FUNDAMENTALS AND APPLICATIONSOF FOURIER TRANSFORMMASS SPECTROMETRY
Editedby
BASEMKANAWATI
AnalyticalBiogeochemistry,HelmholtzZentrum Munchen,Neuherberg,Germany
PHILIPPESCHMITT-KOPPLIN
AnalyticalBiogeochemistry,HelmholtzZentrum M € unchen,Neuherberg,Germany
AnalyticalFoodChemistry,TechnicalUniversityofMunich, Freising,Germany
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Contributors
JefferyN.Agar
DepartmentofChemistryandChemicalBiology,NortheasternUniversity,Boston,MA, UnitedStates
DeborahV.A.deAguiar
ChemistryInstitute,FederalUniversityofGoia ´ s,Goi^ania,Brazil
MichaelaAichler
ResearchUnitAnalyticalPathology,HelmholtzZentrumM € unchen,GermanResearch CenterforEnvironmentalHealth,Neuherberg,Germany
HerveAlexandre
UMRPAMUniversityofBurgundy/AgrosupDijon,InstitutUniversitairedelaVigneetdu Vin,JulesGuyot,Dijon,France
Joa˜oFranciscoAllochioFilho
LaboratoryofPetroleologyandForensicChemistry,DepartmentofChemistry,Federal UniversityofEspı´ritoSanto,Vito ´ ria,Brazil
I.JonathanAmster
DepartmentofChemistry,UniversityofGeorgia,Athens,GA,UnitedStates
FredericAubriet
LaboratoryofChemistryandPhysics—Multi-ScaleApproachofComplexSystems,FR2843 JeanBarriolInstitut,FR3624FrenchHighFieldFT-ICRMassSpectrometryNetwork, LorraineUniversity,ICPM,Metz,France
KonstantinAyzikov
ThermoFisherScientific,Bremen,Germany
VincentCarre
LaboratoryofChemistryandPhysics—Multi-ScaleApproachofComplexSystems,FR2843 JeanBarriolInstitut,FR3624FrenchHighFieldFT-ICRMassSpectrometryNetwork, LorraineUniversity,ICPM,Metz,France
SebastianDillinger
FachbereichChemieandForschungszentrumOPTIMAS,TechnicalUniversity Kaiserslautern,Kaiserslautern,Germany
JianaDuan
DepartmentofChemistry,UniversityofGeorgia,Athens,GA,UnitedStates
MichaelL.Easterling
BrukerDaltonicsInc.,Billerica,MA,UnitedStates
Franc ¸ oisFenaille
PharmacologyandImmunoanalysisUnit(SPI),CEA,INRA,Paris-SaclayUniversity, Gif-sur-Yvette,France
FranciscoFernandez-Lima
DepartmentofChemistryandBiochemistry;BiomolecularSciencesInstitute,Florida InternationalUniversity,Miami,FL,UnitedStates
FedericoFloris DepartmentofChemistry,UniversityofWarwick,Coventry,UnitedKingdom
LenaGmelch
ComprehensiveFoodomicsPlatform,AnalyticalFoodChemistry,TechnicalUniversity Munich,Freising,Germany
MichaelGonsior
UniversityofMarylandCenterforEnvironmentalScience,ChesapeakeBiological Laboratory,Solomons,MD,UnitedStates
MarinaGotthardt
ComprehensiveFoodomicsPlatform,AnalyticalFoodChemistry,TechnicalUniversity Munich,Freising,Germany
RegisD.Gougeon
UMRPAMUniversityofBurgundy/AgrosupDijon,InstitutUniversitairedelaVigneetdu Vin,JulesGuyot,Dijon,France
DmitryGrinfeld ThermoFisherScientific,Bremen,Germany
DanielHemmler
ResearchUnitAnalyticalBioGeoChemistry,HelmholtzZentrumM€ unchen,Neuherberg; ComprehensiveFoodomicsPlatform,AnalyticalFoodChemistry,TechnicalUniversity Munich,Freising,Germany
JasmineHertzog
LaboratoryofChemistryandPhysics—Multi-ScaleApproachofComplexSystems,FR2843 JeanBarriolInstitut,FR3624FrenchHighFieldFT-ICRMassSpectrometryNetwork, LorraineUniversity,ICPM,Metz,France;ComprehensiveFoodomicsPlatform,Analytical FoodChemistry,TechnicalUniversityMunich,Freising;ResearchUnitAnalytical BioGeoChemistry,HelmholtzZentrumMunchen,Neuherberg,Germany
ChristopheJunot PharmacologyandImmunoanalysisUnit(SPI),CEA,INRA,Paris-SaclayUniversity, Gif-sur-Yvette,France
BasemKanawati
ResearchUnitAnalyticalBioGeoChemistry,HelmholtzZentrumMunchen,Neuherberg, Germany
YuryI.Kostyukevich
SkolkovoInstituteofScienceandTechnologyNovayaSt.RussianFederation,Russia
SergeyV.Kovalev
DepartmentofChemistry,M.V.LomonosovMoscowStateUniversity,Moscow,Russia
AntonN.Kozhinov Spectroswiss,EPFLInnovationPark,Lausanne,Switzerland
LisaKreutzer
ResearchUnitAnalyticalPathology;ResearchUnitofRadiationCytogenetics&Research UnitAnalyticalPathology,HelmholtzZentrumMunchen,GermanResearchCenterfor EnvironmentalHealth,Neuherberg,Germany
ValdemarLacerda,Jr.
