Two-Dimensional Correlation Spectroscopy

Preface xi Acknowledgements xiii

1 Introduction 1 1.1 Two-dimensional Spectroscopy 1 1.2 Overview of the Field 3 1.3 Generalized Two-dimensional Correlation 6 1.4 Heterospectral Correlation 9 1.5 Universal Applicability 10

2 Principle of Two-dimensional Correlation Spectroscopy 15 2.1 Two-dimensional Correlation Spectroscopy 15 2.2 Generalized Two-dimensional Correlation 17 2.3 Properties of 2D Correlation Spectra 20 2.4 Analytical Expressions for Certain 2D Spectra 24 2.5 Cross-correlation Analysis and 2D Spectroscopy 31

3 Practical Computation of Two-dimensional Correlation Spectra 39 3.1 Computation of 2D Spectra from Discrete Data 39 3.2 Unevenly Spaced Data 41 3.3 Disrelation Spectrum 43 3.4 Computational Efficiency 43

4 Generalized Two-dimensional Correlation Spectroscopy in Practice 47 4.1 Practical Example 47 4.2 Pretreatment of Data 52 4.3 Features Arising from Factors other than Band Intensity Changes 56

5 Further Expansion of Generalized Two-dimensional Correlation Spectroscopy - Sample-Sample Correlation and Hybrid Correlation 65 5.1 Sample-Sample Correlation Spectroscopy 65 5.2 Hybrid 2D Correlation Spectroscopy 72 5.3 Additional Remarks 74

6 Additional Developments in Two-dimensional Correlation Spectroscopy - Statistical Treatments, Global Phase Maps, and Chemometrics 77 6.1 Classical Statistical Treatments and 2D Spectroscopy 77 6.2 Global 2D Phase Maps 81 6.3 Chemometrics and 2D Correlation Spectroscopy 86

7 Other Types of Two-dimensional Spectroscopy 95 7.1 Nonlinear Optical 2D Spectroscopy 96 7.2 Statistical 2D Correlation Spectroscopy 99 7.3 Other Developments in 2D Correlation Spectroscopy 110

8 Dynamic Two-dimensional Correlation Spectroscopy Based on Periodic Perturbations 115

8.1 Dynamic 2D IR Spectroscopy 115 8.2 Dynamic 2D IR Dichroism Spectra of Polymers 121 8.3 Repetitive Perturbations Beyond DIRLD 153

9 Applications of Two-dimensional Correlation Spectroscopy to Basic Molecules 169 9.1 2D IR Study of the Dissociation of Hydrogen-bonded N-Methylacetamide 170 9.2 2D NIR Sample-Sample Correlation Study of Phase Transitions of Oleic Acid 174 9.3 2D NIR Correlation Spectroscopy Study of Water 176 9.4 2D Fluorescence Study of Polynuclear Aromatic Hydrocarbons 179

10 Generalized Two-dimensional Correlation Studies of Polymers and Liquid Crystals 187 10.1 Temperature and Pressure Effects on Polyethylene 187 10.2 Reorientation of Nematic Liquid Crystals by an Electric Field 195 10.3 Temperature-dependent 2D NIR of Amorphous Polyamide 199 10.4 Composition-based 2D Raman Study of EVA Copolymers 203 10.5 Polarization Angle-dependent 2D IR Study of Ferroelectric Liquid Crystals 209

11 Two-dimensional Correlation Spectroscopy and Chemical Reactions 217 11.1 2D ATR/IR Study of Bis(hydroxyethyl terephthalate) Oligomerization 217 11.2 Hydrogen-Deuterium Exchange of Human Serum Albumin 222

12 Protein Research by Two-dimensional Correlation Spectroscopy 231 12.1 Adsorption and Concentration-dependent 2D ATR/IR Study of ß-Lactoglobulin 232 12.2 pH-dependent 2D ATR/IR Study of Human Serum Albumin 236 12.3 Aggregation of Lipid-bound Cytochrome c 241

13 Applications of Two-dimensional Correlation Spectroscopy to Biological and Biomedical Sciences 245 13.1 2D NIR Study of Milk 246 13.2 2D IR Study of Synthetic and Biological Apatites 251 13.3 Identification and Quality Control of Traditional Chinese Medicines 253

14 Application of Heterospectral Correlation Analysis 257 14.1 Correlation between different Spectral Measurements 257 14.2 SAXS/IR Dichroism Correlation Study of Block Copolymer 258 14.3 Raman/NIR Correlation Study of Partially Miscible Blends 260 14.4 ATR/IR-NIR Correlation Study of BIS(hydroxyethyl terephthalate) Oligomerization 262 14.5 XAS/Raman Correlation Study of Electrochemical Reaction of Lithium with CoO 264

15 Extension of Two-dimensional Correlation Analysis to Other Fields 271 15.1 Applications of 2D Correlation beyond Optical Spectroscopy 271 15.2 2D Correlation Gel Permeation Chromatography (GPC) 271 15.3 2D Mass Spectrometry 281 15.4 Other Unusual Applications of 2D Correlation Analysis 282 15.5 Return to 2D NMR Spectroscopy 283 15.6 Future Developments 288

Index 291