Two-Dimensional Correlation Spectroscopy

Isao Noda, Proctor and Gamble Company, Ohio, USA. Yukihiro Ozaki, Kwansei Gakuin University, Japan.

• Preface xiAcknowledgements xiii1 Introduction 11.1 Two-dimensional Spectroscopy 11.2 Overview of the Field 31.3 Generalized Two-dimensional Correlation 61.3.1 Types of Spectroscopic Probes 71.3.2 External Perturbations 71.4 Heterospectral Correlation 91.5 Universal Applicability 102 Principle of Two-dimensional Correlation Spectroscopy 152.1 Two-dimensional Correlation Spectroscopy 152.1.1 General Scheme 152.1.2 Type of External Perturbations 162.2 Generalized Two-dimensional Correlation 172.2.1 Dynamic Spectrum 172.2.2 Two-dimensional Correlation Concept 182.2.3 Generalized Two-dimensional Correlation Function 192.2.4 Heterospectral Correlation 202.3 Properties of 2D Correlation Spectra 202.3.1 Synchronous 2D Correlation Spectrum 202.3.2 Asynchronous 2D Correlation Spectrum 222.3.3 Special Cases and Exceptions 242.4 Analytical Expressions for Certain 2D Spectra 242.4.1 Comparison of Linear Functions 242.4.2 2D Spectra Based on Sinusoidal Signals 262.4.3 Exponentially Decaying Intensities 282.4.4 Distributed Lorentzian Peaks 292.4.5 Signals with more Complex Waveforms 302.5 Cross-correlation Analysis and 2D Spectroscopy 312.5.1 Cross-correlation Function and Cross Spectrum 312.5.2 Cross-correlation Function and Synchronous Spectrum 322.5.3 Hilbert Transform 332.5.4 Orthogonal Correlation Function and Asynchronous Spectrum 342.5.5 Disrelation Spectrum 353 Practical Computation of Two-dimensional Correlation Spectra 393.1 Computation of 2D Spectra from Discrete Data 393.1.1 Synchronous Spectrum 393.1.2 Asynchronous Spectrum 403.2 Unevenly Spaced Data 413.3 Disrelation Spectrum 433.4 Computational Efficiency 434 Generalized Two-dimensional Correlation Spectroscopy in Practice 474.1 Practical Example 474.1.1 Solvent Evaporation Study 474.1.2 2D Spectra Generated from Experimental Data 484.1.3 Sequential Order Analysis by Cross Peak Signs 504.2 Pretreatment of Data 524.2.1 Noise Reduction Methods 524.2.2 Baseline Correction Methods 534.2.3 Other Pretreatment Methods 544.3 Features Arising from Factors other than Band Intensity Changes 564.3.1 Effect of Band Position Shift and Line Shape Change 564.3.2 Simulation Studies 574.3.3 2D Spectral Features from Band Shift and Line Broadening 595 Further Expansion of Generalized Two-dimensional Correlation Spectroscopy – Sample–Sample Correlation and Hybrid Correlation 655.1 Sample–Sample Correlation Spectroscopy 655.1.1 Correlation in another Dimension 655.1.2 Matrix Algebra Outlook of 2D Correlation 665.1.3 Sample–Sample Correlation Spectra 675.1.4 Application of Sample–Sample Correlation 695.2 Hybrid 2D Correlation Spectroscopy 725.2.1 Multiple Perturbations 725.2.2 Correlation between Data Matrices 725.2.3 Case Studies 735.3 Additional Remarks 746 Additional Developments in Two-dimensional Correlation Spectroscopy – Statistical Treatments, Global Phase Maps, and Chemometrics 776.1 Classical Statistical Treatments and 2D Spectroscopy 776.1.1 Variance, Covariance, and Correlation Coefficient 776.1.2 Interpretation of 2D Disrelation Spectrum 786.1.3 Coherence and Correlation Phase Angle 796.1.4 Correlation Enhancement 806.2 Global 2D Phase Maps 816.2.1 Further Discussion on Global Phase 816.2.2 Phase Map with a Blinding Filter 826.2.3 Simulation Study 836.3 Chemometrics and 2D Correlation Spectroscopy 866.3.1 Comparison between Chemometrics and 2D Correlation 866.3.2 Factor Analysis 876.3.3 Principal Component Analysis (PCA) 876.3.4 Number of Principal Factors 886.3.5 PCA-reconstructed Spectra 896.3.6 Eigenvalue Manipulating Transformation (EMT) 917 Other Types of Two-dimensional Spectroscopy 957.1 Nonlinear Optical 2D Spectroscopy 967.1.1 Ultrafast Laser Pulses 967.1.2 Comparison with Generalized 2D Correlation Spectroscopy 977.1.3 Overlap Between Generalized 2D Correlation and Nonlinear Spectroscopy 987.2 