It has previously been reported that different conformations of oligonucleotides may be detected using a gas-phase hydrogen/deuterium (H/D) exchange performed in the collision cell of a mass spectrometer. The presence of different conformers was postulated based on the bimodal shape of the deuterium distribution and on the ion mobility spectrometry data. Here we implement an in-electrospray ionization source H/D exchange to detect the different conformations of oligonucleotides in the region of ion formation. We observed that the number of H/D exchanges depends considerably on the temperature of the desolvating capillary and varies from 25% at 50°C to 80% at 450°C, but no bimodality in the shape of the deuterium distribution was observed. Such results indicate that in the region of ion formation different conformations of oligonucleotide ions rapidly interconvert one into another.
KattaV.ChaitB.T., “Hydrogen-deuterium exchange electrospray-ionization mass-spectrometry—a method for probing protein conformational-changes in solution”, J. Am. Chem. Soc.115, 6317 (1993). doi: http://dx.doi.org/10.1021/ja00067a054
2.
WalesT.E.EngenJ.R., “Hydrogen exchange mass spectrometry for the analysis of protein dynamics”, Mass Spectrom. Rev.25, 158 (2006). doi: http://dx.doi.org/10.1002/mas.20064
3.
GardE.GreenM.K.BregarJ.LebrillaC.B., “Gas-phase hydrogen–deuterium exchange as a molecular probe for the interaction of methanol and protonated peptides”, J. Am. Chem. Soc. Mass Spectrom.5, 623 (1994). doi: http://dx.doi.org/10.1016/1044-0305(94)85003-8
4.
McLaffertyF.W.GuanZ.Q.HauptsU.WoodT.D.KelleherN.L., “Gaseous conformational structures of cytochrome C”, J. Am. Chem. Soc.120, 4732 (1998). doi: http://dx.doi.org/10.1021/ja9728076
5.
FreitasM.A.HendricksonC.L.EmmettM.R.MarshallA.G., “Gas-phase bovine ubiquitin cation conformations resolved by gas-phase hydrogen/deuterium exchange rate and extent”, Int. J. Mass Spectrom.185, 565 (1999). doi: http://dx.doi.org/10.1016/S1387-3806(98)14172-6
6.
PriceN.P.J., “Oligosaccharide structures studied by hydrogen–deuterium exchange and MALDI-TOF mass spectrometry”, Anal. Chem.78, 5302 (2006). doi: http://dx.doi.org/10.1021/ac052168e
7.
BalbeurD.WidartJ.LeyhB.CravelloL.De PauwE., “Detection of oligonucleotide gas-phase conformers: H/D exchange and ion mobility as complementary techniques”, J. Am. Chem. Soc. Mass Spectrom.19, 938 (2008). doi: http://dx.doi.org/10.1016/j.jasms.2008.03.018
8.
Green-ChurchK.B.LimbachP.A.FreitasM.A.MarshallA.G., “Gas-phase hydrogen/deuterium exchange of positively charged mononucleotides by use of Fourier-transform ion cyclotron resonance mass spectrometry”, J. Am. Chem. Soc. Mass Spectrom.12, 268 (2001). doi: http://dx.doi.org/10.1016/S1044-0305(00)00222-1
9.
SoloukiT.FreitasM.A.AlomaryA., “Gas-phase hydrogen/deuterium exchange reactions of fulvic acids: An electrospray ionization Fourier transform ion cyclotron resonance mass spectral study”, Anal. Chem.71, 4719 (1999). doi: http://dx.doi.org/10.1021/ac990185w
10.
KostyukevichY.KononikhinA.PopovI.NikolaevE., “Simple atmospheric hydrogen/deuterium exchange method for enumeration of labile hydrogens by electrospray ionization mass spectrometry”, Anal. Chem.85, 5330 (2013). doi: http://dx.doi.org/10.1021/ac4006606
11.
HemlingM.E.ConboyJ.J.BeanM.F.MentzerM.CarrS.A., “Gas-phase hydrogen-deuterium exchange in electrospray-ionization mass-spectrometry as a practical tool for structure elucidation”, J. Am. Chem. Soc. Mass Spectrom.5, 434 (1994). doi: http://dx.doi.org/10.1016/1044-0305(94)85059-3
KostyukevichY.KononikhinA.PopovI.NikolaevE., “Conformational changes of ubiquitin during electrospray ionization as determined by in-ESI source H/D exchange combined with high-resolution MS and ECD fragmentation”, J. Mass Spectrom.49, 989 (2014). doi: http://dx.doi.org/10.1002/jms.3409
14.
