Molecular Mechanism for the Interactions of Hofmeister Cations with Macromolecules in Aqueous Solution
| Autor: | Chad I. Drexler, Halil I. Okur, Paul S. Cremer, Ellen E Bruce, Bradley A. Rogers, Nico F. A. van der Vegt, Sina Stegmaier, Sylvie Roke |
|---|---|
| Přispěvatelé: | Okur, Halil I. |
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Aqueous solution Inorganic chemistry Salt (chemistry) General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Chloride Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry chemistry Amide Side chain medicine Counterion Solubility Macromolecule medicine.drug |
| Zdroj: | Journal of the American Chemical Society |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Ion identity and concentration influence the solubility of macromolecules. To date, substantial effort has been focused on obtaining a molecular level understanding of specific effects for anions. By contrast, the role of cations has received significantly less attention and the underlying mechanisms by which cations interact with macromolecules remain more elusive. To address this issue, the solubility of poly(N-isopropylacrylamide), a thermoresponsive polymer with an amide moiety on its side chain, was studied in aqueous solutions with a series of nine different cation chloride salts as a function of salt concentration. Phase transition temperature measurements were correlated to molecular dynamics simulations. The results showed that although all cations were on average depleted from the macromolecule/water interface, more strongly hydrated cations were able to locally accumulate around the amide oxygen. These weakly favorable interactions helped to partially offset the salting-out effect. Moreover, the cations approached the interface together with chloride counterions in solvent-shared ion pairs. Because ion pairing was concentration-dependent, the mitigation of the dominant salting-out effect became greater as the salt concentration was increased. Weakly hydrated cations showed less propensity for ion pairing and weaker affinity for the amide oxygen. As such, there was substantially less mitigation of the net salting-out effect for these ions, even at high salt concentrations. |
| Databáze: | OpenAIRE |
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