(552) Ibid., 177, 244 (1960). (553) Usatenko, Y. I., Tulyupa, F. M., Zavodskaua Lab. 26. 783 (1960). (554) Vaniman, R. E., Hoiligaugh, F. D., Kanzelmeyer, J. H., ANAL.CHEM.31, 1783 (1959). (555) Vanwinkle, Q., Kraus, K. A., U. S. Patent 2,910,345 (Oct. 27, 1959). (556) Vdovenko, V. M., Alekseeva, N. A., Radiokhimiya 1,450 (1959). (557) Vdovenko, V. M., Krivokhatskii, A. S., Ibid., 1,454 (1959). (558) Vdovenko, V. M., Krivokhatskii, A. S., Zhur. Neorg. Khim. 5,494 (1960). (559) Vdovenko, V. M., Lipovskii, A. A., Kuzina, M. G., Ibid., 4, 2502 (1959). (560) Vdovenko, V. M., Smirnova, E. A., Radiokhimiya 2, 291 (1960). (561) Vecera, Z., Bieber, B., Hutnickd Zisty. 14, 56 (1959). (562) Velten. R. J., Goldin. A. S.. ANAL. ' CHEM. 33,128 (1961). ' (563) Vesely, V., Beranova, H., Maly, J., Collectaon Czechoslov. Chem. Communs. 25, 2622 (1960). (564) Vignes, A,, J . china. phys. 57, 966 (1960). (565) Ibid., p. 980. (566) Ibid., p. 991. (567) Ibid., p. 999. (568) Vlacil, F., Zatka, V., Chem. prilmsyl 11, 139 (1961). (569) Voicu, V., Dema, I., Acad. rep. populare Romine, Studii cercetiiri chim. 7, 431 (1959). (570) Vondrak, J., Rylek, M., Collection Czechoslov. Chem. Communs. 26, 307 (1961). (571) Vouk, V. B., Weber, A. O., Analyst 85,46 (1960). (572) Vozzella, P. A., Powell, A. S., Gale, R. H., Kelly, J. E., ANAL.CHEM. 32, 1430 (1960). (573) Vydra, F., Pribil, R., Talanta 3, 72 (1959). (574) Wakamatsu, S., Japan Analyst 8, (5), 298 (1959).
(575) Ibid., 9, 858 (1960). (576) Walkden, J., U. K. Atomic Energy Authoritv Reots. AERE-AM-21: AERE-AM-53. I i959). (5773-Ibid:l AE-alAMl22, (1959). (578) Ibid., AERE-AM-45, (1959). (579) Ibid., AERE-AM-50, (1959). (580) Walkden. J.. Heathfield. K. E.. ' Ibid., AERE-AM-32, September 1959. ' (581) Wallace, R. M., Pollack, H., U. S. Atomic Energy Comm. Rept. DP-411, IlQiQ) ,----,.
(582) Warr, J. J., Cuttitta, F., U.S. Geol. Surv. Profess. Paper 400B, 483 (1960). (583) Warren, C. G., Suttle, J. F., J . Inorg. &Nuclear Chem. 12,336 (1960). (584) Watkinson, J. H., ANAL. CHEM. 32, 981 (1960). (585) Watts, H., Australian J . Chem. 14, 15 (1961). (586) Weaver, B., Harner, D. E., J . Chem. Eng. Data 5,260 (1960). (587) Weaver, B., Kappelmann, F. A,, U. S. Atomic Energy Comm. Rept. ORNL-2863, Feb. 12, 1960. (588) Weidmann, G., Can. J . Chem. 38. ' 459 (1960). (589) Werner, L., Perlman, I., Calvin, M., U. S. Patent 2,894,805 (July 14,1959). (590) Wezranowski, E., Nukleonika 5, 677 (1960). (591) White, J. C., U. S. Atomic Energy Comm. Rept. CF-59-4-100, April 1959. (592) Ibid., CF-59-4-106, (1959). (593) White, J. C., Kelly, P., Li, N. C., J . Inorg. & Nuclear Chem. 16,337 (1961). (594) White, J. C., Ross, W.J., U. S., Atomic Energy Comm. Rept. NAS-NS3102, (1961). 1595) Wilburn. N. P.. Ibid.. HW-66386. ,
I
(596) Wild, F. E., U. K. Atomic Authority Rept. AERE-AM-28, (597) Williams, K. T., Wilson, ASAL. CHEW. 33,244 (1961). (598) m7ilson. H. N.. Skinner. ' Ret. trav. chim. 79,574 (1960). '
Energy (1959). J. R.,
J. M..
(599) Wilson, R. B., Jacobs, W. D., ANAL.CHEM.33, 1650 (1961). (600) Wood. D. F.. Nicholls. H. A.. ' Akalyst 85, 139 (1960). (601) Yagodin, G. A., Mostovaya, 0. A., Zhur. Priklud. Khim. 33. 2459 (1960). (602) Yagodin, G. A., Mostovaya, O..A., Chekmarev, A., Izvest. Vysshikh Ucheb. Zavednit Khim. i Khim. Tekhnol. 3, 135 (1960). (603) Yamamura, S. S., ANAL.CHEM.32, 1896 (1960). (604) Yanagihara, T., Matano, N., Kawase, A., Japan Analyst 8, 10 (1959). (605) Ibid., p. 14. (606) Yatsimirskii, K. B., Izvest. Vysshikh Ucheb.Zavedenit Khim. i Khim. Tekhnol. 3, 823 (1960). (607) Yoshimori, T., Takeuchi, T., Japan Analyst 9, 689 (1960). (608) Yoshimori, T., Tomida, Y., Takeuchi, T., Ibid., 10, 156 (1961). (609) Young, J. P., White, J. C., Ball, R. G., ANAL.CHEM.32,928 (1960). (610) Zharovskii, F. G., Ukrain. Khim. Zhur. 25, 245 (1959). (611) Zhivopistsev, V. P., Minin, A. A., Zavodskaya Lab. 26, 1346 (1960). (612) Ziegler, M., Angew. Chem. 71, 522 (1959). (613) Ziegler. M., Naturwissenschaften46, ' 353 (1959): ' (614) Ibid., p. 492. (615) Zieeler. M.. Z. anal. Chem. 171, 111 ' (1959).' ' (616) Ibid., 180, 348 (1961). (617) Ibid., p. 351. (618) Ziegler, M., Glemser, O., vonBaekmann, A., Z. anal. Chem. 172,105 (1960). (619) Ziegler, M., Horn, H. G., Ibid., 166 (5), 362 (1959). (620) Ziegler, M., Sbrzesny, H., Glemser, O., Ibid., 167, 96 (1959). (621) Ibid., 173, 411 (1960). (622) Zingaro, R. A., White, J. C., J . Inorg. & Nuclear Chem. 12,315 (1960).
Review of Fundamental DeveloDments in Analvsis
Fluorometric Analysis Charles E. White, University of Maryland, College Park, Md. Alfred Weissler,' Laboratory of Technical Development, National Heart Institute, Bethesda, 7 4, Md.
T
REVIEW covers the 2-year period from approximately Kovember 1959 (397) to December 1961. Only a selected group of references are included. Chapters on fluorometric analysis (406) and fluorescence and phosphorescence (411) have appeared in books dealing with instrumental analysis. A section on fluorophotometry and phosphorimetry is included in a n encyclopedia of spectroscopy (64). Many of the papers given in a symposium on energy transfer in the liquid and solid HIS
1 Author of the Organic and Biological part. Present address, Air Force Office of Scientific Research, Washington 25, D. C.
states are of interest to the general topic of fluorescence (72). The correction of fluorescent spectra for the variations in intensity of the exciting source and for the characteristics of the measuring devices has always been troublesome. Parker and Rees (269) have published a n excellent general discussion on this topic including quantum efficiency considerations. Parker (264) also has presented a general paper on spectrofluorimetry as well as one on fluorescence escitation spectra and fluorescence sensitivity (265). White, Ho, and Keimer (399) have presented methods for corrections of both fluorescence excitation spectra and fluorescence emission spectra as determined with the Aminco-Bowman spectrofluorometer. The procedure as
outlined may be applied to other instruments. It should be noted that the values in column 1 of table one of this article (399) are in relative quanta whereas the remainder are given in relative energy. Braunsberg and James (40) have also published observations on fluorometric determinations with the Aminco-Bowman instrument. Bowen (54) and Lippert ($01) have reviewed the conditions and considerations necessary for the presentations of fluorescence spectra. d convenient method of obtaining corrections for fluorescence emission spectra from 360 to 750 mfi is by use of the fluorescence compounds as described by Lippert and his associates ($02). This has been supplemented by a group of dyes covering the range from 450 to 610 mfi (266). VOL. 34, NO. 5, APRIL 1962
0
81 R
Data on quinine sulfate from 390 to 580 mp for calibrating emission spectra are given by Melhuish (225). Eisenbrand (87) has shown that the fluorescence intensity of quinine sulfate is constant in 0.01 to 0.2N H2S04, but a t concentrations greater than 0.2N HzSOa or a t pH greater than 2, it is not constant. The effect of perchloric acid, glacial acetic acid, buffers, and chloride concentration is also shown (90). Hercules and Frankel (137) have suggested the use of silica as a standard for measuring fluorescence yield. The effect of the solvent on fluorescent yield (56, 169) and the relation of absorption and fluorescence spectra to the solvent (168) have been discussed in several papers. With the use of a liquid light filter, 120 grams of hydrated copper sulfate per liter, Zyuskin (422) has shown that fluorescence in the red, far red, and infrared regions can be used to detect colorless substances on paper chromatograms and absorption columns. APPARATUS
A commercial energy recording spectrofluorometer which is still in the stage of custom-made production has been designed by Slavin, Mooney, and Palumbo (341) of the Perkin-Elmer Corp. This instrument is designed for solids and records the excitation spectrum a t a constant energy level and the emission spectrum as proportional to the energy output of the sample. hloss (242) has also designed an apparatus for direct determination of excitation spectra by means of a monitoring system. He indicates that Unicam Instruments Ltd. is developing a spectrofluorometer with a double beam system. A news note (419) states that the Carl Zeiss Co. a t the Dusseldorf Instrument Exhibit demonstrated its spectrofluorometer. This instrument has a 1.25-meter optical bench and 0.5-ml. cells. Goldzieher et al. (122) have compared the performance of two new spectrofluorometers which were made from commercially available units and compared them to the Aminco-Bowman model. -4 high resolution spectrofluorometer has been designed for measurements a t 77' K. as well as normal temperatures (293). Olsen (261) has combined a Zeiss spectrometer with a microscope to form a rapid scanning microspectrofluorometer. A fluorometer designed for the measurement of a very weak luminescence can be used also for paper chromatograms and crystals (329). Another instrument for both solids and liquids has been described by Cerrai and Rossi (65). Esikov and Men'shikov (98) claim measurement in the order of 5 X 1O-I4 amp. per division for their solution fluorometer. Sill (339) has designed an accessory for the Carey 82 R
*
ANALYTICAL CHEMISTRY
spectrophotometer for the measurement of fluorescent spectra. He has also (340) recorded the transmission spectra of a selection of filters for colorimetric and fluorometric analysis which will be useful. Nebbia (263) uses a n adaptation of the Beckman DU spectrophotometer where the fluorescence emission is passed through the monochromator for fluorescence spectra measurements. Bailey (14) has designed a fluorometer especially for measurement of fluorescence on paper, and Takemoto (568) has modified a spectrofluorometer for scanning paper strips. The commercial Turner fluorometer now has an accessory to measure fluorescence on paper strips (372). A liquid helium cryostat has been designed in which the fluorescence spectra of four solid specimens may be obtained (204). A number of reports have appeared on instruments for the measurement of fluorescent life times in the order of 10-10, IO-" seconds, but since these are not usually designed for the analytical laboratory, only three references are included here (20, 28, 383). An apparatus for the quantitative determination of the thermoluminescence of minerals measures the total luminescence from a 0.5-gram sample from 25' to 600' C. (198). Fluorescent screens for ultraviolet absorption can be made by impregnating filter paper with an ethanolic solution of l-methyl4-(5-pentyl-2-oxazoyl)pyridinium toluene-p-sulfonate (280). These are used to detect ultraviolet absorbing substances. A system for the reduction of current fluctuations in the Farrand spectrofluorometer replaces the batteries for the phototube and the ammeter with line operated units (213). A photo detecting instrument has been devised which has a flat wavelength response in various parts of the spectrum from 200 to 1000 mp (223). This may find application in fluorescence A Turner spectra measurements. fluorometer with a recording attachment is used by Carpenter to follow water movement in the Baltimore harbor with rhodamine B as the tracer