LaboratoryofPetroleologyandForensicChemistry,DepartmentofChemistry,Federal UniversityofEspı´ritoSanto,Vito ´ ria,Brazil
AlbertT.Lebedev DepartmentofChemistry,M.V.LomonosovMoscowStateUniversity,Moscow,Russia
YouzhongLiu
UMRPAMUniversityofBurgundy/AgrosupDijon,InstitutUniversitairedelaVigneetdu Vin,JulesGuyot,Dijon,France
AlexanderMakarov
ThermoFisherScientific,Bremen,Germany
FrancoMoritz
ResearchUnitAnalyticalBioGeoChemistry,HelmholtzZentrumMunchen,Neuherberg, Germany
KonstantinO.Nagornov
Spectroswiss,EPFLInnovationPark,Lausanne,Switzerland
GereonNiedner-Schatteburg
FachbereichChemieandForschungszentrumOPTIMAS,TechnicalUniversity Kaiserslautern,Kaiserslautern,Germany
EugeneN.Nikolaev
SkolkovoInstituteofScienceandTechnologyNovayaSt.RussianFederation,Russia
PeterB.O’Connor DepartmentofChemistry,UniversityofWarwick,Coventry,UnitedKingdom
IgorPereira
ChemistryInstitute,FederalUniversityofGoia ´ s,Goi^ania,Brazil
WandersonRoma˜o
LaboratoryofPetroleologyandForensicChemistry,DepartmentofChemistry, FederalUniversityofEspı´ritoSanto,Vito ´ ria;FederalInstituteofEspı´ritoSanto, VilaVelha;NationalInstituteofForensicScienceandTechnology(INCTForensic), Vito ´ ria,Brazil
ChloeRoullier-Gall
UMRPAMUniversityofBurgundy/AgrosupDijon,InstitutUniversitairedelaVigneetdu Vin,JulesGuyot,Dijon,France
MichaelRychlik
ComprehensiveFoodomicsPlatform,AnalyticalFoodChemistry,TechnicalUniversity Munich,Freising,Germany;CentreforNutritionandFoodSciences,QueenslandAlliance forAgricultureandFoodInnovation(QAAFI),UniversityofQueensland,Brisbane, Australia
PhilippeSchmitt-Kopplin
ResearchUnitAnalyticalBioGeoChemistry,HelmholtzZentrumMunchen,Neuherberg; ComprehensiveFoodomicsPlatform,AnalyticalFoodChemistry,TechnicalUniversity Munich,Freising,Germany
Jorg-PeterSchnitzler
HelmholtzZentrumMunchen,InstituteofBiochemicalPlantPathology,ResearchUnit EnvironmentalSimulation,Neuherberg,Germany
YuryO.Tsybin
Spectroswiss,EPFLInnovationPark,Lausanne,Switzerland
GessicaVasconselos
ChemistryInstitute,FederalUniversityofGoia ´ s,Goi^ania,Brazil
BoniekG.Vaz
ChemistryInstitute,FederalUniversityofGoia ´ s,Goi^ania,Brazil
JoelleVinh
LaboratoryofBiologicalMassSpectrometryandProteomics,CNRSUSR3149,ESPCI Paris,PSLUniversity,Paris;TGEFT-ICRCNRS,France
GlebVladimirov
SkolkovoInstituteofScienceandTechnologyNovayaSt.RussianFederation,Russia
AxelKarlWalch
ResearchUnitAnalyticalPathology,HelmholtzZentrumM€ unchen,GermanResearch CenterforEnvironmentalHealth,Neuherberg,Germany
KarlPeterWanczek
InstituteofInorganicandPhysicalChemistry,UniversityofBremen,Bremen,Germany
Foreword
Thisbookprovidesawide-rangingdescriptionofthecurrentstateoftheart inFouriertransformmassspectrometry.Asdescribedinseveralchapters, beginninginlate1973withthefirstFTioncyclotronresonancemassspectrum(showingjustasingleCH4+ peak),thefieldhassinceexploded,with installationofnearly1000FT-ICRMSplusseveralthousandorbitrap instruments.
FTmassanalyzersofferthehighestmassresolution(e.g.,baselineseparationofionsdifferinginmassbylessthanthemassofanelectron)andmass accuracy(masserroraslowasafewppb).Thosefiguresofmerithave recentlybeenimprovedbyincreasedmagneticfieldstrength(FT-ICR) orsmaller-sizeiontrap(orbitrap),aswellasphasecorrectiontodouble themassresolvingpower(FT-ICRandorbitrap),andfrequency-multiple detectionforenhancementofFT-ICRmassresolvingpowerbyfactors of2–4.Conversely,foragivenmassresolvingpower,dataacquisition canbespeededuptoachieveLC-MSwithoutcompromisingchromatographicresolution.Instrumentationimprovementsinioninjection,ion trapping(dynamicallyharmonizedICRcell;“nadel”ICRcell,Cassini quadrupolarcell),excitation,anddetectioncontinuetobeguidedbyion trajectorysimulations.
MultifacetedapplicationshavebeenenabledbycouplingFTmassanalyzerswithgas-andliquid-chromatography(collectedfractionsoron-line), trappedionmobilitysource,variousionizationmethods(e.g.,electron impact,laserdesorption/ionization,MALDI,electrospray,photoionization),variousionfragmentationmethods(ion-neutralcollisions,IRand UVphotodissociation,electroncapture,electrontransfer,surface-induced dissociation).FTMShashadparticularlyhighimpactinproteomics (MS/MSidentificationofproteinaminoacidsequences,includingposttranslational(chemical)modificationsnotaccessiblefromcorresponding DNAbasesequences,andpetroleomics(predictionofthepropertiesand behaviorofpetroleumanditsproductsbasedondetailedorganiccompositionalanalysis),andisexpandingintovariousother“-omics”fields(food, geochemistry,environment,forensics,carbohydrates,lipids,metabolism, etc.)andinmolecularimaginginbiochemistryandmedicine.
