. Radioanal. Lett. 1978, 32, 35. (426) Minski, M. J.; Girling. C. A.; Peterson, P. J. Radiochem. Radioanal. Lett. 1977, 3 0 , 179. (427) Hineman, P. S.; Giuffre. G.; Litman, R. Radiochem. RadiOaMl. Lett. 1978, 33, 361. (428) Gallorini, M.; Greenberg, R. R.; Gills, T. E. Anal. Chem. 1978, 50, 1479. (429) Sato, N.; Kato, T.; Suzuki, N. J . Radioanal. Chem. 1977, 36, 221. (430) Dyson, N. A.; Simpson, A. E.; Dabek, J. T. J . Radioanal. Chern. 1978, 46. 309. (431) Paradellis, T. Eur. J . Nucl. Med. 1977, 2, 277. (432) Cesareo, R.; Gigante, G. E. Boll. Soc. Ita/. Blol. Sper. 1977, 53, 1054. (433) King, R. T. J. Sci. Food Agric. 1977, 28, 631. (434) Linder, H. R.; Seltner, H. D.; Schreiber. 8. Anal. Chem. 1978. 5 0 , 896. (435) Mittler, A.; Barnes, B. K.; Litman, R.; Holton, F.; Barry, E. F. Anal. Chem. 1977, 49, 432. (436) Trzebska-Jeske, 1.; Rutkowska, U. Rocz. Panstw. Zakl. Hig. 1978, 29, 197. (437) Jones, J. W.; Gajan, R. J.; Boyer, K. W.; Fiorino, J. A. J . Assoc. Off. Anal. Chem. 1977. 60, 826. (438) Bruno, P.; Caselli, M.; Di Fano, A.; Fragale, C. Analyst (London) 1978, 103. 868. (439) Bishara, S.W.; El-Samrnam, F.M. Mlcrochem. J . 1977, 22, 442. (440) Franzke, C.; Ruick, G.; Schmidt, M. Nahrung 1977, 21, 417. (441) Manuilova, T. A.; Spektor, L. A.; Konservn. Ovoshchesuch. Prom. 1977, 48 (3), 35. (442) Lapitskaya, S. K.; Sviridenko, V. G. Zh. Anal. Khim. 1978, 33, 1583. (443) Mikhailova, G. K.; Shakhova, I. D.; Khim. Volokna 1977, 19 (3), 74. (444) Franke, J. P.; de Zeeuw. R. A. J . Anal. Toxicol. 1977, 1. 291. (445) Oehrne, M.; Lund, W.; Jonsen, J. Anal. Chlm. Acta 1978, 100, 389. (446) Valenta, P.; Riitrel, H.; Nurnberg, H. W.; Stoppler, M. fresenius' 2.Anal. Chem. 1977, 285, 25. (447) Moorhead, E. D.; Doub, W. H., Jr. Anal. Lett. 1977, IO, 673. (448) Deldime, P.; van Zieleghem, A. Cerevlsia 1977, 2, 21. (449) Williams. H. L.; Johnson, D. J.; Haut, M. J. Clin. Chem. 1977, 23, 237. (450) Szymanska, J. A,; Zychowicz, M. Chem. Anal. (Warsaw) 1977, 22, 985.
Electron Spin Resonance John R. Wasson" and Jorge E. Salinas Ellestad Research Laboratories, Lithium Corporation of America, P.O. Box 795, Bessemer City, North Carolina 280 16
This review covers the published literature from July 1977 to July 1979 although a few citations of other work are also included. Thousands of articles containing ESR information were published during the two-year span covered by this 50 R
0003-2700/80/0352-50R$Ol .OO/O
review ( 1 ) . Hence, no attempt can be made at inclusive citation, even ever so briefly, in the space available for the present effort. Rather, this review is intended to serve as a guide to the current literature and provide an eclectic selection
0 1980 American
Chemical Society
ELECTRON SPIN RESONANCE John R . Wasson is the director of the chemical division of the research department of Lithium Corporation of America. He was born in St. Louis, Mo., and received his education at the University of Missouri-Columbia (B.S., 1963; M.A., 1966) and Illinois Institute of Technology (Ph.D., 1970). He is the author or cc-author of more than 100 research papers, reviews, and technical articles. His publications and interests are in the areas of magnetic resonance spectroscopy, transition metal and organometallic chemistry, and inorganic polymers and colloids. He is a member of the American Chemical Society, American Association for the Advancement of Science, The Chemical Society (London), Phi Lambda Upsilon, and Sigma XI.