(499). INORGANIC
General. Additional data on the fluorescence excitation spectra and absorption spectra of the chelates of Al, Be, Th, Zr, B, and Li show the same close correlation of these two types of spectra as is evidenced in the case of pure organic compounds (400). The emission spectra of these chelates are also given in this article. Turkevich (371) has reported on a study of the reaction of 50 rhodanines and 10 thiazolidine-2,4-diones as spot test reagents with various metal ions. Filter
paper was impregnated with the reagents and spotted with the metal ions. He concludes that the rhodanines are group reagents for Ag+, Hgzf2, Cu+, C U + ~ ,A u + ~ , Pd+2, and Ptf4, and the thioazolidines are group reagents for La+3 and U02+2 in addition to the ions listed above. Stolyarov and Grigor'ev have applied luminescence methods to the microchemical detection of a number of elements with a sensitivity of 0.1 to 0.0005 pg. in 0.003 ml. (349). The methods are based on the formation of fluorescent products by introduction of microquantities of the elements into compounds or crystals as CaO or KI, or by usual chemical reactions. Examples are the detection of T1 aTith KI, Ga Rith rhodamine B, P b with pyridine and KI, and arsenic with ferrocyanide. Fluorescent reactions are also given for Sb and Sn. The reaction products of 8-quinolinol with some 30 ions have been surveyed (176) with respect to their fluorescence colors, extraction a i th CCl,, proper pH for extraction, and spot reactions on paper. Popovych and Rogers (285) have continued their study of the metal 8-quinolates as to the function of solvents and substituents on the fluorescence. The studies of Umland and Meckenstock (374, 376) on the partition of the metal complexes of 8-quinolinols1 substituted in the 7-position, between mater and chloroform have shown some interesting effects such &s the quantitative extraction of the calcium complex when the chloroform contains 2% n-butylamine. The widely distributed blue fluorescence between 430 and 480 mp which is found in many minerals and commercial chemicals has been shown to be caused by traces of organic materials probably from atmospheric dust (389). Holzbecher (140) has made metal chelates with 12 salicylaldehyde condensation products and determined some factors influencing the fluorescence intensity. He also studied the metal chelates of the condensation products of resorcylaldehyde with hydrazine and aromatic amines with 11 metal ions (141). The sensitivity of the fluorescence reactions of quercetin with salts of -41, Be, Ga, In, Y, La, Mg, and Zn has been determined, and their optimum p H ranges have been established (179). .4n article by Schwarzenbach (322) mill be of interest to anyone dealing with metal chelates. Aluminum. While no new fluorescence reagents have appeared for aluminum, several well known methods have been improved. The A1 complex with Pontachrome BlueBlack R is shown to be readily extracted with amyl alcohol from the ammonium acetate buffer solution a t a p H of 4.8 to 5.4. The extracted complex is reported to have its maxi-
mum a t 593 mp (153). Will (404) has extended the morin method and uses it for the determination of aluminum in boiler water in the parts per billion range. I n the application of o-salicylideneaminophenol, a p H range of 5.66.2 is important, and the acetate buffer is freed of aluminum by passage through an ion exchange column with 5-chloro2,2’4’ - trihydroxyazobenzene - 3sulfonic acid as a complexing agent (38). The use of 8-quinolinol for the determination of aluminum in magnesium metal (106) and in plant tissue (307) requires the removal of iron. All Gal and I n may be determined simultaneously after separation of their chlorides on a chromatogram by a spray of 8-quinolinol in a methanol-chloroform-water (12 to 12 to 1 by volume) mixture (212). Hematoxylin serves as an end point indicator for the titration of aluminum with KF (344). Antimony. Benzoin, which has been used as a fluorescence quantitative reagent for boron and germanium and a qualitative reagent for zinc for many years, has now been reported to give a quantitative reaction with both zinc and antimony (36). A crystal phosphor of CaO and antimony formed as in the normal bead test with calcium carbonate, and an antimony solution will detect 1 X pg. of antimony in a limiting dilution of 1 in 10’0 (347). A luminescent phosphor is also produced with K P e (CnT),. I n this case a drop of the reagent is evaporated to dryness on a watch glass; a drop of the antimony solution is added and again allowed to dry (347). Beryllium. Korenman and Grishin (177) have tested about 150 anthraquinone and azo dyes for reactions with Be and Al. About 50 gave positive reactions. Salts of Sc, In, Th, Zr, Cr, Zn, and Mg also gave fluorescent reactions; those of Fe+3, Cu, Ca, and Ba did not. United States Bureau of Mines Reports give two fluorescence field tests for beryllium; one uses morin (a%$),and the other uses quinizarin (82). The determination of Be with morin in low grade ores (azo), in bronzes ( I @ ) , and in the air (390) has also been described. I n each case directions are given for the removal of likely interferences. I n a micro method sensitive to 5 X l o d 4 pg. of Be per ml. with morin, Bril and Pruvot (42) advocate the use of additional alcohol and show that the complex consists of 3 atoms of Be to 2 moles of morin. 8-Hydroxyquinaldine is recommended for the gravimetric, volumetric, spectrophotometric, or fluorometric determination of Be; A1 does not interfere with this reagent (243). Boron. The benzoin method for boron has been the subject of two extensive articles. Parker and Barnes
(267) show that the method is sensitive to 0.03 p.p.m. in sea water and is more reliable than the titrimetric method. The use of an excitation wavelength a t 405 mp is suggested to decrease the decomposition of the benzoin. A chromate filter is also suggested to remove the Raman lines. These authors show that the method is applicable to the analysis of boron in steel and silicon. Elliott and Radley (92) have also studied the benzoin method and shown that the fluorescence is more intense in formamide than in alcohol. Glycine is ineffective as a buffer in formamide, but isopropylamine and isobutylamine are effective bases in both solvents. Both of the above articles show that this system must be free from oxygen. Huffman (146) advocates the use of boron-free plastic containers for samples since paper cartons and glass often contain water soluble boron. It should be noted that some plastics contain boron, but the polyethylene laboratory bottles seem free of it. Calcium, Copper, and “Metalfluorochromic” Indicators. The direct titration of Ca, Ba, and Sr can be accomplished with Calcein Blue, a condensation product of methylumbelliferone, formaldehyde, and iminodiacetic acid (403), or with Calcein (11) as indicators. A mixed indicator of fluorescein complexone and phenolphthalein complexone seems to give better endpoints in the presence of sodium ions (366) than does the fluorescein reagent alone. Synthesis of umbellikomplexon and xanthokomplexon indicators of the Calcein type has been described by Eggers (85). Another fluorochromic indicator for the titration of calcium is from the N:N:N‘: N’ tetracarboxymethyl derivatives of benzidines (19). Korbl and Svoboda (174) object to the use of the term “metalfluorochromic” indicator and prefer their term of prior usage “metallofluorescent”; a further comment on this is given by Wilkins (402). Methods have also been described for the titration of copper and manganese (588) and chromium, iron, and thorium (384) with the use of the Calcein type indicators. A method for the estimation of copper in the 10 p.p.b. range to as low as 0.007 p.p.b. depends on the treatment of silver activated ZnS with copper solution followed by heat. The result gives a green fluorescence in contrast to the original blue (300). A Tesla coil or 365 mp radiation is used to excite the fluorescence. Gallium. The rhodamine B complex with gallium has been confirmed as a 1 to 1 ratio of the type, RHGaC14, where R = rhodamine B (70). Rhodamine S has been found to be a more selective reagent for gallium than rhodamine 6G ( S S I ) , and a procedure
has been outlined for its use in the analysis of ores (330). Interfering ions are reduced with TiCla, and the complex is extracted with benzene and ethyl ether (9 to 1). Rhodamine S was preferred over the common reagents tested. The gallium-rhodamine S complex is also extracted with a mixture of benzene and butyl acetate as in the determination of Ga in Zn (183). Korenman, Sheyanova, and Kunshin (178) tested 9-dihydroxy azo dyes as reagents for gallium and concluded that 8 - amino - 2 - (3 - chloro 2hydroxy - 5 - nitrophenylazo) - 1naphthol-3,6 disulfonic acid (“gallion”) gave the best results with a sensitivity of 1 in lo6. Lukin and Bozhevol’nov (209) favor their compound 2,2’,4’-trihydroxy - 5 - chloroazobenzene - 3 - sulfonic acid (lumogallion IREA). This is sensitive to 0.01 pg. of Ga in 5 ml. of water and 0.005 pg. in 5 ml. of isoamyl alcohol. Holzbecher (142) has suggested the use of resorcylaldehyde formylhydrazone as a reagent for Sc, Gal Zr on paper chromatograms. Scandium and Ga yield a blue fluorescence, and Zr yields a blue-green. The limiting sensitivities are Sc, 0.04; Ga, 0.06; Zr, 0.5 pg. These chelates are stable in strongly acidic media. After the removal of indium, morin can be used to determine Ga from 0.005 to 0.5 pg. per 10 ml. However, the spectrophotometric determination appears to be more accurate than the fluorometric with this reagent (46). The 8-quinolinol complex with gallium is said to show a reversion in the calibration curve above 11 mg. of Ga per ml. (184, 186). This complex extracts readily with chloroform, and with an extraction pH of 2.6 to 2.7 only indium interferes (163). Milaev used the fluorescence of the ether extraction of Ga 8-quinolinol in the determination of Ga in Pb, Zn, and Cu (233). Germanium. Korenman, Durina, and Emelin (176) have made an extensive study of the hydroxyanthraquinones as color and fluorescence reagents for germanium. 1,2,4,5,6,8 - Hexahydroxyanthraquinone and 1,4-dihydroxyanthraquinone are reported to give a pinkish red color and yellow fluorescence, respectively, which can be noted in ordinary light. The fluorescence results seem more selective than the colorimetric, but both have about the same sensitivity. Indium. Rhodamine 3B is described as a fluorometric reagent for indium sensitive to 0.02 pg. (SO). The reaction medium is 2.5M HBr, and the complex is extracted with benzene. Many elements such as A1 and Ga do not interfere, but 14 other ions including Au+3, Tl+3, Fe+3, and Znf2 produce a fluorescence. The use of morin as a reagent for gallium and
