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Book Review Bioanorganische Chemie. (Series Teubner Studienbcher Chemie.) By W. Kaim and B. Schwederski

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BOOK REVIEWS
New Books to Mark the Coming-of-Age
of Bioinorganic Chemistry
Bioinorganic chemistry has now matured into a well established area of research and has become an essential part
of the education of new chemists. This is well illustrated by
the first four books reviewed below. However, a comparison
of these gives a hint of a new development. Whereas three of
the books treat bioinorganic chemistry from a classical
standpoint which, although interdisciplinary, is predominantly based on the concepts of inorganic chemistry, the
book by J. J. R. Frausto d a Silva and R. J. P. Williams
strongly emphasizes the biological aspects. The latter viewpoint can be characterized as the “biological chemistry of the
elements”, a broadly based subject ranging from inorganic
chemistry (i.e., the chemistry of the elements) to molecular
biology; thus it includes bioinorganic chemistry in the conventional sense, but extends beyond it.
Bioanorganische Chemie. (Series : Teubner Studienbucher
Chemie.) By W Kaim and B. Schwederski. Teubner, Stuttgart. 1991. XII, 450 pp., paperback D M 44.80.-ISBN 3519-03505-7
At last here is an up-to-date and comprehensive textbook
of bioinorganic chemistry! According to the cover blurb it is
intended for use by students who have already attended a
basic course of lectures in chemistry. In fact, in order to use
the book to full advantage it is necessary (and sufficient) for
readers to have a basic knowledge of the three core areas of
chemistry as well as of biochemistry. However, to suggest
only students as potential readers is too restrictive.
The authors have avoided following a rigid plan of arranging the contents according to either chemical elements o r
biological functions, and have thus freed the readers and
themselves from unnecessary restrictions-especially with
regard to presenting an overall view of bioinorganic chemistry. The result is an interesting and lively book. The detailed contents mainly follow a sequence that is of proven
didactic value: presenting the experimental facts, explaining
these on the basis of proposed models, and drawing attention to more far-reaching relationships. The text is supported
by over 400 figures, tables, structural formulas, reaction
schemes, and equations.
Two introductory chapters, the first giving a historical
survey and indicating the present importance, and the second introducing some basic principles, are followed by 17
chapters devoted to special topics such as photosynthesis,
A n g w . C7irm. lnr. Ed. EngI. 1993, 32, No. 2
Q VCH Verlagsgesellschaft mhH,
hemoproteins, nickel-containing enzymes, biomineralization,
and chemotherapy. Practically all the areas of bioinorganic
chemistry are covered. The book concludes with a bibliography, a glossary of terms, and a good keyword index.
Particular attention has been given to providing up-to-date
literature references, citing publications up to and including
1991. Readers are likely to have different views on whether
or not the large number of literature references (over 700) is
appropriate-probably those engaged in research will say
that it is, whereas students will be less inclined to agree.
The glossary explains just under a hundred terms very
briefly, typically in two lines. In view of the assumed previous knowledge of the readers, the extremely short definitions
seem unnecessary in many cases; examples are diamagnetism, entropy (“ a thermodynamic quantity measuring the
degree of disorder in a system”), extinction coefficient, Lewis
base, Lewis acid, molecular orbital, and the primary, secondary, and tertiary structure of a protein. Instead of these
it would have been better to include expressions that are less
familiar to chemists, such as “fakultativ aerob” (Facultatively, o r optionally, aerobic) o n page 326.
A similar difficulty arises with some of the special sections
inserted into the text, typically one or two pages in length
and distinguished by a gray background, that deal with
physical methods o r theoretical models. Some of the explanations of complicated measurement and evaluation procedures are too superficial. Expressions such as “data sets”, “the
phase problem” (in the determination of structures by X-ray
diffraction), “a method that is not unambiguous” (in connection with X-ray absorption spectroscopy), and “quadrupole splitting” (in Mossbauer spectroscopy) are used with
little or no explanation. However, there are other such sections (e.g., those on the entatic state-catalysis by enzymes,
electron spin resonance I + 11, mirror image isomers in octahedral complexes) that are well presented.