Jorge E. Sallnas is currently a research chemist in the Research Department of Lithium Corporation of America. He was born in Cali, Colombia, S.A. and received his undergraduate training at the University of Hamburg, Germany. He graduated with an M.S degree in chemistry from Florida Atlantic University in 1975. His research interests include nuclear magnetic resonance spectroscopy, coenzyme and flavanoid chemistry. He is a member of the American Chemical Society.
of articles cited for their contributions to the advances and/or applications of ESR spectrometry. Comments on the literature of electron spin resonance have been made previously (1) but it is worth noting that the Chemical Society (London) Specialist Reports on ESR spectroscopy are recommended sources for beginning literature searches. A number of computer search services are available, particularly those serving to maintain current awareness. In addition to sources mentioned earlier (I,Z), a new source of current computer searches of the magnetic resonance literature has become available from the Institute for Scientific Information, 325 Chestnut Street, Philadelphia, Pa. 19106.
BOOKS AND REVIEWS The book edited by Berliner ( 7 ) on spin labeling extends an earlier effort to provide perspective for a seemingly ever growing number of applications for spin labels and probes. In a more fundamental vein, Harriman’s text ( 5 ) affords a mathematical development of the subject. The books on ESR (2-8) provide coverage of a range of topics as do the reviews cited in Table I. For convenience, the references for Table I are collected separately in the bibliography.
APPARATUS AND SPECTRAL ANALYSIS A simple and inexpensive modification of a Ka-band EPRIENDOR spectrometer making it possible to measure electron spin echos at 35 GHz has been described (9). A longitudinal strain modulation system, consisting of a composite transducer, amplitude transformer, and a resonator with the sample under investigation has been designed for use in ESR and optical spectroscopy (10). The applicability of SQUID magnetometers to the detection of EPR a t mK temperature has been demonstrated (11). This method of detection is particularly well-suited for systems with long spin-lattice relaxation times. A gas-flowing measuring head for an ESR spectrometer has been described (12). A flat glass Microslide tubing cell for lossy samples has been reported (13). An inexpensive temperature controller, which can be used with ESR and NMR spectrometers, consisting of a heater-sensor assembly, a feedback amplifier, and a power supply has been described (14). An approximate method for estimating variance and covariance of EPR determined eigenvalues and eigenvectors has been described (15) using the hyperfine coupling tensor as an example. A theoretical evaluation of ESR transition probability determinations has been presented (16). Parameters of a spin Hamiltonian for the description of ESR spectra of
Table I. Reviews topic
ref.
