Journal
ELECTROPHORESIS
Volume 35, Issue 5, Pages 617-624Publisher
WILEY
DOI: 10.1002/elps.201300544
Keywords
EOF markers; Ion-specific effects; Ion-specific mobilization; Molecular dynamics simulations; Neutral analytes
Funding
- Charles University
- Ministry of Education, Youth and Sports [MSM0021620857]
- Czech Science Foundation [P208/12/G016]
- Academy of Sciences
- Alexander-von-Humboldt (AvH) Stiftung, Germany
- IMPRS in Dresden
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Small neutral organic compounds have traditionally the role of EOF markers in electrophoresis, as they are expected to have zero electrophoretic mobility in external electric fields. The BGE contains, however, ions that have unequal affinities to the neutral molecules, which in turn results in their mobilization. In this study we focused on two EOF markersthiourea and DMSO, as well as on N-methyl acetamide (NMA) as a model of the peptide bond. By means of CE and all atom molecular dynamics simulations we explored mobilization of these neutral compounds in large set of Hofmeister salts. Employing a statistical mechanics approach, we were able to reproduce by simulations the experimental electrophoretic mobility coefficients. We also established the role of the chemical composition of marker and the BGE on the measured electrophoretic mobility coefficient. For NMA, we interpreted the results in terms of the relative affinities of cations versus anions to the peptide bond.
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