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Book Details
Abstract
Field-cycling NMR relaxometry is evolving into a methodology of widespread interest with recent technological developments resulting in powerful and versatile commercial instruments. Polymers, liquid crystals, biomaterials, porous media, tissue, cement and many other materials of practical importance can be studied using this technique.
This book summarises the expertise of leading scientists in the area and the editor is well placed, after four decades of working in this field, to ensure a broad ranging and high quality title. Starting with an overview of the basic principles of the technique and the scope of its use, the content then develops to look at theory, instrumentation, practical limitations and applications in different systems.
Newcomers to the field will find this book invaluable for successful use of the technique. Researchers already in academic and industrial settings, interested in molecular dynamics and magnetic resonance, will discover an important addition to the literature.
Rainer Kimmich is an emerited professor of physics at the University of Ulm. The subject of the proposed book, Field-Cycling NMR Relaxometry, is the research methodology he has been working on over four decades starting in the seminal stages of the technique. A large part of the roughly 300 papers he has authored or co-authored refer to this technology and its applications. He has published two monographs including chapters on this variant of NMR relaxometry.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Preface | v | ||
| Contents | vii | ||
| Chapter 1 Principle, Purpose and Pitfalls of Field-cycling NMR Relaxometry | 1 | ||
| 1.1 Revelation and Analytical Representation of Molecular Fluctuations | 1 | ||
| 1.1.1 From Molecular Motions to Spin-Lattice Relaxation | 5 | ||
| 1.1.2 What Time Scale of Autocorrelation Functions Do We Probe in NMR Relaxometry? | 16 | ||
| 1.1.3 The Field-cycling Principle | 17 | ||
| 1.1.4 Technical Limits | 20 | ||
| 1.1.5 Physical Limits | 21 | ||
| 1.2 Exchange in Heterogeneous and Multi-phase Systems | 23 | ||
| 1.2.1 Exponential and Non-exponential Relaxation Curves | 25 | ||
| 1.2.2 Exchange Relative to the Time Scale of Correlation Functions | 26 | ||
| 1.3 Remarks on Correlation Functions and Their Parallelism with Relaxation Functions | 31 | ||
| 1.3.1 Calculation of Correlation Functions | 31 | ||
| 1.3.2 Parallelism of Correlation and Relaxation Functions | 36 | ||
| 1.3.3 Superposition of Restricted Fluctuations | 37 | ||
| 1.4 Concluding Remarks | 39 | ||
| References | 39 | ||
| Chapter 2 Essentials of the Theory of Spin Relaxation as Needed for Field-cycling NMR | 42 | ||
| 2.1 Perturbation Theory of Spin Relaxation | 42 | ||
| 2.2 High-field Relaxation Theory | 47 | ||
| 2.3 Relaxation Theories for an Arbitrary Magnetic Field | 51 | ||
| 2.3.1 Non-Zeeman Energy Level Structure | 51 | ||
| 2.3.2 Relaxation in Paramagnetic Systems | 55 | ||
| 2.4 Superparamagnetic Systems | 60 | ||
| 2.5 Stochastic Liouville Approach | 61 | ||
| 2.6 Dipole-dipole Relaxation Mechanism at Low Field | 63 | ||
| References | 64 | ||
| Chapter 3 New Trends in Field-cycling NMR Technology | 67 | ||
| 3.1 Introduction | 67 | ||
| 3.2 Historical Frame | 68 | ||
| 3.3 Machines and Applications | 69 | ||
| 3.3.1 Relaxometry | 69 | ||
