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Polymorphism in Molecular Crystals [Hardback]

(, Department of Chemistry, Ben-Gurion University of the Negev, Beer Sheva, Israel)
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Bernstein (chemistry, Ben-Gurion U. of the Negev) presents a comprehensive text and sourcebook on the polymorphism of molecular crystals for practitioners and advanced students in disciplines concerned with the organic solid state. Chapters include historical background; controlling polymorphic form; analytical techniques for studying and characterizing polymorphs; structure-property relations; polymorphism of pharmaceuticals, dyes, pigments, and high-energy materials; and polymorphism and patents. Annotation (c) Book News, Inc., Portland, OR (booknews.com)

Polymorphism - the multiplicity of structures or forms - is a term that is used in many disciplines. In chemistry it refers to the existence of more than one crystal structure for a particular chemical substance. The properties of a substance are determined by its composition and by its structure. In the last two decades, there has been a sharp rise in the interest in polymorphic systems, as an intrinsically interesting phenomenon and as an increasingly important component in the development and marketing of a variety of materials based on organic molecules (e.g. pharmaceuticals, dyes and pigments, explosives, etc.). This book summarizes and brings up to date the current knowledge and understanding of polymorphism of molecular crystals, and concentrates it in one comprehensive source. The book will be an invaluable reference for students, researchers, and professionals in the field.

Recenzijas

... clear, vigorous, well-written and very readable ... There seems to be nothing relevant that Bernstein has not included; his scholarship and command and study of the vast literature are remarkable ... an excellent work. * Current Engineering Practice * Joel Bernstein's book represents the single most important source for the development of critical understanding of polymorphism and its commercial and industrial importance and might well play a decisive role in categorizing and reorganizing problems and endeavours on polymorphism-related research. * Current Engineering Practice * Prof. Joel Bernstein displays an impressive grasp of the subject of polymorphism, making possible a lot of information more accessible to the interesed reader. * Current Engineering Practice * ... an excellent resource book and a very good read ... can be recommended strongly both for content and interest. * Robert Gould, Crystallographic Newsletter * ... a delight to review this eagerly awaited tome ... 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, Cryst. Growth Des. *

Introduction and historical background
1(28)
Introduction
1(1)
Definitions
2(7)
Polymorphism
2(2)
Pseudopolymorphism, solvates, and hydrates
4(4)
Conventions for naming polymorphs
8(1)
Is this material polymorphic?
9(10)
Occurrence of polymorphism
9(1)
Literature sources of polymorphic compounds
10(5)
Polymorphic compounds in the Cambridge Structural Database
15(2)
Powder Diffraction File
17(1)
Patent literature
17(1)
Polymorphism of elements and inorganic compounds
17(1)
Polymorphism in macromolecular crystals
18(1)
Historical perspective
19(8)
Commercial/industrial importance of polymorphism-some additional comments
27(2)
Fundamentals
29(37)
Introduction
29(1)
Thermodynamics of polymorphic molecular crystals
29(13)
The Phase Rule
29(2)
Thermodynamic relations in polymorphs
31(1)
Energy vs temperature diagrams-the Gibbs free energy
32(2)
Enantiotropism and monotropism
34(1)
Phase diagrams in terms of pressure and temperature
35(3)
Heat-of-transition rule
38(1)
Heat-of-fusion rule
38(2)
Entropy-of-fusion rule
40(1)
Heat-capacity rule
40(1)
Density rule
40(1)
Infrared rule
41(1)
Kinetic factors determining the formation of polymorphic modifications
42(3)
Structural fundamentals
45(21)
Form vs habit
46(3)
Structural characterization and comparison of polymorphic systems
49(1)
Presentation of polymorphic structures for comparison
49(17)
Controlling the polymorphic form obtained
66(28)
General considerations
66(1)
Aggregation and nucleation
67(5)
Thermodynamic vs kinetic crystallization conditions
72(2)
Monotropism, enantiotropism, and crystallization strategy
74(1)
Concomitant polymorphs
75(14)
Crystallization methods and conditions
76(4)
Examples of different classes of compounds
80(6)
The structural approach
86(3)
Disappearing polymorphs
89(3)
Control of polymorphic crystallization by design
92(2)
Analytical techniques for studying and characterizing polymorphs
94(57)
Introduction
94(1)
Optical/hot stage microscopy
94(10)
Thermal methods
104(7)
X-ray crystallography
111(14)
Infrared spectroscopy
125(6)
Raman spectroscopy
131(2)
Solid state nuclear magnetic resonance (SSNMR) spectroscopy
133(11)
Scanning electron microscopy
144(2)
Atomic force microscopy (AFM) and scanning tunnelling microscopy (STM)
146(1)
Density measurements
147(1)
New technologies and `hyphenated techniques'
147(1)
Are two samples polymorphs of the same compound?
148(1)
Concluding remarks
149(2)
Conformational polymorphism: intra- and intermolecular energetics
151(37)
Introduction
151(1)
Molecular shape and energetics
152(1)
Intermolecular interactions and energetics
152(4)
The search for examples of conformational polymorphism
156(1)
Presenting and comparing conformational polymorphs
157(1)
Some examples of conformational polymorphism
157(7)
What are conformational polymorphs good for?
164(1)
Computational studies of the energetics of polymorphic systems
165(4)
Some exemplary studies of conformational polymorphism
169(13)
The computational prediction of polymorphs
182(6)
Polymorphism and structure-property relations
188(52)
Introduction
188(1)
Bulk properties
189(34)
Electrical conductivity
189(8)
Organic magnetic materials
197(7)
Photovoltaicity and photoconductivity
204(3)
Nonlinear optical activity and second harmonic generation
207(6)
Chromoisomerism, photochromism, thermochromism, mechanochromism, etc.
213(10)
Thermal phase changes and the thermosalient effect-`hopping' or `jumping' crystals
223(1)
Molecular properties
223(11)
Infrared and Raman spectroscopy
224(1)
UV/Vis absorption spectroscopy
225(6)
Excimer emission
231(3)
Excited state diffraction studies
234(1)
Photochemical reactions
234(3)
Thermal reactions and gas-solid reactions
237(1)
Pressure studies
238(1)
Concluding remarks
239(1)
Polymorphism of pharmaceuticals
240(17)
Introduction
240(1)
Occurrence of polymorphism in pharmaceuticals
241(2)
Drug substances
241(1)
Excipients
242(1)
Importance of polymorphism in pharmaceuticals
243(6)
Dissolution rate and solubility
243(1)
Bioavailability
244(5)
Microscopy and thermomicroscopy of pharmaceuticals
249(1)
Thermal analysis of pharmaceuticals
250(1)
The importance of metastable forms
251(2)
The importance of amorphous forms
253(2)
Concluding remarks
255(2)
Polymorphism of dyes and pigments
257(18)
Introduction
257(2)
Occurrence of polymorphism among pigments
259(1)
Polymorphism in some specific groups of pigments
259(12)
Quinacridones
259(4)
Perylenes
263(1)
Phthalocyanines
264(6)
Some other pigments-old and new
270(1)
Isomorphism of pigments
271(4)
Polymorphism of high energy materials
275(22)
Introduction
275(1)
The `alphabet' of high energy molecular materials
276(2)
Individual systems
278(19)
Aliphatic materials
278(9)
Aromatic materials
287(10)
Polymorphism and patents
297(11)
Introduction
297(1)
Ranitidine hydrochloride
298(3)
Cefadroxil
301(3)
Terazosin hydrochloride
304(1)
Aspartame
305(2)
Concluding remarks
307(1)
References 308(93)
Index 401