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B O O K REVIEWS Contributions to t h e Theory of Chemical Kinetics. A Study of the Connection between Thermodynamics and Chemical Rate Processes. By THOR.A. BAK. 1%’. A . Benjamin, Inc., 2165 Broadway, S e w York 25, S . T. 1963. 101 pp. 15 X 23 c m . Price, $550. I t is a pleasure t o note t h a t D r . Bak’s most interesting book on chemical kinetics is now accessible t o t h e broad audience it deserves. The problems discussed are of significance, and the treatments are elegant and lucid. T h e book is not a general introduction into the theoretical aspects of chemical kinetics; rather, a limited number of topics are treated rigorously and in detail. Students in advanced courses in thermodynarriics, statistical mechauics, a n d kinetics will find this book excellent supplementary reading, a n d t h e specialist will find the book and its bibliography (through 1958) quite useful. Bak first discusses the application of the principle of minimum entrop3- production in steady states; diffusion, nucleation, sets of consecutive first-order reactions, and LeChatelier’s principle are treated. He then turns to t h e question of oscillating reactions, often thought t o be of biological interest, and employs t h e methods of Krylnv and Bogoliubov t o investigate t h e qualitative behavior of solutions t o nonlinear rate equations which m a y show oscillatory behavior. T h e theory of electrodiffusion in steady arid alternating fields is then presented, and application is made to systems in which electrodiffusion is coupled t o chemical reaction. The mathematical t r e a t m e n t of electrodiffusion is adapted to the analysis of chromatography, which is briefly discussed. T h e next portion of the book is concerned with the problem of the presence of irreversibility in a world whose equations of motion itre reversible. Bak shows how such irreversibility appears for certain limiting cases; t h e general problem remains to inspire and baffle t h e theoretician. T h e last chapter of the book deals with the statistical mechanical treatment of chemical reactions by methods similar t o those employed by Kraiiiers. The reaction system is treated as a canonical system in contact with a lattice ( t h e thermostat), and the Liouville equation for the entire system (including t h e lattice) is then exaniinetl. I was pleased t o see t h a t the editors have retained t h e Danish flavor of t h e book. I t is t o be regretted t h a t t h e price of t h e book, a short paperback, is such a s to make it unavailable t o most students.
L - ~ I V E R S I T Y OF ROCHESTER SEIV YORK ROCHESTER,
DAVIDJ . WILSOS
catalysis with pyridoxal covered, b u t also much information is included on such allied subjects as antimetabolites of pyridoxal, purification and properties of enzymes, physiological effects associated with the presence or absence of the vitamin, and t h e metabolism of pyridosal. T h e book contains 1fj separate papers, t h e first eight of wliich deal with the mechanism of catalysis with pyridoxal studied in model reactions. Generally speaking, these eight papers were written in clear and concise language, a n d enough experimental d a t a were included so t h a t t h e reader can clearly filllon- tlie reasoning of the authors in arriving a t conclusions. T h e findings reported in these chapters mostly seemed significant in providing bases for an understanding of t h e mechanism of catalysis of pyridoxal, althougli a complete picture is still not available. The next eight papers present a clear view of \vhat is known about the chemistry of pyridoxal phosphate catalysis in enzymatic transamination. T h e major portion of t h e remaining chapters is devoted t o discussions of individual enzymes t h a t are either k n o w t o contain or suspected of containing pyridoxal phosphate as a prosthetic group. Some of these investigations make significant contributions t o knowledge of the tnechatiistns of action of these enzymes. However, a number of the papers contain mostly descriptions of purification procedures and general properties of enzymes a n d , thus, are of little value to the reader interested in understanding the mechanisms of enzymatic action. I n assessing t h e plus values of t h e book, one could probably agree t h a t there is some merit in having all of the knowledge of vitamin Bs compiled into a book and presented with d a t a so t h a t oue can critically evaluate t h e conclusions of t h e authors. T h e discussions a t t h e close of each chapter were in some cases very spirited and in most cases interesting and valuable. T h e first and last chapters of t h e book deserve special mention because they provide excellent summaries of the history of pyddoxal is [first chapter b y E. E. Snellj and t h e current state of dge of t h e subject (last chapter b y A . Braunstein). In general, the book makes a favorable impression and should certainly be a welcome addition t o t h e biochemistry sections of science libraries, although t h e relatively high cost is a factor t h a t m a y influence individuals in deciding whether or not t o add the book to their private libraries. GESE M. B R O W N DIVISIUKOF BIOCHEMISTRY OF BIOLOGY DEPARTMEST XfASSACHUSETTS I SSTITUTE O F TECHXOLOCY ~ZASSACHUSETTS CAMBRIDGE,
Chemical a n d Biological Aspects of Pyridoxal Catalysis. Proceedings of a Symposium of t h e International Union of Biochemistry, Rome, October, 1962. Edited by E. E. SSELL, 1’. h l . FASELLA, .A. BRAUNSTEIS,and .I. Kossr FASELLI. The Nacmillan Co., 60 Fiith Ave., New T o r k 11, N . Y . 1961. xv 599 pp. 10 X 2 X 5 cm Price, $20.00.