| 3.3.2 Double Irradiation | 70 | ||
| 3.3.3 Zero and Earth's Field | 70 | ||
| 3.3.4 Field-cycling MRI | 70 | ||
| 3.4 Technology | 71 | ||
| 3.4.1 Power Management | 71 | ||
| 3.4.2 Magnet Technology | 74 | ||
| 3.4.3 FFC Magnet Current Control Strategy | 79 | ||
| 3.4.4 Magnetic Field Compensation | 81 | ||
| 3.4.5 Field Homogeneity Versus Electrical Parameters | 82 | ||
| 3.5 Concluding Remarks and Future Perspectives | 83 | ||
| References | 84 | ||
| Chapter 4 Broadband Fast Field-cycling Relaxometer: Requirements, Instrumentation and Verification | 88 | ||
| 4.1 Introduction | 88 | ||
| 4.2 Requirements for FFC Relaxometers | 91 | ||
| 4.3 Instrumentation | 95 | ||
| 4.3.1 Setup Overview | 95 | ||
| 4.3.2 Magnetic System | 95 | ||
| 4.3.3 Electronics | 99 | ||
| 4.3.4 Probe Head Design | 103 | ||
| 4.4 Experimental Verification | 105 | ||
| 4.4.1 Detection Field Homogeneity and Stability | 106 | ||
| 4.4.2 Switching Transients Control | 107 | ||
| 4.4.3 Low-field Calibration | 108 | ||
| 4.4.4 Effects of Evolution Field Instabilities | 112 | ||
| 4.5 Conclusion | 113 | ||
| Acknowledgments | 114 | ||
| References | 115 | ||
| Chapter 5 Specific Aspects of the Design of Field-cycling Devices | 118 | ||
| 5.1 Introduction | 118 | ||
| 5.2 Power Systems | 119 | ||
| 5.2.1 The Insulated-gate Bipolar Transistor | 121 | ||
| 5.2.2 Solution Shunting IGBTs | 122 | ||
| 5.2.3 The Switching Solution | 124 | ||
| 5.2.4 The Linear Source | 127 | ||
| 5.3 Magnets | 130 | ||
| 5.3.1 Air-core Magnet | 130 | ||
| 5.3.2 The Ferromagnetic Solution | 131 | ||
| 5.4 Control | 134 | ||
| 5.5 Conclusion | 135 | ||
| Acknowledgments | 136 | ||
| References | 136 | ||
| Chapter 6 Signal Enhancement for Fast Field-cycling Relaxometry by Dynamic Nuclear Polarization: Basic Principles, Hardware and Methods | 138 | ||
| 6.1 Introduction | 138 | ||
| 6.2 Basic Principles of Overhauser DNP and Solid-effect DNP | 141 | ||
| 6.3 Common Radicals for DNP-FFC | 149 | ||
| 6.4 Hardware Requirements for DNP-FFC | 151 | ||
| 6.5 Choice of the Polarization Field Strength and Microwave Frequency | 154 | ||
| 6.6 Sample Heating Effects | 157 | ||
| 6.7 A Pulse Sequence for DNP-FFC | 159 | ||
| 6.8 Conclusion | 160 | ||
| Acknowledgments | 161 | ||
| References | 161 | ||
| Chapter 7 Relaxometry at Very Low Frequencies by Rotating-frame Techniques for Complementing the Frequency Domain Explored by Field Cycling | 165 | ||
| 7.1 Introduction | 165 | ||
| 7.2 Theoretical Survey | 167 | ||
| 7.2.1 Relaxation by Randomly Varying Magnetic Fields | 167 | ||
| 7.2.2 Dipolar Relaxation (Like Spins) | 172 | ||
| 7.3 Experimental Method for Measuring R1ρ | 172 | ||
| 7.4 Connection Between R1 and R1ρ Dispersion Curves | 173 | ||
| 7.4.1 Connection in the Case of Relaxation by Random Fields | 173 | ||
| 7.4.2 Attempt to Use the ‘‘Like Spins\" Relaxation Mechanism | 173 | ||
| 7.4.3 A Complete Dispersion Curve: from a Frequency Very Close to Zero to Several Hundred Megahertz | 176 | ||
| 7.4.4 The Data Point at Zero Frequency | 178 | ||
| 7.5 Conclusion | 178 | ||
| References | 179 | ||
| Chapter 8 Application of Field-cycling 1H NMR Relaxometry to the Study of Translational and Rotational Dynamics in Liquids and Polymers | 181 | ||
| 8.1 Introduction | 181 | ||
| 8.2 Theoretical Background | 183 | ||
| 8.2.1 Intra- and Intermolecular 1H Relaxation in Simple Liquids | 183 | ||
