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NMR spectroscopy explained PDF

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NMR SPECTROSCOPY EXPLAINED NMR SPECTROSCOPY EXPLAINED Simplified Theory, Applications and Examples for Organic Chemistry and Structural Biology Neil E. Jacobsen, Ph.D. University of Arizona Copyright©2007byJohnWiley&Sons,Inc.Allrightsreserved PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey PublishedsimultaneouslyinCanada Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorbyany means,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptaspermittedunder Section107or108ofthe1976UnitedStatesCopyrightAct,withouteitherthepriorwrittenpermissionofthe Publisher,orauthorizationthroughpaymentoftheappropriateper-copyfeetotheCopyrightClearanceCenter, Inc.,222RosewoodDrive,Danvers,MA01923,(978)750-8400,fax(978)750-4470,oronthewebat www.copyright.com.RequeststothePublisherforpermissionshouldbeaddressedtothePermissions Department,JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ07030,(201)748-6011,fax(201) 748-6008,oronlineathttp://www.wiley.com/go/permission. LimitofLiability/DisclaimerofWarranty:Whilethepublisherandauthorhaveusedtheirbesteffortsin preparingthisbook,theymakenorepresentationsorwarrantieswithrespecttotheaccuracyorcompletenessof thecontentsofthisbookandspecificallydisclaimanyimpliedwarrantiesofmerchantabilityorfitnessfora particularpurpose.Nowarrantymaybecreatedorextendedbysalesrepresentativesorwrittensalesmaterials. Theadviceandstrategiescontainedhereinmaynotbesuitableforyoursituation.Youshouldconsultwitha professionalwhereappropriate.Neitherthepublishernorauthorshallbeliableforanylossofprofitoranyother commercialdamages,includingbutnotlimitedtospecial,incidental,consequential,orotherdamages. Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactourCustomer CareDepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)572-3993orfax (317)572-4002. Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmay notbeavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteat http://www.wiley.com. WileyBicentennialLogo:RichardJ.Pacifico LibraryofCongressCataloging-in-PublicationData: Jacobsen,NeilE. NMRSpectroscopyExplained:SimplifiedTheory,ApplicationsandExamplesforOrganicChemistryand StructuralBiology/NeilEJacobsen,Ph.D. p.cm. ISBN978-0-471-73096-5(cloth) 1. Nuclearmagneticresonancespectroscopy.2. Chemistry,Organic.3. Molecularbiology. I.Title. QD96.N8J332007 543(cid:2).66--dc22 2007006911 PrintedintheUnitedStatesofAmerica 10987654321 CONTENTS Preface xi Acknowledgments xv 1 FundamentalsofNMRSpectroscopyinLiquids 1 1.1 IntroductiontoNMRSpectroscopy, 1 1.2 Examples:NMRSpectroscopyofOligosaccharidesandTerpenoids, 12 1.3 TypicalValuesofChemicalShiftsandCouplingConstants, 27 1.4 FundamentalConceptsofNMRSpectroscopy, 30 1 2 InterpretationofProton( H)NMRSpectra 39 2.1 Assignment, 39 2.2 EffectofB FieldStrengthontheSpectrum, 40 o 2.3 First-OrderSplittingPatterns, 45 2.4 TheUseof1H–1HCouplingConstantstoDetermineStereochemistry andConformation, 52 2.5 SymmetryandChiralityinNMR, 54 2.6 TheOriginoftheChemicalShift, 56 2.7 