Advances in Inorganic Chemistry (eBook)

Cover 1
ADVISORY BOARD 3
copyright 4
table of contents 5
PREFACE 9
ERRATUM 11
INTRODUCTION: GENERAL THEORY OF NUCLEAR RELAXATION 13
I. What is Nuclear Relaxation? 13
A. LONGITUDINAL RELAXATION 15
B. TRANSVERSE RELAXATION 19
C. THE ROTATING FRAME ... 23
D. CROSS-RELAXATION ... 23
E. CROSS-CORRELATION ... 27
II. Relaxation Mechanisms 30
A. INTERACTION WITH RAN... 30
B. RELAXATION BY CHEMIC... 34
C. SCALAR RELAXATION OF ... 38
D. RELAXATION BY DIPOLAR... 39
E. QUADRUPOLAR RELAX... 42
III. Water NMRD in Diamagnetic Systems 43
A. PUREWATER 44
B. WATER IN PROTEIN SOL... 44
REFERENCES 1 49
NMR RELAXATION IN SOLUTION OF PARAMAGNETIC COMPLEXES:RECENT THEORETICAL PROGRESS FOR S=1 51
I. Introduction 52
II. The ‘‘Classical’’ Theory 54
A. THE SOLOMON^BLOEMB... 54
B. THE MODIFIED SOLOMON... 58
C. VALIDITY OF THE POINT-... 60
D. THE REDFIELD RELAX... 62
III. The Curie-Spin Relaxation and Related Topics 65
A. THE CURIE-SPIN RELAX... 65
B. PARAMAGNETIC CROSS... 66
IV. The General (Slow-Motion) Theory 69
A. THE REDFIELD LIMIT AND ... 70
B. THE LATTICE AND THE ZFS 73
C. THE EFFECTS OF ZFS ... 79
V. Electron Spin Relaxation and the PRE in Some Limiting Cases 81
A. HIGHLY SYMMETRIC SYS... 83
B. SLOWLY-ROTATING, LOW... 84
C. RAPIDLY-ROTATING SYS... 89
D. ELECTRON SPIN DYNA... 92
VI. Spin-Dynamics Models 93
VII. Outer-Sphere Relaxation 95
A. GENERAL ASPECTS 96
B. OUTER-SPHERE PRE AND... 98
C. OUTER-SPHERE RELAX... 102
D. CHEMICAL EXCHANGE 105
VIII. Molecular Vibrations, Electron Spin Relaxation and the PRE 105
IX. Concluding Remarks 110
ACKNOWLEDGMENTS 2 110
REFERENCES 2 111
1H NMRD PROFILES OF PARAMAGNETIC COMPLEXES AND METALLOPROTEINS 115
I. From the NMRD Profile to the Electron Relaxation Mechanism 115
A. DEPENDENCE OF THE ... 116
B. THE ORIGIN OF ELECT... 123
C. ELECTRON RELAXATION ... 125
II. From the NMRD Profile to the Structural and Dynamic Parameters 150
A. DEPENDENCE OF THE ... 151
B. COPPER COMPLEXES ... 160
C. IRON COMPLEXES AND ... 163
D. MANGANESE COMPLEX... 165
E. OTHER TRANSITION... 168
F. GADOLINIUM COMPLEXES... 172
III. Magnetic Coupled Systems 173
A. NUCLEAR AND ELECT... 173
B. EXAMPLES 176
IV. Conclusions 178
ACKNOWLEDGMENTS 3 179
REFERENCES 3 179
Gd(III)-BASED CONTRAST AGENTS FOR MRI 183
I. General Remarks 183
II. Contributions to the Relaxivity 186
A. INNER-SPHERE CONTRI... 188
B. OUTER-SPHERE CONTRI... 194
C. SECOND-SPHERE CONTR... 199
III. Relevant Parameters in Fitting the NMRD Profiles of Contrast Agents 202
A. THE HYDRATION NUMBER q 202
B. THE Gd^H DISTANCE rH 204
C. THE ROTATIONAL CORRE... 205
D. THE EXCHANGE CORRE... 208
E. THE ELECTRON SPIN ... 209
IV. Methods for Improving Relaxivity 210
A. INCREASE OF THE HYD... 210
B. LENGTHENING OF tR 215
C. OPTIMIZATION OF tM 219
V. Responsive Contrast Agents 222
A. pH SENSITIVE 224
B. TEMPERATURE SENSITIVE 228
C. AGENTS SENSITIVE TO ... 229
D. ENZYME RESPONSIVE 230
E. AGENTS SENSITIVE TO ... 233
VI. Insights for Molecular Imaging Applications 236
VII. Final Remarks 241
REFERENCES 4 242
RELAXATION BY METAL-CONTAINING NANOSYSTEMS 249
I. Super-Paramagnetic Particles 249
A. INTRODUCTION 249
B. PHENOMENOLOGICAL ... 252
C. HIGH ANISOTROPYMODEL 255
D. SMALL CRYSTAL AND ... 257
E. RELAXATION OFAGGLO... 260
F. LARGE SPHERE OF FER... 261
G. APPLICATIONOF THE REL... 264
II. Ferritin, an Iron-Storage Protein 265
A. THE IRON-STORING FER... 265
B. PROTON RELAXATION BY... 269
