Anal. Chem. 1980, 52, 185R-199R (278) Sedunov, V. K., Men'shikova, T. Ya., Mitrofanov, K. P., Reiman, S. I . , Rokhlov, N. I., Met. Sci. Heat Treat. (Engl. Transl.), 19, 742 (1977). (279) Sekhon, S. S.,Kamal, R . , J . Appl. Phys.. 49, 3444 (1978). (280) Seregin, P. P., Nasredinov, F. S., Bakhtiyarov, A. Sh., Phys. Status Solidi B , 91, 35 (1979). (281) Seregin, P. P., Nasredinov, F. S., Vasil'ev, L. N., Phys. Status Solidi A . 45, 11 (1978). (282) Shechter. H., Suzzanne, J., Dash, J. D., JPhys. (Paris), 40, 467 (1979). (283) Shenoy, G. K., Wagner, F. E.. Ed., "Mossbauer Isomer Shifts", NorthHolland Publishing Co., Amsterdam, 1978, 956 pages. (284) Shibuya, M., Endo, K., Sano, H., Bull. Chem. Soc. Jpn., 51, 1363 (1978). (285) Simmons, G. W., Leidheiser, H., Jr., "Characterization of Metal and Polymer Surfaces: Volume 1, Metal Surfaces", L.-H. Lee, Ed., Academic Press, New York, 1977, p 49. (286) Singh, A. K., Jain, B. K., Chandra, K., J . Phys. D , 11, 55 (1978). (287) Sitek, J., Kruziiak. J., Tomasich, M., Cirak, J., Prejsa, M., Phys. Status SoiidiA, 47, 287 (1978). (288) Smith, G. V., Liu, J. H., Saporoschenko, M., Shiley, R., fuel, 57, 41 (1978). (289) Sokol'skii, D. V., Aiekseeva, G. K., Khlystov. A. S..Ashkevich, V. I., Kotova, G. N., React. Kinet. Catal. Lett., 6, 59 (1977). (290) Solomon, H. D., Levinson, L. M., Acta Metall., 26, 429 (1978). (291) Soltwisch, M., Elwenspoek, M., Quitmann, D., AIP Conference Proceedings, No. 38: Workshop on New Directions in Mossbauer Spectroscopy", G. J. Perlow, Ed.. American Institute of Physics, New York, 1977, p 114. (292) SDencer. C. D.. Smith. P. A.. Stillwell. R. P.. J. Phvs. Chem. Solids. 39, ' 103 i1978). (293) Spiering, H., Nucl. Instrum. Methods, 154, 295 (1978). (294) Spiering, H., Hosl, S.,Vogel, H., Phys. Status Solidi 8 , 85, 87 (1978). (295) SDierina. H.. Witzaall. R.. Hvoerfine Interact.. 5 . 265 11978). (296j Siadnik:'Z. M.. M;ssbauer€ff. Ref. Data J . , 1, 217 (1978). (297) Stevens, J. G., Bowen, L. H., Anal. Chem., 50, 176R (1978). (298) Stevens, J. G.. Trooster, J. M., J . Chem. Soc., Daiton Trans., 740 (1979). (299) Stiller, A. H., McCormick, B. J., Russell, P. E., Montano. P. A,, J . Am. Chem. Soc., 100, 2553 (1978). (300) Stiller. A. H., Renton, J. J., Montano, P. A,, Russell, P. E., fuel, 57, 447 (1978). (301) Syn, C. K., F u b , B., Morris, J. W., Jr., Metall. Trans. A, 9A, 1635 (1978). (302) Syono, Y., Ito, A., Horie, O.,J. Phys. SOC.Jpn.. 46, 793 (1979). (303) Takeda, Y., Naka, S.. Takano, M., Shinjo, T., Takada, T., Shimada, M., Mater. Res. Bull., 13, 61 (1978). (304) Taragin, M. F., Nucl. Instrum. Methods., 150, 607 (1978). (305) Teiilet, J., Job, D., Varret, F.. Chappert, J., Nucl. Instrum. Methods, 155, 97 (1978). (306) TenutaAzevedo, A. L.. da Silva, E., Scr. Metall., 12, 113 (1978). (307) Tewari, S. P., Swaminathan, K.. Solid State Commun., 24, 65 (1977). (308) Tominaga, T., Sato, H., Radiochem. Radioanal Lett., 33, 53 (1978). (309) Tominaga, T., Takeda, M., Mabuchi, H..Emoto, Y., Archaeometry, 20, 135 (1978). (310) Townsend, M. G., Webster, A. H., Horwood. J. L.,Roux-Buisson. H., J . Phys. Chem. Solids, 40, 183 (1979). (311) Trammell, G. T., Hannon, J. P., Phys. Rev. B , 18, 165 (1978). (312) Tricker, M. J., J . Mater. Sci., 14, 995 (1979). (313) Tricker, M. J., Ash, L. A., Jones, W., Surf. Sci., 79, L333 (1979).
