二维相关谱图专题培训课件

二维相关谱图Two-Dimensional(2D)Spectroscopy2Generalized2DCorrelationSpectroscopyGenerallyapplicabletoabroadrangeofspectroscopictechniquesBasedonasetofspectraldatafromasystemundersomeperturbationEither

time-dependent

orstaticspectramaybeusedEnhancespectralresolutionbyspreadingpeaksalongtheseconddimensionSelectivedevelopmentof2Dpeaksprovidesbetteraccess

toinformationnotreadilyobservableinconventional1DspectraSignofcrosspeakstodeterminerelativedirectionofintensitychangesandsequentialorderofeventsComparisonofdifferentspectraldataviahetero-correlation3Generalized2DCorrelationSpectroscopyI.Noda,Appl.Spectrosc.,47,1329(1993).Perturbation-based2Dcorrelationspectroscopy4

AppliedSpectroscopy,vol.54,no.7,July,2000.(Specialissueongeneralized2Dcorrelationspectroscopy)Y.OzakiandI.Noda,Eds.Two-DimensionalCorrelationSpectroscopy,AIPConferenceproceedings503,AIP:Melville,2000.ReferenceLiterature5Book6GeneralizedTwo-DimensionalCorrelationSpectroscopyElectromagneticProbeAcquisitionof2DCorrelationSpectraChemicalSystemDynamicSpectra2DCorrelationSpectraExternalPerturbationTemperature,pressure,time,concentration,electromagneticfield……IR,NIR,laser……77

SystemI(n)S(t)PerturbationInput

Output...Cross-correlationfunction=F(n1,n2)+iY(n1,n2)

SynchronousspectrumF(n1,n2)=SimilarityofsignaldependenceontAsynchronousspectrumY(n1,n2)=Dissimilarityofsignaldependenceont2DCorrelationAnalysisComparisonoftwosignalsmeasuredatdifferentnalongt

8Generalized2DCorrelationFormalismDynamicspectrumFouriertransform2DcorrelationspectrawhereF(n1,n2)

=

synchronousspectrumY(n1,n2)

=

asynchronousspectrum9PracticalComputationalMethodDiscretespectralsamplingDiscreteHilberttransform2DcorrelationspectrawhereRapidandstraightforwardcomputationof2Dcorrelationspectra10Synchronouscorrelationspectrum:F(n1,n2)Autopeaksatdiagonalpositionsrepresenttheextentofperturbation-induceddynamicfluctuationsofspectralsignalsCrosspeaksrepresentsimultaneous

changesofspectralsignalsattwodifferentwavenumbers,suggestingacoupledorrelatedoriginofintensityvariationsIfthesignofacrosspeakispositive,theintensitiesatcorrespondingwavenumbersareincreasing(ordecreasing)together.Ifthesignisnegative,oneisincreasing,whiletheotherisdecreasing.11Asynchronouscorrelationspectrum:Y(n1,n2)CrosspeaksdeveloponlyiftheintensityvariesoutofphasewitheachotherforsomeFourierfrequencycomponentsofsignalfluctuationsThesignofacrosspeakispositiveiftheintensitychangeatn1occursbeforen2.Thesignofacrosspeakisnegativeiftheintensitychangeatn1occursaftern2.TheabovesignrulesarereversedifF(n1,n2)<0.12Polystyrene/PolyethyleneBlendPolystyrenePolyethylene

PSandPEareimmiscible(phaseseparated)Nomolecularlevelinteractions–(CH2CH)n––(CH2CH2)n–13Polystyrene/PolyethyleneBlend

SeparatesynchronouscorrelationsforPSandPEbandsAsynchronouscorrelationbetweenPSandPPEbands

AsynchronicitywithinPSbands(backbonevs.sidegroup)14SelectivelyDeuteratedPolystyrenevs.–(CH2CH)n––(CD2CD)n–15AtacticPoly(methylmethacrylate)16PureGroupFrequencySpectraofPMMAS.K.DirlikovandJ.L.KoenigAppl.Spectrosc.33,555(1979).A.EstermethylB.AlphamethylC.Methylene17AtacticPMMA

EstermethylpeaksareinthesynchronousspectrumalmostexclusivelyAlphamethylandmethylenefoundintheasynchronousspectrum18HumanHairKeratinAssignments(cm-1)a-helix1661,1649b-likeextendedchainsandturns1679,1669,16451641,1620Disorderedstructures165619Polystyrene/DOPBlendDioctylphthalate(DOP)Perdeuteratedpolystyrene20PlasticizedPolystyrene