Free radicals in enzymatic systems Paramagnetic intermediates in photosynthetic systems Copper in biological systems Interaction of spin labels with transition metals EPR of transition ions as a probe of structural (phase) changes General review Electron-electron d o u b l e resonance Imperfections and radiation-induced decomposition of azides Free radical reactions and ESR Vibronically coupled systems Optical detection of magnetic resonance in semiconductors Excitation and ionization of 5-halouracils Solvation Boron nitride, boron, and boron carbide Alkali biphenyl ion pairs Spin label and probe studies of polymeric solids and melts Polymer deformation and fracture Fiber science Determination of uranium isotopic abundance Ionic fluorine-containing free radicals Free radicals in biological systems Transient radicals in solution Biradicals as spin probes Fluorine-containing radicals in single organic crystals Radiation damage in DNA constituents and DNA Nitroxide spin label synthesis and chemistry Photosynthesis Magnetic probes of metal binding sites in copper proteins Iron-sulfur centers of succinate dehydrogenase Photosystem I1 Molecular and conformational equilibria MO theory and magnetic resonance parameters Actinides ELDOR Lipid membranesESR techniques Organic radicals Inorganic and organometallic radicals
1 2, 13
3 4
5 6 , 34 7 8
3 10
11 12 14 15 16 17 18 19 20 21 2 2 , 38 23 24 25
26 27 28 29 30 31 32 33 35 36 37 39 40
oriented radicals were calculated. They are described within an approximate electron propagator framework (17 ) . Spinspin splittings have been analyzed (18) for two nonequivalent electron spins. The resulting equations are applied to the simulation of the ESR spectra of spin-labeled copper complexes exhibiting electron-electron coupling. ESR parameters for a p’ ion in a crystal field taking into account lattice vibrations have been derived (19). Tris(acety1acetonato)chromium(II1) has been examined down to -100 “C in a eutectic liquid crystal mixture of EBBA and MBBA. The dependence of the parameters on the magnetic field intensity was determined (20). A simple method for calculation cf the exact axial resonance fields of quintet ESR transitions and their relation to powder spectra has been reported (21). Third-order perturbation theory has been employed (22)to obtain expressions for the energy levels of 55Mn(II)in the presence of an external magnetic field with axial and orthorhombic distortions in the crystal field. The expressions have been used to simulate line 1/2) fine structure transition shapes for the central (1 2 in ESR spectra of Mn(1 ) in complexes with enzymes. The perturbation theory method for obtaining the value of the axial crystal-field parameter D in a powder sample of Mn(I1) complexes from the relative intensities of the main hyperfine ESR lines has been revised (23). Calculations based on precise numerical diagonalization of the spin Hamiltonian were made and are in agreement with those based on perturbation theory, up to a value of about DIH, = 0.044, Le., D = 150 G a t X-band frequencies. Analytical solutions for locating extra absorption peaks in “polycrystalline” EPR spectra of systems with anisotropic g-factor and hyperfine structure have been obtained
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and general conditions for the existence of these peaks formulated (24). The rapid computer simulation of 9.5- and 35-GHz EPR and saturation-transfer EPR spectra obtained employin finite Zeeman modulation amplitudes and microwave fielcf intensities has been discussed (25) and computer algorithms have been developed. A tape library of computed saturation transfer EPR spectra has become available (26)for a range of several common experimental variables; the content of the library is limited to spectra appropriate to nitroxide spin labels. A program is described for time averaging of ESR spectra to improve sensitivity (27). A second program calculates line position, intensities, accumulation, and splitting constants for nitroxide radicals. Two computer programs that can be used to simulate EPR-spectra of effective spin-l/2 biochemical systems have been reported (28)as have computer programs (23)to simulate EPR spectra of effective spin-1/2 in frozen aqueous samples.
ANALYTICAL APPLICATIONS Precision and accuracies of approximately *170 can be obtained for concentration measurements by using proper methods for double integration of the EPR signal (30). An inexpensive technique for obtaining low-temperature (77 K) ESR spectra has been detailed (31). ESR has been employed to characterize the free radicals in several coals, coal fractions, and pyrolyzed coals (32). An ESR method for the determination of titanium (detection limit 0.1 Hg mL) in the presence of niobium has been developed (33). he preparation and utilization of chromium-doped corundum as an intensity standard in E P R has been reported (34). Absorbance, ESR, and MCD measurements (self-consistent) have been employed (35) to determine Fe(I1) and Fe(II1) in MgO. An analytical method for determining Eu(I1) in HCl media in the concentration range 30-1500 ppm has been described (36). Di- and triorganotin derivatives react very smoothly with substituted o-aminophenols in the presence of air oxygen to form stable paramagnetic derivatives. The complexes are easily detected a t concentrations of M (37). The determination of serum lipase can be achieved using a lipid-soluble nitroxide dissolved in an olive oil emulsion (38). A study of the redox titration of chromatium minutissimum chromatophores has been reported (39)which employed ESR spectroscopy. This work affords yet another example of the application of ESR to the study of redox titrations.
