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Article

Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method

Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische Universität Darmstadt, 64287 Darmstadt, Germany
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Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Nanomaterials 2020, 10(8), 1460; https://doi.org/10.3390/nano10081460
Received: 24 June 2020 / Revised: 21 July 2020 / Accepted: 22 July 2020 / Published: 25 July 2020
(This article belongs to the Special Issue Nanoscale Thermodynamics)
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 (Δ1/Γs) and compressibility (Δχs) 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. View Full-Text
Keywords: small system method; thermodynamics of small systems; hydration shell thermodynamics; finite size correction small system method; thermodynamics of small systems; hydration shell thermodynamics; finite size correction
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MDPI and ACS Style

Tripathy, M.; Bharadwaj, S.; B., S.J.; van der Vegt, N.F.A. Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method. Nanomaterials 2020, 10, 1460. https://doi.org/10.3390/nano10081460

AMA Style

Tripathy M, Bharadwaj S, B. SJ, van der Vegt NFA. Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method. Nanomaterials. 2020; 10(8):1460. https://doi.org/10.3390/nano10081460

Chicago/Turabian Style

Tripathy, Madhusmita, Swaminath Bharadwaj, Shadrack J. B., and Nico F.A. van der Vegt. 2020. "Characterizing Polymer Hydration Shell Compressibilities with the Small-System Method" Nanomaterials 10, no. 8: 1460. https://doi.org/10.3390/nano10081460

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