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Book Review Organic Eletrochemistry. An Introduction and a Guide. 3rd Edition (revised and enlarged). Edited by H. Lund and M. M. Baizer

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ponential autocatalysis should be feasible if the proper model system is used. The strategy might be to search for linking
reactions which modulate the molecular recognition process.
The linkage must generate a template molecule that forms
less stable salt bridges with itself than with its precursors.
Current studies aim to couple the modulation of molecular
recognition with the generation of chiral template molecules
to find an approach towards asymmetric autocatalysis.
Received: October 18, 1991 [Z 4976 IE]
German version: Angew. Chem. 1992, 104, 626
Reviews: a) G. von Kiedrowski in 40 Jahre Funds der ChemischenIndustrie
(Ed.: Verband der Chemischen Industrie), VCI publications, Frankfurt,
1990; b) G. von Kiedrowski, Origins L f e , in press; c) L. E. Orgel, Cold
Spring Harbor Symp. Quant. Biul. 1987,7,9-16; d) G. F. Joyce, ibid. 1987,
7, 41-51.
a) G. M. Whitesides, Angew. Chem. 1990,102,1247- 1257; Angew. Chem.
Int. Ed. Engl. 1990,29, 1209-1218; b) J. S. Lindsey, New J. Chem. 1991,
f5, 153-180.
Cf. essays in Artificial L f e . The Proceedings of an Interdisciplinary Workshop on the Synthesis and Simulation of Living Systems Held September,
f987 in Los Alamus, New Mexico (Ed.: C. G. Langton), Addison-Wesley,
Redwood City, USA, 1989.
G. von Kiedrowski, Angew. Chem. 1986, 98,932-934; Angew. Chem. In!.
Ed. Engl. 1986,25,932-935.
G. von Kiedrowski, B. Wlotzka, J. Helbing, Angew. Chem. 1989, fOf,
1259-1261; Angew. Chem. Int. Ed. Engl. 1989,28, 1235-1237.
G. von Kiedrowski, B. Wlotzka, J. Helbing, M. Matzen, S. Jordan, Angew.
Chem. 1991, f03, 456-459, 1066; Angew. Chem. Int. Ed. Engl. 1991,30,
423-426,892.
W. S. Zielinski, L. E. Orgel, Nature (London) 1987, 327, 346-347.
T. Tjivikua, P. Ballester, J. Rebek, Jr., J. Am. Chem. SUC.1990, 112, 12491250; J. S. Nowick, Q. Feng, T.Tjivikua, P. Ballester, J. Rebek, Jr., ibid.
1991, 113, 8831-8839.
Meanwhile, template-free approaches towards self-replicating systems
were also reported: P. A. Bachmann, P. Walde, P. L. Luisi, J. Lang, J. Am.
Chem. Soc. 1990, ff2,8200-8201; cf. M. Zeleny, G. J. Klir, K. D. Hufford
in ref. [3], pp. 125-139.
For other supramolecular applications of salt-bridges with guanidinium
and amidinium salts see: a) G. Miiller, J. Riede, F. P. Schmidtchen, Angew.
Chem. 1988,100,1514-1577; Angew. Chem. Int. Ed. Engl. 1988,27,15161518; b) A. Echaverren, A. Galan, J.-M. Lehn, J. de Mendoza, .l
Am.
Chem. SUC. 1989, 111, 4994-4995; c) M. Gobel, D. Reckenbeil in
Chemiedozententagung 1991 (Ed. : D. Dopp), University of Duisburg,
Duisburg, 1991.
[I I] Compounds 1were equipped with alkyl groups to increase the solubility of
the corresponding anils sufficiently. Synthesis of compounds 1 will be
described elsewhere. 2-Formylphenoxyacetic acids were used instead of
the corresponding 2-formylbenzoic acids, since in the latter case it was not
possible to prevent an intramolecular attack of the carboxylic group on the
anil bond (ring closure).
[I21 Compounds l a and 2a (each 50 mM in [DJDMSO) were allowed to react
inthepresenceofO,0.11,0.26,and0.37mol% of3ainNMRtubessealed
by melting. The formation of phenoxyacetic acid 3 a was monitored at a
frequency of 500 MHz by observing the following resonances: b = 1.321
1.42 (tBu la/3a), 7.2217.56 (3’-H la/3a), 10.3918.86 (CH = O / C H = N).
The formation of3a is reversible; the equilibrium constant was determined
as K = 5.73 1 at T = 50°C. The concentration of the primary adduct is
below the limit of detection for the given NMR technique.
