核磁共振波谱（兰州大学） Chapter 10_NOE

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1、Chapter10NuclearOverhauserEffect(NOE)1H-1HProximityThroughSpaceNuclearOverhauserEffectN-δSIW2NNWSWI1W1I0SN+δIW1WS1W-nOeCrossrelaxation0:W+nOe2:saturatedN–½δN–½δSI(1)IN–½δN–½δN+½δ(2)N+½δIISI:αα−ββ=3/2δN+½δN+½δsaturatedafter(1),(2)theNOEdisappearsNuclearOverhaus

2、erEffectInternucleardistancesinathree-spinsystemIr.HA+-BrMAMrMXIr.HArAABrrABCBCAXXrACACInternucleardistancesr=rABAC:inathree-spinsystemNOE(HC)=0twodifferentarrangementsinathree-spinsystemNuclearOverhauserEffectNOE’sinalinearfour-spinsystemIr.HB-0.4Ir.HD0.70.84

3、9.9CDAB45.549.244.3-18.4-16.26.34670relativedistanceNOEmeasurementNOEdifferenceexperimentsH4H2.saturationof2Ir.H3thepeaksH11.‘off-resonance’experimentH+NOE(enhancedpeak)1Hresidualpeak3.NOEdifference2spectra:subtracting(2)-(1)failuretoperfectH3selectivityinthet

4、hesaturatedsaturationresonancepeakH4Distinguishingbetweencitraconicacid&mesaconicacidusing1DNOEdifferencespectracitraconicacid(cis)mesaconicacid(trans)transIr.MeNOEdifferencecistransmesaconic1HNMRciscitraconic1DNOEDifferenceSpectrab12%+NOEHcIr.MeMeHac+NOEHb15%

5、d-3%Hda-NOENOEdiff.bdac‘off-resonance’1DNOEDifferenceSpectraHcHaHbHc21.8%Hb11.2%Ir.Ha22.1%HaIr.HbHc-2.2%6.9%HaIr.HcHb-2.4%nOediff.HaHbHc1DNOEDifferenceSpectraIr.10-CH317105nOe12.9%H5H5,H171DNOEDifferenceSpectra2118NOE19Me11Ir.CH+NOE3286-NOEHHH6βH8Ir.19-CH32β1β

6、H11βH2aSelectiveheteronuclear1H-13CNOEDifferenceSpectraonacompoundcontainingat-butylgroup(CH)C-__3NOE(80%)Ir.CH3nOediff.CH3DMSOC13CNMRSelectiveheteronuclear1H-13CNOEDifferenceSpectraIr.H4(NOE)C4C1disappeared(NOE)C1(NOE)C3C5nOediff.13CNMR2D1H-1HNOESY(NuclearOve

7、rhauserandExchangeSpectroscopY)F1noisestripsforthefourCH_3SymmetrizationartifactsinNOESY(NOE)(NOE)F1quadratureimages2DNOESYspectrumofapenicillinderivativeHDOH3βCH3αCH3H5NOE(βCΗ3,αCH3)α(βΗ3,βCH3)NOE(αΗ5,αCH3)2DNOESYspectrumofailanthoneNOEβ-OHα-OH__b,dd__a,ccbaN

8、OEcdab2DNOESYspectrumofaphanamol1511458β3NOE118β,114,1111333,5NOENOE4458β8NOE155,15155Comparisonofphase-sensitiveNOESYandCOSY-90ospectraoflysozymephase-sensitiveNOESYCOSY-90oF1F2