Hydrogen bonding in glassy trehalose-water system : Insights from density functional theory and molecular dynamics simulations
Kocherbitov, Vitaly LU ; Music, Denis and Veryazov, Valera LU
(2024)
In Journal of Chemical Physics
160(8).
- Abstract
We report a detailed density functional theory and molecular dynamics study of hydrogen bonding between trehalose and water, with a special emphasis on interactions in the amorphous solid state. For comparison, water-water interactions in water dimers and tetramers are evaluated using quantum calculations. The results show that the hydrogen bonding energy is dependent not only on the geometry (bond length and angle) but also on the local environment of the hydrogen bond. This is seen in quantum calculations of complexes in vacuum as well as in amorphous solid states with periodic boundary conditions. The temperature-induced glass transition in the trehalose-water system was studied using molecular dynamics simulations with varying... (More)
We report a detailed density functional theory and molecular dynamics study of hydrogen bonding between trehalose and water, with a special emphasis on interactions in the amorphous solid state. For comparison, water-water interactions in water dimers and tetramers are evaluated using quantum calculations. The results show that the hydrogen bonding energy is dependent not only on the geometry (bond length and angle) but also on the local environment of the hydrogen bond. This is seen in quantum calculations of complexes in vacuum as well as in amorphous solid states with periodic boundary conditions. The temperature-induced glass transition in the trehalose-water system was studied using molecular dynamics simulations with varying cooling and heating rates. The obtained parameters of the glass transition are in good agreement with the experiments. Moreover, the dehydration of trehalose in the glassy state was investigated through a gradual dehydration with multiple small steps under isothermal conditions. From these simulations, the values of water sorption energy at different temperatures were obtained. The partial molar enthalpy of mixing of water value of −18 kJ/mol found in calorimetric experiments was accurately reproduced in these simulations. These findings are discussed in light of the hydrogen bonding data in the system. We conclude that the observed exothermic effect is due to different responses of liquid and glassy matrices to perturbations associated with the addition or removal of water molecules.
(Less)
- author
- Kocherbitov, Vitaly
LU
; Music, Denis
and Veryazov, Valera
LU
- organization
- publishing date
- 2024-02-28
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 160
- issue
- 8
- article number
- 084504
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- pmid:38411233
- scopus:85186274717
- ISSN
- 0021-9606
- DOI
- 10.1063/5.0194537
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2024 Author(s).
- id
- d7a9b6b3-f183-4805-b5e3-f4f947cad6a6
- date added to LUP
- 2024-03-18 08:16:39
- date last changed
- 2024-04-15 05:28:33
@article{d7a9b6b3-f183-4805-b5e3-f4f947cad6a6,
abstract = {{<p>We report a detailed density functional theory and molecular dynamics study of hydrogen bonding between trehalose and water, with a special emphasis on interactions in the amorphous solid state. For comparison, water-water interactions in water dimers and tetramers are evaluated using quantum calculations. The results show that the hydrogen bonding energy is dependent not only on the geometry (bond length and angle) but also on the local environment of the hydrogen bond. This is seen in quantum calculations of complexes in vacuum as well as in amorphous solid states with periodic boundary conditions. The temperature-induced glass transition in the trehalose-water system was studied using molecular dynamics simulations with varying cooling and heating rates. The obtained parameters of the glass transition are in good agreement with the experiments. Moreover, the dehydration of trehalose in the glassy state was investigated through a gradual dehydration with multiple small steps under isothermal conditions. From these simulations, the values of water sorption energy at different temperatures were obtained. The partial molar enthalpy of mixing of water value of −18 kJ/mol found in calorimetric experiments was accurately reproduced in these simulations. These findings are discussed in light of the hydrogen bonding data in the system. We conclude that the observed exothermic effect is due to different responses of liquid and glassy matrices to perturbations associated with the addition or removal of water molecules.</p>}},
author = {{Kocherbitov, Vitaly and Music, Denis and Veryazov, Valera}},
issn = {{0021-9606}},
language = {{eng}},
month = {{02}},
number = {{8}},
publisher = {{American Institute of Physics (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Hydrogen bonding in glassy trehalose-water system : Insights from density functional theory and molecular dynamics simulations}},
url = {{http://dx.doi.org/10.1063/5.0194537}},
doi = {{10.1063/5.0194537}},
volume = {{160}},
year = {{2024}},
}