質(zhì)譜法優(yōu)秀公開課課件

第八章質(zhì)譜法MassSpectroscopy(MS)質(zhì)譜儀的一般結(jié)構(gòu)真空系統(tǒng)進(jìn)樣系統(tǒng)離子檢測(cè)器數(shù)據(jù)系統(tǒng)質(zhì)量分析器離子源大氣樣品機(jī)械泵，分子渦輪泵，擴(kuò)散泵，離子泵，升華泵氣體：氣相色譜儀(GC/MS)液體：液相色譜儀(LC/MS)固體：固體進(jìn)樣桿(DIP,DCI)電子倍增器，多通道板檢測(cè)器光電倍增管，陣列檢測(cè)器通常的離子化方法電子轟擊離子化 EI化學(xué)電離離子化 CI正化學(xué)電離離子化 PCI負(fù)化學(xué)電離離子化 NCI大氣壓力離子化 API電噴霧離子化 ESI大氣壓化學(xué)電離離子化 APCIGC/MSLC/MS離子化和碎片離子化硬無(wú)碎片有碎片APIEICI軟質(zhì)量分析器四極桿~80%的臺(tái)式質(zhì)譜儀(~3000/年)HP,PE,TMQ,Shimadzu離子阱~20%的臺(tái)式質(zhì)譜儀(~700/年)Varian,TMQ飛行時(shí)間(ToF)目前用戶較少(50-60/年)Leco,Micromass,TMQ扇形磁場(chǎng)通常不是臺(tái)式儀器四極質(zhì)量分析器++++飛行時(shí)間質(zhì)量分析器++++所有離子同時(shí)啟動(dòng)小的離子移動(dòng)速度快測(cè)量已知距離下的速度(飛行時(shí)間)扇形磁場(chǎng)質(zhì)量分析器+++離子通過(guò)變化的磁場(chǎng)和電場(chǎng)被傳輸ElectronImpactIonization(EI)e-e-e-e-e-SamplefromGCfilament++++FragmentionQPPositiveChemicalIonization

(PCI)fromgascylinderfilamente-e-e-e-e-QPCH4

CH5+C2H5+SamplefromGCH+-CH4[M+1]-C2H4PositiveChemicalIonization(PCI)Reagentgasmoleculesareionizedfirst.Samplemoleculesareionizedmainlyby損rotontransfer?Quasimolecularionseasilyproducedusefulformolecularweightverification.

+PCIspectrumMethylstearateM.W.298ComparisonofEIandPCIEImodePCImodeFragmentMolecularweightNegativeionformationbyelectroncapture(associativeresonancecapture)

MX+e-(~0eV)MX-.X:positiveelectronaffinitypartCH4e-MXCH4+CH3+HCH4CH4CH4e-MX-質(zhì)譜圖的樣子?EI和CI的質(zhì)譜圖50100150200250300350400450500550m/z0100%51051151250100150200250300350400450500550m/z0100%241213510242EIOOOCF3CF3CH3NCI…掃描50到300amu流入質(zhì)譜儀的化合物質(zhì)譜圖...60801001201401601802002202402602803000100%240241斷裂機(jī)理1.σ斷裂2.α斷裂5.Mclafferty重排ConfigurationofGCMS

MassSpectrometerGasChromatographInterfaceIonsourcebox

IonSourceDesign

-Increasedionizationefficacy-InterfaceThesampleseparatedbyGCwillbeintroducedthroughthisinterface.

FilamentIongeneratedbyfilamentwillgivetheelectronimpacttothesampletoproducethesampleionization.Ionsourcebox

IonLens

-Highionintroductiontomassanalyzer-

Thisionlensisfunctioningforeffectiveintroductiontomassanalyzer.OptimizationforadjustmentofthisionlenswillbedonebyPCautomatically.