KostyukevichY.KononikhinA.PopovI.SpasskiyA.NikolaevE., “In ESI-source H/D exchange under atmospheric pressure for peptides and proteins of different molecular weights from 1 to 66 kDa: The role of the temperature of the desolvating capillary on H/D exchange”, J. Mass Spectrom.50, 49 (2015). doi: http://dx.doi.org/10.1002/jms.3535
KostyukevichY.KononikhinA.PopovI.KharybinO.PerminovaI.KonstantinovA.NikolaevE., “Enumeration of labile hydrogens in natural organic matter by use of hydrogen/deuterium exchange Fourier transform ion cyclotron resonance mass spectrometry”, Anal. Chem.85, 11007 (2013). doi: http://dx.doi.org/10.1021/ac402609x
17.
KostyukevichY.KononikhinA.PopovI.StarodubtsevaN.KukaevE.NikolaevE., “Letter: Separation of tautomeric forms of [2-nitrophloroglucinol-H]− by an in-electrospray ionization source hydrogen/deuterium exchange approach”, Eur. J. Mass Spectrom.20, 345 (2014). doi: http://dx.doi.org/10.1255/ejms.1282
18.
KostyukevichY.KononikhinA.ZherebkerA.PopovI.PerminovaI.NikolaevE., “Enumeration of non-labile oxygen atoms in dissolved organic matter by use of 16O/18O exchange and Fourier transform ion-cyclotron resonance mass spectrometry”, Anal. Bioanal. Chem.406, 6655 (2014). doi: http://dx.doi.org/10.1007/s00216-014-8097-9
19.
AhmedA.KimS., “Atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry—a method to differentiate isomers by mass spectrometry”, J. Am. Chem. Soc. Mass Spectrom.24, 1900 (2013). doi: http://dx.doi.org/10.1007/s13361-013-0726-6
20.
ChoY.AhmedA.KimS., “Application of atmospheric pressure photo ionization hydrogen/deuterium exchange high-resolution mass spectrometry for the molecular level speciation of nitrogen compounds in heavy crude oils”, Anal. Chem.85, 9758 (2013). doi: http://dx.doi.org/10.1021/ac402157r
21.
Abi-GhanemJ.GabelicaV., “Nucleic acid ion structures in the gas phase”, Phys. Chem. Chem. Phys.16, 21204 (2014). doi: http://dx.doi.org/10.1039/C4CP02362E
22.
MoJ.J.E.ToddG.C.HakanssonK., “Characterization of nucleic acid higher order structure by gas-phase H/D exchange in a quadrupole-FT-ICR mass spectrometer”, Biopolymers91, 256 (2009). doi: http://dx.doi.org/10.1002/bip.21134
23.
ArcellaA.DreyerJ.IppolitiE.IvaniI.PortellaG.GabelicaV.CarloniP.OrozcoM., “Structure and dynamics of oligonucleotides in the gas phase”, Angew. Chem. Int. Ed.54, 467 (2015). doi: http://dx.doi.org/10.1002/ange.201406910
24.
GiddenJ.BushnellJ.E.BowersM.T., “Gas-phase conformations and folding energetics of oligonucleotides: Dtg− and dGT−”, J. Am. Chem. Soc.123, 5610 (2001). doi: http://dx.doi.org/10.1021/ja015940d
25.
BohrerB.C.AtlasevichN.ClemmerD.E., “Transitions between elongated conformations of ubiquitin [M + 11H]11+ enhance hydrogen/deuterium exchange”, J. Phys. Chem. B115, 4509 (2011). doi: http://dx.doi.org/10.1021/jp2008495
26.
NousiainenM.VainiotaloP.DerrickP.J.CooperH.J.HoxhaA.FatiD.TrayerH.R.WardD.G.TrayerI.P., “Calcium and peptide binding to folded and unfolded conformations of cardiac Troponin C. Electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry”, Eur. J. Mass Spectrom.8, 471 (2002). doi: http://dx.doi.org/10.1255/ejms.523
27.
KharlamovaA.DeMuthJ.C.McLuckeyS.A., “Vapor treatment of electrospray droplets: Evidence for the folding of initially denatured proteins on the sub-millisecond time-scale”, J. Am. Chem. Soc. Mass Spectrom.23, 88 (2012). doi: http://dx.doi.org/10.1007/s13361-011-0258-x
28.
RobinsonE.W.WilliamsE.R., “Multidimensional separations of ubiquitin conformers in the gas phase: Relating ion cross sections to H/D exchange measurements”, J. Am. Chem. Soc. Mass Spectrom.16, 1427 (2005). doi: http://dx.doi.org/10.1016/j.jasms.2005.04.007
