Anal. Chem. 1990, 62, 150R-155R (429) Womack. J. D.; Mann, C. K.; Vlckers, T. J . Appl. Specfrosc. 1989, 43 (3), 527-531. (430) ReWh, W.; Bett-nn, H. Appl. SpeCbapC. 1988, 42(3), 520-521. (431) MRomo, T.; Ichise, M.; Kojima, T. Buns&/ Kagaku 1988, 37 (12), T223-T227. (432) Cotton, T. M. A&. Spectrosc. (Chlchester. UK) 1988. IB(8pectrosc. Surf.), 91-153. (433) Vo Mnh, T.; Alak, A.; Moody. R. L. Smctrochim. Acta. Part 6 1987. 438 (4-5), 805-815. (434) Gerrell, R. L. Anal. Chem. 1989, 61 (81, 401A-402A, 404A, 406A408A, 410A-411A. (435) N e b , 1. R.; Efremov, R. 0.; Chumartov, 0.D. Vsp. f k . NaM. 1988, 154 (3), 459-498; chem.Abstr. 1988. 708: 182968~. (438) Creightm, J. A. A&. Spectrosc. (Chichester, UK) 1988, 16 (SpecttDSC. Swf.). 37-69. (437) Angel, S. M.; Sharma, S. K. U S US4.781,458 (C1 358-301; GOlN21185), 1st Nov 19888 Appi. 128, 159, 30th Nov 1987. (438) Force, R. K. Anal. Chem. 1088, 60(18), 1987-1989. (439) Shindo, H. Stud. Org. Chem. (Amsterdam) 1987, 30 (Recent Adv. ElectrWg. Synth.), 405-408. (440) Berttrod, A.; Laserna, J. J.; Wlnefordner, J. D. J . pharm. 6iomer.I. Anel. 1987, 6 (8-8), 599-808. (441) Torres T a g , E. L. 1988, 118 pp. Avail Univ Microfflms Int; Order No DA8718051. From Dlss. Abstr. Int. 6 1987, 48 (4), 1029. (442) Chese, D. B.; Parkinson, B. A. Appl. Spectrosc. 1988, 42 (7), 1188-1187. (443) Crookell, A.; Fleigchmann, M.; Hanniet. M.; Hendra, P. J. Chem. Phys. Len. 1868. 149 (2). 123-127. (444) Angel. S. M.;'Katz, L. F.; Archibald, D. D.; Honigs, D. E. App/. SpectrOSC. 1888, 43 (3), 387-372. (445) Angel, S. M.; Myrlck, M. L. Anal. Chem. 1989. 61 (15), 1848-1652. (448) Martin, F.; hieto, A. C.; De Saja, J. A.; A r m , R. J . Mol. Struct. 1888, 174, 383-368. (447) Kim, J. H.; Cotton, T. M.; Uphaus, R. A.; Moebius, D. J . Phys. Cham. 1989, 93 (9), 3713-3720. (448) Dorain, P. B. Report 1988, TR-7; Order No ADA191275, 11 pp. Avail. NTIS From Gov. Rep. Announce. Index (U S) 1988, 88 (15), Abstr. No 838, 215. (449) h a i n , P. B. 1988, TR-6; Order No ADA191512. 9 pp, Avail. NTIS From Gov. Rep. Announce. Index (U S) 1988, 86 (15), Abstr. No 838, 173. (450) ECSkokrofg, K. M.; Negm. S.; Taiaat, H. Roc. SPI€-Int. SOC. Opt. fng. 1888, 1009(Surf. Meas. Charact.), 302-308. (451) Ahern, A. M.; Gemell, R. L. Lengmu/r 1988. 4 (5). 1182-1168. (452) KOgM. E. J . Md. Struct. 1988, 173, 389-378. (453) @I'd R. L.; , Beer, K. D. Spectrochkn. Acta, Part 6 1987, 436 (4-5), 817-828. (454) Eckbreth, A. C.; StufRebeam, J. H. Mater. Res. Soc. Symp. Roc. 1888, 117 (Process Megn.: Meter., Combust., Fusion), 217-228. (455) Tsuchlya, U.; Ohya, M. K-I 1987, 22 (5), 305-316; Chem. Abstr. 1888, 108: 13097k. (458) Alden. M. KflntoVW8 E M . (MOSCOW) 1988, 15 (6), 1173-1184; Chem. Abstr. 1988, 109: 118288~.
(457) Valentine, J. J. Repr. Pap.-Am. Chem. Soc. Dlv. Fuel Chem. 1989, 34 (2). 493-497. (458) Alden, M.; Wendt, W. Appl. S p e c t r ~ ~ 1888, c. 42 (8), 1421-1427. (459) England, W. A.; Ali, A. Appl. Spec&osc. 1988, 42 (e), 1412-1421. (460) Wenzei, N.; Trautmann, B.; Gross-wude, H.; Schlemmer, 0.; Wek. B.; Marowsky, 0. Opt. Commun. 1088, 68 (1). 75-79. (461) Yueh, F. Y.; Beiting, E. J. Appl. Opt. 1988, 27(15), 3233-3243. (482) Spiberg, P.; Cahen, C.; Deschamps, P. J . Phys. Colbq. 1987, (C7), C7-7571'27-760. (483) Fujii, S.; Gomi, M. AIAA J . 1088, 26 (3), 31 1-315. (464) Fujii, S. NASA Tech. Memo. 1987, NASA-TM-100498, NASl.15:100498, Avail. NTIS From Sci. Tech. Aerosp. Rep. 1988, 28 (3), AbStr. NO N88-12353. (485) Lucht, R. P.; Tee% R. E.; Green, R. M.; Palmer, R. E.; Ferguson, C. R. Combust. SCi. Technol. 1987, 55(1-3), 41-61. (486) Attal-Tretoot, B.; Berlemont, P.; Taran. J. P. Spn'nger Ser. Opt. Scl. 1987. 55 (Laser Spectrosc. 8). 328-329. (467) Robertson. G. N. Roc. SPIE-lnt. Soc.qpt. fng. 1988, 674 (Roc.. Int. Congr. High Speed Photogr. Photonics, 17th. 1988. Voi 2), 582-570. (488) Barth, H. D.; Jackschath, C.; Pertsch, T.; Haisken, F. Appl. Phys. 6 1988, 645 (4), 205-214. (469) Marowsky. G.; Slenczka, A. Springer Ser. Opt. Sci. 1987. 55 (Laser Spectrosc. 8), 333-334. (470) Vu, T. H.; Field, R. AIP Conf. Proc. 1087, 160 (Adv. Laser Sci.-2), 693-695. (471) Kawasaki, M.; Kawai, E.; %to, H.; Sugai, K.; Hanabusa, M. Jpn. J . APPl. PhYS., Part 1 1987, 26 (9), 1395-1399. (472) Lueckerath, R.; Balk, P.; Flscher, M.; Grundmann, D.; Hertling, A,; Richter, W. C h e m / c s 1987, 2 (4), 199-205. (473) Hata, N.; Mutsude, A.; Tanaka, K. Roc.-flectrmhem. Soc. 1887, 87-8 (Proc. Int. Conf. Chem. Vapor. Deposition, loth, l987), 922-931. (474) Hata. N.; Matsuda, A.; Tanaka, K. J. Appl. Phys. 1987, 61 (8, Pt l), 3055-3060. (475) Lau, A.; Pfeiffer, M.; Werncke, W. Stud. Phys. Theor. Cham. 1987, 45 (Laser Scattering Spectrosc. Bioi. Objects), 127-132. (478) Kohles, N.; Lauberau, A. Chem. Phys. Len. 1987, 138(4), 385-370. (477) Takahashi, H. Kenkyu Hokoku-Asahi, Garasu Kogyo Gljutsu Shorekai 1987, 51, 181-192; Chem. Ab&. 1988, 109: 1194882. (478) Pinnick, R. G.;Biswas, A.; Chylek, P.; Armstrong, R. L.; Latifi, H.; Creegan, E.; Srivastava. V.; Jarzembski, M.; Fernandez, G. Opt. Lett. 1988, 13 (6). 494-496. (479) Qian. S.;Wang, J.; Li, Y. Chim. Phys. Lett. 1088, 5 (5), 205-208. (480) Golombok, M.; b e , D. P. Chem. Phys. Lett. 1988, 151 (1-2), 161-165. (481) Kurizki, G.; Nitzan, A. Jerusalem Symp. Quantum Chem. Biochem. 1987, 20 (Large Finke Syst.), 173-177. (482) Lavwel, B.; Mibt, G.; Saint-Loup, R.; Gonze, M. L.; Santos, J.; Berger. H.; Bonamy, J.; Robert, D. J . Phys. Collog. 1987, (C7), C7-781lC7-782. (483) Schauer, M. W.; Peiiin, M. J.; Blwer, B. M.; Gruen, D. M. AIP Conf. Roc. 1887, 160 (Adv. Laser Sci-2), 417-419. (484) Borysow, J.; Taylor, R. H.; Keto, J. W. Opt. Commun. 1988, 68 (I), 80-86.
