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 -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...
Gespeichert in:
| Veröffentlicht in: | International journal of molecular sciences 2020-08, Vol.21 (17), p.6222 |
|---|---|
| Hauptverfasser: | , , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | |
|---|---|
| container_issue | 17 |
| container_start_page | 6222 |
| container_title | International journal of molecular sciences |
| container_volume | 21 |
| creator | Zeindlhofer, Veronika Hudson, Phillip Pálvölgyi, Ádám Márk Welsch, Matthias Almarashi, Mazin Woodcock, H Lee Brooks, Bernard Bica-Schröder, Katharina Schröder, Christian |
| description | In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in
-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. |
| doi_str_mv | 10.3390/ijms21176222 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7503397</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2439494570</sourcerecordid><originalsourceid>FETCH-LOGICAL-c412t-2eaaa3c36e470785680c2fa4ef6482f06c06c677468bdb83aa7ed289a471ead23</originalsourceid><addsrcrecordid>eNpVkU1LxDAQhoMofqzePEvAq6tpkjatB2FdP2FFQcVjmLapmyVN16QV668366qsEJKBeeadmbwI7UfkmLGMnOhZ7WkUiYRSuoa2I07pkJBErK_EW2jH-xkhlNE420RbjKYi1LBt9Hppwba6qZXTnxACi5sKjz40GNPj8VQ7MPhcz6fK9saf4ofGwILMjcJ3F_hR1535LvNYW_wCrXIYbInPu7Y3tWqnvQmXcrtoowLj1d7PO0DPV5dP45vh5P76djyaDAse0XZIFQCwgiWKCyLSOElJQSvgqkp4SiuSFOEkQvAkzcs8ZQBClTTNgItIQUnZAJ0tdeddXquyULYNG8i50zW4Xjag5f-M1VP52rxLEZPwnSIIHP4IuOatU76Vs6ZzNswsKWcZz3gsSKCOllThGu-dqv46REQubJGrtgT8YHWqP_jXB_YFaRWLPA</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2439494570</pqid></control><display><type>article</type><title>Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether</title><source>MDPI - Multidisciplinary Digital Publishing Institute</source><source>MEDLINE</source><source>EZB-FREE-00999 freely available EZB journals</source><source>PubMed Central</source><creator>Zeindlhofer, Veronika ; Hudson, Phillip ; Pálvölgyi, Ádám Márk ; Welsch, Matthias ; Almarashi, Mazin ; Woodcock, H Lee ; Brooks, Bernard ; Bica-Schröder, Katharina ; Schröder, Christian</creator><creatorcontrib>Zeindlhofer, Veronika ; Hudson, Phillip ; Pálvölgyi, Ádám Márk ; Welsch, Matthias ; Almarashi, Mazin ; Woodcock, H Lee ; Brooks, Bernard ; Bica-Schröder, Katharina ; Schröder, Christian</creatorcontrib><description>In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in
-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.</description><identifier>ISSN: 1422-0067</identifier><identifier>ISSN: 1661-6596</identifier><identifier>EISSN: 1422-0067</identifier><identifier>DOI: 10.3390/ijms21176222</identifier><identifier>PMID: 32872113</identifier><language>eng</language><publisher>Switzerland: MDPI AG</publisher><subject>Anions ; Biphenyl Compounds - chemistry ; Catalysis ; Cations ; Chirality ; Complex formation ; Experiments ; Free energy ; Hydrogen ; Hydrogenation ; Influence ; Ionic Liquids - chemistry ; Ligands ; Molecular Dynamics Simulation ; Molecular Structure ; Polarity ; Quantum Dots ; Simulation ; Solvents ; Stereoisomerism ; Water - chemistry</subject><ispartof>International journal of molecular sciences, 2020-08, Vol.21 (17), p.6222</ispartof><rights>2020. This work is licensed under http://creativecommons.org/licenses/by/3.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><rights>2020 by the authors. 2020</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c412t-2eaaa3c36e470785680c2fa4ef6482f06c06c677468bdb83aa7ed289a471ead23</citedby><cites>FETCH-LOGICAL-c412t-2eaaa3c36e470785680c2fa4ef6482f06c06c677468bdb83aa7ed289a471ead23</cites><orcidid>0000-0003-3539-273X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC7503397/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC7503397/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32872113$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zeindlhofer, Veronika</creatorcontrib><creatorcontrib>Hudson, Phillip</creatorcontrib><creatorcontrib>Pálvölgyi, Ádám Márk</creatorcontrib><creatorcontrib>Welsch, Matthias</creatorcontrib><creatorcontrib>Almarashi, Mazin</creatorcontrib><creatorcontrib>Woodcock, H Lee</creatorcontrib><creatorcontrib>Brooks, Bernard</creatorcontrib><creatorcontrib>Bica-Schröder, Katharina</creatorcontrib><creatorcontrib>Schröder, Christian</creatorcontrib><title>Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether</title><title>International journal of molecular sciences</title><addtitle>Int J Mol Sci</addtitle><description>In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in
