The Chemical Educator, Vol. 11, No.5, Media Reviews, © 2006 The Chemical Educator
Handbook of Raman Spectroscopy: From the Research Laboratory to the Process Line. Ian R. Lewis and Howell G. M. Edwards, Editors. Marcel Dekker: New York, NY; Basel, Switzerland, 2001 (http://www.dekker.com). xiii + 1054 pp, hardcover. 18.3 ´ 25.9 cm. $239.95. Ordering Information: email (North, South, and Central America) firstname.lastname@example.org, email@example.com; (Europe, Asia, Middle East, Africa) firstname.lastname@example.org; email@example.com. When ordered in bulk quantities, discounts are offered (For information contact Special Sales/Professional Marketing, Marcel Dekker, 270 Madison Ave., New York, NY 10016; Telephone, (212) 696-9000; FAX, (212) 685-4540). ISBN 0-8247-0557-2.
Sir Chandrasekhara Venkata Raman (1888–1970) [1–4] and K. S. Krishnan’s (1898–1961) reports of 1928 on “a new type of secondary radiation” [5, 6] earned Raman, the Palit Professor of Physics at Calcutta University [7, 8] the 1930 Nobel Prize in Physics “for his work on the scattering of light and for the discovery of the effect named after him” . He was the first Asian to receive a Nobel Prize in science. Applications of the effect have evolved into a standard chemical method.
In his presentation speech Professor Henning Pleijel of Svenska Kungliga Vetenskapsakademien (the Swedish Royal Academy of Sciences), after enumerating some of the applications of the effect known at that time, concluded:
Thus the Raman effect has already yielded important results concerning the chemical constitution of substances: and it is to foresee that the extremely valuable tool that the Raman effect has placed in our hands will in the immediate future bring with it a deepening of our knowledge of the structure of matter .
Pleijel’s prediction has come true to an unanticipated degree as new and multifaceted applications of Raman’s discovery have been developed. The Raman effect [5, 6], the phenomenon observed in the scattering of light as it passes through a transparent medium and undergoes a change in frequency and a random alteration in phase caused by a change in rotational or vibrational energy of the scattering molecules, has evolved into a powerful tool for investigating various aspects of molecular structure.
From its discovery until World War II, when an infrared spectrometer became commercially available, Raman spectroscopy was the predominant vibrational spectroscopic technique. Since the widespread adoption of IR spectroscopy it has undergone two periods of expansion in uses. The first, beginning during the 1960s, coincided with the development of the double monochromator, the laser, and electronic methods of signal detection. The second, current period, beginning in about 1985, has been driven by the introduction of laser-line blocking filters, the demonstration and adoption of FT-Raman spectroscopy, and the adoption of charge-coupled device detectors as the preferred detector.
These instrumental developments have dramatically increased the applications of Raman spectroscopy. Up to the mid-1980s it was considered a purely academic research tool with some industrial applications. Now, two groups are using the technique. The first is composed almost entirely of academics and scientists working in government laboratories, while the second consists of academics, industrial problem solvers, process and control engineers, and quality control technicians who began to use or reuse Raman spectroscopy as a tool from the late 1980s.
Raman spectra can detect interactions between molecules. For example, if hydrogen bonds are present, Raman displacements corresponding to the C–H and C=O vibrations appear at much lower values than normal. Because Raman spectra exhibit fewer peaks than infrared spectra, peak overlap in mixtures is less frequent, making quantitative measurements simpler.
Formerly, the weakness of the scattered radiation was the greatest deterrent to widespread application of Raman spectroscopy as an analytical technique. Furthermore, fluorescence could swamp the effect, only homemade instruments were available, costs were high, samples required long exposure times, spectra of colored samples could not be obtained, and considerable skill was needed to obtain consistent results . Commercial instruments began to appear only during the early 1950s. Because the more intense the primary radiation source, the greater the intensity of the Raman spectra, lasers began to be incorporated into instruments in the 1960s. Porto and Wood’s first use of a laser in Raman spectroscopy in 1962 led to increased interest in the technique . In 1986 Hirschfield and Chase’s report on the feasibility of Fourier-transform Raman spectroscopy provided further impetus to research with Raman’s technique . Also, use of charge-coupled-device detection with conventional instruments contributed to the renaissance of Raman spectroscopy. Combining microscopy with Raman instruments yielded imaging abilities, and advances in optics, improved detectors, and miniature instruments have led to new applications.
Raman studies can now be carried out in situ and even in hostile environments . For example, the Haskin Research Group first proposed the use of Raman spectroscopy for in situ mineralogical analysis in 1994. Its Mars Microbeam Raman Spectrometer (MMRS) was originally under development at the Jet Propulsion Laboratory as part of the Athena scientific instrument rover payload selected for the 2001 and 2003 Mars Surveyor missions, which were cancelled, and the Raman spectrometer was omitted from the Athena payload on the 2003 Mars Exploration Rovers (MER) because it was not yet flight-ready. However, development of the MMRS is continuing in anticipation of a landed Mars mission in 2009 [12, 13].
In short, improvements through the decades since its discovery have transformed a method that earlier was primarily of academic interest into a highly powerful, practical tool with a variety of commercially available instruments and installations in industrial and academic laboratories around the world.
