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Book Reviews Biomineralization: Principles and Concepts in Bioinorganic Materials Chemistry. Stephen Mann. Oxford University Press, New York, 2001.
With this book, the author successfully bridges the gap between traditional inorganic chemistry textbooks and the primary literature in biomineralization research. While those beginning research in the area will welcome this book, it could also be used as the core of a graduate or advanced undergraduate course. In these cases, links to the primary literature are provided in extensive lists of further reading at the end of each chapter. The book also could serve as a useful supplement to an in-depth bioinorganic chemistry course that includes biomineralization as a subtopic. Finally, because it is written in a familiar style, the book is easy to read and could be enjoyed at a more relaxed level by scientists curious about the subject. As the title indicates, the book is organized according to principles and concepts, most of which have been derived over the past 20-30 years of case studies. After a brief introduction to the book in chapter one, the next two chapters provide a broad overview of subject. Chapter two is a descriptive introduction to biomineral types and functions, while chapter three outlines the general principles and concepts that are covered more thoroughly in subsequent chapters. Chapter four describes the thermodynamics and kinetics principles needed to understand precipitation and crystallization, while chapters five through eight cover in detail the mechanisms and principles that are at the core of the book. Boundry-organized biomineralization, organic matrix-mediated biomineralization, morphogenesis, and biomineral tectonics each are treated in separate chapters. The book closes with a chapter on biomineralinspired materials chemistry. Using examples taken largely from the author’s own research, the link is made between elucidating biomineralization processes and applying them to materials chemistry. The book is written in the style of a textbook with plenty of illustrations, including chemical structures and schematic drawings. Most spectacular, however, are the optical and electron micrographs of the elaborate micron and submicron biomineral objects. As in a textbook, concepts, photos, and illustrations are not provided individual citations, but the extensive lists of further reading at the end of each chapter principally include important entries into the primary literature. Daniel R. Talham University of Florida CG020033L 10.1021/cg020033l
Polymorphism in Molecular Crystals. Joel Bernstein. Oxford University Press, New York, 2002. ISBN 0198506058. Keeping with the spirit of this new book by Joel Bernstein, here’s a quote: “Dear sir or madam will you
read my book it took me years to write will you take a look?” (Lennon and McCartney, 1966). When the Crystal Growth and Design editorial office e-mailed me and asked if I could recommend anybody to do this job, I said, “You bet! I’ll read the book; I’ll take a look”, and what a delight it is to review this eagerly awaited tome. The inner circle of the polymorphism world knew this was coming and knew that it took years to write. It was worth the wait. There are very few books that have attempted to deal specifically with the subject of polymorphism. When I first started in the field, Verma and Krishna’s book was really all that existed. More recently, Garti and Sato produced a volume specifically related to fats and fatty acids, and now, here comes a book that aims to “summarize and to bring up to date the current knowledge and understanding of polymorphism in molecular crystals, and concentrate it in one source”. There is no doubt that this aim has been met. Let’s start with an overall impression. Bernstein writes well, and this makes the going pretty easy. Of course, like most people (I imagine), the first thing I did was to check and see which and how many of my papers were in the bibliography. I counted 12 with nothing major missing. So, my personal ego was satisfied! The developing chapters cover definitions, history, fundamentals of thermodynamics, kinetics and structure, analytical techniques, structure-property relations, details of specific classes of material, and examples of litigation. Nothing seems to have been overlooked. The artwork, which includes many color micrographs, is exceptional. The two chapters on explosive and pigmentary systems are slightly catalog-like in format, and the chapter dealing specifically with pharmaceuticals contains few surprises. This is finesthe beauty is that it’s all here in one place, and that is worth a lot. Likewise, Chapter 2, on fundamentals, largely follows a standard format. I found this a mixed blessing. Because most of the examples of crystallization of polymorphic systems that appear in the following chapters have taken place from solutions, I was disappointed that no attempt was really made to deal with solubility diagrams. On the other hand, one of my all-time favorite sections is 2.4.3 concerning the presentation of polymorphic structures for comparison. In trying to understand the relation between structure and other features, it is essential to have a clear grasp of the similarities and differences between polymorphic structures. For the noncrystallographer, this can be a daunting task. Here, Bernstein outlines the basic rules and works through anthranilic acid to show how graph sets can help. This, together with Chapters 1 (Introduction and Historical Background), 3 (Controlling the Polymorphic Form Obtained), 4 (Analytical Techniques), 5 (Conformational Polymorphism), and 6 (Structure-Property Relationships), forms the meat of the book. Bernstein is on home groundscrystal structures, graph sets, conformational issues, and history. In the latter context, I really appreciated the extracts from Groth’s 1906 book, the discussion of Ostwald’s rule including Findlay’s photos
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of 2,4-dibromoacetanilide (how did he find these?), and in the concluding chapter some extracts from patents. Any reviewer comes with “baggage”, and mine of course is associated with the crystallization process. How does Bernstein address this issue? Actually, he does it with quintessential bravery and vigor. Throughout the book, he makes every attempt to report the solvent and other experimental conditions that led to a certain structure. This is no mean feat, and at one level, is fantastic because there is no other repository of this information other than the original (mostly crystallographic) papers. At another level, it is disappointing to the reader because often, inevitably, these data appear to offer nothing more than recipes. For example, who on earth would guess that crystallization of the κ form of mannitol would require a boric acid/methanol solution? What do such examples tell us about controlling polymorphic form. On this point, Bernstein falls back on an old argument from organic chemistry about thermodynamic and kinetic conditions. This is really about the rates of forward and backward reactions and how far the compositions are from equilibrium. I’m not comfortable with the application of this idea to crystallization. Crystallization processes involve metastability (you cannot grow a crystal at equilibrium!) so that in most systems even though you may cool or evaporate quickly or slowly the crystallization event will occur when the metastable limit is exceeded. Mostly, phase diagrams are not known and almost no one measures the composition of the liquid phase at the point of crystallization; so, whether crystallization has taken place rapidly or slowly is also mostly not known. Here, I think Bernstein has missed a trick. This could have
been a wonderful opportunity to explain how to perform a controlled crystallization experiment at low and high driving forcesswhat to avoid, what to measure, and most importantly, when to look. To do this, he would have needed more about solutions in Chapter 2, and of course, one of the big problems here for any author is that although much structural data exist, very few phase diagrams (solubility curves) are available for polymorphic systems. In the end, this limits our ability to show how thermodynamics and kinetics come together to determine crystallization outcomes and means; luckily, we have more research to do. Having got this off my chest, let me mention a few other gems. Chapter 4 on analytical techniques is excellent. I liked the section on thermal microscopy and thought that there might be some real lessons here for companies contemplating high throughput screening. Chapter 6 on structure-property relationships is also really good. I remember being involved with nonlinear optic materials in ICI in the mid 1980s and particularly enjoyed seeing this topic reviewed. For anyone who might doubt the commercial impact of solid state chemistry, try Chapter 10syou’ll soon change your mind. In the end, the proof of the pudding is in the eating, and in my opinion, Bernstein has served us a nutritional feast here. Enjoy! Roger J. Davey UMIST, Manchester, U.K. CG020039A 10.1021/cg020039a
