Book Reviews

G. GOVIL and R. V. HOSUR NMR Basic Principles and Progress, Vol. 20-Conformation of Biological Macro- molecules-New Results from NMR. Series Editors: P. Diehl, E. Fluck and R. Kosfeld, Springer-Verlag, Berlin, Heidel- berg, New York, 1982. 216 + viii pp. Cloth: DM 148, approx. US $68.90. ISBN 3-540-

Conformational studies on molecules in sol- ution have proved to be among the most important applications of high resolution NMR spectroscopy. Although one usually cannot obtain a complete three-dimensional definition of the overall shape of the molecule as from x-ray crystallography, valuable information can be obtained for various fragments of the molecule from NMR studies. These fragments usually have torsion angles which can be related to three- bond coupling constants or have pairs of spatially close nuclei which can be located using nuclear Overhauser enhancement (NOE) effects. Sometimes the analysis is complicated by the molecule existing as a rapidly interconverting mixture of confor- mations: however, in favourable cases infor- mation about the populations of the confor- mers can also be extracted. The recent de- velopments in 2-D NMR methodology which allow simplification of complex spectra and extensive NOE studies on large molecules such as proteins offer exciting possibilities for determining conformations of large molecules and of defining confor- mational changes which accompany ligand binding to the macromolecules. Thus the present textbook written by Professors Govil and Hosur appears at a time when there are sufficient data available to make a good assessement of the contributions made by NMR to conformational studies of biological molecules. The authors have aimed at covering the complete range of biological systems dealing with amino acids, peptides and proteins, nucleosides, nuc- leotides, nucleic acids, polysaccharides, phospholipids and with interactions between nucleic acids and proteins. The book contains a very clear account of the conformational analysis of the smaller molecules (such as peptides and nucleotides). However, its very comprehensive coverage could have been improved by giving more detailed consider- ation to the problems encountered when dealing with interconverting mixtures of conformations. In this regard it would have been useful for the authors to assess more critically some of the many papers from which they quote.

A very useful feature of the book is the comprehensive coverage of the literature in this area (more than 1200 references). This provides an invaluable reference source but unfortunately one penalty of the wide

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coverage is that in many cases the authors can present only a brief account of the results from the various studies. The short section on polysaccharides is a very useful contribution since this subject is usually neglected in biological texts.

The most disappointing aspect of the book is that it does not include any details of the exciting advances made in protein conformational studies over the last two years. For example, the elegant studies on bovine pancreatic trypsin inhibitor (BPTI) from Professor Wiithrich’s laboratory re- ceive only a mention in the reference list. The text could have been considerably ex- tended to cover the larger molecular weight systems in more detail.

However, because of its useful presenta- tion of the conformational analysis of smal- ler biological molecules and the excellent literature coverage, this book is a very wel- come addition to the biological texts already available.

J. FEENEY National Institute for Medical Research

G. C. LEVY (Editor) ACS Symposium Series Vol. 191-NMR Spectroscopy: New Methods and Applica- tions ACS, Washington, DC, 1982, 398+ix pp. us $59.95

This volume is based on a symposium held at the 181st meeting of the American Chemical Society from 29 March to 3 April, 198 1. The contributions are reproduced from the camera-ready copy provided by the authors, with the result that the reader is presented with a variety of typescripts and some inconsistencies in nomenclature, use of symbols and clarity of diagrams. Presum- ably this expedient has been followed with a view to rapid publication. However, it is now almost 20 months since the symposium took place, consequently some of the ‘re- cent’ developments presented have already become somewhat dated. Such is the current pace of events in NMR spectroscopy. Some of the blame for this apparent delay must be apportioned to those contributors whose manuscripts were not made available until February 1982.

