Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether

Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether

In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in <i>n</i>-butylmethylether and water. In addition to the impact of the cations and solvent molecules on the free energy profile of rotation, we also explore if chiral...

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Main Authors: Veronika Zeindlhofer, Phillip Hudson, Ádám Márk Pálvölgyi, Matthias Welsch, Mazin Almarashi, H. Lee Woodcock, Bernard Brooks, Katharina Bica-Schröder, Christian Schröder
Format: Article
Language:English
Published: MDPI AG 2020-08-01
Series:International Journal of Molecular Sciences
Subjects:
chiral ionic liquids
biphenyl
chirality transfer
molecular dynamics simulations
Online Access:https://www.mdpi.com/1422-0067/21/17/6222
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spelling doaj-6853730f15ab4ee2bc1165a8119733e02020-11-25T02:58:46ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672020-08-01216222622210.3390/ijms21176222Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and ButylmethyletherVeronika Zeindlhofer0Phillip Hudson1Ádám Márk Pálvölgyi2Matthias Welsch3Mazin Almarashi4H. Lee Woodcock5Bernard Brooks6Katharina Bica-Schröder7Christian Schröder8Department of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, AustriaLaboratory of Computational Biology, National Heart, Lung, and Blood Institute (NHLBI), National Institutes of Health (NIH), Bethesda, MD 20892, USAInstitute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, 1060 Vienna, AustriaDepartment of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, AustriaDepartment of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, AustriaDepartment of Chemistry, University of South Florida, Tampa, FL 33620, USALaboratory of Computational Biology, National Heart, Lung, and Blood Institute (NHLBI), National Institutes of Health (NIH), Bethesda, MD 20892, USAInstitute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, 1060 Vienna, AustriaDepartment of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, AustriaIn this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in <i>n</i>-butylmethylether and water. In addition to the impact of the cations and solvent molecules on the free energy profile of rotation, we also explore if chirality transfer between a chiral cation and the biphenylic anion is possible, i.e., if pairing with a chiral cation can energetically favour one conformer of the anion via diastereomeric complex formation. The quantum-mechanical calculations are accompanied by polarizable MD simulations using umbrella sampling to study the impact of solvents of different polarity in more detail. We also discuss how accurate polarizable force fields for biphenylic anions can be constructed from quantum-mechanical reference data.https://www.mdpi.com/1422-0067/21/17/6222chiral ionic liquidsbiphenylchirality transfermolecular dynamics simulations
collection DOAJ
language English
format Article
sources DOAJ
author Veronika Zeindlhofer
Phillip Hudson
Ádám Márk Pálvölgyi
Matthias Welsch
Mazin Almarashi
H. Lee Woodcock
Bernard Brooks
Katharina Bica-Schröder
Christian Schröder
spellingShingle Veronika Zeindlhofer
Phillip Hudson
Ádám Márk Pálvölgyi
Matthias Welsch
Mazin Almarashi
H. Lee Woodcock
Bernard Brooks
Katharina Bica-Schröder
Christian Schröder
Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
International Journal of Molecular Sciences
chiral ionic liquids
biphenyl
chirality transfer
molecular dynamics simulations
author_facet Veronika Zeindlhofer
Phillip Hudson
Ádám Márk Pálvölgyi
Matthias Welsch
Mazin Almarashi
H. Lee Woodcock
Bernard Brooks
Katharina Bica-Schröder
Christian Schröder
author_sort Veronika Zeindlhofer
title Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
title_short Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
title_full Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
title_fullStr Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
title_full_unstemmed Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether
title_sort enantiomerization of axially chiral biphenyls: polarizable md simulations in water and butylmethylether
publisher MDPI AG
series International Journal of Molecular Sciences
issn 1661-6596
1422-0067
publishDate 2020-08-01
description In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in <i>n</i>-butylmethylether and water. In addition to the impact of the cations and solvent molecules on the free energy profile of rotation, we also explore if chirality transfer between a chiral cation and the biphenylic anion is possible, i.e., if pairing with a chiral cation can energetically favour one conformer of the anion via diastereomeric complex formation. The quantum-mechanical calculations are accompanied by polarizable MD simulations using umbrella sampling to study the impact of solvents of different polarity in more detail. We also discuss how accurate polarizable force fields for biphenylic anions can be constructed from quantum-mechanical reference data.
topic chiral ionic liquids
biphenyl
chirality transfer
molecular dynamics simulations
url https://www.mdpi.com/1422-0067/21/17/6222
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