A number of texts on Raman spectroscopy, most of which have concentrated on either theory or instrumentation, FT-Raman, and dispersive spectrometer, are currently available [14–20]. However, according to the editors of the Handbook of Raman Spectroscopy,
When we first conceived this book, there was not a single reference source whose basis was (a) Can Raman spectroscopy be of use? and if it can, (b) what type of instrumentation will allow the user to obtain the most useful data? We have tried to identify as many areas of topical interest as possible, that will be appropriate to the second group of Raman practitioners described above. We have drawn together and blended industrial and academic spectroscopies to produce a comprehensive text for modern Raman spectroscopists (p vi).
Ian R. Lewis, who received his Ph.D. degree in 1992 from the University of Bradford, West Yorkshire, England, is Research Products Manager at Kaiser Optical Systems, Inc., Ann Arbor, Michigan and the author of more than 50 research articles and is a reviewer for several international journals. He has lectured on infrared and Raman spectroscopy and its applications in the U.S.A. and abroad and has chaired sessions at numerous international conferences. In addition to his editorial work on the handbook, he is a coauthor of Chapter 3 and author of Chapter 23.
Howell G. M. Edwards, who received his D.Phil. degree from Oxford University, is Professor of Molecular Spectroscopy in the Department of Chemical and Forensic Sciences at Bradford University. The author of more than 450 articles, he is a frequent international lecturer on the applications of Raman spectroscopy, a Fellow of the Royal Society of Chemistry, Adjunct Scientist of the Mars Express Beagle 2 Mission, and a member of the editorial boards of the Journal of Raman Spectroscopy, Spectrochimica Acta, the Internet Journal of Vibrational Spectroscopy, and the Asian Journal of Spectroscopy. He is also author of the handbook’s final chapter, Chapter 26.
Lewis and Edwards’ handbook, printed on acid-free paper as Volume 28 in Dekker’s Practical Spectroscopy Series, is an international venture; the 48 contributors work in academic, governmental, and industrial laboratories in nine countries (United States, 18; the United Kingdom, nine; The Netherlands, eight; Germany, four; Canada, France, Spain, and Switzerland, two each; and Denmark, one). At least one of them, Charles K. Mann, coauthor of Chapter 6, who shared an office with me at our first teaching positions—at the University of Texas (1955), is deceased.
In one unified compilation the handbook contains 26 chapters, ranging in length from 10 to 104 pages, which include 2869 references to articles, book chapters, books, and dissertations, some as recent as 2000, 558 figures as well as tables, mathematical and chemical equations, and an index (10 double-column pages), which facilitates location of material.
The early chapters deal with the principles of Raman theory, instrumentation and its appropriate selection, important instrumental measurement parameters, use of data for the practitioner’s benefit, and extracting significant analytical information from recorded data. Where appropriate, specific examples are provided to illustrate the necessary concepts. The later chapters give extensive coverage of applications where Raman spectroscopy has proven to be an appropriate technique. Specific case studies provide useful guidelines for the scientist intending to embark on the use of the method as well as the more experienced spectroscopist who plans to expand his or her use of Raman spectroscopy into newer applications.
The chapters, together with their number of figures, references, and pages, are as follows:
1. Theory of Raman Scattering (17 references, 10 pp, the shortest chapter).
2. Evolution of Raman Instrumentation—Application of Available Technologies to Spectroscopy and Microscopy (9 figures, 87 references, 30 pp).
3. Raman Spectroscopy and Its Adaptation to the Industrial Environment (45 figures, 266 references, 104 pp, the longest chapter).
4. Raman Spectroscopy: Confocal and Scanning Near-Field (36 figures, 96 references, 46 pp).
5. Raman Imaging (37 figures, 88 references, 59 pp).
6. The Quest for Accuracy in Raman Spectra (12 figures, 20 references, 25 pp).
7. Chemometrics for Raman Spectroscopy (7 figures, 75 references, 32 pp).
8. Raman Spectra of Gases (27 figures, 280 references, 42 pp).
9. Raman Spectra Applied to Crystals: Phenomena and Principles, Concepts and Conventions (40 figures, 68 references, 74 pp).
10. Raman Scattering of Glass (41 figures, 79 references, 46 pp).
11. Raman Spectroscopic Applications to Gemmology (20 figures, 39 references, 21 pp).
12. Raman Spectroscopy on II–VI-Semiconductor Nanostructures (19 figures, 306 references, 57 pp).
13. In Vivo Raman Spectroscopy (19 figures, 52 references, 26 pp).
14. Some Pharmaceutical Applications of Raman Spectroscopy (7 figures, 52 references, 17 pp).
15. Low-Frequency Raman Spectroscopy and Biomolecular Dynamics: A Comparison Between Different Low-Frequency Experimental Techniques. Collectivity of Vibrational Modes (17 figures, 42 references, 23 pp).
16. Raman Spectroscopic Studies of Ion-Ion Interactions in Aqueous and Nonaqueous Electrolyte Solutions (25 figures, 387 references, 66 pp).
17. Environmental Applications of Raman Spectroscopy to Aqueous Systems (21 figures, 159 references, 49 pp).
18. Raman and Surface Enhanced Resonance Raman Scattering: Applications in Forensic Science (12 figures, 19 references, 16 pp).