Thechapterssummarizetheactualstateoftheartinthefieldasforexampletwo-dimensionalFT-ICRMS/MS,whichyieldsasingle2Dspectrum
thatconnectseachprecursorionwithallofitsproductions.Otherchapters describegas-phaseion-moleculechemistryandlow-temperatureinorganic clusters.
Insummary,FTMSinstrumentsnowextendtovirtuallythefullrangeof massanalysisapplications,therebysettingnew“goldstandards”whichserve toguidesubsequence“targeted”analysiswithlower-resolutioninstruments.
AlanG.Marshall
RobertO.LawtonProfessorofChemistry&Biochemistry
FoundingDirectorandChiefScientist, IonCyclotronResonanceProgram, NationalHigh MagneticFieldLaboratory FloridaStateUniversity Tallahassee,FL,UnitedStates
Preface
Theworldofmassspectrometryisexpandingrapidlyinthiscenturythanks tomanyadvancesinphysics,electronics,vacuumtechnologyandmathematicalconsiderations,especiallyinthefieldofstatisticaldataanalysisand engineering.Thereforeastrongneedemergedtowritethisbook,which addressesmanyaspectsoftechnicalfundamentalsinthephysicsofmass spectrometricFTMSanalyzersandionbeamguidesaswellasdiverseapplicationsinmanyfieldsofnaturalandlifescience.
Herewegiveabriefaccountonthediversetopicswhichareincludedin thiscomprehensivebook:
Chapter1 addressesthehistoricaldevelopmentsinthewell-knownFourierTransformIonCyclotronResonanceMassSpectrometryFT-ICR-MS. Chapter1 doesnotonlylistthemainhistoricaldevelopmentsofthe FT-ICRbutalsoitdatesbacktotheinventionofICR,priortoimplementationoftheeffectiveFourierTransform(FT)algorithmtospeedupthe wholeICRexperimentalsetup,byenablingthegreattechnologicaltransfer frommagneticfieldscantotherapidfrequencychirp“allionsexcitation” forICRdetection.
Chapter2 addressestechnicalfundamentalsintheefficientOrbitrapmass analyzer,showingitsphysicalprincipleofoperation,dealingwithnonideal orbitrapgeometriesandshowingtheirpossiblecalibration,andgivingsome advancesinsignalprocessingwhicharesteadilygrowingintherecenttime. Thereaderwillfindapplicationstothisgreatmassanalyzernotonlyin Chapter2 butalsoin Chapters5,11,15,16,17and21,whichdiscuss advancedfundamentals,metabolomics,forensics,petroleomics,proteomics andfoodomics,respectively.
AdvancesinthenewParacellICRmassanalyzercanbefoundin Chapters3and4.Inthisrespect,thereaderwillespeciallygetadvanced knowledgeonthephysicaldevelopmentsoftheParacell,showingalsowith sophisticatediontrajectorysimulationsonsupercomputerswithmore sophisticatediontrajectorysimulatorsbeyondSIMIONthechallengesthat couldbeovercomeinICRtoreducespace-chargeeffectsandcoalescences andalsoenhancebothresolutionandacquisitiontime.
Chapter5 discussesmassresolvingpowercharacteristicsinbothOrbitrap andICRmassanalyzersforachievingultra-highresolutionspectrainabroad massrange.Thisdiscussionisassistedbyrobustandclearmathematical
equationstofacilitateunderstandingthedifferencesintheresolutionbehaviorasafunctionof m/z.Thischapteralsoaddressesdatareduction approachesandalsoshowsthepossibleconversionfromraw(full)toline shape(reducedprofile)massspectrawiththeirprosandcons.
Extensivedataprocessingstrategiesarediscussedin Chapter6,where magnitudeandabsorptiondetectionmodesinFT-ICRarediscussedingreat detailaswellasmanynon-FourierTransformtechniques.Calibration,apodization,denoisingandbatchprocessingaswellasisotopicbeatpatternsare alsotreated. Chapter6 representsalsodifferentsuccessfulstrategiesandalso discussesadvancedICRcontrolunitsforFT-ICR-MSautomationtogive thereadersomehands-onexperienceforachievingafullFTMSacquisitiontimeinvestment.
Chapter7 isdedicatedforexplainingallthefundamentalsandalsoshowingmanysuccessfulapplicationsinthefieldoftwodimensionalFT-ICR-MS. Dataacquisitionandprocessingaswellasimportantdenoisingalgorithmsare alsodiscussedtherewhicharespecificto2D-FT-ICR-MS.
