{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84366"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84366","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Investigation of Non-Linear Chromatographic Retention Behavior for Two Homologous Series of Bis Analytes","abstract":"Curved plots of retention factor vs. number of methylenes have been obtained for members of two homologous series of diamides. With alcohol modified mobile phases, plots of normalized HPLC retention factor vs. number of methylenes show maxima for retention for members of the homologous series of bis naproxen amides and bis 3,5-dinitrobenzoyl amides. The maximum retention and amount of curvature for each plot is column-independent, suggesting an analyte phenomena is being observed. Maximum retention for the bis 3,5-DNB amides is found for the homologues with 5-6 methylene groups in all solvents investigated. In contrast, maximum retention for the bis naproxen amide homologues with 3-8 methylene groups is correlated with the polarity of the mobile phase. Mono analytes of these two series do not show the same retention behavior but show normal chromatographic retention. The experimental results are interpreted in light of the analyte-specific equilibria associated with the folding of the bis derivatives. Mono analytes have no such competing mechanism available to them so normal retention behavior is both expected and found. In non-alcohol modified mobile phases, normal chromatographic retention behavior is found for both the bis- and mono-functional analytes of both series. This interesting experimental observation implicates a much more complicated phenomenon is occurring than simple folding of the bis analytes. Solvophobic effects may induce folding in homologues which otherwise find folding thermodynamically unfavorable increasing the complexity of the retention data.","abstract_html":"Curved plots of retention factor vs. number of methylenes have been obtained for members of two homologous series of diamides. With alcohol modified mobile phases, plots of normalized HPLC retention factor vs. number of methylenes show maxima for retention for members of the homologous series of bis naproxen amides and bis 3,5-dinitrobenzoyl amides. The maximum retention and amount of curvature for each plot is column-independent, suggesting an analyte phenomena is being observed. Maximum retention for the bis 3,5-DNB amides is found for the homologues with 5-6 methylene groups in all solvents investigated. In contrast, maximum retention for the bis naproxen amide homologues with 3-8 methylene groups is correlated with the polarity of the mobile phase. Mono analytes of these two series do not show the same retention behavior but show normal chromatographic retention. The experimental results are interpreted in light of the analyte-specific equilibria associated with the folding of the bis derivatives. Mono analytes have no such competing mechanism available to them so normal retention behavior is both expected and found. In non-alcohol modified mobile phases, normal chromatographic retention behavior is found for both the bis- and mono-functional analytes of both series. This interesting experimental observation implicates a much more complicated phenomenon is occurring than simple folding of the bis analytes. Solvophobic effects may induce folding in homologues which otherwise find folding thermodynamically unfavorable increasing the complexity of the retention data.","abstract_has_math":false,"creators":["Kelly, Kevin"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Pirkle, William H."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:08Z","date_published":"2015-09-25T22:14:08Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Analytical"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9737155"],"render_values":[{"text":"(MiAaPQ)AAI9737155","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84366","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Pirkle, William H."]},{"key":"dc:creator","label":"Author","values":["Kelly, Kevin"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:08Z","10000-01-01","1997"]},{"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, Analytical"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84366","(MiAaPQ)AAI9737155"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Curved plots of retention factor vs. number of methylenes have been obtained for members of two homologous series of diamides. With alcohol modified mobile phases, plots of normalized HPLC retention factor vs. number of methylenes show maxima for retention for members of the homologous series of bis naproxen amides and bis 3,5-dinitrobenzoyl amides. The maximum retention and amount of curvature for each plot is column-independent, suggesting an analyte phenomena is being observed. Maximum retention for the bis 3,5-DNB amides is found for the homologues with 5-6 methylene groups in all solvents investigated. In contrast, maximum retention for the bis naproxen amide homologues with 3-8 methylene groups is correlated with the polarity of the mobile phase. Mono analytes of these two series do not show the same retention behavior but show normal chromatographic retention. The experimental results are interpreted in light of the analyte-specific equilibria associated with the folding of the bis derivatives. Mono analytes have no such competing mechanism available to them so normal retention behavior is both expected and found. In non-alcohol modified mobile phases, normal chromatographic retention behavior is found for both the bis- and mono-functional analytes of both series. This interesting experimental observation implicates a much more complicated phenomenon is occurring than simple folding of the bis analytes. Solvophobic effects may induce folding in homologues which otherwise find folding thermodynamically unfavorable increasing the complexity of the retention data.","Made available in DSpace on 2015-09-25T22:14:08Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9737155.pdf: 4077969 bytes, checksum: 44b715c19a6eaccc27b85781e0a208cc (MD5) Previous issue date: 1997","Embargo set by: Seth Robbins for item 85647 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","82 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1997."]},{"key":"dc:title","label":"Title","values":["Investigation of Non-Linear Chromatographic Retention Behavior for Two Homologous Series of Bis Analytes"]}]}],"canonical_facts":{"dc:contributor":["Pirkle, William H."],"dc:creator":["Kelly, Kevin"],"dc:date":["2015-09-25T22:14:08Z","10000-01-01","1997"],"dc:description":["Curved plots of retention factor vs. number of methylenes have been obtained for members of two homologous series of diamides. With alcohol modified mobile phases, plots of normalized HPLC retention factor vs. number of methylenes show maxima for retention for members of the homologous series of bis naproxen amides and bis 3,5-dinitrobenzoyl amides. The maximum retention and amount of curvature for each plot is column-independent, suggesting an analyte phenomena is being observed. Maximum retention for the bis 3,5-DNB amides is found for the homologues with 5-6 methylene groups in all solvents investigated. In contrast, maximum retention for the bis naproxen amide homologues with 3-8 methylene groups is correlated with the polarity of the mobile phase. Mono analytes of these two series do not show the same retention behavior but show normal chromatographic retention. The experimental results are interpreted in light of the analyte-specific equilibria associated with the folding of the bis derivatives. Mono analytes have no such competing mechanism available to them so normal retention behavior is both expected and found. In non-alcohol modified mobile phases, normal chromatographic retention behavior is found for both the bis- and mono-functional analytes of both series. This interesting experimental observation implicates a much more complicated phenomenon is occurring than simple folding of the bis analytes. Solvophobic effects may induce folding in homologues which otherwise find folding thermodynamically unfavorable increasing the complexity of the retention data.","Made available in DSpace on 2015-09-25T22:14:08Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9737155.pdf: 4077969 bytes, checksum: 44b715c19a6eaccc27b85781e0a208cc (MD5) Previous issue date: 1997","Embargo set by: Seth Robbins for item 85647 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","82 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1997."],"dc:identifier":["http://hdl.handle.net/2142/84366","(MiAaPQ)AAI9737155"],"dc:language":["eng"],"dc:subject":["Chemistry, Analytical"],"dc:title":["Investigation of Non-Linear Chromatographic Retention Behavior for Two Homologous Series of Bis Analytes"],"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":"2026-07-22T22:26:23Z"}