19. Application of Raman Spectroscopy to Organic Fibers and Films (13 figures, 101 references, 50 pp).
20. Raman Spectroscopy of Catalysts (11 figures, 222 references, 35 pp).
21. Application of IR and Raman Spectroscopy to the Study of Medieval Pigments (16 figures, 33 references, 28 pp).
22. Raman Spectra of Quasi-Elemental Carbon (43 figures, 121 references, 56 pp).
23. Process Raman Spectroscopy (33 figures, 175 references, 55 pp).
24. The Use of Raman Spectroscopy to Monitor the Quality of Carbon Overcoats in the Disk Drive Industry (11 figures, 37 references, 24 pp).
25. Raman Spectroscopy in the Undergraduate Teaching Laboratory (7 figures, 13 references, 11 pp).
26. Raman Spectroscopy in the Characterization of Archæological Materials (30 figures, 35 references, 34 pp).
In short, Lewis and Edwards’ comprehensive reference/text presents the latest principles of Raman theory, analysis, instrumentation, and measurement along with discussions of the benefits of Raman spectroscopy in a variety of academic and industrial fields as well as its use in new disciplines. I recommend it as an essential guide for general and Raman spectroscopists; organic, inorganic, analytical, polymer, material, and environmental chemists; biochemists; process and chemical engineers; physicists; instrument design specialists; biomedical and biotechnological researchers; forensic scientists; pharmacologists; and upper-level undergraduate and graduate students in these disciplines. It also belongs in both academic and industrial research libraries.
References and Notes
1. Kauffman, G. B. Sir Chandrasekhara Venkata Raman (1888–1970) and Raman Spectroscopy. Chemistry Education 1988, 5 (1) (July–September), 5–8.
2. Kauffman, G. B. Profile of a Scientist: Sir Chandrasekhara Venkata Raman: The Development of Raman Spectroscopy. Today's Chemist 1989, 2(1) (February), 26–27.
3. Miller, F. A.; Kauffman, G. B. C.V. Raman and the Discovery of the Raman Effect. J. Chem. Educ. 1989, 66, 795–801.
4. Kauffman, G. B. Chandrasekhara Venkata Raman—The Man and His Effect: A Diamond Anniversary Retrospect. Chem. Educator 2003, 8, 383–388; DOI 10.1333/s00897030744a.
5. Raman, C.V. A new radiation. Indian J. Phys. 1928, 2, 387–398.
6. Raman, C. V.; Krishnan, K. S. A new type of secondary radiation. Nature (London) 1928, 121, 501–502. By apparent coincidence this classic letter appeared on March 31, 1928, the same day as the lecture published in the Indian Journal of Physics (reference 5).
7. Venkata Raman: Biography. In The Nobel Foundation, Nobel Lectures including Presentation Speeches and Laureates’ Biographies: Physics 1922–1941; Elsevier Publishing Company: Amsterdam—London—New York, 1965; pp 276–277; http://www.nobel.se/physics/laureates/1930/raman-bio.html (accessed Jan 2007).
8. Raman, Sir C. V. The molecular scattering of light. Nobel Lecture, December 11, 1930. In The Nobel Foundation, Nobel Lectures including Presentation Speeches and Laureates’ Biographies: Physics 1922–1941; Elsevier Publishing Company: Amsterdam—London—New York, 1965; pp 267–275; http://nobelprize.org/nobel_prizes/physics/laureates/1930/index.html (accessed Jan 2007).
9. The Nobel Prize in Physics 1930; http://www.nobel.se/physics/laureates/1930 (accessed Jan 2007).
10. Pleijel, H. The Nobel Prize in Physics 1930: Presentation Speech. In The Nobel Foundation, Nobel Lectures including Presentation Speeches and Laureates’ Biographies: Physics 1922–1941; Elsevier Publishing Company: Amsterdam—London—New York, 1965; pp 263–266; http://www.nobel.se/physics/laureates/1930/press.html (accessed Jan 2007).
11. Ferraro, J. R. The 75th Anniversary of the Raman Effect. Chem. Heritage Fall, 2003, 21 (3), 4.
12. Planetary Surface Materials—Haskin Research Group— MMRS: in situ Planetary Raman Spectroscopy. http://epsc.wustl.edu/haskin-group/raman.htm (accessed Jan 2007).
13. in situ Planetary Raman Spectroscopy: Mission & MMRS Teams. http://epsc.wustl.edu/haskin-group/Raman/missions.htm.
14. Gilson, T. R.; Hendra, P. J., Eds. Laser Raman Spectroscopy; Wiley-Interscience: New York, 1970.
15. Lascombe, J.; Huong, V., Eds. Raman Spectroscopy; Wiley: New York, 1982.
16. Chang, R. K.; Furtak, T. E., Eds. Surface Enhanced Raman Spectroscopy; Plenum Press: New York, 1982.
17. Parker, F. S. Applications of Infrared, Raman, and Resonance Raman Spectroscopy and Biochemistry; Plenum Press: New York, 1983.
18. Phillips, D.; Atkinson, G. H. Time-Resolved Laser Raman Spectroscopy; Taylor & Francis: London/New York, 1987.
19. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds: Theory and Applications in Inorganic Chemistry (Volume A); Applications in Coordination, Organometallic, and Bioinorganic Chemistry (Volume B); 5th ed., Wiley-Interscience: New York, 1997.
20. Ferraro, J. R.; Nakamoto, K.; Brown, C. W. Introductory Raman Spectroscopy, 2nd ed.; Academic Press: Boston, MA, 2002.
