{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/114057"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/114057","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Enzyme-like catalysis by single chain nanoparticles that use transition metal cofactors","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","abstract_has_math":false,"creators":["Xiong, Thao Mee"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Zimmerman, Steven C","Chan, Jefferson","Fout, Alison R","Moore, Jeffrey S"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-04-29T21:58:21Z","date_published":"2022-04-29T21:58:21Z","updated_at":"2026-07-22T22:24:54Z","subjects":["Chemistry"],"languages":["en","eng"],"rights":["Copyright 2021 Thao Mee Xiong"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/114057","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steven C","Chan, Jefferson","Fout, Alison R","Moore, Jeffrey S"]},{"key":"dc:creator","label":"Author","values":["Xiong, Thao Mee"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-04-29T21:58:21Z","2024-04-29T21:58:46Z","2021-12","2021-11-11"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2021 Thao Mee Xiong"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/114057"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","The student, Thao Mee Xiong, accepted the attached license on 2021-11-08 at 13:26.","The student, Thao Mee Xiong, submitted this Dissertation for approval on 2021-11-08 at 13:34.","This Dissertation was approved for publication on 2021-11-11 at 14:35.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17191 on 2022-04-29 at 16:09:33","Made available in DSpace on 2022-04-29T21:58:21Z (GMT). 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First, we developed a noncovalently cross-linked amphiphilic polymer with covalently attached catalyst that allows substrate binding for higher catalytic activity. Next, I developed a modular approach in which a noncovalently cross-linked SCNP formed from the folding of an amphiphilic polymer selectively binds catalyst “cofactors” and substrates to increase their proximity and resultant catalytic activity. The polymers were synthesized by free radical polymerization and post-polymerization functionalization with amines and characterized by NMR, GPC, and DLS. Fluorescence studies demonstrated the SCNP’s ability to increase the catalytic activity of a Cu-catalyzed alkyne-azide cycloaddition reaction and the Ru-catalyzed cleavage of allylcarbamate groups compared to the free catalysts. A small library of Cu and Ru catalysts with different alkyl chain lengths, functional groups, and charges was used to develop a structure-activity relationship. Ligand binding to the SCNP was identified and characterized by NOESY and STD NMR experiments. These results demonstrate the potential of this plug-and-play strategy for obtaining functional transition metal-SCNPs. We also utilized polymers for ketal-based cross-linked polyamide microcapsules. Under acidic conditions, the microcapsules degrade and release anticorrosion active agents. They were embedded in commercially available coatings to obtain self-protecting coatings."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Enzyme-like catalysis by single chain nanoparticles that use transition metal cofactors"]}]}],"canonical_facts":{"dc:contributor":["Zimmerman, Steven C","Chan, Jefferson","Fout, Alison R","Moore, Jeffrey S"],"dc:creator":["Xiong, Thao Mee"],"dc:date":["2022-04-29T21:58:21Z","2024-04-29T21:58:46Z","2021-12","2021-11-11"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","The student, Thao Mee Xiong, accepted the attached license on 2021-11-08 at 13:26.","The student, Thao Mee Xiong, submitted this Dissertation for approval on 2021-11-08 at 13:34.","This Dissertation was approved for publication on 2021-11-11 at 14:35.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17191 on 2022-04-29 at 16:09:33","Made available in DSpace on 2022-04-29T21:58:21Z (GMT). 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First, we developed a noncovalently cross-linked amphiphilic polymer with covalently attached catalyst that allows substrate binding for higher catalytic activity. Next, I developed a modular approach in which a noncovalently cross-linked SCNP formed from the folding of an amphiphilic polymer selectively binds catalyst “cofactors” and substrates to increase their proximity and resultant catalytic activity. The polymers were synthesized by free radical polymerization and post-polymerization functionalization with amines and characterized by NMR, GPC, and DLS. Fluorescence studies demonstrated the SCNP’s ability to increase the catalytic activity of a Cu-catalyzed alkyne-azide cycloaddition reaction and the Ru-catalyzed cleavage of allylcarbamate groups compared to the free catalysts. A small library of Cu and Ru catalysts with different alkyl chain lengths, functional groups, and charges was used to develop a structure-activity relationship. Ligand binding to the SCNP was identified and characterized by NOESY and STD NMR experiments. These results demonstrate the potential of this plug-and-play strategy for obtaining functional transition metal-SCNPs. We also utilized polymers for ketal-based cross-linked polyamide microcapsules. Under acidic conditions, the microcapsules degrade and release anticorrosion active agents. 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