In Vivo NMR Spectroscopy, 2nd Edition

591 Pages·2007·21.798 MB·English

by  Robin A. de Graaf(auth.)

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In Vivo NMR Spectroscopy – 2nd Edition
In Vivo NMR Spectroscopy – 2nd Edition: Principles and Techniques Robin A. de Graaf
(cid:1)C 2007 John Wiley & Sons, Ltd. ISBN: 978-0-470-02670-0
i
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In Vivo
NMR Spectroscopy
– 2nd Edition
Principles and
Techniques
ROBINA.DEGRAAF
YaleUniversity,Connecticut,USA
iii
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LibraryofCongressCataloging-in-PublicationData
DeGraaf,RobinA.
InvivoNMRspectroscopy:principlesandtechniques/RobindeGraaf.–2nded.
p.;cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-02670-0(cloth:alk.paper)
1.Nuclearmagneticresonancespectroscopy. 2.Magneticresonanceimaging. I.Title.
[DNLM: 1.MagneticResonanceSpectroscopy–diagnosticuse. 2.MagneticResonance
Spectroscopy–methods. QU25D321i2007]
QP519.9.N83D4 2007
616.07(cid:3)548–dc22 2007018548
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iv
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Contents
Preface xiii
ListofAbbreviationsandSymbols xv
1 BasicPrinciples 1
1.1 Introduction 1
1.2 ClassicalDescription 2
1.3 QuantumMechanicalDescription 4
1.4 MacroscopicMagnetization 6
1.5 Excitation 8
1.6 BlochEquations 11
1.7 FourierTransformNMR 14
1.8 ChemicalShift 18
1.9 DigitalFourierTransformNMR 20
1.9.1 Multi-scanPrinciple 20
1.9.2 Time-domainFiltering 20
1.9.3 Analog-To-DigitalConversion 22
1.9.4 ZeroFilling 25
1.10 Spin–spinCoupling 26
1.10.1 SpectralCharacteristics 30
1.11 T Relaxation 33
1
1.12 T RelaxationandSpin-echoes 36
2
1.13 Exercises 38
References 41
2 InVivoNMRSpectroscopy–StaticAspects 43
2.1 Introduction 43
2.2 ProtonNMRSpectroscopy 43
2.2.1 Acetate(Ace) 45
2.2.2 N-AcetylAspartate(NAA) 45
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vi Contents
2.2.3 N-AcetylAspartylGlutamate(NAAG) 52
2.2.4 AdenosineTriphosphate(ATP) 52
2.2.5 Alanine(Ala) 53
2.2.6 γ-AminobutyricAcid(GABA) 54
2.2.7 AscorbicAcid(Asc) 54
2.2.8 Aspartate(Asp) 55
2.2.9 Choline-containingCompounds(tCho) 55
2.2.10 Creatine(Cr)andPhosphocreatine(PCr) 57
2.2.11 EthanolamineandPhosphorylethanolamine(PE) 58
2.2.12 Glucose(Glc) 59
2.2.13 Glutamate(Glu) 59
2.2.14 Glutamine(Gln) 61
2.2.15 Glutathione(GSH) 62
2.2.16 Glycerol 62
2.2.17 Glycine 63
2.2.18 Glycogen 63
2.2.19 Histamine 64
2.2.20 Histidine 65
2.2.21 Homocarnosine 65
2.2.22 β-Hydroxybutyrate(BHB) 66
2.2.23 Myo-Inositol(mI)andscyllo-Inositol(sI) 66
2.2.24 Lactate(Lac) 67
2.2.25 Macromolecules 68
2.2.26 Phenylalanine 70
2.2.27 Pyruvate 70
2.2.28 Serine 71
2.2.29 Succinate 71
2.2.30 Taurine(Tau) 72
2.2.31 Threonine(Thr) 72
2.2.32 Tryptophan(Trp) 73
2.2.33 Tyrosine(Tyr) 73
2.2.34 Valine(Val) 74
2.2.35 Water 74
2.2.36 Intra-andExtramyocellularLipids(IMCLandEMCL) 75
2.2.37 Deoxymyoglobin(DMb) 76
2.2.38 CitricAcid 77
2.2.39 Carnosine 78
2.3 Phosphorus-31NMRSpectroscopy 78
2.3.1 IdentificationofResonances 79
2.3.2 IntracellularpH 80
2.4 Carbon-13NMRSpectroscopy 82
2.4.1 IdentificationofResonances 82
2.5 Sodium-23andPotassium-39NMRSpectroscopy 85
2.6 Fluorine-19NMRSpectroscopy 89
2.6.1 IdentificationofResonances 89
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Contents vii