JCouplingtoOtherNMR-ActiveNuclei, 61 2.8 Non-First-OrderSplittingPatterns:StrongCoupling, 63 2.9 MagneticEquivalence, 71 3 NMRHardwareandSoftware 74 3.1 SamplePreparation, 75 3.2 SampleInsertion, 77 3.3 TheDeuteriumLockFeedbackLoop, 78 vi CONTENTS 3.4 TheShimSystem, 81 3.5 TuningandMatchingtheProbe, 88 3.6 NMRDataAcquisitionandAcquisitionParameters, 90 3.7 NoiseandDynamicRange, 108 3.8 SpecialTopic:OversamplingandDigitalFiltering, 110 3.9 NMRDataProcessing—Overview, 118 3.10 TheFourierTransform, 119 3.11 DataManipulationBeforetheFourierTransform, 122 3.12 DataManipulationAftertheFourierTransform, 126 4 Carbon-13(13C)NMRSpectroscopy 135 4.1 Sensitivityof13C, 135 4.2 Splittingof13CSignals, 135 4.3 Decoupling, 138 4.4 HeteronuclearDecoupling:1HDecoupled13CSpectra, 139 4.5 DecouplingHardware, 145 4.6 DecouplingSoftware:Parameters, 149 4.7 TheNuclearOverhauserEffect(NOE), 150 4.8 HeteronuclearDecouplerModes, 152 5 NMRRelaxation—Inversion-RecoveryandtheNuclear OverhauserEffect(NOE) 155 5.1 TheVectorModel, 155 5.2 OneSpininaMagneticField, 155 5.3 ALargePopulationofIdenticalSpins:NetMagnetization, 157 5.4 Coherence:NetMagnetizationinthex–yPlane, 161 5.5 Relaxation, 162 5.6 SummaryoftheVectorModel, 168 5.7 MolecularTumblingandNMRRelaxation, 170 5.8 Inversion-Recovery:MeasurementofT Values, 176 1 5.9 Continuous-WaveLow-PowerIrradiationofOneResonance, 181 5.10 HomonuclearDecoupling, 182 5.11 PresaturationofSolventResonance, 185 5.12 TheHomonuclearNuclearOverhauserEffect(NOE), 187 5.13 SummaryoftheNuclearOverhauserEffect, 198 6 TheSpinEchoandtheAttachedProtonTest(APT) 200 6.1 TheRotatingFrameofReference, 201 6.2 TheRadioFrequency(RF)Pulse, 203 6.3 TheEffectofRFPulses, 206 6.4 QuadratureDetection,PhaseCycling,andtheReceiverPhase, 209 CONTENTS vii 6.5 ChemicalShiftEvolution, 212 6.6 Scalar(J)CouplingEvolution, 213 6.7 ExamplesofJ-couplingandChemicalShiftEvolution, 216 6.8 TheAttachedProtonTest(APT), 220 6.9 TheSpinEcho, 226 6.10 TheHeteronuclearSpinEcho:ControllingJ-CouplingEvolution andChemicalShiftEvolution, 232 7 CoherenceTransfer:INEPTandDEPT 238 7.1 NetMagnetization, 238 7.2 MagnetizationTransfer, 241 7.3 TheProductOperatorFormalism:Introduction, 242 7.4 SingleSpinProductOperators:ChemicalShiftEvolution, 244 7.5 Two-SpinOperators:J-couplingEvolutionandAntiphaseCoherence, 247 7.6 TheEffectofRFPulsesonProductOperators, 251 7.7 INEPTandtheTransferofMagnetizationfrom1Hto13C, 253 7.8 SelectivePopulationTransfer(SPT)asaWayofUnderstanding INEPTCoherenceTransfer, 257 7.9 PhaseCyclinginINEPT, 263 7.10 IntermediateStatesinCoherenceTransfer, 265 7.11 Zero-andDouble-QuantumOperators, 267 7.12 SummaryofTwo-SpinOperators, 269 7.13 RefocusedINEPT:AddingSpectralEditing, 270 7.14 DEPT:DistortionlessEnhancementbyPolarizationTransfer, 276 7.15 ProductOperatorAnalysisoftheDEPTExperiment, 283 8 ShapedPulses,PulsedFieldGradients,andSpinLocks: Selective1DNOEand1DTOCSY 289 8.1 IntroducingThreeNewPulseSequenceTools, 289 8.2 TheEffectofOff-ResonancePulsesonNetMagnetization, 291 8.3 TheExcitationProfileforRectangularPulses, 297 8.4 SelectivePulsesandShapedPulses, 299 8.5 PulsedFieldGradients, 301 