LL CyanInorganic Complexes. By C H R . K L I X B ~ ~JIIRGENSEN, amid European Research Institute, ColognJ-, Geiieva, Switzerland Academic Preqs, I n c . , Ltti., Berkeley Square House, Berkeley Square, London, W l , England. 1968. 230 p p 16 X 23 5 cin. Price, 67.50.
Anyone interested in reading this book t o gain a complete analysis of how pyridoxal phosphate functions a s a coenzyme in enzymatic reactions will be disappointed t o learii t h a t almost a s much remains t o be learned as is already knnwn a b o u t this subject. Although there is general agreement among researchers i n this field t h a t the Braunstein-Snell theory of t h e mechanism of actimi ( ~ f pyridoxal is fundamentally correct, there remain disagreements concerning t h e details of the chemical events associated with t h e functioning of this compound. Also, a nuinher of experimental observations have been made t h a t cannot yet be explained t o everyone’s satisfaction. These uncertxitiities exist largely because of the complexities of the problems ivitli which the experimentalist is confronted. T h e developm e n t of new experimental techniques, such as tlie temperaturej u m p method already being used (see the chapter by Fasella and H:lrrimes i n tlie bonk I, offers renewed hopes for a more conipletc undcrstaiiditig of this subject. Certainly, it must be said t h a t the subject of vitamiti Bfi has keen tliorouglily covered i n this book. The title, “Chemical and Rioli~gical.Ispects of Pyridoxal Catalysis,” is used in its broadest Geiiw, hecause not only is the subject of the mechanism of
T h e classical valency theories provided principles t h a t allowed t h e deduction and classification of t h e compounds capable of existence; their aim was not t o elucidate t h e nature of chemical bonds. Modern theories of valency are of a different character because of our belief t h a t all cheinical phenomena a r e t h e consequences of t h e known laws of physics, and much effort is being spent in showing t h a t certain chemical phenomena can indeed be derived from these laws. .Inlong theoretical chemists, C h r . Klixbull Jgrgenseii is outstanding for his intense interest in chemical reality and for his efforts towards its classification. His concepts of t h e nephelauxetic effect and optical electronegativities are t h e results of surveying a large body of experimental facts anti have grown nut of t h e same t y p e of reasoning a s tlie atoiiiicity concept of Kekul6 anti tlic coordiiiation principle of Werner. IVhat Jorgenseti believes t o be t h e most fruitful tlieoretical background for :I coiiiprelieiision of inorganic complex cheinistry has beeii iiinde t h e content of his book “Orbitals in Atoms and Molecules” (.\cadeniic Press, 1963). T h e book t o be discussed liere rnay he described as a confrot~tatioiiof these theoretical principles with chemical reality. Inorganic complexes are defined as clusters MX.y or I v l & l ’ ~ - ~of a central a t o m M surrounded b y
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