MotionsofaromaticgroupsofPSandDOParesynchronizedDOPaliphaticchainsmoveasynchronously(independently)withrespecttoPSphenylrings21RemolaModelofPlasticizationrem’o-ra,n.[L.,hinderance.]1.Anyofseveralfishes(gereraEchenecis,Remora,familyEchneididae),withasuctionaldiskontheheadbywhichtheyclingtootherfishesortoships.2.Aclog;drags;hinderence.22PS/PVMEBlendsPolystyrene(chain-deuterated)Poly(vinylmethylether)23d3PS/PVME(25:75)Blend24d3PS/PVME(25:75)Blend

BandsplitofPVMEmethoxylgroupsinto2815cm-1and2824cm-1MotionofPVME2815cm-1issynchronizedwithPSphenyl25FTNIRSpectraofOleylAlcohol26Thermal2DNIRofOleylAlcohol

Associated“polymers”decrease,asmonomersincreaseNotadirectconversion(asynchronouspeaks)Intermediatestates(e.g.,dimers)exist27Thermal2DNIRofOleylAlcoholRotationalisomersTransGauche28Thermal2DNIRofOleylAlcohol29CrystallizationofNodaxTM(PHBHx)30CrystallizationofNodaxTM

(PHBHx)

Highlyorderedcrystals(I)growfirstwhenNodaxTMiscooledfromthemelt

Lessordered(II)crystalsgrowlater,whiletheamorphouscomponentkeepsdecreasingasthetemperatureisfurtherlowered31Two-DimensionalCorrelationSpectroscopy<IR,IR><Raman,Raman>(SAXS,SAXS><UV,UV><NIR,NIR>etc.or<IR,Raman><SAXS,IR><ESR,Acoustic><Microwave,SANS><UV,NMR>etc.3233无定形聚酰胺的二维近红外相关光谱研究摘要利用二维近红外相关光谱研究了25–200℃的无定形聚酰胺。检测到5种不同的CH结构，其中两种对温度相应较灵敏，检测到自由的和氢键结合的NH，其中自由的NH又分为两种。34中红外近红外吸收峰归属表35近红外变温实验结果Temperature-dependentFTNIRspectraobtainedfrom25to200℃oftheinvestigatedamorphouspolyamideinthespectralrange5400–7000

cm−1.聚酰胺中不同氢键结构BrukerIFS88,256scan,4cm-1,5℃step6765cm-16535cm-1特征峰随温度上升的变化规律波数(cm-1)峰位置峰强度6765不变快速增加6650不变小幅增加6535蓝移减弱6650cm-136二维相关谱图

(6200–6900cm-1)6535/67656250/6765

6765

2ν(NH)f6535/6765正峰负峰6740/6780

6350/6765自相关同步谱图负交叉峰说明吸收峰变化的方向相反，正峰则表示相同6250,6350ν(NH)+ν(CH)

65352ν(NH)b

6535变化先于6765

结论6350变化先于6765

6780变化先于6740

6650的存在6765可能来源于6740与6780两个峰

37二维相关谱图

(5400–6200cm-1)56902νs(CH2)60102νas(CH)59802νas(CH)59002νas(CH)58102νas(CH2)正峰负峰自相关5690/58105690/58105900/60105980/6010同步谱图存在五个自相关峰5810变化先于5690结论6010变化先于5900,598038二维相关谱图(5400–6200vs6200–6900cm-1)5690590059806010581067652ν(NH)f6535CH与NH振动区域的关联5690,5990,5980变化先于6765结论6535变化先于5690,5990,59805810与6010对温度变化敏感39聚丙烯膜中水扩散的二维ATR-FTIR光谱研究摘要利用二维ATR-FTIR光谱研究水在聚丙烯膜中的扩散动力学。通过研究1800-1500cm-1区域，分析得到三种不同结构水分子：强氢键结合水(1676)，中强氢键结合水(1645)及自由水(1592)40课题研究背景ATR-FTIRspectrumofsorbedwaterinS-PPintherange4000-650cm-1.水的伸缩振动区域(3000-4000cm-1)重叠峰较多，分析困难水的弯曲振动区域(1500-1700cm-1)重叠峰较少，强度偏低通过二维相关分析手段提高谱图分辨率分析水的弯曲振动区域41变温实验条件及数据ATR-FTIRspectraofO-Hbendingbandintherange1750-1540cm-1.将聚丙烯溶于二甲苯后浇膜，在室温下于真空烘箱中存放24h制样方法仪器及实验Nexus470及ATR压板附件，16scan，4cm-1将吸水滤纸附于膜表面,每2.5min采集数据42二维相关谱图

