Abstract
A pulsed dual electrospray ionization source has been developed to generate positive and negative ions for subsequent ion/ion reaction experiments. The two sprayers, typically a nano-electrospray emitter for analytes and an electrospray emitter for reagents, are positioned in a parallel fashion close to the sampling orifice of a triple quadrupole/linear ion trap tandem mass spectrometer (Sciex Q TRAP). The potentials applied to each sprayer are alternately pulsed so that ions of opposite polarity are generated separately in time. Ion/ion reactions take place after ions of each polarity are sequentially injected into a high-pressure linear ion trap, where axial trapping is effected by applying an auxiliary radio frequency voltage to the end lenses. The pulsed dual electrospray source allows optimization of each sprayer and can be readily coupled to any spray interface with no need for instrument modifications, provided the potentials required to transmit the ion polarity of interest can be alternated in synchrony with the emitter potentials. Ion/ion reaction examples such as charge reduction of multiply charged protein ions, charge inversion of peptides ions, and protein-protein complex formation are given to illustrate capabilities of the pulsed dual electrospray source in the study of gas-phase ion/ion chemistry.
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Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Electrospray ionization for mass-spectrometry of large biomolecules. Science 1989, 246, 64–71.
Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Electrospray ionization principles and practice. Mass Spectrom. Rev. 1990, 9, 37–70.
McLuckey, S. A.; Stephenson, J. L., Jr. Ion/ion chemistry of high-mass multiply charged ions. Mass Spectrom. Rev. 1999, 18, 83–86.
Pitteri, S. J., McLuckey, S. A. Recent developments in the ion/ion chemistry of high-mass multiply charged ions. Mass Spectrom. Rev., in press.
Stephenson, J. L., Jr.; McLuckey, S. A. Ion/ion proton transfer reactions for protein mixture analysis. Anal. Chem. 1996, 68, 4026–4032.
Stephenson, J. L., Jr.; McLuckey, S. A. Charge manipulation for improved mass determination of high-mass species and mixture components by electrospray mass spectrometry. J. Mass Spectrom. 1998, 33, 664–672.
Pan, P.; McLuckey, S. A. Electrospray ionization of protein mixtures at low pH. Anal. Chem. 2003, 75, 1491–1499.
McLuckey, S. A.; Wu, J.; Bundy, J. L.; Stephenson, J. L., Jr.; Hurst, G. B. Oligonucleotide mixture analysis via electrospray and ion/ion reactions in a quadrupole ion trap. Anal. Chem. 2002, 74, 976–984.
McLuckey, S. A.; Reid, G. E.; Wells, J. M. Ion parking during ion/ion reactions in electrodynamic ion traps. Anal. Chem. 2002, 74, 336–346.
Stephenson, J. L., Jr.; McLuckey, S. A. Ion/ion reactions in the gas phase: Proton transfer reactions involving multiply-charged proteins. J. Am. Chem. Soc. 1996, 118, 7390–7397.
Wells, J. M.; Stephenson, J. L., Jr.; McLuckey, S. A. Charge dependence of protonated insulin decompositions. Int. J. Mass Spectrom. 2000, 203, A1-A9.
Reid, G. E.; Wu, J.; Chrisman, P. A.; Wells, J. M.; McLuckey, S. A. Charge state dependent sequence analysis of protonated ubiquitin ions via ion trap tandem mass spectrometry. Anal. Chem. 2001, 73, 3274–3281.
Newton, K. A.; Chrisman, P. A.; Reid, G. E.; Wells, J. M.; McLuckey, S. A. Gaseous apomyoglobin ion dissociation in a quadrupole ion trap: [M + 2H]2+ − [M + 21H]21+. Int. J. Mass Spectrom. 2001, 212, 359–376.
Engel, B. J.; Pan, P.; Reid, G. E.; Wells, J. M.; McLuckey, S. A. Charge state dependent fragmentation of gaseous protein ions in a quadrupole ion trap: bovine ferri-, ferro-, and apo-cytochrome. c. Int. J. Mass Spectrom. 2002, 219, 171–187.
Chrisman, P. A.; McLuckey, S. A. Dissociations of disulfide-linked gaseous polypeptide/protein anions: Ion chemistry with implications for protein identification and characterization. J. Proteome Res. 2002, 1, 549–557.