Electron Spin Resonance Mysore Narayana Shell Development Company, Westhollow Research Center, P.O. Box 1380,Houston, Texas 77251-1380
TI$ article covers electron s in resonance (ESR) literature pubhshed during the period orJuly 1985 to December 1988. A lar e number of reviews, both generic and topic specific, have %een ublished durin this period along with an even larger numier of pa ers. 8bviously it is not ossible to do 'ustice to all the exceient articles that ap aretfin this period kecause of space, time, and sometimes Q limitations of the reviewer. Thus an attempt was made to reduce the bibliographic detail that a review usually gets into and place emphasis on the nonroutine nature of some of the huge number of papers published in this eriod. It was felt that it might be useful to the eneral auAence to have an easy reference to the various otter reviews mentioned above and, hence, a tabular form is given at the end of this article. Pulsed ESR techniques enjoyed some prominence during this period with numerous articles devoted to applications of electron spin echo modulation (ESEM) spectroscopy (1). Of particular interest is the technique described by Pfenni er et al. (2). In this novel time-domain technique, considera%le
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resolution improvement is achieved in powder patterns. When anisotropy is present in either Zeeman, fine structure, or hyperfine structure terms, specific crystallite orientations could be selected on the basis of sudden changes of the static magnetic field direction during the time interval between the microwave pulses of conventional two- or three-pulse electron spin echo sequences. Single or double jumps of the magnetic field vector were shown to be useful in the study of transition-metal complexes (2). Milov et al. (3)discussed the possibility of using ESEM as a method of tomography. By combination of the conventional ESEM experiment with pulsed magnetic field gradients, a s atial distribution of the parama netic centers could be ottained. The resolution of the metfmd is dependent on the to the ratio of the inverse of phase memory time (T2-!) magnetic field gradient and thus allows the possibilit to achieve a resolution higher than that in conventional JSR tomogra hy. The tReoretica1 aspects involving better incorporation of
0003-2700/90/0362-150R$09.50/00 1990 American Chemical Society
ELECTRON SPIN RESONANCE Mysofa N.¶I.¶Y.¶M received a BSc in physics and chemistry in 1970, a MSc in physics in 1972. and a PhD in physics in 1977, ai1 hom Osmania University. Hyderabad. India. He carried out postdoctoral research at Wayne Stale University and the University 01 Houslon. His current research involve^ the use 01 solution and solid-state nuclear msgnetic resonance techniques and electron spin resonance Io characterize c~laiys1s. polymers, and oils.
Fitzgerald and Weiss studied (15) the effects of solvents on cation-anion and cation-cation interactions in sulfonated polystyrene ionomers. ESR studies showed that the cations were primarily associated in bulk, while in solutions the extent of isolation of cations increased with increased polarity of the solvents. Mass spectrometric and ESR studies of allylic peroxyl radicals generated in the gas-phase reaction between the allylic radicals and oxygen were carried out and the peroxyl radicals appear to undergo free rotation even at 110 K (16). From an EPR study of Ziegler-type catalyst support on silica gel, Dah1 et al. (17) concluded that exchange of titanium and aluminum takes place irrespective of which of the metal complexes is anchored to the support. I t was also observed that the exchange is slow if there are no chlorine ligands on the aluminum complex. The homogeneity and molecular dynamics of linear and nuclear quadrupolar interartions into the simulation metho star-branched polystyrene containing a spin probe were dedolow of ESEM spectra also received ronsiderahle attention termined by double modulation ESR methods (18). Peroxy ( 4 ) . Dikanov et al. described a method to eliminate the mntrix radicals were used to probe the motion in polymers with contribution to modulatinns observed in G E M spectrn of different crystalinities (29). The ferromagnetic resonance of radicals, whirh makes use of appropriate frequency filters in cobalt particles supported on silica was studied and effects the prrliminarv process step (51 instead of the conventional of particle size on the spectra are described (20). A fast suhtrnction routines. method for analyzing ESR spectra hy computer and to extract Direct otiservation of one-dimensional electron spin the proton coupling constants was described by Motten, transport in organir ronductors by the electron spin echo field Duling, and Schreiber (21). gradient technique was desrribed hy .Maresch et RI. (6). Mehring et al. (22) described pulsed ENDOR, spin-echo Se\,eral interesting studies of inter- and intramolecular double resonance, TRIPLE resonance, and numerous other electron-elertron exchange interartion via KSH ohservations novel schemes in a recent article. hare tiem carried out, and the detnils ran he found in the ESE and ESR methods were used to characterize polarons fairly comprrhensive article puhlished recently t71. in donor- and acceptor-doped poly@-phenylene) (23). The ESR imaging has not received as much attention as its two techniques appear to give conflicting predictions for the counterpart in NMR did but it has not tiren completely ig. line width behavior as a function of temperature in this nored either. Sevrral groups are currently active in this field conducting polymer. ENDOR methods were used to char(8). KSH imaging with one spectral dimension and m e spatial acterize the perylene radicals adsorbed on activated alumina dimension was achitved (80,by obtaining spectra at a series and silica-alumina powders (24). On the basis of simulations of mngnetic field gradients with subsequent processing tiy of the hyperfine interactions and multifrequency ESR meahack-prnjection image-reconstruction algorithm. The adsurements, it was concluded that the same radical species vantnyr of such a technique was illustrated with samples forms on both types of activated support. conruining organir radicals, some rxhihiting hyperfine Sakai and Imamura (25)studied the molecular weight destrurture in soluttnn. Berliner, Wan, and Fujii described the pendence of polymer adsorption at solid-liquid interfaces use u i ESR imnging tu characterize sidvrnt swelling and diffusion into sdid polymers in a noninvasive fashiun (8~). using ESR. Rachdi and Bernier (26) studied