The AutoSpec 6F mass spectrometer is a large, floor standing instrument comprising a pair of commercial EBE geometry (AutoSpec) mass spectrometers coupled in series to provide a hybrid EBE–EBE configuration (E and B being, respectively, electrostatic and magnetic sectors.) It was designed in close collaboration between Professor R. Flammang and VG Analytical in Manchester, UK. It is equipped with five collision cells and allows the recording of high-energy collision-induced dissociation (CID), mass analyzed ion kinetic energy spectrometry and neutralization–reionization mass spectrometry data as well as consecutive MSn analyses. The field-free regions between sectors allow the study of unimolecular decomposition products from long-lived metastable ions. The mass spectrometer became even more versatile when a radio frequency-only quadrupole collision cell was installed between the second and the third electric sector. This allows the study of associative ion/molecule reactions in the low kinetic energy regime. Bimolecular chemical reactions were performed inside the quadrupole cell when a neutral reagent was introduced and the reaction products were analyzed by high-energy CID in the downstream sectors. This paper recounts the history and summarizes the capabilities of this versatile instrument.
De HoffmannE.StroobantV., Mass Spectrometry: Principles and Applications.John Wiley and Sons Ltd, Chichester, UK (2002).
2.
HeckA.J.R.van den HeuvelR.H.H., “Investigation of intact protein complexes by mass spectrometry”, Mass Spectrom. Rev.23, 368 (2004). doi: 10.1002/mas.10081
3.
ColeR.B., Electrospray Ionization Mass Spectrometry. Fundamentals, Instrumentation and Applications.John Wiley and Sons Ltd, Chichester, UK (1997).
4.
HillenkampF.Peter-KatalinicJ., MALDI-MS. A Practical Guide To Instrumentation, Methods and Applications.Wiley-VCH, Weinheim, Germany (2007).
5.
WhiteF.A.WoodG.M., Mass Spectrometry. Applications in Science and Engineering.John Wiley and Sons Ltd, Chichester, UK (1986).
6.
TraegerJ.C., “Appearance energies”, in The Encyclopedia of Mass Spectrometry, Fundamentals of and Applications to Organic (and Organometallic) Compounds, Vol. 4, Ed by NibberingN.M.M., Elsevier, Amsterdam, The Netherlands, p. 19 (2005).
7.
NguyenM.T., “Use of potential energy surfaces to understand decomposition” in The Encyclopedia of Mass Spectrometry, Fundamentals of and Applications to Organic (and Organometallic) Compounds, Vol. 4, Ed by NibberingN.M.M., Elsevier, Amsterdam, The Netherlands, p. 297 (2005).
8.
DuckworthH.E.BarberR.C.VenkatasubramanianV.S., Mass Spectroscopy, 2nd Edn.Cambridge University Press, Cambridge, UK (1986).
9.
SlenoL.VolmerD.A., “Ion activation methods for tandem mass spectrometry”, J. Mass Spectrom.39, 1091 (2004). doi: 10.1002/jms.703
10.
PorterC.J.BeynonJ.H.AstT., “The modern mass spectrometer. A complete chemical laboratory”, Org. Mass Spectrom.16, 101 (1981). doi: 10.1002/oms.1210160302
11.
TurecekF., “The modern mass spectrometer: A chemical laboratory for unstable neutral species”, Org. Mass Spectrom.27, 1087 (1992). doi: 10.1002/oms.1210271019
12.
TurecekF., “Thermochemical and kinetic factors controlling fragmentation”, in The Encyclopedia of Mass Spectrometry, Fundamentals of and Applications to Organic (and Organometallic) Compounds, Vol 4, Ed by NibberingN.M.M., Elsevier, Amsterdam, The Netherlands, p. 1 (2005).
13.
CooksR.J.BeynonJ.H.CaprioliR.M.LesterG.R. (Eds), Metastable Ions.Elsevier, Amsterdam, The Netherlands (1973).
14.
McLaffertyF.W.TurecekF., Interpretation of Mass Spectra, 4th Edn.University Science Books, Mill Valley, California, USA (1993).
15.
McLaffertyF.W. (Ed), Tandem Mass Spectrometry.John Wiley and Sons Ltd, Chichester, UK (1983).
16.