George B. Kauffman
California State University, Fresno, firstname.lastname@example.org
Biological Inorganic Chemistry: Structure & Reactivity. Ivano Bertini, Harry B. Gray, Edward I. Stiefel, and Joan Selverstone Valentine, Editors. University Science Books: 55D Gate Five Road, Sausalito, CA 94965, 2007. www.uscibooks.com. Figures, tables, xxv + 739 pp; 21.0 ´ 27.1 cm; hardcover. $98.25; a 10% discount is offered if orders are placed through the Web site: https://uscibo.c2.ixwebhosting.com/html/fr_order_form.htm; ISBN 1-891389-43-2.
In the preface to this long awaited and unique textbook for 21st-century courses in bioinorganic chemistry the editors declare:
Life depends on the proper functioning of proteins and nucleic acids that very often are in combinations with metal ions. Elucidation of the structures and reactivities of metalloproteins and other metallobiomolecules is the central goal of biological inorganic chemistry (p xxiii).
One of the great challenges in the field is deducing how a specific gene sequences for a metalloprotein. Knowledge of genomic maps should contribute to the goal of understanding the molecular mechanisms of life. Specific annotations to a sequence frequently suggest that metals are required for protein function, but it is currently not possible to read that information from the sequence alone. Bioinorganic research is critically important in this context.
Eleven elements are necessary for all forms of life on Earth, and some 13 more are essential components of most living species. An additional seven or eight elements are required by some organisms. The more than 30 elements required for the diversity of life are highlighted in a periodic table of elements of biological relevance (p 2).
The six familiar elements—carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulfur, which are adequately dealt with in biochemistry textbooks, provide the building blocks for major cellular components including proteins, nucleic acids, lipids-membranes, polysaccharides, and metabolites. However, life cannot survive with only these principal elements, and more than 20 additional elements are needed for most species to function. Nerve impulse conduction, hydrolysis and formation of adenosine triphosphate (ATP), gene expression regulation, control of cellular processes and signaling, and catalysis of many key metabolic reactions require elements beyond the “big six.” Understanding the roles that metallic and nonmetallic elements play in biological systems is the goal of biological inorganic chemistry and the theme of the book under review.
The elements involved in the following life processes include: Na, K, and Cl, charge balance and electrolytic conductivity; Ca, Zn, Si, and S, structure and templating; Ca, B, and NO, signaling; P, Si, and C, Brønsted acid–base buffering; Zn, Fe, Ni, and Mn, Lewis acid–base catalysis; Fe, Cu, and Mo, electron transfer; V, Fe, Co, Ni, Cu, Mo, and W, group transfer (for example, CH3, O, and S); V, Mn, Fe, Co, Ni, Cu, W, S, and Se, redox catalysis; H, P, S, Na, K, and Fe, energy storage; and Ca, Mg, Fe, Si, Sr, Cu, and P, biomineralization. The structures of many components of the systems that evolution has adapted to perform these essential functions are now known. Also, many relationships between structure and function have been clarified, and the electronic, structural, mechanistic, and genetic underpinnings of these relationships are being revealed for the first time. Furthermore, bioinorganic chemistry has deeply impacted environmental science and medicine, which are dealt with in Chapters II and VII of the book, respectively.
The book has been many years in the making and was class-tested both at Princeton University and the University of California, Los Angeles and revised and re-revised before publication. The suggestions of students who were taught with it were incorporated into the text.
The editors of Biological Inorganic Chemistry are all leading contributors to the field who have contributed chapters in addition to their editorial duties. Ivano Bertini (b. 1940), Professor of Chemistry at the Centro di Risonanze Magnetiche (CERM, Magnetic Resonance Center), Università degli Studi di Firenze, received his Ph.D. (1964) and Libera Docenza (1969) degrees from the Università degli Studi di Firenze. His research interests include studies of paramagnetic metalloproteins from the genetic expression to spectroscopic investigations and the solution structure of paramagnetic metalloproteins by nuclear magnetic resonance. He is a coauthor of Chapters I, III, IV, and X.1.
Harry B. Gray (b. 1935), Arnold O. Beckman Professor of Chemistry and Director of the Beckman Institute, California Institute of Technology, received his B.S. degree (1957) from Western Kentucky University and his Ph.D. degree (1960) from Northwestern University, where he worked with Fred Basolo and Ralph G. Pearson. After spending a postdoctoral year (1960–1961) with Carl J. Ballhausen at the University of Copenhagen, he became Assistant Professor of Chemistry (1961–1963), Associate Professor (1963–1965), and Professor (1965–1966) at Columbia University. A member of the National Academy of Sciences (NAS) since 1971, he has studied the synthesis, structures, and reactions of inorganic coordination compounds and the electronic structures and electron-transfer reactions of metalloproteins. His American Chemical Society awards include the Award in Pure Chemistry (1970), Award in Inorganic Chemistry (1978), Award for Distinguished Service in the Advancement of Inorganic Chemistry (1984), Alfred Bader Award in Bioinorganic or Bioorganic Chemistry (1990), Priestley Medal (the society’s highest honor, 1991), and the George C. Pimentel Award in Chemical Education (2001). In addition to 16 honorary degrees, he was the first Luigi Sacconi Memorial lecturer (1996), and he received the National Medal of Science, the United States’ highest award to a scientist (1986), and the NAS Award in the Chemical Sciences (2003). He is the coauthor of Chapters I and X.2.
