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Nuclear Magnetic Resonance Spectroscopy: An Introduction to Principles, Applications, and Experimental Methods, 2nd Edition

Nuclear Magnetic Resonance Spectroscopy: An Introduction to Principles, Applications, and Experimental Methods, 2nd Edition

Joseph B. Lambert , Eugene P. Mazzola , Clark D. Ridge

ISBN: 978-1-119-29528-0

Oct 2018

480 pages

$76.99

Description

Combines clear and concise discussions of key NMR concepts with succinct and illustrative examples

Designed to cover a full course in Nuclear Magnetic Resonance (NMR) Spectroscopy, this text offers complete coverage of classic (one-dimensional) NMR as well as up-to-date coverage of two-dimensional NMR and other modern methods. It contains practical advice, theory, illustrated applications, and classroom-tested problems; looks at such important ideas as relaxation, NOEs, phase cycling, and processing parameters; and provides brief, yet fully comprehensible, examples. It also uniquely lists all of the general parameters for many experiments including mixing times, number of scans, relaxation times, and more.

Nuclear Magnetic Resonance Spectroscopy: An Introduction to Principles, Applications, and Experimental Methods, 2nd Edition begins by introducing readers to NMR spectroscopy - an analytical technique used in modern chemistry, biochemistry, and biology that allows identification and characterization of organic, and some inorganic, compounds. It offers chapters covering: Experimental Methods; The Chemical Shift; The Coupling Constant; Further Topics in One-Dimensional NMR Spectroscopy; Two-Dimensional NMR Spectroscopy; Advanced Experimental Methods; and Structural Elucidation.

  • Features classical analysis of chemical shifts and coupling constants for both protons and other nuclei, as well as modern multi‐pulse and multi-dimensional methods
  • Contains experimental procedures and practical advice relative to the execution of NMR experiments
  • Includes a chapter-long, worked-out problem that illustrates the application of nearly all current methods
  • Offers appendices containing the theoretical basis of NMR, including the most modern approach that uses product operators and coherence-level diagrams

By offering a balance between volumes aimed at NMR specialists and the structure-determination-only books that focus on synthetic organic chemists, Nuclear Magnetic Resonance Spectroscopy: An Introduction to Principles, Applications, and Experimental Methods, 2nd Edition is an excellent text for students and post-graduate students working in analytical and bio-sciences, as well as scientists who use NMR spectroscopy as a primary tool in their work.

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Preface to First Edition xiii

