1. Guanidinium can both Cause and Prevent the Hydrophobic Collapse of Biomacromolecules
- Author
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Joachim Dzubiella, Pavel Jungwirth, Paul S. Cremer, Tinglu Yang, William Hunn, Halil I. Okur, Jan Heyda, Jana Hladílková, and Kelvin B. Rembert
- Subjects
Phase transition ,Salt (chemistry) ,FOS: Physical sciences ,02 engineering and technology ,Condensed Matter - Soft Condensed Matter ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Article ,Ion ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Physics - Chemical Physics ,Cations ,Spectroscopy, Fourier Transform Infrared ,Sulfate ,Hydrophobic collapse ,Guanidine ,chemistry.chemical_classification ,Chemical Physics (physics.chem-ph) ,General Chemistry ,Polymer ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,3. Good health ,Crystallography ,chemistry ,Others ,Excluded volume ,Soft Condensed Matter (cond-mat.soft) ,Thermodynamics ,0210 nano-technology ,Peptides ,Hydrophobic and Hydrophilic Interactions ,Macromolecule - Abstract
A combination of Fourier transform infrared and phase transition measurements as well as molecular computer simulations, and thermodynamic modeling were performed to probe the mechanisms by which guanidinium salts influence the stability of the collapsed versus uncollapsed state of an elastin-like polypeptide (ELP), an uncharged thermoresponsive polymer. We found that the cation's action was highly dependent upon the counteranion with which it was paired. Specifically, Gnd+ was depleted from the ELP/water interface and was found to stabilize the collapsed state of the macromolecule when paired with well-hydrated anions such as sulfate. Stabilization in this case occurred via an excluded volume (or depletion) effect, whereby sulfate was strongly partitioned away from the ELP/water interface. Intriguingly, at low salt concentrations, Gnd+ was also found to stabilize the collapsed state of the ELP when paired with SCN-, which is a strong binder for the ELP. In this case, the anion and cation were both found to be enriched in the collapsed state of the polymer. The collapsed state was favored because the Gnd+ crosslinked the polymer chains together. Moreover, the anion helped partition Gnd+ to the polymer surface. At higher salt concentrations (>1.5 M), GndSCN switched to stabilizing the uncollapsed state because a sufficient amount of Gnd+ and SCN- partitioned to the polymer surface to prevent cross-linking from occurring. Finally, in a third case, it was found that salts which interacted in an intermediate fashion with the polymer (e.g. GndCl) favored the uncollapsed conformation at all salt concentrations., 20 pages, 6 figures
- Published
- 2017