Edward I. Stiefel (1942–2006), the first holder of the Ralph W. Dornte Lecturer with the rank of Professor of Chemistry at Princeton University since 2001, received his A.B. degree from New York University and his Master’s and Ph.D. degrees (1967) from Columbia University, where he worked with Harry B. Gray. He was a faculty member at the State University of New York, Stony Brook, Senior Scientific Advisor at ExxonMobil Corporate Strategic Research, and Senior Investigator at the Charles F. Kettering Research Laboratory. He was the principal architect of the cleanup of the “Exxon Valdez” oil spill in Alaska (1989). His research involved the bioinorganic, coordination, and environmental chemistry of transition metal ions, particularly the roles played by “trace” elements such as iron, molybdenum, and tungsten in the biogeochemical cycles of the major elements such as carbon, nitrogen, and sulfur; nitrogen fixation; the molybdenum cofactor; the role of metalloenzymes and catalysts in the origins and evolution of life; and the role of ferritin and bacterioferritin, which he codiscovered, in the storage, sequestration, and delivery of iron for cellular processes. The author of more than 150 articles, author or editor of several books [1–3], a holder of 30 U.S. patents, and the 2003 Luigi Sacconi Memorial Lecturer, he received the Exxon Golden Tiger Award for Technical Innovation (1996) and the ACS Award in Inorganic Chemistry (2000).
Stiefel died of pancreatic cancer on September 4, 2006 in New Brunswick, NJ at the age of 64 [4–7]. An unusual interdiscliplinary chemist who bridged industry and academia, pure chemistry and applications, he was lauded by Harry B. Gray as “a scholar’s scholar….In every problem he tackled, he had a phenomenal ability to see the big picture” . He was the coauthor of Chapters I and XII.6 and author of Chapter II, and the book is “dedicated to Jeannette [his widow, who assisted with the editing] and Ed Stiefel, with admiration and affection.”
Joan Selverstone Valentine (b. 1945), Professor of Chemistry and Biochemistry at the University of California, Los Angeles, received her A. B. (1967) and Ph.D. (1971) degrees from Smith College and Princeton University, respectively. She was a Research Associate at Stanford University (1971) and a National Institutes of Health Postdoctoral Fellow (1972) at Princeton. A recipient of the Alpha Chi Sigma Faculty Research Award, Smith Medal, and McCoy Award, she was the 2006 Luigi Sacconi Memorial Lecturer and is Editor-in-Chief of Accounts of Chemical Research. She was elected to the National Academy of Sciences in 2006. Her current research involves transition metals, chemistry and biochemistry of dioxygen and superoxide, copper–zinc superoxide dismutase and Lou Gehrig’s disease, metalloprotein redesign by site-directed mutagenesis, metalloenzymes, models for metal-containing oxygenase enzymes, metalloporphorin chemistry, and yeast studies of oxidative stress and antioxidants. She is the coauthor of Chapter I and Tutorial II and author of Chapters XI.1 and XI.2.
Although most (39) of the Biological Inorganic Chemistry’s 62 academic and industrial contributors are Americans, it is an international venture with world renowned authorities from the United Kingdom (six), Italy (five), Portugal and Sweden (three each), Germany (two), and Canada, France, Japan, and New Zealand (one each).
A special feature of this book is its use of the strong connection to the genomic revolution that has dramatically enhanced our ability to define the function of gene products in living organisms. The volume is divided into two main parts. Part A (ca. 28 percent of the text) contains general overviews of broad areas of the field and introductory material necessary for understanding the material in Part B. These chapters are generally longer, more pedagogically oriented, and contain bibliographies allowing the reader to access the material in further depth. Chapters III and IV are prerequisites for studying much of the material in the text. Chapters II and V–VII are overviews of large sub-areas of bioinorganic chemistry. Part B (ca. 71 percent of the text) contains more specific treatments of metal ions in biological systems and provides detailed coverage with general and specific cited references. Its goal is to bring the reader up to state of the art in each sub-area of the field.
The 14 chapters are divided into numbered sections and subsections, each with classified bibliographies, which include not only thousands of articles and books as recent as 2005 but also web sites. Hundreds of numbered figures and unnumbered figures as well as chemical and mathematical equations and tables (some as long as three pages) are provided. There is a separate 24-page section (between pp 646 and 647) of figures in color that appear in black and white elsewhere in the book. The two tutorials (pp 657–694 and pp 695–712) greatly enhance the pedagogical value of the volume, and the editors recommend that readers consult them before dealing with those parts of the text that require a strong background in biology and biochemistry.
Appendix I (3-1/2 double-column pages) alphabetically lists the abbreviations used in the text from ABC (ATP binding cassette) to ZRE (Zinc responsive element). Appendix II (nine double-column pages) is a glossary of terms common in bioinorganic chemistry from Acetogens to Zinc finger. Appendix III, “The Literature of Biological Inorganic Chemistry” (two double-column pages), provides an annotated, classified list of journals, review series, texts, and special issues.
Recently a large number of three-dimensional metalloprotein structures have been determined by X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy. The editors recommend that the reader examine these structures in color in the Protein Data Bank (PDB). Therefore, for every protein for which a 3D structure is available, the four-letter PDB ID is given. By accessing the PDB on the Internet (http://www.rcsb.org/pdb) readers can view in full detail and manipulate the structure on their computers. Appendix IV (one page) introduces readers to the PDB so that they can view, rotate, zoom, and color structures. Since examining these images in conjunction with the text will help readers get a feel for any given structure and understand the textual material, the editors suggest that use of the PDB be an integral part of any course based on their text.