the role of spin-orhit coupling on the ESR of alkali-doped polyacetylene. Rapid determination of translational diffusion coeftiriens The room temperature line width was found to increase with using ESH imaging in anisotropic solvents was descrttied Iiy Cleary et al. @[I. The use of Fourier transiorms of the conincreasing atomic number of the dopant. The thermoxidative rentration profile to determine the diffusiun roefficient was stability of poly(etbylene terephthalate) was shown to increase with increasing concentration of the stabilizing phosphorus discussed and an approximate raptd nnalflical terhnique complex, as evidenced by the changes in the ESR intensities presented. The use of Imp gap resonators (LGR) to enhance semitivity (27). has tieen well documented. In a recent report (9)the magnetic DeCray and Rieger (28)described a new method to interresonnnre applications (ESR. ENDOH, ESEM. e1c.J nf a pret ESR complex powder patterns, particularly suited for distributed rou ling technique were described, the gist of organometallic radicals. whirh is the romgined use of a regular TE,, ravity and a LGR Formation of radicals and catalytic activity of ZSM-5 type centered in the ronventional cavity. zeolites in unsaturated hydrocarbon conversions was studied iiuzakura and Knmachi ( 1 0 ) studied the magnetic prop. by Kucherov et al. (29). The selective blocking of the external erties uf polymers containing nitroxyl. tetraphenylporphin sites by 2,4,&trimethylpyridine does not prevent the formation complexes of Cu. Ag. or Co in the side chains. A weak anof benzene or xylene radicals, thus indicating the radical tiferromagnetic interaction was otiaerved in polymers with Cu formation to be inside the zeolite channels. The role of or Co while the polymer containtnr An showed the Dresence chemisorbed oxygen in the processes of aromatic cation radical of strongly inteiaciing sites. formation on H-ZSM-5 and H-Mordenite is discussed. Gerlock. Bauer. and Briees determined hv ESR the nitrBalcar, Dosedlova, and Matyska (30)studied the interacoxide kinetio, in acrylicmel&ne coatin& Photodegradation tions of tungsten hexachloride with esters of carboxylic acids. and photostabilization kinetics were discussed (11). Specific reactions that result in the formation of ESR-active Harbour, Walzak, and Julien described (12)the ESR spectra tungsten species and in the formation of active WCL-based of unoxidized, oxidized, devolatalized, and surface-modified catalysts for metathesis of unsaturated esters were discussed. carbon blacks. The inherent ESR signal was found to correlate Electric field effects on the antiferromagnetic ESR spectra with the surface functionalities. The ESR signal generated of iron borate crystals were measured via peak shifts and were by electrochemical reduction also correlated with the surface found to be dependent on the environment of Fe(II1) (31). functional groups hut was an order of magnitude larger in The reaction of calcium atoms with substituted benzene intensity. It is speculated that these sites are localized. vapors was examined by ESR and the intermediate anion The coordination properties of surface V'+ ions of reduced radicals were directly observed (32). Photoresponsive polyV20, supported in silica were studied by electron paramagnetic mers that change their magnetic properties upon illumination resonance (EPR) after adsorption of various probe molecules. in the visible region were studied by ESR. Changes in conThe spectral resolution was greatly enhanced by use of third firmation and new hyperfine interactions were observed in derivative spectra. The influence of various adsorbates was these functional polymers containing zirconium (33). Drawdiscussed (13). ing-induced peroxy radicals in pure silica optical fibers were ESR and ESE methods were used to investigate the inobserved by ESR and their formation mechanism was disfluence of cocations, site symmetry, and oxidation-reduction cussed in terms of a thermally activated transition model (34). cycles on various probes, generated by either ion exchange or The method of detecting homogeneous line widths from inhigh-energy radiation, in aluminosilicates (14). homogeneously broadened ESR spectra, via the use of double
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modulation techniques was used in con'unction with the conventional ESR methods to study mo ecular motion in s in-labeled cn>ss-linkedpolymers. The influence of cross-link &sit y and solvent concentration on both local and overall motion was analyzed (35). Spectra of various d' ions doped in vitreous oxidic hosts were resented and the similarities between the spectra were correEted with the similarities in the stereochemistry of the , ligand polyhedra is seen ions. A marked tendency to form C which increased with the oxidation number of the ions under investieation (36). In a pillared smectite clay both mobile and irnmobde Cu(II) species were observed by ESR. The presence of immobile species even though there was sufficient interlayer spacing to allow hydration is suggestive of strong adsorption sites (37). The Newman superposition model was used to develo equations relating the positions of four near neighbor ions re ative to a central paramagnetic ion. The constraints and failures of the equations in a fitting procedure were critically examined using Fe(II1) in quartz as an example of quasi-tetrahedral surroundings (38). Disproportionation of nitro en monoxide on CaHY-t e zeolites was studied by ESR. h e kinetics are discusserf% the basis of a mechanistic model of the dis ro ortionation of NO to N20 (39). Formation of superoxe &aJum complexes in the reaction of alladium salts with g20or KO in solutions was studied%y ESR. The reactivity 9i.e. oxiiation of simple olefins, CO etc.) and structure of these complexes were examined in the light of quantum chemical calculations (40). ESR was used to establish the high-spin ground states of paramagnetic species in polycarbenes. A guiding principle for the approach from the organic molecular superparamapeta to macroscopic ferromagnets is develo ed (41). Rotational correlation times were estimated from t e ESR studies of ion radicals captured by surfactant micellar solutions (42). The isomerization of n-butenes over Y zeolites loaded with ionic and neutral sodium clusters was investigated. With the help of in situ ESR of the workin catalyst, intracrystalline metallic clusters were found to be t i e active entities for double bond shift and cis-trans isomerization (43). The application of ESR methods to characterize high-temperature superconductors