{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22478"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22478","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Electrogenerated chemiluminescence of isoluminol and acridinium esters in flow injection analysis and HPLC","abstract":"Electrogenerated chemiluminescence (ECL) is the process in which electrochemically generated reactants undergo high energy electron transfer reactions in solution to generate excited state molecules which relax to the ground state with emission of light. Such reactions offer several advantages in analysis. Specifically, in situ reagent generation eliminates band-broadening and dilution effects associated with the solution addition of reagents. In addition precise control over the spatial and temporal characteristics of the light emission is gained. Motivated by these advantages, this research focused on the study and application of the electrogenerated chemiluminescence reactions of isoluminol and acridinium esters.","abstract_html":"Electrogenerated chemiluminescence (ECL) is the process in which electrochemically generated reactants undergo high energy electron transfer reactions in solution to generate excited state molecules which relax to the ground state with emission of light. Such reactions offer several advantages in analysis. Specifically, in situ reagent generation eliminates band-broadening and dilution effects associated with the solution addition of reagents. In addition precise control over the spatial and temporal characteristics of the light emission is gained. Motivated by these advantages, this research focused on the study and application of the electrogenerated chemiluminescence reactions of isoluminol and acridinium esters.","abstract_has_math":false,"creators":["Littig, Janet Holmstrom"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Nieman, Timothy A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:41:09Z","date_published":"2011-05-07T13:41:09Z","updated_at":"2026-07-22T22:25:20Z","subjects":["Chemistry, Analytical"],"languages":["eng"],"rights":["Copyright 1992 Littig, Janet Holmstrom"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236522","(UMI)AAI9236522"],"render_values":[{"text":"AAI9236522","href":null,"code":true},{"text":"(UMI)AAI9236522","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22478","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Nieman, Timothy A."]},{"key":"dc:creator","label":"Author","values":["Littig, Janet Holmstrom"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:41:09Z","10000-01-01","1992"]},{"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"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1992 Littig, Janet Holmstrom"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236522","(UMI)AAI9236522","http://hdl.handle.net/2142/22478"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Electrogenerated chemiluminescence (ECL) is the process in which electrochemically generated reactants undergo high energy electron transfer reactions in solution to generate excited state molecules which relax to the ground state with emission of light. Such reactions offer several advantages in analysis. Specifically, in situ reagent generation eliminates band-broadening and dilution effects associated with the solution addition of reagents. In addition precise control over the spatial and temporal characteristics of the light emission is gained. Motivated by these advantages, this research focused on the study and application of the electrogenerated chemiluminescence reactions of isoluminol and acridinium esters.","Initial research involved the ECL reaction of an isoluminol derivative, 4-isothiocyanatophthalhydrazide (ILITC). The derivative was synthesized and characterized prior to use as a label for amino acid determination. In analysis, chromatographic separation of ILITC-amino acids preceded the ECL detection. A drastic reduction in ECL efficiency was observed upon coupling of ILITC to the amino acid analytes. Experiments suggested that although an ILITC-amino acid coupling reaction occurs, the resultant product has lost CL activity. Additional studies illustrated a correlation between CL activity and the conditions used to couple ILITC to the analyte. In spite of difficulties associated with loss of CL activity, the ECL determination of ILITC-amino acids (1 nmol) and the feasibility of on-line analyte derivatization were demonstrated.","The ECL reaction of acridinium esters was studied and shown to proceed via the electrochemical generation of hydrogen peroxide (a reagent necessary for the CL reaction). In further fundamental studies of the acridinium ester decomposition reactions, kinetic parameters associated with this decay were determined and applied in a model for pH optimization. The use of ECL for the determination of acridinium ester-labeled species was demonstrated via the successful quantitation (to 50 fmol) of lysine labeled with a hydroxysuccinimide acridinium ester. Instrumental configurations for use of ECL detection in immunoassay were validated; however, loss of ECL signal in the presence of BSA and human TSH antibodies hindered application of acridinium ester ECL detection to model immunoassay reactions.","Made available in DSpace on 2011-05-07T13:41:09Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236522.pdf: 7729672 bytes, checksum: 68697970e51bc857a3135db9aec49148 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:57:53Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:11-05:00 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":["Electrogenerated chemiluminescence of isoluminol and acridinium esters in flow injection analysis and HPLC"]}]}],"canonical_facts":{"dc:contributor":["Nieman, Timothy A."],"dc:creator":["Littig, Janet Holmstrom"],"dc:date":["2011-05-07T13:41:09Z","10000-01-01","1992"],"dc:description":["Electrogenerated chemiluminescence (ECL) is the process in which electrochemically generated reactants undergo high energy electron transfer reactions in solution to generate excited state molecules which relax to the ground state with emission of light. Such reactions offer several advantages in analysis. Specifically, in situ reagent generation eliminates band-broadening and dilution effects associated with the solution addition of reagents. In addition precise control over the spatial and temporal characteristics of the light emission is gained. Motivated by these advantages, this research focused on the study and application of the electrogenerated chemiluminescence reactions of isoluminol and acridinium esters.","Initial research involved the ECL reaction of an isoluminol derivative, 4-isothiocyanatophthalhydrazide (ILITC). The derivative was synthesized and characterized prior to use as a label for amino acid determination. In analysis, chromatographic separation of ILITC-amino acids preceded the ECL detection. A drastic reduction in ECL efficiency was observed upon coupling of ILITC to the amino acid analytes. Experiments suggested that although an ILITC-amino acid coupling reaction occurs, the resultant product has lost CL activity. Additional studies illustrated a correlation between CL activity and the conditions used to couple ILITC to the analyte. In spite of difficulties associated with loss of CL activity, the ECL determination of ILITC-amino acids (1 nmol) and the feasibility of on-line analyte derivatization were demonstrated.","The ECL reaction of acridinium esters was studied and shown to proceed via the electrochemical generation of hydrogen peroxide (a reagent necessary for the CL reaction). In further fundamental studies of the acridinium ester decomposition reactions, kinetic parameters associated with this decay were determined and applied in a model for pH optimization. The use of ECL for the determination of acridinium ester-labeled species was demonstrated via the successful quantitation (to 50 fmol) of lysine labeled with a hydroxysuccinimide acridinium ester. Instrumental configurations for use of ECL detection in immunoassay were validated; however, loss of ECL signal in the presence of BSA and human TSH antibodies hindered application of acridinium ester ECL detection to model immunoassay reactions.","Made available in DSpace on 2011-05-07T13:41:09Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236522.pdf: 7729672 bytes, checksum: 68697970e51bc857a3135db9aec49148 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:57:53Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:11-05:00 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":["AAI9236522","(UMI)AAI9236522","http://hdl.handle.net/2142/22478"],"dc:language":["eng"],"dc:rights":["Copyright 1992 Littig, Janet Holmstrom"],"dc:subject":["Chemistry, Analytical"],"dc:title":["Electrogenerated chemiluminescence of isoluminol and acridinium esters in flow injection analysis and HPLC"],"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":"2026-07-22T22:25:20Z"}