Statistical 2D Correlation Spectroscopy 997.2.1 Statistical 2D Correlation by Barton II et al. 997.2.2 Statistical 2D Correlation by Šašic and Ozaki 1027.2.3 Other Statistical 2D Spectra 1097.2.4 Link to Chemometrics 1097.3 Other Developments in 2D Correlation Spectroscopy 1107.3.1 Moving-window Correlation 1107.3.2 Model-based 2D Correlation Spectroscopy 1108 Dynamic Two-dimensional Correlation Spectroscopy Based on Periodic Perturbations 1158.1 Dynamic 2D IR Spectroscopy 1158.1.1 Sinusoidal Signals 1158.1.2 Small-amplitude Perturbation and Linear Response 1168.1.3 Dynamic IR Linear Dichroism (DIRLD) 1178.1.4 2D Correlation Analysis of Dynamic IR Dichroism 1198.2 Dynamic 2D IR Dichroism Spectra of Polymers 1218.2.1 Polystyrene/Polyethylene Blend 1228.2.2 Polystyrene 1278.2.3 Poly(methyl methacrylate) 1298.2.4 Human Skin Stratum Corneum 1338.2.5 Human Hair Keratin 1348.2.6 Toluene and Dioctylphthalate in a Polystyrene Matrix 1378.2.7 Polystyrene/Poly(vinyl methyl ether) Blend 1418.2.8 Linear Low Density Polyethylene 1448.2.9 Poly(hydroxyalkanoates) 1488.2.10 Block Copolymers 1508.2.11 Summary 1528.3 Repetitive Perturbations Beyond DIRLD 1538.3.1 Time-resolved Small Angle X-ray Scattering (SAXS) 1538.3.2 Depth-profiling Photoacoustic Spectroscopy 1588.3.3 Dynamic Fluorescence Spectroscopy 1658.3.4 Summary 1669 Applications of Two-dimensional Correlation Spectroscopy to Basic Molecules 1699.1 2D IR Study of the Dissociation of Hydrogen-bonded N-Methylacetamide 1709.2 2D NIR Sample–Sample Correlation Study of Phase Transitions of Oleic Acid 1749.3 2D NIR Correlation Spectroscopy Study of Water 1769.4 2D Fluorescence Study of Polynuclear Aromatic Hydrocarbons 17910 Generalized Two-dimensional Correlation Studies of Polymers and Liquid Crystals 18710.1 Temperature and Pressure Effects on Polyethylene 18710.2 Reorientation of Nematic Liquid Crystals by an Electric Field 19510.3 Temperature-dependent 2D NIR of Amorphous Polyamide 19910.4 Composition-based 2D Raman Study of EVA Copolymers 20310.5 Polarization Angle-dependent 2D IR Study of Ferroelectric Liquid Crystals 20911 Two-dimensional Correlation Spectroscopy and Chemical Reactions 21711.1 2D ATR/IR Study of Bis(hydroxyethyl terephthalate) Oligomerization 21711.2 Hydrogen–Deuterium Exchange of Human Serum Albumin 22212 Protein Research by Two-dimensional Correlation Spectroscopy 23112.1 Adsorption and Concentration-dependent 2D ATR/IR Study of β-Lactoglobulin 23212.2 pH-dependent 2D ATR/IR Study of Human Serum Albumin 23612.2.1 N Isomeric Form of HSA 23712.2.2 N–F Transition Region of HSA 23912.3 Aggregation of Lipid-bound Cytochrome c 24113 Applications of Two-dimensional Correlation Spectroscopy to Biological and Biomedical Sciences 24513.1 2D NIR Study of Milk 24613.2 2D IR Study of Synthetic and Biological Apatites 25113.3 Identification and Quality Control of Traditional Chinese Medicines 25314 Application of Heterospectral Correlation Analysis 25714.1 Correlation between different Spectral Measurements 25714.2 SAXS/IR Dichroism Correlation Study of Block Copolymer 25814.3 Raman/NIR Correlation Study of Partially Miscible Blends 26014.4 ATR/IR–NIR Correlation Study of BIS(hydroxyethyl terephthalate) Oligomerization 26214.5 XAS/Raman Correlation Study of Electrochemical Reaction of Lithium with CoO 26415 Extension of Two-dimensional Correlation Analysis to Other Fields 27115.1 Applications of 2D Correlation beyond Optical Spectroscopy 27115.2 2D Correlation Gel Permeation Chromatography (GPC) 27115.2.1 Time-resolved GPC Study of a Sol–Gel Polymerization Process 27215.2.2 2D GPC Correlation Maps 27415.2.3 Reaction Mechanisms Deduced from the 2D GPC Study 27915.3 2D Mass Spectrometry 28115.4 Other Unusual Applications of 2D Correlation Analysis 28215.5 Return to 2D NMR Spectroscopy 28315.5.1 2D Correlation in NMR 28315.5.2 Generalized Correlation (GECO) NMR 28415.5.3 2D Correlation in Diffusion-ordered NMR 28415.6 Future Developments 288Index 291