8.6 CombiningShapedPulsesandPulsedFieldGradients: “ExcitationSculpting”, 308 8.7 CoherenceOrder:UsingGradientstoSelectaCoherencePathway, 316 8.8 PracticalAspectsofPulsedFieldGradientsandShapedPulses, 319 8.9 1DTransientNOEusingDPFGSE, 321 8.10 TheSpinLock, 333 8.11 Selective1DROESYand1DTOCSY, 338 8.12 Selective1DTOCSYusingDPFGSE, 343 8.13 RFPowerLevelsforShapedPulsesandSpinLocks, 348 viii CONTENTS 9 Two-DimensionalNMRSpectroscopy: HETCOR,COSY,andTOCSY 353 9.1 IntroductiontoTwo-DimensionalNMR, 353 9.2 HETCOR:A2DExperimentCreatedfromthe1DINEPTExperiment, 354 9.3 AGeneralOverviewof2DNMRExperiments, 364 9.4 2DCorrelationSpectroscopy(COSY), 370 9.5 UnderstandingCOSYwithProductOperators, 386 9.6 2DTOCSY(TotalCorrelationSpectroscopy), 393 9.7 DataSamplingint andthe2DSpectralWindow, 398 1 10 AdvancedNMRTheory:NOESYandDQF-COSY 408 10.1 SpinKinetics:DerivationoftheRateEquationforCross-Relaxation, 409 10.2 DynamicProcessesandChemicalExchangeinNMR, 414 10.3 2DNOESYand2DROESY, 425 10.4 ExpandingOurViewofCoherence:QuantumMechanics andSphericalOperators, 439 10.5 Double-QuantumFilteredCOSY(DQF-COSY), 447 10.6 CoherencePathwaySelectioninNMRExperiments, 450 10.7 TheDensityMatrixRepresentationofSpinStates, 469 10.8 TheHamiltonianMatrix:StrongCouplingandIdealIsotropic (TOCSY)Mixing, 478 11 InverseHeteronuclear2DExperiments:HSQC,HMQC,andHMBC 489 11.1 InverseExperiments:1HObservewith13CDecoupling, 490 11.2 GeneralAppearanceofInverse2DSpectra, 498 11.3 ExamplesofOne-BondInverseCorrelation(HMQCandHSQC) Without13CDecoupling, 501 11.4 ExamplesofEdited,13C-DecoupledHSQCSpectra, 504 11.5 ExamplesofHMBCSpectra, 509 11.6 StructureDeterminationUsingHSQCandHMBC, 517 11.7 UnderstandingtheHSQCPulseSequence, 522 11.8 UnderstandingtheHMQCPulseSequence, 533 11.9 UnderstandingtheHeteronuclearMultiple-BondCorrelation (HMBC)PulseSequence, 535 11.10 StructureDeterminationbyNMR—AnExample, 538 12 BiologicalNMRSpectroscopy 551 12.1 ApplicationsofNMRinBiology, 551 12.2 SizeLimitationsinSolution-StateNMR, 553 12.3 HardwareRequirementsforBiologicalNMR, 558 12.4 SamplePreparationandWaterSuppression, 564 12.5 1HChemicalShiftsofPeptidesandProteins, 570 CONTENTS ix 12.6 NOEInteractionsBetweenOneResidueandtheNextResiduein theSequence, 577 12.7 Sequence-SpecificAssignmentUsingHomonuclear2DSpectra, 580 12.8 MediumandLong-RangeNOECorrelations, 586 12.9 Calculationof3DStructureUsingNMRRestraints, 590 12.10 15N-Labelingand3DNMR, 596 12.11 Three-DimensionalNMRPulseSequences:3DHSQC–TOCSY and3DTOCSY–HSQC, 601 12.12 Triple-ResonanceNMRonDoubly-Labeled(15N,13C)Proteins, 610 12.13 NewTechniquesforProteinNMR:ResidualDipolarCouplings andTransverseRelaxationOptimizedSpectroscopy(TROSY), 621 AppendixA:APictorialKeytoNMRSpinStates 627 AppendixB:ASurveyofTwo-DimensionalNMRExperiments 634 Index 643

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For more information about Wiley products, visit our web site at http://www.wiley.com Appendix A: A Pictorial Key to NMR Spin States. 627. Appendix B: A .. three of the frequencies of the piano chord. Fourier transform will then
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