[I31 The following reaction model based upon the square-root law was chosen
for the evaluation of the experimental time courses of NMR integrals with
the computer program SimFit [14]: 1) l a + 2a$3a + H,O. 2) l a
2a + 0.5 3 a +1.5 3 a H,O. The apparent rate constants-as determined by SimFit-are ( T = 50°C): k, = (1.50 ? 0 . 2 4 ) ~
M-~s-’,
k-, = kJ5.73 M-lS-l, k, = (2.46 f 0 . 2 5 ) ~
M-3’2S-1.
[14] G. von Kiedrowski, 1991, unpublished. Program SimFit (Nonlinear Fitting by Dynamic Simulation) processes the kinetic data of experimental
concentration-time traces for any given reaction model. As many as 16
different experiments with varying initial concentrations can by evaluated
in a single run. Reaction equations are introduced as input at run-time (i.e.
no compiling and linking prior to program start), the program then generates the corresponding set of differential equations and the concentration
derivatives (Jacobi matrix). The user may choose either the Runge-Kutta
algorithm or a modified Gear algorithm as the method of integration.
Nonlinear curve-fitting (by least squares) may be achieved either with the
simplex algorithm or with the Newton-Raphson algorithm. The output
includes the calculated concentration profiles, the rate constants, and the
corresponding variances and covariances. The program supports the input
of symbolic assignments of the concentrations of mechanistic species to
observable concentrations (expressions with sums and differences). Thus,
it is also applicable in those kinetic studies where only the total concentrations can be monitored (e.g. in the case of intermediate complexes which
form and dissociate rapidly). In our laboratory, SimFit has proven a valuable tool for a large number of mechanistic studies.
[I51 The autocatalytic efficiency E has been defined as the factor by which the
rate of the autocatalytic synthesis exceeds that of the nonautocatalytic
synthesis, for a template concentration of 1 M [6].
[I61 Normally a square-root law is expected, since a template duplex of type 5
should be more stable than a ternary complex of type 4 for entropic reasons.
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BOOK REVIEWS
Organic Electrochemistry. An Introduction and a Guide. 3rd
Edition (revised and enlarged). Edited by H . Lund and
M . M . Baizer. Marcel Dekker, New York, 1991. XXII,
1550 pp., hardcover $234.00.-ISBN 0-8247-8154-6
For nearly twenty years now, “Baizer and Lund” has had
the status of a proven and highly regarded standard work,
which is oriented specifically towards organic chemists, and
provides a broad survey of the many wide-ranging applications of organic electrochemistry. This revised and enlarged third edition takes account of the rapid developments
occurring in the field, resulting in a book that contains nearly
400 more pages than the second edition. The revision has
656
0 VCH Verlagsgesellschaft mbH, W-6940 Weinheim, 1992
0570-0833/92/0505-0656$3.50+ ,2510
Angew. Chem. Int. Ed. Engl. 31 (1992) Nu. 5
been carried out in a responsible and critical way, so that not
only have several chapters on recent developments been
added, but also some on topics that are now less important
have been taken out, transfering those parts that are still
relevant into other chapters. The editors have succeeded in
enlisting 30 internationally recognized and experienced scientists, all actively engaged in the research and teaching of
their specialist areas, to write the 36 chapters.
Compared with the two earlier editions the structure of the
book has changed only slightly. It begins with four chapters,
totaling 250 pages, in which the basic principles and methods
of electrochemistry are described. At several points here a
deliberate decision has been made to avoid too detailed a
mathematical description. Chapter 5 will certainly be very
useful for newcomers to the field, as it offers much practical
advice on how to carry out electrochemical experiments. The
part of the book that follows is arranged in traditional organic chemistry style, classified according to types of electrodes and electrophoric groups, and consisting of over
350 pages. Reactions at the cathode are dealt with first, for
hydrocarbons, halides, nitro compounds and related substances, carbonyl compounds, azomethines, and carboxylic
acids and derivatives. This is followed by reactions at the
anode, for hydrocarbons, carboxylic acids, nitrogen compounds, oxygen compounds, and sulfur compounds. Four
further chapters then deal with the electrochemistry of
heterocycles, electrochemical reactions as key steps in the
synthesis of natural products and pharmaceuticals, the importance of electrochemistry in the exploitation of biomasses, and electrochemical reactions of organometallic compounds and coordination compounds. This part of the book
is followed by detailed discussions of the various types of
electrode reactions (reductive coupling, oxidative coupling,
detachment and removal of protecting groups, anodic substitution, anodic fluorination). Here, of course, a small degree of overlapping with other chapters is unavoidable. A
separate chapter is also devoted to the stereochemical aspects of organic electrode reactions. This is followed by three
chapters on indirect electrochemical synthesis. Under the
heading “Present and Future Applications” some topical
applications-orientated areas are discussed, including industrial electrochemistry, electrochemical polymerization processes, modified electrodes, conducting polymers, and
photoelectrochemistry. This section concludes with an
assessment of future needs and opportunities.