CouplingofFTMSmassanalyzerstoionmobilitycellsandtochromatographicsystemsisdiscussedin Chapters8and11,respectively. Chapter9 showsmanyapplicationsofFT-ICR-MStomedicalimagingofcancerbiologicaltissuesand Chapter10 showsdiversecouplingoflasersourcesfor ionizationtoFT-ICR-MSwithmanydiscussedinorganicapplications. Manymetabolomicsapplicationscanbefoundinboth Chapter11 forOrbitrapand Chapter12 forFT-ICR-MS.Thelatterchaptershowsalsothe importanceofmassdifferencenetworksforrevealingnotonlythecompositionalelementalspaceincomplexmixturesbutalsogoingindeepdetail beyondit(seedetailsin Chapter12).Environmentalapplicationsrelated toaquaticandsedimentchemistrycanbefoundin Chapter13,whereasdeep discussionsforpeptidesequencingcanbefoundinboth Chapters14and17. ForensicFTMSapplicationsaregivenin Chapter15,whilemanyapplicationsinthefieldofpetroleomicsexistin Chapter16.Manychallengesin proteomicsandproteoformsaregreatlydiscussedin Chapter19,which showsthetransitionfromthecomprehensivedescriptionofexhaustiveproteometofunctionalproteomicsbytheuseofFTMS.Both Chapters18and 19 showsdiverseFT-ICR-MSapplicationsintothegasphaseionchemistry, doneinseveralICRcells,whichserveaselectronicreagentglass(electronic reactor).Keyphysicalchemistrythermodynamicandkineticdatacouldbe achievedinthepast40yearswithFT-ICR-MSandtheyarediscussedfor thecaseofinorganicelementsandtheirsubstancesasareviewin Chapter18, focusingonnonmetalapplications,whileChapter19discussesFT-ICR-MS
investigationsofseveralinorganicmetalclusterionsandalsoshowthe advantageofcoldICRcellrelativetotraditionalambienttemperatureoperationmode.Thelastthreechapters,showsdeepFT-ICR-MSinvestigations inglycomics,foodomicsandbio-oilanalysis.WithcomprehensivetreatmentsofthesediverstopicsofFTMSapplications,thereaderwillgetthoroughuptodateknowledge(someofwhichareverypractical),whichcan helpthereadertofurtherrunandovercomesomescientificchallengeswhile runningfurtherFTMSapplications.Despitethecomplexphysicaland mathematicalfundamentalsoftheFTMSmassanalyzers,everyefforthas beendonefromtheeditorialsidetomakeeverychapterasclearaspossible andthereforeaccessibletoalargeaudienceofscientificreaders.Wehope thatthereaderwillenjoyalsoreadingtheseveryinterestingchapters.
Theeditors
Acknowledgments
Theeditorsthankallbookchaptercontributorsfortheirgreateffortsand timespenttoadduptodatescientificknowledgefromtheirgreathandsonexpertise.Weenjoyedcooperatingtogetherwithmanyauthors,who providedexcellentreviewsandmanyexplanationstoourscientificqueries tomakethisbookasclearaspossible.
BasemKanawatigreatlythanksprofessorKarlPaterWanczekforhis valuablecommentsandassistance,whilepreparingthisbook.Heisthefirst scientist,whointroducedmeinthepasttoadvancedICR-MStechniques, withitsdiversefundamentalphysicalandchemicalelements,rangingfrom experimentalphysicsstudiesandiontrajectorysimulationsinseveralICR celldesignstoapplicationsofthistechniqueinstudyingmanygasphase ion-moleculereactionsandionenergetics.
TheeditorsalsothankallElsevier’steammembersforwitnessingand greatlyassistingthedevelopmentofthisextensivebook.Withtheirhelp, wecouldallcontributetomaketheproductionofthiscomprehensivebook areality.
KarlPeterWanczek*,BasemKanawati†
Introduction
Thisreviewcoversinstrumentationandtheoryaswellasapplications,which opennewfieldsinscientificresearch.Therefore,thefirstdecadeswill occupymorespacethanthemorerecentyears.Thematerialispresented inachronologicalsequenceofeventstofacilitateahistoricalpointofview throughthediscussion.Thereviewisnotintendedtobecomprehensive, butapersonalviewoftheauthorsofthemostimportantdevelopments inthefield.
Fourdifferentiontrapsareknown:
– Penningtrap [1–3] (iontrappingbyDCelectricalfieldsandahomogeneousmagneticfield),“ICRcells”
– Paultrap [4,5] (iontrappingbyRFelectricalfields),
– Kingdontrap [6] (iontrappingbyDCfields)and
– Combinedtrap [7] (acombinationofthePaulandPenningtrapping principles).
Penningtrapsarecoveredasfarastheyareemployedinioncyclotronresonance(ICR)massspectrometryandFouriertransformioncyclotron—FT ICR—massspectrometry.AlsocoveredareICRdriftcellsemployedinthe earlytimesoftheICRtechnique.IntheICRdriftcellionsdriftoncycloidal pathsalongthelongitudinalaxis,guidedbymagneticandelectricfields(see textbelow).
Inphysics,precisionmeasurementsofatomicmassesandfundamental constantsareperformedwithPenningtraps.WithICR,elementarysteps ofchemicalreactionsandion-moleculereactions,whichnormallyoccur atnear-thermalenergies,arestudied.AftertheinventionoftheFourier transformtechnique,analyticalapplicationsdominate.TheICRmethod developedindependentlyfromthephysicalapplicationsuntilearly1980s (cf.Ref. [8]:InthisICRvolume,forthefirsttime,physicalapplications ofPenningtrapsaredescribedbyG.Gr€afffromtheInstituteofPhysics, UniversityofMainz,inthechapter:“precisiondeterminationofcyclotron frequenciesoffreeelectronsandions,”pp.318–325).
SeveralpublicationsofgeneralinterestinICRhavebeenpublished.The firstbookwaswrittenbyLehmanandBursey [9] in1976.Thebookby MarshallandVerdun [10] presentsadetailedgeneralintroduction.Early reviewsin1971byGray [11],byBeauchamp [12],byFutrell [13] andin 1973byHartmannetal. [14] coveredthenewmethodologycomprehensively.Severalreviews [15–18] ofearlyICRdevelopmentwerepublished, andmorerecently [19,20] HartmannandWanczek [8,21] editedtwo
volumesinLectureNotesinChemistryonICRSpectrometryin1978and 1982whichcoveredmanyaspectsofthedevelopmentofthefield.
