A computational model for protein ionization by electrospray based on gas-phase basicity

Roberto Marchese, Rita Grandori, Paolo Carloni, Simone Raugei

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Identifying the key factor(s) governing the overall protein charge is crucial for the interpretation of electrospray-ionization mass spectrometry data. Current hypotheses invoke different principles for folded and unfolded proteins. Here, first we investigate the gas-phase structure and energetics of several proteins of variable size and different folds. The conformer and protomer space of these proteins ions is explored exhaustively by hybrid Monte-Carlo/molecular dynamics calculations, allowing for zwitterionic states. From these calculations, the apparent gas-phase basicity of desolvated protein ions turns out to be the unifying trait dictating protein ionization by electrospray. Next, we develop a simple, general, adjustable-parameter-free model for the potential energy function of proteins. The model is capable to predict with remarkable accuracy the experimental charge of folded proteins and its well-known correlation with the square root of protein mass.

Original languageEnglish
Pages (from-to)1903-1910
Number of pages8
JournalJournal of the American Society for Mass Spectrometry
Volume23
Issue number11
DOIs
Publication statusPublished - Nov 2012

Fingerprint

Alkalinity
Ionization
Gases
Proteins
Ions
Potential energy functions
Protein Unfolding
Electrospray Ionization Mass Spectrometry
Electrospray ionization
Protein Subunits
Molecular Dynamics Simulation
Phase structure
Mass spectrometry
Molecular dynamics

Keywords

  • Density functional theory calculations
  • Electrospray ionization
  • Gas-phase basicity
  • Molecular-dynamics
  • Monte-Carlo sampling
  • Protein ionization
  • Simulations

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

Cite this

A computational model for protein ionization by electrospray based on gas-phase basicity. / Marchese, Roberto; Grandori, Rita; Carloni, Paolo; Raugei, Simone.

In: Journal of the American Society for Mass Spectrometry, Vol. 23, No. 11, 11.2012, p. 1903-1910.

Research output: Contribution to journalArticle

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