-
VOL. 34, NO. 5, APRIL 1962
83 R
indium has been studied with the idea of arriving a t a set of optimum conditions. Citric, tartaric, and sulfosalicylic acids cannot be used to mask either of the elements since these complexes are more stable than those with morin. The maximum fluorescence of indium was in acetate buffer p H 3.6, and the sensitivity was 8.8 x 10-7N. Lanthanides. Gadolinium in metallic beryllium may be determined quantitatively by the fluorescence of the phosphor, Thoz-Gd (13). The phosphor is formed through a process in which the beryllium nitrate-thorium nitrate mixture in a series of crucibles is treated with varying amounts of gadolinium nitrate, heated to dryness, and ignited a t 1000° C. The beryllium nitrate solution contains also some LiCl to act as a flux and Na2S04to aid in the sintering. The ignited material is ground to a powder and excited with a spark to produce the luminescence. The method is sensitive to Gd in the final mixture. X similar method is used to determine small amounts of Gd, Eu, and Sm in metallic thorium (196). Europium is reported (683) to be determined quickly and easily by the fluorescence of its bead prepared in fused sodium and strontium chlorides. The divalent and some trivalent lanthanides give intense luminescence with calcium fluoride (44, 409). The fluorescence spectra of dysprosium chloride is shown to contain about 400 lines from the ultraviolet to the infrared regions which are so intense that they are easily obtained with a large spectrograph (69). Fassel (101) has briefly discussed the analytical spectroscopy of the lanthanides. Soden (343) shows that the fluorescence of the lanthanide hexa-antipyrine triiodide crystal permits the determination of terbium in parts per million in high purity gadolinium and yttrium sources. Magnesium. Bis(salicy1idene)ethylenediamine may be used as either a fluorometric or absorbometric reagent for magnesium in a slightly alkaline dimethylformamide solution of MgClz (398). The sensitivity is pg. per ml. Another new 3.6 X fluorescence reagent for magnesium is an addition product of a diazo-compound derived from 2-amino-4-chlorophenol-6-sulfonic acid and barbituric acid (328). The reaction medium is water buffered a t pH 10 to 10.5 with glycine and acetone (4 to 1). The sensitivity is 0.2 pg. in 5 ml., and calcium interferes a t 100 times iVlg and barium a t 1000 times Mg. Schachter (317 ) has described an 8-quinolinol method for magnesium in urine which is based on the difference in the fluorescence intensity in aqueous-ethanolacetate buffers a t pH 3.5 and 6.5. The fluorescence is measured a t 530
84R
0
ANALYTICAL CHEMISTRY
mp and excited a t 420 mp; calcium does not interfere. Ruthenium. Bivalent ruthenium forms a fluorescent complex with 5methyl-1-,lo-phenanthroline which may be used to determine 0.3 to 2 pg. of Ru within i2% (381). Selenium and Silicon. The fluorometric determination of selenium with 3,3’-diaminobenzidine has been the subject of a number of papers. Cousins (68) extracts the Se complex with toluene and measures the fluorescence a t 580 mp with the excitation a t 450 mp. I n the analysis of animal tissue, plants, and soil, Watkinson (891) complexes the Se with toluene 3,4-dithiol and extracts with a misture of 1 to 1 ethylene chloride and carbontetrachloride. Parker and Harvey (268) have shown that the Se complex is monopiazselenole [5 - (3,4 - diaminophenyl)-piazselenole], not the diapiazselenole as originally assumed. Elliott and Radley (93) have shown that silicon isolated as sodium silicate produces a green fluorescence with benzoin in an alkaline formamide solution. Mannitol is used to complex boron, and hydroxylamine hydrochloride is added to retard the oxidation of benzoin. This method is accurate to 2 pg. of silicon. Tin and Thallium. Anderson, Garnett, and Lock (16) have continued their investigation of substituted naphthalenes as reagents for tin. A microchemical detection of tin is given as a bright yellow fluorescence of the crystal formed with potassium iodide (848). The lower valence of Hg, T1, Ag, and Cu gives a similar test. The fluorescence emission bands of a single crystal of TlCl a t the temperature of liquid nitrogen and irradiated with 365 mp is given as blue with a maximum a t 460 mp, orange 620 mp, and deep red a t 740 mp (368). Uranium. A review of the fluorometric methods and fluorometers for the determination of uranium is given by Haas (127). A number of authors have described their apparatus used in the fused pellet system. Haran (169) indicates a stabilized circuit with a synchronus detector and a very small band width. Leng (193) has a design that handles 56 samples and performs fusion and measurement in automatic sequence. Ohashi (660) constructed an oven to produce cakes 36 mm. in diameter and about 4 mm. high. Grigor’ev, Lukyanov, and Duderova (166) describe an electric furnace and a rapid method of preparing the fused beads. Particular techniques for separations from various sources occupy several papers, for example, from coal ashes, and rock samples (320),from zirconium and hafnium (387), from urine (3, 699, 407). Sagi and Rao (310) have devised a method for the determination
of uranium wherein the uranium is reduced in a Jones reductor and titrated with ferric iron with rhodamine 6G as a fluorescent indicator. The error is within 0.40/,, and 22 references are given. Another semiquantitative method for uranium is based on the intense fluorescence of uranyl ion adsorbed on silica gel (354). This will detect below 1bg., and 0.001% uranium can be detected in a I-gram sample. While not directly analytical, an article of interest deals with the formula of the chelates of U, Th, and Sc with 2-methyl8-quinolinol (379). Zinc and Zirconium. The acid base indicator, salicylaldehyde semicarbazone, serves as a fluorescent quantitative reagent for zinc in a p H range of 6.15-6.4 (37). Of 20 cations tested, only aluminum caused a similar fluorescence. Zirconium concentrations of 200 pg. or lower may be titrated with fluoride in 6N HC1 using morin as a fluorescent indicator (850). Fletcher has made an extensive study of the reaction of the dye, 2,2,’4‘-trihydroxyazobenzene-5-sulfonic acid, with zirconium (109, 110). Data have been recorded on color and fluorescent results of 22 organic compounds with 6 solvents on paper with both zirconium and yttrium (163). Hercules has used quercetin for the fluorometric determination of zirconium after extraction with thenoyltrifluoroacetone (136). Nonmetals. The titration of fluoride ion with Alf3 using morin as an indicator under ultraviolet light has been improved to a titration error of 0.005 mg. for a range of 0.047 to 1.45 mg. of fluoride (385). d solution of ZrOClz may also be used to titrate fluoride using morin as an indicator (172) with a mean error of rtO.9% for fluoride concentrations of 2 to 40 mg. in 10 to 20 ml. The normal fluorescent method for the determination of uranium is described as a rapid qualitative and quantitative method for fluoride. I n this case, the fluoride containing compound is melted with uranyl nitrate and sodium carbonate ( 9 ) . Mercaptans and sulfides may be titrated with tetrakis(acetoxymercuri)fluorescein (41.2). Small quantities of ozone may be determined by its effect on the fluorescence color and intensity of luminol (3-aminophthalhydrazide), fluorescein, and fuchsine when adsorbed on silica gel (2’76). Air samples were drawn through silica gel columns impregnated with the above compounds. The height of the column where the fluorescence was extinguished was proportional to the ozone content of the sample, For luminol an extinguished segment of 1 mm. corresponded to 0.15 pg. of Os, for fluorescein it was 0.34, and for fuchsine 0.39. Luminol was least affected by NOz. A fluorometric method for the deter-
mination of phosphorus in silicon depends on the reaction of phosphomolybdic acid with thiamine in isobutyl alcohol to produce thiochrome (234). BognAr (32) has described the use of 3,6 - diamino - 4 - ethoxyacridine lactate and an oxidation product of Trypan red ((3.1. 228.50) as fluorescent absorption indicators for the titration of isocyanide and halide ions with silver nitrate. Riboflavine and Aurazin G (C.I. Basic Yellow 6) may also be used for the titration of isocyanide and Maglada red (C.I. Basic Red 6) for thiocyanate (31). A paper on the analysis of nonmetallic inclusions by luminescence presents an interesting qualitative application of fluorescence (194). Briefly the technique is as follows: A drop of water is placed on a microscope slide, and a small quantity of crushed mineral is placed in i t (quartz, corundum magnetite, etc.). This is dried and a cover glass placed over it. The material is examined under ultraviolet light, and any fluorescence is noted. A drop of 10-6M fluorescein in alcohol or acridine in acetone is introduced under the cover glass. Quartz fluoresces originally red and is bright golden yellow after treatment with fluorescein. Corundum fluoresces dark green and after treatment is light green; sulfides and magnetite do not fluoresce with or without the fluorochrome. The hydroxyphthalic acids and their derivatives have been reported as highly fluorescent materials which serve as useful oxidation-reduction indicators (116, 117). Among these are: 3,6dihydroxyphthalic acid and its dimethyl ester, 4,5 - dichloro - 3,6 - dihydroxyphthalimide, and 4,5 - dibromo - 3,6dihydroxyphthalonitrile. The intensity and color of the fluorescence is dependent on pH. These compounds are useful also in bromide and chloride titrations with mercuric nitrate in the presence of potassium ferricyanide. Chemiluminescence. T h e work on biacridine derivatives as chemiluminescence indicators in the titration of acids has been continued (S73). This article is concerned with the titration of weak acid with compounds and techniques which Turowska and her associates have previously reported for strong acids. The chemiluminescence of the reaction of nitric oxide with atomic oxygen has been studied by Broida, Schiff, and Sugden (43) and has been applied to the determination of impurities in air (181). I n this case, the impurities are measured by the decrease in luminosity of the reaction. Erdey and Buzas have given the details for the preparation and use of siloxene as an indicator in a number of redox reactions (97) and have produced an excellent article on the theory of the luminol type indicators. They conclude that lucigenin is the best of
