Catalysis in chemistry and enzymology (Jencks, William P.) - Journal

DOI: 10.1021/ed047pA860.2. Publication Date: December 1970. Cite this:J. ... molecular orbital theory (Offenhartz, Peter O'D.) Journal of Chemical Edu...
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Atomic and Molecular Orbital Theory Peter O'D. Offcnharlz, Amherst College. McGraw-Hill Book Comnanv. -New York, 1970. r i i i + 3 6 i p p . Figs. and tables. 15 X 23.5 cm. $15. ~

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Y m KANGPAN Boston College Chestnut Hill. Mass. 02167

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Catalysis in Chemistry and Enzymology William P. J a c k s , Brsndeis University, Waltham, Massachusetts. McGrsw-Hill Book Co., Inc., New York, 1969. xvi 644 pp. Figs. and tables. 16 X 23.5 om. $14.50.

Quantum chemistry has become one of the essential courses in chemistry departments for almost fifteen years or so. However, what topics should be included in this course and how these subiects should ~ be presented are still diflicult and open questions. This fact is reflected by the great number of textbooks an quantum chemistry published in the last five years. The present book offers another alternative far the quantum chemistry course. The author briefly describes the history of quantum mechanics in the first chapter. The Dirac formulation of quantum mechanics is introduced in chapter two in an elementary manner. After the treatment of angular momentum in ohapter three, the particle in a. box, the harmonic oscillator, creation and snnihilabion operators, rotation-vibration spectroscopy, the hydrogen atom and Slxter-type orbitals and atomic unit- are discussed in chapter four. In chapter five, approximate methods, i.e., the variation theorem and perturbation theory, are briefly described. For perturbation theary, only non-degenerete time independent pertubation theory is treated here. In chapter six, t,he eketronic structure of atoms are discussed in s. quite extensive manner. The electronic states of diatomic molerules are int~odoced in chapter seven, fallowed by a chapter on group theory and granp representat,ions. Ligand field theory is treated in chapter nine and general orbital theory is presented in chapter ten. In chapter ten, the derivation of the Roothaarl-Hartree-Fock equations for closed shells is shown in great detail, and open-shell equations are also presented. Besides these, excited states of closed-shell systemr and confignration interaction are also discussed. Finally, the theory developed in c h a p ter ten is applied to approximate treatments of large molecules. The 7 electron approximation, the Hiickel method, the method of Pariser, Parr and Pople, alter"ant hydrocarbons, complete neglect of differential overlap and the method of Newton, Boer, and Lipscomh are described. Throughout the book, physical and chemical CollCeDt5 rather than mathema-

a n appropriate title from a readers point of view. This book is an extremely clear, readable, yet rigorous account of those mechanisms of catalysis of organic reactions which also are likely to be important in enzyme-catalyzed reactions. Part I of the book (Chapters 1-5) deals wit,h mechanisms of catalysis, Part I1 (Chapters 6-9) describes the forces existent in aqueous solution which effect transition-state structnre and ligand binding to macromolecules, and the final section (Chapters 10 and 11) contains an account of the mechanism of reactions involving carbony1 and acyl groups along with the final chapter (11) on practical kinetics. Chapter 11 is very useful to anyone interested in mechanistic chemistry; it is a short account of the usefulness of kinet,ic data as well as t,helimit,stions and cautions t o be obsenredin collectinz these data. The first chapter t i t l e d ' ~ ~ ~ r o x i m n t i o n examines the catalytic result of bringingreact,ants and cat,alyst into close approximation as in intramolecular catalysis where the two groups are held in close proximity on the same molecule. The chapter on Covalent. Catalysis (2) considers some of the evidence supporting covalent enzyme intermediates and the catalytic advantages of such intermediates. I n the section on nucelophilie cat,alysis there is an extensive discussion of the struct,ural factors influencing nucleophilicity. Electrophilic eat,nlysis is illustmted by reactions requiring thiamine and pyridoxal as coenzymes. This discussion is a particularly informative consideration of the structural features of these coenzymes which allow them to facilitate 60 many reactions which require stabilization of negative charge in the substrate molecule. Chapter 3 considers acid-base catalysis and the role this nlavs in enzvme reactions.