HarrisonA.G., Chemical Ionization Mass Spectrometry, 2nd Edn.CRC Press, Boca Raton, Florida, USA (1992).
17.
HourietR.RolliE.FlammangR.MaquestiauA.BouchouxG., “Gas-phase protonation and methyl cation transfer from methyl halide ions”, Org. Mass Spectrom.22, 770 (1987). doi: 10.1002/oms.1210221203
18.
FlammangR.GerbauxP.MorkvedE.H.WongM.W.WentrupC., “Generation of new nitrile N-sulfides (NCCNS, R2NCNS, H3CSCNS and ClCNS) as ions and neutrals in the gas phase: Tandem mass spectrometry, flash vacuum pyrolysis and ab initio MO study.”J. Phys. Chem.100, 17452 (1996). doi: 10.1021/jp9618800
19.
LevsenK.SchwarzH., “Collisional activation mass spectrometry: A new probe for determining the structure of ions in the gas phase”, Angew. Chem. Int. Ed.15, 509 (1976). doi: 10.1002/anie.197605091
20.
SchalleyC.A.HornungG.SchroderD.SchwarzH., “Mass spectrometry approaches to the reactivity of transient intermediates”, Chem. Soc. Rev.27, 91 (1998). doi: 10.1039/a827091z
EberlinM., “Triple-stage pentaquadrupole (QqQqQ) mass spectrometry and ion/molecule reactions”, Mass Spectrom. Rev.16, 113 (1997). doi: 10.1002/(SICI)1098-2787(1997)16:3<113::AID-MAS1>3.0.CO;2-K
28.
BouchouxG.NguyenM.T.SalpinJ.-Y., “Condensation reactions between 1,3-butadiene radical cations and acetylene in the gas phase”, J. Phys. Chem. A104, 5778 (2000). doi: 10.1021/jp001000o
29.
van GarderenH.F.RuttinkP.J.A.BurgersP.C.McGibbonG.A.TerlouwJ.K., “Aspects of the CH5N2 potential energy surface ions CH3NHNH, CH3NNH2 and CH2NHNH2 and radicals CH2NHNH2, studied by theory and experiment”, Int. J. Mass Spectrom. Ion Process.121, 159 (1992). doi: 10.1016/0168-1176(92)80061-5
30.
LavoratoD.TerlouwJ.K.GargelT.K.KochW.McGibbonG.A.SchwarzH., “Observation of the Hammick intermediate: Reduction of the pyridine-2-ylid ion in the gas phase”, J. Am. Chem. Soc.118, 11898 (1996). doi: 10.1021/ja961954l
31.
SchalleyC.SchröderD.SchwarzH., “A neutralization-reionization mass spectrometric study of alkyl hydroperoxide cation radicals and four distinguishable [CH3O2](+) isomers”, Int. J. Mass Spectrom. Ion Process.153, 173 (1996). doi: 10.1016/0168-1176(96)04360-1
32.
MaquestiauA.Van HaverbekeY.De MeyerC.FlammangR.PeriauxJ., “Modification d'un spectromètre de masse à géométrie inversée et applications à l'étude de processus collisionnels”, Bull. Soc. Chim. Belg.85, 69 (1976). doi: 10.1002/bscb.19760850107
33.
MaquestiauA.Van HaverbekeY.FlammangR.AbrassartM.FinetD., “Mass-analyzed ion kinetic energy spectrometry with a modified AEI MS 902 spectrometer”, Bull. Soc. Chim. Belg.87, 765 (1978). doi: 10.1002/bscb.19780871005
34.
BatemanR.H.BrownJ.LefevereM.FlammangR.Van HaverbekeY., “Applications in gaseous ion and neutral chemistry using a 6-sector mass spectrometer”, Int. J. Mass Spectrom. Ion Process.115, 205 (1992). doi: 10.1016/0168-1176(92)85042-X
35.
FlammangR.Van HaverbekeY.BraybrookC.BrownJ., “A new hybrid mass spectrometer for the investigation of ion–molecule reactions”, Rapid Commun. Mass Spectrom.9, 795 (1995). doi: 10.1002/rcm.1290090916
36.
RameshV.ReddyP.N.BhanuprakashK.SrinivasR.FlammangR.DechampsN.GerbauxP., “C2H2S radical cations: Application of tandem mass spectrometry methodologies”, Int. J. Mass Spectrom.263, 289 (2007). doi: 10.1016/j.ijms.2007.03.007
37.
