二維相關(guān)譜圖專題培訓課件

二維相關(guān)譜圖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無定形聚酰胺的二維近紅外相關(guān)光譜研究摘要利用二維近紅外相關(guān)光譜研究了25–200℃的無定形聚酰胺。檢測到5種不同的CH結(jié)構(gòu)，其中兩種對溫度相應較靈敏，檢測到自由的和氫鍵結(jié)合的NH，其中自由的NH又分為兩種。34中紅外近紅外吸收峰歸屬表35近紅外變溫實驗結(jié)果Temperature-dependentFTNIRspectraobtainedfrom25to200℃oftheinvestigatedamorphouspolyamideinthespectralrange5400–7000

cm?1.聚酰胺中不同氫鍵結(jié)構(gòu)BrukerIFS88,256scan,4cm-1,5℃step6765cm-16535cm-1特征峰隨溫度上升的變化規(guī)律波數(shù)(cm-1)峰位置峰強度6765不變快速增加6650不變小幅增加6535藍移減弱6650cm-136二維相關(guān)譜圖

(6200–6900cm-1)6535/67656250/6765

6765

2ν(NH)f6535/6765正峰負峰6740/6780

6350/6765自相關(guān)同步譜圖負交叉峰說明吸收峰變化的方向相反，正峰則表示相同6250,6350ν(NH)+ν(CH)

65352ν(NH)b

6535變化先于6765

結(jié)論6350變化先于6765

6780變化先于6740

6650的存在6765可能來源于6740與6780兩個峰

37二維相關(guān)譜圖

(5400–6200cm-1)56902νs(CH2)60102νas(CH)59802νas(CH)59002νas(CH)58102νas(CH2)正峰負峰自相關(guān)5690/58105690/58105900/60105980/6010同步譜圖存在五個自相關(guān)峰5810變化先于5690結(jié)論6010變化先于5900,598038二維相關(guān)譜圖(5400–6200vs6200–6900cm-1)5690590059806010581067652ν(NH)f6535CH與NH振動區(qū)域的關(guān)聯(lián)5690,5990,5980變化先于6765結(jié)論6535變化先于5690,5990,59805810與6010對溫度變化敏感39聚丙烯膜中水擴散的二維ATR-FTIR光譜研究摘要利用二維ATR-FTIR光譜研究水在聚丙烯膜中的擴散動力學。通過研究1800-1500cm-1區(qū)域，分析得到三種不同結(jié)構(gòu)水分子：強氫鍵結(jié)合水(1676)，中強氫鍵結(jié)合水(1645)及自由水(1592)40課題研究背景ATR-FTIRspectrumofsorbedwaterinS-PPintherange4000-650cm-1.水的伸縮振動區(qū)域(3000-4000cm-1)重疊峰較多，分析困難水的彎曲振動區(qū)域(1500-1700cm-1)重疊峰較少，強度偏低通過二維相關(guān)分析手段提高譜圖分辨率分析水的彎曲振動區(qū)域41變溫實驗條件及數(shù)據(jù)ATR-FTIRspectraofO-Hbendingbandintherange1750-1540cm-1.將聚丙烯溶于二甲苯后澆膜，在室溫下于真空烘箱中存放24h制樣方法儀器及實驗Nexus470及ATR壓板附件，16scan，4cm-1將吸水濾紙附于膜表面,每2.5min采集數(shù)據(jù)42二維相關(guān)譜圖

(1500–1800cm-1)Asynchronous2Dcorrelationspectraofwaterbendingbandintherange1720-1540cm-1.1676/16451645/1592正峰負峰峰位置TypeIwater1676TypeIIwater1645TypeIIIwater1592強氫鍵結(jié)合水中強氫鍵結(jié)合水極弱氫鍵結(jié)合水（自由水）不同結(jié)構(gòu)水先后順序：1645→1676→159243相關(guān)機理解釋聚丙烯膜TypeITypeIITypeIII一般純水中以TypeII型水分子居多，TypeIII型水分子體積較大，因此移動速度比TypeII型水分子慢，PP膜中孔道被水填滿后，TypeI型水分子結(jié)構(gòu)出現(xiàn)順序44尼龍6中脫水過程的二維近紅外相關(guān)光譜研究摘要利用二維近紅外相關(guān)光譜研究了不同溫度下（50和80℃）時尼龍6的脫水行為。實驗表面在不同溫度下，尼龍6存在不同脫水機理。45實驗條件及儀器設備SamplePreparationTreatmentAImmersedinawaterbathover12

hHeatedat80

°Cforabout1.5

hBImmersedinawaterbathover16

hHeatedat50

°Cforabout2

hCKeptinadesiccatorHeatedat80

°Cforabout1.5

hDKeptinadesiccatorHeatedat50

°Cforabout2.5

h樣品制備及處理條件儀器及實驗條件Nexus470FT-IR/NIR，液氮冷卻MCT檢測器，分辨率4cm-1分別在50和80℃恒溫掃描100min,掃描范圍3000-11000cm-146尼龍6近紅外光譜歸屬

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)尼龍6近紅外光譜歸屬表4780℃時尼龍膜脫水譜圖Near-infraredspectraofsampleAintherange9000–4000

cm?1recordedevery10

minduringisothermaltreatmentat80

°C.5200cm-1峰強隨時間變化圖脫水過程呈現(xiàn)非線性變化48樣品A二維相關(guān)譜圖

(5000–5350cm-1)5280/52305230/5140

5181

ν2

(OH)+ν3(OH)正峰負峰自相關(guān)5230變化先于5280

結(jié)論5230變化先于5140

5181cm-1峰可能有三個來源

5280：自由水分子(s0)5230：一端氫鍵水分子(s1)5140：兩端氫鍵水分子(s2)80

℃49樣品B二維相關(guān)譜圖

(5000–5350cm-1)5280/51405240/5140

5181

ν2

(OH)+ν3(OH)正峰負峰自相關(guān)5140變化先于5280

結(jié)論5140變化先于5240

兩端氫鍵水分子(s2)50℃自由水分子(s0)一端氫鍵水分子(s1)變化先于50實驗結(jié)果機理解釋5280：自由水分子(s0)5230：一端氫鍵水分子(s1)5140：兩端氫鍵水分子(s2)80℃溫度較高，能量較大50℃溫度較低，能量較小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(同步譜)AsynchronousSpectra(異步譜)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