Factual errors and inaccuracies are very few in relation to
the wealth of information contained in the book. Although
it is true that thiolates can stabilize high oxidation states of
metal centers (p. 123), the authors should certainly have
mentioned that for this to occur it is necessary for the normal
reaction yielding the organic disulfide (with reduction of the
metal ion) to be blocked. In Equation (7.1 1) the reducing
agent needed to form [Fe,S,(RS),]’is not shown. In Equation (10.10) the formula of the ortho-quinone is incorrect. In
the catalytic cycle of the Cu,Zn-superoxide-dismutase (p. 21 8)
the imidazole ring coordinated at stages 3 and 4 must be
neutral, not anionic. The statement on page 237 that a bridging by N, between two metal centers in the nitrogenase is not
possible is at least misleading, since an Mo-N,-Fe configuration has in fact been discussed in the literature for the
actual cluster model shown (Eq. (1 1.23)). Changes in bone
structure in cases of chronic cadmium poisoning are probably
caused not so much by direct replacement of Ca by Cd as by
the indirect effects of kidney damage (through interference
with the calcium and phosphate metabolism). On page 348
the impression is given that carcinogenic effects of chromate
in humans have not yet been proven. In fact, however, zinc
chromate is classified as a human carcinogen (see the MAK
register). I found about 30 printing errors in the book.
These minor defects do not alter the favorable overall impression of the book. As already indicated above, the potential readership is not confined to students. The book is of
interest to everyone who wishes to obtain an overview of
bioinorganic chemistry and already has an adequate knowlW-6940 Weinheim, 1993
0570-OR33193j0202-0299 B 10.00+ .Xi0
299
edge of general chemistry. Advanced chemistry students
should definitely have a copy, and the relatively low price
should help to make that possible.
It is desirable that an English language edition should be
made available very soon, and the book should then have an
excellent prospect of gaining a reputation beyond the German-speaking world as a standard work on bioinorganic
chemistry.
The Biological Chemistry of the Elements. The Inorganic
Chemistry of Life. By J. J. R. Frausfo da Silva and R. J. P.
Williams. Clarendon Press, Oxford, 1991. XXI, 561 pp.,
hardcover E 60.00. -ISBN 0-19-855598-9
A preliminary thumbing through this book already reveals
some unusual features in form and content. The text is arranged in short sections with headings that stand out clearly,
and a liberal use is made of space, all of which makes for
excellent clarity. A wide margin occupies the left-hand third
of each page, and is frequently used for figures and tables.
Quite a number of the figures present biological information; for example, there are diagrams of a hepatocyte and a
nerve cell, organelles (mitochondrion, chloroplast, etc.), the
skeleton of a lizard, and many schematic diagrams of cells of
a wide variety of types, showing cell membranes with material and energy flows.
The interconnections between inorganic chemistry, (bio)physical chemistry, biochemistry, and molecular biology are
emphasized in a wealth of examples. The program of the
book can be illustrated by three quotations. Page 147: “The
function of an element or a compound in biology has to be
seen in the context of where and when it combines and how
it moves, is used, and is removed.” Page 155 : “The complexity of the uses of energy, the fact that the whole system is
constantly multiplying and growing or repairing, that it can
maintain shape o r alter it, and that the several operations are
timed require a continuous monitoring, feedback, communication and energy network.” Page 521: “The central hypothesis is that the evolving nature of living systems ... is a
product of an interaction between the properties of inorganic
elements ... and an ever-evolving organic chemistry dependent on these properties.”
The book is divided into three sections containing altogether 22 chapters. The first section is concerned mainly with
coordination chemistry and physicochemical and biochemical aspects. Some of the topics discussed are the relative
abundance, bioavailability, and speciation of different elements, compartmentelation in biological systems, kinetic
and energetic aspects, the special role of hydrogen, and biological macromolecules. The second section is the bioinorganic core of the book, consisting of 12 chapters dealing with
individual elements, groups of elements. and the forms in
which each element can occur (e.g., iron in the form of
heme). The third section is concerned with biominerals and
biological shapes, homeostasis, morphogenesis, and evolution, and lastly with the use of the elements by man (ecological, toxicological, and medical aspects). A detailed index
completes the book. The lists of references given at the end
of most of the chapters have deliberately been kept short,
with a high proportion of review articles.