Hogan, J. M.; McLuckey, S. A. Charge state dependent collision-induced dissociation of native and reduced porcine elastase. J. Mass Spectrom. 2003, 38, 245–256.
Coon, J. J.; Syka, J. E. P.; Schwartz, J. C.; Shabanowitz, J.; Hunt, D. F. Anion dependence in the partitioning between proton and electron transfer in ion/ion reactions. Int. J. Mass Spectrom. 2004, 236, 33–42.
Syka, J. E. P.; Coon, J. J.; Schroeder, M. J.; Shabanowitz, J.; Hunt, D. F. Peptide and protein sequence analysis by electron transfer dissociation mass spectrometry. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 9528–9533.
Pitteri, S. J.; Chrisman, P. A.; Hogan, J. M.; McLuckey, S. A. Electron transfer ion/ion reactions in a three-dimensional quadrupole ion trap: Reactions of doubly and triply protonated peptides with SO ·−2 . Anal. Chem. 2005, 77, 1831–1839.
Chrisman, P. A.; Pitteri, S. J.; Hogan, J. M.; McLuckey, S. A. SO −·2 electron transfer ion/ion reactions with disulfide linked polypeptide ions. J. Am. Soc. Mass Spectrom. 2005, 16, 1020–1030.
Hogan, J. M.; Pitteri, S. J.; Chrisman, P. A.; McLuckey, S. A. Complementary structural information from a tryptic N-linked glycopeptide via electron transfer ion/ion reactions and collision-induced dissociation. J. Proteome Res. 2005, 4, 628–632.
Mather, R. E.; Todd, J. F. J. The quadrupole ion store (Quistor). 7. Simultaneous positive-negative ion mass-spectrometry. Int. J. Mass Spectrom. Ion Phys. 1980, 33, 159–165.
McLuckey, S. A.; Glish, G. L.; Van Berkel, G. J. Multiple stages of mass-spectrometry in a quadrupole ion trap mass-spectrometer—prerequisites. Int. J. Mass Spectrom. Ion Processes 1991, 106, 213–235.
Stephenson, J. L., Jr.; McLuckey, S. A. Adaptation of the Paul trap for study of the reaction of multiply charged cations with singly charged anions. Int. J. Mass Spectrom. Ion Processes 1997, 162, 89–106.
Wells, J. M.; Chrisman, P. A.; McLuckey, S. A. “Dueling” ESI: Instrumentation to study ion/ion reactions of electrospray-generated cations and anions. J. Am. Soc. Mass Spectrom. 2002, 13, 614–622.
Badman, E. R.; Chrisman, P. A.; McLuckey, S. A. A quadrupole ion trap mass spectrometer with three independent ion sources for the study of gas-phase ion/ion reactions. Anal. Chem. 2002, 74, 6237–6243.
Wells, J. M.; Chrisman, P. A.; McLuckey, S. A. Formation of protein-protein complexes in vacuo. J. Am. Chem. Soc. 2001, 123, 12428–12429.
Wells, J. M.; Chrisman, P. A.; McLuckey, S. A. Formation and characterization of protein-protein complexes in vacuo. J. Am. Chem. Soc. 2003, 125, 7238–7249.
Gunawardena, H. P.; McLuckey, S. A. Synthesis of multi-unit protein hetero-complexes in the gas phase via ion-ion chemistry. J. Mass Spectrom. 2004, 39, 630–638.
He, M.; McLuckey, S. A. Increasing the negative charge of a macroanion in the gas phase via sequential charge inversion reactions. Anal. Chem. 2004, 76, 4189–4192.
He, M.; McLuckey, S. A. Two ion/ion charge inversion steps to form a doubly protonated peptide from a singly protonated peptide in the gas phase. J. Am. Chem. Soc. 2003, 125, 7756–7757.
Xia, Y.; Liang, X.; McLuckey, S. A. Sonic spray as a dual polarity ion source for ion/ion reactions. Anal. Chem. 2005, 77, 3683–3689.
Ogorzalek-Loo, R. R.; Udseth, H. R.; Smith, R. D. Evidence of charge inversion in the reaction of singly charged anions with multiply charged macroions. J. Phys. Chem. 1991, 95, 6412–6415.
Ogorzalek-Loo, R. R.; Udseth, H. R.; Smith, R. D. A new approach for the study of gas-phase ion-ion reactions using electrospray ionization. J. Am. Soc. Mass Spectrom. 1992, 3, 695–705.