ErvastiH.K.JobstK.J.GerbauxP.BurgersP.C.RuttinkP.J.A.TerlouwJ.K., “The reaction of the acrylonitrile ion CH2=CH–C=N•+ with HCN: Proton-transport catalysis vs ionized pyrimidine”, Chem. Phys. Lett.482, 211 (2009). doi: 10.1016/j.cplett.2009.10.017
38.
BrownJ.FlammangR.GovaertY.PlisnierM.WentrupC.Van HaverbekeY., “Electron ionization and chemical ionization mass spectrometry of heterocumulenes produced by flash-vacuum pyrolysis”, Rapid Commun. Mass Spectrom.6, 245 (1992). doi: 10.1002/rcm.1290060405
39.
FlammangR.Barbieux-FlammangM.GerbauxP.WentrupC.WongM.W., “Characterization of cyanogen N-oxide radical cations (NCCNO) in the gas phase by tandem mass spectrometry methodologies and ab initio calculations”, Bull. Soc. Chim. Belg.106, 545 (1997). doi: 10.1002/chin.199811071
40.
GerbauxP.FlammangR.MorkvedE.H.WongM.W.WentrupC., “Generation of nitrile N-selenides, RC≡NSe, as neutrals and radical cations in the gas phase”, Tetrahedron Lett.39, 533 (1998). doi: 10.1016/S0040-4039(97)10228-3
41.
PedersenC.Th.FlammangR.GerbauxP.FanghanelE., “3,6-Dihydro[1,2]dithiolo[4,3-c][1,2]dithiole-3,4-dithione and oxo analogues: A comparative study of the thermal (FVP) and electron ionization (EI) induced fragmentations”, J. Chem. Soc. Perkin Trans.2, 1403 (1998). doi: 10.1039/a800654g
42.
FlammangR.GerbauxP.Barbieux-FlammangM.PedersenC.Th.BechT.MorkvedE.H.WongM.W.WentrupC., “Formation and characterization of methoxy isothiocyanate (CH3ON = C=S) and methyl cyanate N-sulfide (CH3OC = N+–S−) as radical cations and neutrals in the gas phase”, J. Chem. Soc. Perkin Trans.2, 1683 (1999). doi: 10.1039/a903057c
43.
LiasS.G.BartmessJ.E.LiebmanJ.F.HolmesJ.L.LevinR.D.MallardW.G., “Gas phase ion and neutral thermochemistry”, J. Phys. Chem. Ref. Data17(suppl.1) (1988).
44.
DelwicheJ.P.PraetM., “Ion–molecule reactions in CS2 and COS studied by ‘time-of-flight’ mass spectrometry”, Adv. Mass Spectrom.6, 829 (1974).
45.
GerbauxP.Van HaverbekeY.FlammangR.WongM.W.WentrupC., “Generation of nitrile N-sulfide (RCNS) radical cations and neutrals via ion–molecule reactions: Tandem mass spectrometry and ab initio MO study”, J. Phys. Chem. A101, 6970 (1997). doi: 10.1021/jp971170+
46.
GerbauxP.FlammangR.PedersenC.Th.WongM.W., “Characterization of new sulfide ions (C2S3) from ethenedithione by ion–molecule reactions”, J. Phys. Chem. A103, 3666 (1999). doi: 10.1021/jp984121l
47.
GerbauxP.FlammangR.WentrupC.WongM.W., “Characterization of C2S4•+ isomers by mass spectrometry and ab initio molecular orbital calculations”, Int. J. Mass Spectrom.210/211, 31 (2001). doi: 10.1016/S1387-3806(01)00406-7
48.
GerbauxP.Van HaverbekeY.FlammangR., “Ion–molecule reaction of pyridine with CS3 radical cations: Experimental evidence for the production of pyridine N-thioxide distonic ions”, J. Mass Spectrom.32, 1170 (1997). doi: 10.1002/(SICI)1096-9888(199711)32:11<1170::AID-JMS573>3.0.CO;2-4
49.
GerbauxP.SalpinJ.-Y.BouchouxG.FlammangR., “Thiosulfoxides (X2S=S) and disulfanes (XSSX): First observation of organic thiosulfoxides”, Int. J. Mass Spectrom.195–196, 239 (2000). doi: 10.1016/S1387-3806(99)00227-4
50.