(1500–1800cm-1)Asynchronous2Dcorrelationspectraofwaterbendingbandintherange1720-1540cm-1.1676/16451645/1592正峰负峰峰位置TypeIwater1676TypeIIwater1645TypeIIIwater1592强氢键结合水中强氢键结合水极弱氢键结合水（自由水）不同结构水先后顺序：1645→1676→159243相关机理解释聚丙烯膜TypeITypeIITypeIII一般纯水中以TypeII型水分子居多，TypeIII型水分子体积较大，因此移动速度比TypeII型水分子慢，PP膜中孔道被水填满后，TypeI型水分子结构出现顺序44尼龙6中脱水过程的二维近红外相关光谱研究摘要利用二维近红外相关光谱研究了不同温度下（50和80℃）时尼龙6的脱水行为。实验表面在不同温度下，尼龙6存在不同脱水机理。45实验条件及仪器设备SamplePreparationTreatmentAImmersedinawaterbathover12

hHeatedat80

°Cforabout1.5

hBImmersedinawaterbathover16

hHeatedat50

°Cforabout2

hCKeptinadesiccatorHeatedat80

°Cforabout1.5

hDKeptinadesiccatorHeatedat50

°Cforabout2.5

h样品制备及处理条件仪器及实验条件Nexus470FT-IR/NIR，液氮冷却MCT检测器，分辨率4cm-1分别在50和80℃恒温扫描100min,扫描范围3000-11000cm-146尼龙6近红外光谱归属

Near-infraredspectrarecordedfromtheoriginalfilmsofsampleA(–)andsampleC(…)atroomtemperature.Wavenumber(cm−1)Tentativeassignment183103*ν(CH2)72202*νas(CH2)

+

δ(CH2)27020ν1(OH)

+

ν3(OH)6750ν1(OH)

+

ν3(OH)and2*ν(NH)f65002*ν(NH)b358602*νas(CH2)457402*νs(CH2)55280ν2(OH)

+

ν3(OH)(s0)5230ν2(OH)

+

ν3(OH)(s1)5140ν2(OH)

+

ν3(OH)(s2)64990ν(NH)b

+

amideI74880ν(NH)b

+

amideII4718AmideI

+

2*amideII84628ν(NH)b

+

amideIII94374νs(CH2)

+

δ(CH2)104283νs(CH2)

+

δ(CH2)4230νs(CH2)

+

γw(CH2)4193νs(CH2)

+

γ(CH2)尼龙6近红外光谱归属表4780℃时尼龙膜脱水谱图Near-infraredspectraofsampleAintherange9000–4000

cm−1recordedevery10

minduringisothermaltreatmentat80

°C.5200cm-1峰强随时间变化图脱水过程呈现非线性变化48样品A二维相关谱图

(5000–5350cm-1)5280/52305230/5140

5181

ν2

(OH)+ν3(OH)正峰负峰自相关5230变化先于5280

结论5230变化先于5140

5181cm-1峰可能有三个来源

5280：自由水分子(s0)5230：一端氢键水分子(s1)5140：两端氢键水分子(s2)80

℃49样品B二维相关谱图

(5000–5350cm-1)5280/51405240/5140

5181

ν2

(OH)+ν3(OH)正峰负峰自相关5140变化先于5280

结论5140变化先于5240

两端氢键水分子(s2)50℃自由水分子(s0)一端氢键水分子(s1)变化先于50实验结果机理解释5280：自由水分子(s0)5230：一端氢键水分子(s1)5140：两端氢键水分子(s2)80℃温度较高，能量较大50℃温度较低，能量较小s0s1s2s2s1s2s1s051FTIRand2D-IRSpectroscopicStudy

onPolyN-isopropylacrylamide(PNIPAM)

52PNIPAMFilmPNIPAMAqueousSolution2DIR53

PolyN-isopropylacrylamide

(PNIPAM)

