Felix Franks - Böcker

The overall theme of Volume 2 is water in crystalline solids: the ice polymorplis, salt and organic hydrates. from simple molecules to proteins, and the nature of the equated proton in solid hydrates (and in the vapour phase). The advent of neutron diffraction, coupled with major instrumental and theoretical developments has led to insights into the structure, energetics and dynamics of hydrated solids.

Interest in water will continue to grow for a long time to come. It will continue to spread over a large number of disciplines and technologies. Research into water in all its aspects has become so diverse that even those with a direct interest find it impossible to keep up with the original literature beyond a very limited range. On the other hand, scientists want to keep in touch with a wide spectrum of basic and applied research on water and the role played by aqueous solvents in physical, chemical, biological, technological and environmental processes. Water Science Reviews contains three or four critical reviews of the type previously published in the seven volume work Water - A Comprehensive Treatise. Some reviews update previously published topics, while others feature areas of Water Sciences that have never yet been reviewed. A common focus is the central position adopted by water in the systems and processes described.

Interest in water in all its forms and in all its properties will continue to grow for a long time to come. It will spread over a large number of disciplines and technologies. Research into water in all its aspects has become so diverse that even those with a direct interest find it impossible to keep up with the original literature beyond a very limited range. On the other hand, scientists want to keep in touch with a wide spectrum of basic and applied research on water and the role played by aqueous solvents in physical, chemical, biological, technological and environmental processes. Water Science Reviews contains three or four critical state-of-the-art reviews of the type previously published in the seven volume work Water - A Comprehensive Treatise. Some reviews will update previously published topics, while others will feature areas of Water Sciences that have never yet been reviewed. A common focus will be the central position adopted by water in the systems and processes described. A selective bibliography will direct interested readers to the original source literature.

The fourth volume of Water Science Reviews presents three fascinating accounts of hydration phenomena in collodial systems. O. Fennell Evans and David Miller provide a reappraisal of the role of water in promoting amphiphilic assembly and structure. Donald Eagland's review of water-soluble polymers highlights those which show unique solution properties or where there is contention as to the explanation for the behaviour. The final review, from Kenneth Newman, deals with the hydration of surfaces, a topic of profound scientific and technological importance.

Interest in water will continue to grow for a long time to come. It will continue to spread over a large number of disciplines and technologies. Research into water in all its aspects has become so diverse that even those with a direct interest find it impossible to keep up with the original literature beyond a very limited range. On the other hand, scientists want to keep in touch with a wide spectrum of basic and applied research on water and the role played by aqueous solvents in physical, chemical, biological, technological and environmental processes. Water Science Reviews contains three or four critical reviews of the type previously published in the seven volume work Water - A Comprehensive Treatise. Some reviews update previously published topics while others feature areas of Water Sciences that have never yet been reviewed. A common focus is the central position adopted by water in the systems and processes described.

Cold is the single most important enemy of life, and this book, first published in 1985, discusses the responses of living organisms to low temperatures. Subfreezing temperatures in particular affect the properties of water, which is essential to life, and the book describes the physics and chemistry of water in the context of physiology. Injury from cooling and the way in which organisms respond and survive, as well as the mechanism of cold hardening in micro-organisms, insects and plants are discussed. The laboratory exploitation of low temperatures to preserve life and to protect labile materials against freeze damage is also considered.

Interest in water will continue to grow for a long time to come. It will continue to spread over a large number of disciplines and technologies. Research into water in all its aspects has become so diverse that even those with a direct interest find it impossible to keep up with the original literature beyond a very limited range. On the other hand, scientists want to keep in touch with a wide spectrum of basic and applied research on water and the role played by aqueous solvents in physical, chemical, biological, technological and environmental processes. Water Science Reviews contains three or four critical reviews of the type previously published in the seven volume work Water - A Comprehensive Treatise. Some reviews update previously published topics, while others feature areas of Water Sciences that have never yet been reviewed. A common focus is the central position adopted by water in the systems and processes described.

Interest in water will continue to grow for a long time to come. It will continue to spread over a large number of disciplines and technologies. Research into water in all its aspects has become so diverse that even those with a direct interest find it impossible to keep up with the original literature beyond a very limited range. On the other hand, scientists want to keep in touch with a wide spectrum of basic and applied research on water and the role played by aqueous solvents in physical, chemical, biological, technological and environmental processes. Water Science Reviews contains three or four critical reviews of the type previously published in the seven volume work Water - A Comprehensive Treatise. Some reviews update previously published topics while others feature areas of Water Sciences that have never yet been reviewed. A common focus is the central position adopted by water in the systems and processes described.

The fourth volume of Water Science Reviews presents three fascinating accounts of hydration phenomena in collodial systems. O. Fennell Evans and David Miller provide a reappraisal of the role of water in promoting amphiphilic assembly and structure. Donald Eagland's review of water-soluble polymers highlights those which show unique solution properties or where there is contention as to the explanation for the behaviour. The final review, from Kenneth Newman, deals with the hydration of surfaces, a topic of profound scientific and technological importance.

