An introduction to physical properties of large ... - ACS Publications

Dec 1, 1981 - An introduction to physical properties of large molecules in solution(Richards, E. G.; Dover, S. D.). Matthew Tirrell. J. Chem. Educ. , ...
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An Introduction t o t h e Chemistry a n d Biochemistry ol Pyrimidines, Purines, a n d Pteridines Derek T. Hurst, John Wiley 8 Sons, New York. 1980. v 266 pp. Figs. and tables. 23.4 X 15.4 cm. $39.00.

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The stated purpose of this h w k is "to cover the basic chemistry of pyrimidines, purines, and pteridines a t a level suitable for undergraduate and research students of chemistry, biochemistry, and pharmaceutical chemistry and to provide an introduction to the biochemistry and biochemical uses of these compounds a t a level suitable for undergraduate and postgraduate chemists." The book achieves the first part of the goal reasonably well by presenting the basic chemistry and physical properties of the three major groups of heterocycles in a concise, well-organizedmanner. Individuals who have taken a good undergraduate organic chemistry course and wish t o learn about these important heterocyclic compounds will orofit ~ u h s t a n t i a hfrom studvine , .. the first Eour c h a p t r r ~uf this wiurnr. The iattcr half of the brwk does nut serve thr stated purpclst. nearly a> well. H ~ n d e r iwho h a w not had previous exposure to biochemistry to gain some understanding of the importance of higher order structure of biological macramolecules to the function of biochemical pathways will not he well served by the chaoters dealine with biochemistrv. I susneet that chemlsri, undrrgradunteand portgrad"ate, w~ll1r.nefit only i n n very general wny ~

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from the presentation of the material on coenzymes and biosynthesis of nueleotides, nuckic acids, and proteins. The material is presented in a manner that might lead the uninitiated to conclude that mixing the appropriate coenzymes and precursors will lead to end products without the aegis of enzymes. In order t o cover the broad scope of the content of this h w k in the limitednumber of pages the author has briefly placed each subject in perspective and then presented the basic aspects pertaining to the topic without much detail. Again, this works quite well when dealing with the chemistry and properties of each major class of compounds. I t is much less successful in the areas that deal with the biochemical aspects of the compounds. The reader is directed t o reference lists for detailed treatments of the subject matter. The author was correct in stating that some of the information will be out of date. I was surprised a t the small number of citations dated as late as 1978. Technically, the book is well prepared with usable table of contents and index. I found one feature that may be confusing to readers who are not very familiar with the general area of tautomeric forms of heterocycles. In chapter 3 the author indmted that hydroxy, thione, and amino forma will be used throughout unless a particular need exists for use of the alternate tautomerie forms. The author has not been consistent in this usage, particularly in the biochemistrychapters. For example, on page 161 IMP is written as the 6-oxofom whereas on page 162 in continuing the biochemical pathway, IMP is written as

the 6-hydroxy tautomer. This occurs quite frequently in the book. Overall, I think the book pravides a good introduction into the chemistry and properties of pyrimidines, purines, and pteridines. On the other hand, it is not nearly so suitable as a n introduction to the biochemistry of these compounds. Allan L. Bieber Arizona State University Tempe. AZ 85281

An Introduction t o Physical Properties

of Large Molecules in Solution E. G. Richards, and S. D. Dover, Cambridge Univ. Press. New York. First Edltion, 1980. xvii pp. Figs. and tables. 15 X 22% cm. $9.95.

Dr. Richards' book sticks quite closely to the rather limited territory outlined in the title. The book is aimed at undergraduate students in physics, chemistry, and biology and seems to be written a t a level appropriate for this level of student. It is quitedefinitely a textbook designed to he accompanied by a set of lectures. I t would not serve well as a reference book since there is (as noted in Richards' preface), ". . .little attempt t o review the experimentally observed facts relating to red macromolecules. .", hut rather an emphasis on broad underlying principles (Continued o n page A378)

