Two-Dimensional (2D) NMR Methods

TWO-DIMENSIONAL (2D) NMR METHODS Practical guide explaining the fundamentals of 2D-NMR for experienced scientists as well as relevant for advanced students Two-Dimensional (2D) NMR Methods is a focused work presenting an overview of 2D-NMR concepts and techniques, including basic principles, practical applications, and how NMR pulse sequences work. Contributed to by global experts with extensive experience in the field, Two-Dimensional (2D) NMR Methods provides in-depth coverage of sample topics such as: Basics of 2D-NMR, data processing methods (Fourier and beyond), product operator formalism, basics of spin relaxation, and coherence transfer pathways Multidimensional methods (single- and multiple-quantum spectroscopy), NOESY (principles and applications), and DOSY methods Multiple acquisition strategies, anisotropic NMR in molecular analysis, ultrafast 2D methods, and multidimensional methods in bio-NMR TROSY (principles and applications), field-cycling and 2D NMR, multidimensional methods and paramagnetic NMR, and relaxation dispersion experiments This text is a highly useful resource for NMR specialists and advanced students studying NMR, along with users in research, academic and commercial laboratories that study or conduct experiments in NMR.

Dedication v List of Contributors xvii Preface xix 1 Basics of Two-dimensional NMR 1 Malcolm H. Levitt 1.1 Introduction 1 1.2 Spin Dynamics 2 1.3 One-dimensional Fourier NMR 6 1.4 Two-dimensional NMR 11 1.5 Summary 14 2 Data Processing Methods: Fourier and Beyond 19 Vladislav Orekhov, Pawel Kasprzak, and Krzysztof Kazimierczuk 2.1 Introduction 19 2.2 Time-domain NMR Signal 19 2.3 NMR Spectrum 20 2.4 The Most Important Features of FT 20 2.5 Distortion: Phase 23 2.6 Kramers-Kronig Relations and Hilbert Transform 23 2.7 Distortion: Truncation 25 2.8 Distortion: Noise and Multiple Scans 27 2.9 Distortion: Sampling and DFT 27 2.10 Quadrature Detection 30 2.11 Processing:Weighting 31 2.12 Processing: Zero Filling 33 2.13 Fourier Transform in Multiple Dimensions 33 2.14 Quadrature Detection in Multiple Dimensions 36 2.15 Projection Theorem 37 2.16 ND Sampling Aspects and Sparse Sampling 40 2.17 Reconstructing Sparsely Sampled Data Sets 41 2.18 Deconvolution 42 3 Product Operator Formalism 47 Rolf Boelens and Robert Kaptein 3.1 Introduction 47 3.2 Product Operators and Time Evolution 48 3.3 Time Evolution of the Product Operators 55 3.4 Applications 59 3.4.1 Spin-echo Experiments 59 3.5 Two-dimensional Experiments 66 4 Relaxation in NMR Spectroscopy 93 Matthias Ernst 4.1 Introduction 93 4.2 Theory 95 4.3 Relaxation in Spin-1/2 Systems: Dipolar and CSA Relaxation 104 4.4 Other Relaxation Mechanisms 125 4.5 Concluding Remarks 130 5 Coherence Transfer Pathways 135 David E. Korenchan and Alexej Jerschow 5.1 Coherence Transfer Pathways: What and Why? 135 5.2 Principles of Coherence Selection 137 5.3 Coherence Transfer Pathway Selection by Phase Cycling 140 5.4 Cogwheel Phase Cycling 146 5.5 Coherence Transfer Pathway Selection by Pulsed-field Gradients 147 5.6 Comparison Between Phase Cycling and Pulsed-field Gradients 150 5.7 CTP Selection in Heteronuclear Spin Systems 150 5.8 Additional Approaches to Coherence Selection 151 6 Nuclear Overhauser Effect Spectroscopy 153 P.K. Madhu 6.1 Introduction 153 6.2 Nuclear Overhauser Effect 153 6.3 Measurement of NOE 161 6.4 Heteronuclear NOE 161 6.5 NOE Kinetics 162 6.6 Nuclear Overhauser Effect Spectroscopy, NOESY 164 6.7 Rotating-frame NOE, ROE 166 6.8 Relative Signs of Cross Peaks 168 6.9 Generalised Solomon’s Equation 169 6.10 NOESY and ROESY: Practical Considerations and Experimental Spectra 