GerbauxP.Van HaverbekeY.FlammangR., “Pyridine N-selenide radical cations: Synthesis, characterization, neutralization and ion–molecule reactions in the gas phase”, Int. J. Mass Spectrom.184, 39 (1999). doi: 10.1016/S1387-3806(98)14214-8
51.
GerbauxP.FlammangR.MorkvedE.H.WongM.W.WentrupC., “Nitrile N-selenide (RC≡NSe) and isoselenocyanate (RN = C=Se) neutrals and radical cations by selenation of nitriles and isonitriles: Tandem mass spectrometry and ab initio studies”, J. Phys. Chem. A102, 9021 (1998). doi: 10.1021/jp9824454
52.
FlammangR.GallezL.Van HaverbekeY.WongM.W.WentrupC., “An unexpected effect of the nature of the collision gas in collisional activation mass spectrometry”, Rapid Commun. Mass Spectrom.10, 232 (1996). doi: 10.1002/(SICI)1097-0231(19960131)10:2<232::AID-RCM471>3.0.CO;2-D
53.
FlammangR.GerbauxP.WongM.W., “Identification of singlet and triplet SCNO+ cations in the gas phase: Theory and experiment”, Chem. Phys. Lett.300, 183 (1999). doi: 10.1016/S0009-2614(98)01365-7
54.
FlammangR.HenrotteV.GerbauxP.NguyenM.T., “Collisional interaction of ionized pyridine N-oxides with various targets in a new hybrid mass spectrometer”, Eur. J. Mass Spectrom.6, 3 (2000). doi: 10.1255/ejms.299
55.
GerbauxP.SciamannaV.FlammangR.NguyenM.T., “High energy collisional activation of the molecular ions of thiophene-2-one with different target gases”, J. Mass Spectrom.36, 97 (2001). doi: 10.1002/jms.108
56.
AubryC.HolmesJ.L., “The behavior of oxygen as a collision-induced dissociation target gas”, J. Am. Soc. Mass Spectrom.12, 23 (2000). doi: 10.1016/S1044-0305(00)00201-4
57.
LinY.MayerP.M., “Do the O2 Schumann–Runge bands participate in keV collision-induced dissociation experiments?”, J. Am. Soc. Mass Spectrom.22, 75 (2011). doi: 10.1007/s13361-010-0011-x
58.
LiW.K.ChiuS.W.MaZ.X.LiaoC.L.NgC.Y., “Adiabatic ionization energy of CH3SSCH3”, J. Chem. Phys.99, 8440 (1993). doi: 10.1063/1.465619
59.
ChengB.M.EberhardJ.ChenW.C.YuC.H., “Ionization energy of HSSH”, J. Chem. Phys.107, 5273 (1997). doi: 10.1063/1.474891
RenieE.E.MayerP., “Confirmation of the long-lived tetra-nitrogen (N4) molecule using neutralization–reionization mass spectrometry and ab initio calculations”, J. Chem. Phys.120, 10561 (2004). doi: 10.1063/1.1705571
65.
NguyenM.T.NguyenT.L.MebelA.M.FlammangR., “Azido-nitrene is probably the N4 molecule observed in mass spectrometric experiments”, J. Phys. Chem. A107, 5452 (2003). doi: 10.1021/jp034017q
66.
FlammangR.SrinivasR.NguyenM.T.GerbauxP., “OCCO, NNCO and NNNN radical cations”, Eur. J. Mass Spectrom.13, 173 (2007). doi: 10.1255/ejms.844
67.
GerbauxP.Barbieux-FlammangM.Van HaverbekeY.FlammangR., “Characterization of ionized heterocyclic carbenes by ion–molecule reactions”, Rapid Commun. Mass Spectrom.13, 1707 (1999). doi: 10.1002/(SICI)1097-0231(19990915)13:17<1707::AID-RCM701>3.0.CO;2-0
68.
HammerumS., “Distonic radical cations in gaseous and condensed phase”, Mass Spectrom. Rev.7, 123 (1988). doi: 10.1002/mas.1280070202
69.
StirkK.M.OrlowskiJ.C.LeeckD.T.KenttamaaH.I., “The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide”, J. Am. Chem. Soc.114, 8604 (1992). doi: 10.1021/ja00048a038
70.