ChemicalStructureLCST～32℃54FTIRspectraofPNIPAM20wt%D2Osolution(28≒40℃)55

QuantitativeAnalysisReversibledehydration/hydrationprocessofC-Hgroup1LCSTLCST56Two-stepdehydration/hydrationprocessofCH32Dehydrationofside-chain>main-chainaggregation

3InvestigationofCHBands-2DIR

(2981,2970)+,+(2970,2927)+,+57123465NCOH6Two-stepdehydrationmechanismofCH346558InvestigationofAmideIband-FTIRWavenumber(cm-1)Assignment1649ν(C=O…D-N)1624ν(C=O…D-O-D

)

f(C=O…D-N)=A1649/[A1649+A1625*(ε1649/ε1625)]

59InvestigationofAmideIband-2DIR

C=O…D-O-D>

C=O…D-N(1649,1624)-,+1624>164960DehydrationandHydrationofN-D:SpectralDensityMethodMacromolecule,1996,29,6761

TheformationanddestructionofN-H…O-H>C=O…H-O-H

61DehydrationofCH3(I)BreakageofN-D…O-DDiffusionandaggregationofthemainchainsFormationofC=O…D-NBreakageofC=O…D-ODehydrationofCH3(II)DynamicsmechanismofPNIPAM20wt%D2Osolutionduringheating6220wt%HeatingFurtherHeatingDynamicsofchainsinPNIPAMaqueoussolutionduringheating63Assignmentsofovertoneandcombinationbands

intheNIRspectrumofPNIPAMWavenumber(cm-1)Assignmenta3437ν(N-H)fb3300ν(N-H)bc3190AmideI+AmideIId3070AmideBe2968νas(CH3)f2929νas(CH2)g2912ν(CH)h2874νs(CH3)i2850νs(CH2)j1646AmideIk1546AmideIIl1469δas(CH3)m1458δas(CH2)n1387δs(CH3)o1368δs(CH2)p1280AmideIII1260q1173CH3skeletalr1155CH2skeletals1132CH3rockingt1096CH2rocking68742×ν(N-H)f66002×ν(N-H)b6370AmideB+ν(N-H)b6262(AmideI+AmideII)+AmideB61402×AmideB59362×νas(CH3)58582×νas(CH2)58242×ν(CH)57482×νs(CH3)57002×νs(CH2)5155ν(OH)+δ(OH)4946ν(N-H)b+

AmideI4846ν(N-H)b+

AmideII4723AmideB+AmideI4623AmideB+AmideII4580ν(N-H)b+

AmideIII45522×AmideI+AmideIII4437νas(CH3)+δas(CH3)4369νs(CH3)+δas(CH3)4352νas(CH3)+δs(CH3)4308νs(CH2)+δas(CH2)4266νs(CH3)+δs(CH3)4218νs(CH2)+δs(CH2)4141νas(CH3)+CH3skeletal4098νas(CH3)+CH3rocking4064νas(CH3)+CH2rockingMIRSpectrumofPNIPAMfilm(RT)

64NIRSpectrumofPNIPAMfilm(RT)

Wavenumber(cm-1)Assignment167362×ν(N-H)f265502×ν(N-H)b36368AmideB+ν(N-H)b46258(AmideI+AmideII)+AmideB561402×AmideB659332×νas(CH3)758892×νas(CH2)858232×ν(CH)957732×νs(CH3)1056752×νs(CH2)115135ν(OH)+δ(OH)124945ν(N-H)b+

AmideI134878ν(N-H)b+

AmideII144701AmideB+AmideI154623AmideB+AmideII164580ν(N-H)b+

AmideIII1745292×AmideI+AmideIII184408νas(CH3)+δas(CH3)194335νs(CH3)+δas(CH3)204329νas(CH3)+δs(CH3)214298νs(CH2)+δas(CH2)224243νs(CH3)+δs(CH3)234214νs(CH2)+δs(CH2)244138νas(CH3)+CH3skeletal254098νas(CH3)+CH3rocking264052νas(CH3)+CH2rockingAssignmentsofovertoneandcombinationbands

intheNIRspectrumofPNIPAM65Deuterationstudies-MIR&NIRMIRSpectrum

NIRSpectrum

IntensityChange:PeakofAmidegroups66VariableTemperature

Study

-MIRA[ν(NH)b]ChangeofNHbonding67VariableTemperature

Study

-NIRA[2×

ν(NH)f]ChangeoffreeNHgroups682DIR-NHgroupsvs.CHgroupsDuringheating,modificationsofNH>conformationalchangesofhydrocarbonchains2×ν(NH)b>2×