the indicators of this type for hydrogen peroxide (96). The effect of iodide, bromide, thiocyanate ions, and of phenol, resorcinol, and like compounds, on the inhibition of the chemiluminescence of luminol is reported (232). The logarithm of the induction period of the luminol is proportional to the concentration of cyanide ion, and this relationship may be used for its determination (246). The use of luminol on paper disks is recommended for the determination of ozone in the air (22). Chemiluminescence has been shown to be very widespread in the oxidation of many organic compounds (333), and sensitive detectors may produce more analytical reagents. X-ray fluorescence methods are not included in this review since this subject is covered under spectroscopy. ORGANIC AND BIOLOGICAL
9 novel ultrasonic method for converting aromatic acids into fluorescent hydroxylated derivatives has been described by Weissler and Wasileski (395) and applied to the determination of microgram amounts of phthalic acid. Two procedures have been reported (62, 364) for the determination of phthalic acid by heating with resorcinol and sulfuric acid to form fluorescein. Gallic acid a t p H 10 shows green fluorescence, which Kisilevich (166) has used in a volumetric method based on discharge of the fluorescence by CuS04. Hippuric acid has been determined (94) by its fluorescence in 70y0 HzS04. Simple fluorometric procedures adapted to biological material are given for salicylic acid by Chirigos and Udenfriend (61) and for gentistic acid by Xepras (654). I n the separation of 18 naphtholsulfonic acids by paper chromatography, the spots are detected by their fluorescence after treatment with 1% p-nitrobenzenediazonium tetrafluoroborate (173). Naphthionic acid has been determined fluorometrically with good sensitivity and linearity (88). A large number of aromatic amines can be converted into fluorescent anils by cyanogen bromide and so analyzed with the help of paper chromatography (311). Strong interest in the catecholamines has continued, with attention to defining optimum conditions for the various procedures. Adrenaline and noradrenaline can be determined separately in the ferricyanide oxidation method by measuring the fluorescence of the solution a t two sets of excitationemission wavelengths (99, 187, 188). The ethylenediamine condensation method has been studied a t length by Nadeau, Joly, and Sobolewski (160, 250, 251) with the finding that a molybdate pretreatment gives reproducible
and enhanced fluorescence. Yoshinaga (416) found that the ethylenediamine method, although sensitive, lacks specificity. I n the Lund procedure using Rho2oxidation at p H 4 for adrenaline and pH 6 for noradrenaline, precise timing is necessary (79) and other improvements in technique are suggested (100); if sulfite is present, it must first be destroyed (48). Iodine also may be employed as the oxidant, a t pH 4.4 and 7.2, respectively (162). The presence of sulfhydryl compounds causes losses in the oxidation of catecholamines to fluorescent products (306). For the estimation of adrenochrome in blood, Payza and Mahon (274) have made an improvement by deleting ascorbic acid from their original procedure, which had been found unreliable because of unstable high blanks (292). The steroids represent another area of great activity in fluorometric analysis. Levin, Irvin, and Johnston have described a spectrofluorometric determination of bile acids (195). The Silber method for corticosteroids, based on the fluorescence in sulfuric acid, has been tested and improved by several workers (126, 13S, 239); Braunsberg and James (41) have used the method for determining cortisone, hydrocortisone, corticosterone, and 11-P-hydroxyandrostenedione. For free hydrocortisone and corticosterone in plasma, procedures have been simplified by makmg separations through extraction rather than chromatography (308, 346). Various procedures for estrogens have been published, in which the fluorescence of estrone, estradiol, and estriol is developed by heating with 70% HzS04 (144, 150) or more concentrated acid (51, 380); the specificity may be increased by extraction of the fluorescence with p-nitrophenol solution (154, 155, 353). I n the analysis of blood or urine for estrogens, chromatographic separations on alumina columns are very useful (144, 150, 287). Another possible way to distinguish between estradiol and estrone is their differential rate of development of fluorescence with cold sulfuric acid (50). Pretreatment with methanolic KOH greatly enhances the sulfuric acid fluorescence of several steroids, including progesterone (369). The effects of various experimental conditions on the fluorescence of eight natural estrogens have been studied (18). Many steroids give characteristic fluorescence when their spots on paper are sprayed with 15% HSP04 and heated (417). An interesting method for diethylstilbestrol in beef liver, sensitive to a few parts per billion, has been described by Goodyear and Jenkinson (123, l24), who measured the increase in fluorescence produced photochemically in ethyl alcohol solution by intense ultraviolet VOL 34, NO. 5, APRIL 1962
b
85 R
irradiation. For routine determination of coumestrol (an estrogen of isoflavone structure found in clover and lucerne), the fluorescence of the paper-chromatographic spot is compared with standards (206, 206). The fluorometric determination of vitamins is reviewed with 53 references by Tabata (357). -4study of analytical methods for multivitamin preparations emphasizes the value of fluorometry (161). I n the determination of thiamine by thiochrome fluorescence, improvements have been proposed which include a micro adaptation (96), the use of methanol in the ferricyanide oxidation step ( C l O ) , and a better blank obtained by pretreating an aliquot with benzenesulfonyl chloride (165). A sensitive assay for pyridoxamine is based on conversion into intensely fluorescent pyridoxal cyanohydrin (367). Several improved procedures have been published for the fluorometric determination of riboflavin in foods (78, 114, 166, 219) and in tissues (52, 246). Riboflavin and its nucleotides were quantitatively determined on paper chromatograms (413). Hemmerich, Prijs, and Erlenmeyer (134,135)have investigated the fluorescence and paper-chromatography characteristics of a set of derivatives of riboflavin and lumiflavin. The absorption and fluorescence properties of seven lumazines (pteridine derivatives) have been published (203). For the determination of isoniazid in blood, Peters (279) got excellent results by the reaction with cyanogen bromide to yield a fluorescent derivative. A micromethod for isoniazid uses a preliminary alkaline hydrolysis, yielding N2H4, which is then condensed with a naphtholaldehyde to produce the strongly fluorescent aldazine (238). Isoniazid itself is recommended as a spray reagent for traces of certain flavonoids on paper chromatograms (130). Flavones extinguish the fluorescence of rhodamine B, whereas flavanones do not (256). The fluorescence of flavonols and related compounds on paper is reduced by Benedict's reagent if o-dihydroxy groups are present, but is enhanced if the two hydroxy groups are nonadjacent (295). Activation and emission wavelengths have been listed for a large number of coumarins (396) and furocoumarins or psoralens (271). Ichimura has determined warfarin by its fluorescence a t pH 10 in ethyl alcohol (149), and also berberine by a fluorescence method (148). Fluorometric analyses for quinine and quinidine in biological fluids are described in several papers (15, 16, 116, 361, 362). Eisenbrand and Raisch (90, 91) have studied the effects of halide ion, salt, and acid concentrations on the fluorescence intensity of quinine. Tetracycline antibiotics form highly fluorescent complexes with calcium 86 R
ANALYTICAL CHEMISTRY
and barbiturates, which are the basis of a sensitive method by Kohn (170). Fluorescence makes possible the localization of various tetracyclines bound to mitochondria (84), worms (366), macromolecules ( 1 7 l ) , and bony structures (119, 247, 263). Quercetin ingestion also causes fluorescence of bone (896). Fluorometric assays have been published for several other pharmaceuticals, including reserpine (131, 211), glutethimide ( I S $ ) , ergotamine (389), mechlorethamine or mustargen (226), acriflavine (26), rifomycin B (326), and cotarnine or Stypticin (147). Polycyclic aromatic hydrocarbons and their fluorescence continue as objects of intensive study by those interested in carcinogenesis (27, 80) and air pollution (313, 363). Fluorescence spectra are recorded for many such compounds in iso-octane (199) and in pentane solution (314) and also for a large number of compounds in thin solid films (27, 277). Experimental conditions for qualitative and quantitative fluorescence analysis of aromatic hydrocarbons and heterocyclics have been discussed (67, 377), and successful fluorometric determinations of several mixtures have been performed (200, 366). For 3,4benzopyrene in cigarette smoke ( 2 4 , 272) or biological material (273), the fluorescence is measured after chromatography on alumina; the emission spectrum is affected by ozone (240) and also develops fine structure a t 83' K. which affords improved analytical specificity ( 2 4 ) . An even lower temperature of 4.2' K. was found necessary by Wolf (408) to obtain the true fluorescence spectrum of naphthalene. The luminescence of chrysene crystals and solutions a t 77" K. has been measured (269), and the general problem of the origin of hyperfine structure in lowtemperature emission spectra of aromatic hydrocarbons has been discussed (336). Perylene crystals fluoresce orange a t 77' K., but the solutions fluoresce blue, and some of these blue lines may be used for the determination of perylene in crude oil (278). Polarized absorption and fluorescence spectra of 2,6-dimethylnaphthalene a t different temperatures have been recorded (421). Absorption and emission spectra are also reported for anthracene and some derivatives (6, 59, 60), naphthacene in anthracene crystal (63), pyrene in fluorene crystal (319), and biphenyl hydrocarbons and their oxygen and sulfur analogs (197). Some of the polynuclear hydrocarbons have been detected as fluorescent impurities in liquid paraffin and organic solvents (83). Sawicki and associates (316) reported a fluorometric determination for traces of carbazole in air. Concentration quenching has been noted in the fluorescence of pyrene (111), and a study has been