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Reviewed in this Issue Derek T. Hurst, An introduction t o t h e Chemistry and Biochemistry of Pyrimidines. Purines, and Pteridines E. G. Richams and S. D. Dover, An Introduction t o Physical Properties of Large Molecules in Solution Robert Dinell, Association Theory: The P h a s e s of Matter and their Transformations H Tadokoro. Structure of Crystalline Polymers N. J. Turro, Urea-Formaldehyde Resins R. L. Flurrv. ..Jr... Svmmetw Grouos Theow and Chemical Aoolications Walter Jennings a n d Takayuki Shibarnoto. Qualitative Analysis of Flavor and Fragrance Volat~lesby Glass Capillary Gas Chromatography R. Pauncz. Spin Eigenfunctions Construction and Use J a c k A. Gerlovich a n d Gary E. Downs, Better Science Through Safety E. M. Goodger, Alternative Fuels, Chemical Energy Resources V. L. Snoeyink and 0.Jenkins, Water Chemistry W. Ranney. Synthetic Oils and Additives for Lubricants (Advances Since 1977) New Volumes in Continuing S e r i e s

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Volume 58

Reviewer Allan L. Bieber Matthew Tirreii William J. Peer William T. Winter H. J a m e s Harwood J a m e s L. Bills JJL

E. W. Anacker Malcolm M. Renfrew Buddhadev S e n W. G. Breck J. H. J o n e s

Number 1 2

December 1981

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and descriptive concepts. There are also verk few citations of original scientific literature. The focus on physical properties in salution permits treatment of this subject matter in more depth and in a more satisfactory manner than can be found in any other introductory polymer science text, especially the ones which attempt to cover the entire field. The emphasis in this hook isdecidedly, but not exclusively, on biological macromolecules. The hook contains nine chapters and five appendices. Chapter 1 is a nice introduction t o the science of laree .. molecules.. puint~ngmrt the interesting and important parnllels in rhr drvelo~rnrntsot inelymrr zcwncr and dl&I wiencr.'l'hpw I* n ~ l h ing on polymer synthesis, biological or otherwise, in this book. Chapter 2, on molecular interactions, is nicely done but rather poorly integrated into the material of the rest of the book. There are sections an multipole interactions, induction forces, dispersion forces, exclusion forces, hydrogen and hydrophobic bonding, as well as on intramolecular rotation potentials. Chapters 3 and 4 are quite lucid standard treatments of equilibrium thermodynamics and configurational statistics of large molecules. There is an especially welldone simplified discussion of the FloryKrigbaum theory of dilute polymer solutions. On ther other hand, the distinction between the theta temperature and the critical console temperature is left a bit obscure, especially by homework problem 3.5. (There is overall a good selection of homework problems following each chapter.) Chapter 5 treats helix-coil transitions. Chapter 6 an gels concentrates more on swelling phenomena and isvery brief for those interested in mechanical properties of rubber. Chapters 7 and 8 on scattering and hydrodynamics, respectively, are good, with the important exception of an adequate treatment of quasi elastic light scattering, a technique gaining users in biophysics and chemistry very rapidly. Chapter 9 is devoted t o the important topic of polyelectrolvtes. ~ i c h o r d , ' book makw s w r y ftwmble impreswn on this rr, i w p r I t i. dr3ignrd oc il tevthmk and wa\rl,l srrec w r y urll in a course designed to cover the above subject matter. Matthew Tirreil Department of Chemical Engineering and Materials Science University of Mimesole Minneapolis, MN 55455

Association Theory: The P h a s e s of Matter a n d their Transformations Roberf Ginell, Elsevier Scientific, New York, 1979. xii 224 pp. Figs. and tables. 25 X 17 cm. $47.25.

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This monograph is an exposition of the author's theorv which attemots t o describe thcstntesofmattrr a d trau4ionq brt\rrrn thr ~ L I I P S The . mean, fur arcwnpli:llin,: t l l i c gala1 I: a n eq11wit n (11 state which h,,, the ~

A378

same form as the van der Waals equation of state but isdifferent from thevan der Waals equation in that (a) molecular association is explicitly accounted for, and (b) the two empirical parameters are interpreted somewhat differentlv so that the eouation can he made to apply & all states of matter. The book begins with a brief historiealreview of equations of state for gases and cantinues with a detailed mathematical description of the association of l-mers (monomers) into species containing up t a m 1-mers. The next chapter justifies the author's eauation of state and the next c h a ~ t e r discusses the nature of molecular association.. T h t t m c herwen mc,lrrulrt ir;a;mmcu t u lw svmmrtric, leadmg, ln rh? author', wordc. to rlectrojmtlr and o l e c t r ~ m a ~ n rh~uwh . 'l'hc number of ways aggregates of hard spheres, represented by beads, can bond (contact of two spheres is considered to be banding) is discussed in detail; the author has mede madels of associated species pnsisting of up to 19 hard spheres. The author's main conclusion from this exercise is that "solids are composed of particles in exact 4- or 6-symmetry," whereas the unimers (monomers) of the associated species in liquids "are arranged in inexact 5-symmetry." This conclusion is important for the phenomenological discussion of phase transitions which follows in the next chapter. For example, crystallization of a supercooled solution when the solution is stirred is ascribed by the author to the break-up, in the liquid, of associated species in inexact 5-symmetry caused by the energy of stirring and the subsequent rearrangement of the fragments into the exact G-symmetry species of the solid. Four chapters are concerned with derivine. from exoerimental data. oarameters for ihe author's eouation of

