A Graduate Course in NMR Spectroscopy

Description

This textbook is designed for graduate students to introduce the basic concepts of Nuclear Magnetic Resonance spectroscopy (NMR), spectral analysis and modern developments such as multidimensional NMR, in reasonable detail and rigor. The book is self-contained, so, a unique textbook in that sense with end of chapter exercises included supported by a solution manual. Some of the advanced topics are included as Appendices for quick reference. Students of chemistry who have some exposure to mathematics and physics will benefit from this book and it will prepare them to pursue research in different branches of Chemistry or Biophysics or Structural Biology. ​ Preface Recommended Books for Further Reading Contents 1: Basic Concepts Learning Objectives 1.1 Nuclear Spin and Magnetic Moments 1.2 Nuclear Spins in a Magnetic Field Box 1.1: Calculation of 1.3 Spin-Lattice Relaxation 1.4 Spin Temperature 1.5 Resonance Absorption of Energy and the NMR Experiment 1.5.1 The Basic NMR Spectrometer 1.6 Kinetics of Resonance Absorption 1.7 Selection Rules Box 1.2: The Relationship Between () and (I+, I-) Operators and the Effect of I+, I- Operators on Spin-State I, m> 1.8 Line Widths 1.9 Bloch Equations 1.10 More About Relaxation 1.11 Sensitivity 1.12 Summary 1.13 Further Reading 1.14 Exercises 2: High-Resolution NMR Spectra of Molecules Learning Objectives 2.1 Introduction 2.2 Chemical Shift 2.2.1 Anisotropy of Chemical Shifts 2.2.2 Factors Influencing Isotropic Chemical Shifts 2.3 Spin-Spin Coupling 2.4 Analysis of NMR Spectra of Molecules 2.4.1 First-Order Analysis 2.4.2 Quantum Mechanical Analysis Box 2.1: Fundamental Properties of Angular Momentum Operators 2.4.2.1 Two-Spin AB Case 2.4.2.2 NMR Spectra of Three Coupled Nuclei 2.5 Dynamic Effects in the NMR Spectra 2.5.1 Two-Site Chemical Exchange 2.5.2 The Collapse of Spin Multiplets 2.5.3 Conformational Averaging of J-values 2.6 Summary 2.7 Further Reading 2.8 Exercises 3: Fourier Transform NMR Learning Objectives 3.1 Introduction 3.2 Principles of Fourier Transform NMR 3.3 Theorems on Fourier Transforms 3.4 The FTNMR Spectrometer 3.5 Practical Aspects of Recording FTNMR Spectra 3.5.1 Carrier Frequency and Offset 3.5.2 RF Pulse 3.5.3 Free Induction Decay (FID) and the Spectrum 3.5.4 Single-Channel and Quadrature Detection 3.5.5 Signal Digitization and Sampling 3.5.6 Folding of Signals 3.5.7 Acquisition Time and Resolution 3.5.8 Signal Averaging and Pulse Repetition Rate 3.6 Data Processing in FT NMR 3.6.1 Zero Filling 3.6.2 Digital Filtration or Window Multiplication or Apodization 3.7 Phase Correction 3.8 Dynamic Range in FTNMR 3.9 Solvent Suppression 3.10 Spin Echo 3.11 Measurement of Relaxation Times 3.11.1 Measurement of T1 Relaxation Time 3.11.2 Measurement of T2 Relaxation Time 3.12 Water Suppression Through the Spin Echo: Watergate 3.13 Spin Decoupling 3.14 Broadband Decoupling 3.15 Bilinear Rotation Decoupling (BIRD) 3.16 Summary 3.17 Further Reading 3.18 Exercises 4: Polarization Transfer Learning Objectives 4.1 Introduction 4.2 The Nuclear Overhauser Effect (NOE) 4.2.1 Experimental Schemes 4.3 Origin of NOE 4.3.1 A Simplified Treatment 4.3.2 A More Rigorous Treatment 4.4 Steady-State NOE 4.5 Transient NOE 4.6 Selective Population Inversion 4.7 INEPT 4.7.1 INEPT Has the Following Disadvantages 