Tripathy, Madhusmita ; Bharadwaj, Swaminath ; Shadrack Jabes, Barnabas ; Vegt, Nico F. A. van der (2021)
Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method.
In: Nanomaterials, 2020, 10 (8)
doi: 10.26083/tuprints-00018651
Artikel, Zweitveröffentlichung, Verlagsversion
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Kurzbeschreibung (Abstract)
The small-system method (SSM) exploits the unique feature of finite-sized open systems, whose thermodynamic quantities scale with the inverse system size. This scaling enables the calculation of properties in the thermodynamic limit of macroscopic systems based on computer simulations of finite-sized systems. We herein extend the SSM to characterize the hydration shell compressibility of a generic hydrophobic polymer in water. By systematically increasing the strength of polymer-water repulsion, we find that the excess inverse thermodynamic correction factor (∆1/Γ∞s) and compressibility (∆χs) of the first hydration shell change sign from negative to positive. This occurs with a concurrent decrease in water hydrogen bonding and local tetrahedral order of the hydration shell water. The crossover lengthscale corresponds to an effective polymer bead diameter of 0.7 nm and is consistent with previous works on hydration of small and large hydrophobic solutes. The crossover lengthscale in polymer hydration shell compressibility, herein identified with the SSM approach, relates to hydrophobic interactions and macromolecular conformational equilibria in aqueous solution. The SSM approach may further be applied to study thermodynamic properties of polymer solvation shells in mixed solvents.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2021 |
| Autor(en): | Tripathy, Madhusmita ; Bharadwaj, Swaminath ; Shadrack Jabes, Barnabas ; Vegt, Nico F. A. van der |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method |
| Sprache: | Englisch |
| Publikationsjahr: | 2021 |
| Publikationsdatum der Erstveröffentlichung: | 2020 |
| Verlag: | MDPI |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Nanomaterials |
| Jahrgang/Volume einer Zeitschrift: | 10 |
| (Heft-)Nummer: | 8 |
| Kollation: | 14 Seiten |
| DOI: | 10.26083/tuprints-00018651 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/18651 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichung aus gefördertem Golden Open Access |
| Kurzbeschreibung (Abstract): | The small-system method (SSM) exploits the unique feature of finite-sized open systems, whose thermodynamic quantities scale with the inverse system size. This scaling enables the calculation of properties in the thermodynamic limit of macroscopic systems based on computer simulations of finite-sized systems. We herein extend the SSM to characterize the hydration shell compressibility of a generic hydrophobic polymer in water. By systematically increasing the strength of polymer-water repulsion, we find that the excess inverse thermodynamic correction factor (∆1/Γ∞s) and compressibility (∆χs) of the first hydration shell change sign from negative to positive. This occurs with a concurrent decrease in water hydrogen bonding and local tetrahedral order of the hydration shell water. The crossover lengthscale corresponds to an effective polymer bead diameter of 0.7 nm and is consistent with previous works on hydration of small and large hydrophobic solutes. The crossover lengthscale in polymer hydration shell compressibility, herein identified with the SSM approach, relates to hydrophobic interactions and macromolecular conformational equilibria in aqueous solution. The SSM approach may further be applied to study thermodynamic properties of polymer solvation shells in mixed solvents. |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-186512 |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Anorganische Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie |
| Hinterlegungsdatum: | 22 Jul 2021 07:30 |
| Letzte Änderung: | 03 Jul 2024 02:47 |
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| Suche nach Titel in: | TUfind oder in Google |
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- Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method. (deposited 22 Jul 2021 07:30) [Gegenwärtig angezeigt]
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