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Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method

Tripathy, Madhusmita ; Bharadwaj, Swaminath ; Shadrack Jabes, Barnabas ; van der Vegt, Nico F. A. (2021):
Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method. (Publisher's Version)
In: Nanomaterials, 10 (8), MDPI, ISSN 2079-4991,
DOI: 10.26083/tuprints-00018651,

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Item Type: Article
Origin: Secondary publication via sponsored Golden Open Access
Status: Publisher's Version
Title: Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method
Language: English

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.

Journal or Publication Title: Nanomaterials
Volume of the journal: 10
Issue Number: 8
Publisher: MDPI
Collation: 14 Seiten
Classification DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Divisions: 07 Department of Chemistry > Fachgebiet Anorganische Chemie
07 Department of Chemistry > Physical Chemistry
Date Deposited: 22 Jul 2021 07:30
Last Modified: 07 Mar 2022 13:59
DOI: 10.26083/tuprints-00018651
Corresponding Links:
URN: urn:nbn:de:tuda-tuprints-186512
URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/18651
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