Arecentcontributiontothehistoryofmassspectrometryisin“The EncyclopediaofMassSpectrometry,”Vol.9,PartA [22].ThevolumecontainsahistoryofICRbyC.L.Wilkins [23] withmanydetails.
Developmentsbefore1970
InICR,theionsweretrappedinordriftedthroughanICRcellatreduced pressureanddetectedwiththeaidofimagecurrent [24],inducedinthecell platesbyacoherentionmotion.Thecoherentmotionisgeneratedbyexcitationofoneofthecharacteristicionfrequencies.Themethodhasmany similaritieswithNMRspectroscopy.TheionsarepresentintheICRcell afterdetection.Ingeneral,onlyionsofonechargepolaritycanbetrapped, negativeionsorpositiveions.
TheOmegatronofSommeretal. [25] employedcyclotronresonance excitationandchargedetectionofions.TheOmegatronwasutilized widely.Severalimprovementswereintroduced [26].BytheHipplegroup afurtherinstrumentwasdescribed,whichemployedtheioncyclotron motionforfocusing:ThetrochoidalmassSpectrometer [27].Goudsmit [28] describedaTime-of-Flightmassspectrometerwherethetrajectory oftheionsisinsideamagneticfield.
Averyadvancedinstrument,theMass“Synchrometer,”wasbuiltby SmithandDamm [29].Highharmonicsoftheioncyclotronfrequencywere employedformassdeterminationwithhithertounparalleledaccuracy.Coggeshall [30] firstdescribedthepathofionsandelectronsinnonuniform crossedelectricandmagneticfields.In1962,Grahametal. [31,32] describedanICRinstrumentanddiscussedthedeterminationofcollision crosssections.AdetaileddescriptionoftheICRspectrometerfollowed [33].
1965
Llewellyn [34] ofVarianAss.filedapatentofanICRspectrometerwithdrift ICRcellandionresonancedetectionwiththeaidofamarginaloscillator (Poundbox [35,36]):
“Aspectrometerisdescribedwhichemploysioncyclotronresonanceandenergy absorptioninmassanalysis.Inanevacuatedenvelopeionsareformedinthefirst oftworegionswhicharesubjectedtostaticmagneticandelectricfieldsdisposedat rightanglestoeachotherandtothecommonaxisofthetworegions.Theionsare causedbytheinteractionofthefieldstomovewithcycloidalmotionintothe
secondregionwhichisadditionallysubjectedtoanoscillatingelectricfieldinthe samedirectionasthestaticfield.Theionsinresonancewiththeoscillatingfield absorbenergytherefromandseparatefromthenonresonantions.Theenergy absorbedbytheresonantionsisthendetectedasameasureoftheresonantions.” (Abstractofpatent)
Furthermore,thisICRcellhadathirdregionfortotalioncurrentmeasurement.Thespectrometerwasproducedandnamed“Syrotron.”Theinstrumenthadasmallmassrange,below m/z ¼ 200andaresolutionof m/Δm 1000.Becausetheearlymarginaloscillatorsoperatedatconstant frequency,themagneticfieldhadtobescannedforamassspectrum.The scanwasslow.However,theinstrumentallowedtoinvestigateionmoleculereactions,ionchemicalreactionmechanismsatlowpressureunder singlecollisionconditionsat(near)-thermalenergies.Thenewtechnique waseasytooperate.Asaconsequenceofthisgreatdevelopment,anewfield ofchemistrywasopened.Thefirstprototypeinstrumentwenttothe BaldeschwielergroupatStanfordUniversity,achemistrygroup.Many fundamentalpublicationsfollowedbythisgroup,byformermembersof thegroupwhowenttootherplaces,andby“newcomers.”Mostofthese publicationsopenednewresearchfieldsforthefirsttime.
1966
TheBaldeschwielergrouppublishedareportonioncyclotrondoubleresonanceforthestudyofthemechanismsofion-moleculereactionswiththe aidofkineticenergydependence [37].Ionsareresonantlyirradiatedto increasetheirkineticenergy.Themechanismoftheion-moleculereactions ofamixtureofCD4 andN2 wasinvestigated.Afterelectronimpactionization,themixturecontainedasmallproportionofions.Therefore,inthe ICRcell,allion-moleculereactionsareofpseudo-firstorder.
1967
Atheoryofcollision-broadenedICRspectrawasdevelopedbyBeauchamp [38].TheBaldeschwieler [39] grouppublishedadetailedinvestigationofa complicatedionchemicalreactionsystem,generatedfromchloroethylene. TheenormouspotentialoftheICRmethodwasshownforthefirsttime. Dunbar [40] studiedtheenergydependenceofion-moleculereactions. AdescriptionoftheinstrumentwasgivenbyBaldeschwieleretal. [41]. Theauthorsstated:“thecharacteristicsusedintheobservationandmeasurementofionmoleculereactionsarethen:
1. Theionlifetimesextendto100ms.
2. Thepathlengthsoftheionsextendto100m.
3. Theelectricfieldscanbeassmallas10mV/cm.
4. Ionsofspecificchargetomassratiocanbeacceleratedbytheapplication ofresonantradiofrequencyfields.”(p.113).
1968
Newgroupsappeared.Theyallemploymoreorlesslaboratory-rebuilt,SyrotronICRspectrometers.BowersandEllemanfromJETPropulsionLaboratoryandBeauchamp,nowatCaliforniaInstituteofTechnology,studied theion-moleculereactionsofolefins [42].BraumanandBlair [43],atStanfordUniversity,directlymeasuredgas-phaseaciditieswithprotontransfer reactionsanddoubleresonanceexperiments.Henisandcoworkersfrom MonsantoCompanyinvestigatedtheionchemistryofmethanol [44],and describedadetectionschemewithelectronenergymodulation [45].Kaplan [46],laterattheUniversityofCincinnati,identifiedcollision-inducedfragmentationwithioncyclotrondoubleresonanceICDR.KingandElleman [47] fromJetPropulsionLaboratorystudiedion-moleculereactionsof hexafluoroethane.
