Modeling the maximum charge state of arginine-containing peptide ions formed by electrospray ionization

A model for the gas-phase proton transfer reactivity of multiply protonated molecules is used to quantitatively account for the maximum charge states of a series of arginine-containing peptide ions measured by Downard and Biemann (Int. J. Mass Spectrom. Ion Processes1995,148, 191–202). We find that our calculations account exactly for the maximum charge state for 7 of the 10 peprides and are off by one charge for the remaining 3. These calculations clearly predict the trend in maximum charge states for these peptides and provide further evidence that the maximum charge state of ions formed by electrospray ionization is determined by their gas-phase proton transfer reactivity.

[1]  P. Schnier,et al.  ELECTROSTATIC FORCES AND DIELECTRIC POLARIZABILITY OF MULTIPLY PROTONATED GAS-PHASE CYTOCHROME C IONS PROBED BY ION/MOLECULE CHEMISTRY , 1995 .

[2]  Brian T. Chait,et al.  Probing conformational changes in proteins by mass spectrometry , 1990 .

[3]  C. Fenselau,et al.  Structural Determinants of Gas Phase Basicities of Peptides , 1993 .

[4]  J. Fenn,et al.  Ion formation from charged droplets: Roles of geometry, energy, and time , 1993, Journal of the American Society for Mass Spectrometry.

[5]  K. Siu,et al.  Electrospray mass spectrometry of some proteins and the aqueous solution acid/base equilibrium model in the negative ion detection mode☆ , 1993 .

[6]  K. Siu,et al.  Electrospray Mass Spectrometric Study of Protein-Ketone Equilibria in Solution , 1994 .

[7]  G. Glish,et al.  Reactions of Dimethylamine with Multiply Charged Ions of Cytochrome c , 1990 .

[8]  C. Beddell,et al.  Mechanism of production of ions in electrospray mass spectrometry , 1993 .

[9]  D. S. Gross,et al.  Experimental Measurement of Coulomb Energy and Intrinsic Dielectric Polarizability of a Multiply Protonated Peptide Ion Using Electrospray Ionization Fourier-Transform Mass Spectrometry , 1995 .

[10]  R. Cole,et al.  Disparity between solution‐phase equilibria and charge state distributions in positive‐ion electrospray mass spectrometry , 1994 .

[11]  D. S. Gross,et al.  Structure of Gramicidin S (M + H + X)2+ Ions (X = Li, Na, K) Probed by Proton Transfer Reactions , 1996 .

[12]  C. Fenselau,et al.  Proton affinity of arginine measured by the kinetic approach , 1992 .

[13]  P. Schnier,et al.  Tandem mass spectrometry of large biomolecule ions by blackbody infrared radiative dissociation. , 1996, Analytical chemistry.

[14]  K. Biemann,et al.  Charging behavior of highly basic peptides during electrospray ionization. A predilection for protons , 1995 .

[15]  Richard D. Smith,et al.  Proton transfer reactions of multiply charged peptide and protein cations and anions , 1995 .

[16]  K. Hiraoka,et al.  Formation of multiply charged ions of the oligopeptide Arg-Arg-Arg by electrospray ionization , 1992 .

[17]  D. S. Gross,et al.  MEASUREMENT OF COULOMB ENERGY AND DIELECTRIC POLARIZABILITY OF GAS-PHASE DIPROTONATED DIAMINOALKANES , 1995 .

[18]  J. Henion,et al.  The determination of protein, oligonucleotide and peptide molecular weights by ion-spray mass spectrometry. , 1988, Rapid communications in mass spectrometry : RCM.

[19]  P. Schnier,et al.  On the maximum charge state and proton transfer reactivity of peptide and protein ions formed by electrospray ionization , 1995, Journal of the American Society for Mass Spectrometry.

[20]  C. G. Edmonds,et al.  Effect of reducing disulfide-containing proteins on electrospray ionization mass spectra. , 1990, Analytical chemistry.

[21]  P. Kebarle,et al.  From ions in solution to ions in the gas phase - the mechanism of electrospray mass spectrometry , 1993 .

[22]  M. Mann,et al.  Electrospray ionization for mass spectrometry of large biomolecules. , 1989, Science.

[23]  F. Röllgen,et al.  Desolvation of ions and molecules in thermospray mass spectrometry , 1989 .

[24]  Richard D. Smith,et al.  Principles and practice of electrospray ionization—mass spectrometry for large polypeptides and proteins , 1991 .

[25]  Richard D. Smith,et al.  Detection of high molecular weight starburst dendrimers by electrospray ionization mass spectometry , 1995 .

[26]  P. Schnier,et al.  Conformations and folding of lysozyme ions in vacuo. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[27]  K. Siu,et al.  Are the electrospray mass spectra of proteins related to their aqueous solution chemistry? , 1992, Journal of the American Society for Mass Spectrometry.