{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21823"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21823","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"High-pressure NMR studies of isomerizational exchange rates in liquids","abstract":"The effect of pressure on exchange rates, of varied systems in condensed media, were observed and typically related to stochastic theoretical models of exchange processes. Rates of exchange were determined using, the total line shape analysis method in chapters two and three, peak areas and saturation transfer in chapter four, and rotating frame spin lattice relaxation measurements in chapter five. Chapter six details some properties of high pressure high resolution NMR probes. Increasing solvent pressure on N,N-dimethyltrichloroacetamide (chapter two) was shown to decrease the rate of rotation about the amide bond. In order to fit the data favorably the Grote-Hynes model, which takes into account the frequency dependence of the friction, was applied. The opposite effect was seen for the rotation of coordinated ethylene in $\\pi$-cyclopentadienyldiethylenerhodium (chapter three). In this case the data was fit best using the model developed by Skinner and Wolynes. The effect of pressure on the denaturation of lysozyme was determined using the peak areas of the histidine-15$\\sp{1\\varepsilon}$ resonance in both the native and denatured forms. The data indicated the possibility of a second major denatured structure under these conditions, while thermal denaturation techniques indicated only one major denatured structure. Individual rate constants of folding and unfolding were also determined using saturation transfer experiments on this same resonance. The effect of pressure on the conformational isomerization of cyclohexane in CS2 was studied using rotating frame spin lattice relaxation techniques (chapter five). By using this method rate constants were obtained which were two orders of magnitude larger than those which could be obtained by the line shaper analysis technique. Increasing solvent pressure increased the isomerization rate by combining this data with previously collected data, it was determined that the barrier to isomerization is pressure independent, and that eyclohexane falls in the inertial regime of the Kramers' model.","abstract_html":"The effect of pressure on exchange rates, of varied systems in condensed media, were observed and typically related to stochastic theoretical models of exchange processes. Rates of exchange were determined using, the total line shape analysis method in chapters two and three, peak areas and saturation transfer in chapter four, and rotating frame spin lattice relaxation measurements in chapter five. Chapter six details some properties of high pressure high resolution NMR probes. Increasing solvent pressure on N,N-dimethyltrichloroacetamide (chapter two) was shown to decrease the rate of rotation about the amide bond. In order to fit the data favorably the Grote-Hynes model, which takes into account the frequency dependence of the friction, was applied. The opposite effect was seen for the rotation of coordinated ethylene in <span class=\"etd-inline-math\">&pi;</span>-cyclopentadienyldiethylenerhodium (chapter three). In this case the data was fit best using the model developed by Skinner and Wolynes. The effect of pressure on the denaturation of lysozyme was determined using the peak areas of the histidine-15$\\sp{1\\varepsilon}$ resonance in both the native and denatured forms. The data indicated the possibility of a second major denatured structure under these conditions, while thermal denaturation techniques indicated only one major denatured structure. Individual rate constants of folding and unfolding were also determined using saturation transfer experiments on this same resonance. The effect of pressure on the conformational isomerization of cyclohexane in CS2 was studied using rotating frame spin lattice relaxation techniques (chapter five). By using this method rate constants were obtained which were two orders of magnitude larger than those which could be obtained by the line shaper analysis technique. Increasing solvent pressure increased the isomerization rate by combining this data with previously collected data, it was determined that the barrier to isomerization is pressure independent, and that eyclohexane falls in the inertial regime of the Kramers&#x27; model.","abstract_has_math":true,"creators":["Campbell, Douglas Michael"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Jonas, Jiri"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":null,"date_issued":"10000-01-01","date_published":"10000-01-01","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Physical"],"languages":["eng"],"rights":["Copyright 1991 Campbell, Douglas Michael"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210756","(UMI)AAI9210756"],"render_values":[{"text":"AAI9210756","href":null,"code":true},{"text":"(UMI)AAI9210756","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21823","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Jonas, Jiri"]},{"key":"dc:creator","label":"Author","values":["Campbell, Douglas Michael"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["10000-01-01","2011-05-07T13:20:13Z","1991"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Physical"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Campbell, Douglas