Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid-solid phase transitions, but with structural and dynamical signatures that map onto known regions of water's phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 +/- 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga4L612- host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga4L612- supramolecular construct.

An isolated water droplet in the aqueous solution of a supramolecular tetrahedral cage / Sebastiani, Federico; Bender, Trandon A; Pezzotti, Simone; Li, Wan-Lu; Schwaab, Gerhard; Bergman, Robert G; Raymond, Kenneth N; Toste, F Dean; Head-Gordon, Teresa; Havenith, Martina. - In: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA. - ISSN 0027-8424. - STAMPA. - 117:(2020), pp. 32954-32961. [10.1073/pnas.2012545117]

An isolated water droplet in the aqueous solution of a supramolecular tetrahedral cage

Sebastiani, Federico;
2020

Abstract

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid-solid phase transitions, but with structural and dynamical signatures that map onto known regions of water's phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 +/- 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga4L612- host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga4L612- supramolecular construct.
117
32954
32961
Sebastiani, Federico; Bender, Trandon A; Pezzotti, Simone; Li, Wan-Lu; Schwaab, Gerhard; Bergman, Robert G; Raymond, Kenneth N; Toste, F Dean; Head-Gordon, Teresa; Havenith, Martina
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2158/1288128
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