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Book Review Chemistry and Structure at Interfaces New Laser and Optical Techniques. Edited by R. B. Hall A. B

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axes of rotation are not mentioned. Crucially important
explanations are often dismissed too briefly, e.g. that of
Miller indices. Occasionally there appears without warning an unexplained term such as “difference maps”.
Yet despite all the criticisms of individual topics, the
book is a considerable success, and a useful addition to the
major resources available for the study of chemistry. A final, particularly impressive, chapter is entitled “Case Histories”, and gives instructive examples of the practical application of what has been learned previously. The reader
can also test how well he has learned the material by
means of the problems that are set, with answers given at
the end only for every second one; this contributes to a
useful dialogue between student and teacher.
Kurt Dehnicke [NB 844 IE]
Fachbereich Chemie
der Universitat Marburg (FRG)
The Organic Chemistry of Nucleic Acids (Volume 24 in the
series Studies in Organic Chemistry). By Y. Mizuno. Elsevier, Amsterdam 1986. 342 pp., bound, HFI 245.00.ISBN 0-444-99521-8
The compactness of this book and its broadly worded
title lead one to expect a standard reference work rather
than an introduction. The preface restricts the scope implied by the title by stating that the length of the chapters
is not related to their importance, and furthermore that the
main emphasis is on Japanese papers.
The short introduction recalls the history of nucleic
acids in chemistry and elaborates the important role which
they play in nature. It culminates with a description of the
synthesis of the gene for somatostatin, and its expression
in E. coli. This topic is again taken up briefly in the chapter
on “Genetic Engineering” at the end of the book.
The main emphasis of the book and at the same time its
best chapters are those on synthesis and reactions of nucleosides, which is the author’s speciality. Here also the
outstanding contributions made by Japanese investigators
become evident. Apart from the mainly historical considerations and those that are included for the sake of completeness, an especially useful feature is the evaluation of
the various synthetic routes to purine and pyrimidine nucleosides. The advantages and disadvantages of the individual methods are given, together with the currently preferred method for each case. A great many compounds of
pharmacological interest, which are obtained by isolation
from microorganisms, by chemical synthesis, or by enzymatic or microbial processes, are listed.
Of the chapters on nucleic acid syntheses, that on the
RNA synthesis is almost more instructive than that on the
DNA synthesis, as the former is more elaborated on from a
chemical point of view. The informative chapter on “DNA
Drug Interaction”, which provides the pharmaceutical
chemist with a short review of the interaction mechanisms
of both covalent and non-covalent intercalators, crosslinkers, and D N A splitting agents, deserves special mention. A
weak point is the analytical section, which besides the sequencing of DNA and RNA includes only a brief mention
of I3C and 31PNMR spectroscopy.
It is a pity that this book, which, according to the author,
aims to provide students, lecturers and interested organic
chemists in general with a readily comprehensible insight
into nucleic acid chemistry, will probably fail to attain that
objective because of its considerable cost. For the expert
the book gives an overview of the extent of the Japanese
contributions in this field. So far as the presentation of the
I I98
book is concerned, I would have liked to see the many
printing errors corrected, and a clear numbering system
used for the formulae so that a non-specialist might follow
the formulae charts more easily. This book can definitely
be recommended for those pharmaceutical chemists who
have an interest in what is going on in the area of nucleosides and nucleotides of pharmacological importance.
Jouchim Engels [NB 803 IE]
Institut fur Organische Chernie
der Universitat Frankfurt/Main (FRG)
Chemistry and Structure at Interfaces: New Laser and Optical Techniques. Edited by R . B. Hall and A . B. Ellis.
VCH Publishers, Deerfield Beach 1986. xiv, 351 pp.,
bound, DM 175.00.-1SBN 0-89573-311-0
The development of lasers and the availability of synchrotron radiation have had an enormous influence on all
those fields of research in which electronic excitation can
be used either to trigger physical or chemical processes, o r
to detect them. This book was stimulated by a three-day
symposium held by the American Chemical Society in
March 1983 on the theme “Photoprocesses at Solid Surfaces”. It contains six seminar papers from this symposium, which have been updated by the authors to mid1985.