A nine triple-column-page index in small type makes this textbook extremely user-friendly.
The contents of the volume should give prospective buyers some idea of its coverage of the various topics:
· • Chapter I. Introduction and Text Overview (three sections, one figure, 3 pp, the shortest chapter)
Part A. Overviews of Biological Inorganic Chemistry (129 pp)
· Chapter II. Bioinorganic Chemistry and the Biogeochemical Cycles (seven sections, 15 figures, 24 pp)
· Chapter III. Metal Ions and Proteins: Binding, Stability, and Folding (six sections, 16 figures, 11 pp)
· Chapter IV. Special Cofactors and Metal Clusters (three sections, six figures, four tables, three schemes, 14 pp)
· Chapter V. Transport and Storage of Metal Ions in Biology (eight sections, six figures, one table, 21 pp)
· Chapter VI. Biominerals and Biomineralization (four sections, 12 figures, one table, 16 pp)
· Chapter VII. Metals in Medicine (six sections, 15 figures, five tables, 30 charts, 41 pp)
Part B. Metal Ion Containing Biological Systems (516 pp)
· Chapter VIII. Metal Ion Transport and Storage (six sections, 16 figures, 36 pp)
· Chapter IX. Hydrolytic Chemistry (five sections, 44 figures, five tables, 54 pp)
· Chapter X. Electron Transfer, Respiration, and Photosynthesis (four sections, 53 figures, six tables, 90 pp)
· Chapter XI. Oxygen Metabolism (eight sections, 77 figures, six tables, 124 pp, the longest chapter)
· Chapter XII. Hydrogen, Carbon, and Sulfur Metabolism (seven sections, 64 figures, three tables, 114 pp)
· Chapter XIII. Metalloenzymes with Radical Intermediates (seven sections, 37 figures, three tables, two schemes, 56 pp)
· Chapter XIV. Metal Ion Receptors and Signaling (four sections, 34 figures, 42 pp)
· Tutorial I. Cell Biology, Biochemistry, and Evolution (five sections, 14 figures, four tables, 38 pp)
· Tutorial II. Fundamentals of Coordination Chemistry (eight sections, 11 figures, one table, 18 pp)
The editors assert:
Biological inorganic chemistry is a very hot area. It has been our good fortune to work with many exceptionally talented contributors in putting together a volume that we believe will be a valuable resource both for young investigators and for more senior scholars in the field (p xxiii).
I concur with their statement, and I heartily recommend this exciting book as an excellent senior- and graduate-level textbook as well as a reference source for both students and seasoned researchers alike. With its cutting-edge material, it should remain definitive for many years to come.
1. Stiefel, E. I.; Coucouvanis, D.; Newton, W. E. Molybdenum Enzymes, Cofactors, and Model Systems; Oxford University Press: Oxford/New York, 1993.
2. Stiefel, E. I.; Matsumoto, K., Eds. Transition Metal Surface Chemistry: Biological and Industrial Significance; Oxford University Press: Oxford/New York, 1996.
3. Karlin, K. D.; Stiefel, E. I., Eds. Progress in Inorganic Chemistry, Vol. 52: Dithiolene Chemistry: Synthesis, Properties, and Applications; John Wiley & Sons: Hoboken, NJ, 2003.
4. Morel, F. M. M.; Groves, J. T. Retrospective: Edward I. Stiefel (1942–2006). Science December 1, 2006, 314, 1406.
5. Dr. Edward I. Stiefel, 64, Chemistry Professor, Princeton University. http://www.uscibooks.com/stiefel.htm (accessed Jan 2007).
6. Prof. Edward I. Stiefel. http://www.cerm.unifi.it/ FondSacc/stiefel.html (accessed Jan 2007).
7. Dismukes, G. C.; Hecht, M. H.; Chianelli, R.; Spiro, T. G.; Groves, J. T. Remembering Edward I. Stiefel. J. Inorg. Biochem. January, 2007, 101 (1), vii–viii.
George B. Kauffman
California State University, Fresno, email@example.com
Multiple Bonds between Metal Atoms 3rd Edition. F. Albert Cotton, Carlos A. Murillo, and Richard A. Walton, Editors. Springer Science and Business Media, Inc.: New York/Boston/Dordrecht/London/Moscow, 2005 (http://springeronline.com). xxx + 818 pp, hardcover. 17.2 ´ 25.7 cm. $149.00. Ordering Information: email, firstname.lastname@example.org; Springer, 233 Spring Street, New York, NY 10013; Telephone, (212) 460-1500; (800) SPRINGER; FAX, (212) 460-1575. ISBN 0-387-25084-0; online version: ISBN 0-387-2582904.