applications. I n my opinion, the present book would be useful for those who are only interested in using the new concepts, or the results of quant,um meohanics to relate to the physical or chemical problems or for formulating experiments imaginei tively and interpreting them correctly. Therefore i t is suitable for use as a quantum chemistry textbook for organic or inorganic chemistry majors and some physical chemistry students. For thearetical chemists, quantum chemists, chemical physicists, or physical ehemisk who will do work which requires understanding of fairly advanced quantum mechanical

ysis. I n his discusfiion (Chapter 4) of the difficult topic of isotope effects, the author is brief yet clear and rigorous. Bot,h primary and secondary isotope effects have been examined, and the author emphasises the cautions whichmust be exercised in the interpretation of isotope effect. The chapler on stress, distortion, and conformational change (Chapter 5) includes explanations of induced-fit, nonproductive binding and strain theory as t.hey pertain t o specificity in enzyme cstalysis. (Calinwd on page A88Z)

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Journal of Chemical Education

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book reviews This book should prove a fairly good text fur graduate student,sinterested in the study of enzyme catnlysis. One difficdty in its use as a text is the overwhelming amaont of detail included; moch of the specific informnt,ion could be omitted in light of t h e interests and hackgronnd of t,he students. Parts of t h e book, such as the chapter on isotope effect, should be required reading fur s t ~ ~ d e ninterested ts in physicnl-organic chemistry. I n addition there is nn shundance of carefully referenced information on specific reaction mechanisms which will now be easily aecessible t o teachers of bath physical-organic chemistry nnd biochemist,ry. JAM^ T . MCFARLAND lnrliluln of Mol~rvlarBiology Uniumitv of Oregon Eugmr, O w g m 8740.9 The Chemistry of Life: Eight Lecturer on the Hirtery of Biochemistry

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Edited l,v Josczlh A'rcdhnm. P. R . S.. Gonville and Caiw CoIIegc, Cambridge, Englnlrtl. Univcrsity Press. Cnmbridge, Ihglaral, 3970. xxx 202 pp. Figs. and piet,ures. W.50.

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This book is n collceliou of eight lectures, given duriug 10% to 1961 i n n s e i k a t Cnmhridgo Uuiversity n ~ , d e rthe suspicesof tho 1)epxrtmnltaf thc IIislory nud Philosophy of Seicwe in Cambridge University. I h c h lecl~trr rovcw n major aspect of tho devslopmcnt of l,iochcmist,ry. Swcn of lhe leol~werwe1.c givc~lnnd written by emi~tent.British I,iocl~omist~s, while the cighth lerlom wns wl.iltw, hy nn ootstrtnding Cacchnslnvakinn professiotral historinn of soio~rrc. Thwe is also illuminating nnd irlt,ercstill~i ~ t ~ ~ ~ d n c t , i u n by the d i t n r . The topics discussed are: photosynthesis, enzymes xnd hiologirnl oxidnlions, x history of microbiolc,gy, bioehemical signposts it) rteuwlogy, nriimnl hormones, vit,nrnins, historicnl f o ~ ~ ~ r d n l i o ofn s modern L~ioahemistry, n r d nineleenth (.entnry p i o n e ~ rBrilish hioelremisls. I h c h lrotwer dcvelaped Iris topic in his own style. The leehrt.es art. well written (ill the British st j e ) and :we illtereslhg to read. I3seh chapter has x hr.ief bibliography. The aver:we letlglh of each lecture ir 15-20 p:lgrs excepl, for bhe one on neurolom (65 pages) nnrl nnimnl hormones (31 pages). Some of lhr rhnptws, notnbly on enzymes mrl b i o h g i d oxidatinn, were written by :m authority in the field, and it~elurlepeizot~alc~,mrnents, while others were merely histurimd sumrnnrias. Some were in~mnplete, e.g., lhc rhlpler 01) photosynt,hesis inrludrd no mcut,iori of the work of Calvin, whilc athor rhnpters were quite complete. This hook is n good hist,oricnl summery of some significant area* i t r biochemistry. The reviewer was p n ~ . t i c ~ ~ l nfnscinaled dy by {.he story of Ludwig Thudit.hum, described as " t h e greatest of all rcrchvnl chemists" hut m e who was not i n f w o r with the scientific lenders nf his day. Thc book .iecms t,o he free from typo-

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Journol o f Chemical Education