also received quite a bit of attention in this period. ESR spectra of the su rconducting phase of yttrium barium cop er oxide were d t o explore the possible role of CU(II)-CU(~V)airs in the superconductivity of the title compound (44). %ossible mechanisms for disproportionation of copper ions in adjacent octahedra are discussed. Microwave absorption studies of yttrium barium copper oxide showed a stron magnetic field dependence and considerable hysteresis Eelow the superconducting transition temperature (45).Microwave absorption measurements usin a conventional ESR apparatus were shown to rovide a nove leadless technique for the detection of Josep on Junctions and their size in superconductive Ba-Y-Cu oxides (46). The superconductingoxlde ceramics of the R b C u O7type (where R = Y, Ho, Sm, Eu) were studied by ESR. The results were compared with those for simple salts of copper and lanthanides. The concentrations of paramagnetic centers were estimated and the valence of copper ion in the studied ceramics is discussed (47). The temperature and concentration dependence of the ESR s ectra of YBa2(Cul-,Zn,) O7 was measured to study the e ression of the superconductin transition temperature as :8nction of Zn concentration. tpectra were attributed to Cu ions in the vicinity of the grain boundaries. The results are discussed in terms of a possible localization of d electrons (48). Gadolinium ions were shown to be sensitive probes to characterize slight changes of structural environment in powder samples of the lanthanum-copper-oxide superconductor family. Significant line shifts were observed near the orthorhombic-tetragonal phase transition followed by eventual vanishing of the spectral lines after the transition (49). From the ESR studies of copper in yttrium barium copper oxide, Bente and Siebert proposed that the ESR signal can be used to determine the oxygen deficiency in the superconducting oxides (50). McKinnon, Morton, and Pleizier examined the EPR silence in the newly discovered superconductor Bi,Ca&,C&Ol,. At 77 K only the zero field resonance is seen, while none is observed at high tem ratures other than the impurity resosimilarities to yttrium barium copper nances, indicating
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oxide. Possible scenarios are discussed (51). ESR evidence for a drastic difference of spin dynamics between superconductingand nonsu rconducting lanthanum barium copper oxide was obtained Kikuchi and Ajiro (52) by using Mn(II) ions as dopant. The magnetic slowing down associated with a progressive freezing of the Cu spins was observed in the nonsuperconducting oxides. ESR techni ues were used to study the in situ photochemistry of aisorbed dibenzyl ketone radicals on porous silica. Interradical interactions were observed with intermediate pore sizes of the support (53). ESR, NMR, IR, and XPS were used to investi ate the titanium-hydrogen species, formed at the support in.kh/TiO, catalysts. A model is proposed, to explain generation of oxygenated compounds on these catalysts, based on the assumption that the CO molecules interact with the hydride-like species (54). The ferromagnetic ESR of Ni crystallib, formed by hydrogen reduction of NiC12 on silica showed anomalies at low frequencies. These anomalies were attributed (55)to the changes in the FCC surface structure of the Ni lattice and the formation of superparamagnetic clusters. Molybdenum and tungsten sulfides prepared by thermal decom osition of the respective tetrathiometallates were studiefby ESR (56). A part of the signal is ascribed to sulfur chains. Variations of spin concentrations as a function of heat treatment temperature were measured and discussed in terms of transport properties of these solids. Raman and ESR spectra were used (57) to characterize Mo03-MO/Si02 (M = Co, Ni, Mn). Co and Ni were found to enhance the reducibility of the catalysts. The concentration of MOW) was shown to influence the conversion and selectivity in oxidation of pro ne. Reeulta were discussed in terms of the nucleo hilic and erctrophilic character of the oxy en species an the stability of the surface intermediates. rom an ESR study of 0;radicals formed in/on the channel zeolib, a new s was shown (58) to form when the zeolite is p r e t r e a t e G z NH This treatment apparently generates low coordination M o b ) sites inside the zeolite channels, not found on oxide surfaces, which can interact in a partially covalent manner with molecular oxygen. Direct evidence for the detection of intermediate radicals of nucleic acid constituents induced by ultrasound in argonsaturated aqueous solutions is obtained by spin-trapping combined with ESR. The results indicate that radicals enerated by "sonolysis" were identical with those generate by conventionalphotolysis. Structure of the radicals is discussed (59). ESR in the two-dimensional electron gas of GaAs4Gai,As heterostructures was studied at high fields and high microwave frequencies (14.5T and 70 GHz). The resonances within a certain Landau level are only observed at magnetic field values that place the Fermi level between the corresponding spin levels (60). With chromate ions generated by y irradiation as probes, ESR was used (61)to determine the temperature dependence of ionic rearrangements and domain nucleation around the antiferroelectric transition temperature of a series of dihydrogen arsenates and phosphates. The robe selection q d sample pre aration methodology were iscussed in d e a l . ESR of N&+ free radical was used to investigate the ferroelectric to antiferroelectric transition in lithium ammonium sulfate crystals (62). Onset of inequivalency of sites as well as twinning was detected at the transition. Cobalt clusters prepared by reducing CoNa-Y zeolite with hydrogen at 500 "C were characterized by ferromagnetic resonance and hydrogenation of carbon monoxide. The cluster size was estimated to be 5-13 A and was dependent on reduction r i d and concentration of cobalt ions in the s t a r t i n g materiaR6.3). ESR was used to characterize carbon containin finely dispersed iron obtained by partial oxidation of napht%a (64). The spectra showed stron dependence on presence of water va or or oxygen but no e fect was seen upon adsorption of N8, N 0, SOz, CO,, or Hz.The observed signal is speculated to be d2ue to superparamagnetic iron and its interaction with the carbon matrix (64).An electroactivepolymeric surfactant with pendant long-chain viologen redox groups was synthesized (65), and films of it on g!assy C electrodes were characterized by ESR, microscopic, and electrochemical techniques.