4
SELECTED PARAMAGNETIC MATERIALS A description has been provided (40) of experiments on photoexcited triplet states of aromatic molecules in which the phase coherence between the individual spins manifests itself. The phosphorescence spectra, zero-field splittings and decay rates from the spin sublevels of the T, states of 1-indanone at 1.2-4.2 K have been examined (41)using zero-field optically detected magnetic resonance (ODMR) and compared with those of acetophenone. The triplet state zero-field splitting parameters and intersystem crossing decay constants for the individual triplet spin sublevels of Mg tetraphenylchlorin and Mg porphine dissolved in pyridine have been presented (42). The preparation of vitamin B l Z b single crystals doped with paramagnetic BIzrhas been reported (43). A comparison of ESR spectra obtained from bovine bone samples after mechanical degradation, y irradiation and mechanical degradation followed by y irradiation has been made (44). Radicals formed from collagen predominate. Dilute aqueous and methanol solutions of (Me3C)zN0have been examined (45) using ESR spectrometry and changes in the I4N hyperfine coupling constant and in the line widths were measured in the presence of a range of 24 added electrolytes. The results are discussed in terms of two equilibria, one involving the gain or loss of hydrogen bonds to the NO oxygen atom, and the other involving the cation and resulting in changes in hydrogen bond strengths. A tanol derivative of benzo-15-crown-5has been synthesized and employed (46) to examine alkali metal complexation.
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A method of generation of N-acyl-N-alkyl (nitroxide radicals by photolysis of N-nitroamides has been reported ( 4 7 ) . ESR parameters are reported for 17 radicals of the type RCONR'O. High resolution spectra suggest that the radicals prefer a trans conformation about the CO-N bond and that rotation about the N-R' u-bond is inhibited. An ESR study of the porphyrin-sensitized photooxidation of 2,2,6,6-tetramethylpiperidine to the corresponding nitroxide shows that the porphyrins examined are able to generate singlet oxygen although the efficiency of the process is dependent on the side chains and is also inhibited by incorporation of metal ions into the porphyrin molecules (48). The efficiency of porphyrins as sensitizers is controlled by the lifetime of their lowest triplet state. ESR studies of transition metal ion binding to humic acid (49) and the mobility and orientation of charged molecules in hectorite clays ( 5 ) have been described. Both V 0 2 + (51) and the protonated form of 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (52) have been employed as spin probes of hectorite clays. X-irradiation of chlorate-doped potassium chlorate crystals generates C103 radicals. The limit of detection of chlorate ions is 1 ppm using standard equipment (53). Yellow phosphorus dissolves in disulfuric acid to give SOz and a blue solution containing the S5+ radical (54). ESR has been employed (55)to partially characterize the brownish black precipitate formed by mixing TiC1, and Al(BH,), in organic solvents. The precipitate is a catalyst for the polymerization of ethylene, isoprene, and methyl methacrylate. The forbidden (Am = 2) transitions of Mn(I1) in A1203 have been determined and interpreted (56). Structural transformations of aluminum-molybdenum catalysts have been employed (57) using ESR techniques. Techniques for preparing and stabilizing Oz- from the thermal decomposition of NzO over y-AlZO3have been