Following a brief introduction to recent developments in NMR instrumentation and methods by Levy and Craik, there are 16 chapters dealing with specific aspects of the modern NMR scene. Developments in NMR instrumentation are covered by chap- ters on ultra high-field NMR by Wehrli, NMR Spectroscopy at 600MHz by Bothner-By and Dadok, and on NMR at

high pressure by Jonas. The first two of these accounts trace the improvements in magnet technology over the past 30 years and provide some examples of the various types of elegant experiment which may be performed at fields up to 14.1 T. The advan- tages of high field instruments for biomedi- cal studies are clearly shown.

Multinuclear high resolution NMR FT spectroscopy at high pressure is adequately reviewed and examples are presented of 13C NMR experiments on rhodium carbonyl clusters under high pressures of CO/H, to illustrate applications to homogeneous catalytic processes. Pressure effects on con- formational inversion in cyclohexane are also discussed, as well as those on relaxation and transport behaviour of compressed supercritical water and on the dynamic structure of a number of disordered systems.

Chapters dealing with NMR methods in- clude those by Ernst on the information content of two-dimensional Fourier spec- troscopy, by Hore and Kaptein on photo- chemically induced dynamic nuclear polari- zation of biological molecules using continu- ous wave and time-resolved methods and five contributions relating to the employ- ment of solid state NMR techniques. Recent advances in the field of solid state NMR are demonstrated in these accounts. Schaefer et al. have written on chemical bond labelling and double cross-polarization NMR, while I3C NMR spectra of amines adsorbed on y-alumina, obtained by means of a unique spinner design, are dealt with by Dawson et al.; the solid state NMR of linear and cyclic peptides is presented by Gierasch et al., I3C NMR characterization of solid fossil fuels is covered by Maciel and Sullivan while Jelinski et al. discuss some I3C NMR studies of thermoplastic elastomers. These are in- teresting accounts and serve to illustrate the burgeoning interest in high-resolution solid state NMR studies.

The remainder of the book consists of reports dealing with NMR applications, mostly on solutions, of specific nuclei. Not surprisingly, 13C features prominently in this list. London deals with an NMR study on 13C enriched amino acids and peptides, the metabolism of I3C labelled substrates is re- ported on by Matwiyoff ef al. following a I3C NMR investigation of intact cells, tis- sues and organs while Hilliard et al. present the results of some studies on DNA dynamics obtained by multiple field natural abundance I3C NMR spectroscopy.

Deuterium NMR is covered by Smith and Monatsch while Laszlo deals with some *”a NMR studies of cation binding by natural and synthetic ionophores. Studies on DNA conformation and dynamics by means of 31P NMR spectroscopy are presented by Cohen and Chen. The book concludes with

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BOOK REVIEWS

a 28 page index, which is useful despite some alphabetic shuffling on page 377.

It is unfortunate that the anachronism of 'chemical shift anisotropy' appears to be given credence in this book. A scalar cannot be anisotropic whereas a tensor may be so. Thus a plea for chemical shielding aniso- tropy! However, it has to be admitted that compiling a multi-author volume is not an easy task, and occasional apparent slips from the NMR Bushido should not be pounced upon too avidly.

The editor and his team of contributors have performed a useful service to the gen- eral NMR readership. The present volume provides a flavour of many of the dramatic developments in the methodology and ap- plication of NMR to biological and chemical problems which have been reported during the past ten years. Hence it is perhaps churl- ish to point to those areas of current NMR activity which are treated rather scantily in this book. Nevertheless, more consideration of heavy nuclei NMR, and detailed accounts on multiple-pulse techniques, NMR imaging and multiple quantum NMR would have served to enhance its appeal. Perhaps these are among the topics to be covered in another symposium.

