title: Influence of Hofmeister Ions on the Structure of Proline-Based Peptide Models: A Combined Experimental and Molecular Modeling Study.
abstract: The influence of three sodium salts, covering a wide range of the Hofmeister series, on the conformation of three proline-based peptide models in aqueous solution is examined using a combination of nuclear magnetic resonance spectroscopy and molecular dynamics simulations. The anions preferentially interact with the cis conformers of the peptide models, which is rationalized by the respective electrostatic potential surfaces. These preferred interactions have a strong impact on the thermodynamics of the cis/trans equilibria, leading to a higher population of the cis conformers. In distinct cases, these equilibria are nearly independent of temperature, showing that the salts are also able to stabilize the conformers over wide temperature ranges.
authors.affiliation: Department of Chemistry, Organic Chemistry, University of Cologne , Greinstrasse 4, 50939 Cologne, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Bröhl
authors.affiliation: Department of Chemistry, Organic Chemistry, University of Cologne , Greinstrasse 4, 50939 Cologne, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Albrecht
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Yong
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Edward
authors.identifier: 0000-0002-6309-1347
authors.initials: E
authors.lastname: Maginn
authors.affiliation: Department of Chemistry, Organic Chemistry, University of Cologne , Greinstrasse 4, 50939 Cologne, Germany.
authors.forename: Ralf
authors.identifier: 0000-0003-2282-6586
authors.initials: R
authors.lastname: Giernoth
mesh_terms: D007477:Ions / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D011392:Proline / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007477:Ions; D010455:Peptides; D011392:Proline