| 8.2.2 Particularities in Polymer Melts | 188 | ||
| 8.3 Results | 192 | ||
| 8.3.1 Simple Liquids | 192 | ||
| 8.3.2 Polymers | 198 | ||
| 8.4 Outlook | 202 | ||
| References | 202 | ||
| Chapter 9 Nuclear Magnetic Relaxtion Dispersion of Water-Protein Systems | 207 | ||
| 9.1 Introduction | 207 | ||
| 9.2 Protein Solutions | 209 | ||
| 9.3 Rotational Immobilization | 212 | ||
| 9.4 Paramagnetic Effects in Immobilized Systems | 220 | ||
| 9.5 Aggregation | 221 | ||
| 9.6 High-field Water Dispersion in Aqueous Protein Systems | 223 | ||
| 9.7 Conclusion | 225 | ||
| Acknowledgments | 225 | ||
| References | 225 | ||
| Chapter 10 Environmental Applications of Fast Field-cycling NMR Relaxometry | 229 | ||
| 10.1 Introduction | 229 | ||
| 10.2 T1 Values and Molecular Motions | 231 | ||
| 10.3 The Basic Experiment and the Models for Data Elaboration in Environmental Analysis | 232 | ||
| 10.4 Fast Field Cycling in Understanding Solid-state Environmental Compartments | 239 | ||
| 10.4.1 Understanding Soils with Fast Field-cycling NMR Relaxometry | 239 | ||
| 10.4.2 Field Cycling and Sediments | 243 | ||
| 10.5 Fast Field Cycling in Understanding Liquid-state Environmental Compartments | 244 | ||
| 10.5.1 Inorganic Water Solutions Investigated by Fast Field-cycling NMR Relaxometry | 244 | ||
| 10.5.2 Field-cycling NMR Relaxometry and Dissolved Organic Matter (DOM) | 246 | ||
| 10.6 Dynamics of Nutrients in Soil Solution as Revealed by Fast Field-cycling NMR Relaxometry | 247 | ||
| 10.7 Conclusions and Perspectives | 250 | ||
| References | 252 | ||
| Chapter 11 NMR Relaxometry in Liquid Crystals: Molecular Organization and Molecular Dynamics Interrelation | 255 | ||
| 11.1 Introduction to Liquid Crystals | 255 | ||
| 11.2 Fundamentals of NMR Relaxation | 259 | ||
| 11.2.1 Molecular Motions and Relaxation Mechanisms | 263 | ||
| 11.2.2 Translational Self-diffusion | 267 | ||
| 11.2.3 Collective Motions | 274 | ||
| 11.3 Review of Spin-Lattice Relaxation in Different Liquid Crystal Phases | 275 | ||
| 11.3.1 Isotropic Phases of Liquid Crystals | 276 | ||
| 11.3.2 Blue Phases | 278 | ||
| 11.3.3 Nematic and Chiral Nematic Phases | 279 | ||
| 11.3.4 Smectic Phases | 282 | ||
| 11.3.5 Columnar Phases | 289 | ||
| 11.3.6 Lyotropic Phases | 292 | ||
| 11.3.7 Liquid Crystals in Nano Porous Glasses | 293 | ||
| 11.4 Final Remarks and Outlook | 295 | ||
| 11.5 Appendix | 297 | ||
| References | 298 | ||
| Chapter 12 Interfacial and Intermittent Dynamics of Water in Colloidal Systems as Probed by Fast Field-cycling Relaxometry | 303 | ||
| 12.1 Introduction | 303 | ||
| 12.2 Molecular Intermittent Interfacial Dynamics | 305 | ||
| 12.2.1 Bridge and Relocation Statistics | 305 | ||
| 12.2.2 Spectral Density of Intermittent Dynamics | 306 | ||
| 12.2.3 Case of Relocation Statistics with Algebraic Tail at Long Time | 307 | ||
| 12.3 Probing Intermittent Interfacial Dynamics by NMRD | 309 | ||
| 12.4 NMRD in Various Colloidal Systems | 311 | ||
| 12.4.1 Very Large Flat Interface: the Case of Plaster | 311 | ||
| 12.4.2 Finite Flat Surfaces and Escape Process: the Case of a Clay Dispersion | 314 | ||
| 12.4.3 Probing Other Colloidal Shapes: The Case of a Rigid Cylindrical Colloid | 316 | ||
| 12.5 Conclusion | 318 | ||
| Acknowledgments | 319 | ||
| References | 320 | ||
| Chapter 13 Field-cycling Relaxometry of Polymers | 322 | ||