G. A. WEBB University of Surrey

G. A. WEBB (Editor) Annual Reports on NMR Spectroscopy, Vol. 13 Academic Press Inc. (London) Ltd., 1982. 399 pp. f53.80, US $99.50 ISBN 0-12- 505313-4

This volume contains four reviews on widely differing topics. The first two relate to or- ganic chemistry, and cover NMR studies of mono- and oligosaccharides and of al- kaloids, respectively. The former is 57 pages in length, and discusses much material of NMR interest, including summaries of re- levant two-dimensional and relaxation ex- periments, contained in a very useful section of 20 pages on assignment techniques. De- tails of chemical applications follow, and cover work on less-common nuclei as well as on 'H and I3C. The chapter on alkaloids is in a very different format and is entirely on chemical shifts and coupling constants, grouped into sections according to alkaloid

type. This review updates two previous ones in the same area. Although there is, perhaps, room for compilations of this type in the literature, they make boring reading, and I seriously question whether 'Annual Reports' is the place for them. Unfortu- nately, this article is the longest of the four, occupying 150 pages, and I cannot imagine it will help to entice many individuals to purchase the volume.

The third review, of 108 pages, concerns thallium NMR, updating the relevant chap- ter of 'NMR and the Periodic Table' and written by the same group. Again, the em- phasis is on tabulating results (no fewer than 64 pages are entirely tabular) which does not make for exciting reading here either! Moreover, the exceptionally large variation of chemical shifts with solvent for thallium makes one question whether such tabulation is the best way of presenting the data. To my mind the most valuable section is the 19 pages on solid-state and related NMR studies. The final chapter, 67 pages in length, is about rotational correlation times. This is a timely review and has an attractive format-it starts by discussing correlation models, then describes results for a wide range of quadrupolar and sp in3 nuclei, and finishes by describing tests of the various models. I found this arrangement very helpful.

The volume ends with 13 pages of a sub- ject index which, because of the differing nature of the four reviews, appears to me to be almost worthless-separate indices to the reviews would be preferable (if such indi- ces are wanted at all). Altogether, the vol- ume is a mixed bag, but it does add some further value to the series as a whole, and it is not entirely reasonable to offer a critique on one volume alone!

R. K. HARRIS University of East Anglia

J. D. MEMORY and N. K. WILSON NMR of Aromatic Compounds John Wiley and Sons, New York, 1982. 252 +xi pp. f33

That this excellent book has been attempted at all is remarkable in view of the very extensive literature devoted to research in this broad area. That a distillation has been achieved to yield a readable and balanced

coverage of necessary theory and experi- mental methods, along with results and ap- plications, is extremely laudable.

The book comprises seven chapters on: fundamental aspects of NMR; theory of chemical shifts in aromatic compounds; ex- perimental chemical shifts of 'H and "F; I3C and heteroatom chemical shifts; spin- spin coupling constants; relaxation times and other time-dependent phenomena; and experimental techniques. Of course the selection of material from so much available is inevitably a personal one, and alternative topics and data for other compounds might have been included; the choices made, how- ever, generally encompass the more defini- tive studies while also including some stimulating newer work. The authors have included a large quantity of literature while highlighting each topic with well organized examples.

Many lucid reviews are included, e.g. of the complex and often contradictory theories of substituent effect on 'H and I3C chemical shifts and on coupling constants, while there are useful examples of the infor- mation to be gained from dynamic processes in the aromatic series. The mention of chemical shifts of heteroatoms in aromatic compounds is especially welcome. The coverage is especially strong in the area in which Professor Memory is already well known-the quantum theory of chemical shifts; any spectroscopist trying to interpret 'H shifts in aromatic molecules will ap- preciate the neat summaries of the strengths and weaknesses of the various ring-current theories.

Many data are summarized in tables, but both here and occasionally in the text one might have hoped for more consistency in the application of IUPAC nomenclature and numbering. Although the inclusion of struc- tures of named compounds avoids confusion in this respect, valuable space could have been saved by avoiding the necessity of presenting the structures for so many de- rivatives. Illustrations are mostly clear and informative, and a compound index is in- cluded as well as the subject index.

In conclusion, in spite of the fairly high price for this relatively short book, no prac- tising organic NMR spectroscopist can afford to be without it.

KEITH D. BARTLE Department of Physical Chemistry

The University of Leeds

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