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Table I. Table of Reviews ref ESR: Inorganic and organometallic radicals Raman and ESR studies of thermal history of amorphous SiOz recombination mechanisms in amorphous semiconductors deduced from resonance measurements microscopic identification of defects in semiconductors experimental approaches to measurement of intramolecular electron transfer rates EPR lineshapes of biological molecules ESE method to analyze spatial distribution of paramagnetic centers EPR and advanced EPR studies of biological systems Molecular information from ESR spectra Magnetic resonance in graphite intercalation compounds Applications of EPR to heterogeneous systems ESR and NMR applied to minerals EPR of copper clusters in molecular metal oxides ESR spin-label studies of lipid-protein interactions New insights into EPR, applications to DNA ESR spectroscopy of some new free radicals containing sulfur and nitrogen Magnetic resonance of metal clusters in catalysis ESR of transition-metal lanthanide and actinide ions in solids ESR spectroscopy of antibiotics applications of ESR in polymer chemistry Electron spin resonance (review 7/83 to 8/85) EPR in surface and coordination chemistry modern EPR related methods in surface science and heterogeneous Catalysis transition-metalions EPR in paramagnetic hosta metastable triplet states of transition-metal tetroxo anions EPR of transition-metalimpurities in ABOBferroelectrics spin-spin interactions in weakly interacting dimers ESR and fluorescence polarization in molecular rheology ESR studies of free radical metabolites of toxic chemicals Solitons in polyacetylene Interpretation of ESR spectra of organic radicals ESR applications to polymer physics-molecular motion antiferromagnetic resonance among organic conductors electron transport in organic conductors; special magnetic resonance techniques ESR studies on radical polymerization catalyst characterization (spectroscopic & thermal techniques) a spin through the past (ESR applications to archaeology, anthropology and paleontology) dating and radiation dosimetry with ESR EPR and ita applications to biophysical systems organic radicals in solution magnetic properties of polymers with systems of conjugated bonds ESR and NMR of transienta and micromechanisms in laser-induced polymerization photons and spins in the service of polymer science advances in EPR tomography: methods and applications McGavin and Tennant (66) obtained transformation matrices that allow coordinate rotations and interrelations between parameter seta for alternative expressions of the spinHamiltonian. ESR was used to characterize the reversed micelles formed by the tertiary system Aerosol OT-isooctanewater. The resulta were used to discuss the structural or anization of such reversed micelles (67). Mehring et al. (68)introduced a novel type of multiple quantum spectroscopy, the multiple quantum ENDOR. By applying this technique to the soliton in trans-poly(acetylene), it is demonstrated that a large number of protons are coupled to the electron spin of the soliton dmplaying a wide range of hyperfine couplings. M etic susceptibility measurements were made for supportrziegler-Natta catalysts (69) and the observed s in concentrations sup rt the number of spins measured by d R . Since these n u m c r s were considerably lower than that measured by electrochemical methods, the presence of Ti3 ion clusters in the reduced formulations of these catalysts is proposed. The double modulation ESR phenomenon was thoroughly studied from experimental and theoretical points of view by Giordano et al. (70). The techni ue is shown to be very effective for slow-motion studies, an! the avoidance of inhomogeneous broadening allows the direct connection of the line width to the relaxation parameters of a single spin packet. A new method of observing the quantum size effect of ultrafine zinc particles was roposed by Bandow and Kimura (71).By addition of an E#R active ion as a spin probe, the electronic state of the conduction electrons of the ultrafine
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particles is indirectly monitored. When the particle size becomes very small, phonons of proper wavelength no longer exist, thus preventing transfer of energy from the s in system to the phonon bath. The quantum size effect on tI !e phonon dispersion is discussed in detail. evidence for a a-allyl metal hydride, supposed intermediates involved in the isomerization of alkenes, was obtained in the reaction of ground-state aluminum atoms with propene on solid inert hydrocarbon surfaces at 77 K (72). A program for second-order simulation of isotropic EPR spectra was developed for Apple I1 Plus. Some applications of such a simulation are discussed (73). Brock and Muus (74) described a Fourier filtering method to eliminate noise in the data of CIDEP experiments. This method appears to provide a si ificant improvement in signal to noise ratio for timeresored experiments but preferentially in regions where the signal to noise is already good enough to distinguish the resonances from random noise. Gorcester and Freed (75) described the use of ESR experiments based on techniques of two-dimensional Fourier transform correlation spectroscopy in determination of ma netization transfer rates in motionally narrowed nitroxiies. Spectral enhancement based upon linear prediction with singular value decomposition was applied to project 2D absorption line shapes and to improve the signal to noise ratio. Hiromitsu and Kevan (76)described an improved analysis of transient ESR signals of photoexcited triplet states with specific application to chlorophyll a, the improvement coming via a modification of the mixing ratio of the spin wave functions. ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990
