现代仪器分析第八章质谱法PPT课件

-,1,第八章质谱法,MassSpectroscopy(MS),-,2,质谱仪的一般结构,真空系统,进样系统,离子检测器,数据系统,质量分析器,离子源,大气,样品,机械泵，分子涡轮泵，扩散泵，离子泵，升华泵,气体：气相色谱仪(GC/MS)液体：液相色谱仪(LC/MS)固体：固体进样杆(DIP,DCI),电子倍增器，多通道板检测器光电倍增管，阵列检测器,-,3,通常的离子化方法,电子轰击离子化EI化学电离离子化CI正化学电离离子化PCI负化学电离离子化NCI大气压力离子化API电喷雾离子化ESI大气压化学电离离子化APCI,GC/MS,LC/MS,-,4,离子化方式,分子量,非极性,极性,EI/CI,ESI,APCI,100,000,1000,-,5,离子化和碎片,离子化,硬,无碎片,有碎片,API,EI,CI,软,-,6,质量分析器,四极杆80%的台式质谱仪(3000/年)HP,PE,TMQ,Shimadzu离子阱20%的台式质谱仪(700/年)Varian,TMQ飞行时间(ToF)目前用户较少(50-60/年)Leco,Micromass,TMQ扇形磁场通常不是台式仪器,-,7,-,8,-,9,扇形磁场质量分析器,离子通过变化的磁场和电场被传输,-,10,-,11,四极质量分析器,-,12,离子阱,原理与四极杆的非常相似，离子被存储在RF和DC场中，扫描场逐出精确m/z的离子。,-,13,飞行时间质量分析器,所有离子同时启动小的离子移动速度快测量已知距离下的速度(飞行时间),-,14,-,15,ElectronImpactIonization(EI),e-,e-,e-,e-,e-,SamplefromGC,filament,+,+,+,+,Fragmention,QP,-,16,ElectronImpactIonization(EI),Thermalelectrons(ca.70eV)hitmoleculesandionizethem.Amplefragmentions=amplestructuralinformationFingerprint,EIspectrumMethylstearateM.W.298,-,17,PositiveChemicalIonization(PCI),fromgascylinder,filament,QP,CH4,CH5+C2H5+,SamplefromGC,H+,-CH4,M+1,-C2H4,-,18,PositiveChemicalIonization(PCI),Reagentgasmoleculesareionizedfirst.Samplemoleculesareionizedmainlyby損rotontransfer?Quasimolecularionseasilyproducedusefulformolecularweightverification.,+,PCIspectrumMethylstearateM.W.298,-,19,ComparisonofEIandPCI,EImode,PCImode,-,20,NegativeChemicalIonization(NCI),Negativeionformationbyelectroncaptureassociativeresonancecapturedissociativeresonancecaptureion-pairproductionNegativeionformationbyion-moleculereactionsprotontransferchargeexchangenucleophilicadditionnucleophilicdisplacement,-,21,Negativeionformationbyelectroncapture(associativeresonancecapture),MX+e-(0eV)MX-.,X:positiveelectronaffinitypart,CH4,MX,CH4,+,CH3,+,H,CH4,CH4,CH4,e-,MX,-,-,22,质谱图的样子?,EI和CI的质谱图,m/z,0,100,%,510,511,512,m/z,0,100,%,241,213,510,242,EI,NCI,-,23,扫描50到300amu流入质谱仪的化合物,质谱图.,-,24,-,25,断裂机理,1.断裂,-,26,2.断裂,-,27,3.i断裂,-,28,4.逆Diels-Alder反应,-,29,5.Mclafferty重排,-,30,-,31,-,32,-,33,-,34,ConfigurationofGCMS,MassSpectrometer,GasChromatograph,Interface,Ionsourcebox,-,35,IonSourceDesign-Increasedionizationefficacy-,InterfaceThesampleseparatedbyGCwillbeintroducedthroughthisinterface.,FilamentIongeneratedbyfilamentwillgivetheelectronimpacttothesampletoproducethesampleionization.,Ionsourcebox,-,36,IonLens-Highionintroductiontomassanalyzer-,Thisionlensisfunctioningforeffectiveintroductiontomassanalyzer.OptimizationforadjustmentofthisionlenswillbedonebyPCautomatically.,-,37,QuadrupoleRod-MinimizelossesintransittotheQuadrupole-,MainRodSpecificiononlycanbepassedbytheelectronicfieldintoQuadrupoleRodwhichiscontrolledbyPC.,PreRod,Fromionsource,Todetector,-,38,rotarypumpturbomolecularpump(151L/sec),turbomolecularpump(151L/sec),rotarypump,Goodvacuumsystem-MinimizelossesintransittotheQuadrupole-,-,39,TurboMolecularPump,AircooledandoilfreeTurbomolecularPump(TMP)withlubricantimpregnatedceramicbearingsismaintenancefreeforupto25,000hours.Provideshighqualityvacuuminlessthan5mins.,-,40,Iondetection,Negativeiondetection,Positiveiondetection,-,41,GCMS-QP5050ANCIsensitivity,200fgHexachlorbenzene,NCIspectrum,Masschromatogramofm/z284,-,42,OFN(octafluoronaphthalene)NCIscanmode,OutstandingHighSensitivity,scanrangem/z60-310,0.5secinterval,200fgS/N30,-,43,GCMS-QP5050ANCIpesticidesdate3,10pgCyanophosNCImassspectrum,phosphoruspesticides10pg,-,44,ComparisonbetweenEIandNCIextractfromcabbage(pesticidesadded),EIscanningmode,-,45,NCIscanningmode,ComparisonbetweenEIandNCIextractfromcabbage(pesticidesadded),-,46,PrincipleofProgramedtemperaturevaporize(PTV),PTV,100C,split,MS,50-250C,Solventwillbevaporizedandexhausted.Samplewillbeconcentrated.,-,47,OptimizationofPTVconditions,SelectionofpackingmaterialsTenaxGC20%OV-120%OV-1720%Dexil300ShincarbonACarbopackCTraptemperatureDesorptiontemperatureTemperatureprogram,-,48,Very-Large-VolumeInjectionusingPTVEffectofTemperatureonTrapefficiency,-,49,Very-Large-VolumeInjectionusingPTVTemperatureandSplitratioProgram,-,50,Very-Large-VolumeInjectionusingPTV2ppbeachPesticidesinn-hexane1000uLInjection,AnalyticalConditionsGC17AVer.2DB130mX0.25mm50C(4)-160C-280C20C/min5C/minPTV70C(1)-100C(1)-280C30C/min250C/minWiderangeFTD1pA280CCarriergasHe150kPaPrecolumnTenaxGC,-,51,FeaturesofGCMSQP-5050A,OutstandinghighsensitivityExtendedmassrangeupto900amuVersatileMode-EI/PCI/NCI/DICompactDesignEasyOperationusingWindowsSoftwareEasytuning-PFTBAbuiltinstandardEasymaintenance,-,52,AnalysisofCoconutoil,-,53,MSSpectrumofC48,-,54,-,55,-,56,-,57,DIoption,Thedirectinletoptionallowslessvolatileorthermallylabilesamplestobedirectlyintroducedintothemassspectrometer.MixturesofcompoundswhichhavedifferentboilingpointscanbepositivelyidentifiedbyprogrammingtheDIprobetemperature.,-,58,Applicationusingdirectinletprobe,-,59,Front-openionchambersystem-easymaintenance-,-,60,DualFilamentsSystem-easymaintenance-,-,61,LCMS-QP8000Validation