Spectroscopy of Pharmaceutical Solids

dk5783fm.pdf......Page 2
Spectroscopy of Pharmaceutical Solids......Page 11
Preface......Page 13
Contents......Page 15
Contributors......Page 19
NATURE OF ELECTROMAGNETIC RADIATION......Page 20
Table of Contents......Page 0
CLASSICAL DESCRIPTION OF ELECTROMAGNETIC RADIATION......Page 22
THE QUANTUM THEORY OF ELECTROMAGNETIC RADIATION......Page 27
IONIZATION AND EXCITATION OF ATOMS......Page 31
DEVELOPMENT OF THE QUANTUM THEORY......Page 36
OVERVIEW OF SPECTROSCOPY......Page 47
SUMMARY......Page 49
General Spectroscopy......Page 50
WAVE MECHANICAL DESCRIPTION OF THE HYDROGEN ATOM......Page 52
Solution of the Angular Equation......Page 56
Solution of the Radial Equation......Page 57
Wave Functions of the Hydrogen Atom and Hydrogen-Like Atoms......Page 59
Energy Levels and Spectroscopy of the Hydrogen Atom......Page 60
Electron Spin......Page 64
The Pauli Exclusion and Aufbau Principles, and Multielectron Atoms......Page 67
Spectroscopy of Core Electron States......Page 70
X-RAY ABSORPTION SPECTROSCOPY......Page 72
XAS Studies of Inorganic Compounds......Page 76
The XAS Studies of Metallo-Proteins......Page 78
REFERENCES......Page 83
X-RAY EMISSION SPECTROSCOPIES......Page 86
X-RAY PHOTOELECTRON SPECTROSCOPY......Page 88
Experimental Details......Page 89
Assignment of Observed XPS Bands and their Chemical Shifts......Page 90
Applications of XPS to the Characterization of Solids......Page 92
X-RAY FLUORESCENCE SPECTROSCOPY......Page 96
Experimental Details......Page 98
Qualitative XRF Analysis......Page 100
Quantitative XRF Analysis......Page 101
REFERENCES......Page 106
MOLECULAR ORBITAL (MO) THEORY OF ORGANIC MOLECULES......Page 109
LCAO-MO THEORY......Page 111
LCAO-MO THEORY AND THE SPECTROSCOPY OF DIATOMIC MOLECULES......Page 115
Symmetry of Polyatomic Molecules and its Effect on their Electronic States......Page 122
Worked Example: The Electronic Spectroscopy of Formaldehyde......Page 126
…Transitions......Page 130
…Transitions......Page 132
Charge Transfer Transitions......Page 135
REFERENCES......Page 137
INTRODUCTION......Page 139
CATEGORIES OF LIGHT REFLECTANCE......Page 140
THEORY ASSOCIATED WITH DIFFUSE REFLECTANCE MEASUREMENTS......Page 142
INSTRUMENTATION FOR THE MEASUREMENT OF DIFFUSE REFLECTANCE......Page 145
QUANTITATIVE MEASUREMENT OF COLOR......Page 147
APPLICATIONS OF UV/VIS DIFFUSE REFLECTANCE SPECTROSCOPY TO THE STUDY OF SOLIDS HAVING PHARMACEUTICAL INTEREST......Page 152
Studies of Color Stability in Solid Dose Formulations......Page 153
Studies of Solid-State Reactions in Formulated Materials......Page 155
USE OF ADSORBED INDICATORS FOR THE EVALUATION OF SURFACE ACIDITY AND BASICITY......Page 159
REFERENCES......Page 165
INTRODUCTION......Page 168
PHOTOPHYSICAL PROCESSES IN ISOLATED ORGANIC MOLECULES......Page 169
PHOTOPHYSICAL PROCESSES ASSOCIATED WITH INTERACTING MOLECULES......Page 174
Intermolecular Energy Transfer......Page 175
Photophysics of Associated Molecules......Page 180
Photophysics in the Solid State......Page 184
Steady-State Photoluminescence Spectroscopy......Page 187
Time-Resolved Luminescence Spectroscopy......Page 190
Photophysical Measurements in the Time Domain......Page 191
Photophysical Measurements in the Frequency Domain......Page 193
PHOTOLUMINESCENCE AND THE STRUCTURE OF ORGANIC MOLECULES......Page 195
STUDIES OF LUMINESCENCE IN THE CRYSTALLINE STATE......Page 196
PHOTOLUMINESCENCE FROM MOLECULES ADSORBED ON SURFACES......Page 201
Xanthene Dyes as Surface Probes......Page 202
Pyrene as a Surface Probe......Page 204
RTP of Adsorbed Luminescent Molecules......Page 205
Photophysical and Mechanistic Studies......Page 207
Studies of Substrate Surfaces Appropriate for RTP Work......Page 209
Analysis of Mixtures......Page 212
Compounds Having Pharmaceutical Interest......Page 213
REFERENCES......Page 215
INTRODUCTION......Page 222
MOTION OF NUCLEI IN MOLECULES......Page 223
ROTATION AND VIBRATION IN DIATOMIC MOLECULES......Page 227
VIBRATIONAL ENERGY LEVELS AND SPECTROSCOPY OF DIATOMIC MOLECULES......Page 230
The Harmonic Oscillator Model......Page 231
Spectroscopy of a Harmonically Oscillating Diatomic Molecule......Page 233
Vibrational Modes and Wave Functions of Polyatomic Molecules......Page 236
Electric Dipole Absorption Spectroscopy of the Fundamental Modes of Polyatomic Molecules......Page 237
Raman Spectroscopy of the Fundamental Modes of Polyatomic Molecules......Page 239
