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Book Review Metals in Biological Systems. By M. J. Kendrick M. T. May M. J. Plishka and K. D

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literature (about 850 citations!). A few minor criticisms follow. Chapter 2 on “Crystallographic Computing” seems a
little out of place, and it would probably have been better to
treat this subject in conjunction with “Solution and Refinement of Crystal Structures”. The treatment of molecular
crystals could definitely have been improved by omitting the
discussion of bonding theory, which is in any case very elementary, and instead devoting more space to molecular mechanics. Lastly, the index could have been made rather more
comprehensive.
To summarize, this book can certainly be recommended,
and the remarkably low price is a further reason for approval. However, one might ask: is it only for the specialist?
Happily it is not. It is exactly because it treats the more
chemical and physical aspects of crystals and crystal structures that it should also be read by those who are interested
only in the results of crystal structure determinations. If at
the same time these readers take a glance a t the sections on
techniques, so much the better. However, all readers must be
prepared to recognize that the authors make few concessions
to those who would prefer a non-mathematical treatment.
Gerhard Miiller
Fakultat fur Chemie
der Universitat Konstanz (FRG)
Chemistry of the Solid-Water Interface. Processes at the Mineral-Water and Particle-Water Interface in Natural Systems. By W Stumm. Wiley, Chichester, 1992. X, 428 pp.,
paperback 2 32.50.-ISBN 0-471-57672-7
The distribution and reactions of substances present in
water are crucially affected by processes at the solid-water
interfaces, and consequently the understanding of interfacial
reactions has become one of the most important tasks for
modern chemistry and neighboring disciplines. Where the
interest is combined with ecological aspects, this task offers
a particularly attractive field for those involved in water
research. Werner Stumm, one of the leading pioneers of systematic water research, has made an important contribution
towards the solution of this problem.
By approaching the subject from a physicochemical standpoint and making use of the latest knowledge, the author has
written a textbook that is of value not only to water chemists
but also to geochemists, chemical engineers, and others with
an interest in aquatic systems. What are the main aspects
covered? The introduction at once identifies adsorption, surface complexation, and colloids as topics for detailed consideration. This is followed by necessary digressions into the
coordination chemistry of oxide surfaces with both inner
sphere and outer sphere complexes and into surface charges,
including an impressive image of a lead sulfide surface obtained by scanning tunneling microscopy (STM), which is
also reproduced on the book’s dust-cover.
The substances dealt with in the chapter on adsorption
include synthetic surface-active agents from detergents, soilderived substances, and various others that cannot be precisely identified but are of hydrological importance. Modern
approaches to this topic emphasize the importance of kinetics and reversibility. The role of surface-controlled solvation
processes in weathering is discussed in relation to precipitation studies, and the behavior of minute particles is considered from the standpoints of nucleation and solubility. On
the important topic of the stability of colloidal systems the
author discusses the particleeparticle interactions in considerable detail. In contrast, the chapter on the reactivity and
Angeiv. Clicm. I n / . EN‘. Engl. 1993, 32, No. 7
3;
solubility of carbonates is relatively brief, giving the impression that readers are expected to be already familiar with this
classical topic. Under redox processes the vanadates find a
place as comparative outsiders alongside the iron and manganese compounds usually considered in this context.
The book ends with two chapters written by Stumm’s
coworkers: one on heterogeneous photochemistry (B. Sulberger) and another on trace levels of elements in surface
waters (L. Sigg). Both articles begin with the theoretical fundamentals and lead up to examples illustrating the practical
importance of the results. Not surprisingly, iron again
emerges here as the main performer!
The literature references given for each of the eleven chapters are a good representative selection. The many schemes
and diagrams are a useful aid to understanding the otherwise
not readily digestible text. The didactic value of the book lies
in its successful progression from simple considerations
through more complex ideas to the applications. The textbook character is reinforced by the appendixes attached to
the individual chapters, which include amplification of particular points, examples from practical situations, and exercise problems. It is unfortunate that this excellent approach
has only been consistently followed in the early chapters.
Also students would have greatly appreciated being given
solutions, which they could use when appropriate, to the
often quite difficult exercise problems. However. even without such help they will benefit greatly from working through
this well written and sturdily produced book. It will quickly
find a place on the desks of those who teach water science
and others working in the field of heterogeneous aquatic
systems.