(NH)f>2×νas(CH3)>2×νas(CH2)69ApplicationofTwo-DimensionalCorrelationSpectroscopyandPerturbationCorrelationMovingWindowSupramolecularSelf-AssemblyThermodynamicMechanismofASpecialMesogen-JacketedLiquidCrystallinePolymer04July202370GeneralizedTwo-DimensionalCorrelationSpectroscopyReferencespectrum(averagespectrum):Dynamicspectrum:Synchronous2Dcorrelationspectrum:Asynchronous2Dcorrelationspectrum:Hilbert-NodatransformationmatrixPerturbationVariableSpectralVariable7171GeneralizedTwo-DimensionalCorrelationSpectroscopy【Advantagesof2Dcos】SynchronousSpectra(同步谱)AsynchronousSpectra(异步谱)Enhancethespectralresolution;Discernthespecificordertakingplaceunderperturbation.(Noda’sRule)ABABSynchronouspositiveAsynchronousnegativeConclusion:AandBbothdecrease(orincrease);BdecreasespriortoA7272GeneralizedTwo-DimensionalCorrelationSpectroscopyPerturbationCorrelationMovingWindowApplicationPDBVT–poly[di(butyl)vinylterephthalate]Contents7373PerturbationCorrelationMovingWindowMovingWindow2DCorrelationSpectroscopy(2000)M.ThomasandH.Richardson,Vib.Spectrosc.,24,137-146,(2000).PerturbationCorrelationMovingWindow2DCorrelationSpectroscopy(2006)ShigeakiMorita,etal.,Appl.Spectrosc.,60,398-406,(2006).searchforthetransitionpointssearchforthetransitionpointsmonitorcomplicatedspectralvariationsalongperturbationvariable7474AcquisitionofMovingWindowSpectraPerturbationCorrelationMovingWindowPerturbationVariable(Temperature)75SpectralVariable75PCMW2D(synchronous):PCMW2D(asynchronous):Morita,S.;Shinzawa,H.;Noda,I.;Ozaki,Y.AppliedSpectroscopy2006,60,398-406.【PCMW2D】【MW2D】PerturbationCorrelationMovingWindowIntroduceexternalperturbationvariableintocorrelationequations7676PerturbationCorrelationMovingWindowSynchronousAsynchronousSpectralChange＋＋＋０＋ー０＋０００ーー＋ー０ーー(Inthecaseoflinerincrementperturbation)【RulesofPCMW2D】AbsorbanceTemperature77Anti-S-shapedS-shaped7778SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVTMainchainLCPHighstrengthandmodulusPolycondensationSidechainLCPPhotoelectronicresponsePolyadditionMesogen-JacketedLCPAmorphousstateΔTheflexiblemainchainsareconstrainedtotakeanextendedchainconformationRigidchainFlexiblechainUSAGermanyOnlyacovalentlinkageorashortspacerMolecularstructureofMJLCP7879SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVTPMPCSShen,Y.;Wu,P.Y.;Noda,I.;Zhou,Q.F.J.Phy.Chem.B2005,109,6089-6095.Yin,X.Y.;Wan,X.H.;Cheng,S.Z.D.;Zhou,Q.F.J.Am.Chem.Soc.2003,125,6854.PDBVTRigidsidegroupsFlexiblesidegroups2DhexagonalcolumnarphaseBeforeLCphasetransitionAfterLCphasetransitionNematicphaseMechanism?7980SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVT【ConventionalIRspectra】【Differentialspectra】(referencespectrum:35oC)CHstretchingCOstretchingTwosplittingbands8081SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVT【PerturbationCorrelationMovingWindow】LCphasedevelopment:70~110oCLCphasetransition:≈90oCDSC:noobservableLCphasetransitionWAXD:100oCBoltzmannfitting8182SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVTCHstretchingCOstretchingCH&CO【2DCorrelationSpectra】(70~110oC)AsynchronousSynchronous8283SupramolecularSelf-AssemblyThermodynamicMechanismofPDBVT1732>2837>3041,2987>1710>1714>2871>2958>2900>2935Specificorder(70~110oC)

ν(CO)(1732)>νs(CH2)>νar,νas(CH3)(disorder)>ν(CO)(1710)>ν(CO)(1714)>νs(CH3)>νas(CH3)>ν(CH)>νas(CH2)(sidechains)COCH2

CH3,ph