“Examination of the Gas-Solid and Metal-Support Interfaces in Supported Catalysts by Near Edge X-ray Absorption Spectroscopy”, by J. A . Horsley and F. W. Lytle,
is a comparatively short contribution (23 pp.) dealing
mainly with results obtained using synchrotron radiation
on small clusters of platinum, iridium and rhodium. The
interpretation of the results emphasizes the role played by
the d-electrons of such clusters in their interaction with adsorbates.
In the next paper “Final-State-Resolved Studies on Molecule-Surface Interactions” (59 pp.), D.S. King and R . R .
Cuuunugh describe a very demanding, but highly inforrnative technique, whereby one can get an insight into the distribution of energy between the different modes of excitation of a molecule following its interaction with a surface.
For this purpose one makes use of either the fluorescence
of the molecules following selective excitation by lasers, o r
the resonance ionization which generates ions with single
or multiple charges, as determined by the absorption of the
molecule. U p to now the molecule used as a model has in
nearly all cases been NO, whose spectroscopic properties
are especially well understood. In this article the authors
describe studies of the energy distribution following thermal desorption or after scattering of a molecular beam at
single crystal surfaces.
R . B. Hull and S . J. Bares, in their paper “Pulsed-LaserInduced Desorption Studies of the Kinetics of Surface
Reactions” (65 pp.), deal exclusively with the thermal desorption of adsorbed molecules by heating of the support.
By using a laser beam the heating can be confined to a
very small region, thus allowing one to sample small parts
of surfaces and follow the progress of chemical reactions
which take place during a gradual heating process. Using
this technique one can also, by repeated irradiation of a
small surface region, monitor the transport of material by
surface diffusion.
Second order processes in non-linear optics can occur at
boundary surfaces as a consequence of asymmetry. In the
article “Applications of Optical Second-Harmonic Generation to Surface Science” by Y. R . Shen (56 pp.), some examples are given showing how this process can be used to
Angew. Chem. Int. Ed. Engl. 26 (1987) No. I 1
study adsorbed molecules, particularly with regard to their
orientations. Since this effect depends on the strength of
the local electromagnetic field at the surface, it can be used
to measure the field, a capability which is important for
the SERS effect discussed in the next paper.
Surface-enhanced Raman spectroscopy (SERS) has already been reviewed in numerous articles. D . A. Weitz, M .
Moskovits, and J . A. Creighton, in their article “SurfaceEnhanced Raman Spectroscopy with Emphasis on LiquidSolid Interfaces” (51 pp.), support the view that the only
significant factor in the SERS effect is the amplification of
the electromagnetic field by resonance phenomena in
small particles or at rough surfaces, which is highly controversial. There are many indications that a considerable
contribution to the very high enhancement factors of lo5I O6 arises from specific chemical interactions between the
adsorbate and the substrate. The SERS effect is of importance in its application to investigating problems of practical interest, some of which are briefly discussed here. An
example is adsorption on small catalyst particles.
The luminescence observed from semiconductors, either
following excitation by absorption of light or as a result of
the injection of minority carriers, comes from the bulk material. However, its intensity is surface-dependent, since
the radiation yield is determined essentially by the amount
of radiationless recombination occurring at the surface. In
his contribution “Luminescent Properties of Semiconductor Electrodes” (100 pp.), A. B. Ellis describes the experimental requirements for observing the phenomena that occur at semiconductor electrodes, and the theoretical models used to analyze the results. The main interest in such
experiments is in evaluating semiconductors for energy
conversion purposes, as the yield in photoelectrochemical
cells is limited essentially by surface recombination.
All these articles provide interesting and stimulating
ideas on the use of lasers and other optical techniques for
the characterization of interfaces. The techniques that are
proposed are still undergoing development, but undoubtedly have great potential for the future.
Heinz Gerischer [NB 812 IE]
Fritz-Haber- Institut
der Max-Planck-Gesellschaft, Berlin-Dahlem
Molecular Structure and Energetics. Edited by J. F. Liebman and A . Greenberg. VCH Verlagsgesellschaft, Weinheim/VCH Publishers, Deerfield Beach, FL 1986. Vol.
