Nonclassical Hydrophobic Effect in Micellization : Molecular Arrangement of Non-Amphiphilic Structures
Uchman, Mariusz ; Abrikosov, Alexei I. LU ; Lepšík, Martin ; Lund, Mikael LU
and Matějíček, Pavel
(2018)
In Advanced Theory and Simulations
1(1).
- Abstract
Micellization brought about by nonclassical hydrophobic effect invokes enthalpy as the driving force. Thus, the underlying molecular phenomena differ from the entropically dominated hydrophobic effect. In quest for a molecular-scale understanding, we report on the molecular arrangement of nonamphiphilic structures of an anionic boron cluster compound, COSAN. We synergistically combine experimental (NMR and calorimetry) and theoretical (molecular dynamics and quantum chemical calculations) approaches. The experimental data support the mechanism of closed association of COSAN, where the self-assembly is driven by the enthalpy contribution to the free energy. Molecular dynamics simulations in explicit solvent show that water molecules form... (More)
Micellization brought about by nonclassical hydrophobic effect invokes enthalpy as the driving force. Thus, the underlying molecular phenomena differ from the entropically dominated hydrophobic effect. In quest for a molecular-scale understanding, we report on the molecular arrangement of nonamphiphilic structures of an anionic boron cluster compound, COSAN. We synergistically combine experimental (NMR and calorimetry) and theoretical (molecular dynamics and quantum chemical calculations) approaches. The experimental data support the mechanism of closed association of COSAN, where the self-assembly is driven by the enthalpy contribution to the free energy. Molecular dynamics simulations in explicit solvent show that water molecules form a patchy network around COSAN molecules, giving rise to the strong hydrophobic self-association. In the second solvation shell, water forms a slightly hydrophilic “spot” close to the C-H segments of the cluster. The simulations further show a counterintuitive short-range [COSAN]−∙∙∙[COSAN]− attraction and Na+∙∙∙[COSAN]− repulsion. Quantum chemical calculations reveal a major role of solvation in stabilizing the contact pairs. Further, the calculations show the parallel/X-shape geometrical arrangements of COSAN dimers as the most preferred. Lastly, dihydrogen bonding are found to influence the structure of micelles. In summary, we provide a molecular view of nonclassical micellization that can be extended to other amphiphiles like boranes.
(Less)
- author
- Uchman, Mariusz
; Abrikosov, Alexei I.
LU
; Lepšík, Martin
; Lund, Mikael
LU
and Matějíček, Pavel
- organization
- publishing date
- 2018-01-01
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- metallacarboranes, molecular dynamics simulations, nonclassical hydrophobic effect, quantum mechanics, self-assembly
- in
- Advanced Theory and Simulations
- volume
- 1
- issue
- 1
- article number
- 1700002
- pages
- 10 pages
- publisher
- Wiley-Blackwell
- external identifiers
-
- scopus:85084918685
- ISSN
- 2513-0390
- DOI
- 10.1002/adts.201700002
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- id
- 70265ee1-3ffd-429d-9973-74277bc6f48f
- date added to LUP
- 2021-11-12 13:06:32
- date last changed
- 2023-02-19 06:23:18
@article{70265ee1-3ffd-429d-9973-74277bc6f48f,
abstract = {{<p>Micellization brought about by nonclassical hydrophobic effect invokes enthalpy as the driving force. Thus, the underlying molecular phenomena differ from the entropically dominated hydrophobic effect. In quest for a molecular-scale understanding, we report on the molecular arrangement of nonamphiphilic structures of an anionic boron cluster compound, COSAN. We synergistically combine experimental (NMR and calorimetry) and theoretical (molecular dynamics and quantum chemical calculations) approaches. The experimental data support the mechanism of closed association of COSAN, where the self-assembly is driven by the enthalpy contribution to the free energy. Molecular dynamics simulations in explicit solvent show that water molecules form a patchy network around COSAN molecules, giving rise to the strong hydrophobic self-association. In the second solvation shell, water forms a slightly hydrophilic “spot” close to the C-H segments of the cluster. The simulations further show a counterintuitive short-range [COSAN]<sup>−</sup>∙∙∙[COSAN]<sup>−</sup> attraction and Na<sup>+</sup>∙∙∙[COSAN]<sup>−</sup> repulsion. Quantum chemical calculations reveal a major role of solvation in stabilizing the contact pairs. Further, the calculations show the parallel/X-shape geometrical arrangements of COSAN dimers as the most preferred. Lastly, dihydrogen bonding are found to influence the structure of micelles. In summary, we provide a molecular view of nonclassical micellization that can be extended to other amphiphiles like boranes.</p>}},
author = {{Uchman, Mariusz and Abrikosov, Alexei I. and Lepšík, Martin and Lund, Mikael and Matějíček, Pavel}},
issn = {{2513-0390}},
keywords = {{metallacarboranes; molecular dynamics simulations; nonclassical hydrophobic effect; quantum mechanics; self-assembly}},
language = {{eng}},
month = {{01}},
number = {{1}},
publisher = {{Wiley-Blackwell}},
series = {{Advanced Theory and Simulations}},
title = {{Nonclassical Hydrophobic Effect in Micellization : Molecular Arrangement of Non-Amphiphilic Structures}},
url = {{http://dx.doi.org/10.1002/adts.201700002}},
doi = {{10.1002/adts.201700002}},
volume = {{1}},
year = {{2018}},
}