Nonclassical Hydrophobic Effect in Micellization: Molecular Arrangement of Non-Amphiphilic Structures

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10386217" target="_blank" >RIV/00216208:11310/18:10386217 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/18:00498554

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/adts.201700002" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/adts.201700002</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adts.201700002" target="_blank" >10.1002/adts.201700002</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Nonclassical Hydrophobic Effect in Micellization: Molecular Arrangement of Non-Amphiphilic Structures

Popis výsledku v původním jazyce

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 (NM R 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 &quot;spot&quot; close to the C-H segments of the cluster. The simulations further show a counterintuitive short-range [COSAN](-)center dot center dot center dot[COSAN] - attraction and Na+center dot center dot center dot[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.

Název v anglickém jazyce

Nonclassical Hydrophobic Effect in Micellization: Molecular Arrangement of Non-Amphiphilic Structures

Popis výsledku anglicky

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 (NM R 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 &quot;spot&quot; close to the C-H segments of the cluster. The simulations further show a counterintuitive short-range [COSAN](-)center dot center dot center dot[COSAN] - attraction and Na+center dot center dot center dot[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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Advanced Theory and Simulations (online)

ISSN

2513-0390

e-ISSN

—

Svazek periodika

1

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

—

Kód UT WoS článku

000449746300002

EID výsledku v databázi Scopus

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