(314) Tripathi, K. C., Sarma, P. R., Gupta, H. M., J . Polym. Sci: Polym. Lett. Ed., 16, 629 (1978). (315) Trooster, J. M., de Valk, W., Hyperfine Interact., 4, 457 (1978). (316) Tsankov, L., Bonchev, Ts., Bulg. J . Phys., 5, 149 (1978). (317) Tseng, P. K., Chuang, S. Y., Chen, H. S..J . Appl. Phys., 5 0 , 4292 (1979). (318) Uehara, S.,Maeda, Y., "Proceedings of the International Conference D. Barb, D. 'Tarina, Ed., Docuon Mossbauer Spectroscopy, Volume l", mentation Office. Central Institute of Physics, Bucharest, p 17. (319) Uehara, S., Maeda, Y., Annu. Rep. Res. React. Inst., Kyoto Univ., 11, 189 (1978). (320) Unknown Editors, J . Phys. (Paris), Colloq. C2,40 (1979), 704 pages. van Diepen, A. M., Popma, T. J. A., Solid State Commun., 27, 121 (32;1)978). (322) van Diepen, A. M., Vledder, H. J., Langereis, C.. Appl. Phys., 15, 163 (1978). (323) van Rossum, M., de Bruyn, J., Dezsi, I., Langouche. G., Coussement, R.. Phys. Status SolidiA, 52, K31 (1979). (324) van Rossum, M., de Bruyn, J., Langouche, G., de Potter, M., Coussement, R., Phys. Lett. A , 73, 127 (1979). (325) Varret, F., Naudin. F., Rev. Phys. Appl., 14, 613 (1979). Malysheva. T. V., Geochem. Int. (Engl. (326) Vdovykhin, G. P., Grachev, V. I., Transl.), 14(3), 119 (1977). (327) Vereshchak, M. F., Zhetbaev, A. K., Ibragimov, Sh. Sh., Phys. Status SolidiA, 52, 415 (1979). (328) Vertes, A., Leidheiser, H., Jr., Varsanyi. M. L., Simmons, G. W., Kiss, L., J . Electrochem. Soc.. 125, 1946 (1978). (329) Viegers, M. P. A. Trooster, J. M., "AIP Conference Proceedings, No. 38: Workshop on New Directions in Mossbauer Spectroscopy", G. J. Perlow, Ed., American Institute of Physics, New York, 1977, p 102. (330) Viegers, M. P. A., Trooster, J. M., Bouten, P. C P., Peters-Rit, T., J . Chem. Soc., Dalton Trans.. 2074 (1977). (331) Vincze, I . , Solid State Commun., 25, 689 (1978). (332) Vincze, I., Babic, E., Solid State Commun., 27, 1425 (1978). (333) Vollenbroek, F. A., Bouten, P. C. P., Trooster, J. M., van den Berg, J. P., Bour, J. J., Inorg. Chem., 17, 1345 (1978). (334) Von Eynatten, G., Bommel, H. E., Appl. Phys., 14, 415 (1977). (335) Wagner, F. E., Wortmann, G.. "Hydrogen in Metals I. Basic Properties". G. Alefeld, J. Volkl, Ed., Springer-Verlag, Berlin, 1978, p 131. (336) Wang, G. W., Chirovsky. L. M., Lee, W. P., Becker, A. J., Groves, J. L.. Nucl. Instrum. Methods, 155, 273 (1978). (337) Weiss, H., Langhoff, H., Z.Phys. B , 33, 365 (1979). (338) Wenzel, H., Sherif, A. Kh. Opalenko, A. A., Kuz'min, R. N.,Insfrum. Exp. Tech. USSR(€ngl. Trans/.), 20, 262 (1977). (339) Wickberg, J. N., Eck, J. S., Radiat. Eff., 38, 83 (1978). (340) Williamson, D. L., Dale, J. H., Josephson, W. D., Roberts, L. D., Phys. Rev. B , 17, 1015 (1978). (341) Williamson. D. L., Schupmann. R. G., Materkowski. J. P., Krauss, G., Mefall. Trans. A , 10, 379 (1979). (342) Wit, H. P., Niesen, L., de Waard, H.,Hyperfine Interact., 5, 233 (1978). (343) Wong, H., Sedney, D., Reiff, W. M., Frankel, R. B., Meyer. T. J., Salmon, D., Inorg. Chem.. 17, 194 (1978). (344) Yarmarkin. V. K.. Teslenko. S. P.. Knvazev. A, I.. Phvs. Status Solid; ' 45, 63 (1978). (345) Zimmermann, R . , Konig, J . Phys. Chem. Solids, 38, 779 (1977). (346) Zolotoyabko, E. V., Kashcheev, V. N., J . Phys. C , 10, 4599 (1977).