Fritz H . Frimmel
Lehrstuhl fur Wasserchemie
der Universitat Karlsruhe (FRG)
Metals in Biological Systems. By M . J. Kendrick, M . 7: May,
M . J. Plishka and K. D. Robinson. Ellis Horwood, New
York, 1992. 183 pp., hardcover $68.00.-1SBN 0-13577 721-5
There has been a need for an updated text a t this level to
cover short ( 5 - 10 lecture) undergraduate courses in the fastmoving field of metals in biological systems, so this publication will be of interest to students and teachers of the subject.
The subject is now a required component of most chemistry
courses, and is taught to students of biochemistry and medicinal chemistry. The book aims to provide both introductory
and background material to the subject for over a dozen
metal ions, together with details of physical techniques required for their study. The authors faced the considerable
problem of what to leave out in such a book. Their selection
of topics is pertinent and timely, but may not suit all potential readers. The book appears to aim at the market already
covered by the more detailed book of M. N. Hughes (1972,
2981) o r that by R. W! Hay (1983). Despite the advantage of
its more recent publication date, the book under review is
unlikely to replace these established texts, although it could
be used to supplement either.
Certain aspects of this book make it unsuitable as an undergraduate text; indeed only sections of it could be recommended, and then only if accompanied by errata slips. The
coverage of the topics is very uneven, betraying the four
different hands involving in the writing, and a lack of cohesive
overview of the camera-ready copy. The introduction illustrates the uneven approach, comprising a brief 1 -2-page sum-
VCH Verla~sgesellsc.hafim h H , 0-69451 Weinheim, 1993
057U-0833/93/0707-1105 $ 10.00f ,2510
1105
mary of the relevant elements via the Periodic Table, followed
by three pages on the entatic state. Introductory coverage of
proteins and amino acids perversely takes two pages in the
middle of the 45-page chapter on physical techniques. Extensive biochemical background is assumed elsewhere.
Of the other 16 chapters, most are 4-6-page essays on a
single element; the depth and coverage of these varies idiosyncratically, with the focus generally on metal ions as enzyme activators. The chapter on iron (25 pages) covers much
of the expected ground and provides 8 references (the most
recent 1982), but omits from the Fe-S protein section any
mention of the Fe,S, clusters, while the vanadium chapter
(8 pages, 17 references mostly to recent primary sources) is
generous for the present state of knowledge. The treatment
of calcium, magnesium, and sodium in short separate chapters
is very perfunctory-for calcium, only calmodulin-dependent
processes are mentioned, with nothing on the mechanism of
skeletal muscle control, one of the best-known allosteric processes in biology; nor is there any mention of the major role
of calcium in bones and teeth. The sodium coverage has
almost a page on non-biological ligands, and potassium does
not merit a chapter on its own. Ion channels are not mentioned. Likewise, an effect of tungstate on steroid receptor
complexes is quoted, but the short zinc chapter makes no
mention of the much better understood zinc fingers. On the
other hand, cobalt, manganese, moIybdenum, and nickel are
covered at about the right introductory level, as also are
inorganic drugs.
Many whose native tongue is not English will read such
texts; it is especially incumbent on authors to ensure clarity
of text and accuracy in science and grammar, so that beginners will not be confused. The authors of this text did not
succeed. Amongst the obvious slips, labels on legends did not
match those on the figures or sometimes the text; a Nobelist’s name is given two spellings on opposite pages, 66 and
67 (both wrong!); the crystal structure resolution for calmodulin is quoted on page 46 as 3.0 8, (long outdated) while on
page 59 it is stated that no structure has been obtained! The
number of grammatical and other trivial slips is high for such
a short text, and the whole book clearly lacked an overall
editorial survey. Any future edition will no doubt put right
these faults. In the meantime, publishers should note that
there is still a market for an updated text at this level.
Joyce C. Lockhart
Department of Chemistry
University of Newcastle upon Tyne (UK)
Theoretical Aspects of Physical Organic Chemistry. The SN2
Mechanism. By S. S. Shaik, H. B. Schlegel, and S. Wove.
Wiley, New York, 1992. XV, 285 pp., hardcover $47.50.ISBN 0-471-84 041 -6.