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ELECTRON SPIN RESONANCE LITERATURE CITED (1) Kevan. L. Ace. Chem. Res. 1987, 20, 1-7. 5.; Schwelger, A.; Foner, J.; Emst, R. R. Chem. phys. Lett. (2) ffenn-, 1988, 757, 199-204. (3) Mbv, A. D.; Pusep, A. Yu.; Dzuba, S. A.; Tsvetkov, Yu. D. Chem. phys. Lett. 1985, 7 79 (5), 421-425. (4) (a) Shubln, A. A.; Dlkanov, S. A. J . Map. R m . 1965, Sr(2), 185-93. (b) Whg, M.; Narayane, M.; Kevan, L. J . Chem. phys. 1985, 83, 1478-1484. (c) W a r b , D.; Kevan, L. J. Chem. phys. 1987, 87, 6323-6330. (d) Flannigan. H. L.; Singel, D. J. J. Chem. phys. 1988, 89 (4), 2585-2586. (5) Dikanov, S. A.; Astashkln, A. V.; Tsvetkov, Yu. D. Chem. Phys. Lett. 1988, 744 (3), 251-257. (6) Maresch, G. G.; h p p , A.; Mehring, M.; Von Shuetz, J. U.; Wolf, H. C. J . php. (bsUIES, f r . ) 1985, 46 (3), 461-464. (7) Eaton, 0. R.; Eaton, S. S. Ace. Chem. Res. 1988, 27 (3), 107-113. (8) (a) Mabmpo, M. M.; Eaton, (3. R.; Eaton, S. S. J . Wgn.Reson. 1987, 72(3), 449. (b) Ohno, K. Appl. specbpsc. Rev. 1986, 22, 1. (c) Eaton. S. S.; Eaton, G. R. - m y 1966, 7,32. (d) Maresch, G. G.; Grupp, A.; Mehrlng, M.; VOn ShWtz, J. U. Synth. Met. 1986, 76 (2), 181-166. (e)Mkrer, L. J.; Wan, X.: FNI. H. J . P@"7. Sd., C : Lett. 1988. 24 (11h 587-595. (t) Cleary, D. A.; Shin, Y.-K.; Schneider, D. J.; Freed, J. H. J. Magn. Reson. 1988, 79(3), 474-492. (9) Anderson, J. R.: Venters, R. A,; Bowman, M. K.; True, A. E.; Hoffman, B. M. J . Magn. R m . 1985, 65, 165-168. (10) Nozakwa, S.; Kamachl, M. Makromd. Chem.. Suppl. 1985, 72polym. SpeCiRc Prop.), 255-283. (11) *lock, J. L.; Baw, D. R.; Brlggs, L. M. ACS Symp. Ser. 1985, No. 280 (Polym. Stab. Degrad.), 119-135. (12) Harbour, J. R.; Walzak, M. J.; Julien. P. Carbon 1985, 23(2), 185-191. (13) Che, M.; Canosa, B.; Gonzalez-Ellpe, A. R. J. phys. Chem. 1986, 90 (4), 618-621. (14) (a) Trlf. E.; Nkula, A. phys. Stehrs S O H E 1988, 733(2), 683-686. (b) Soc.,fam&y Trans 7 1988, 82(1), brayam, M.; Kevan, L. J . 0. 213-232. (c) Brown, D. R.; Kevan, L. J . phys. Chem. 1988, 90 (6). 1129-1 133. (d) Popovlch, 0. M.; Bugaenko, L. T.; Pobzova, A. K. Ra&t. phys. chem.1986, 27(3), 171-174. (e) Popovlch, G. M.; Polozova, A. K.; Bwenko, L. T. Zh. f k . Khkn. 1986, 60(2), 386-389. (15) Flbgerald, J. J.; Webs, R. A. ACS Symp.Ser. 1986, No. 3 0 2 ( W o m blc Interact. ~ c r o m o lsyst.), . 35-53. (16) Mach, K.; Novakova, J.; Hanu, V.; DOleMk, 2. Co/lecf.Czech. Chem. C O ~ 1986, . 57 (12), 2675-2684. (17) DaM, I. M.; HehrOfWn, s.: SlOtfeldt-EllingsWl, D.J . Md. Catal. 1988, 35 (1). 55-63. (18) Veksll, 2.; Rakvln, 8.; Andrels, M.; Grublslc-GaUot, 2.; Lutz, P. Makromd. Chem. RapHCommun. 1988, 7(11), 691-695. (19) (a) Charnulitrat, W.; Kevan, L. Redlet. phys. Chem. 1986. 28 (2), 145-147. (b) Aknso-Amlgo, M. G.; Schllck, S. S. Macromoms 1987, 20 (4), 795-801. (20) Moerke, W.; Drevs, H. 2. Chem. 1986, 26(9), 343. (21) Motten, A. G.; Dullng, D. R.; Schrelber, J. J . Magn. Reson. 1987, 77 (l), 34-44. (22) Mehrlng, M.; Hoefer, P.; Orupp, A. Ber. Bunsen-Gss. Phys. Chem. 1987, 9 7 ( l l ) , 1132-1137. (23) Klspert, L. D.; Jomph, J.; Tang, J.; Bowman, M. K.; Van Brakel, G. H.; NWIS, J. R. Synlh.AM. 1987, 77(1-3), 617-622. (24) Clerkson, R. 8.; Belford, R. L.; Rothenberger, K. S.; Crookham, H. C. J . Catel. 1987, f06 (2), 500-511. (25) Sakal, H.; Imamura, Y. Bull. Chem. SOC. Jpn. 1987. 60 (4), 1261- 1267. (26) Rachdl, F.; Bernier, P. P. Synlh.Met. 1987, 77(1-3), 401-404. (27) Turner, R. C. Txt. Res. J . 1986, 56(11), 712-714. (28) W a y , J. A.; R w r , P. H. E d . Magn. Reson. 1988, 8(3-4), 95-101. (29) Kucherov, A. V.; SRnkln, A. A.; Kondrat'ev, D. A,; Bondarenko, T. N.; Rublnshteln, A. M.; Mlnachev, Kh. M. J. Mol. Catal. 1986, 3 7 (l), 107- 115. (30) Balcar, H.; Dosedlova, A.; Matyska, B. CoWt. Czech. Chem. Commun. 1986, 57 (4), 753-762. (31) Bldwrln, M. 1.; WW, V. M. W .Tvenl. Tela 1987, 29(8), 2509-2510. (32) (a) Mochida, K.; Mizuno, Y. chem. Lett. 1988, (7), 1125-1128. (b) Mochida, K.; Mlzuno. Y. EuH. Chem. Soc. Jpn. 1987. 60(1), 273-276. (33) Ueda, H.; Yonemura, M.; Seklne. T. J . Meter. Sei. 1987, 22 (9), 3349-3352. (34) H M O , Y.; HanafUSe, H. J . A w l . PhJ'S. 1987. 62 (4), 1433-1436. (35) Andrds, M.; Rakvin, B.; Vksll, 2. J . Pdym. Scl. Part E : polvm. phys. 1987, 25 (8). 1709-1716. (38) Go#steln, A.; Chlrkrc, V.; Becherscu, D. J . Non-Cvst. SOWS1987, 92 ( 2 4 , 271-277. (37) Braddell, 0.; Barklb, R. C.; Doff, D. H.; Gangas. N. H. J.; McKimm, A. 2 . FhP. chem.1987, 757 (1-2), 157-164. (38) Mombourauette, M. J.: Well. J. A. J . Chem. Phys. 1987, 8 7 (6). ' 3385-3391. ' (39) Kanno, Y.; Matsul. Y.; Imal, H. J. Inclwlon phenom. 1887, 5 (3),
m.
___
385-395. _..
(40) Talsl, E. P.; Babenko. V. P.; Shubh, A. A.; Chlnakov, V. D.; Neklpelov, V. M.; Zamaraev, K. I. Inorg. Chem. 1987, 26(23), 3781-3878. (41) Iwamva, H. Shd. C k m . ( A m s t d a m ) 1986. 25, (New Synth. Methodol. Funct. Intereating Compd.) 403-420. (42) Sues, K.; Memwa, K.; Fujihka. M.; Aoyagul. S. E d . (%em. Soc.Jpn. 1987, 60 (a), 2221-2226. (43) MartcmS, L. R. M.; Grobet. P. J.; Vennelren. W. J. M.; Jacobs, P. A. stud. surf. W.Catal. 1968, 28, (New Dev. Zeolite Scl. Technol.) 935-9At - -- - . .. (44) astry, M. D.; Dahrl, A. G. I.; Babu, Y.; Kadam, R. M.; Yakml, J. V.; Iyer, R. M. Nature (London) 1987, 330, 49-51.
m.
154R 9 ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990