The renaissance of inorganic chemistry that began in the 1950s  progressed, like most scientific advances, on a number of fronts by a vast number of researchers, usually in uncoordinated steps. However, occasionally a large area of chemistry is primarily the result of the work of a single group. According to 1981 Nobel laureate Roald Hoffmann, in his foreword to the first edition of Multiple Bonds between Metal Atoms, universally recognized as a classic:
Such a story is that of metal–metal bonding. A recognition of the structural and theoretical significance of the Re–Re bond by F. A. Cotton in 1964  was followed by a systematic and rational exploration of metal–metal bonding across the transition series. Cotton and his able co-workers have made most such complexes. The consistent and proficient use of X-ray crystallography results in their studies, not only for structure determination but as an inspiration to further synthetic chemistry, has served as a model for modern inorganic research. Much of the chemistry of metal–metal multiple-bonded species—and interesting chemistry it is indeed—is due to F. A. Cotton and his students. Throughout this intellectual journey into fresh chemistry they have been guided by a lucid theoretical framework. Their bounteous achievement is detailed in this book. I want to record here my personal thanks to them for providing us with the psychological satisfaction of viewing a scientific masterpiece [3, p xiii].
Although Cotton’s determination of the structure of the [Re2Cl8]2– ion was initially considered by many chemists as an “anomaly” or rare bonding mode, his subsequent work established that this ion was the progenitor of a vast new area of chemistry. Because by the early 1980s the synthetic methodologies, reaction chemistries, and bonding theories were well understood and had reached a level of maturity to justify a comprehensive treatise, Cotton and Walton wrote their monograph on this class of inorganic molecules that do not conform to classical bonding theories. They placed in historical perspective the most important discoveries in the field and discussed all the pertinent literature through the end of December, 1980, while referring to key developments emerging during the early part of 1981, when the manuscript was in press.
During the decade following the publication of Multiple Bonds the field of multiple metal–metal bond chemistry underwent a much more rapid growth than in all the period prior to 1981, and metal–metal bonding became accepted as a major pattern in transition metal complexes, especially in low oxidation states. This fact and the favorable response to the first edition caused the authors to write a second edition , which included not only complete coverage of those topics appearing in the first edition but also all significant advances published up to December, 1900 as well as most of the literature appearing throughout 1991, the period of the final stages of manuscript preparation. The dramatic increase in the literature necessitated some compromise in the depth of certain topics in order to keep the book to a reasonable length.
Several years after the publication of the 2nd edition, it became clear to Cotton and Walton that a new up-to-date monograph would be needed and that, because of the accelerating expansion of research in the field, two or even three authors could not deal with the daunting task of preparing such a monograph. Therefore they and Carlos A. Murillo invited 11 chemists, all with the ability to write authoritatively by virtue of their own hands-on research experience, to contribute to a multiauthored volume. The result is the present 3rd edition, dedicated “to all of our past and present coworkers.” All 14 coauthors, including the editors, work in American university or governmental laboratories, and six of them hail from Texas A&M University, where Cotton has worked since 1972.
Frank Albert (“Al”) Cotton, born in the year (1930) and place (Philadelphia, PA) of my birth, is the W. T. Dougherty–Welch Foundation Distinguished Professor of Chemistry and Director of the Laboratory for Molecular Structure and Bonding at the Texas A&M University. He received his A.B. (1951) and Ph.D. (1955) degrees from Temple University and Harvard University, respectively. Al Cotton and his career can only be described in superlatives. His research, which has resulted in more than 1600 publications, and its impact on inorganic chemistry are unparalleled, and his work on metal–metal bonds, particularly on quadruple bonds, is “one of the stunning creative accomplishments of twentieth-century chemistry” . Furthermore, his research, teaching, textbook writing, and formulation of national policy for science and technology have earned him almost every major award, including the National Medal of Science (1982); the Priestley Medal (1998), the American Chemical Society’s highest honor; and two dozen honorary degrees. For more than two decades he has ranked consistently with Nobel laureates Linus Pauling and John A. Pople as one of the three most cited authors in chemistry. The Cotton Medal, named in his honor to recognize excellence in chemical research, has been awarded annually since 1995. Cotton coauthored Chapter 1 and wrote Chapters 3, 4, and 16 of the 3rd edition of Multiple Bonds. Al has recently suffered a cerebral hemorrhage. His many friends and colleagues wish him a full and complete recovery.
Carlos A. Murillo (b. 1951), Senior Lecturer in Chemistry at Texas A&M University, received his B.S. degree from the Universidad de Costa Rica in 1973 and his Ph.D. degree from Texas A&M in 1976. He collaborated with Cotton on the latest (6th) edition of one of the most popular and widely used inorganic texts of all time, colloquially known as Cotton and Wilkinson . He coauthored Chapter 1 and wrote Chapters 2, 11, and 14 of Multiple Bonds.
Richard A. Walton (b. 1939), the John A. Leighty Distinguished Professor of Inorganic Chemistry at Purdue University, received his B.Sc. (1961) and Ph.D. (1964) degrees from the University of Southampton, England and served as a Postdoctoral Fellow at the University of Manchester (1964) and as a Research Associate at the Massachusetts Institute of Technology (1965). His research interests have involved the preparation, structure, and reactivity of transition metal halides; electrochemistry of transition metal complexes; and polyhydride complexes of the heavier transition metals. He is particularly concerned with dimetal complexes containing metal–metal quadruple bonds and electron-rich triple bonds as well as the exploitation of the chemical and electrochemical redox properties of transition metal complexes as a means of generating highly reactive species in unusual oxidation states. He coauthored Chapter 1 and wrote Chapter 8 of Multiple Bonds.