C. THEORY OF FERRITIN-IND... 277
D. FERRITIN IN MRI 281
III. Gd(III)-Loaded Porous Systems as MRI Contrast Agents 283
A. ZEOLITE PARTICLES AS ... 283
B. CLAY MINERALS 286
C. EQUATIONS DESCRIBING ... 288
D. OTHER Gd(III)-LOADED, ... 291
E. CONCLUSION, GENERAL ... 293
IV. Paramagnetic Micelles and Lipsomes 293
A. STRUCTURE OF PARAMA... 294
B. STRUCTURE OF LIPOS... 294
C. PROTON RELAXIVITY AND... 295
D. RELAXIVITY OF MICELLAR... 296
E. RELAXIVITY OF LIPOS... 297
REFERENCES 5 299
MAGNETIC RELAXATION DISPERSION IN POROUS AND DYNAMICALLY HETEROGENEOUS MATERIALS 303
I. Introduction 6 303
II. The Magnetic Relaxation Dispersion 305
III. Relaxation Dispersion of Mobile Liquids in Inorganic Matrices 306
A. HIGHLY PURIFIED SYSTEMS 306
B. NATURAL SYSTEMS 312
IV. Proton Rich Solid Phases 321
A. CROSS-RELAXATION 321
B. THE SOLID PROTON CO... 326
C. POROUS PROTONIC SOLIDS 330
V. Rotational Dynamics of Liquids at Surfaces 331
REFERENCES 6 334
WATER AND PROTON EXCHANGE PROCESSES ON METAL IONS 337
I. Introduction 7 337
II. Concepts of Solvent Exchange Reactions 339
A. CLASSIFICATION OF MEC... 339
B. THE VOLUME OF ACTIV... 341
III. Water Exchange Rate Constants Measured by Oxygen-17 NMR 343
A. EXPERIMENTAL NMR TEC... 343
B. SLOW EXCHANGE STUD... 344
C. SWIFT AND CONNICK APP... 346
D. WATER EXCHANGE ON DI... 349
IV. Water Exchange on Main Group and d-Transition Metal Ions 350
A. MAIN GROUPMETAL IONS 350
B. FIRST-ROW d-TRANSIT... 355
C. SECOND AND THIRD ROW... 357
D. HYDROLYZED TRIVALENT... 360
E. PROTON EXCHANGE ON ... 361
F. WATER EXCHANGE ON ... 363
V. Water Exchange on f-Transition Metal Ions 365
A. WATER EXCHANGE ON ... 365
B. WATER EXCHANGE ON ... 368
C. WATER EXCHANGE ON ... 376
D. WATER EXCHANGE ON ... 377
VI. Appendix: Ligand Abbreviations, Formulae and Structures 378
ACKNOWLEDGMENTS 7 385
REFERENCES 7 385
NUCLEAR MAGNETIC RELAXATION STUDIES ON ACTINIDE IONS AND MODELS OF ACTINIDE COMPLEXES 391
I. Introduction 8 391
II. Actinide Ions 393
A. Menþ ACTINIDE IONS 393
B. ACTINYL DIOXO CATIONS ... 396
III. Questions of Nuclear Interest 404
A. REPROCESSING OF NUC... 404
B. MIGRATION OFACTINIDES ... 408
IV. Conclusions 411
ACKNOWLEDGMENTS 8 411
REFERENCES 8 411
TECHNICAL ASPECTS OF FAST FIELD CYCLING 415
I. Introduction 9 416
II. Premises of FFC NMR Relaxometry 419
III. The FFC Magnet 420
A. GENERAL CONSIDER... 420
B. OPTIMAL CONFIGUR... 421
C. ELECTRIC AND GEOMET... 423
D. EXAMPLE OF A REAL 1... 425
IV. Magnet Power Supply 431
A. GENERAL CONSIDER... 431
B. HISTORIC SOLUTIONS ... 432
C. SWITCHING TIME CONSID... 434
D. WHY THE BIPOLAR CONF... 436
E. POWER REGULATION ... 437
F. ACTIVE COMPENSATION ... 439
V. Cooling System 440
VI. Signal Detection Probe 442
VII. Control Console 443
VIII. FFC Data Acquisition Sequences 445
A. SPECIAL FFC FEATURES... 445
B. BASIC STRUCTURE OF ... 449
C. ELEMENTARY FFC SEQ... 450
IX. Acquisition and Evaluation of Complete Relaxation Curves 451
A. ARRAYED T1 MEASURE... 451
B. EFFECTS OF FIELD-SW... 454
C. DATA ACCUMULATION ... 455
D. EVALUATION OF THE ... 458
E. FACTORS INFLUENCING ... 460
F. OPTIMIZATION OF RELAX... 462
X. Signal Detection and Analysis 464
A. Hardware Detection 465
B. POST-DETECTION SIGNAL... 465
C. NMR SIGNAL EXCITATION ... 466
XI. Advanced FFC Sequences 471
A. THERMALLY BALANCED ... 471
B. INVERSION RECOVERY 472
C. JEENER^BROEKAERT DIP... 474
XII. Conclusions and Perspectives 474
REFERENCES 9 476
index 481
CONTENTS OF PREVIOUS VOLUMES 491