There are about 450 figures and tables, plus many reaction
equations and structural formulas. The consistently high
quality of the figures and the commendably low incidence of
printing errors show that the book has been carefully prepared. Some errors worth pointing out are as follows: on
page 44 “ I pm = 100 A’’ is wrong; on page 45 the sulfide
S-atoms of the Fe,S, cluster cannot have free terminal
bonds; on pages 152 and 522 an incorrect formula is given
for the anion of shikimic acid; in the formula for glutathione
on page 455 the positions of the glycine and cysteine groups
should be interchanged.
“The Biological Chemistry of the Elements” is an attractive book and is a pleasure to read. The authors have sought
to present a comprehensive picture, including both the biochemical states and the processes, covering both the spatial
and the temporal (e.g., evolutionary) aspects. From the reader’s standpoint a broad background knowledge is desirable
as a starting basis. This work is not suitable as a student
textbook, and is presumably not intended as such; in any
case, the high price alone will deter students from buying it.
The book should be of great interest to those engaged in
research and teaching in chemistry and biology, especially in
the areas of complex chemistry, bioinorganic chemistry, biochemistry, and molecular biology. Other books suitable as
introductions and accompaniments to the study of this
work are: Biounorguniscke Ckemie, by W Kaim and B.
Schwederski (see above) and Molecular Biology of the Cell,
by B. Alberts, D. Bray, J. Lewis, M . Raff, K. Roberts, and
J. D. Watson.
Bioinorganic Chemistry. (Series: Progress in Inorganic
Chemistry, Vol. 38.) Edited by S. 1 Lippard. Wiley, New
York, 1990. XV, 535 pp., paperback E 28.30.-ISBN 0471-52945-1
This volume contains eight review articles on current areas
of research in bioinorganic chemistry, based on contributions to the Fourth International Conference on Bioinorganic Chemistry held in 1989 in Cambridge (USA).
In the first article R. H. Holm, S. Ciurli, and J. A. Weigel
begin with a short introduction to the chemistry of iron-sulfur clusters, then go on to describe studies with model compounds aimed at mimicking the effects of the protein matrix
on Fe,S, centers. Special attention is then devoted to Fe,S,
cubane-type clusters with nonequivalent iron atoms.
0. Hayaishi, 0. Takikawa, and R. Yoshida contribute a
review of the heme-containing enzyme indoleamine2,3-dioxygenase. Here, unfortunately, inorganic aspects only
receive marginal attention, and therefore a more appropriate
place for this article would be in a series on biochemistry.
Iron and manganese proteins containing (p-oxo)dimetal
centers take part in a variety of biochemical processes. Perhaps the best known of these proteins is the dioxygen carrier
hemerythrin. L. Que, Jr., and A. E. True describe these
metalloproteins and numerous smaller complexes that serve
as models for their active centers. This is the longest chapter
(104 pp.), and also contains the greatest number of literature
references. The authors have succeeded in giving a very clear
account of the combined use of spectroscopic, X-ray crystallographic, magnetochemical, and electrochemical methods
to study proteins and model complexes.
An article by P. Hendry and A. M. Sargeson deals with
biologically important reactions of phosphate derivatives
and discusses their mechanisms. Complexes formed by inert
metal ions have proved to be especially useful for such mechanistic studies. The central theme is the intramolecular attack of metal-coordinated nucleophiles such as OH- or
NH; on neighboring phosphate ligands.
B. E. Bowler, A. L. Raphael, and H. B. Gray discuss theoretical and experimental aspects of long-range electron transfer (ET) in donor-acceptor complexes and proteins. The ET
rate is shown to depend on various factors, such as the electronic coupling, the distance between donor and acceptor,
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