{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/122190"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/122190","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of acid-amplifying polymers","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2025-12-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2025-12-01","abstract_has_math":false,"creators":["Aguilar-Romero, Jazmin Emilia"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Zimmerman, Steve C","Leal, Cecilia","Guironnet, Damien","Han, Hee-Sun"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023-12","date_published":"2023-12","updated_at":"2026-07-22T22:25:00Z","subjects":["Degradable Polymers","Drug Delivery"],"languages":["en","eng"],"rights":["Copyright 2023 Jazmin Aguilar-Romero"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/122190","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steve C","Leal, Cecilia","Guironnet, Damien","Han, Hee-Sun"]},{"key":"dc:creator","label":"Author","values":["Aguilar-Romero, Jazmin Emilia"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2023-12","2023-08-03"]},{"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":["Degradable Polymers","Drug Delivery"]}]},{"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 2023 Jazmin Aguilar-Romero"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/122190"]}]},{"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 2025-12-01","The student, Jazmin Aguilar-Romero, accepted the attached license on 2023-07-20 at 01:10.","The student, Jazmin Aguilar-Romero, submitted this Dissertation for approval on 2023-07-20 at 01:15.","This Dissertation was approved for publication on 2023-08-03 at 10:33.","DSpace SAF Submission Ingestion Package generated from Vireo submission #19745 on 2024-03-01 at 13:47:34","Polymeric drug delivery systems have been explored extensively as vehicles to selectively transport small molecules, proteins, and other cargo. Although drug delivery systems have demonstrated advantages, such as decreased drug toxicity and stabilization of sensitive cargo, most polymers still face the issue of endosomal entrapment. Not escaping the endosome prevents drug delivery vehicles from releasing their contents into target sites. Various strategies have been developed to probe the mechanism of and promote endosomal escape with limited success. In this dissertation, I report the design of acid-amplifying small molecules and polymers for use in drug delivery to promote endosomal escape. Acid amplifiers were primarily utilized for applications in photolithography and photoresists. Although their properties can benefit pH-responsive drug delivery systems, acid amplifiers have remained largely untapped for biological applications. Additionally, most previously reported acid amplifiers require extensive heating for activation and produce acutely toxic byproducts. Chapter 2 investigates the design, synthesis, and studies of a novel acid amplifier that can be degraded at room temperature for use in drug delivery. The acid amplifier contains an acetal group that is hydrolyzed under acidic conditions to enable a quinone methide elimination that produces HCl. The degradation of the acid amplifier was monitored with 1H NMR and pH studies, which demonstrated rapid exponential conversion of the acid amplifier and an exponential drop in pH in physiologically relevant conditions. To incorporate the acid amplifier into polymers, RAFT and ROMP polymers were synthesized with side chains containing the acid amplifier. Chapter 3 describes the synthesis of these polymers and further studies. A ROMP copolymer with acid amplifier and a hydrophilic copolymer demonstrated an exponential drop in pH in fully aqueous acidic conditions at room temperature, improving upon a previously developed acid-amplifying polymers that required heating. In Chapter 4, I change topics to focus on the application of acid amplifiers to form degradable ROMP polymers for robust materials. A cyclooctene iodoacetal was synthesized and successfully polymerized via ROMP to form linear polyolefins. The acetals in the linear polymer fully hydrolyzed within 2 h in mixed aqueous organic solvent at 90 °C. Additionally, the cyclooctene iodocetal monomer was successfully copolymerized with cyclooctadiene, supporting that the acid amplifying monomer could be used to form a range of polymers."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Development of acid-amplifying polymers"]}]}],"canonical_facts":{"dc:contributor":["Zimmerman, Steve C","Leal, Cecilia","Guironnet, Damien","Han, Hee-Sun"],"dc:creator":["Aguilar-Romero, Jazmin Emilia"],"dc:date":["2023-12","2023-08-03"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2025-12-01","The student, Jazmin Aguilar-Romero, accepted the attached license on 2023-07-20 at 01:10.","The student, Jazmin Aguilar-Romero, submitted this Dissertation for approval on 2023-07-20 at 01:15.","This Dissertation was approved for publication on 2023-08-03 at 10:33.","DSpace SAF Submission Ingestion Package generated from Vireo submission #19745 on 2024-03-01 at 13:47:34","Polymeric drug delivery systems have been explored extensively as vehicles to selectively transport small molecules, proteins, and other cargo. Although drug delivery systems have demonstrated advantages, such as decreased drug toxicity and stabilization of sensitive cargo, most polymers still face the issue of endosomal entrapment. Not escaping the endosome prevents drug delivery vehicles from releasing their contents into target sites. Various strategies have been developed to probe the mechanism of and promote endosomal escape with limited success. In this dissertation, I report the design of acid-amplifying small molecules and polymers for use in drug delivery to promote endosomal escape. Acid amplifiers were primarily utilized for applications in photolithography and photoresists. Although their properties can benefit pH-responsive drug delivery systems, acid amplifiers have remained largely untapped for biological applications. Additionally, most previously reported acid amplifiers require extensive heating for activation and produce acutely toxic byproducts. Chapter 2 investigates the design, synthesis, and studies of a novel acid amplifier that can be degraded at room temperature for use in drug delivery. The acid amplifier contains an acetal group that is hydrolyzed under acidic conditions to enable a quinone methide elimination that produces HCl. The degradation of the acid amplifier was monitored with 1H NMR and pH studies, which demonstrated rapid exponential conversion of the acid amplifier and an exponential drop in pH in physiologically relevant conditions. To incorporate the acid amplifier into polymers, RAFT and ROMP polymers were synthesized with side chains containing the acid amplifier. Chapter 3 describes the synthesis of these polymers and further studies. A ROMP copolymer with acid amplifier and a hydrophilic copolymer demonstrated an exponential drop in pH in fully aqueous acidic conditions at room temperature, improving upon a previously developed acid-amplifying polymers that required heating. In Chapter 4, I change topics to focus on the application of acid amplifiers to form degradable ROMP polymers for robust materials. A cyclooctene iodoacetal was synthesized and successfully polymerized via ROMP to form linear polyolefins. The acetals in the linear polymer fully hydrolyzed within 2 h in mixed aqueous organic solvent at 90 °C. Additionally, the cyclooctene iodocetal monomer was successfully copolymerized with cyclooctadiene, supporting that the acid amplifying monomer could be used to form a range of polymers."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/122190"],"dc:language":["en","eng"],"dc:rights":["Copyright 2023 Jazmin Aguilar-Romero"],"dc:subject":["Degradable Polymers","Drug Delivery"],"dc:title":["Development of acid-amplifying polymers"],"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":"2026-07-22T22:25:00Z"}