(45) Pakulis, E. J.; Osada, T. phys. Rev. E: condens. Matter. 1988, 3 7 (10-B). 5940-5942. (46) PdC, M.; Rakvln, B.; Rester, M.; Brnicevic, N.; Dulclc, A. phys. Rev. E : condens. Matter 1988, 37 (l), 522-524. (47) Brandt, N. B.; Moshchalkov, V, V.; Glpplus, A. A.; Tkkhonov, A. N.; Orabol, I. E.; Kaul, A. R.; Tret'yakov, Yu. D. fk. Tverd. Tela (Lenlngrad) 1988, 30 (4), 1210-1214. (46) Gondaves, A. M. P.; Jee, C. S.; Nlchols. D.; Crow, J. E.; Myer, G. H.; Salomon, R. E.; Schbttman, P. Wter.Res. Soc. Symp. Roc. 1988, 99 (HWTemp. Supercond.) 583-586. (49) Gervak, F.; Bassat, J. M.; De R a m , P.; Sknon, P.; Odler, P. SORdStete Commun. 1988, 67(3). 307-310. (50) knte. K.; Slebert, D. phys. SWus soydy A 1988, 7 0 6 (l), k57-k59. (51) McKlnnon, W. R.; Morton, J. R.; Plelzler, 0. SdMState Commun. 1988, 66 (10). 1093-1095. (52) Klkuchl, H.; Ajlro, Y. J . phys. Soc. Jpn. 1988, 57 (a), 2628-2631. (53) Turro. N. J.; Waterman, K. C.; Welsh, K. M.; Paczkowskl, M. A.; Zlmmt, M. B.; Cheng, C. C.; Mahler, W. Ungmuk ISM, 4 (3). 877-681. (54) Munoz, A.; OOnralez-EUpe. A. R.; Munuera, G.; Espinoe, J. P.; Rives-Arnau, V. spectrochlm. Acta, PaHA 1987, 43A (12), 1599-1605 (55) Slinkln, A. A.; Kucherov, A. V.; Yuffa, A. Ya.; Stakheev, A. Yu.; Fedorovskaya, E. A. Kkret. Katal. 1987, 28 (5), 1281-1265. (56) Deroide, E.; Belougne, P.; Zanchetta. J. V. J . phys. Chem. SOW 1987, 48 (12), 1197-1205. (57) Grabowski, R.; Sloczynskl, J.; Dyrek, K.; Labanowska, M. Appl. Catal. 1987, 32 (1-2), 103-115. (58) Huang, M.;Johns. J. R.; &we, R. F. J . phys. Chem. 1988, 92 (9, 1291-1295. (59) Kondo, T.; Krlshna, C. M.; Rlesz, P. Int. J . Radat. E M . Relat. Shrd. phys., Chem. Med. 1968, 53(2), 331-342. (60) Dobers, M.; Von Kiltzing, K.; Welman, G. phys. Rev. E : condens. Matter 1988, 38 (81, 5453-5456. (61) Dalal, N. S.; Reddoch, A. H. Can. J . Chem. 1988, 66(8),2045-2053. (82) Tsal, S. F.; Yu, J. T. J . h y s . Soc. Jpn. I S M , 57 (7), 2540-2549. (63) Kim. J. C.; Woo, S. I. Appl. Catal. 1988, 39(1-2), 107-121. (64) Banerjl, S.; Adhya, S. K.; Ghosh, S. K. Carbon 1988, 26(4). 461-483. (65) Tsw. Y. M.;Llu, H. Y.; Bard, A. J. J. Elecbochem. Soc. 1988, 735(7), 1669-1 675. (66) McOavin, D. 0.; Tennant, W. C. Mol. Phys. 1985, 55 (4), 853-866. (67) Haerlng, G.; Lulsl, P. L.; Hauser, H. J. phys. Chem. 1988, 92 (12), 3574-358 1. (68) Mehrlng, M.; Hoefer, P.; Kaess, H.; Grupp, A. Europhys. Lett., 1988, 6(5),463-8. (69) Johnston, D. C.; Brant. p.: Smca, A. N. J . &tal. 1988, 773 (1). ' 250-255. (70) Qlordano. M.; Leporini, D.; Martinel#,M.; Pardl, L.; Santucci, S.; Umeton, C. phys. Rev. A : Gen. phys. 1988. 38(4). 1931-1942. (71) Bandow, S.;Klmura, K. J . phys. Soc.Jpn. 1988, 57(8). 2805-2811. (72) Hlsted, M.; Howard, J. A,; Monis, H.; Mile, B. J. Am. Ghem. Soc. 1988, 7 70 (28), 5290-5292. (73) Joela, H. cornput. Chem. 1988, 72 (2), 189-206. (74) Brock, J. B.; Muus, L. T. J . Magn. Reson. 1988, 78 (l), 142-144. (75) Gorcester, J.; Freed, J. H. J . W g n . Reson. 1988, 78 (2), 292-301. (76) Hkomfisu, I.; Kevan. L. J . Chem. phys. I S M , 88(2), 891-695. (77) Symons, M. C. R. Electron Spin Reson. 1985, 9 , 87-138. (78) Galeener. F. L. J. Non-Cryst. SdMS 1985, 77(1-3), 373-388. (79) Morlgekl, K. J . Non-Clyst. SOW1985, 77-78(1). 583-592. (80) Schnelder, J. Mater. Res. Soc. Symp. Roc. 1985, 46(mlcrosc. Identit. Electron. Defects Semicond.), 13-25. (81) Richardson, D.E. Comments I m g . Chem. 1985, 3 (6), 387-384. (82) Salerno, J. C. Blochem. Soc. Trans. 1985, 73(3), 611-615. (83)184-217. Raitsimring, A. M.; Sallkhov, K. M. Bull. Magn. Reson. 1985, 7 (4), (84) Dalton, L. R.; Ed.; EPR and Advanced EPR fides of Eldoglcel Systems; CRC Press: Boca Raton, FL, 1985. (85) Weltner, W., Jr.; Van Zee.R. J. Comp. ab InMo Quantum Chem. Exp. SmaI Mol.; Proc. Symp. Meeting Date 1984; Bartlett, R. J.. Ed.; 1985, Reidel: Dordrecht, Netherlands, 1985: pp 1-16. (86) Estrade-Szwarckopf, H. Helv. phys. Acta 1985, 58(1), 139-161. (87) Che,M.; Ben Taarit, Y. A&. CORoid Interfern Sd. 1985,23,235-255. (88) McWhlnnle, W. R. Chem. &nd/ng Spectrosc. M/ner. Chem.; Berry. F. J., Vaughan, D. J., Eds.; Chapman 8 Hall: London, U.K.. 1985; pp 209-249. (89) Kokoszka, Ci.; Padula, F.; Siedle, A. R. W . Inorg. Copper Chem. Roc. Conf. Copper cocvd.chem.2nd. meeting date 1984; Karlln, K. D., Zubieta, J., Eds.; Adenine Press: Guilderland, NY, 1986; Vol. 1, pp 209-222. (90) (a) Devawc, P. F.; Seigneuret, M. Bkahkn. Blophys. Acta 1985. 822(1), 63-125. (b) Marsh, D. Rog. Rot&-LlpM Interact. 1985, 7 , 243-272. (91) Pllbrow, J. R. Roc. Asia-Pac. phys. Conf., 2nd; Meeting Date 1986; Chandrasekhar, S., Ed.; World Sci.: Singapore, 1986; Vol. 2. pp 914-934. (92) Sutcllffe, L. H. J . Specbosc. 1988, 7(1), 131-135. (93) Knoezlnger, H. Stw'. S w f . Sei. Catal. 1988, 29 (Met. Clusters Catl.) 187-207. (94) Buckmaster, H. A. Magn. Reson. Rev. 1988, 7 7 (3), 81-204. (95) Yang, 0. C.; Aszabs, A. Drugs pharm. Sei. 1986, 27(Mod. Anal. Antibkt.), 183-198. (96) HI, D. J. T.; O'Donnell, J. H.; Pomery, P. J. Electron Spin Reson. 1986, 70A. 84-1 15. (97) Wasson, J. R. Anal. Chem. 1988, 58, 81R-84R. (98) Che, M.; Bonnevlot, L. 2. phys. Chem. 1987. 152 (1-2), 113-129. (99) Hemkrg, M. Z . phys. Chem. 1987, 157 (1-2), 35-50. (100) Gibson, J. F. Electron Spln Reson. 1987, 7oB, 39-92. (101) Mishra, S. K. Magn. Reson. Rev. 1987, 12(3). 191-243. A 1987, A71 (5), 809-821. (102) Van der Waals, J. H. Acta phys. el.,
Anal. Chem. ISSO, 62, 155R-169R (103) MuelkK, K. A. New Dev. WcI. Mgn.Reeon. Magn. Reson. OUenrUn Elecdon., Spc. cdbp. AAoRERE, 7th; MmtIng Date 1985; Ursu, I., H a w , K. H., E&.; CIP Reas: Bucharest, 1985; pp 211-223. (104) K ~ ~ z w sC., P. Ekcirw, spk, R e e ~ n 1087, . 108, 1-38. (105) Donner, M.; M u k , S.; Stoltz, J. F. C h . Hemomed. 1087, 7 (I), 33-45. (108) Mason, R. P.; Stdte, K.; Morehouse. K. M. Br. J . Csncer Suppl. 1987, 55 (8). 183-171. (107) Roth. S.; Bleier, H. A&. RIP. 1987, 36 (4). 385-482. (108) BuIWX, N. J. J . C b m . E&. 1087, 64 (II), 907-914. (109) Kashhkvabara, H.; Shlmada, S.; Horl. Y.; Sakaguchl, M. A&. Pol)m. Sei. 1087, 82, 141-206. (110) Coulon, C.; Laversanne, R. NATO ASI Ser., Ser.B 1987. 155 (LowDlmna. Conduct. Super&.), 135-138. (I 11) Mehring, M. NATO ASI Ser. B 1987, 155 (LowDimens. Conduct. Su185-193.