-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.</description><subject>Anions</subject><subject>Biphenyl Compounds - chemistry</subject><subject>Catalysis</subject><subject>Cations</subject><subject>Chirality</subject><subject>Complex formation</subject><subject>Experiments</subject><subject>Free energy</subject><subject>Hydrogen</subject><subject>Hydrogenation</subject><subject>Influence</subject><subject>Ionic Liquids - chemistry</subject><subject>Ligands</subject><subject>Molecular Dynamics Simulation</subject><subject>Molecular Structure</subject><subject>Polarity</subject><subject>Quantum Dots</subject><subject>Simulation</subject><subject>Solvents</subject><subject>Stereoisomerism</subject><subject>Water - chemistry</subject><issn>1422-0067</issn><issn>1661-6596</issn><issn>1422-0067</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><sourceid>8G5</sourceid><sourceid>BENPR</sourceid><sourceid>GUQSH</sourceid><sourceid>M2O</sourceid><recordid>eNpVkU1LxDAQhoMofqzePEvAq6tpkjatB2FdP2FFQcVjmLapmyVN16QV668366qsEJKBeeadmbwI7UfkmLGMnOhZ7WkUiYRSuoa2I07pkJBErK_EW2jH-xkhlNE420RbjKYi1LBt9Hppwba6qZXTnxACi5sKjz40GNPj8VQ7MPhcz6fK9saf4ofGwILMjcJ3F_hR1535LvNYW_wCrXIYbInPu7Y3tWqnvQmXcrtoowLj1d7PO0DPV5dP45vh5P76djyaDAse0XZIFQCwgiWKCyLSOElJQSvgqkp4SiuSFOEkQvAkzcs8ZQBClTTNgItIQUnZAJ0tdeddXquyULYNG8i50zW4Xjag5f-M1VP52rxLEZPwnSIIHP4IuOatU76Vs6ZzNswsKWcZz3gsSKCOllThGu-dqv46REQubJGrtgT8YHWqP_jXB_YFaRWLPA</recordid><startdate>20200828</startdate><enddate>20200828</enddate><creator>Zeindlhofer, Veronika</creator><creator>Hudson, Phillip</creator><creator>Pálvölgyi, Ádám Márk</creator><creator>Welsch, Matthias</creator><creator>Almarashi, Mazin</creator><creator>Woodcock, H Lee</creator><creator>Brooks, Bernard</creator><creator>Bica-Schröder, Katharina</creator><creator>Schröder, Christian</creator><general>MDPI AG</general><general>MDPI</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7X7</scope><scope>7XB</scope><scope>88E</scope><scope>8FI</scope><scope>8FJ</scope><scope>8FK</scope><scope>8G5</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>CCPQU</scope><scope>DWQXO</scope><scope>FYUFA</scope><scope>GHDGH</scope><scope>GNUQQ</scope><scope>GUQSH</scope><scope>K9.</scope><scope>M0S</scope><scope>M1P</scope><scope>M2O</scope><scope>MBDVC</scope><scope>PIMPY</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>PRINS</scope><scope>Q9U</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-3539-273X</orcidid></search><sort><creationdate>20200828</creationdate><title>Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether</title><author>Zeindlhofer, Veronika ; Hudson, Phillip ; Pálvölgyi, Ádám Márk ; Welsch, Matthias ; Almarashi, Mazin ; Woodcock, H Lee ; Brooks, Bernard ; Bica-Schröder, Katharina ; Schröder, Christian</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c412t-2eaaa3c36e470785680c2fa4ef6482f06c06c677468bdb83aa7ed289a471ead23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Anions</topic><topic>Biphenyl Compounds - chemistry</topic><topic>Catalysis</topic><topic>Cations</topic><topic>Chirality</topic><topic>Complex formation</topic><topic>Experiments</topic><topic>Free energy</topic><topic>Hydrogen</topic><topic>Hydrogenation</topic><topic>Influence</topic><topic>Ionic Liquids - chemistry</topic><topic>Ligands</topic><topic>Molecular Dynamics Simulation</topic><topic>Molecular Structure</topic><topic>Polarity</topic><topic>Quantum Dots</topic><topic>Simulation</topic><topic>Solvents</topic><topic>Stereoisomerism</topic><topic>Water - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zeindlhofer, Veronika</creatorcontrib><creatorcontrib>Hudson, Phillip</creatorcontrib><creatorcontrib>Pálvölgyi, Ádám Márk</creatorcontrib><creatorcontrib>Welsch, Matthias</creatorcontrib><creatorcontrib>Almarashi, Mazin</creatorcontrib><creatorcontrib>Woodcock, H Lee</creatorcontrib><creatorcontrib>Brooks, Bernard</creatorcontrib><creatorcontrib>Bica-Schröder, Katharina</creatorcontrib><creatorcontrib>Schröder, Christian</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Health & Medical Collection</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Medical Database (Alumni Edition)</collection><collection>Hospital Premium Collection</collection><collection>Hospital Premium Collection (Alumni Edition)</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Research Library (Alumni Edition)</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>ProQuest One Community College</collection><collection>ProQuest Central Korea</collection><collection>Health Research Premium Collection</collection><collection>Health Research Premium Collection (Alumni)</collection><collection>ProQuest Central Student</collection><collection>Research Library Prep</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Health & Medical Collection (Alumni Edition)</collection><collection>Medical Database</collection><collection>Research Library</collection><collection>Research Library (Corporate)</collection><collection>Publicly Available Content Database</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central China</collection><collection>ProQuest Central Basic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>International journal of molecular sciences</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zeindlhofer, Veronika</au><au>Hudson, Phillip</au><au>Pálvölgyi, Ádám Márk</au><au>Welsch, Matthias</au><au>Almarashi, Mazin</au><au>Woodcock, H Lee</au><au>Brooks, Bernard</au><au>Bica-Schröder, Katharina</au><au>Schröder, Christian</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether</atitle><jtitle>International journal of molecular sciences</jtitle><addtitle>Int J Mol Sci</addtitle><date>2020-08-28</date><risdate>2020</risdate><volume>21</volume><issue>17</issue><spage>6222</spage><pages>6222-</pages><issn>1422-0067</issn><issn>1661-6596</issn><eissn>1422-0067</eissn><abstract>In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in
-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.</abstract><cop>Switzerland</cop><pub>MDPI AG</pub><pmid>32872113</pmid><doi>10.3390/ijms21176222</doi><orcidid>https://orcid.org/0000-0003-3539-273X</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1422-0067 |
| ispartof | International journal of molecular sciences, 2020-08, Vol.21 (17), p.6222 |
| issn | 1422-0067 1661-6596 1422-0067 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7503397 |
| source | MDPI - Multidisciplinary Digital Publishing Institute; MEDLINE; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| subjects | Anions Biphenyl Compounds - chemistry Catalysis Cations Chirality Complex formation Experiments Free energy Hydrogen Hydrogenation Influence Ionic Liquids - chemistry Ligands Molecular Dynamics Simulation Molecular Structure Polarity Quantum Dots Simulation Solvents Stereoisomerism Water - chemistry |
| title | Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-05T15%3A26%3A09IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Enantiomerization%20of%20Axially%20Chiral%20Biphenyls:%20Polarizable%20MD%20Simulations%20in%20Water%20and%20Butylmethylether&rft.jtitle=International%20journal%20of%20molecular%20sciences&rft.au=Zeindlhofer,%20Veronika&rft.date=2020-08-28&rft.volume=21&rft.issue=17&rft.spage=6222&rft.pages=6222-&rft.issn=1422-0067&rft.eissn=1422-0067&rft_id=info:doi/10.3390/ijms21176222&rft_dat=%3Cproquest_pubme%3E2439494570%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2439494570&rft_id=info:pmid/32872113&rfr_iscdi=true |