QuadrupoleRod

-MinimizelossesintransittotheQuadrupole-MainRodSpecificiononlycanbepassedbytheelectronicfieldintoQuadrupoleRodwhichiscontrolledbyPC.PreRodFromionsourceTodetectorrotarypumpturbomolecularpump(151L/sec)turbomolecularpump(151L/sec)rotarypumpGoodvacuumsystem-MinimizelossesintransittotheQuadrupole-

TurboMolecularPump

AircooledandoilfreeTurbomolecularPump(TMP)withlubricantimpregnatedceramicbearingsismaintenancefreeforupto25,000hours.Provideshighqualityvacuuminlessthan5mins.Iondetection

+7.5kV-+e--0.7~3.0kVAMP-7.5KV+e--0.7~3.0kVAMPe-NegativeiondetectionPositiveiondetectionGCMS-QP5050ANCIsensitivity200fgHexachlorbenzeneNCIspectrum

Masschromatogramofm/z284OFN(octafluoronaphthalene)NCIscanmodeOutstandingHighSensitivity

scanrangem/z60-310,0.5secinterval200fgS/N>30

GCMS-QP5050ANCIpesticidesdate310pgCyanophosNCI

massspectrumphosphoruspesticides10pgComparisonbetweenEIandNCIextractfromcabbage(pesticidesadded)EIscanningmodeNCIscanningmodeComparisonbetweenEIandNCIextractfromcabbage(pesticidesadded)PrincipleofProgramedtemperaturevaporize(PTV)PTV

100CsplitMS50-250CSolventwillbevaporizedandexhausted.Samplewillbeconcentrated.OptimizationofPTVconditionsSelectionofpackingmaterialsTenaxGC 20%OV-120%OV-1720%Dexil300ShincarbonACarbopackC TraptemperatureDesorptiontemperatureTemperatureprogramVery-Large-VolumeInjectionusingPTV

EffectofTemperatureonTrapefficiencyVery-Large-VolumeInjectionusingPTV

TemperatureandSplitratioProgramVery-Large-VolumeInjectionusingPTV

2ppbeachPesticidesinn-hexane1000uLInjectionAnalyticalConditions

GC17AVer.2

DB130mX0.25mm

50C(4)-160C-280C

20C/min5C/min

PTV

70C(1)-100C(1)-280C

30C/min250C/min

WiderangeFTD1pA280C

CarriergasHe150kPa

PrecolumnTenaxGCFeaturesofGCMSQP-5050AOutstandinghighsensitivityExtendedmassrangeupto900amuVersatileMode-EI/PCI/NCI/DICompactDesignEasyOperationusingWindowsSoftwareEasytuning-PFTBAbuiltinstandardEasymaintenanceAnalysisofCoconutoilMSSpectrumofC48DIoptionThedirectinletoptionallowslessvolatileorthermallylabilesamplestobedirectlyintroducedintothemassspectrometer.MixturesofcompoundswhichhavedifferentboilingpointscanbepositivelyidentifiedbyprogrammingtheDIprobetemperature.Applicationusing

directinletprobeFront-openionchambersystem

-easymaintenance-

DualFilamentsSystem

-easymaintenance-

LCMS-QP8000Validation,ProductivityandMassDetectionWhatkindofbenefits

LC/MSuserscanget?PowerfulqualitativecapabilitySelectivequantitativecapability

M/ZM/ZM/ZWhatkindofbenefits

LC/MSuserscanget?PowerfulqualitativecapabilitySelectivequantitativecapability

A:100D:150B:100C:150m/z=150TICm/z=100ABCDHPLCMSNewShimadzuLCMS

QP-8000QP-8000isLC/MSwithAPIinterfacewhichisdesignedtobearoutineLCdetectorinournewVPseriesHPLCsystem.LCMSInterfaceCurvedDesolvationLine(CDL)DeflectorProbeSprayChamberSkimmerLensStack

RPTMP1TMP2QuadrupoleAPISprayChamberAPISprayChamberESIProbe(EasytochangetoAPCIProbe)APIProbeESIandAPCIprobesareincludedasstandard.Theycanbeappliedtovariouskindsofsamples.Allyouhavetodotoswitchtheionizationmethodistochangetheprove.APCIprobeESIProbeMobilephase,LCflowrateandNebulizerflowrateslightlyinfluencespraycondition.Youcanadjusttheprobepositiontothebestforeachcondition.TheAPCIprobecontainscoronadischargeneedle.SononeedtochangetheAPIspraychamber.EasyMaintenanceSkimmerLensstackaccessSprayChamberAccessYoucanpickitupfromuppersidewithoutanytools.Youcanremovethespraychamberfromthefrontside.Itwillbeeasytowashthispartafteranalysis.StandardSyringePumpSyringefordirectsampleinjectionSyringeforstandardsampleofcalibrationLCMSApplicationMassSeparation