170 6.11 Conclusions 170 7 DOSY Methods for Studying Non-equilibrium Molecular and Ionic Systems 175 Muslim Dvoyashkin, Monika Schoönhoff, and Ville-Veikko Telkki 7.1 Introduction 175 7.2 Spatial Spin "Encoding" Using Magnetic Field Gradient 175 7.3 Formation of NMR Signal and Spin Echo in the Presence of Field Gradient 176 7.4 NMR of Liquids in An Electric Field: Electrophoretic NMR 178 7.5 Ultrafast Diffusion Measurements 186 7.6 Ultrafast Diffusion Exchange Spectroscopy 189 8 Multiple Acquisition Strategies 195 Nathaniel J. Traaseth 8.1 Introduction 195 8.2 Types of Multiple Acquisition Experiments 195 8.3 Utilization of Forgotten Spin Operators 196 8.4 Application of Multiple Acquisition Techniques 198 8.5 Modularity of Multiple Detection Schemes and Other Novel Approaches 201 8.6 Future of Multiple Acquisition Detection 202 9 Anisotropic One-dimensional/Two-dimensional NMR in Molecular Analysis 209 Philippe Lesot and Roberto R. Gil 9.1 Introduction 209 9.2 Advantages of Oriented Solvents 210 9.3 Description of Useful Anisotropic NMR Parameters 213 9.4 Adapted 2D NMR Tools 221 9.5 Examples of Polymeric Liquid Crystals 226 9.6 Contribution to the Analysis of Chiral and Prochiral Molecules 232 9.7 Structural Value of Anisotropic NMR Parameters 248 9.8 Conformational Analysis in Oriented Solvents 276 9.9 Anisotropic 2H 2D NMR Applied to Molecular Isotope Analysis 277 9.10 Anisotropic NMR in Molecular Analysis: What You Should Keep in Mind 281 10 Ultrafast 2D methods 297 Boris Gouilleux 10.1 Introduction 297 10.2 UF 2D NMR Principles: Entangling the Space and the Time 299 10.3 Specific Features of UF 2D NMR 305 10.4 Advanced UF Methods 307 10.5 UF 2D NMR: A Versatile Approach 311 10.6 Overview of UF 2D NMR Applications 316 10.7 Conclusion 326 11 Multi-dimensional Methods in Biological NMR 333 Tobias Schneider and Michael Kovermann 11.1 Introduction 333 11.2 Experimental Approaches 334 11.3 Case Studies 338 12 TROSY: Principles and Applications 365 Harindranath Kadavath and Roland Riek 12.1 Introduction 365 12.2 The Principles of TROSY 366 12.3 Practical Aspects of TROSY 371 12.4 Applications of TROSY 374 12.5 Transverse Relaxation-optimization in the Polarization Transfers 379 12.6 15N Direct Detected TROSY 380 12.7 [1H,13C]-TROSY Correlation Experiments 380 12.8 Applications to Nucleic Acids 382 12.9 Intermolecular Interactions and Drug Design 383 12.10 Conclusion 383 13 Two-Dimensional Methods and Zero- to Ultralow-Field (ZULF) NMR 395 K.L. Ivanov, John Blanchard, Dmitry Budker, Fabien Ferrage, Alexey Kiryutin, Tobias Sjolander, Alexandra Yurkovskaya, and Ivan Zhukov 13.1 Introduction and Motivation 395 13.2 EarlyWork 396 13.3 Two-dimensional NMR Measured at Zero Magnetic Field 397 13.4 Nuclear Magnetic Resonance at Millitesla Fields Using a Zero-Field Spectrometer 403 13.5 Field Cycling NMR and Correlation Spectroscopy 404 13.6 ZERO-Field - High-Field Comparison 409 13.7 Conclusion and Outlook 412 14 Multidimensional Methods and Paramagnetic NMR 415 Thomas Robinson, Kevin J. Sanders, Andrew J. Pell, and Guido Pintacuda 14.1 Introduction 415 14.2 NMR Methods for Paramagnetic Systems in Solution 416 14.3 NMR Methods for Paramagnetic Systems in Solids 423 15 Chemical Exchange 435 Ashok Sekhar and Pramodh Vallurupalli 15.1 Introduction 435 15.2 Bloch-McConnell Equations 436 15.3 Studying Exchange Between Visible States 443 15.4 Studying Exchange Between a Visible State and Invisible State(s) 448 15.5 Summary 458 Acknowledgments 459 References 459 Appendix A Proton-Detected Heteronuclear and Multidimensional NMR 461 Christian Griesinger, Harald Schwalbe, Jürgen Schleucher, and Michael Sattler Index 553