Tang, K.; Lin, Y.; Matson, D. W.; Kim, T.; Smith, R. D. Generation of multiple electrosprays using microfabricated emitter arrays for improved mass spectrometric sensitivity. Anal. Chem. 2001, 73, 1568–1663.
Shneider, B. B.; Douglas, D. J.; Chen, D. D. Y. Multiple sprayer system for high-throughput electrospray ionization mass spectrometry. Rapid Commun. Mass Spectrom. 2002, 16, 1982–1990.
Jiang, L.; Moini, M. Development of multi-ESI-sprayer, multi-atmospheric-pressure-inlet mass spectrometry and its application to accurate mass measurement using time-of-flight mass spectrometry. Anal. Chem. 2000, 72, 20–24.
Hannis, J. C.; Muddiman, D. C. A dual electrospray ionization source combined with hexapole accumulation to achieve high mass accuracy of biopolymers in Fourier transform ion cyclotron resonance mass spectrometry. J. Am. Soc. Mass Spectrom. 2000, 11, 876–883.
Takahashi, Y.; Fujimaki, S.; Kobayashi, T.; Morita, T.; Higuchi, T. Accurate mass determination by multiple sprayers nano-electrospray mass spectrometry on a magnetic sector instrument. Rapid Commun. Mass Spectrom. 2000, 14, 947–949.
Satomi, Y.; Kudo, Y.; Sasaki, K.; Hase, T.; Takao, T. Accurate mass measurement in nano-electrospray ionization mass spectrometry by alternate switching of high voltage between sample and reference sprayers. Rapid Commun. Mass Spectrom. 2005, 19, 540–546.
Zhou, F.; Shui, W.; Lu, Y.; Yang, P.; Guo, Y. High accuracy mass measurement of peptides with internal calibration using a dual electrospray ionization sprayer system for protein identification. Rapid Commun. Mass Spectrom. 2002, 16, 505–511.
Wolff, J.; Eckers, C.; Sage, A. B.; Giles, K.; Bateman, R. Accurate mass liquid chromatography/mss spectrometry on quadrupole orthogonal acceleration time-of-flight mass analyzers using switching between separate sample and reference sprays. 2. Applications using the dual-electrospray ion source. Anal. Chem. 2001, 73, 2605–2612.
Nepomuceno, A. I.; Muddiman, D. C.; Bergen, H. R., III; Craighead, J. R.; Burke, M. J.; Caskey, P. E.; Allan, J. A. Dual electrospray ionization source for confident generation of accurate mass tags using liquid chromatography Fourier transform ion cyclotron resonance mass spectrometry. Anal. Chem. 2003, 75, 3411–3418.
Yang, L.; Mann, T. D.; Little, D.; Wu, N.; P., C. R.; Rudewicz, P. J. Evaluation of a four-channel multiplexed electrospray triple quadrupole mass spectrometer for the simultaneous validation of LC/MS/MS methods in four different preclinical matrixes. Anal. Chem. 2001, 73, 1740–1747.
Hager, J. W. A new linear ion trap mass spectrometer. Rapid Commun. Mass Spectrom. 2002, 16, 512–526.
Wu, J.; Hager, J. W.; Xia, Y.; Londry, F. A.; McLuckey, S. A. Positive ion transmission mode ion/ion reactions in a hybrid linear ion trap. Anal. Chem. 2004, 76, 5006–5015.
Londry, F. A.; Hager, J. W. Mass selective axial ion ejection from a linear quadrupole ion trap. J. Am. Soc. Mass Spectrom. 2003, 14, 1130–1147.
Xia, Y.; Wu, J.; McLuckey, S. A.; Londry, F. A.; Hager, J. W. Mutual storage mode ion/ion reactions in a hybrid linear ion trap. J. Am. Soc. Mass Spectrom. 2005, 16, 71–81.
He, M.; Emory, J. F.; McLuckey, S. A. Reagent anions for charge inversion of polypeptide/protein cations in the gas phase. Anal. Chem. 2005, 77, 3173–3182.
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Published online September 22, 2005
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Xia, Y., Liang, X. & McLuckey, S.A. Pulsed dual electrospray ionization for In/In reactions. J Am Soc Mass Spectrom 16, 1750–1756 (2005). https://doi.org/10.1016/j.jasms.2005.07.013
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DOI: https://doi.org/10.1016/j.jasms.2005.07.013