made of the effect of chain length on fluorescence characteristics in polystyrene and polyphenyl acetylene (113). The relation between luminescence spectra and chemical structure has been investigated by many workers, including those interested in the effects of pH (248) and solvent (58, 378) on hydrogen bonding between polar substituents in aromatic rings (303, 420). Particular attention has been paid to naphthalene and its derivatives ( 4 l 6 ) , naphthols and diols a t 77' K. ( I % ) , hydroxynaphthoic acids (249) and naphthalimides (414). Changes caused by 1o-n-ering the temperature to 77' K. have been studied in the spectra of several phthalimides and some dyes (182). The use of fluorescence line spectra is reviewed with 53 references (336). Lazo (191) has described a fluorometric determination for 6-hydroxyfluoran. A specific spot test for 2hydroxy-1,4-naphthoquinone (312) is the rose-red fluorescence obtained on paper after condensation with o-phenylene diamine. Feigl's spot tests include a number based on fluorescence (103, 104). Hydrazines may be detected by the intense yellow fluorescence resulting from reaction with salicylaldehyde ( I 04) or vanillin (286). I n the aliphatic field, spectrofluorometry has been used to distinguish pure olive oil from treated oil (75, 288) and to determine lubricating oil mist in air (266). Luminescence spectra of petroleum products a t 90' K. have been compared with those a t room temperature (387). Improvements in the fluorescent indicator adsorption analysis of petroleum products include a new apparatus (6) and the addition of 4% water to the dyed silica gel (258). Acetone in urine may be analyzed by its quenching effect on the fluorescence of 2-naphthol (146). Urine analysis by a fluorescence chromatographic method can show the presence of diabetes (332). Another method for acetone (39) is to condense it with 2diphenylacetylindane - 1,3 - dione - 1hydrazone to yield an azine with bright yellow fluorescence; a similar formation of fluorescent azines serves for the detection of aldehydes such as glyoxal, pyruvaldehyde, or salicylaldehyde (316 ) . Glycerin may be determined by conversion to quinoline and measurement of the fluorescence of the latter (86, 89) ; a micro adaptation of the method is useful in determining serum triglycerides (227). Hexose sugars have been estimated by heating with 5-hydroxy-1 (2H)-naphthalenone in sulfuric acid, to yield a product fluorescing a t 532 mF; pentoses do not interfere (287). Blecher (29) determines 2-deoxy-~-glucose by condensation with 3,5-diaminobenzoic acid to produce a fluorophore. Ketoses and aldoses may be differentiated on paper
chromatograms by their dissimilar fluorescence after treatment with sulfosalicylic acid (301). Creatine has been determined by condensation with ninhydrin (67), and agmatine by condensation with o-phthalaldehyde (66), in both cases with the formation of highly fluorescent products. Histamine in blood (257) or brain (334) may also be determined fluorometrically after reaction with o-phthalaldehyde. For the detection of amino acids on paper chromatograms by fluorescence, the sensitivity can be much increased with 1,2 - naphthoquinone - 4 - sulfonate (262). Hess and Udenfriend (139) determine tryptamine in tissues by treatment with formaldehyde, then with H 2 0 2 ,to obtain the highly fluorescent norharman. Tryptamine has also been determined with a simplified Zeiss fluorometer ( 7 ) . Other tryptophan metabolites, kynurenine and xanthurenic acid, can be determined fluorometrically in urine after chromatography (161, 180). The luminescence spectra a t 77" K. of phenylalanine, tyrosine, and tryptophan, and also several proteins, have been compared with those a t room temperatures (386). Weber has studied the polarization of the fluorescence in tyrosine, tryptophan, and related compounds (392), as well as tyrosine fluorescence in the albumins (393) and the pH dependence of fluorescence in tyrosine copolymers (305). Teale (569, 360) has measured the excitation and emission spectra and absolute quantum yields for 21 globular proteins in neutral solution. The fluorescence of botulinum toxin (318) and tetanus and diphtheria toxoids (376) has been investigated. A fluorometric microdetermination of serum albumin uses vasoflavine dye as the reagent ( 2 4 , and a similar principle of fluorescent staining with protoporphyrin serves for the detection of various serum proteins after paper electrophoresis (323, 324, 325). The powerful technique of identifying proteins or microorganisms by their immunochemical reaction with fluorescent antibodies is the subject of several reviews (252, 281), one with 76 references (25). Specific applications include the diagnosis of schistosomiasis (309) and treponemal infection (74), intracellular localization of polyoma virus (218),and Rous sarcoma virus (217), detection of C-reactive protein (121), identification of Listeria monocytogenes (342), and pleuropneumonia like organisms (216), study of cell development (182, 208), and staining of red cells (81, 157). Chadwick and coworkers have measured the fluorescence depolarization in dyelabeled proteins (64) and also investigated the unreacted fluorescent material which leads to nonspecific staining (56, 56). A simplified method
is given (159) for removal of the material responsible for nonspecific staining. Other papers describe the preparation of fluorescein isocyanate reagent (66, 231), a new labelling procedure (298), two new fluorescent dyes, aminorosamine B (33) and l-dimethylaminonaphthalene - 5 - sulfonyl chloride (4), and various aspects of the technique (76,105, 297). Of the reported enzymic fluorometric methods, one group consists of enzyme assay by the liberation of a fluorescent product, such as the assay of phosphatases with naphthyl phosphates as substrates (46, 47, 241). A similar method was used for N-acetyl-j3-glucosaminidase (192). Another group involves measuring the fluorescence of the reduced form of diphosphopyridine nucleotide coenzyme, as in the determination of lactic acid in serum (20?'), or hexose phosphates in muscle (327); alternatively, the oxidized form of DPN can be condensed with methyl ethyl ketone to give a fluorophore, as in Laursen's assay of lactic dehydrogenase (189) or glutamic-oxalacetic transaminase (130). Fluorescence has been used to explore enzyme binding (107, 108), particularly in glutamic dehydrogenase (2, 112, 355) and other dehydrogenases (186, 361, 406). When phosphopyridine nucleotides are determined fluorometrically, the presence of phenols causes low results (221). Coproporphyrin in urine may be determined by its intrinsic fluorescence (102, 215, 228). Porphyrin fluorescence has been studied also in minerals of biologic origin (77), squamous cell carcinoma (118), and planarians (210), and as perturbed by metal atoms (8). An assay for gibberellic acid is based on its blue fluorescence after treatment with HzS04 (362). Traces of the phosphorothioate pesticides known as Bayer 21/199 and Bayer 22,408 may be determined in biological materials, after chromatographic separations, by fluorometry (12, 120). Transmission of the alkaloid sanguinarine in milk is detectable by the green fluorescence of a metabolic product (128). A spectrofluorometric method for the estimation of benzoquinolizines, such as emetine, in biological fluids and tissues is based on the measurement of the fluorescence after these substances are dehydrogenated with mercuric acetate (321). The method is sensitive between 0.03 and 0.2 pg. per gram or ml. of biological material. The admixture of American red wines in others can be detected by the presence of malvidine diglucoside, which has characteristic paper-chromatography properties, including brick-red fluorescence (294). The fluorescence of extracts of Chelidonium majus serves for identification purposes (326). -4spherosome fluorescence in leaf epider-
mis cells was produced by several oxazine dyes (255). Fluorescent brighteners have applications in biology (73) and elsewhere (394). Acridine Orange staining of cells reveals microscopic structure by the induced fluorescence (291); the Acridine Orange staining characteristics of E . coli are altered greatly by ultrasonic radiation (290). Deoxyribonucleic acid in cells may be demonstrated by staining with a fluorescent acriflavine Schiff reagent, after HC1 hydrolysis with the liberation of aldehyde groups (71, 164). The cross reaction between the Cypridina and Apogon luminescent systems has been studied spectroscopically (338). A few articles have been published on fluorescence techniques in paper chromatography. One of these is for nonspecific detection by dipping the developed and dried paper in either quinine or sulfosalicylic acid solution, which shows up the spots against an intensely fluorescent background (302). Another paper (1) describes a method for making permanent photographic records of fluorescence chromatograms without a camera. An important application of chemiluminescence is the assay of adenosine triphosphate by measuring the chemiluminescence intensity it gives in luciferin-luciferase solution (222); renewed interest is due to the recent proof of structure and synthesis of D-luciferin from firefly tails (401). Methanol and ethanol in mixtures may be determined by their catalytic effect on the chemiluminescence of diacridine derivatives caused by H202 (230). In the chemiluminescent oxidation of polyphenols by ozone, adding Rhodamine B gives a great increase in light intensity (23). Luminescence phenomena have been studied from many physico-chemical viewpoints, including decay times (229) as in acriflavine phosphorescence (167, sag), absolute quantum yields for 27 dyes (418)' quenching by salts (Wid), concentration quenching (236)) and oxygen quenching (370). Studies have been made of the sonoluminescence caused by ultrasonic irradiation of liquids (158, 3&), and of luminescence quenching in scintillation counting (21, 276). Fluorescence has been investigated in guanine solutions and spots on paper ( I ? ) , the 8-quinolinols (284), the antibody-hapten reaction (382), and the photolysis of thionine (270). LITERATURE CITED
(1) Abelson, D., Nature 188, 850 (1960).
(2) Adelstein, S. J., Mee, L. K., Biochem. J. 80, 406 (1961). (3) Akai kaishi 2, 3 : (4)Albrecht, biol. 6 , 49 (1961). ( 5 ) Alexander, P. W., Lacey, A. R., VOL. 34, N O . 5, APRIL 1962
87 R
Lyons, L. E., J . Chem. Phys. 34, 2200 (1961). (6) Allen, J. G., Wood, J. C. S., ASTM Bull. 49, 238 (1959). (7) Allgen, L. G., Funke, K. E., Nauckhoff, B., Scand. J . Lab. Clin. Invest. 13, 390 (1961). (8) Allison, J. B., Becker, R. S., J . Chem. Phys. 32, 1410 (1960). (9) AlmAssy, G., Kotsis, E., BordBs, E., Magyar Tudomdnyos Akad., K h . Tudinn4nyok Osztdlyknak, Kozlemdnyei 13, 45 (1960). (10) Aminco Lab. News, Am. Inst. Co., Silver Spring, Md., March 10, 1960. (11) Anderson, C. A., Adams, J. M., MeDougall, D., J . Agr. Food Chem. 7, 256 (1959). (12) Anderson, J. R. A,, Garnett, J. L., Lock, L. C., Anal. Chim. Acta 22, 1 (1960). (13) Arapova, E. Ya., Baranova, E. G., Levshin, V. L., Timofeeva, T. V., Trofimov, A. K., Feofilov, P. P., Trudy Komissii, Anal. Khim., Akad. Nauk S.S.S.R. 12, 344 (1960). (14) Bailey, G. F., ANAL. CHEM.32, 1726 (1960). (15) Balatre, P. H., Lefhvre, C., Ann. phurm. franc. 18, 481 (1960). (16) Balatre, P., Lefbvre, C., Merlen, J. F., Ann. biol. ctin. (Paris) 18, 228 (1960). (17) BarskII, I. Ya., Biokhimiya 24, 823 (1959). (18) Bauld, W. S., Givner, M. L., Engel, L. L., Goldaieher, J. W., Can. J . Biochem. and Physiol. 38, 213 (1960). (19) Belcher, R., Rees, D. T., Stepleir, W. T., Talanta 4, 78 (1960). (20) Bennett, R. G., Rev. Sci. Instr. 31, 1275 (1960).
