Solvation shell thermodynamics of extended hydrophobic solutes in mixed solvents
| العنوان: | Solvation shell thermodynamics of extended hydrophobic solutes in mixed solvents |
|---|---|
| المؤلفون: | Swaminath Bharadwaj Gourishankar, Nico Van der Vegt, Madhusmita Tripathy |
| المصدر: | The Journal of Chemical Physics. 156:164901 |
| بيانات النشر: | AIP Publishing, 2022. |
| سنة النشر: | 2022 |
| مصطلحات موضوعية: | Solutions, Physics::Biological Physics, Quantitative Biology::Biomolecules, Polymers, Methanol, Solvents, Thermodynamics, Urea, Water, General Physics and Astronomy, Physics::Chemical Physics, Physical and Theoretical Chemistry |
| الوصف: | The ability of various cosolutes and cosolvents to enhance or quench solvent density fluctuations at solute–water interfaces has crucial implications on the conformational equilibrium of macromolecules such as polymers and proteins. Herein, we use an extended hydrophobic solute as a model system to study the effect of urea and methanol on the density fluctuations in the solute’s solvation shell and the resulting thermodynamics. On strengthening the solute–water/cosolute repulsive interaction, we observe distinct trends in the mutual affinities between various species in, and the thermodynamic properties of, the solvation shell. These trends strongly follow the respective trends in the preferential adsorption of urea and methanol: solute–water/cosolute repulsion strengthens, urea accumulation decreases, and methanol accumulation increases. Preferential accumulation of urea is found to quench the density fluctuations around the extended solute, leading to a decrease in the compressibility of the solvation shell. In contrast, methanol accumulation enhances the density fluctuations, leading to an increase in the compressibility. The mode of action of urea and methanol seems to be strongly coupled to their hydration behavior. The observations from this simple model is discussed in relation to urea driven swelling and methanol induced collapse of some well-known thermo-responsive polymers. |
| تدمد: | 1089-7690 0021-9606 |
| DOI: | 10.1063/5.0090646 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::705ffc160325445360be2515a7983e9f https://doi.org/10.1063/5.0090646 |
| رقم الانضمام: | edsair.doi.dedup.....705ffc160325445360be2515a7983e9f |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 10897690 00219606 |
|---|---|
| DOI: | 10.1063/5.0090646 |