{"id":{"repo_id":"siu-theses","oai_identifier":"oai:opensiuc.lib.siu.edu:dissertations-1250"},"canonical_url":"https://search.dev.ndltd.org/etd/siu-theses/oai:opensiuc.lib.siu.edu:dissertations-1250","repository":{"repo_id":"siu-theses","name":"Southern Illinois University","base_url":"https://opensiuc.lib.siu.edu/do/oai/"},"display":{"title":"'Amplifying' the NMR signatures of host-guest interactions and molecular structure using liquid-crystalline matrices and polarization enhancement of nuclear spins","abstract":"Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to investigate the structure and dynamics of host-guest systems. NMR spectroscopy has gained attention because of its high spectral information content for studies of molecules in the solid state and in solution. However, the main weakness of NMR is the inherent low detection sensitivity. Host-guest interactions are weak; therefore these interactions can be particularly difficult to study due to weak spectral response. NMR methods are currently the best solution for measuring these responses with atomic-scale precision. Improving upon these limitations is the main goal of this dissertation research using laser-polarized xenon, liquid crystals, and polarization exchange pulse sequences. The first five chapters review the basics of NMR spectroscopy that is used throughout this dissertation. Chapters one and two concern the fundamental elements of liquid-state and liquid-crystal NMR spectroscopy. The third chapter deals with the properties of organic thermotropic and lyotropic liquid crystals including the ZLI 1132 and PBLG. Chapter four presents the theoretical and experimental aspects of optical pumping laser-polarized xenon and properties of xenon. An overview of the dissertation research is described in chapter six. Chapter seven describes the procedures for synthesizing many of the cryptophanes used in the NMR experiments in this dissertation. The cryptophanes synthesized include cryptophane-A, cryptophane-223, and cryptophane-E as well as the water-soluble derivatives of each. The eighth and ninth chapters investigate the binding kinetics of hydrocarbon and hydrogen gases to cryptophane-111 in organic solutions. Chapter ten illustrates the utility of liquid crystalline-aligned cryptophanes (<italic>bis</italic>- and cryptophane-A) reintroducing dipolar couplings in solution. Chapter eleven describes the exploitation of the reintroduced dipolar coupling of the guest molecule to transfer the abundant <super>1</super>H nuclear spin magnetization to the rare <super>13</super>C spins to enhance NMR detection sensitivity using an adiabatic Hartmann-Hahn cross polarization pulse sequence. Chapter twelve describes cryptophanes of varying cavity size to probe the host-guest dynamic coupling (with chloroform as a guest ligand) aligned in PBLG. Finally, chapter thirteen introduces preliminary xenon @ cryptophanes aligned in liquid crystals to achieve intermolecular polarization transfer.","abstract_html":"Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to investigate the structure and dynamics of host-guest systems. NMR spectroscopy has gained attention because of its high spectral information content for studies of molecules in the solid state and in solution. However, the main weakness of NMR is the inherent low detection sensitivity. Host-guest interactions are weak; therefore these interactions can be particularly difficult to study due to weak spectral response. NMR methods are currently the best solution for measuring these responses with atomic-scale precision. Improving upon these limitations is the main goal of this dissertation research using laser-polarized xenon, liquid crystals, and polarization exchange pulse sequences. The first five chapters review the basics of NMR spectroscopy that is used throughout this dissertation. Chapters one and two concern the fundamental elements of liquid-state and liquid-crystal NMR spectroscopy. The third chapter deals with the properties of organic thermotropic and lyotropic liquid crystals including the ZLI 1132 and PBLG. Chapter four presents the theoretical and experimental aspects of optical pumping laser-polarized xenon and properties of xenon. An overview of the dissertation research is described in chapter six. Chapter seven describes the procedures for synthesizing many of the cryptophanes used in the NMR experiments in this dissertation. The cryptophanes synthesized include cryptophane-A, cryptophane-223, and cryptophane-E as well as the water-soluble derivatives of each. The eighth and ninth chapters investigate the binding kinetics of hydrocarbon and hydrogen gases to cryptophane-111 in organic solutions. Chapter ten illustrates the utility of liquid crystalline-aligned cryptophanes (&lt;italic&gt;bis&lt;/italic&gt;- and cryptophane-A) reintroducing dipolar couplings in solution. Chapter eleven describes the exploitation of the reintroduced dipolar coupling of the guest molecule to transfer the abundant &lt;super&gt;1&lt;/super&gt;H nuclear spin magnetization to the rare &lt;super&gt;13&lt;/super&gt;C spins to enhance NMR detection sensitivity using an adiabatic Hartmann-Hahn cross polarization pulse sequence. Chapter twelve describes cryptophanes of varying cavity size to probe the host-guest dynamic coupling (with chloroform as a guest ligand) aligned in PBLG. Finally, chapter thirteen introduces preliminary xenon @ cryptophanes aligned in liquid crystals to achieve intermolecular polarization transfer.","abstract_has_math":false,"creators":["Chaffee, Kathleen Elizabeth"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"Campus Only Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Goodson, Boyd"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008-01-01T08:00:00Z","date_published":"2008-01-01T08:00:00Z","updated_at":"2026-07-24T04:33:39Z","subjects":["cross polarization","cryptophanes","host-guest chemistry","liquid crystals","NMR spectroscopy","supramolecular"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://opensiuc.lib.siu.edu/dissertations/250","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Goodson, Boyd"]},{"key":"dc:creator","label":"Author","values":["Chaffee, Kathleen