Freeze-drying, in the past popular in the food industry, has more recently been adopted by the pharmaceutical industry as a standard method for the production of stable solid preparations. Freeze-drying of Pharmaceuticals and Biopharmaceuticals is the first book to specifically describe this process, as related to the pharmaceutical industry. The emphasis of this book is on the properties of the materials processed, how effective formulations are arrived at, and how they are stored and marketed. Beginning with a historical overview of the process, Freeze-drying of Pharmaceuticals and Biopharmaceuticals briefly describes the processes and equipment involved, including: the physics, chemistry and biochemistry associated with freezing, aspects of formulation development, primary and secondary drying; the economics and engineering of scaling up; and, most importantly, attributes of the dried product. It also discusses in detail the science behind freeze-drying, such as the properties of crystalline and amorphous solids. The book concludes with selected case studies and discusses the future of freeze-drying, advances in alternative drying methods, and concludes with an extensive bibliography. This book, written by a leading expert in the field, is aimed primarily at product and process developers in the biopharmaceutical industry and academia.

An understanding of the behavioural properties of water is fundamental to gaining an appreciation of many scientific processes and principles. Science students and teachers will therefore find Water not only interesting reading but also of considerable relevance to their studies.

Proteins are the servants of life. They occur in all component parts of living organisms and are staggering in their functional var- ty, despite their chemical similarity. Even the simplest single-cell organism contains a thousand different proteins, fulfilling a wide range of life-supporting roles. Their production is controlled by the cell’s genetic machinery, and a malfunction of even one protein in the cell will give rise to pathological symptoms. Additions to the total number of known proteins are constantly being made on an increasing scale through the discovery of mutant strains or their production by genetic manipulation; this latter technology has become known as protein engineering. The in vivo functioning of proteins depends critically on the chemical structure of individual peptide chains, but also on the detailed folding of the chains themselves and on their assembly into larger supramolecular structures. The molecules and their fu- tional assemblies possess a limited in vitro stability. Special methods are required for their intact isolation from the source material and for their analysis, both qualitatively and quantitatively. Proteins are also increasingly used as “industrial components,” e.g., in biosensors and immobilized enzymes, because of their specificity, selectivity, and sensitivity. This requires novel and refined proce- ing methods by which the protein isolate can be converted into a form in which it can be utilized.

The chapters making up this volume had originally been planned to form part of a single volume covering solid hydrates and aqueous solutions of simple molecules and ions. However, during the preparation of the manu­ scripts it became apparent that such a volume would turn out to be very unwieldy and I reluctantly decided to recommend the publication of sepa­ rate volumes. The most sensible way of dividing the subject matter seemed to lie in the separation of simple ionic solutions. The emphasis in the present volume is placed on ion-solvent effects, since a number of excellent texts cover the more general aspects of electrolyte solutions, based on the classical theories of Debye, Huckel, On sager, and Fuoss. It is interesting to speculate as to when a theory becomes "classical." Perhaps this occurs when it has become well known, well liked, and much adapted. The above-mentioned theories of ionic equilibria and transport certainly fulfill these criteria. There comes a time when the refinements and modifications can no longer be related to physical significance and can no longer hide the fact that certain fundamental assumptions made in the development of the theory are untenable, especially in the light of information obtained from the application of sophisticated molecular and thermodynamic techniques.

Since the publication of the previous volumes many new aspects of the physical and life sciences have been developed in which the properties of water play a dominant role. Although, according to its preface, Volume 5 was to be the last one of the treatise, these recent developments have led to a revision of that statement. The present volume and its companion, still in preparation, deal with topics that were already mentioned in the preface to Volume 5 as gaining in importance. The recent development of X-ray and, more particularly, neutron scattering techniques have led to studies of "structure" in aqueous solutions of electrolytes on the one hand, and to the role of water in protein structure and function on the other. Both these topics have reached a stage where reviews of the present state of knowledge are useful. The application of ab initio methods to calculations of hydration and conformation of small molecules has a longer history, but here again a critical summary is timely. The role of solvent effects in reaction kinetics and mechanisms should have had a place in Volume 2 of this treatise, but, as sometimes happens, the author who had taken on this task failed tQ live up to his promise. However, since 1972 the physical chemistry of mixed aqueous solvents has made considerable strides, so that the belated discussion of this topic (by a new author) is built on evidence that was not available at the time of publication of Volume 2.

. The Place of Water among Liquids . . . . . . . . . . . . . . . 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 . . . . . . . . . . Principles of Structure and Spectra: The Born-Oppenheimer Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 . . . . . . . . Perturbed Hartree-Fock Method . 74 .