(44) Buchanan, R. A., Murphy, J., J. Opt. SOC.Am. 51,1476 (1961). (45) Burstone, M. S., J . Natl. Cancer Inst. 24, 1199 (1960). (46) Busev, A. N., Shkrobot, E. P., Vestnik Moskov. Univ., Ser. Mat., Mekh.. Astron., Fiz. i Khim. 4. 199 (1959j. (47) Campbell, D. M., Moss, D. W., Clin. Chim. Acta 6, 307 (1961). (48) Canback, T., Harthon, J. G. L., J . Pharm. Pharmacol. 11, 764 (1959). (49) Carpenter, J. H., Public Works 91, 110 (19601. (50) Carraz; G., Beriel, M., Ann. endocrinol. Paris 20, 775 (1959). (51) CBdard, L., Pathol. et hiol., Semaine h8p. 8 , 901 (1960). (52) Cerletti, P., Ipata, P. L., Biochem. J . 75. 119 (1960). (53) Cek-ai, E., Rossi, G., Energia nucleare (k’ilan) 6,, 399 (1959). (54) Chadwick, C. S., Johnson, P., Richards, E. G., Nature 186,239 (1960). (55) Chadwick, C. S., Nairn, R. C., Immunology 3, 363 (1960). (56) Chadwick, C. S., Nairn, R. C., McEntegart, M. G., Biochem. J . 73, 41P (1959). (57) Chaudet, J. H., Kaye, W. I., ANAL. CREM.33, 113 (1961). (58) Cherkasov, A. S., Izvest. Akad. Nauk S.S.S.R., Ser. Fiz. 24, 591 (1960). (59) Cherkasov, A. S., Optics and Spectroscopy 7, 211 (1959). (60) Cherkasov, A. S., Vember, T. M., Optics and Spectroscopy 4,319 (1959). (61) Chirigos, M. A,, Udenfriend, S., J. Lab. Clin. Med. 54, 769 (1959). (62) Chomse, H., Arend, I., Chem. Tech. 11, 377 (1959). (63) Choudhury, N. K., Ganguly, S. C., Proc. Roy. SOC.A259, 419 (1960). (64) Clark. G. L.. “Encvclouedia of Spectroscopy,” Reinhold,* Ne’w York, 1961. (65) Cohn, V. H., Jr., Shore, P. A., Anal. Biochem. 2, 237 (1961). (66) Colobert, L., Demont, G., Domanski, B., Compt. rend. SOC. biol. 153, 1029 (1959). (67) Conn, R. B., Jr., Clin. Chem. 6, 537 (1960). (68).Cousins, F. B., Australian J . Exptl. Bzol. Med. Sci. 38, 11 (1960). (69) Crosswhite, H. M., Dieke, G. H., J . Chem. Phys. 35, 1535 (1961). (70) Culkin, F., Riley, J. P., Anal. Chim. Acta 24, 413 (1961). (71) Culling, C. F. A., Vassar, P. S., A . If. A . Arch. Pathol. 71, 76 (1961). (72) Daniels, F., ed., “Photochemistry in the Liquid and Solid State,” Wiley, New York, 1960. (73) Darken, M. A., Science 133, 1704 (1961). (74) Deacon, W. E., Freeman, E. M., Harris, A., Proc. SOC. Exptl. Biol. Med. 103, 827 (1960). (75) De Francesco, F., Olii minerali, grassi e saponi, colori e vernici 36, 73 (1959). (76) deLong, R., Nature 190, 1126 (1961). (77) DBriberB, M., Bull. SOC. franc. min&aZ. et crist 84, 94 (1961). (78) Deutsch, M. J., Pillsbury, H. C., Schiaffino, S. S., LOV,H. W., J. Assoc. Offic. Aar: Chem’ists 43. 42 (1960). (79)- Dienitbier, E., Balik, ‘J., &sopis ldkdru c‘esk9ch 98, 16 (1959). (80) Dikun, P. P., Voprosy Onkol. 6, 75 (1960). (81) Donath, T., Lengyel, I., Acta Histochem. 9, 260 (1960). (82) Dressel, W. M., Ritchey, R. A., U. S. Bur. Mines, Inform. Circ. 7946, (1960). (83) Diuckrey, H., Schmahl, D. R., Preussmann, R., Arzneimittel-Forsch. 9, 600 (1959). ~
(39) Brandt, R., Cheronis, N. D., Microchem. J . 5, 110 (1961). (40) Braunsberg, H., James, V. H. T., Anal. Biochem. 1,443 (1960). (41) Ibid., p. 452. (42) Bril, J., Pruvot, E., Mikrochim. Acta 1960, 577. (43) Broida, H. P., Schiff, H. I., Sugden, T. M., Trans. Faraday SOC.57, 259 (1961). 88R
ANALYTICAL CHEMISTRY
(84) du Buy, H. G., Showacre, J. L., Science 133, 196 (1961). (85) Eggers, J. H., Talanta 4, 38 (1960). (86) Eisenbrand, J., Angew. Chem. 72, 592 (1960). (87) Eisenbrand, J., 2. Anal. Chem. 179, 170 (1961). (88) Eisenbrand, J., Meyer, H., Ibid., 174, 414 (1960). (89) Eisenbrand, J., Raisch, M., Ibid., 177, 1 (1960). (90) Ibid., 179, 352 (1961). (91) Ibid., p. 406. (92) Elliott, G., Radley, J. A, Analyst 86, 62 (1961). (93) Elliott, G., Radley, J. A., ATAL. CHEY. 33, 1623 (1961). (94) Ellman, G. L., Burkhalter, A,, LaDou, J., J . Lab. Clin. Med. 57, 813 11961). --,\ - -
(95) El-Sabban, M. Z., El-Maghrabi, M. S., J . Egypt. Med. Assoc. 40, 831 (1957). (96) Erdey, L., Buzas, I., Anal. Chim. Acta 22. 524 (1960’1. (97) Erdey, L.,‘ Buzas, I., Polos, L., 2. Anal. Chem. 169, 187, 263 (1959). (98) Esikov, A. D., Men’shikov, V. V., Lab. Delo 7, 22 (1961). (99) Euler. U. S. v.. Lishaiko. F..’ Acta ’ Physiol. ’Scand. 45,‘ 122 (1459). (100) Ihid., 51, 348 (1961). . 32, No. (101) Fassel, V. A,, ~ ~ N A LCHEX 11, 19A (1960). . (102) Fedorov. G. M.. Lab. Delo 7. No. ‘ 3,’13 (1961): (103) Feigl, F., “Spot Tests in Organic L4nalyeis,”Elsevier, New Pork, 1960. (104) Feigl, F., Amaral, J. R., Gentil, V., Mikrochim. Acta 1957, 726. (105) Felton, L. C., JlcMillion, C. R., Bnal. Biochem. 2, 178 (1961). (106) Fioletova, A. F., Zhur. Anal. Khim. 14, 739 (1959). (107) Fisher, H. F., McGregor, L. L., Biochem. Biophys. Acta 38, 562 (1960). (108) Ibid., 43, 557 (1960). (109) Fletcher, M. H., ANAL. CHEM.32, 1822 (1960). (110) Ibid., p. 1827. (111) Forster, Th., Angew. Chem. 72, 716 (1960). (112) Frieden, C., Biochim. Biophys. Acta, 47, 428 (1961). (113) Gachkovskii, V. F., Doklady Akad. Ifauk S.S.S.R. 133, 1388 (1960). (114) Gassmann, B., Sahrung, 4, (2), 140 (1960). (115) Gelfman, K.,Seligson, D., Am. J . Clin. Path. 36, 390 (1961). (116) Geyer, R., Steinmetzer, H., Wiss. 2. Tech. Hochsch. Chem. Leuna-Merseburg 2, 423 (1959/1960). (117) Geyer, R., Steinmetzer, H., Angew. Chem. 72, 634 (1960). (118) Ghadially, F. N., Neish, W.J. P., Kature 188, 1124 (1960). (119) Ghosez, J. P., Arch. hiol. 70, 169 (1959). (120) Giang, P. A., J . Agr. Food Chem. 9, 42 (1961). (121) Goldwasser, R., Rozansky, R., Nature 190, 1020 (1961). (122) Goldzieher, J. W., Bauld, W. S., Engel, L. L., Givner, M. L., Can. J . Biochem.~ Physio1.-38, 238 (1960): ’
~
~
125) Grigor’ev, V. F., Luk .l26) Guillemin, R., Clay Lipscomb, H. S., Smith, J. D., Clin. M e d . 53, 830 (1959). (12!) ,Haas, W. E. L., Rev. fac. cienc., Onzv. Lisboa. 2A SBr. B7. 77 (1959/ . , 1960). (128) Hakim, S. -4. E., Mijovic, V., Walker, J., Nature 189, 201 (1961).
(129) Haran. E. N.. J . Sci. Instr. 38, 273 (1961). ' (130) Hawker, C. D., Margraf, H. W., Weichselbaum, T. E., ANAL. CHEM. 32, 122 (1960). (131) Haycock, R. P., Sheth, P. B., Mader, W. J., J . Amer. Pharm. Assoc., Sci. Ed. 48, 479 (1959). (132) Ibid., 49, 673 (1960). (133) Hedner, P., Acta Pharmacol. Toxicol. 18, 65 (1961). (134) Hemmerich, P., Helv. Chim. Acta. 43, 1942 (1960). (135) Hemmerich, P., Prijs, B., Erlenmeyer, H., Ibid., 42, 2164 (1959). (136) Hercules, D. M., Talanta 8, 485 (1961). (137) Hercules, D. M., Frankel, H., Science 131, 1611 (1960). (138) Hercules, D. M., Rogers, L. B., J . Phys. Chem. 64,397 (1960). (139) Hess, S. M., Udenfriend, S., J . Pharmacol. Exptl. Therap. 127, 175 (1959). (140) Holzbecher, Z., Collection Czechoslov. Chem. Communs. 24, 3915 (1959). (141) Ibid., 25, 977 (1960). (142) Ibid., 26, 1204 (1961). (143) Holzbecher, Z., Pokorny, J., Chem. listy 54, 470 (1960). ( I 44) Hosoi, RI., Kanazawa Daigaku Kekkaku Kenkydsho Xemp8 16, 145
(171) Kohn, K. W., Nature 191, 1156 (1961). (172) Kolarik, Z., Collection Czechoslov. Chem. Communs. 25, 2228 (1960). (173) Kolsek, J., Perpar, M., ChemikerZtg. 83, 712 (1959). (174) Korbl, J., Svoboda, V., Talanta 3, 370 (1960). (175) Korenman, I. M., Avrova, N. F., Trudu Khim. i Khim. Tekhnol. 1. 138
f1958). \_.._,.
(145) Huffman, C., Jr., U . S. Geol. Survey, Profess. Papers KO. 40043, B493 (1960). (146) Hynie, I., Vecerek, B., Wagner, J., tasopis lkkciru Eeskjch 99, 88 (1960). (147) Ichimura, Y., Bunseki Kagaku 8 , 557 (1959). (148) Ibid., 10, 1097 (1961). (149) Ichimura, Y., Yakugaku Zasshi 79, 1079 (1959). (150) Inai, T:, Shikoku Igaku Zasshi 16, 735 (1960). (151) Indemans, A. W. M., Rademakers, H. E. J., Pharm. Weekblad 95, 377 (1960). 52) Ishibashi, M., Shigematsu, T., Xshika-iva, Y., Bull. Inst. Chem. R e search, Kyoto Unio. 37, 191 (1959). 53) Ishibashi, AI., Shigematsu, T., Nishikawa, Y., Nippon Kagaku Zasshi 81, 259 (1960). 54) Ittrich, G., Acta Endocrinol. 35, 34 (1960). 55)'1ttrich, G., 2. physiol. Chem. 312, 1 (1958). (156) Janicki, J., Kamiriski E., Getreide u. Mehl 9. 9 (19591. (157) Jankovic,' B. 'D., Acta Haematol. 22, 278 (1959). (158) Jarman, P., Proc. Phys. SOC.73, 628 (1959). (159) Johnson, G. D., Nature 191, 70 (1961). (160) Joly, L. P., Nadeau, G., Ibid., 184, 1483 (1959). (161) K'alab, ' M., Collection Czechoslov. Chem. Communs. 25, 1220 (1960). (162) Kaliman, P. A., Voprosy Med. Khim. 6, 635 (1960). (163) Kallistratos, G., Pfau, A., Ossowski, B., Anal. Chim. Acta 22. 195 (1960). (164) Kasten, F. H., Burtbn, V.; Glover, P., Nature 184, 1797 (1959). (165) Kawasaki, C., Itoh, T., Bitamin 13, 391 (1957). (166) Kisilevich, G. A., Ukrain. Khim. Zhur. 25,237 (1959). (167) Kielyak, G. M., Optics and Spectroscom 6. 144 (1959). (168) Klochkov, 'V. P., Fiz. Sbornik L'vov Gosudarst Univ. 3, 71 (1957). (169) Kochemirovskii, A. S., Reenikova, I . I., Optics and Spectroscopy 8, 206 (1960). (1702 Kohn, K. W., ANAL. CHEM.33, 862 (1961).
