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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MDPI AG
2020-08-01
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author | Veronika Zeindlhofer Phillip Hudson Ádám Márk Pálvölgyi Matthias Welsch Mazin Almarashi H. Lee Woodcock Bernard Brooks Katharina Bica-Schröder Christian Schröder |
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 |
collection | DOAJ |
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. |
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issn | 1661-6596 1422-0067 |
language | English |
last_indexed | 2024-03-10T16:44:53Z |
publishDate | 2020-08-01 |
publisher | MDPI AG |
record_format | Article |
series | International Journal of Molecular Sciences |
spelling | doaj.art-6853730f15ab4ee2bc1165a8119733e02023-11-20T11:40:44ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672020-08-012117622210.3390/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 |
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 |
title | 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_short | 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 |
topic | chiral ionic liquids biphenyl chirality transfer molecular dynamics simulations |
url | https://www.mdpi.com/1422-0067/21/17/6222 |
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