1969
ClowandFutrell [48] fromtheUniversityofUtah,observedcharge exchangebyICDR.HuntressandBeauchamp [49] adaptedtheICRtechniqueforPenningionization.BenzeneionizationbymetastableN2 was investigated.IsotopicexchangereactionsofCH4-D2 andCD4-H2 mixtures andthemechanismofself-inducedlabelingofmethanebyTritiumwere investigatedbyInoueandWexler [50] ofArgonneNationalLaboratory. O’MalleyandJennings [51] investigatedtheionchemistryofacetylene.JenningsandcoworkersattheUniversityofSheffield,Englandwerethefirst researchgroupoutsidetheUnitedStates.Thepublicationsrefs. [49] and [51] appearedinthejustestablishednew“JournalofMassSpectrometry andIonPhysics.”
Developmentsfrom1970to1980
From1970onbesidesmanynewresearchareasandnewICRgroups,severalmajorimprovementsoftheICRtechniquewereachieved.
1970
McIver [52] introducedthetrappedionanalyzerICRcell.Contrarytothe ICRdriftcell,thiscellhasonlyasingleregion.Thecellhastrappingplates
onbothendstotraptheions.Nowtheionsaregenerated,trapped,reacted, anddetectedinasinglecellbyapulsescheme.ThistrappedionICRcellisa simplifiedPenningtrapwithplanarelectrodes.Comparedtothedriftcell, sensitivityandtrappingtimeweregreatlyincreased.Thenewcelltherefore allowedtostudyion-moleculereactionsofhighkineticorder,acapability providedbynoothertechniqueinthefield.Burseyetal. [53],Universityof NorthCarolina,firstrealizedtheanalyticalpotentialofICRspectrometry. Theydescribedacetylationasasoftchemicalionizationtechnique.The chemicalionization(CI)agentwasgeneratedbyion-moleculereactions intheICRcellinlargeyields.
ClowandFutrell [54] fromtheUniversityofUtahstartedadetailed studyofthekineticenergydependenceofion-moleculereactionrates.They utilizedanICRdriftcellwithfoursectionstoreduceelectricfieldpenetrationanddistortion.TheDjerassigroup [55],fromStanfordUniversity, applieddriftcellICRtechniquetostudyingreatdetailthestructureof theC3H6O+ ionformedfromaliphaticketonesinthedoubleMcLafferty rearrangement.Twodetailedstudiesofrateconstantsdetermination [56] anddoubleresonancesignalinterpretation [57] werepublishedbytheJenning’sgroup.Fromthedependenceofhalf-widthandhalf-heightofpower absorptionlines,HenisandMabie [58] studiedindetailthelifetimeofnegativeions.Anextremelyhighlifetimeof500 μswasmeasuredfortheSF6 ion.Lebert [59],fromtheHartmanngroup,Johann-Wolfgang-Goethe UniversityofFrankfurt/Main,publishedashortaccountonICR.Marshall andButrill [60],StanfordUniversity,presentedageneralmethodtocalculateion-moleculereactionsrateconstantsfromICRspectra.
Bowersetal. [61],UniversityofCaliforniaatSantaBarbara,describedan accuratemethodforrelativeprotonaffinitydeterminationwiththeaidof equilibriumreactions.Therelativeprotonaffinitiesoftrimethylamine,pyrrolidine,azetidine,andpiperidineweredeterminedwithanaccuracyof 0.2kcal/molorlower.
1971
Dunbar [62],CaseWesternReserveUniversity,showedthatwiththeICR techniqueionscanbephotodissociatedmass-selectively.TheionsCH3Cl+ andN2O+ wereinvestigated.ForsterandBeauchamp [63] studiedtheion chemistryofironpentacarbonylindetailandestablishedICRinthefield oftransitionmetalcomplexes.GrossandMcLafferty [64],CornellUniversity,identifiedC3H6+ structuralisomerswiththeaidofcharacteristic
9 HistoricaldevelopmentsinFTICRmassspectrometry
ion-moleculereactions.Huntress [65],JetPropulsionLaboratory,obtained informationaboutionpowerabsorptionfromthecompletesolutionofthe equationofmotionandmeasuredmomentumtransferrateconstantsforseveralions.Marshall [66],attheUniversityofBritishColumbia,developeda comprehensivetheoryforICRabsorptionlineshapesforreactiveand unreactiveionspecies.McIverandDunbar [67] describedpulsedioncyclotrondoubleresonance.Smith,UniversityofUtah,andKevan [68],Wayne StateUniversity,determinedtotalchargetransfercrosssections.Smythetal. [69] usedacontinuouslytunablelasertodeterminephotodetachmentcross sectionsofPH2 andNH2 .
1972
Liederetal. [70] describedamethodfordeterminationofion-molecule collisionfrequenciesfromtheirkineticenergydependencebyphasecoherentpulsedICR.SeveralnewICRgroupsappearedintheliterature:From theUniversit edeParis-Sud,Centred’Orsey,MarxandMauclaire [71] describedpositiveandnegativeion-moleculereactionsinammonia.
McAllister [72],C.S.I.R.O.,investigatedelectronimpactexcitationspectra.Tse [73] ,UniversityofHongKong,studiedthereactivityofthe CHO + ionbyioncyclotrondoubleresonancespectrometry.Tsuboi etal. [74] ,UniversityofElectro-Communications,describedtheconstructionofanICRspectrometersimilartotheVarianinstrument. RiverosandTiedemann [75] ,UniversityofSaoPaulo,describedthe gasphaseprotonationsiteofformamide.
