Chirality Transfer from Chiral Solutes and Surfaces to Achiral Solvents: Insights from Molecular Dynamics Studies

dc.contributor.authorWang, Shihaoen
dc.contributor.departmentChemistryen
dc.contributor.supervisorCann, Natalie M.en
dc.date2009-09-24 00:25:15.174
dc.date.accessioned2009-09-25T15:59:35Z
dc.date.available2009-09-25T15:59:35Z
dc.date.issued2009-09-25T15:59:35Z
dc.degree.grantorQueen's University at Kingstonen
dc.descriptionThesis (Ph.D, Chemistry) -- Queen's University, 2009-09-24 00:25:15.174en
dc.description.abstractChirality can be induced in achiral solvent molecules located near a chiral molecule or surface, but there have been very few systematic studies in this field either experimentally or theoretically. The focus of this thesis is to study the chirality transfer from chiral molecules to achiral solvents. To capture the chirality transfer in solvent molecules, a solvent model that is sensitive to the changes in the environment is needed. We developed new polarizable and flexible models based on an extensive series of ab initio calculations and molecular dynamics simulations. The models include electric field dependence in both the atomic charges and the intramolecular degrees of freedom. Modified equations of motion are required and we have implemented a multiple time step algorithm to solve these equations. Our methodology is general and has been applied to ethanol as a test. For other solvents in our simulations, such as 2-propanol, limited models are used. The chirality transfer from chiral solutes to achiral solvents and its dependence on the solute and solvent characteristics are then explored using the new polarizable models in molecular dynamics simulations. The chirality induced in the solvent is assessed based on a series of related chirality indexes originally proposed by Osipov[Osipov et al., Mol. Phys.84, 1193(1995)]. Two solvents are considered: Ethanol and benzyl alcohol. The solvation of three chiral solutes is examined: Styrene oxide, acenaphthenol, and n-(1-(4-bromophenyl)ethyl)pivalamide (PAMD). All three solutes have the possibility of hydrogen-bonding with the solvent, the last two may also form π-π interactions, and the last has multiple hydrogen bonding sites. The chirality transfer from chiral surfaces to achiral solvents is also explored. Emphasis is placed on the extent of this chirality transfer and its dependence on the surface and solvent characteristics is explored. Three surfaces employed in chiral chromatography are examined: The Whelk-O1 interface; a phenylglycine-derived chiral stationary phase (CSP); and a leucine-derived CSP. The solvents consist of ethanol, a binary n-hexane/ethanol solvent, 2-propanol, and a binary n-hexane/2-propanol solvent. Molecular dynamics simulations of the solvated chiral interfaces form the basis of the analysis and position dependent chirality indexes are analyzed in detail.en
dc.description.degreePhDen
dc.format.extent18308886 bytes
dc.format.mimetypeapplication/pdf
dc.identifier.urihttp://hdl.handle.net/1974/5202
dc.language.isoengen
dc.relation.ispartofseriesCanadian thesesen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectcomputational chemistryen
dc.subjectmolecular dynamicsen
dc.subjectchirality transferen
dc.titleChirality Transfer from Chiral Solutes and Surfaces to Achiral Solvents: Insights from Molecular Dynamics Studiesen
dc.typethesisen
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