2.6.2 FluorinatedDrugs,Anaesthetics,andFluorodeoxyglucose
Metabolism 90
2.6.3 FluorinatedProbes 92
2.7 Exercises 93
References 95
3 InVivoNMRSpectroscopy–DynamicAspects 111
3.1 Introduction 111
3.2 Relaxation 112
3.2.1 GeneralPrinciplesofDipolarRelaxation 112
3.2.2 NuclearOverhauserEffect 118
3.2.3 AlternativeRelaxationMechanisms 119
3.2.4 InVivoRelaxation 122
3.3 MagnetizationTransfer 128
3.3.1 CreatineKinase 130
3.3.2 InversionTransfer 131
3.3.3 SaturationTransfer 131
3.3.4 ATpases 134
3.3.5 FastMagnetizationTransferMethods 135
3.3.6 Off-resonanceMagnetizationTransfer 136
3.3.7 ChemicalExchangeDependentSaturationTransfer 141
3.4 Diffusion 141
3.4.1 PrinciplesofDiffusion 141
3.4.2 DiffusionandNMR 143
3.4.3 AnisotropicDiffusion 152
3.4.4 RestrictedDiffusion 156
3.5 DynamicCarbon-13NMRSpectroscopy 158
3.5.1 GeneralSet-up 160
3.5.2 MetabolicModeling 162
3.5.3 Substrates 166
3.5.4 Applications 171
3.6 Hyperpolarization 171
3.6.1 “BruteForce”Hyperpolarization 172
3.6.2 OpticalPumpingofNobleGases 173
3.6.3 Para-hydrogen-inducedPolarization(PHIP) 175
3.6.4 DynamicNuclearPolarization 177
3.7 Exercises 179
References 181
4 MagneticResonanceImaging 191
4.1 Introduction 191
4.2 MagneticFieldGradients 192
4.3 SliceSelection 193
4.4 FrequencyEncoding 195
4.5 PhaseEncoding 201
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4.6 SpatialFrequencySpace 202
4.7 FastMRISequences 206
4.7.1 Echo-planarImaging 208
4.8 ContrastinMRI 212
4.8.1 T andT RelaxationMapping 213
1 2
4.8.2 FastT andT RelaxationMapping 214
1 2
4.8.3 MagneticFieldB Mapping 216
0
4.8.4 MagneticFieldB Mapping 218
1
4.8.5 AlternativeImageContrastMechanisms 219
4.8.6 FunctionalImaging 220
4.9 ParallelMRI 222
4.10 Exercises 225
References 229
5 RadiofrequencyPulses 233
5.1 Introduction 233
5.2 SquareRFPulses 233
5.3 SelectiveRFPulses 239
5.3.1 SincPulses 239
5.3.2 GaussianandHermitianPulses 243
5.3.3 MultifrequencyRFPulses 246
5.4 PulseOptimization 247
5.4.1 Shinnar–LeRouxAlgorithm 248
5.5 DANTERFPulses 254
5.6 CompositeRFPulses 255
5.7 AdiabaticRFPulses 258
5.7.1 RotatingFramesofReference 259
5.7.2 AdiabaticHalfandFullPassagePulses 262
5.7.3 PlaneRotationsandRefocusedComponent 268
5.7.4 AdiabaticFullPassageRefocusing 269
5.7.5 AdiabaticPlaneRotationPulses 269
5.7.6 VariableAngleAdiabaticPlaneRotationPulse,BIR-4 271
5.7.7 ModulationFunctions 274
5.7.8 Offset-independentAdiabaticity 275
5.8 PulseImperfectionsandRelaxation 276
5.9 PowerDeposition 280
5.10 MultidimensionalRFPulses 283
5.11 Spectral–spatialRFPulses 289
5.12 Exercises 290
References 292
6 SingleVolumeLocalizationandWaterSuppression 297
6.1 Introduction 297
6.2 SingleVolumeLocalization 299
6.2.1 ImageSelectedInVivoSpectroscopy(ISIS) 299
6.2.2 ChemicalShiftDisplacement 302
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Contents ix
6.2.3 StimulatedEchoAcquisitionMode(STEAM) 306
6.2.4 PointResolvedSpectroscopy(PRESS) 310
6.2.5 SignalDephasingwithMagneticFieldGradients 311
6.2.6 EffectsofImperfectRFPulses 317
6.2.7 LocalizationbyAdiabaticSelectiveRefocusing
(LASER) 320
6.2.8 ChemicalShiftDisplacement–Scalar-coupledSpins 322
6.3 WaterSuppression 325
6.3.1 BinomialandRelatedPulseSequences 326
6.3.2 FrequencySelectiveExcitation 333
6.3.3 FrequencySelectiveRefocusing 337
6.3.4 RelaxationBasedMethods 338
6.3.5 Non-water-suppressedNMRSpectroscopy 340
6.4 Exercises 341