McMahonandBeauchamp [76] closedtherearofthesourceregionofa driftICRcelltooperateitinatrappingmode.Theionsaretrappedinthe sourceregionofthecellanddriftedtotheanalyzerregionfordetection.
Sharpetal. [77] developedadetailedtheoryoftrappedionmotionfor thetrappedionICRcell,recentlydevelopedbyMcIver.SmithandFutrell [78,79] presentedanewtandemmassspectrometerwithaDempstermass spectrometeras1ststageandanICRspectrometeras2ndstage.
1973
Anewcompany,Dynaspec [80],offeredanICRmassSpectrometer,ICR9 R,basedontheVarianinstrument.HuntressandSimms [81] constructedan ICRdetectorbasedonaQ-meterwithgreatlyextendedfrequencyrange, evenelectronscouldbedetected.McIver [82],nowinUniversityof
CaliforniaatIrvine,presentedasolid-statemarginaloscillatorforpulsed ICRspectroscopy.
AnicichandBowers [83] describedanapproximate,relativelysimple methodtodetermineabsoluteion-moleculerateconstantsfromICRdrift cellmeasurements.H3+ ionsformedinthereactionofH2+ +H2 arehighly excited.Bowersetal. [84] showedtheinfluenceofexcitation/de-excitation oftheseionsontheproductdistributionofreactionswithCH3NH2, CH3OHandCH3SHandcomparedtheresultswithquasiequilibriumtheory.Thegrouphasgreatinterestintheoryofion-moleculeinteractionsand publishedaseriesofpapers.Ion-polarmoleculecollisionsareinvestigated [85–87] Interestinthisfieldisverygeneral:vanderHart [88],University ofLeiden,proposedtousetotalabsorptionintensitiesforrateconstantdetermination.Buttrill [89] investigatedthetemperaturedependenceofmomentumtransfercollisionrateconstants.Gasphaseion-moleculereactionsof highlydelocalizedanionsareremarkablyslow.Braumanetal. [90] showed thatthistypeofion-moleculereactionisaccessibletocatalysis.Thegroupof Dunbar [91] performedfundamentalstudiesinionphotoninteraction.Jaffe etal. [92],TheWeizmannInstituteofScienceatRehovot,studiedionmoleculereactionsinionizednitrogen.Nibbering [93],Universityof Amsterdam,employedadirectinsertionprobetostudyisomericions.
1974
ComisarowandMarshall [94] introducedtheFouriertransformtechnique intoICR.ThepatentgrantedtotheauthorswasassignedtoNicoletTechnologyCorporation [95].Themethodoperateswithafixedfrequencypulse whichexcitesamassrangeofionsfollowedbybroadbanddetection,digitizationofthetime-domaintransientresponse,anddigitalFouriertransformation.Thesameauthorsdescribedfrequencysweepexcitation [96] and selective-phaseFTICR [97]:In-phase(dispersion),90° out-of-phase (absorption),andabsolute-value(squarerootofthesumofthesquaresof theabsorptionanddispersion)ioncyclotronresonancespectrawereproduced.TheseinventionschangedthewholeICRtechnique.Itsoonwas appliedbymostresearchgroups.AnICRspectrumcouldnowberecorded byafastfrequencysweep.Slowmagneticfieldscanwasnolongernecessary. Sensitivity,massrange,andresolutionweredramaticallyextended.
McIverandBaranyi [98] reachedamassresolutionof m/Δm ¼ 5700for theN2+/CO+ doubletwiththetrappedioncellandadvancedmarginaloscillatordetection.Marxetal. [99] mountedanICRcellandanelectronspin
resonance(ESR)cavityinthesamemagneticfield,opticaldetectionofions wasalsopossible.Afterelectronimpactionizationofammonia,NH2 radicals andexcitedradicalscouldbedetected.ThegroupofDunbar [100],Case WesternReserveUniversity,analyzedcomplexion-moleculereaction pathwaysbysingleanddoubleresonanceexperiments.Itwasshownthat themaineffectofdoubleresonanceirradiationisionejection.Thegroup [101] investigatedphotodissociationspectraingreatdetail.Incooperation withtheoreticalchemists,Hehreetal. [102] confirmedtheBaker-Nathan orderofalkylsubstituenteffects:(Me > Et > i-Pr > t-Bu).Eyler [103], nowatNationalBureauofStandards,employedanintracavitylasertechniquetoenhancetheyieldoflaser-inducedionicprocesses,inthiscase photodetachmentofOH– ions.Eyleretal. [104],allNationalBureauof Standards,analyzedthecleavageofcarbonylbondinthereactionswithcarbonhalideions.BowieandWilliams [105],UniversityofAdelaide,studied theionchemistryoforganiccyanides.
1975
ComisarowandMarshall [106] investigatedthemassresolutiondependence fromseveralexperimentalparameters.Atatime-domaintransientacquisitiontimeof102.4msaresolutionof m/Δm ¼ 25,600at m/z 28was reached.LiederandBrauman [107] wereabletodetectneutralproducts ofion-moleculereactionswithastaticgassampletechniqueonthebasis oflongtrappingtimesinthetrappedionICRcell.McIveretal. [108] proposedachemicalionizationmethodforanalysisofsampleswithvaporpressuresinthe10 10 Torrrange.ViehlandandMason,BrownUniversityat Providence,andWhealton [109],UniversityofColorado,developedarigorouskinetictheoryforcollisionbroadenedICRlines,whichappliesforall ion-neutralintermolecularpotentialsandmassratios.