This Volume, the last of the series, is devoted to water in its metastable forms, especially at sub-zero temperatures. The past few years have wit­ nessed an increasing interest in supercooled water and amorphous ice. If the properties of liquid water in the normal temperature range are already eccentric, then they become exceedingly so below the normal freezing point, in the metastable temperature range. Water can be supercooled to -39°C without too much effort, and most of its physical properties show a re­ markable temperature dependence under these conditions. Although ade­ quate explanations are still lacking, the time has come to review available knowledge. The study of amorphous ice, that is, the solid formed when water vapor is condensed on a very cold surface, is of longer standing. It has achieved renewed interest because it may serve as a model for the liquid state. There is currently a debate whether or not a close structural relation­ ship exists between amorphous ice and supercooled water. The nucleation and growth of ice in supercooled water and aqueous solutions is also still one of those grey areas of research, although these topics have received considerable attention from chemists and physicists over the past two decades. Even now, the relationships between degree of supercooling, nucleation kinetics, crystal growth kinetics, cooling rate and solute concentration are somewhat obscure. Nevertheless, at the empirical level much progress has been made, because these topics are of considerable importance to biologists, technologists, atmospheric physicists and gla­ ciologists.

vi the information collected and discussed in this volume may help toward the achievement of such an objective. I should like to express my debt of gratitude to the authors who have contributed to this volume. Editing a work of this nature can strain long­ established personal relationships and I thank my various colleagues for bearing with me and responding (sooner or later) to one or several letters or telephone calls. My special thanks once again go to Mrs. Joyce Johnson, who bore the main brunt of this seemingly endless correspondence and without whose help the editorial and referencing work would have taken several years. F. FRANKS Biophysics Division Unilever Research Laboratory Colworth/ Welwyn Colworth House, Sharnbrook, Bedford January, 1973 Contents Contents of Volume 1 ............................. . . . . . .. . . .. xv Contents of Volume 3 ........................ '. . . . . . . . . . . . xvi . . . . Contents of Volume 4 . . . . . . . . . . . . . . . . . . . . . . . . .. . . . xvii . . . . . . . . . . . Chapter 1 The Solvent Properties of Water F. Franks 1. Water, the Universal Solvent-the Study of Aqueous Solutions 2. Aqueous Solutions of Nonelectrolytes ................. . 5 2.1. Apolar Solutes ................................. . 6 2.2. Polar Solutes .................................. . 19 2.3. Ionic Solutes Containing Alkyl Residues-"Apolar Electrolytes" ................................... . 38 3. Aqueous Solutions of Electrolytes .................... . 42 3.1. Single Ion Properties ............................ . 42 3.2. Ion-Water Interactions ......................... . 43 3.3. Interionic Effects ............................... . 47 4. Complex Aqueous Mixtures 48 Chapter 2 Water in Stoichiometric Hydrates M. Falk and O. Knop 1. Introduction. . . . . .. . . . . . . . . . . . . . . . . . . . . . . 55 . . . . . . . . . . . . . 2. Symmetry and Types of Environment of the H0 Molecule 2 in Crystals .......................................... 57 vii Contents viii 2.1. Site Symmetry. . . . . . . . . . . . . . . . . . . . . . . . . 57 . . . . . . . . . .

This volume is the last in the series comprising "Water-A Comprehensive Treatise. " It was originally planned to combine aqueous solutions of macro­ molecules and disperse systems in one volume, but largely because of the extensive coverage required by recent developments in aqueous solutions of proteins and synthetic polymers I decided to separate topics dealing with water in disperse systems. The systems treated in the present volume are of a complex nature so that the theoretical frameworks established earlier in Volume 1 and utilized in Volumes 2 and 3 cannot at the present time be applied. On the other hand the systems discussed in Volumes 4 and 5 in particular, border on the many biological and technological areas where important attributes are related to the common factor-water. Included among such diverse problem areas are food processing and preservation, cryopreservation, paper and textile finishing, membrane processes, hemodynamics, etc. It is to be hoped that in days to come some of the results and principles discussed in these five volumes can be applied to improve our understanding of the complex in­ teractions in medically and industrially important spheres of scientific ac­ tivity. An age seems to have passed since the concept of creating this treatise was first discussed, and since work began on Volume 1, much has happened in the science of Water; some of the recent developments were highlighted at this year's Gordon Research Conference in Plymouth, N. H.

Proteins are the servants of life. They occur in all com- nent parts of living organisms and are staggering in their fu- tional variety, despite their chemical similarity. Even the simplest single-cell organism contains a thousand different p- teins, fulfilling a wide range of life-supporting roles. Additions to the total number of known proteins are being made on an increasing scale through the discovery of mutant strains or their production by genetic manipulation. The total international protein literature could fill a medi- sized building and is growing at an ever-increasing rate. The reader might be forgiven for asking whether yet another book on proteins, their properties, and functions can serve a useful purpose. An explanation of the origin of this book may serve as justification. The authors form the tutorial team for an int- sive postexperience course on protein characterization or- nized by the Center for Professional Advancement, East Brunswick, New Jersey, an educational foundation. The course was first mounted in Amsterdam in 1982 and has since been repeated several times, in both Amsterdam and the US, with participants from North America and most European countries. In a predecessor to this book, emphasis was placed on the role of protein isolation in the food industry, because at the time this reflected the interests of most of the participants at the course. Today, isolated proteins for food use are extracted from yeasts, fungal sources, legumes, oilseeds, cereals, and leaves.