The Nobel award to R. A. Marcus for his efforts to relate
thermodynamic and kinetic properties in order to describe
the “simplest” chemical reaction, the transfer of a single
electron, has certainly renewed interest in methods for the
theoretical description of chemical reactions. In this book
the authors set out to analyze S N 2 reactions by means of a
semi-quantitative model on the basis of quantum-mechanical valence-bond considerations with configuration interaction. Their model also includes elements of the Marcus theory. According to the authors, “the model leads not only to
linear free-energy relationships, the Marcus equation, and
the Leffler-Hammond postulate, but also accounts for the
role of frontier MO’s, orbital symmetry, and so forth”.
1106
8 VCH
Verla~sgesellschafimhH. 0-69451 Weinhein?, 1993
Therefore, the book as a whole is also intended to serve as a
general introduction to physical organic chemistry. The
reader is first given a short introduction to the history of this
discipline, starting with Menschutkin; nearly half the citations are to the authors’ own publications. In the first chapter (36 pp.) the reader is made familiar with some fundamental concepts of physical organic chemistry. The Brefnsted
relationship, the significance of its exponent x , the BellEvans-Polanyi principle, and the Leffler-Hammond postulate are lucidly presented. A brief introduction to the Marcus
theory is also given. However, other books or articles, such
as those by L. Eberson, would d o better service to beginners.
The properties of energy hypersurfaces are described in
Chapter 2 (47 pp.), mainly from a quantum-chemical point
of view. The reader is confronted with numerical methods
for the determination of stationary points on these hypersurfaces, even though these are not needed for the following
discussions. In the next chapter (41 pp.), the basics of MOand VB-models are presented in a mathematical fashion,
taking the hydrogen atom and its radical anion and cation as
examples. The authors’ state correlation model is introduced
in connection with the exchange reaction between H,and H.
The thermodynamic parameters of an S N 2 reaction, such as
the ionization potentials and electron affinities of the reactants, are defined in Chapter4 (27pp.), and methods for
determining them are discussed. Parameters of importance
for the model are deduced from them. In Chapter 5 (62 pp.)
the thermodynamic and kinetic parameters are interrelated
for the analysis of identity SN2reactions in the gas phase
and in solution. Activation barriers and geometries of
transition states are calculated by a b initio methods in combination with the authors’ model, and are compared with
experimental data. The final chapter (49 pp.) treats nonidentity reactions. Author and subject indexes conclude the
book.
The authors’ aim is to make the virtues of their model
known to a wider audience (their previous work is described
in the preface as “seminal”). Justification for such an intention should be provided by the model’s predictive power. For
a publication designed as a textbook it is reasonable to expect authors to adopt a more critical approach to their own
results than in original papers. Despite the authors’ claim on
page IX that “All of these predictions [of the model] were
consistent with experimental data ...”, a literature search
yields at least one exception. On the basis of elements of the
model presented in this book it was concluded that the
direct reaction of nucleophiles with radical cations should be
a “forbidden” process (A. Pross, L. Am. Chem. Soc. 1986,
108, 3537). This prediction proved to be incorrect, as shown
experimentally (N. M . M. Nibbering, H. Schwarz et al., ibid.
1987, 109, 4810; see also H. I. Kettamaa et al., Chem. Rev.
1992,92, 1649). At least a little hint ought to have been given
to the reader, as the book covers the literature up to 1988 (in
some instances up to 1990).
This book certainly cannot serve as an introduction to
physical organic chemistry. Firstly, it covers only one part of
this discipline, though an important one. Secondly, many
aspects are treated so briefly that the novice is likely to misunderstand them, for example the Marcus theory and the a b
initio M O methods. Topics that are not necessary to understand the model or its consequences are given much space,
especially the lucid but essentially superfluous chapter on the
numerical analysis of hypersurfaces. The authors’ predilection for abbreviations tends to make the reader feel uncomfortable. Most often, they are explained only once (sometimes never, as in the cases of the R R K M theory or the
“CEPA” approximation), but are used throughout the book.
0570-0833193/0707-1106 S 10.00i- .ZSIO
Angen. Chem. hi.Ed.
Engf. 1993. 32. N o . 7
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