A,
Enzymes in Analytical Chemistry Myer M. Fishman Department of Chemistry, The City College of the City University of New York, New York, New York 10031
Over the years, there has been a steady growth in the use of enzymes as analytical tools in the industrial, medical, pharmaceutical, clinical, and food fields. The literature has become rather extensive and continues to grow each year. Much of the recent literature has been periodically reviewed in this Journal (I&$), and the last such review covered the period January 1976 through December 1977. This one now attempts to cover the period .January 1978 through December 1979. However, out of sheer necessity, because the literature has become so voluminous, not all that has appeared in print has found its wag' into this article. Each time a review has been written, there usually appear special monographs, reports on symposia, etc.. and this continues to be a rich source of information for those who are interested in establishing a new base (6-21). For many reasons, enzymes were being used on a n increasing scale. Characterized as being both specific and sensitive, yet easy t o use and reproducible. enzymes were 0003-2700/80/0352- 185R$01 .OO/O
Myer M. Fishman is Professor of Cheniistry and Chairman of the Biochemistry Division of the Chemistry Department at the City College of the City University of New York. He received his B.S. degree in Chemistry from the City College and the M.S. and PhD. degrees from the University of Minnesota. His research interests have included the use of dextran as a plasma expander, intravenous infusion of fat emulsions. carcinogenesis of plastics, and the interaction of macromolecules with antibiotics and dyes. He is a member of the ACS. Sigma Xi, the American Association for Cancer Research, and the American Society of Biological Chemists.
shown to be rather unique but powerful catalysts. However, there were serious limitations to their use on any regular basis. 1980 American Chemical Society
185 R
ENZYMES I N ANALYTICAL CHEMISTRY
a c; d
.-" L
186H
A N A L Y I I C A L L H ~ M I ~ ~ VOL P Y 5 2 NO 5 APRIL 1 Y d O
4 .-
L
ENZYMES I N ANALYTICAL CHEMISTRY
+
k w
m
1
E
0
-
%
3
a Do
a
in
3
I
hc
-z .-
i
5
% C
-hcS
ANALYTICAL CHEMISTRY, VOL. 52,
NO. 5,
APRIL 1980
187R
ENZYMES IN ANALYTICAL CHEMISTRY
d
188R
ANALYTICAL CHEMISTRY, VOL. 52,
NO. 5 , APRIL 1980
ci
ENZYMES I N ANALYTICAL CHEMISTRY h
Q,
Y
Y
0
4
z Y 3
N
c
h
h
(I]
Ev
8 v
y1
m w n
.-V i L
.-V
0.
