The cluster formation of 17 small dipeptides with different primary structures and vanillic acid was investigated by means of a neutral laser desorption and supersonic beam expansion followed by multi-photon ionization time of flight mass spectrometry. The structures of these clusters have been characterized by mass spectrometric methods as well as by density functional theory calculations. It shows that the structure of the cluster from a dipeptide and vanillic acid is described by a hydrogen bond between the phenolic group of the vanillic acid and the N-terminal amino function of the dipeptide. The intensity of the cluster ion and the main fragmentation product, the protonated peptide ion, can be linked to the proton affinity of the peptide. Furthermore, the fragmentation reactions of the protonated peptide are accompanied by extensive hydrogen rearrangements yielding both a and y fragments. The intensities of these fragments follow the proton affinity of the dipeptide.
BrutschyB., “Chemical Reactions in Mixed Molecular Clusters Studied by Resonant Two-Photon Ionization”, Ber. Bunsenges. Phys. Chem.96, 1154 (1992).
2.
TaubitzJ.LuningU.GrotemeyerJ., “Mass Spectra of Hydrogen bonded Heterodimers. A Comparison of ESI- and REMPI-ReTOF-Mg”, Chem. Commun. in press, (2004).
3.
DeyM.GrotemeyerJ., “Cluster Formation of Biomolecules in the Gas Phase”, Eur. Mass Spectrom.1, 22 (1995).
4.
GrotemeyerJ., “Mass Spectrometry with Light: Processes and Results”, Proc. Indian Society for Mass Spectrometry, Ed by AggarvalS.K.25, 109 (2003).
5.
(a) SchlagE.W.SheuS.-Y.YangD.-Y.SelzleH.L.LinS.H., “Theory of Charge Transport in Polypeptides”, J. Phys. Chem. B104, 7790 (2000); (b) WysockiV.H.TsapraillisG.SmithL.L.BreciL.A., “Mobile and Localized Protons: A Framework for Understanding Peptide Dissociations”, J. Mass Spectrom.35, 1399 (2000).
6.
LiaoP.C.AllisonJ., “Ionization Processes in Matrix-assisted Laser Desorption/Ionization Mass Spectrometry”, J. Mass Spectrom.30, 408 (1995).
7.
GrotemeyerJ.SchlagE.W., “Multiphoton-Ionisations-Massenspektrometrie; ein neues Hilfsmittel in derAnalytik”, Angew.Chem.100, 461 (1988).
8.
MeffertA.GrotemeyerJ., “Formation, Stability and Fragmentation of Biomolecular Clusters in a Supersonic Jet investigated with Nano- and Femtosecond Laser Pulses”, Ber. Bunsenges. Phys. Chem.102, 459 (1998).
9.
(a) RizzoT.R.ParkY.D.PeteanuL.A.LevyD.H., “Electronic spectrum of the amino acid tryptophan cooled in a supersonic molecular beam”, J. Chem. Phys.83, 4819 (1985); (b) RizzoT.R.LevyD.H., “Multi Photon Ionization Spectroscopy of Biologically Related Molecules in a Supersonic Molecular Beam”, in Laser and Mass Spectrometry, Ed by LubmanD.H., Oxford University Press, Oxford, UK, pp. 402 (1990).
10.
BoeslU.GrotemeyerJ.WalterK.SchlagE.W., “High Resolution Time-of-Flight Mass Spectrometry with Laser Desorption and Laser Ionization”, Anal. Instrum.16, 151 (1987).
11.
BirrC., Aspects of Merrifield Peptide Synthesis. Springer Verlag, New York, USA (1978).
12.
ThomasA.F., “Deuterium Labelling in Organic Chemistry. Appleton-Century-Crofts, New York, USA (1971).
13.
FrischA.1M.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.MontgomeryJ.A.JrVrevenT.KudinK.N.BurantJ.C.MillamJ.M.IyengarS.S.TomasiJ.BaroneV.MennucciB.CossiM.ScalmaniG.RegaN.PeterssonG.A.NakatsujiH.HadaM.EharaM.ToyotaK.FukudaR.HasegawaJ.IshidaM.NakajimaT.HondaY.KitaoO.NakaiH.KleneM.LiX.KnoxJ.E.HratchianH.P.CrossJ.B.AdamoC.JaramilloJ.GompertsR.StratmannR.E.YazyevO.AustinA.J.CammiR.PomelliC.OchterskiJ.W.AyalaP.Y.MorokumaK.VothG.A.SalvadorP.DannenbergJ.J.ZakrzewskiV.G.DapprichS.DanielsA.D.StrainM.C.FarkasO.MalickD.K.RabuckA.D.RaghavachariK.ForesmanJ.B.OrtizJ.V.CuiQ.BaboulA.G.CliffordS.CioslowskiJ.StefanovB.B.LiuG.LiashenkoA.PiskorzP.KomaromiI.MartinR.L.FoxD.J.KeithT.Al-LahamM.A.PengC.Y.NanayakkaraA.ChallacombeM.GillP.M.W.JohnsonB.ChenW.WongM.W.GonzalezC.PopleJ.A., Gaussian 03, Revision. Gaussian, Inc., Pittsburgh PA, USA (2003).