1976
Aoyagietal. [110],HokkaidoUniversityatSapporo,studiedthemechanism ofC3H3+ reactionsinbenzeneionchemistry.Defreesetal. [111] describeda methodtoobtainelectronicabsorptionspectraofions,iftheionsshowdifferentreactivitiesingroundandexcitedstates.FreiserandBeauchamp [112] studiedtheelectronimpactdissociationoftrappedions.
AtkinsandClugston [113],UniversityofOxford,developedaquantum mechanicalapproachforthecalculationofionmotionandinstantaneous powerabsorption.BarkerandRidge [114],UniversityofDelaware,
proposedastatisticaltheorytoyieldquantitativevaluesforion-polarneutral momentumtransfercollisionfrequencies.ComisarowandMarshall [115] derivedthefundamentalequationsforlinewidthandresolutioninFTICR.
1977
HunterandMcIver [116] developedtherapidscanICRtechnique:Atconstantmagneticfield,ionstrappedinthetrappedioncellwereexcitedbya rapidfrequencyscanningRFsignalandthetransientsignalwasrecorded. Duetotherapidscanrate,thedetectedsignalwasgreatlydistorted,but cross-correlationwiththeundisturbedsignalofasinglemasscanbeused torecoverthetruemassspectrum.Bowersetal. [117] describedatemperaturedependentICRcellforthetemperaturerangefrom80Kto450Kfor thestudyofreactiveandmomentumtransferrateconstants.Hartmannand Chung [118] employedaminimizedwavepacketapproachforaquantumtheoreticaltreatmentofionmotioninICRcells.
1978
McIver [119] describedapulsedICRspectrometer,basedonhistrappedion ICRcell.Comisarowetal. [120] incorporatedioncyclotrondoubleresonanceintheFouriertransformspectrometer.Thesameauthor [121] developedtherotatingmonopolesignalmodelforICR.Aoyagi [122] ofJeol studiedquasipeaksinioncyclotrondoubleresonancewiththeJeolICR spectrometerJIC-3B,equippedwithathreesectionsdriftcell.
1979
CodyandFreiser [123] introducedelectronimpactexcitationforthedissociationofions(EIEIO).Atheoryofsignal-to-noiseratiowasgivenbyMarshall [124] forawiderangeofexperimentalconditions.Hartmannetal. [125] presentedtheSchrodingerequationequivalenttotheLangevinequationto describecollisionallydampedionmotioninanICRcell.Dunbar [126] exploredcouplingofioncyclotronmotionwithionspinviatherelativistic Hamiltonian,andwithionrotation,viaitsequivalencetotheStarkeffect.
1980
AllemannandKellerhals,SpectrospinAG,andWanczek [127],University ofBremen,developedanewFouriertransformICRspectrometerwitha superconductingmagnetwith4.7Tfieldstrength.Themagnethadaverticalroomtemperatureboreandsolenoidalfieldgeometry.Extremelyhigh
resolutionof m/Δm ¼ 1.5 106 at m/z ¼ 166andtrappingtimesof >12h wereachieved.ThisinitiatedanewgenerationofICRspectrometers,operatingathighmagneticfields.ThespectrometerwasproducedbySpectrospin(Bruker)andnamedCMS47.Withatrappedcell,Whiteetal. [128] showedgreatresolutionandsignal-to-noiseimprovement,bothofwhich couldbeincreasedsimultaneously.AcylindricaltrappedionICRcellfor anelectromagnetwasdescribedbyLeeetal. [129].Dunbaretal. [130] inventedsimultaneoustwophotonirradiationofgas-phaseionsintheinfraredandvisiblewavelengthrange.Thishadimplicationsforthenatureof multiphotoneventsandrelaxationprocessesingas-phasespecies.Amano [131] developedatheoryofimagecurrentdetectionfromfirstprinciples forthemarginaloscillatorandFouriertransformtechniques.Twofurther publicationsweredealingwithdetectiontheory:McIveretal. [132] developedacompletelineshapetheoryforbroadbanddetection.Marshalland Roe [133] investigatedresponsetofrequency-sweepexcitation.Hartmann etal. [134] appliedtheminimizedwavepackettocalculatetheshiftofion cyclotronresonancefrequencyduetocouplingwithionrotation.Asmall shiftof10 6 waspredicted.
Developmentsfrom1981to1990
InatrappedionICRcell,generation,trapping,reactionanddetectionof ionsareperformed“tandem-in-time.”Thispresentsdifficulties,especially ifonewantstoobtainhighmassresolutionatlowpressure,whichisessential foranalyticalapplications.Themajormethodicaldevelopmentinthe1980s wastosolvethisproblem.Twomethodswereintroduced:Thedualcelland theexternalionsourceoutsidetheroomtemperatureboreofthesuperconductingmagnet.ThedualcellconfigurationofLittlejohnandGhaderi [135] ofNicoletInstrumentCorporationunitestwotrappedionICRcellswitha commontrappingelectrodeinthehomogeneousregionofthesuperconductingmagnet.Thecommontrappingelectrodehasapinhole,sothat thecellscanbepumpeddifferentially,andapressuregradientcanbemaintained.Forexample,ionscanbegenerated,reactedandtrappedinthecell withhigherpressure,thentransferredthroughthepinholeintothelower pressurecellforhighresolutiondetection.Themethodwasdescribedby Codyetal. [136] indetail.Thetransferofionsfromonecelltotheother wasstudiedbyHonovichandMarkey [137].MauclaireandMarx [138] introducedthetricyclotronwiththreecascadedICRcellsconnectedby ionfunnelsandseparatelypumped.
