Contents
Foreword XI
List of Contributors XIII
Introduction 1
H. W. Siesler
General Remarks 1
Basic Principles of Vibrational Spectroscopy 3
Instrumentation 7
Process-Monitoring 9
References 10
Origin of Near-Infrared Absorption Bands
L. Bokobza
Introduction 11
Principles of Near-Infrared Spectroscopy
The Diatomic Molecule 12
The Harmonic Oscillator 12
Anharmonic Oscillator 14
The Polyatomic Molecule 17
Harmonic Approximation I7
Influence of Anharmonicity 18
Degenerate Vibrations 22
Symmetry Considerations 24
Fermi and Darling-Denisson Resonances 27
Chemical Assignments of NIR Bands
Group Frequencies 33
C-H Absorptions 33
0-H Absorptions 34
N-H Absorptions 35
Deuteration 35
Polarisation Measurements 35
Two-Dimensional Correlation Spectroscopy 39
Conclusion 39
References 39
Instrumentation for Near-Infrared Spectroscopy 43
s. Kuwutu
Configuration of Near-Infrared Spectrometers 43
Interference-Filter Spectroscopy 45
Principle of Interference-Filter Spectroscopy 45
Wavelength Scanning 48
Diffraction-Grating Spectroscopy 49
Principle of Diffraction-Grating Spectroscopy 49
Wavelength Scanning for Grating Spectroscopy
Multichannel Spectroscopy with a Polychromator 55
Production Methods of Reflection-Type Diffraction Gratings
Spectroscopy with Acousto-Optical Diffraction Gratings 57
Schematics of Acousto-Optical Diffraction Gratings 58
Characteristics of Spectroscopy by Bragg Diffraction
Application and Materials of Acousto-Optical Elements
Fourier-Transform Spectroscopy 62
Principle of Fourier-Transform Spectroscopy 63
Characteristics of Fourier-Transform Spectroscopy 64
Optical Throughput Advantage 65
Multiplexing Advantage 65
Resolution 65
Various Types of Michelson Interferometer
Polarisation Interferometer 66
FT-NIR Raman Spectroscopy 67
Multichannel Fourier-Transform Spectroscopy 68
Principle of Multichannel Fourier-Transform Spectroscopy
Multichannel Fourier-Transform Spectroscopy
with a Polarising Interferometer with a Savart Plate
Comparison of Spectrometers 72
References 72
New Techniques in Near-Infrared Spectroscopy 75
S. Kuwata
Near-Infrared Light Sources 75
Thermal Radiation 75
Tungsten Halogen Lamp 76
Nichrome Heater and Globar 76
Laser and Light Emitting Diode
Light Emitting Diode and Semiconductor Laser
Other Lasers 78
Near-Infrared Detectors 78
Photoconduction Effect 79
The Photovoltaic Effect 79
Multi-Channel Detectors 81
Optical Elements for the Near-Infrared Region
References 83
Near-infrared FT-Raman Spectroscopy 85
Y Furukawa
Introduction 85
Principles of FT-Raman Spectrometry 86
Raman Scattering 86
FT-Raman Measurement 88
Apodisation Function and Line Shape
Resolution 92
Sampling Frequency 93
Intensity Calibration 95
Instrumentation 96
Applications 98
Various Materials 99
Double Modulation Measurements 104
Pulsed Excitation – Synchronous Sampling
Pulsed Excitation – Asynchronous Sampling
Time-Resolved Measurements 109
Conclusion 112
References 11 2
Sampling and Sample Presentation
S. Kawano
Sampling 115
Sample Preparation 115
Grinding 115
Slicing or Cutting 11 6
Shredding and Juicing 116
Homogenising 11 7
Temperature Control 1 17
Moisture Control 117
Sample Presentation 118
Relative Absorbance 118
Transmission, Reflection, Transflection and Interaction
Sample Cell or Sample Holder I19
Sample Cell for Whole Grains 120
Sample Cell for a Powdered Sample
Sample Cell for Pastes 121
Sample Cell for Liquids 122
Fruit Holder 123
Sample Holder for Single Kernels
Fibre Optics 124
References 124
Fundamental Chemometric Methods 125
H. M. Heise and R. Winzen
Introduction 125
Quantitative Analysis 126
Beer’s Law, a Simple Physical Model
A Full Spectrum Method: CLS 129
Inverse Multivariate Calibrations 132
Wavelength Selection for Multivariate Calibrations
Qualitative Analysis 139
Signal Processing 143
Why Data Pretreatment? 143
Techniques and Algorithms 145
Local Filters 145
Smoothing 145
Derivatives 147
Baseline Correction Methods 149
Multiplicative Corrections 150
Orthogonal Signal Correction (OSC) 153
Instrument Standardisation and Calibration Transfer
New Developments 156
Artificial Neural Networks 156
Genetic Algorithms 158
References 159
Two-Dimensional Near-Infrared Correlation Spectroscopy 163
Y Ozaki
Introduction 163
Generalised Two-Dimensional NIR Correlation Spectroscopy
Background 164
Mathematical Treatment 166
Properties of Generalised Two-Dimensional Correlation Spectra
Two-Dimensional NIR Correlation Spectroscopy Proposed
by Barton et al. 169
Sample-Sample Correlation Spectroscopy 172
Sample-Sample Correlation spectroscopy 172
References 177
Applications in Chemistry 179
Y Ozaki
Introduction 179
NIR Studies of Hydrogen Bonds, Hydration and Self-Association
of Basic Compounds 179
Water 180
Fatty Acids 188
Alcohols 193
Proteins 198
Chemometrics Approach to Basic Chemical Problems
Determination of the Physical and Chemical Properties of Water
Discrimination of 24 Kinds of Alcohols by PCA 204
Resolution Enhancement of NIR Spectra by Loadings Plots 208
References 210
Applications to Polymers and Textiles
H. W. Siesler
Introduction 213
Selected Analytical Applications 21 6
Specific Features of NIR Spectroscopy 222
Polymer Optical Fibres 224
Fundamental Polymer Research by NIR Spectroscop
The Study of Diffusion of Alcohols and Water
in Polyamide 11 [21] 226
Rheo-optical FT-NIR Spectroscopy of Poly(Dimethylsiloxane)/
Polycarbonate Block Copolymers 234
References 244
213
226
Application to Industrial Process Control 247
H. W. Siesler
Introduction 247
Advantages of NIR-Spectroscopic Process Analysers 249
Instrumentation for NIR-Spectroscopic Process Analysers
Applications 252
References 267
Application to Agricultural Products and Foodstuffs 269
S. Kawano
Introduction 269
Grains and Seeds 269
Fruits and Vegetables 273
Livestock Products 278
Marine Products 280
Beverages 281
Other Processed Food 282
References 284
Applications of Near-Infrared Spectroscopy in Medical Sciences
H. M. Heise
Introduction 289
Applications in Clinical Chemistry 290
Measurement Techniques and Chemometrics 290
Biofluid Assays 298
Near-Infrared Spectroscopy of Tissues 302
General Pathology Studies 302
Near-Infrared Spectroscopic Analyses of Skin
Noninvasive Metabolite Monitoring 312
Short-Wave Near-Infrared Spectroscopy for Medical Monitoring
Noninvasive Pulsatile Near-IR Spectroscopy 31 7
Monitoring of Blood-Tissue Oxygenation
and Cytochrome Redox Status 321
Near-Infrared Tomography 326
Concluding Remarks 327
References 328
Appendix 335
References 339
Subject index 341