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rrplanntims art nut in nmcordancr nirh yrmrdlly hrld vwws The final c h n p t ~vc.n r lain, a qualitallrr rrplonnrlm of th? rritiv:tl state. According to the author's view, the degree of association in the critical state is intermediate between that of the gas and liquid. One consequence is that, whereas gases and liquids transmit light because the size of associated species in gases is too small to interfere with light but the size of associated speciesin liquidsis toolarge tointerfere with light, a t the critical point the sizeof the associated species is appmpriate far interfering with the transmission of light, giving rise to critical onslescence. planations a t each step in its exposition are well done so that this is a hook undergraduates can understand. Nevertheless, contrary to the author's intentions, the lack of mathematical rigor in most applications makes this hook inappropriate for an advance course. William J. Peer Cornell University Ithaca, NY 14850 Structure of Crystalline Polymers H. Tadokoro, John Wiley 8 Sons., New York, 1979. xvii 465 pp. Figs. and tables. 16 X 23.5 cm.

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Journal of Chemical Education

The appearance of a cogent and comprehensive monograph often heralds the matu-

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ration of a narrow technical specialty into a widely accepted and practiced scientific tool. Unfortunately, despite this attempt, the study of molecular geometry in crystalline polymers will continue to await such a volume. The hook is basically well-organized with six substantive chapters covering configuration and conformation in polymers; crystal and molecular symmetry; X-ray fiber diffraction; vibrational spectrosopy; potential energy calculations and a review of structural studies on several classes of synthetic polymers sandwiched between short introductory and concluding remarks. A fundamental problem is the author's tendency to perpetuate the artificial harriers between structural studies on bio- and synthetic polymers. Although X-ray fiber diffraction studies of poly(ethy1ene terephthalate), poly(ethylene oxide), etc., and spectroscopic investigations of polyethylene, polyaxymethylene, etc.. are described in considerable detail, DNA and other polynucleotides, cellulose and otherpolysaecharides, collagen, keratin, and synthetic polypeptides are almost totally ignored. The absence of these important fiber-forming substances leads t o a highly distorted view of both the devleopment and state of the art in this discipline. There are also several places where the author abruptly terminates incorrect or incomplete discussions of important technical points. For example, in the chapter on conformation, the fiber period is cursorily described as the "special repeat length of the polymer chain in thk crystalline region" (p. 12). The discussion of symmetry attempts to intraduce simultaneously the Schoenfliesand Hermann-Mauguin nomenclature and will probably be very difficult reading for most beginning graduate students. The chapter on X-ray methods makes several unusual pronouncements. In contradiction with standard practice in most fiber diffraction laboratories, theauthorstates that flat-film techniquesare not suitable for the measurement of the fiher period (p. 16). The Lorentz factor (p. 60) is presented in terms of the single-crystal rotation form despite a substantial body of literature detailing the inadequacy of this approach. No mention is made of the digital image-processing procedures now being developed by I. H. Hall, R. D. B. Fraser, and others. In describing the mathematics of conformational modelling, the author alludes on p. 91 to new equations of his own which replace and improve upon the usually emplayed Miyazawa equations. He proceeds to describe an application of these equations but never informs the reader of their precise formulations. The discussion of potential energy calculations totally ignores the substantial body of work from Ramachandran's laboratory, although this is probably just a consequence of the synthetic polymer bias. The chapter reviewing structures of specific polymers is largely unnecessary. The 2nd 3dition of the "Polymer Handbook" includes % f a rmore comprehensive bibliography and ;urnmation of lattice constants than will be Found herein. Despite these serious problems, Professor radokoro's hook is not without merit. It is, to .his reviewer's knowledge, the first attempt n draw together material widely dispersed hrough the crystallographic, polymer, and ipeetroscopic literature. Previously the

(Continued on page A380)