Vibrational Spectroscopy of Biological and Polymeric Materials

Cover Page......Page 1
Title Page......Page 4
ISBN 1574445391......Page 5
Preface......Page 8
Acknowledgments......Page 10
Editors......Page 12
Contributors......Page 14
Table of Contents......Page 16
1 Studying the Viscoelastic Behavior of Liquid Crystalline Polyurethanes Using Static and Dynamic FT-IR Spectroscopy......Page 18
1.1 Introduction......Page 19
1.2.2 Theory of Dynamic Infrared Spectroscopy......Page 21
1.2.3 Two-Dimensional Infrared Correlation Spectroscopy......Page 23
1.3.1 Static Linear Dichroism......Page 25
1.3.2 Dynamic FT-IR Spectroscopy......Page 26
1.4.1 Overall Synthetic Design26......Page 27
1.4.2 Molecular Architecture and Structure......Page 30
1.4.3 Dichroic Ratio of LC Segmented Copolymer......Page 33
1.4.4 Orientation Function of Polyurethane Molecular Components......Page 35
1.4.5 Interdependence of the Orientation Behavior of LC Layers and Hard Segment Domains......Page 39
1.4.6 In-Phase and Out-of-Phase Dynamic Spectra48......Page 40
1.4.7 Viscoelastic Response of the SCLCP......Page 44
1.5 Conclusions......Page 47
References......Page 49
2 Stress/Strain Measurements in Fibers and Composites Using Raman Spectroscopy......Page 52
2.1 Background......Page 53
2.2.1 Conventional Measurements......Page 55
2.2.2.1 Fiber Optic Microprobes......Page 56
2.2.2.2 Microprobes Incorporating Solid-State Lasers......Page 57
2.3.1 Application of Tensile and Compressive Loading......Page 59
2.3.2.1 Carbon Fibers......Page 62
2.3.2.2 Aramid Fibers......Page 63
2.4 Converting Spectroscopic Data into Fiber Stress/Strain Curves in Tension and Compression......Page 64
2.5 Assessing the Efficiency of the Fiber/Matrix Bond in Composites......Page 66
2.5.2.1 Effect of Fiber Treatment......Page 68
2.5.2.2 Effect of Fiber Sizing......Page 71
2.5.3.1 Stress Transfer in Composites......Page 74
2.5.3.2 As-Received Composite Plates and Tows......Page 75
2.5.3.3 Composites Containing Induced Discontinuities......Page 85
2.6.1 Methodology......Page 90
2.6.2.1 Thermoplastic Composites......Page 91
2.6.2.2 Thermosetting Composites......Page 92
2.7 Stress-Concentration Measurements in Notched Laminates......Page 94
2.8 Stress-Concentration Measurements in Cross-Ply Composites......Page 99
2.9 Bulk Strain Measurements in Composites Using Fiber Optics......Page 103
References......Page 113
3 FT-IR Spectroscopy of Ultrathin Materials......Page 116
3.1 Introduction......Page 117
3.2.1.2 Surface Pressure Studies......Page 118
3.2.2 Surface Potential Studies......Page 121
3.2.3 Langmuir Films of AChE......Page 123
3.3.1 Langmuir-Blodgett Films of Chlorophyll-a......Page 124
3.3.2 Langmuir-Blodgett Films of AChE......Page 125
3.4.1 Surface-Normal Incidence Transmission Spectroscopy......Page 126
3.4.3 RA Spectrometry......Page 135
3.5 ER Technique......Page 142
3.6 Transmission and RA Spectral Analyses of L-B films......Page 146
3.7 Application Studies of ER Spectral Analyses of L-B and Langmuir films......Page 151
3.8 ATR Spectroscopy and Related Techniques......Page 158
3.9 Polarization-Modulation Infrared Reflection Absorption Spectroscopy (PM-IRAS)......Page 163
3.9.1.1 Analysis of AChE Secondary Structure at the Air-Water Interface......Page 164
3.9.2.1 DPPC and DPPA Monolayers......Page 168
3.9.2.2 AChE-Substrate Interaction at the Air-Water Interface......Page 170
3.10 Chemometric Analysis for Surface Chemistry......Page 171
References......Page 174
4 Two-Dimensional Correlation Spectroscopy of Biological and Polymeric Materials......Page 180
4.1 Introduction......Page 181
4.2.1 Mathematical Background......Page 183
4.2.1.2 Generalized 2D Correlation Spectrum......Page 184
4.2.1.5 Representation of 2D Correlation Spectra by Linear Algebra......Page 186
4.2.2 Synchronous and Asynchronous Spectra......Page 187
4.3.1 Sample-Sample 2D Correlation Spectroscopy......Page 188
4.3.2 Statistical 2D Correlation Spectroscopy......Page 189
4.4 Applications of Two-Dimensional Correlation Spectroscopy......Page 190
4.4.1.1 Premelting Behavior of Nylon 12 Studied by 2D-NIR Correlation Spectroscopy......Page 191
4.4.1.2 Thermally-Induced 2D-IR Spectroscopy of Linear Low-Density Polyethylene......Page 196
4.4.1.3 2D-IR Study on the Crystallization Process of Poly(ethylene-2,6-naphthalate)......Page 199
4.4.2.1 2D Correlation Infrared Rheo-Optics of Bombyx mori Fibroin Film......Page 203
4.4.2.2 2D Attenuated Total Reflection/IR Spectroscopy Study of Adsorption-Dependent and Concentration- Dependent Structural Changes in b-Lactoglobulin in Buffer Solutions......Page 206
4.4.3 Other Applications......Page 214