E
e f
m
.-
'0
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5 , APRIL 1980
189R
ENZYMES I N ANALYTICAL CHEMISTRY
E
.e
5
0
z
20 a
.S 8
U
-E
5
.e
2
B
k
n
i
4
V
n" 2
m
w
Y
L
0:
z -c 0
5
2
5
'Z * w
E
O 0
4
c a 0 k V
2 .
P,
-
h
E
I
G 0
190R
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
.-V i F.
f
-8
.e
0
ENZYMES I N ANALYTICAL CHEMISTRY
9:
8
..
+ E rn
-E v
a
Y
L
-s
h
-0 0 0
P ai
4
E
h
Y
rn
8
v
4 ai
5
.-
V
.-V
Y L
u
E
0 0 f Y
a
e
Y
B
.-V
+
2
0
Y
c,
G
2 h
c
v-
b ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
191 R
ENZYMES
IN
ANALYTICAL CHEMISTRY
'El
F
8 -0
E0
A
4
V 0
.-E
E
.-0
h
E
2
P
v
.-0Li Y
V
.C
.-
c)
Y
3
Y
0
c
0
a
e 7
G: h
h
e.
192R
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
e3 Y v
ENZYMES I N ANALYTICAL CHEMISTRY
+
h
1 g ELI L
W
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
193R
ENZYMES I N ANALYTICAL CHEMISTRY
h
U U w
h
v CI
f
194R
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5 , APRIL 1980
ENZYMES I N ANALYTICAL CHEMISTRY
.^ 2
m
c) u)
-
h
Y
E
w H
z2
V
.e
4 L
E
.-0 Y
E
U
0
a aJ
v1
c M
Y
i
Lo'
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
195 R
ENZYMES IN ANALYTICAL CHEMISTRY
4
h
n
+
h
Y v 3
196R
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
cd
cd
ENZYMES I N ANALYTICAL CHEMISTRY
h
.-LIB
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980
197 R
ENZYMES I N ANALYTICAL CHEMISTRY
cu
0
198R
ANALYTICAL CHEMISTRY, VOL. 52, NO. 5 , APRIL 1980
Anal. Chem. 1980, 52, 199R-214R
They had very limited stability in aqueous solution with a consequent loss of catalytic activity. This was changed with the introduction of immobilized enzymes (10-12). Free or water-soluble enzymes were immobilized or made insoluble by combination with some inert matrix either by entrapment or chemical reaction to ensure insolubility. In either case, it was shown that enzymes retained activity for long periods of time. Thus, it has been noted that a single sample of immobilized glucose oxidase has been used for several thousand determinations ( I O ) . The new developments and the proliferation of publications and patents on immobilized enzymes have led to widespread use and intensive work with automated instrumentation and enzyme electrodes. The high-speed and rather sophisticated instrumentation has, of course, been a tremendous asset in the clinical chemistry laboratory. Enzyme electrodes have probably been the most interesting application of immobilized enzymes. These electrodes have been the combination of an insoluble enzyme with some porous organic polymer which is used as a coating for an electrochemical sensor. These have been especially useful in such systems as whole blood or biological media, where sample preparation has been a major problem. T h e format of this article continues to be that which was
used previously. Again, as was done in the last review, the enzyme nomenclature follows the recommendations of the International Commission of Enzyme Nomenclature (13). LITERATURE CITED
(1) (2) (3) (4) (5)
M. M. Fishman and H. F. Schiff, Anal. Chem., 44, 543R (1972). M. M. Fishman and H. F. Schiff, Anal. Chem., 46, 367R (1974). M. M. Fishman and H. F. Schiff, Anal. Chem., 48, 322R (1976). M. M. Fishman, Anal. Chem., 50, 261R (1978). H. A. Bergmeyer, Ed., "Grundlagen Enzyme Analysis", Gawehn, Karlfried, Verlag Chemie, Weinheim, Germany, 1977. (6) H. A. Bergmeyer, Ed., "Principles of Enzymes Analysis", Verlag Chemie, Weinheim, Germany. 1978. (7) T. M. S. Chang. Ed., "Biomedical Applications of Immobilized Enzymes Proteins", Plenum, New York, 1977. (8) "Methods in Enzymology", Vol. 55 and 56, Academic Press, New York, 1979. (9) A. Meister, Ed., "Advances in Enzymology and Related Areas of Molecular Biology", Vol. 46, 47, 48, 49, Wiley, New York, 1978, 1979. (10) J. Everse, et al., Methods Biochem. Anal., 25, 135 (1979). (11) G. G. Guilbault, and M. H. Sadar, Acc. Chem. Res., 12, 344 (1979). (12) I. Chibata, Ed., "Immobilized Enzymes, Research and Development", Halstead, New York, 1978. (13) Enzyme Nomenclature (1978). Recommendations of the Nomenclature Committee of the International Union of Biochemistry on the nomenclature and classification of enzymes, Academic Press, New York. 1979.