4.8 INEPT+ 4.9 Distortionless Enhanced Polarization Transfer (DEPT) 4.10 Summary 4.11 Further Reading 4.12 Exercises 5: Density Matrix Description of NMR Learning Objectives 5.1 Introduction 5.2 Density Matrix 5.3 Elements of Density Matrix 5.4 Time Evolution of Density Operator ρ 5.5 Matrix Representations of RF Pulses Box 5.1: Density Operator Transformation for the Effect of a Operator Box 5.2: The Calculation of the Direct Product Between Two 2 x 2 Matrices 5.6 Product Operator Formalism 5.6.1 Basis Operator Sets Box 5.3: Matrix Representations of the Operators Iz, Ix, Iy, I+, I-, Iα, and Iβ for the Case of One Spin 5.6.2 Time Evolution of Cartesian Basis Operators 5.6.2.1 Free Evolution Under the Influence of the Hamiltonian 5.6.2.2 Chemical Shift Evolution 5.6.2.3 Scalar Coupling Evolution Box 5.4: Explicit Derivation of Eq. 5.123 Box 5.5: Explicit Derivation of Eq. 5.125 5.6.2.4 Rotation by Pulses 5.6.2.5 Calculation of the Spectrum of a J-Coupled Two-Spin System 5.7 Summary 5.8 Further Reading 5.9 Exercises 6: Multidimensional NMR Spectroscopy Learning Objectives 6.1 Introduction 6.2 Two-Dimensional NMR 6.3 Two-Dimensional Fourier Transformation in NMR 6.4 Peak Shapes in Two-Dimensional Spectra 6.5 Quadrature Detection in Two-Dimensional NMR 6.6 Types of Two-Dimensional NMR Spectra 6.6.1 Two-Dimensional Resolution/Separation Experiments 6.6.1.1 Two-Dimensional Heteronuclear Separation Experiments 6.6.1.2 Two-Dimensional Homonuclear Separation Experiments 6.6.2 Two-Dimensional Correlation Experiments 6.6.2.1 The COSY Experiment 6.6.2.2 Double-Quantum-Filtered COSY (DQF-COSY) 6.6.2.3 Total Correlation Spectroscopy (TOCSY) 6.6.2.4 Two-Dimensional Nuclear Overhauser Effect Spectroscopy (2D-NOESY) 6.6.2.5 Two-Dimensional ROESY 6.6.2.6 Application of Two-Dimensional Homonuclear Experiments in Structural Analysis of Small Organic Molecules: A Case Study... 6.6.3 Two-Dimensional Heteronuclear Correlation Experiments 6.6.3.1 Heteronuclear COSY 6.6.3.2 Heteronuclear Multiple Bond Correlation (HMBC) 6.6.4 Combination of Mixing Sequences 6.7 Three-Dimensional NMR 6.7.1 The CT-HNCA Experiment 6.7.2 The HNN Experiment 6.7.3 The Constant Time HN(CO)CA Experiment 6.7.4 The HN(C)N Experiment 6.8 Summary 6.9 Further Reading 6.10 Exercises Reference 7: Appendix 7.1 Appendix A1: Dipolar Hamiltonian 7.2 Appendix A2: Chemical Shift Anisotropy 7.2.1 Principal Axes and Principal Values 7.3 Appendix A3: Solid-State NMR Basics 7.3.1 Magic Angle Spinning (MAS) 7.3.2 Cross Polarization 7.4 Appendix A4: Selection of Coherence Transfer Pathways by Linear Field Gradient Pulses 7.5 Appendix 5: Pure Shift NMR 7.5.1 Pseudo-Two-Dimensional Data Acquisition 7.5.2 Real-Time Data Acquisition 7.5.3 Homonuclear Band-Selective Decoupling 7.5.4 Zangger-Sterk Real-Time Homonuclear Broadband Decoupling 7.5.5 PSYCHE Homonuclear Broadband Decoupling 7.6 Appendix A6: Hadamard NMR Spectroscopy Correction to: Multidimensional NMR Spectroscopy Correction to: Chapter 6 in: R. V. Hosur, V. M. R. Kakita, A Graduate Course in NMR Spectroscopy, https://doi.org/10.1007/978-... Correction to: Density Matrix Description of NMR Correction to: Chapter 5 in: R. V. Hosur, V. M. R. Kakita, A Graduate Course in NMR Spectroscopy, https://doi.org/10.1007/978-... Solutions to Exercises Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6