m-.),
(112) Kamachi, M. A&. m m . Sei. 1987. 82, 207-275. (113) Austermann, R. L.; Denley, D. R.; Hart, D. W.; Hhnelfarb, P. B.; Irwln, R. M.; Narayana, M.; Tang, S. C.; Yeates, R. C. Anel. Chem. 1987, 59 (12), 68R-102R. (1 14) Robins, D. New Sci. 1988, 117, 49-52. (115) Ikeya, M. Magn. Reson. Rev. 1088, 13(2-3), 91-134. (118) Dougherty. 0. SdnBeporeJ. phys. 1088, 5(1). 107-128. (117) Tabner. B. J. Elecb.on Spin Reson. 1088, 11A, 1-54. (118) Lyubchenko, L. S.; Kozhushnef, M. A. Zh. Fk. f i l m . 1988. 62(9), 2308-2324. (119) Roth, H. K.; Leopold, D. M a k r m l . Chem.. Maeromd. S.y m . . 1988, 18. 219-240. (120) Turro, N. J. P o r n . Prepr. (Am. Chem. Soc.Dlv. Po&m. Chem) 1988, 29 (I), 500. (121) Ewert, U.; Herrling, T.; Schneider. W. Exp. Tech. Phys. 1988, 36 (4/5). 289-297.
Ultraviolet and Light Absorption Spectrometry J. A. Howell* Western Michigan University, Kalamazoo, Michigan 49008
L. G. Hargis University of New Orleans, New Orleans, Louisiana 70148 This review reports the developments in ultraviolet and light absorption spectrometry from January 1988 throu h December 1989,primarily as documented in the Ultravio et & Visible Spectroscopy section of CA Selects, and extends the series of reviews on these topics sponsored by Analytical Chemistr starting with Light Absorption Spectrometry in 1945 (1-3f followed b Ultraviolet Absorption Spectrometry in 1949 (4-8) and comgined Ultraviolet and Light Absorption S ectrometry in 1978 (9,10). This review follows the format ofits predecessors with the subject matter being divided into sections on Chemistry, Physics, and a lications. The applications section is comprised of Taiyes I and 11, which summarize the routine determinations of inorganic and organic substances, respectively. The literature on ultraviolet and light abspr tion spectrometry continues to be so extensive and varied'in scope that citations in this review are limited to those developments which the authors believe are of greatest interest to analytical chemists and those engaged in the chemical analysis of materials. As a result of t h s necessary selectivity, the authors wish to apologize in advance for any errors of j u d gent made in the omission of specific references. e number of review articles appearing yearly on specific aspects of molecular absorption spectrometry continues to increase. An IUPAC committee has reported its recommendations on the nomenclature, symbols, units, and their usage in molecular absorption spectrometry (11). Reviews of reagents used for the determination of a specific substance or oup of substances include those on thiazolylazo reagents (12~semicarbazonees and thiosemicarbazones (13),heterocyclic azo compounds based on thiazole and thiophene (14), and anionic crown ethers (15). A extensive review of the reagents used for the determination of lanthanides has appeared (16). The use of surface-active agents to increase the water solubility, sensitivity, and detection limit of metal com lexes is the topic of four reviews (17-20) and the much broaier to ic of the use of organic reagents in spectrometry is coverexin two others (21,22). Reviews of methods for determining the following particular substances have a peared lanthanides (23,24), inorganic ions (251, carotene &6), chlorophyll (27), estrogen in urine (%), purines and pyrimidines (29),steroids (30),sulfh dry1 compounds (311, surfactants (321, thiols (33), minerals &4), and red wine (35). A number of reviews dealing with s ectrometric techniques have been published, including the !eto instrumentation, and applications of derivative spectropXbtometry (36); simultaneous, multicomponent determinations ( 3 7 , s ) ; rapidscanning, multiwavelength spectrophotometry (39); picose-
P
cond, time-resolved, spectrometry (40); matrix-isolation spectrometry (41);and squeezed-light spectrophotometry (42). The design and analysis of kinetic experiments has been reviewed (43),as well as eneral kinetic methods for both catalyzed and uncatalyzet! reactions (441, kinetic methods utilizing diode-array detectors (45,46), and stopped-flowtime difference analysis (47). Thermooptical spectrometry has been the subject of several reviews including general techniques and applications (48,49), photothermal deflection s ectrometry (50), and thermal lens spectrometry (51-53). !?he general techniques (51) and analytical applications (53) of photoacoustic spectrometry have been reviewed, along with ita use in depth profiling (54). Reviews on the general techni ue of flow-injection analysis (551, ita use in the analysis off% and drugs (561, and the advantages of multiple-peak recordy (57) have been published. Both Fourier (58) and Hadamar (59, 60) transform spectrometry have been reviewed. The topics of other reviews include the determination of dru s in pharmaceuticals based on the formation of metal comdexes (61), the measurement of coatings and solids (62,63), micellar the use of spectrometry in quality assurance solubilization (64), of chemical reagents (65),recent advances in instrumentation and the synthesis of chromophores that have increased the the effects of temperature sensitivity of determinations (66), on equilibrium and its applications in abso tion spectrometry (67), analysis problems of high-purity su'gstances (681, and the applications of principal-component analysis in analytical chemistry (69). Three papers review the early historical development of ultraviolet and light absorption spectrometry (70-72), another discusses the progress realized by the introduction of microprocessors (731, and a fifth describes the development of analytical techniques for trace element determination in agricultural and environmental samples (74). A large number of reviews on fiber optics have appeared including general principles and techniques (75-78), specific applications as remote sensors (7941), use in multivariate analysis (82),use with immobilized indicators (83),and use for dissolved ionic substances (84). The use of detector tubes (85)and lasers (86) in the determinationof gaseous substances has been reviewed as has the use of charge-transfer devices as detectors (87). Detectors for liquid chromatography have been the subject of two reviews, one dealing with photoacoustic and thermal lens devices (88) and the other with photodiode arrays and charge-coupled devices (89). The applications of computers in signal processing (90, 91) and statistical calculation and optimization (92) have been discussed. The performance and
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