( l G i j i e w i s , D. R., Whitaker, T. N., Chapman, C. W., Am. Mineralogist 44, 1121 (1959). (199) Lijinsky, W., Chestnut, A., Raha, C. R., Chicago Med. School Quart. 21, 49 (1960). (200) Lijinsky, W., Raha, C. R., Chestnut, A., ANAL.CHEM.33, 1448 (1961). (201) Lippert, E., J . Opt. SOC.Am. 51, 1466 (1961). (202) Lippert, E., Noegele, W., SieboldBlakenstein I., Staiger, U., Voss, W., 2. anal. Chem. 170, 1 (1959). (203) Lippert, E., Prigge, H., 2. Elektrcchem. 64,662 (1960). (204) Lipsett, F. R., Rev. Sci. Znstr. 32, 840 (1961). (205) Livingston, A. L., Bickoff, E. M., Guggolz, J., Thompson, C. R., ANAL. CHEM.32, 1620 (1960). (206) Livingston, A. L., Bickoff, E. M., Guggolz, J., Thompson, C. R., J . Agr. Food Chem. 9, 135 (1961). (207) Loomis, M. E., J . Lab. Clin. Med. 57, 966 (1961).
(208) Louis, C. J., White, J., Lab. Invest.
9. . , 273 11960). (209) Lukin, A. M., Bozhevol'nov, E. A., J . Anal. Chem. U.S.S.R. 15, 45 (1960). (210) MacRae. E. K.. Science 134. 331 . (1961). (211) Mader, W. J., Haycock, R. P., Sheth, P. B., Connolly, R. J., Shapoe, P. M., J . Assoc. OJic. Agr. Chemists 44, 13 (1961). (212) Magee, R. J., Scott, I. A. P., Talanta 3, 131 (1959). (213) Mahler, D. H., Humoller, F. L., Beensken, H. G., Loch, R. D., ANAL. CHEM.32, 1374 (1960). (214) Majumdar, D. K., 2. physik. Chem. 217, 200 (1961). (215) Maleitzke, G., Rontgen-u. Laboratoriumspraxis 13, L187 (1960). (216) Malizia, W. F., Barile, M. F., Riggs, D. B., Nature 191, 190 (1961). (217) Malmgren, R. -4., Fink, M. A. Mills, W., J . Natl. Cancer Inst. 24, 995 11960). (2i8) Malmgren, R. A., Rabotti, G., Rabson, A. S., Ibid., p. 581. (219) Maloia, L., Birra e Multo 1960 (Aug.), 52.' . (220) May, I., Grimaldi, F. S., ANAL. CHEM.33. 1251 (1961). (221) Mayir, A. M,, Ekperientia 15, 158 (1959). (222) McElroy, W. D., Hastings, J. W., Coulombre, J., Sonnenfeld, V., Arch. Biochem. Biophys. 46, 399 (1953). (223) McPherson, P. M., Sclar, N., Linden, B. R., Brouwer, W., Stair, A. T., Jr., J . Opt. SOC.Am. 51, 767 (1961). (224) McVay, T. N., U . S. Bur. Manes, Rept. Invest. No. 5620 (1960). (225) Melhuish, W. H., J . Phys. Chem. 64, 762 (1960). (226) Mellett, L. B., Woods, L. A., Cancer Research 20, 518 (1960). (227) Mendelsohn, D., Antonis, A., J. Lipid Research 2,45 (1961). (228) Menta, H. E. A., Grotepass, W., African J . Lab. & Clin. Med. 6, 43 (1960). (229) Metcalf, W. S., J. Chem. SOC.1960, 3726. (230) Michalski, E., Turowska, M., Chem. Anal. (Warsaw) 5, 625, 631 (1960). (231) Mikhailov, G. I., Kosnikova, .N. M., Metody Lyuminestsentn. Analzza, Minsk, Akad. Nauk Belorus. S.S.R., Sbornik 1960, 140. (232) Mikulicic, V., Weber, K., Croat. Chem. Acta 32, 157 (1960). (233) Milaev, S. M., Sb. Trud. Vses. Nauch. - Issled. Gorn. - Metallurg. Inst. Tsvet. Met. 5, 41 (1959). (234) Minns, R. E., Mikrochim. Acta 1961, 354. (235) Mix, M., Protoplasma 50, 434 (1959). (236) Mokeeva, G. A., Sveshnikov, B. Ya., Optics and Spectroscopy 9, 317 \ - - - - I .
(1961).
(237) Momose, T., Ohkura, Y., Chem. and Pharm. Bull. 7, 31 (1959). (238) Momose, T., Ueda, Y., Mukai, Y., Watanabe, K.. Yakuaaku Zasshi 80; 225 (1960).' ' (239) Moncloa, F., Peron, F. G., Dorfman, R. I., Endocrinology 65, 717 (1959). (240) Morlin, Z., Saringer, K. M.,Nature 191, 907 (1961). (241) Moss, D. W., Biochem. J . 76, 32P (1960). (242) Moss, D. W., Clin. Chim. Acta 5, 283 (1960). (243) Motojima, K., Proc. U . N . Intern. Conf. Peaceful Uses At. Energy, 8nd Geneta 28, 667 (1958); (244) Muel, B., Lacroix, G., Bull. soc. chim. France 1960, 2139. (245) Murai, F., Okubo, T., Shien, C. K., Bitamin 16, 392 (1959). VOL. 34, NO. 5 , APRIL 1962
89 R
(246) Musha, S., Ito, M., Yama,omot Y., Inamori, Y., Nzppon Kagaku Zasshi 80,1285 (1959). (247) Muzii, E., Nature 189,934(1961). (248) Naboikin, Yu. V., Pavlova, E. N., Zadorozhnyi, B. A., Optics and Spectroscopy 6,231 (1959). (249) Naboikin, Yu. V., Zadorozhny, B. A., Pavlova, E. N., Zbid., 8, 347 (1960). (250) Nadeau, G., Joly, L.-P., Can. J . Biochem. Physiol 37,231 (1959). (251) Nadeau, G., Sobolewski, G., Zbid., p. 441. (252) Nairn, R. C., Endeavour 20, 78 (1961). (253) Nebbia, G., Bull. Sci. Facolta d i Chemica Znd. Bologna 18,35 (1960). (254)Nepras, M., Ceskoslov. jarm. 9, 346 (1960). (255) Neu, R., Arch. Pharm. 292, 431 (1959). (256) Nihongi, T., Iwasaki, S., Tokyo Jikeikai Zka Daigaku Zasshi 74, 949 (1959). (257) Noah, J. W., Brand, A., J . Allergy 31,236 (1961). (258) Norris, T. A., Shirley, J. H., Constantin, C. S., ANAL. CHEW.33, 1556 (1961). (259) Nurmukhametov, P. N., Popova, E. G., Dokunikhin, N. S., Optics and Spectroscopy 9,313 (1960). (260) Ohashi, S., Nippon KBgyB Kaishi 76,530 (1960). (261) Olsen, R. A., Rev. Sci. Znstr. 31, 844 (1960). (262)Opienska-Blauth, J., Sanecka, M., Charezinski, M., J . Chromatog. 3,415 (1960). (263) Owen, L.N., Nature 190,500(1961). (264) Parker, C. A., Analyst 86, 365 (1961). (265) Parker, C. A., Photoelec. Spectrometry Group Bull. No. 13,334 (1961). (266) Parker, C. A., Barnes, W. J. Analyst 85,3 (1960). (267)Zbid., p. 828. (268)Parker, C. A., Harvey, L. G., Zbid., 86,54 (1961). (269)Parker, C. A,, Rees, W. T., Zbid., 85,587 (1960). (270) Parker, C. A., Rees, W. T., Nature 184, 1223 (1959). (271) Pathak, M. A., Fellman, J. H., Zbid., 185,382 (1960). (272) Pavlu, J., Sula, J., thsopis Mk4ru tesk9ch 99,(3-4),101 (1960). (273) Pavlu, J.,Sula, J., Collection Czechoslov. Chem. Communs. 25,2461 (1960). (274) Payza, A. N., Mahon, M. E., ANAL. CHEM.32,17 (1960). (275) Peng, C. T., Zbid., p. 1292. (276) Peregud, E.A,, Stepanenko, E. M., Zhur. Anal. Khim. 15, 96 (1960). (277) Perkampus, H. H., Z. physik. Chem. (Frankjurt)24,1 (1960). (278) Personov, R. I., Zzvest. Akad. Nauk S.S.S.R., Ser. Fiz. 24, 620 (1960). (279) Peters, J. H., Am. Rev. Respirat. Diseases 81,485 (1960). (280) Petersen, D. F.,Murray; A., ANAL. CHEM.32,443 (1960). (281) Petuely, F.,Angew. Chem. 71, 745 ( 1959). (282) Pikulik, L. G., Solomakho, M. A., Znzhener. Fiz. Zhur., A kad. Nauk Belorus. S.S.R. 3 (No. 81, 53 (1960). (283) Poluektov, N. S.,Nikonova, M. P., Redkozemel. Elementy, Akad. S.S.S.R., Znst. Geokhim. i Anal. Khim. 1959, 208. (284) Popovych, O., Rogers, L. B., Spectrochim. Acta 15,584 (1959). (285)Zbid., 16,49,399 (1960). (286) Prachenska, J., Zyka. J., Chem. prumsyl. 10,343 (1960). (287)Preedy, J. R. K., Aitken, E. H., J . Biol. Chem. 236,1297 (1961). (288)Prowedi, F., Boll. lab. chim. 90R
ANALYTICAL CHEMISTRY
provinciali (Bologna) 11, (1)) 3 (1960). (289)Przibram, K.,Nature 188, 657 (1960). (290)Ranade, S. S., Tatake, V. G., Korgaonkar, K. S., Zbid., 189, 931 (1961). \----,
(291) Randles, W. J., Zbid., 187, 964 (iefin) ,- - - - ,. (292) Randrup, A., Munkvad, K., Am. J . Psychiat. 117,153 (1960). (293) Rehuoldt, R. E.,King, R. M., Hercules, D. M., ANAL.CHEM.33,1362 (1961 ).