| 13.1 Introduction | 322 | ||
| 13.2 Polymer Molecules, Short and Long | 324 | ||
| 13.2.1 Theory of the Dynamics of Short and Long Polymers | 325 | ||
| 13.2.2 Experimental Results for Polymer Melts | 331 | ||
| 13.3 Polymer Solutions | 339 | ||
| 13.4 Superstructures of Polymer Molecules | 339 | ||
| 13.5 Polymers in Confinement | 344 | ||
| 13.6 Solid Polymers | 345 | ||
| 13.7 Alternative Methods | 349 | ||
| 13.8 Pitfalls and Limitations | 351 | ||
| 13.9 Recent Developments | 354 | ||
| 13.10 Conclusion and Outlook | 355 | ||
| References | 356 | ||
| Chapter 14 Techniques and Applications of Field-cycling Magnetic Resonance in Medicine | 358 | ||
| 14.1 Introduction | 358 | ||
| 14.2 Pulse Sequences for FFC-MRI | 359 | ||
| 14.3 Uses of Fast Field Cycling in Combination with MRI | 359 | ||
| 14.3.1 Field-cycled Proton-Electron Double-resonance Imaging of Free Radicals | 359 | ||
| 14.3.2 Field-cycling Relaxometric MRI | 361 | ||
| 14.3.3 Pre-polarised MRI Using Field Cycling | 362 | ||
| 14.3.4 Delta Relaxation-enhanced Magnetic Resonance (dreMR) | 363 | ||
| 14.4 Magnet Technology for FFC-MRI | 364 | ||
| 14.4.1 Dual Magnet for Pre-polarised MRI | 365 | ||
| 14.4.2 Dual Magnet for dreMR | 366 | ||
| 14.4.3 Dual Magnet for FFC-MRI | 367 | ||
| 14.4.4 Single-magnet FFC-MRI System | 368 | ||
| 14.4.5 Rotating Probe/Sample Approach in In Vivo FFC-MRI | 369 | ||
| 14.5 Techniques for FFC-MRI | 371 | ||
| 14.5.1 Fast Spin Echo | 371 | ||
| 14.5.2 Localised Relaxometry | 372 | ||
| 14.5.3 Keyhole FFC-MRI | 372 | ||
| 14.5.4 Data Processing and Correction Techniques | 373 | ||
| 14.6 Biomedical Applications of FFC | 375 | ||
| 14.6.1 Cancer | 377 | ||
| 14.6.2 Muscular Oedema and Damage | 378 | ||
| 14.6.3 Osteoarthritis | 379 | ||
| 14.7 Conclusion | 381 | ||
| References | 382 | ||
| Chapter 15 High-resolution Applications of Shuttle Field-cycling NMR | 385 | ||
| 15.1 Introduction - Why Use High-resolution Shuttle Field Cycling? | 385 | ||
| 15.2 The Redfield ‘‘Spin Spa | 386 | ||
| 15.3 Typical 31P Profile | 390 | ||
| 15.4 Uses of 31P Shuttle Field-cycling Relaxometry in Biological Systems | 392 | ||
| 15.4.1 Small Molecules Binding to Macromolecules - Probing Bound Molecule Dynamics | 392 | ||
| 15.4.2 Phospholipid Aggregates - Two Dipolar Terms for Vesicles and Micelles | 393 | ||
| 15.4.3 Using Spin-labeled Protein to Characterize Protein Interactions with Small Molecules and phospholipids | 395 | ||
| 15.5 Future of Shuttle Field Cycling? | 402 | ||
| References | 403 | ||
| Chapter 16 Quantum Molecular Tunnelling Studied by Field-cycling NMR | 405 | ||
| 16.1 Introduction | 405 | ||
| 16.2 Coherent and Incoherent Tunnelling | 406 | ||
| 16.3 Incoherent Tunnelling in the Hydrogen Bond: Concerted 1H Transfer in H-bond Dimers | 407 | ||
| 16.4 Coherent Tunnelling in a Quantum Molecular Rotor: The Methyl Group, CH3 | 413 | ||
| 16.4.1 Level-crossing Tunnelling Spectroscopy of CH3 | 416 | ||
| 16.4.2 ESR Tunnel Resonance | 419 | ||
| 16.4.3 Low-field Dipole-Dipole-driven NMR Spectroscopy | 421 | ||
| 16.4.4 Combining Low-field NMR with Level-crossings; Dynamic Tunnelling Polarisation | 423 | ||
| 16.5 Conclusion | 425 | ||
| References | 426 | ||
| Chapter 17 Paramagnetic Complexes and Superparamagnetic Systems | 427 | ||
| 17.1 Introduction | 427 | ||
| 17.2 Paramagnetic Relaxation of Lanthanide Complexes | 428 | ||