Acknowledgments xiv

Preface to Second Edition xv

Acknowledgments xvi

Solutions xvii

Symbols xix

Abbreviations xxi

1 Introduction 1

1.1 Magnetic Properties of Nuclei 1

1.2 The Chemical Shift 6

1.3 Excitation and Relaxation 10

1.4 Pulsed Experiments 13

1.5 The Coupling Constant 16

1.6 Quantitation and Complex Splitting 23

1.7 Commonly Studied Nuclides 25

1.8 Dynamic Effects 28

1.9 Spectra of Solids 30

Problems 33

Tips on Solving NMR Problems 36

References 37

Further Reading 38

2 Introductory ExperimentalMethods 39

2.1 The Spectrometer 39

2.2 Sample Preparation 41

2.3 Optimizing the Signal 42

2.3.1 Sample Tube Placement 42

2.3.2 Probe Tuning 43

2.3.3 Field/Frequency Locking 43

2.3.4 Spectrometer Shimming 44

2.4 Determination of NMR Spectral-Acquisition Parameters 48

2.4.1 Number of Data Points 50

2.4.2 SpectralWidth 50

2.4.3 Filter Bandwidth 52

2.4.4 Acquisition Time 52

2.4.5 Transmitter Offset 52

2.4.6 Flip Angle 52

2.4.7 Receiver Gain 54

2.4.8 Number of Scans 55

2.4.9 Steady-State Scans 55

2.4.10 Oversampling and Digital Filtration 56

2.4.11 Decoupling for X Nuclei 56

2.4.12 Typical NMR Experiments 57

2.5 Determination of NMR Spectral-Processing Parameters 58

2.5.1 ExponentialWeighting 59

2.5.2 Zero Filling 59

2.5.3 FID Truncation and Spectral Artifacts 60

2.5.4 Resolution 62

2.6 Determination of NMR Spectra: Spectral Presentation 63

2.6.1 Signal Phasing and Baseline Correction 63

2.6.2 Zero Referencing 66

2.6.3 Determination of Certain NMR Parameters 66

2.6.3.1 Chemical Shifts and Coupling Constants 66

2.6.3.2 1H Integration 68

2.7 Calibrations 70

2.7.1 PulseWidth (Flip Angle) 70

2.7.2 Decoupler Field Strength 72

Problems 73

References 74

Further Reading 74

3 The Chemical Shift 75

3.1 Factors That Influence Proton Shifts 75

3.1.1 Local Fields 75

3.1.2 Nonlocal Fields 77

3.2 Proton Chemical Shifts and Structure 85

3.2.1 Saturated Aliphatics 85

3.2.1.1 Alkanes 85

3.2.1.2 Functionalized Alkanes 86

3.2.2 Unsaturated Aliphatics 87

3.2.2.1 Alkynes 87

3.2.2.2 Alkenes 88

3.2.2.3 Aldehydes 89

3.2.3 Aromatics 89

3.2.4 Protons on Oxygen and Nitrogen 90

3.2.5 Programs for Empirical Calculations 91

3.3 Medium and Isotope Effects 92

3.3.1 Medium Effects 92

3.3.2 Isotope Effects 95

3.4 Factors That Influence Carbon Shifts 96

3.5 Carbon Chemical Shifts and Structure 98

3.5.1 Saturated Aliphatics 98

3.5.1.1 Acyclic Alkanes 98

3.5.1.2 Cyclic Alkanes 101

3.5.1.3 Functionalized Alkanes 101

3.5.2 Unsaturated Compounds 103

3.5.2.1 Alkenes 103

3.5.2.2 Alkynes and Nitriles 104

3.5.2.3 Aromatics 104

3.5.3 Carbonyl Groups 105

3.5.4 Programs for Empirical Calculations 105

3.6 Tables of Chemical Shifts 106

Problems 110

Further Tips on Solving NMR Problems 119

References 122

Further Reading 122

4 The Coupling Constant 125

4.1 First- and Second-order Spectra 125

4.2 Chemical and Magnetic Equivalence 126

4.3 Signs and Mechanisms of Coupling 132

4.4 Couplings over One Bond 134

4.5 Geminal Couplings 136

4.6 Vicinal Couplings 139

4.7 Long-range Couplings 143

4.7.1 σ–π Overlap 143

4.7.2 Zigzag Pathways 144

4.7.3 Through-Space Coupling 145

4.8 Spectral Analysis 146

4.9 Second-order Spectra 147

4.9.1 Deceptive Simplicity 147

4.9.2 Virtual Coupling 149

4.9.3 Shift Reagents 150

4.9.4 Isotope Satellites 150

4.10 Tables of Coupling Constants 151

Problems 157

References 169

Further Reading 170

5 Further Topics in One-Dimensional NMR Spectroscopy 173

5.1 Spin–Lattice and Spin–Spin Relaxation 173

5.1.1 Causes of Relaxation 173

5.1.2 Measurement of Relaxation Time 175

5.1.3 Transverse Relaxation 176

5.1.4 Structural Ramifications 177

5.1.5 Anisotropic Motion 177

5.1.6 SegmentalMotion 178

5.1.7 Partially Relaxed Spectra 178

5.1.8 Quadrupolar Relaxation 178

5.2 Reactions on the NMR Time Scale 180

5.2.1 Hindered Rotation 181

5.2.2 Ring Reversal 183

5.2.3 Atomic Inversion 183

5.2.4 Valence Tautomerizations and Bond Shifts 185

5.2.5 Quantification 187

5.2.6 Magnetization Transfer and Spin Locking 187

5.3 Multiple Resonance 188

5.3.1 Spin Decoupling 188

5.3.2 Difference Decoupling 190

5.3.3 Classes of Multiple Resonance Experiments 190

5.3.4 Off-resonance Decoupling 191

5.4 The Nuclear Overhauser Effect 194

5.4.1 Origin 194

5.4.2 Observation 195

5.4.3 Difference NOE 198

5.4.4 Applications 199

5.4.5 Limitations 200

5.5 Spectral Editing 200

5.5.1 The Spin–Echo Experiment 201

5.5.2 The Attached Proton Test 201

5.5.3 The DEPT Sequence 204