SPECTROSCOPY OF TRANSITIONS ASSOCIATED WITH OVERTONES AND COMBINATIONS OF FUNDAMENTAL VIBRATIONAL MODES......Page 244
The Anharmonic Oscillator Model......Page 245
Overtone Vibrational Spectroscopy......Page 246
SUMMARY......Page 248
REFERENCES......Page 249
INTRODUCTION......Page 251
SOME FUNDAMENTAL PRINCIPLES OF IR ABSORPTION SPECTROSCOPY......Page 252
INSTRUMENTATION FOR THE MEASUREMENT OF IR SPECTRA IN THE SOLID STATE......Page 255
Alkali Halide Pellet......Page 256
Diffuse Reflectance Technique......Page 257
Attenuated Total Reflectance......Page 258
Microspectroscopy......Page 259
TG/IR Analysis......Page 260
Fiber Optics......Page 261
Qualitative Identification of Pharmaceutical Compounds......Page 262
IR Spectral Studies of Polymorphic Systems......Page 264
IR Spectral Studies of Solvatomorphic Systems......Page 267
IR Spectroscopy Studies of Phase Transformations......Page 269
IR Spectroscopic Studies of Manufacture and Processing......Page 271
Quantitative Analytical Applications......Page 272
IR Spectroscopic Studies During the Preformulation Stage of Drug Development......Page 274
Bioanalytical Applications......Page 276
Chemical Mapping and Imaging......Page 279
REFERENCES......Page 281
INTRODUCTION......Page 286
SOME FUNDAMENTAL PRINCIPLES OF THE RAMAN EFFECT......Page 287
Nonresonant Raman Scattering......Page 288
Resonance Raman Scattering......Page 290
Surface-Enhanced Raman Scattering......Page 291
Spectrometer Types......Page 293
Sampling and Data Acquisition......Page 295
GROUP FREQUENCY CORRELATIONS IN RAMAN SPECTROSCOPY AND EFFECTS OF THE SOLID STATE......Page 298
Qualitative Identification of Pharmaceutical Compounds......Page 301
Raman Spectral Studies of Polymorphic Systems......Page 303
Raman Spectral Studies of Solvatomorphic Systems......Page 306
Raman Spectroscopy Studies of Phase Transformations......Page 308
Raman Spectroscopic Studies of Manufacture and Processing......Page 311
Quantitative Analytical Applications......Page 313
Raman Spectroscopic Studies of the Character of Drug Substances in Formulations......Page 317
Chemical Mapping and Imaging......Page 320
REFERENCES......Page 324
INTRODUCTION......Page 328
Molecular-Scale Phenomena......Page 330
Functional Group Effects......Page 332
Water......Page 333
Temperature Effect......Page 336
NIR Transmittance in the Solid State......Page 337
DR Spectroscopy......Page 340
Theoretical Models of DR......Page 342
Particle Size......Page 346
Hardness and Other Physical Parameters......Page 349
Effective Mass Sampled During NIR Analysis......Page 351
PRACTICE OF NIR SPECTROSCOPY......Page 359
At-Line and Off-Line Instruments......Page 360
On-Line Instruments......Page 366
In-Line Instruments......Page 369
Imaging Spectroscopy......Page 372
Information Technology......Page 377
Data Analysis......Page 380
Data-Analysis Objectives......Page 381
Preprocessing......Page 382
Exploratory Data Analysis......Page 387
NIR Calibration and Estimation......Page 396
Method Development......Page 401
Basic Materials Analysis......Page 404
Analysis of Pharmaceutical Polymers......Page 405
Crystalline Morphology......Page 409
Process Development and Scale-Up......Page 412
Interactive Sampling Systems......Page 413
Remote Sensing......Page 418
Analysis of Finished Products......Page 419
ACKNOWLEDGMENTS......Page 420
REFERENCES......Page 421
Introduction......Page 428
Nuclear Spin Interactions......Page 430
Introduction......Page 435
Proton SSNMR......Page 438
Heteronuclear SSNMR......Page 441
Introduction......Page 442
Previous Reviews......Page 443
Decoupling Techniques......Page 445
CP Techniques......Page 448
Spectral Editing......Page 450
Correlation Techniques......Page 454
Chemical Shift Assignments......Page 464
Molecular Structure from Chemical Shifts and Molecular Modeling......Page 465
Quantification Issues......Page 471
CP Kinetics Approach......Page 473
Quantification of Pharmaceutical Materials......Page 479
Quantification of Natural Organic Matter, Wood, and Tar......Page 484
Polymorphism......Page 488
Fluorine Applications......Page 508
Relaxation and Dynamics......Page 514
Stability......Page 530
Domain Characterization......Page 532
Drug–Drug and Drug–Excipient Interactions......Page 534
Beta-Cyclodextrin Complexes......Page 537
Excipient Characterization......Page 541
Atomic Distance Measurements......Page 542
H-Bonds and Proton Transfer......Page 546
Food and Cosmetic Applications......Page 550
REFERENCES......Page 553