(315) Sawicki, E., Hauser, T. R., Stanley, T. W., Elbert, W., Fox, F. T., ANAL. CHEM.33,1574 (1961). (316) Sawicki, E.,Stanley, T. W., Chemist Analyst 49,107 (1960). (317) Schachter. D.. J . Lab. Clin. Med. (318j Schintz, E. J., Stefanye, D., Spero, L., J . Biol. Chem. 235,3489 (1960). (319) Schmillen,. A.,. Z. Katurforsch. Ida, 5 (1961). (320) Schonfeld, T., ElGarhy, M., Friedmann, C., Veselsky, J., Mikrochim. Acta 1960,883. (321) Schwarte, D.E.,Rieder, J., Clin. Chim. Acta 6,453(1961). (322) Schwarzenbach, G.,ANAL. CHEM. 32,6 (1960). (323) Searcy, R. L.,Bergquist, L. M., Clin. Chim. Acta 5,941 (1960). (324)Searcy, R. L., Korotzer, J. L., Craig, R. C., Bergquist, L. M., Anal. Biochem. 2,385(1961). (325) Semenova, M. N.,Aptechnoe D e b 7, No. 3,26 (1958). (326)Sensi, P., Coronelli, G., Binaghi, A., Farmaco, (Pavia) Ed. pract. 15, 292 (1960). (327)Seraydarian, K., Mommaerta, W. ’
596. (338) Sie, E.H., McElroy, W. D., Johnson, F. H., Haneda, Y., Arch. Biochent. Biophys. 93,286 (1961). (339) Sill, C. W., ANAL.CHEM.33, 1679 (1961). (340)Zbid., p. 1684. (341) Slavin, W.,Mooney, R. W., Palumbo, D. T., J . Opt. SOC.Am. 51, 93 (1961). (342)Smith, C. W., Marshall, J. D., Jr., Eveland. W. C.. Proc. SOC. Ezptl. Bid. Xed. 103,842 (1960). (343) Soden, R. R., J . Appl. Phys. 32, 750 (1961). (344) Solodovnikov, P. P., J . Anal. Chem. U.S.S.R. 16,249 (1961). (345) Srinivasan, D., Holroyd, L. V., J . Appl. Phys. 32,446 (1961). (346) Stewart, C. P., Albert-Recht, F., Osman, L. M., Clin. Chim. Acta. 6, 696 (1961). (347)Stolyarov, K. P., Grigor’ev, N. K., Zhur. Anal. Khim. 14, . 71 (1959). . . (348)Zbid., p. 491. (349) Stolyarov, K. P., Grigor’ev, N. N., Vestnik Leningrad. Univ. 14, No. 22, Ser. Fiz. i. Khim. No. 4,104 (1959). (350)Ibid., 15,No. 10,Ser. Fiz. i. Khim. No. 2, 137 (1960). (351)Strache. F..2. Anal. Chem. 174, ’ 392 (1980). (352) Street, H.V.,Niyogi, S. K., Nature 190,1199 (1961). (353) Strickler, H. S., Wilson, G. A., Grauer, R. C., Anal. Biochern. 2, 486 (1961). (354)Suleck, Z.,Michal, J., Dolezal, J., Chemist Analyst 50,13(1961). (355)Sund, H., Acta. Chern. Scand. 15, ,
I
94n ( i ~ ) 6).i \ - - - - I .
(356) Svoboda, V., Chromg, Ti., Korbl, J., Dorazil, L., Ta(antu 8,249 (1961). (357) Tabata, T., Bztamzn 13,451 (1957). (358) Takemoto,. Y., . Kature 190, 1094 ’ (1961). 1359) Teale. F. W. J.. Biochem. J . 76, ’ 381 (1960). 136C)’i Zbzd.. 80. 14P (19611. (361)Thedrell; H.,Langan, T. A., Acta Chem. Scand. 14,933(1960). (362) Theriault, R. J.,Friedland, W. C., Peterson, M. H., Sylvester, J. C., J . Agr. Food Chem. 9,21 (1961). (363) Thomas, J. F.,. Tebbens, B. D., Sanborn, E. N., Cripps, J. M., Intern. J . Air Pollution 2, 210 (1960). (364) Thommes, GI A,, . Leininger, E., Talanta 5 , 260 (1960). \ - - - I
~
(365) Zbid., 7, 181 (1961). (366) Tobie, J.. E., Beye, H. K., PTOC. SOC.Emtl. Bzol. Med. 104. 137 (1960). (367) Toipfer, E. W., Polansky, M. M:, Hewston, E. M., Anal. Biochem. 2, 463 (1961): (368) Tolstoi, N. A,, Sokolov, V. .4., Zzvest. Akad. Nauk S.S.S.R., Ser. Fiz. 25, 375 (1961). (369) Touchstone, J. C., Murawec, T. ANAL. CHEM. 32, 822 (1960). (370) Tsubomura. H.. Mulliken. R. S.. . J.’Am. Chem. got. 82, 5966 (196Oj. (371) Turkevich, B. M., Farm. Zhur. 1960, 15; Ref. Zhur. Khim. 1960,. 20., Abstr. KO.80,705. (372) Turner, G. K., Associates, Palo .41to. Calif.. Bull. PCD. 1961. (373) Turowska, M., Chem. Anal. (Warsaw) 5, 815 (1960). (374) Umland, F., Meckenstock, K.-U., Angm. Chem. 71, 373 (1959). (375) Umland, F., Meckenstock, K.-U. Z. Anal. Chem. 165, 161 (1959). (376) Vadimov, V. M., Zhur. hfikrobiol., Epidemiol. i. Zmmunobiol. 31, No. 8, 3.5 (imn) ,- - - - ,. (3; Van Duuren, B. L., ANAL. CHEM. 32, 1436 (1960). (378) Tran Duuren. B. L.. J . OTO.Chem. ‘ 26. 2954 119611. ’ (379)’ Van ‘TaGkl, J. H., Wendlandt, W. W., J . Am. Chem. SOC.82, 4821 (1960). (380) Varangot, J., Seeman, h.,CBdard, L., Pathol. et biol., Semaine hap. 5, 19 (1957). (381) Veening, H., Brandt, W. W., ANAL. CHEM.32, 1426 (1960). (382) Velick, S., PTOC.Natl. Acad. Sci. U. S. 46, 1470 (1960). (383) Venetta, E. D., Rev. Sci. Znstr. 30, 450 (1959). (384) Verma, M. R., Agarwal, K. C., J. sci. & Ind. Research (Indaa) 19B, 319 (1960). -
I
(385) Vinnik, M. M., Chepelevetskii, M. L., Soobshcheniya o Nauch.-Issledovate1 Rabotakh i NovoZ Tekh. Nauch. Inst. p o Udobren. i Znsektofunqisidam 1958, ( l o ) , 44; Ref. Zhur. Khim. 1959, 12, Abstr. No. 42115. (386) Vladimirov, Y. A., Burshtein, E. A., Biojizika 5 , 3 8 5 (1960). (387) Vozzella, P. A., Powell, A. S., Gale, R. H., Kelly, J. E., ANAL.CHEM. 32, 1430 (1960). (388) Vydra, F., PEibil, R., Korbl, J., Collection Czechoslov. Chem. Communa. 24, 2623 (1959). (389) Wachsmuth, H., van Koeckhoven, L., J . Pharm. Belg. N . S. 14,461 (1959). (390) Walkley, J., Am. Znd. Hyg. Assoc. J. 20, 241 (1959). (391) Watkinson, J. H., ANAL.CHEM.32, 981 (1960). (392) Weber, G., Biochem. J . 75, 335 (1960). (393) -Idid., 79, 29P (1961). (394) Weeks, L. E., Harris, J. C., Lewis, J. T., Soap Chem. Specialties 35, 66, 277 (1959). (395) Weissler, A., Wasileski, B., ANAL. CHEM.33. 1963 11961). (396) Wheelock, C.’E., i.Am. Chem. SOC. 81, 1348 (1959). (397) White, C. E., ANAL. CHEM. 32. ’ 4 7 (1960): (398) White, C. E., Cuttita, F., Ibid., 31, 2083 (1959). (399) White, C. E., Ho, M., Weimer, E. Q., Zbid., 32, 438 (1960). (400) White, C. E., Bo, M., Weimer, E. Q., Spectrochim. Acta 16, 236, 772 (1960). (401) White, E. H., McCapra, F., Field, G. F.. McElrov. W. D.. J . Am. Chem. SOC. 83,2402 ( i k ) . ’ (402) Wilkins, D. H., Talanta 4 , 80 (1960). (403) Ibid., p. 182.
(404) Will, F., 111, ANAL.CHEM.33, 1360 (1961). (405) Willard, H. H., Merritt, L. L., Dean, J. ,A;) “Instrumental Methods of Analysis, 3rd ed., Chapter 111, Van Nostrand, New York, 1958. (406) Winer, A. D., Biochem. J . 76, 5P (1960). (407) W6dkiewicz, L., Chem. Anal. (Warsaw) 5,985 (1960). (408) Wolf, H. C., Nalurwisscnschaflen 48, 43 (1961). (409) Wood, D. L., Kaiser, W. K., Garrett, C. G. B., Spectrochim. Acta 17, 1101 (1961). (410) W6stmann, B. S., Knight, P. L., Experientia 16, 500 (1960). (411) Wotherapoon, N., Oster, G., in
“Technique of Organic Chemistry,” Vol. 1, Part III,3rd ed., A. Weissberger, Ed., Interscience, New York, 1960. (412) Wronski, M., Z. anal. Chem. 180,
185 (1961). (413) Yagi, K., Okuda, J., Chem. and Pharm. Bull. Tokyo 6, 659 (1958). (414) Yasuda, K., Inukai, K., Ito, K., Nippon Kagaku Zasshi 80, 960, 962 (1959). (415) Yasuda, K., Okabe, K., Ito, K., Zbid., 81, 1361 (1960). (416) Yoshinaga, K., Tohoku J . Ezptl. Med., 70, 261 (1959). (417) Yoshizawa, N., Tokyo Jikeikai Ika Daigaku Zasshi 73, 1568 (1959). (418) Zanker, V., Rammensee, H., Z. physik. Chem. (Frankfurt) 26, 168 (1960’). (419) Zeiss Inst. Co., Chem. Eng. News, 38, Nov. 7, 86 (1960). (420) ZelinskiI, V. V., Reznikova, I. I., Zzvest. Akad. Nauk S.S.S.R.. Ser. Fiz. 24, 607 (1960). (421) Zmerli, A., Poulet, H., J . Chem. Phys. 33, 1177 (1960). (422) Zyuskin, N. M., Zavodskaya Lab. 24, 793 (1958). \ - - - - I -
Review of Fundamental Developments in Analysis
Gas Analysis A. P. Hobbs, The Dow Chemical Co. Midland, Mich.
T
covers published articles on gas analysis from June 1959 to June 1961. Many different methods of gas analysis are still being used other than instrument methods. These are necessary to check instruments and to analyze gases where it is not economical to buy an instrument because of infrequent analysis or one-time analysis. For some time, there has been a need for an up-to-date book on gas analysis. Although the book by Kolthoff et al. (86) is not all devoted to this subject, it should be a good addition to the library of any gas analyst or any analyst who might have to run analysis on gases. HIS REVIEW
OXYGEN
Several analysts have used copper solutions for the determination of oxy-
gen. Konovalov et al. (87) have used a conductometric signaling device for oxygen in nitrogen, argon, helium, etc. The device contains silica gel on which copper has been deposited. The resistance of this silica gel increases as the copper is oxidized. A photoelectric method (97,126,ldf) can be used where copper is oxidized and the color of the oxidized copper solution is used for the determination of the quantity of oxygen present in a gas. The apparatus and method are described. Buchner (22) prefers chromous chloride solutions and describes the method of determination along with precautions necessary to eliminate interfering contaminations in the solution. Ch’eng (24) discusses the mechanism of the chromous chloride method but recommends the Winkler method. Inoue (64) has suggested a modification of the Winkler method to
make it possible to determine oxygen within 0.1 p.p.m. The galvanic analysis for oxygen has been used more and more. Several companies are selling apparatus based on the principle of the Hersch cell. Hersch (68) has given a description of his cell and ways of using it. H e even discusses the use of the cell for the determination of hydrogen by determining the oxygen content of the gas before and after burning and determining the hydrogen by the oxygen used. Marsh (104) haa done the same thing but oxidized the hydrogen with palladium on alumina. Thayer (166) has also pa& ented a galvanic cell for oxygen using different electrodes and different electrolytes. Koyama (88) has suggested the use of potassium bicarbonate as the electrolyte in the cell when used on gas mixtures containing carbon dioxide. VOL. 34, NO. 5, APRIL 1962
91 R