5.6 Sensitivity Enhancement 205

5.6.1 The INEPT sequence 206

5.6.2 Refocused INEPT 208

5.6.3 Spectral Editing with Refocused INEPT 208

5.6.4 DEPT Revisited 210

5.7 Carbon Connectivity 212

5.8 Phase Cycling, Composite Pulses, and Shaped Pulses 213

5.8.1 Phase Cycling 213

5.8.2 Composite Pulses 215

5.8.3 Shaped Pulses 215

Problems 217

References 231

Further Reading 231

6 Two-Dimensional NMR Spectroscopy 237

6.1 Proton–Proton CorrelationThrough J Coupling 237

6.1.1 COSY45 247

6.1.2 Long-Range COSY (LRCOSY or Delayed COSY) 248

6.1.3 Phase-Sensitive COSY (ϕ-COSY) 249

6.1.4 Multiple Quantum Filtration 250

6.1.5 TOtal Correlation SpectroscopY (TOCSY) 252

6.1.6 Relayed COSY 252

6.1.7 J-Resolved Spectroscopy 252

6.1.8 COSY for Other Nuclides 254

6.2 Proton–Heteronucleus Correlation 254

6.2.1 HETCOR 255

6.2.2 HMQC 257

6.2.3 BIRD-HMQC 257

6.2.4 HSQC 260

6.2.5 COLOC 260

6.2.6 HMBC 260

6.2.7 Heteronuclear Relay Coherence Transfer 263

6.3 Proton–Proton CorrelationThrough Space or Chemical Exchange 264

6.4 Carbon–Carbon Correlation 268

6.5 Higher Dimensions 270

6.6 Pulsed Field Gradients 273

6.7 Diffusion-Ordered Spectroscopy 277

6.8 Summary of 2D Methods 279

Problems 280

References 305

Further Reading 306

7 Advanced ExperimentalMethods 309

7.1 Part A: One-Dimensional Techniques 309

7.1.1 T1 Measurements 309

7.1.2 13C Spectral Editing Experiments 311

7.1.2.1 The APT Experiment 311

7.1.2.2 The DEPT Experiment 312

7.1.3 NOE Experiments 313

7.1.3.1 The NOE Difference Experiment 314

7.1.3.2 The Double-Pulse, Field-Gradient, Spin-Echo NOE Experiment 315

7.2 Part B: Two-Dimensional Techniques 316

7.2.1 Two-Dimensional NMR Data-Acquisition Parameters 316

7.2.1.1 Number of Data Points 316

7.2.1.2 Number of Time Increments 317

7.2.1.3 SpectralWidths 317

7.2.1.4 Acquisition Time 317

7.2.1.5 Transmitter Offset 318

7.2.1.6 Flip Angle 318

7.2.1.7 Relaxation Delay 318

7.2.1.8 Receiver Gain 318

7.2.1.9 Number of Scans per Time Increment 319

7.2.1.10 Steady-State Scans 319

7.2.2 Two-Dimensional NMR Data-Processing Parameters 319

7.2.2.1 Weighting Functions 319

7.2.2.2 Zero Filling 321

7.2.2.3 Digital Resolution 321

7.2.2.4 Linear Prediction 322

7.2.3 Two-Dimensional NMR Data Display 324

7.2.3.1 Phasing and Zero Referencing 324

7.2.3.2 Symmetrization 325

7.2.3.3 Use of Cross Sections in Analysis 325

7.3 Part C: Two-Dimensional Techniques: The Experiments 325

7.3.1 Homonuclear Chemical-Shift Correlation Experiments via Scalar Coupling 326

7.3.1.1 The COSY Family: COSY-90∘, COSY-45∘, Long-Range COSY, and DQF-COSY 326

7.3.1.2 The TOCSY Experiment 330

7.3.2 Direct Heteronuclear Chemical-Shift Correlation via Scalar Coupling 331

7.3.2.1 The HMQC Experiment 331

7.3.2.2 The HSQC Experiment 332

7.3.2.3 The HETCOR Experiment 334

7.3.3 Indirect Heteronuclear Chemical-Shift Correlation via Scalar Coupling 335

7.3.3.1 The HMBC Experiment 336

7.3.3.2 The FLOCK Experiment 338

7.3.3.3 The HSQC–TOCSY Experiment 340

7.3.4 Homonuclear Chemical-Shift Correlation via Dipolar Coupling 342

7.3.4.1 The NOESY Experiment 342

7.3.4.2 The ROESY Experiment 343

7.3.5 1D and Advanced 2D Experiments 345

7.3.5.1 The 1D TOCSY Experiment 345

7.3.5.2 The 1D NOESY and ROESY Experiments 347

7.3.5.3 The Multiplicity-Edited HSQC Experiment 347

7.3.5.4 The H2BC Experiment 348

7.3.5.5 Nonuniform Sampling 352

7.3.5.6 Pure Shift NMR 355

7.3.5.7 Covariance NMR 358

7.3.6 Pure Shift-Covariance NMR 362 References 362

8 Structural Elucidation: TwoMethods 365

8.1 Part A: Spectral Analysis 365

8.1.1 1HNMRData 365

8.1.2 13CNMRData 366

8.1.3 The DEPT Experiment 369

8.1.4 The HSQC Experiment 370

8.1.5 The COSY Experiment 370

8.1.6 The HMBC Experiment 372

8.1.7 General Molecular Assembly Strategy 372

8.1.8 A Specific Molecular Assembly Procedure 374

8.1.9 The NOESY Experiment 379

8.2 Part B: Computer-Assisted Structure Elucidation 382

8.2.1 CASE Procedures 383

8.2.2 T-2 Toxin 384

Appendix A Derivation of the NMR Equation 389

Appendix B The Bloch Equations 391

Reference 395

Appendix C Quantum Mechanical Treatment of the Two-Spin System 397

Appendix D Analysis of Second-Order, Three- and Four-Spin Systems by Inspection 409

Appendix E Relaxation 415

Appendix F Product-Operator Formalism and Coherence-Level Diagrams 421

Reference 433

Appendix G Stereochemical Considerations 435

G.1 Homotopics Groups 436

G.2 Enantiotopic Groups 438

G.3 Diastereotopic Groups 440

References 441

Index 443