From the organic chemist’s viewpoint this book makes
easy reading and is clear and comprehensible. The editors
have succeeded in an exemplary way in welding together the
individual contributions to make a consistent whole. However, the book does not always live up to its claim of being
an introduction to electrochemistry, as the reader is too often referred to other textbooks, especially in the presentation
of the fundamental principles. Also many of the methods are
only described very briefly. Nevertheless, this only diminishes the book’s usefulness very slightly; it impresses through
the expert and skillful choice of material, and the wealth of
helpful advice that is offered. Access to original publications
for more advanced study is facilitated by the inclusion of
about 7000 references, backed up by an index of authors,
making the book also a valuable source of information for
the scientist active in this field. Regrettably, though, the subject index is very scanty for a work of this size, and it is
difficult to understand why.
Despite the reservations expressed above, the book can be
recommended without hesitation, as the new “Lund and
Baizer” is certain to be appreciated as a valuable guide and
a mine of information that one cannot afford to be without.
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 5
0 VCH
Manuel Baizer, who was the prime mover behind this book,
sadly died 2’12 years before the completion of the third edition; along with Henning Lund he deserves our sincere gratitude. Unfortunately the high price will be an obstacle to the
book reaching a wide readership, and regrettably it will,
therefore, not be to hand in every laboratory. It is certainly
a must for every library.
Michael Schmittel
Institut fur Organische Chemie
der Universitat Freiburg (FRG)
Biochemical Messengers. Hormones, Neurotransmitters and
Growth Factors. By D. G. Hardie. Chapman & Hall, London, 1991. X, 311 pp., paperback E 13.95.-ISBN 0-41230350-7
The human body consists of over 50 billion cells. Volvox,
the simplest multicellular organism, already consists of
50000 cells. An organism only exists when these interact
cooperatively. Cooperation implies communication: messages must be sent from cell to cell, and in these the transmitting cell must give specific information which the receiving
cell can process and convert into appropriate reactions. In
higher animal organisms there are two large communication
systems, one consisting of neurones and the other of hormones. Both systems are based on essentially the same principles, which is not surprising since there is no doubt that
they have developed in ways that are connected. Both use
molecular messengers and depend for their functioning on
complicated molecular signal processing systems. Because of
their fundamental importance, both are among the most
intensively studied fields of current research. This monograph provides an overview of the present state of knowledge
in these areas.
Hardie’s book encompasses the whole of this very broad
subject. It begins with the “first messengers”, the messenger
molecules of the hormonal and nervous systems, which usually only travel as far as the plasma membrane of the receiver
cell. There the information they carry is converted, through
receptors and their signal transduction mechanisms, into
“second messengers” and their associated intracellular effects. Hardie describes their structures, their biosynthesis,
and the cell biology involved in their storage and distribution. After an excursion into the neurobiology of nerve
impulse transmission, he then continues, via the biochemical
messengers, to the most exciting part of the story, the receptors. Their experimental identification and characterization,
their structures, and the way in which they function, form the
subject matter of the middle section of the book. The concluding chapters deal with the regulation of cell division, and
with gene regulation by steroid hormone receptors that bond
directly to the DNA of the cell nucleus.
Is it appropriate to write monographs dealing with areas
of research that are still in a state of flux? The publication of
books is inevitably a slower and more cumbersome process
than that of review articles, and consequently a book may
already be partly out of date by the time it appears. In any
case, specialists and researchers obtain their information
mainly from the primary literature or from relevant review
articles. However, monographs ’such as that reviewed here
are not intended for the specialist. Hardie is here writing for
advanced students of biochemistry, biology, and pharmacology. From the research scientist’s standpoint his book is best
regarded as a first point of entry. As a textbook for advanced
students it can be recommended unreservedly. It is clearly
Verlagsgesellschaft mbH. W-6940 Weinheim, 1992
0570-0833/92/0505-0657 $ 3 . 5 0 + .25/0
657
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