Michael"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210756","(UMI)AAI9210756","http://hdl.handle.net/2142/21823"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The effect of pressure on exchange rates, of varied systems in condensed media, were observed and typically related to stochastic theoretical models of exchange processes. Rates of exchange were determined using, the total line shape analysis method in chapters two and three, peak areas and saturation transfer in chapter four, and rotating frame spin lattice relaxation measurements in chapter five. Chapter six details some properties of high pressure high resolution NMR probes. Increasing solvent pressure on N,N-dimethyltrichloroacetamide (chapter two) was shown to decrease the rate of rotation about the amide bond. In order to fit the data favorably the Grote-Hynes model, which takes into account the frequency dependence of the friction, was applied. The opposite effect was seen for the rotation of coordinated ethylene in $\\pi$-cyclopentadienyldiethylenerhodium (chapter three). In this case the data was fit best using the model developed by Skinner and Wolynes. The effect of pressure on the denaturation of lysozyme was determined using the peak areas of the histidine-15$\\sp{1\\varepsilon}$ resonance in both the native and denatured forms. The data indicated the possibility of a second major denatured structure under these conditions, while thermal denaturation techniques indicated only one major denatured structure. Individual rate constants of folding and unfolding were also determined using saturation transfer experiments on this same resonance. The effect of pressure on the conformational isomerization of cyclohexane in CS2 was studied using rotating frame spin lattice relaxation techniques (chapter five). By using this method rate constants were obtained which were two orders of magnitude larger than those which could be obtained by the line shaper analysis technique. Increasing solvent pressure increased the isomerization rate by combining this data with previously collected data, it was determined that the barrier to isomerization is pressure independent, and that eyclohexane falls in the inertial regime of the Kramers' model.","Made available in DSpace on 2011-05-07T13:20:13Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210756.pdf: 4225584 bytes, checksum: d67bbbea8af326525b342424fadb817b (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:26Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:43-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["High-pressure NMR studies of isomerizational exchange rates in liquids"]}]}],"canonical_facts":{"dc:contributor":["Jonas, Jiri"],"dc:creator":["Campbell, Douglas Michael"],"dc:date":["10000-01-01","2011-05-07T13:20:13Z","1991"],"dc:description":["The effect of pressure on exchange rates, of varied systems in condensed media, were observed and typically related to stochastic theoretical models of exchange processes. Rates of exchange were determined using, the total line shape analysis method in chapters two and three, peak areas and saturation transfer in chapter four, and rotating frame spin lattice relaxation measurements in chapter five. Chapter six details some properties of high pressure high resolution NMR probes. Increasing solvent pressure on N,N-dimethyltrichloroacetamide (chapter two) was shown to decrease the rate of rotation about the amide bond. In order to fit the data favorably the Grote-Hynes model, which takes into account the frequency dependence of the friction, was applied. The opposite effect was seen for the rotation of coordinated ethylene in $\\pi$-cyclopentadienyldiethylenerhodium (chapter three). In this case the data was fit best using the model developed by Skinner and Wolynes. The effect of pressure on the denaturation of lysozyme was determined using the peak areas of the histidine-15$\\sp{1\\varepsilon}$ resonance in both the native and denatured forms. The data indicated the possibility of a second major denatured structure under these conditions, while thermal denaturation techniques indicated only one major denatured structure. Individual rate constants of folding and unfolding were also determined using saturation transfer experiments on this same resonance. The effect of pressure on the conformational isomerization of cyclohexane in CS2 was studied using rotating frame spin lattice relaxation techniques (chapter five). By using this method rate constants were obtained which were two orders of magnitude larger than those which could be obtained by the line shaper analysis technique. Increasing solvent pressure increased the isomerization rate by combining this data with previously collected data, it was determined that the barrier to isomerization is pressure independent, and that eyclohexane falls in the inertial regime of the Kramers' model.","Made available in DSpace on 2011-05-07T13:20:13Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210756.pdf: 4225584 bytes, checksum: d67bbbea8af326525b342424fadb817b (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:26Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:43-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9210756","(UMI)AAI9210756","http://hdl.handle.net/2142/21823"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Campbell, Douglas Michael"],"dc:subject":["Chemistry, Physical"],"dc:title":["High-pressure NMR studies of isomerizational exchange rates in liquids"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:18Z"}