Magnetic Susceptibility: Instrumentation and Analytical Applications Including Bioscience, Catalysis, and Amorphous Materials L. N. Mulay" and Indumati L. Mulay Department of Materials Science and Engineering, [136 Materials Research Laboratory], The Pennsylvania State University, University Park, Pennsylvania 16802
INTRODUCTION: SCOPE OF THIS REVIEW I n this tenth review on magnetic susceptibility, we survey important trends in instrumentation and applications, especially in the realm of analytical chemistry including bioscience, catalysis, and amorphous magnetic materials. T h e last two categories are becoming technologically very important in recent years. I t will be shown in this tenth review that magnetic susceptibility techniques have proved to be extremely useful in the characterization of these systems a t the micro- and macroscopic levels, dealing with their electronic and bulk structures, analysis of various components present, and so on. T h e first nine reviews appeared during 1962 to 1978 (98,105-112). This 1980 edition covers literature mostly from about January 1978 to December 1979 and some earlier work. In response to a n editorial plea, we have made this review more concise than the previous ones. In doing so, it seemed imperative that we depict the exceptionally novel trends in the instrumentation and applications area and eliminate some that we covered before, without, of course, implying in the least that these are no longer important. Hence, we shall not review the work on lunar samples, which was adequately covered before (108, 109) and work on charge-transfer complexes of the TTF-TCNQ type, which show promise of emerging as new superconductin materials (110). It should be noted that books by Mulay andkoudreaux (102) and excellent reports survey the transition metal and rare earth complexes. The reports (55) are published by the Chemical Society, London. Since this review is concerned with instrumentation and analytical applications, we have focused relatively more attention on practical aspects of instrumentation and have attempted to point out the truly novel trends in the hope that experimentalists will explore challenging 0003-2700/80/0352-199R$05.00/
avenues of instrumentation for specific problem-oriented research and that they will not remain chained to otherwise outmoded techniques. Since classical methods, such as the Faraday and the Gouy techniques, quite surprisingly, continue to be very reliable for the measurement of weak susceptibilities and, since these are relatively less expensive than some of the modern gadgetry, we shall continue to incorporate important modifications and tricks-of-the-trade reported by ingenious workers. Unfortunately, owing to limitations of space, we shall not be able to survey various temperature controlling and measurement devices. Furthermore, while curtailing our usual coverage of the general field of instrumentation, we have stressed applications which are expected to be of special appeal to analytical chemists. Since structural analysis is an important aspect of analytical chemistry, we have included typical examples of such analysis. This was also done in response to requests from our readers. We urge our readers to refer to our earlier reviews (10S112) concerning the scope of areas such as solid state science (that is, chemistry and physics of solids), which is somewhat synonymous with materials science and engineering, in order t o appreciate their interdisciplinary role in science and technology, and to appreciate the relevance of these areas to societal needs and their relationship to analytical chemistry. It should be noted that a few developments in instrumentation and their applications are reviewed under the section on "Applications". The "cgs-emu" and S.I. units are discussed a t the end of this review.
GENERAL LITERATURE Abstract Services a n d New Journals. References should be made to our earlier reviews (107-112) concernin abstract services. A number of topical conferences such as t t e annual
o e! 1980 American Chemical Society
199 R