reported (58). Exchange interactions (Cr3+-Cr3+in LiGa508 (59) and Cr3+-Mo3+)in doped CsMgC1, (60) have been examined experimentally and interpreted. The principal axes of the g and the Cu hyperfine structure tensors do not coincide in bis(diethylthioselenocarbamato)copper(II) (61). The 28ground state diatomic radicals ZnF and CdF have been generated at high temperatures and isolated in solid Ne and Ar matrices at 4 and 12 K, respectively (62). Exposure of solutions of AgC104in acetonitrile to @Coy-rays at 77 K gives Ag(I1) and Ag(0) centers in addition to radicals formed from the solvent (63). Their ESR spectra showed hyperfine features from lo7Ag and lo9Ag together with splittings from four equivalent I4N nuclei. The ESR of Tc(1V) in acidic solution has been observed (64)upon reduction of Te04- using ascorbic acid and other reducing agents. A singlet crystal ESR study of the platinum(II1) bis(maleonitri1e-dithiolate) monoanion doped into the corresponding tetrabutylammonium salt of the gold(II1) monoanion has been interpreted in terms of a half-filled out-of-plane T MO ground state which is extensively delocalized over the ligands (65). At least three metal site environments are apparent in the Q-band spectrum of vanadyl(1V)-labeledhuman serotransferrin and a conformational change at pH 10 can be detected (66). E P R analysis of "invisible" copper in cytochrome oxidase has been described (67). A model for the concentration changes of ceruloplasmin and Fe transferrin(I1) after myocardial infarction has been discussed and confirmed using ESR data (68). It was found that ceruloplasmin concentration increases to a maximum 4 to 1 2 days after myocardial infraction and then i t decreases to normal. At the same time, Fe transferrin concentration decreases to a minimum and then increases up to normal. LITERATURE CITED
(1) Wasson, J. R.; Corvan, P. J. Anal. Chem. 1978, 50, 92R-100R. (2) "Specialist Periodical Report, Vol. 4: Electron Spin Resonance", Ayscough, P. B.. Ed.; Chemical Society: London, 1977. (3) "Chemical and Biochemical Aspects of Electron Spin Resonance Spectroscopy", Symons, M. C. R.; Wiley: New York, 1978. (4) "Magnetic Ions in Metals: A Review of Their Study by Electron Spin Resonance", Taylor, R. H.; Taylor and Francis: London, 1977. (5) "Theoretical Found&ions of Electron Spin Resonance", Harriman, J. E.; Academic Press: New York, 1978. (6) "Multiple Electron Resonance Spectroscopy", Dorio, M. M., Freed, J. H., Ed.; Plenum: New York, 1979. (7) "Spin Labelling 11-Theory and Applications", Berliner, L. J., Ed.; Academic Press: New York, 1979. (8) "Time Domain Electron Spin Resonance", Kevan, L.; Schwartz, R.; Wiley: New York, 1979.
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(63) Symons, M. C. R.; Brown, D. R.; Eastland. G. W. Chem. Phys. Left, 1979, 61, 92-5. (64) Benson, W. R.; Yang, G. C.; Heitzmann, M W.; Ford, L. A. J . Labelled Compd. Radiopharm. 1978, 15, (suppl. vol.), 343-52. (65) Kirmse, R.; Dietzsch, W.; Solovev, B. V. J . Inorg. Nucl. Chem. 1977, 39, 1157-60. (66) White, L. K.; Chasteen. N. D. J . fhys. Chem. 1979,83,279-84. 167) Seiter. C. H. A.: Anaelos. S. C.: Perreault. R. A . Biochem. Bloohvs. . _ Res. Commun. 1977, 78(3),761-5. (68) Cannistraro, S.;Indovina, P. L. fhys. Med. Biol. 1979, 24(1), 197-8. LITERATURE FOR TABLE 1