GerbauxP.Barbieux-FlammangM.TerlouwJ.K.FlammangR., “Definitive characterization of some C5H5N and C6H7N radical cations by associative ion–molecule reactions”, Int. J. Mass Spectrom.206, 91 (2001). doi: 10.1016/S1387-3806(00)00393-6
71.
JobstK.J.De WinterJ.FlammangR.TerlouwJ.K.GerbauxP., “Differenciation of the pyridine radical cation from its distonic isomers by associative ion–molecule reactions with dioxygen”, Int. J. Mass Spectrom.286, 83 (2009). doi: 10.1016/j.ijms.2009.06.012
72.
TurecekF.DrinkwaterD.E.MaquestiauA.McLaffertyF.W., “Neutralization reionization study of C6H6O isomers”, Org. Mass Spectrom.24, 669 (1989). doi: 10.1002/oms.1210240825
73.
LeH.T.FlammangR.GerbauxP.BouchouxG.NguyenM.T., “Ionized phenol and its isomers in the gas phase”, J. Phys. Chem. A105, 11582 (2001). doi: 10.1021/jp012679e
74.
TrupiaL.DechampsN.FlammangR.BouchouxG.NguyenM.T.GerbauxP., “Isomeric recognition by ion/molecule reactions: The ionized phenol–cyclohexadienone case”, J. Am. Soc. Mass Spectrom.19, 126 (2008). doi: 10.1016/j.jasms.2007.10.023
75.
GerbauxP.WantierP.NamP.C.NguyenM.T.BouchouxG.FlammangR., “A specific gas-phase substitution reaction between enol radical cations and tert-butyl nitrite,”Eur. J. Mass Spectrom.10, 889 (2004). doi: 10.1255/ejms.686
76.
BohmeD.K., “Proton transport in the catalyzed gas-phase isomerization of protonated molecules”, Int. J. Mass Spectrom. Ion Process.115, 95 (1992). doi: 10.1016/0168-1176(92)85035-X
77.
HaranczykM.BurgersP.C.RuttinkP.J.A., “Catalysis models for the enolization of the acetaldehyde radical cation”, Int. J. Mass Spectrom.220, 53 (2002). doi: 10.1016/S1387-3806(02)00808-4
78.
van der RestG.NedevH.Chamot-RookeJ.MourguesP.McMahonT.B.AudierH.E., “Proton-transport catalysis in the gas phase. Keto–enol isomerization of ionized acetaldehyde”, Int. J. Mass Spectrom.202, 161 (2000). doi: 10.1016/S1387-3806(00)00242-6
79.
TrikoupisM.A.TerlouwJ.K., “Enolization of gaseous acetone radical cations: Catalysis by a single base molecule”, J. Am. Chem. Soc.120, 12131 (1998). doi: 10.1021/ja983078c
80.
TrikoupisM.A.BurgersP.C.RuttinkP.J.A.TerlouwJ.K., “Self-catalysis in the gas-phase: Enolization of the acetone radical cation”, Int. J. Mass Spectrom.217, 97 (2002). doi: 10.1016/S1387-3806(02)00536-5
81.
ChalkA.J.RadomL., “Ion-transport catalysis: Catalyzed isomerizations of NNH+ and NNCH3+”, J. Am. Chem. Soc.121, 1574 (1999). doi: 10.1021/ja982928l
82.
FlammangR.DechampsN.GerbauxP.NamP.C.NguyenM.T., “The cyclohexadienylidenemethanone radical cation is a more stable distonic isomer of ionized benzaldehyde”, Chem. Phys. Lett.456, 141 (2008). doi: 10.1016/j.cplett.2008.03.036
83.
NelsonE.D.TichyS.E.KenttamaaH.I., “Gas phase reaction of dimethylcarbene radical cation”, J. Chem. Soc. Perkin Trans.2, 2267 (1999). doi: 10.1039/a903936h
84.
AubryC.PolceM.J.HolmesJ.L.MayerP.M.RadomL., “Dimethylcarbene, its radical cation and dication”, J. Am. Chem. Soc.119, 9039 (1997). doi: 10.1021/ja971190p
85.