References 344
7 SpectroscopicImagingandMultivolumeLocalization 349
7.1 Introduction 349
7.2 PrinciplesofSpectroscopicImaging 349
7.3 SpatialResolutioninMRSI 354
7.4 TemporalResolutioninMRSI 357
7.4.1 ConventionalMethods 357
7.4.2 MethodsBasedonFastMRISequences 361
7.4.3 MethodsBasedonPriorKnowledge 365
7.5 LipidSuppression 367
7.5.1 RelaxationBasedMethods 368
7.5.2 OuterVolumeSuppressionandVolume
Pre-localization 368
7.5.3 MethodsUtilizingSpatialPriorKnowledge 371
7.6 SpectroscopicImagingProcessingandDisplay 373
7.7 MultivolumeLocalization 377
7.7.1 HadamardLocalization 378
7.7.2 SequentialMultivolumeLocalization 380
7.8 Exercises 382
References 384
8 SpectralEditingandTwo-dimensionalNMR 389
8.1 Introduction 389
8.2 ScalarEvolution 390
8.3 J-differenceEditing 392
8.4 PracticalConsiderationsofJ-differenceEditing 397
8.5 MultipleQuantumCoherenceEditing 402
8.6 HeteronuclearSpectralEditing 407
8.7 PolarizationTransfer–INEPTandDEPT 409
8.8 Sensitivity 414
8.9 BroadbandDecoupling 416
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x Contents
8.10 Two-dimensionalNMRSpectroscopy 421
8.10.1 CorrelationSpectroscopy(COSY) 422
8.10.2 Spin-echoorJ-resolvedNMR 432
8.10.3 Two-dimensionalExchangeSpectroscopy 434
8.11 Exercises 438
References 440
9 SpectralQuantification 445
9.1 Introduction 445
9.2 DataAcquisition 446
9.3 DataPre-processing 449
9.3.1 PhasingandFrequencyAlignment 450
9.3.2 LineshapeCorrection 450
9.3.3 RemovalofResidualWater 451
9.3.4 BaselineCorrection 453
9.4 DataQuantification 453
9.4.1 Time-andFrequency-domainParameters 454
9.4.2 PriorKnowledge 457
9.4.3 SpectralFittingAlgorithms 460
9.4.4 ErrorEstimation 464
9.5 DataCalibration 466
9.5.1 InternalConcentrationReference 470
9.5.2 ExternalConcentrationReference 472
9.5.3 PhantomReplacementExternalConcentration
Reference 473
9.6 Exercises 473
References 475
10 Hardware 479
10.1 Introduction 479
10.2 Magnets 480
10.3 MagneticFieldHomogeneity 484
10.3.1 OriginsandEffectsofMagneticFieldInhomogeneity
InVivo 484
10.3.2 ActiveShimming 489
10.3.3 ShimmingHardware 492
10.3.4 ManualShimming 492
10.3.5 MagneticFieldMapBasedShimming 494
10.3.6 ProjectionBasedShimming 497
10.3.7 DynamicShimUpdating(DSU) 499
10.3.8 PassiveShimming 502
10.4 MagneticFieldGradients 502
10.4.1 EddyCurrents 506
10.4.2 Pre-Emphasis 508
10.4.3 ActiveShielding 512
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Contents xi
10.5 RadiofrequencyCoils 512
10.5.1 ResonantLCRCircuits 513
10.5.2 RFCoilPerformance 519
10.5.3 SpatialFieldProperties 521
10.5.4 PrincipleofReciprocityI 526
10.5.5 PrincipleofReciprocityII 529
10.6 RadiofrequencyCoilTypes 530
10.6.1 CombinedTransmitandReceiveRFCoils 531
10.6.2 Phased-arrayCoils 532
10.6.3 1H-[13C]and13C-[1H]RFCoils 533
10.6.4 Cooled(Superconducting)RFCoils 536
10.7 CompleteMRSystem 536
10.7.1 RFTransmission 536
10.7.2 SignalReception 537
10.7.3 QuadratureDetection 539
10.7.4 DynamicRange 540
10.7.5 GradientandShimSystems 541
10.8 Exercises 542
References 545
Appendix 549
A1 MatrixCalculations 549
A2 TrigonometricEquations 551
A3 FourierTransformation 551
A3.1 Introduction 552
A3.2 Properties 553
A3.3 DiscreteFourierTransformation 554
A4 ProductOperatorFormalism 554
A4.1 CartesianProductOperators 555
A4.2 SphericalTensorProductOperators 556
References 559
FurtherReading 560
Index 563