Monte Carlo Simulation of Macromolecular Ionization by Nanoelectrospray

Christopher J. Hogan, Pratim Biswas

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

Electrospray ionization (ESI) is commonly used in macromolecular mass spectrometry, yet the dynamics of macromolecules in ESI droplets are not well understood. In this study, a Monte Carlo based model was developed, which can predict the efficiency of electrospray ionization for macromolecules, i.e., the number of macromolecular ions produced per macromolecules electrosprayed. The model takes into account ESI droplet evaporation, macromolecular diffusion within the droplet, droplet fissions, and the statistical nature of the ESI process. Two idealized representations of macromolecular analytes were developed, describing cluster prone, droplet surface inactive macromolecules and droplet surface active macromolecules, respectively. It was found that surface active macromolecules are preferentially ionized over surface inactive cluster prone macromolecules when the initial droplet size is large and the analyte concentration in solution is high. Simulations showed that ESI efficiency decreases with increasing initial droplet size and analyte molecular weight, and is influenced by analyte surface activity, the properties of the solvent, and the variance of the droplet size distribution. Model predictions are qualitatively supported by experimental measurements of macromolecular electrospray ionization made previously. Overall, this study demonstrates the potential capabilities of Monte Carlo based ESI models. Future developments in such models will allow for more accurate predictions of macromolecular ESI intensity.

Original languageEnglish (US)
Pages (from-to)1098-1107
Number of pages10
JournalJournal of the American Society for Mass Spectrometry
Volume19
Issue number8
DOIs
StatePublished - Aug 2008

Bibliographical note

Funding Information:
CJH acknowledges support from an NSF Graduate Research Fellowship. Partial support from a DOD-MURI grant is also acknowledged.

Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.

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