,ProductivityandMassDetection,-,62,WhatkindofbenefitsLC/MSuserscanget?,PowerfulqualitativecapabilitySelectivequantitativecapability,-,63,WhatkindofbenefitsLC/MSuserscanget?,PowerfulqualitativecapabilitySelectivequantitativecapability,A:100,D:150,B:100C:150,m/z=150,TIC,m/z=100,A,B,C,D,-,64,NewShimadzuLCMSQP-8000,QP-8000isLC/MSwithAPIinterfacewhichisdesignedtobearoutineLCdetectorinournewVPseriesHPLCsystem.,-,65,LCMSInterface,CurvedDesolvationLine,(CDL),Deflector,Probe,SprayChamber,Skimmer,LensStack,RPTMP1TMP2,Quadrupole,-,66,APISprayChamber,APISprayChamber,ESIProbe(EasytochangetoAPCIProbe),-,67,APIProbe,ESIandAPCIprobesareincludedasstandard.Theycanbeappliedtovariouskindsofsamples.Allyouhavetodotoswitchtheionizationmethodistochangetheprove.,APCIprobe,ESIProbe,Mobilephase,LCflowrateandNebulizerflowrateslightlyinfluencespraycondition.Youcanadjusttheprobepositiontothebestforeachcondition.,TheAPCIprobecontainscoronadischargeneedle.SononeedtochangetheAPIspraychamber.,-,68,EasyMaintenance,SkimmerLensstackaccess,SprayChamberAccess,Youcanpickitupfromuppersidewithoutanytools.,Youcanremovethespraychamberfromthefrontside.Itwillbeeasytowashthispartafteranalysis.,-,69,StandardSyringePump,Syringefordirectsampleinjection,Syringeforstandardsampleofcalibration,-,70,LCMSApplication,-,71,MassSeparation,Column:STRODS-II(2.0mmI.D.x150mm)Mobilephase:65%acetonitrile-watercontaining0.1%formicacid,0.2ml/min,Maltose,TIC,387,225,195,Glucose,Xylose,-,72,Analysisofmacrolideantibiotics,UV210nm,MDM,SIM,SPM-I,II,SPM-III,OM,DHEM,MDM,-,73,Summary,LCMS-QP8000isaCompactBenchTopLiquidChromatographwithhighperformancesEasyOperationandMaintenanceusingCLASS-8000softwareSelfdiagnosticfunctionsUserloginandsecuritydefinedbyaccesslevels.OLEcustomreportgenerationAffordableprice,-,74,质谱图和色谱图,?,-,75,如果我们注意这个区域.,色谱图?,-,76,在此的细微观察是由许多点组成的.,色谱图-放大,-,77,每个点相对于质量分析器的一个扫描(质谱图).,质谱图,-,78,每个点有一张唯一的质谱图,色谱图上的质谱图,-,79,数据观察-色谱图,样品运行中的每秒我们可获得一张或数张质谱图通常是把检测到的离子叠加在一起获得一个唯一的总的数值这些总的数值然后排列在一起(点对点)产生一个类似的色谱图(TIC).,-,80,每次扫描加和所有的离子得到.,总离子色谱图(TIC),-,81,数据观察-色谱图,我们也能显示某一张质谱图这让我们一个化合物的信息质谱图,-,82,质量色谱图和TIC,TIC,Mass240,-,83,消除背景的影响增加信噪比分离共流出物峰,数据观察-选择离子色谱图,-,84,TIC图上显示的两个接近的流出峰，但每个峰是具有不同质谱指纹的不同化合物.,数据观察-选择离子色谱图,-,85,数据观察-选择离子色谱图,-,86,分离共流出物峰,10.50,11.00,11.50,12.00,12.50,Time,0,100,%,0,100,%,0,100,%,254.23,5.81e4,194.20,6.14e4,TIC,1.57e5,质量254,质量194,TIC,-,87,选择离子色谱图,提取出离子给出更好的信噪比消除背景影响分离共流出物峰提取出离子也能用于:峰的跟踪准确定量,-,88,峰跟踪的实例,爆炸混合物的TIC,哪一