Column:STRODS-II(2.0mmI.D.x150mm)Mobilephase:65%acetonitrile-watercontaining0.1%formicacid,0.2ml/minMaltoseTIC387225195GlucoseXyloseAnalysisofmacrolideantibioticsUV210nmMDMSIMSPM-I,IISPM-IIIOMDHEMMDMSummaryLCMS-QP8000isa

CompactBenchTop

LiquidChromatographwithhighperformancesEasyOperationandMaintenance

usingCLASS-8000softwareSelfdiagnosticfunctionsUserloginandsecuritydefinedbyaccesslevels.OLEcustomreportgeneration

Affordableprice

質(zhì)譜圖和色譜圖?如果我們注意這個(gè)區(qū)域...色譜圖?1.251.501.752.002.252.502.753.003.25Time50100%TIC在此的細(xì)微觀察是由許多點(diǎn)組成的...色譜圖-放大22.242.262.28Time78100%TIC每個(gè)點(diǎn)相對(duì)于質(zhì)量分析器的一個(gè)掃描(質(zhì)譜圖)...60801001201401601802002202402602803000100%240241質(zhì)譜圖

每個(gè)點(diǎn)有一張唯一的質(zhì)譜圖色譜圖上的質(zhì)譜圖數(shù)據(jù)觀察-色譜圖樣品運(yùn)行中的每秒我們可獲得一張或數(shù)張質(zhì)譜圖通常是把檢測(cè)到的離子疊加在一起獲得一個(gè)唯一的總的數(shù)值這些總的數(shù)值然后排列在一起(點(diǎn)對(duì)點(diǎn))產(chǎn)生一個(gè)類似的色譜圖(TIC)...每次掃描加和所有的離子得到...總離子色譜圖(TIC)數(shù)據(jù)觀察-色譜圖我們也能顯示某一張質(zhì)譜圖

這讓我們一個(gè)化合物的信息…

…質(zhì)譜圖質(zhì)量色譜圖和TICTICMass2401.401.601.802.002.202.402.602.803.00Time0100%0100%240.271.41e5TIC4.67e5

消除背景的影響

增加信噪比

分離共流出物峰數(shù)據(jù)觀察-選擇離子色譜圖TIC圖上顯示的兩個(gè)接近的流出峰，但每個(gè)峰是具有不同質(zhì)譜指紋的不同化合物...數(shù)據(jù)觀察-選擇離子色譜圖11.0012.00Time0100%TIC1.57e5數(shù)據(jù)觀察-選擇離子色譜圖100200300400500600m/z0100%254.2194.2507.3334.3399.7100200300400500600m/z0100%194.2580.4402.2226.2460.211.0012.00Time0100%TIC1.57e5分離共流出物峰10.5011.0011.5012.0012.50Time0100%0100%0100%254.235.81e4194.206.14e4TIC1.57e5質(zhì)量254質(zhì)量194TIC選擇離子色譜圖提取出離子給出更好的信噪比消除背景影響分離共流出物峰

提取出離子也能用于:

峰的跟蹤

準(zhǔn)確定量峰跟蹤的實(shí)例0100%TIC2.21e61.002.003.004.005.006.00Time0.525.653.823.251.672.005.594.954.255.725.81爆炸混合物的TIC哪一個(gè)是HMX?HMX的質(zhì)譜圖峰跟蹤406080100120140160180200220240260m/z0100%8472596911389106237131205158分子離子峰峰跟蹤質(zhì)量色譜圖m/z237TIC1.002.003.004.005.006.007.008.009.00Time0100%0100%2.000.525.653.823.251.672.004.954.255.81分離相鄰峰的能力分子離子[M+H]+M.+[M-H]-

分辨率FWHM10%峰谷m/M[M+H]+m/zintensity質(zhì)譜分辨率復(fù)合技術(shù)GC/MS氣相色譜-質(zhì)譜LC/MS液相色譜-質(zhì)譜MS/MS質(zhì)譜-質(zhì)譜MS-MS方法MS1MS2

固定 掃描

子離子

掃描 固定

母離子

掃描 掃描