FlammangR.Van HaverbekeY.GerbauxP.NguyenM.T., “Evidence for the production of propene ion in the gas phase. Reaction of ionized dichlorocarbene with acetone”, Tetrahedron Lett.42, 669 (2001). doi: 10.1016/S0040-4039(00)02101-8
86.
GerbauxP.WantierP.BuryM.De MeyerC.FinetD.Van HaverbekeY., “Gas phase bimolecular reactions between •CH2–(CH2)ln–C+=sO distonic ions and pyridine: A combined experimental and theoretical study”, Eur. J. Mass Spectrom.9, 305 (2003). doi: 10.1255/ejms.551
87.
GerbauxP.Van HaverbekeY.FlammangR., “Experimental and theoretical study of the gas-phase interaction between ionized nitrile sulfides and pyridine”, J. Am. Soc. Mass Spectrom.14, 241 (2003). doi: 10.1016/S1044-0305(02)00912-1
88.
GerbauxP.Barbieux-FlammangM.FlammangR.BouchouxG., “Ion-molecule reactions between ionized nitrile oxides and neutral nitrile”, Int. J. Mass Spectrom.219, 643 (2002). doi: 10.1016/S1387-3806(02)00743-1
89.
DechampsN.FlammangR.GerbauxP.NamP.C.NguyenM.T., “Decarboxylation of metastable methyl benzoate molecular ions”, J. Am. Soc. Mass Spectrom.17, 807 (2006). doi: 10.1016/j.jasms.2006.02.015
90.
FlammangR.DechampsN.BoulvinM.GerbauxP.NamP.C.NguyenM.T., “On the loss of methyl radical from metastable dimethyl terephthalate molecular ions”, Int. J. Mass Spectrom.261, 134 (2007). doi: 10.1016/j.ijms.2006.08.007
91.
FlammangR.DechampsN.GerbauxP.NamP.C.NguyenM.T., “Unimolecular chemistry of metastable dimethyl isophthalate radical cations”, Int. J. Mass Spectrom.275, 110 (2008). doi: 10.1016/j.ijms.2008.05.031
92.
GerbauxP.De WinterJ.FlammangR.NguyenV.S.NguyenM.T., “Metastable dimethyl phthalate molecular ions: Does the loss of a methoxyl radical proceed with or without anchimeric assistance?”, Int. J. Mass Spectrom.290, 127 (2010). doi: 10.1016/j.ijms.2009.12.012
93.
NelsonE.D.LiR.KenttamaaH.I., “Reactions of tert-butyl isocyanide with distonic radical cations”, Int. J. Mass Spectrom.185–187, 91 (1999). doi: 10.1016/S1387-3806(98)14096-4
94.
FlammangR.Barbieux-FlammangM.GualanoE.GerbauxP.LeH.T.NguyenM.T.TurecekF.VivekanandaS., “Ionized benzonitrile and its distonic isomers in the gas phase”, J. Phys. Chem. A105, 8579 (2001). doi: 10.1021/jp011702t
95.
YatesB. F.BoumaW.RadomL., “Ylide dications: An examination of first- and second-row systems”, J. Am. Chem. Soc.108, 6545 (1986). doi: 10.1021/ja00281a018
96.
LeH.T.GerbauxP.FlammangR.NguyenM.T., “Collisional activation of protonated halogeno-pyridines: Different behaviour of target gases”, Chem. Phys. Lett.323, 71 (2000). doi: 10.1016/S0009-2614(00)00491-7
97.
LeH.T.FlammangR.Barbieux-FlammangM.GerbauxP.NguyenM.T., “Ionized aniline and its distonic radical cations isomers”, Int. J. Mass Spectrom.217, 45 (2002). doi: 10.1016/S1387-3806(02)00530-4
98.
FlammangR.Barbieux-FlammangM.GualanoE.GerbauxP.LeH.T.NguyenM.T.TurecekF., “Distonic isomers of ionized benzaldehyde”, Int. J. Mass Spectrom.217, 65 (2002). doi: 10.1016/S1387-3806(02)00532-8
FlammangR.ElgueroJ.LeH.T.GerbauxP.NguyenM.T., “Collisionally induced loss of NO2 radical loss from protonated nitroimidazoles and nitropyrazoles,”Chem. Phys. Lett.356, 259 (2002). doi: 10.1016/S0009-2614(02)00328-7