4.4.3.1 2D-IR Correlation Spectroscopy Study on Pressure- Dependent Changes in the C-H Vibrations of Monolayer Films at the Air-Water Interface......Page 215
4.4.3.2 Applications to Electrochemical Reactions......Page 220
4.4.4 Application of Sample-Sample Correlation Spectroscopy and Statistical 2D Correlation Spectroscopy......Page 225
REFERENCES......Page 229
5 Raman and Mid-Infrared Microspectroscopic Imaging......Page 232
5.1 Introduction......Page 233
5.2 Raman Spectroscopic Imaging......Page 234
5.2.1.2 Rayleigh Line Rejection......Page 235
5.2.2.1 Instrumentation......Page 236
5.2.2.2 Applications......Page 238
5.2.3.1 Instrumentation......Page 239
5.2.3.2 Applications......Page 240
5.2.4.1 Instrumentation......Page 241
5.2.5.1 Instrumentation......Page 242
5.2.5.2 Applications......Page 243
5.2.6.1 Instrumentation......Page 244
5.2.6.2 Applications......Page 247
5.3 Mid-Infrared Spectroscopic Imaging......Page 250
5.3.1.1 FT-IR Spectroscopic Mapping with a Single Element Detector......Page 251
5.3.1.2 Raster-Scan FT-IR Imaging Using Multichannel Detectors......Page 256
5.3.1.3 Global FT-IR Spectroscopic Imaging......Page 257
5.3.2.2 Laser-Diode-Based Imaging......Page 262
References......Page 263
6 Vibrational Circular Dichroism of Biopolymers: Summary of Methods and Applications......Page 270
6.1 Introduction......Page 271
6.2.1 Instrumentation: FT-VCD versus Dispersive VCD......Page 275
6.2.1.1 Dispersive VCD......Page 277
6.2.1.2 FT-VCD......Page 279
6.2.2 Biomolecular VCD Sampling Methods......Page 283
6.2.3 Instrument Comparison with Biopolymer Spectra......Page 285
6.3 Biopolymer VCD Theory Survey......Page 293
6.4 Nucleic Acid VCD Spectra and Applications......Page 294
6.4.1 Empirical Correlation of VCD with Helicity......Page 295
6.4.2 Theoretical Modelling of Nucleic Acid VCD......Page 300
6.5.1 Empirical Correlation with Secondary Structure......Page 301
6.5.2 Peptide VCD Applications......Page 306
6.5.3 Peptide VCD Theory......Page 310
6.6.1 Qualitative Spectral Interpretations......Page 315
6.6.2 Applications of VCD for Protein Structure......Page 319
6.6.3 Protein Secondary Structure Quantitative Analyses......Page 322
6.7 Comparison of Techniques......Page 330
Acknowledgments......Page 331
References......Page 332
7 Membrane Receptor-Ligand Interactions Probed by Attenuated Total Reflectance Infrared Difference Spectroscopy......Page 342
7.1 Introduction......Page 343
7.2.1 Background Theory......Page 345
7.2.2 Linear Dichroism......Page 347
7.3 Triggering Conformational Transitions with Buffer Flow......Page 348
7.3.1.1 IRE Material......Page 350
7.3.1.2 IRE Size and Geometry (Optimization of Signal Strength)......Page 352
7.3.2.1 Planar Supported Bilayers......Page 355
7.3.2.3 Covalent Attachment of Multi-Bilayers......Page 356
7.3.3 Membrane Film Stability......Page 357
7.3.4.1 Minimization of Temperature-Dependent Spectral Artifacts......Page 358
7.4 Ligand-Induced Conformational Change......Page 359
7.4.1 Mapping Conformational States......Page 360
7.4.2 Chemistry of Receptor-Ligand Interactions......Page 363
7.5 Conclusions and Future Directions......Page 365
References......Page 366
8 Step-Scan Time-Resolved FT-IR Spectroscopy of Biopolymers......Page 370
8.1 Introduction......Page 371
8.2 Time-Resolved Vibrational Spectroscopic Techniques......Page 372
8.2.1 Step-Scan Time-Resolved FT-IR Spectroscopy......Page 373
8.2.2 Time Resolution Available with Rapid-Scan Instrumentation......Page 376
8.2.3 Time Resolution Beyond the Rapid-Scan Limit......Page 377
8.2.4 Stroboscopic Time-Resolved FT-IR Spectroscopy......Page 378
8.2.5 Other Approaches to Time-Resolved Vibrational Spectroscopy of Biological Samples......Page 379
8.3.1 Photocyclic Reactions of Naturally Occuring Chromophores......Page 380
8.3.1.1 Retinal Proteins......Page 381
8.3.1.2 Heme Proteins......Page 384
8.3.1.4 Photoactive Yellow Protein......Page 388
8.3.2 Non-Chromophoric Protein Reactions Studied with Step-Scan TR-FT-IR......Page 389
8.4.1 Sources of Noise and Other Errors......Page 390
8.4.1.1 Detector Noise......Page 391
8.4.1.2 Mirror Position Error......Page 400
8.4.1.3 Amplifier/Digitizer Errors......Page 401
8.4.1.4 Sample/Trigger Drift......Page 402
8.4.1.5 Excitation Trigger Noise......Page 405
8.4.1.6 Phase Errors......Page 407
8.4.1.7 Spectral Aliasing (Interferogram Undersampling) Errors......Page 410
8.4.1.8 Selection of Software Parameters for TR-FT-IR Experiments......Page 411
8.4.2.1 Sample Preparation......Page 423
8.4.2.2 Isotope Labeling for Vibrational Assignments......Page 425
8.4.3 Triggering of Photolysis Lasers......Page 430
8.5 Future Perspectives......Page 431
References......Page 432
Index......Page 436