Elizabeth"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Campus Only Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["cross polarization","cryptophanes","host-guest chemistry","liquid crystals","NMR spectroscopy","supramolecular"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://opensiuc.lib.siu.edu/dissertations/250"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to investigate the structure and dynamics of host-guest systems. NMR spectroscopy has gained attention because of its high spectral information content for studies of molecules in the solid state and in solution. However, the main weakness of NMR is the inherent low detection sensitivity. Host-guest interactions are weak; therefore these interactions can be particularly difficult to study due to weak spectral response. NMR methods are currently the best solution for measuring these responses with atomic-scale precision. Improving upon these limitations is the main goal of this dissertation research using laser-polarized xenon, liquid crystals, and polarization exchange pulse sequences. The first five chapters review the basics of NMR spectroscopy that is used throughout this dissertation. Chapters one and two concern the fundamental elements of liquid-state and liquid-crystal NMR spectroscopy. The third chapter deals with the properties of organic thermotropic and lyotropic liquid crystals including the ZLI 1132 and PBLG. Chapter four presents the theoretical and experimental aspects of optical pumping laser-polarized xenon and properties of xenon. An overview of the dissertation research is described in chapter six. Chapter seven describes the procedures for synthesizing many of the cryptophanes used in the NMR experiments in this dissertation. The cryptophanes synthesized include cryptophane-A, cryptophane-223, and cryptophane-E as well as the water-soluble derivatives of each. The eighth and ninth chapters investigate the binding kinetics of hydrocarbon and hydrogen gases to cryptophane-111 in organic solutions. Chapter ten illustrates the utility of liquid crystalline-aligned cryptophanes (<italic>bis</italic>- and cryptophane-A) reintroducing dipolar couplings in solution. Chapter eleven describes the exploitation of the reintroduced dipolar coupling of the guest molecule to transfer the abundant <super>1</super>H nuclear spin magnetization to the rare <super>13</super>C spins to enhance NMR detection sensitivity using an adiabatic Hartmann-Hahn cross polarization pulse sequence. Chapter twelve describes cryptophanes of varying cavity size to probe the host-guest dynamic coupling (with chloroform as a guest ligand) aligned in PBLG. Finally, chapter thirteen introduces preliminary xenon @ cryptophanes aligned in liquid crystals to achieve intermolecular polarization transfer."]},{"key":"dc:title","label":"Title","values":["'Amplifying' the NMR signatures of host-guest interactions and molecular structure using liquid-crystalline matrices and polarization enhancement of nuclear spins"]}]}],"canonical_facts":{"dc:contributor":["Goodson, Boyd"],"dc:creator":["Chaffee, Kathleen Elizabeth"],"dc:description.abstract":["Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to investigate the structure and dynamics of host-guest systems. NMR spectroscopy has gained attention because of its high spectral information content for studies of molecules in the solid state and in solution. However, the main weakness of NMR is the inherent low detection sensitivity. Host-guest interactions are weak; therefore these interactions can be particularly difficult to study due to weak spectral response. NMR methods are currently the best solution for measuring these responses with atomic-scale precision. Improving upon these limitations is the main goal of this dissertation research using laser-polarized xenon, liquid crystals, and polarization exchange pulse sequences. The first five chapters review the basics of NMR spectroscopy that is used throughout this dissertation. Chapters one and two concern the fundamental elements of liquid-state and liquid-crystal NMR spectroscopy. The third chapter deals with the properties of organic thermotropic and lyotropic liquid crystals including the ZLI 1132 and PBLG. Chapter four presents the theoretical and experimental aspects of optical pumping laser-polarized xenon and properties of xenon. An overview of the dissertation research is described in chapter six. Chapter seven describes the procedures for synthesizing many of the cryptophanes used in the NMR experiments in this dissertation. The cryptophanes synthesized include cryptophane-A, cryptophane-223, and cryptophane-E as well as the water-soluble derivatives of each. The eighth and ninth chapters investigate the binding kinetics of hydrocarbon and hydrogen gases to cryptophane-111 in organic solutions. Chapter ten illustrates the utility of liquid crystalline-aligned cryptophanes (<italic>bis</italic>- and cryptophane-A) reintroducing dipolar couplings in solution. Chapter eleven describes the exploitation of the reintroduced dipolar coupling of the guest molecule to transfer the abundant <super>1</super>H nuclear spin magnetization to the rare <super>13</super>C spins to enhance NMR detection sensitivity using an adiabatic Hartmann-Hahn cross polarization pulse sequence. Chapter twelve describes cryptophanes of varying cavity size to probe the host-guest dynamic coupling (with chloroform as a guest ligand) aligned in PBLG. Finally, chapter thirteen introduces preliminary xenon @ cryptophanes aligned in liquid crystals to achieve intermolecular polarization transfer."],"dc:identifier":["https://opensiuc.lib.siu.edu/dissertations/250"],"dc:subject":["cross polarization","cryptophanes","host-guest chemistry","liquid crystals","NMR spectroscopy","supramolecular"],"dc:title":["'Amplifying' the NMR signatures of host-guest interactions and molecular structure using liquid-crystalline matrices and polarization enhancement of nuclear spins"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Campus Only Dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T04:33:39Z"}