| 17.2.1 Paramagnetic Relaxation: Theoretical Model | 428 | ||
| 17.2.2 NMRD Profiles of Paramagnetic Gd Complexes | 434 | ||
| 17.3 Superparamagnetic Relaxation of Iron Oxide Nanoparticles | 435 | ||
| 17.3.1 Superparamagnetic Relaxation: Theoretical Model | 437 | ||
| 17.3.2 Influence of Different Parameters on the Shape of the NMRD Profiles | 441 | ||
| 17.4 Conclusion | 445 | ||
| Acknowledgments | 445 | ||
| References | 445 | ||
| Chapter 18 Probing the Dynamics of Petroleum Fluids in Bulk and Confinement by Fast Field-cycling Relaxometry | 448 | ||
| 18.1 Introduction | 448 | ||
| 18.2 NMRD Analysis of the Structure and Dynamics of Crude Oils in Bulk With and Without Asphaltene | 449 | ||
| 18.3 Dynamics and Wettability of Oil and Water in the Dual Organic and Mineral Porosities of Shale Oils | 455 | ||
| 18.3.1 Theoretical Model for Interpreting the Logarithmic Behaviour of Confined Brine-water NMRD Profile | 456 | ||
| 18.3.2 Theoretical Model for Interpreting the Power-law Behaviour of Confined Oil NMRD Profile | 458 | ||
| 18.4 Conclusion | 459 | ||
| Acknowledgments | 459 | ||
| References | 460 | ||
| Chapter 19 Applications of Field-cycling NMR Relaxometry to Cement Materials | 462 | ||
| 19.1 Introduction | 462 | ||
| 19.2 Cement Hydration and the Development of Porous Structure | 464 | ||
| 19.2.1 Stages of Hydration | 464 | ||
| 19.2.2 Porous Structure of Cement Paste | 467 | ||
| 19.3 Fast Field-cycling NMR Relaxometry and the Relaxation Model | 469 | ||
| 19.3.1 Fast Field-cycling Technique | 469 | ||
| 19.3.2 Relaxation Model | 469 | ||
| 19.4 Temperature Effects on the Hydration Process via FFC Relaxometry | 472 | ||
| 19.4.1 Sample Preparation and Experimental Setup | 473 | ||
| 19.4.2 Results and Discussion | 474 | ||
| 19.5 Effects of Silica Fume Addition on Cement Hydration via FFC Relaxometry | 477 | ||
| 19.5.1 Sample Preparation and Experimental Setup | 479 | ||
| 19.5.2 Results and Discussion | 480 | ||
| 19.6 Cement Hydration in the Presence of Superplasticizers | 482 | ||
| 19.7 Conclusion | 486 | ||
| Acknowledgments | 486 | ||
| References | 486 | ||
| Chapter 20 Application of Fast Field-cycling NMR Relaxometry to Soil Material | 490 | ||
| 20.1 Motivation | 490 | ||
| 20.2 Basics of Soil Physics | 491 | ||
| 20.2.1 Soil Types | 491 | ||
| 20.2.2 Soil Water | 493 | ||
| 20.2.3 Soil Mineralogy | 494 | ||
| 20.3 Relaxation in Porous Media | 495 | ||
| 20.3.1 Brownstein-Tarr Model | 495 | ||
| 20.3.2 Extended Brownstein-Tarr Model | 496 | ||
| 20.4 Results | 500 | ||
| 20.4.1 Saturated Soil Material | 500 | ||
| 20.4.2 Unsaturated Soil Material | 503 | ||
| 20.5 Conclusion | 509 | ||
| Acknowledgments | 509 | ||
| References | 510 | ||
| Chapter 21 Fast Field-cycling NMR Experiments with Hyperpolarized Spins | 512 | ||
| 21.1 Introduction | 512 | ||
| 21.2 Instrumentation | 514 | ||
| 21.3 Theoretical Background | 518 | ||
| 21.3.1 Field Dependence of Relaxation | 519 | ||
| 21.3.2 Polarization Transfer | 523 | ||
| 21.3.3 Relaxation and Coherent Polarization Transfer | 526 | ||
| 21.4 Dynamic Nuclear Polarization | 529 | ||
| 21.5 Optical Nuclear Polarization and Optical Pumping | 530 | ||
| 21.6 Chemically Induced Dynamic Nuclear Polarization | 534 | ||
| 21.7 PHIP/SABRE | 542 | ||
| 21.8 Conclusion and Outlook | 549 | ||
| Acknowledgments | 550 | ||
| References | 550 | ||
| Subject Index | 563 |