14.
StewartJ.J.P., “MOPAC: A General Molecular Orbital Package”, Quant. Chem. Prog. Exch.10, 86, (1990).
15.
ChemOffice 2004 Ultra. CambridgeSoft Corporation, Cambridge, MA, USA.
16.
MeffertA., Diploma Thesis, Bay. Julius Maximillians Universitat, Würzburg, Germany (1994).
17.
WeickhardtC.MoritzF.GrotemeyerJ., “Time-of-Flight Mass Spectrometry: State-of-the-Art in Chemical Analysis and Molecular Science”, Mass Spectrom. Rev.15, 139 (1996).
18.
McLaffertyF.W., The Wiley Registry of Mass Spectral Data, 5th Edition.John Wiley & Sons, New York, USA (1989).
19.
KulleA.GrotemeyerJ., “Multiphoton and Electron Ionisation of some Aromatic Acids”, Eur. J. Mass Spectrom. in preparation.
20.
DeyM.GrotemeyerJ., “Multiphoton Ionization and Photodissociation at Second Order Space Focus: The Amino Acid Tryptophan”, Org. Mass Spectrom.29, 659 (1994).
21.
(a) RosenstockH.M.DraxlK.SteinerB.W.HerronJ.T., “Energetics of Gaseous Ions”, J. Phys. Chem. Ref. Data6, Supp.1, (1977); (b) MormannM.BashirS.DerrickP.J.KuckD., “Gas-Phase Basicities of the Isomeric Dihydroxybenzoic Acids and Gas-Phase Acidities of their Radical Cations”, J. Am. Soc. Mass Spectrom.11, 544 (2000).
22.
MeffertA.GrotemeyerJ., “Formation and Reactions of Cluster Ions From Aromatic Carboxylic Acids Together with Amino Acids”, Isr. J. Chem.41, 79 (2001).
23.
LiasS.G.BartmessJ.E.LiebmanJ.F.HolmesJ.L.LevinR.D.MallardW.G., “Ion Energetics Data” in NIST Chemistry WebBook. NIST Standard Reference Database Number 69, Ed by LinstromP.J.MallardW.G., March 2003. National Institute of Standards and Technology, Gaithersburg MD, USA (http://webbook.nist.gov/).
24.
LucasB.GregoireG.LemaireJ.MaitreP.OrtegaJ.M.RupenyanA.ReismannB.SchermannJ.P.DesfrancoisC., “Investigation of the protonation site in dialanine peptide by infrared multiphoton dissociation spectroscopy”, Phys. Chem. Chem. Phys.6, 2659 (2004).
25.
CsonkaI.P.PaizsB.LendvayG.SuhaiS., “Proton Mobility and Main Fragmentation pathways of protonated Lysyl-Glycine”, Rapid Commun. Mass Spectrom.15, 1457 (2001).
26.
DewarM.J.S.ZoebischE.G.HealyE.F.StewartJ.J.P., “AMI: A New General Purpose Quantum Mechanical Model”. J. Am. Chem. Soc.107, 3902 (1985).
27.
HeyneK.HuseN.NibberingE.T.J.ElsaesserT., “Ultrafast relaxation and anharmonic coupling of O–H stretching and bending excitations in cyclic acetic acid dimers”, Chem. Phys. Lett.382, 19 (2003).
28.
MeffertA., “Untersuchungen zu Ionisation and Reaktionen bioorganischer Cluster in der Gasphase”, PhD Thesis, Bay. Julius Maximilians Universitat, Würzburg, Germany (1997).
29.
(a) PaizsB.SuhaiS., “Towards Understanding the Tandem Mass Spectra of Protonated Oligopeptides. Mechanism of Amide Bond Cleavage”, J. Am. Soc. Mass Spectrom.15, 103 (2004); (b) PaizsB.SchmolzerM.WarnkenU.SuhaiS.HarrisonA.G., “Cleavage of the amide bond ofprotonated dipeptides”, Phys. Chem. Chem. Phys.6, 2691 (2004).
30.
RoepstorffP.FohlmanJ.; “Proposal for a Common Nomenclature for Sequence Ions in Mass Spectra of Peptides”, Biomed. Mass Spectrom.11, 601 (1984).
31.
RahmanO. AbdelGrotemeyerJ.; unpublished results.
32.
(a) RongeH.W.GrutzmacherH. Fr., “Peptide Sequencing by MS-MS Techniques: A Systematic Study.”, Develop. Mass Spectrom.7, 255 (1981); (b) WalterK.LindnerJ.GrotemeyerJ.SchlagE.W.; “Biomolecules in the Gasphase. V. Small Peptides investigated by Multiphoton Mass Spectrometry”, Chem. Phys.125, 155 (1988).