1: Chemical Bonding Models. XIV, 360 pp., bound, DM
240.00 (subscription price DM 210.00).--ISBN 3-52726344-6/0-89573-139-8; Vol. 3: Studies of Organic Molecules. XIV, 385 pp., bound, DM 240.00 (subscription
price DM 2 10.00). -ISBN 3-527-26477-9/0-89573-141-X
A new “open-end” series has been started and the volumes 1 and 3 published first - in the meantime volumes 2
and 4 also appeared - contain 360 und 385 pages respectively; they have been published by the US subsidiary of
VCH Verlagsgesellschaft, our old friend Verlag Chemie, in
the same esthetic way to which we have become accustomed. (The binding is not to my taste but de gustibus not
est disputandum). ,
Each of the two volumes has a general heading and the
contributions chosen fit in reasonably well. Each author
was given much latitude in the relative blending of theory
and experiment and in style. This is perhaps most evident
in the chapters written or co-authored by the editors themAngew. Chem. Int. Ed. Engl. 26 (1987) No. I 1
selves. The standard of the contents, almost without exception, is very high.
In comparing two similar series, published as beautifully
as this one by a competing publisher (“Structure and
Bonding” and “Topics in Current Chemistry”), one finds
similar breadth and homo- or heterogeneity. It is evident
that it is cheaper to print in East or even in West Germany
per individual volume than in the U. S.
Not as a matter of modesty, but as a matter of fact, I
have checked my opinions on chapters further from my realm of understanding with trusted expert colleagues.
Though they remain unidentified, any misjudgements are
solely my responsibility.
Volume 1 contains nine chapters, the first of which (15
pages) is by L. Pauling and 2. S . Herman. What a nice idea
for the opening chapter of a book on chemical bonding!
Although one can always learn from Pauling, 1, of course,
included (albeit Vitamin C is unmentioned), I must abjectly confess my disappointment. I was looking forward
to a much greater treat upon reading the first half of the
title: “Nature of the Chemical Bond Fifty Years Later:” I
expected from the Master a deeper evaluation and perspective than actually touched. The purpose of sub-heading “The Relative Electronegativity of Atoms Seen in Perspective” is achieved. I expected a wider overview on the
nature of the chemical bond, 50 years later, perhaps employing more of “the work of such investigators as Roald
Hoffmann”. Perhaps my judgement is clouded by the nature of the first chapter (by D. J. Cram) in a two-volume
set on cyclophanes.
Chapter 2 by H . A. Bent on “Isoelectronic Molecules”
treats the subject in an incredibly terse manner (30 pages!),
as can be done only by a leading expert; it explains the
concepts involved with well chosen examples. I was sorry
when the beautifully written chapter ended. I should have
been glad to see included the word isolobal.
Chapter 3 by J . F. Liebman and J. Simons discusses
“Carbenes: A Study in Quantitative and Qualitative Theory” (49 pages). Since reviews of carbenes emphasizing the
synthetic viewpoint are plentiful, this one is particularly
In Chapter 4, M . S . Gordon considers “Theoretical Studies of Multiple Bonding to Silicon” (22 pages). The author’s first sentence makes the point of how rapidly this
new field is developing. The length of the chapter is due to
the novelty of the field and though coverage is very good
Si=N bonding might have been added when Si=P is discussed. The author even manages to cite some 1985 references which were available to him, but much has already
appeared in the interim. It is a pity that in this case there is
no addendum (as in Vol. 3) to catch up a bit more. Nevertheless, here is the place to mention that publication has
been relatively fast and many 1984 references are cited
In contradistinction, Chapter 5 by R . B. King on “Topological Relationships in Molecular Structures and Energetics” (26 pages) is disappointing. It not only skims the surface but its latest 1983 reference is to a chapter elsewhere
by the same author on the same general theme. I should
have thought that a chapter with this title ought to have
contained a bit more about graph theory to simple planar
organic compounds if not to those few that cannot be accommodated by a planar graph. Perhaps a more limiting
title could not have led to great expectations.
Chapter 6 by T. P. Fehlner and C. E. Housecroft discusses “Boranes and Heteroboranes” (59 pages). It is a
good introduction to the uninitiated as to structures of
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