(1) Edmondson, D. E. "Biological Magnetic Resonance", Berliner, L. J., Reuben, J., Eds.; Plenum: New York, 1978; Vol. 1. (2) Warden, J. T. Ref. 1. (3) Boas, J. F.; Pilbrow, J. R.; Smith, T. D. Ref. 1, pp 277-342. (4) Eaton, S. S.; Eaton, G. R. Coord. Chem. Revs. 1978,26, 207. (5) Owens, F. J. "Magnetic Resonance of Phase Transitions", Owens, F. J., Pooie. C. P., Jr., Farach, H., Eds.; Academic Press: New York, 1979; Chapter 6. (6) Ingram, D. "Experimental Magnetism", Kalvius, G. M., Tebble. R. S.,Eds.; Wiley: New York, 1979; Voi. 1 (7) Dorio, M. M. Magn. Reson. Rev. 1977, 4 , 105-36. (8) Garrett, W. L.; Marinkas, P. L.; Owens, F. J.; Wiegand, D. A. Energ. Mater. 1977, 1 , 285-382. (9) Bullock, A. T. Annu. Rep. Prow. Chem. Sect. B . 7977 1978,90-104; 1976, 73,71-83. (10) Engleman, R.; Halperin. B. Ann. fhys. ( f a r i s ) 1978, 3 ,453-78. (11) Cavenett, 8. C. J . Lumin. 1979, 18-19; Pt. 2, 846-52. (12) Huettermann, J., JerusalemSymp. Quantum. Chem. Biochem. 1977, 70. 85-98. (13) Weaver, E. C.; Corker, G. A. Encycl. Plant Physiol., New Ser. 1977,5 , 168-1 78. (14) Symons, M. C. R., Annu. Rep. Prog. Chem., Sect. A : Phys. Inorg. Chem. 1977, 73,91-112; Pure Appl. Chem. 1977, 49, 13-26. (15) Geist, D. "Boron and Refractory Borides", Matkovich. V. I . , Ed.; Springer: Berlin, 1977; pp 65-77. (16) DeBoer, E., Klaassen. A. A. K.; Mooii, J. J.: Noordik, J. H. Pure A.m. / . Chem. I979?5 1 , 73-83. (17) Tormaia, P. J . Macromol. Sci., Rev. Macromol. Chem. 1979, C 1 7 , 297-357. (18j~RoilHnce,D. K. ~ p p l Poiym. . Spectrosc. 1978,207-19. (19) Meybeck, A.; Meybeck, J. Appl. Fibre Sci. 1978, 1, 505-56. (20) Ursu, I.; Lupei, V.; Lupei, A,; Voicu. I.Rev. Roum. Phys. 1979, 24, 229-34. (21) Morton, J. R . ; Preston, K. F. A . C . S . Symp. Ser. 1978,6 8 , 386-409. (22) Kayushin, L. P. Acta Biochim. Biophys. Acta Sci. Hung. 1977, 72, 187-90. (23) Wan, J. K. S.;Wong, S. K. Rev. React. Species Chem. React. 1976, 1, 227-61. (24) Parmon. V. N.; Kokorin, A. I.; Zhidomirov. G. M. Zh. Strukt. Khim. 1977, 18, 132-77. (25) Kispert, L. D. ACS Symp. Ser. 1978, 6 6 , 349-85. (26) Sevilia, M. D. Jerusalem Symp. Quantum Chem. Biochem. 1977, 10, 15-25. (27) Keana, J. F. W. Chem. Rev. 1978, 78, 37-64. (28) Evans, M. C. W. Top. fhotosynth. 1977,2,433-64. (29) Peisach, J. Dev. Blochem. 1978, 7 , 285-306. (30) King, T. E.; Ohnishi, T.; Winter, D. B.; Wu, J. T. Adv. Exp. Bo/.1976, 74,182-227. (31) Evans, M. C. W. Biochem. SOC. Trans. 1978, 6 , 906-8. (32) Russell, G. A. Aspects Mech. Organomet. Chem. ( f r o c . Symp.) 1978, 59-108; Brewster, J. H., Ed.; Plenum: New York. (33) Beveridge. D. L. Mod. Theor. Chem. 1977,(Semiempirical Methods Electronic Structure Calc., Part B.) 163-214. (34) Wasson. J. R., "Instrumental Analysis", Bauer, H. H.. Christian, G. D., O'Reilly, J. E., Eds.; Allyn and Bacon: Boston, 1978; Chapter 13. (35) Boatmer, L. A.; Abraham, M. M. Rep. f r o g . fhys. 1978, 4 . 87-155. (36) Dengan. S. K.; Venkataramen, B. R o c . Nucl. Phys. Solidstate fhys. Symp. 1975, 78C,571-5. (37) Gaffney. B. J.; Lin, D. C. Clin. Exp. Ammuno-reprod. 1977,4 , 31-50. (38) Knoles, P. F.: Peake. B. Electron Spin Reson. 1977, 4 . 212-86. (39) Gilbert, B. C. Electron Spin Reson. 1977,4, 11 1-43. (40) Symons, M. C. R . Electron Spin Reson. 1977, 4 , 84-110.
Emission Spectrometry Walter J. Boyko, Peter N. Keliher," and James M. Malloy Chemistry Department, Villanova University, Villanova, Pennsylvania 19085
This is the 17th article in the series of biennial reviews in the field of emission spectrometry/spectroscopy and is the first written by the present authors. This review article will 0003-2700/80/0352-53R$05.00/0
survey selectiuely the emission spectrochemical literature of 1978 and 1979. By agreement, however, flume emission publications are reviewed in the section of this issue entitled 1980 American Chemical Society
53 R
