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Article

Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions

1
Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
2
Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, 00185 Rome, Italy
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Departments of ChiBioFarAm and MIFT, Section of Industrial Chemistry, University of Messina, CASPE-INSTM, V.le F. Stagno d’Alcontres 31, 98166 Messina, Italy
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Departments of ChiBioFarAm, Section of Industrial Chemistry, University of Messina, CASPE-INSTM, V.le F. Stagno d’Alcontres 31, 98166 Messina, Italy
*
Author to whom correspondence should be addressed.
Academic Editor: Olga Abián
Int. J. Mol. Sci. 2021, 22(14), 7547; https://doi.org/10.3390/ijms22147547
Received: 13 May 2021 / Revised: 26 June 2021 / Accepted: 7 July 2021 / Published: 14 July 2021
(This article belongs to the Special Issue From Molecules to Colloids: Recent Advances in Their Chemical Physics)
NMR spectroscopy is used in the temperature range 180–350 K to study the local order and transport properties of pure liquid water (bulk and confined) and its solutions with glycerol and methanol at different molar fractions. We focused our interest on the hydrophobic effects (HE), i.e., the competition between hydrophilic and hydrophobic interactions. Nowadays, compared to hydrophilicity, little is known about hydrophobicity. Therefore, the main purpose of this study is to gain new information about hydrophobicity. As the liquid water properties are dominated by polymorphism (two coexisting liquid phases of high and low density) due to hydrogen bond interactions (HB), creating (especially in the supercooled regime) the tetrahedral networking, we focused our interest to the HE of these structures. We measured the relaxation times (T1 and T2) and the self-diffusion (DS). From these times, we took advantage of the NMR property to follow the behaviors of each molecular component (the hydrophilic and hydrophobic groups) separately. In contrast, DS is studied in terms of the Adam–Gibbs model by obtaining the configurational entropy (Sconf) and the specific heat contributions (CP,conf). We find that, for the HE, all of the studied quantities behave differently. For water–glycerol, the HB interaction is dominant for all conditions; water–methanol, two different T-regions above and below 265 K are observable, dominated by hydrophobicity and hydrophilicity, respectively. Below this temperature, where the LDL phase and the HB network develops and grows, with the times and CP,conf change behaviors leading to maxima and minima. Above it, the HB becomes weak and less stable, the HDL dominates, and hydrophobicity determines the solution. View Full-Text
Keywords: water; local order; relaxation times; self-diffusion; hydrophobic effect water; local order; relaxation times; self-diffusion; hydrophobic effect
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MDPI and ACS Style

Mallamace, F.; Mallamace, D.; Chen, S.-H.; Lanzafame, P.; Papanikolaou, G. Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions. Int. J. Mol. Sci. 2021, 22, 7547. https://doi.org/10.3390/ijms22147547

AMA Style

Mallamace F, Mallamace D, Chen S-H, Lanzafame P, Papanikolaou G. Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions. International Journal of Molecular Sciences. 2021; 22(14):7547. https://doi.org/10.3390/ijms22147547

Chicago/Turabian Style

Mallamace, Francesco, Domenico Mallamace, Sow-Hsin Chen, Paola Lanzafame, and Georgia Papanikolaou. 2021. "Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions" International Journal of Molecular Sciences 22, no. 14: 7547. https://doi.org/10.3390/ijms22147547

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