Every chapter of the 3rd edition is intended to be comprehensive if not encyclopedic. The individual contributors attempted to mention all the pertinent literature references, although the extent of the emphasis accorded to each article necessarily varies. Inasmuch as the literature is now so voluminous, several of the topics that might have been included (or were included in the 2nd edition) have been omitted or were dealt with in only limited detail, for example, treatment of metal–metal bonding in edge-sharing and face-sharing bioctahedra and metal cluster compounds of rhenium. Also, the immense field of catalysis by dirhodium compounds has been restricted to only the area of chiral catalysts.
Physical properties and bonding of many compounds are generally described in two places in the book to varying degrees. Some specific reports on compounds of certain metals are found in the first 15 chapters, while nonelement specific comprehensive discussions are given in Chapter 16. A 14-page list (pp 797–810) provides a selection of the less common abbreviations used in the book. Because the volume is organized by element (or group of elements) and each chapter is divided into numerous sections and subsections with inclusion of extensive tables, the table of contents (pp xxi–xxx) plays the part of an index to a major extent. The eight-double-column-page index (pp 811–818) is thus limited to general topics and concepts that occur often throughout the book, and in most cases individual compounds are not listed there.
The 16 chapters, together with their number of references and pages, should be of interest to owners of previous editions, who are contemplating purchasing the latest edition:
1. Introduction and Survey (66 references, 21 pp).
2. Complexes of the Group 5 Elements (36 references, 11 pp, the shortest chapter).
3. Chromium Compounds (119 references, 34 pp).
4. Molybdenum Compounds (597 references, 114 pp).
5. Tungsten Compounds (150 references, 19 pp).
6. X3M≡MX3 (278 references, 48 pp).
7. Technetium Compounds (81 references, 19 pp).
8. Rhenium Compounds (438 references, 106 pp).
9. Ruthenium Compounds (216 references, 54 pp).
10. Osmium Compounds (71 references, 16 pp).
11. Iron, Cobalt and Iridium Compounds (52 references, 18 pp).
12. Rhodium Compounds (845 references, 125 pp, the longest chapter).
13. Chiral Dirhodium(II) Catalysts and Their Applications (200 references, 42 pp).
14. Nickel, Palladium and Platinum Compounds (221 references, 35 pp).
15. Extended Metal Atom Chains (86 references, 38 pp).
16. Physical, Spectroscopic and Theoretical Results (425 references, 90 pp).
Multiple Bonds between Metal Atoms is among the more than 150 new chemistry books per year that are made available in electronic format in the Springer eBook Collection advertised as “the world’s most comprehensive digitized scientific, technical and medical (STM) book collection,…the first online book collection especially made for the requirements of researchers and scientists.” The collection, which currently consists of more than 12,000 books and increases by more than 300 books annually, is accessible on http://springerlink.com/books, and is intended to increase the rapidity of newly published research.
The collection employs the “portability, searchability, and unparalleled ease of access of PDF and HTML data formats to make access as convenient as possible.” It is designed to provide instantaneous, convenient access to book content wherever and whenever needed, is hyperlinked through easy-to-use browsing and search functions, is searchable on book chapter level, and is integrated with Springer Online Journals. For additional information or to find the local Springer Licensing Manager log onto http://springer.com/ebooks. Also, visit http://reference.springerlink.com for complete details or to sign up for a free 30-day trial.
The 3rd edition of Multiple Bonds between Metal Atoms deals with one of the most active fields of inorganic chemistry that embraces all but two of the d-block transition metals in periodic groups 5–10. It presents an extensive, critical review and discussion of preparations, reactions, bonding, and physical properties of more than 4000 compounds with metal–metal bonds of orders 0.5 to 4, and about 2500 references are cited. I am pleased to recommend it to inorganic and materials chemists and to all scientists concerned with the synthesis, spectroscopy, and structures of transition metal compounds. It also deserves a prominent place on the shelves of academic, industrial, and governmental research libraries.
References and Notes
1. Nyholm, R. S. The Renaissance of Inorganic Chemistry. J. Chem. Educ. 1957, 34, 166–169.
2. Although chromium(II) acetate, Cr2(m-O2CMe)4(H2O)2, prepared by Eugène-Melchoir Peligot in 1844, was the first discovered compound to contain a quadruple bond (a chemical bond between two atoms involving eight electrons that is an extension of the familiar double and triple bonds), its unusual bonding was not recognized for more than a century. It was not until 1964 that a quadruple bond was first characterized—by F. Albert Cotton—in potassium octachlorodirhenate(III), K2 [Re2Cl8]·2H2O).
3. Cotton, F. A.; Walton, R. A. Multiple Bonds between Metal Atoms; foreword by Roald Hoffmann; John Wiley & Sons: New York, NY; Chichester, England, 1982; R. E. Krieger Publishing Co.: Malabar, FL, 1988; xiv + 466 pp.
4. Cotton, F. A.; Walton, R. A. Multiple Bonds between Metal Atoms; 2nd edition; foreword by Jack Lewis; Clarendon Press: Oxford, England, 1993; xxii + 787 pp.
5. Frank Albert Cotton. Contributions to Science. http://www.chem.tamu.edu/rgroup/cotton/ (accessed Jan 2007).
6. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry; 6th Edition; John Wiley & Sons: New York, NY, 1999. For a review see Kauffman, G. B. Chem. Educator 1999, 4, 268–270.
George B. Kauffman
California State University, Fresno, email@example.com