{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/90531"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/90531","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Responsive molecules: 1. Redox-responsive quadruple hydrogen bonding unit 2. Crosslinked dendronized polyols for brighter and more stable dyes 3. Photoresponsive proton gate for cross-membrane transfer","abstract":"This thesis reports studies in three separate contexts that show how responsiveness can be introduced or tuned in different molecular systems thus providing desirable control over material properties. In Chapter 2, we designed a new quadruple hydrogen-bonding module (eDAN). The binding affinity of this molecule towards its partner (DeUG) was specifically controlled by redox reactions without affecting other hydrogen-bonding recognition pairs in the system. This orthogonal switch was successfully applied to tune supramolecular polymer blends (Scheme 0.1). In Chapter 3, we developed a scalable and general synthetic approach to solubilize and stabilize different classes of organic fluorophores, which may be useful in bioimaging. The crosslinked dendronized polymeric structure obtained by ring opening metathesis polymerization and intra-molecular ring close metathesis reduced the responsiveness of dyes toward reactive excited species (Scheme 0.2). In Chapter 4, we designed the first synthetic photoresponsive proton gate incorporated in a lipid layer. The new proton carrier features a boronic acid head-group for proton transfer, a stiff stilbene body for photoresponsiveness, and an alkyl tail for lipid incorporation. The light-induced cross-membrane proton transfer was quantified by the activity of an O2 reduction catalyst buried under the lipid layer by electrochemistry. This molecular switch mimics the natural system allowing precise control of proton relocation without perturbing the proton thermodynamics (Scheme 0.3).","abstract_html":"This thesis reports studies in three separate contexts that show how responsiveness can be introduced or tuned in different molecular systems thus providing desirable control over material properties. In Chapter 2, we designed a new quadruple hydrogen-bonding module (eDAN). The binding affinity of this molecule towards its partner (DeUG) was specifically controlled by redox reactions without affecting other hydrogen-bonding recognition pairs in the system. This orthogonal switch was successfully applied to tune supramolecular polymer blends (Scheme 0.1). In Chapter 3, we developed a scalable and general synthetic approach to solubilize and stabilize different classes of organic fluorophores, which may be useful in bioimaging. The crosslinked dendronized polymeric structure obtained by ring opening metathesis polymerization and intra-molecular ring close metathesis reduced the responsiveness of dyes toward reactive excited species (Scheme 0.2). In Chapter 4, we designed the first synthetic photoresponsive proton gate incorporated in a lipid layer. The new proton carrier features a boronic acid head-group for proton transfer, a stiff stilbene body for photoresponsiveness, and an alkyl tail for lipid incorporation. The light-induced cross-membrane proton transfer was quantified by the activity of an O2 reduction catalyst buried under the lipid layer by electrochemistry. This molecular switch mimics the natural system allowing precise control of proton relocation without perturbing the proton thermodynamics (Scheme 0.3).","abstract_has_math":false,"creators":["Li, Ying"],"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.","Gewirth, Andrew A.","van der Donk, Wilfred A.","Murphy, Catherine J."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-07-07T19:53:43Z","date_published":"2016-07-07T19:53:43Z","updated_at":"2026-07-22T22:26:32Z","subjects":["stimuli-responsive"],"languages":["en"],"rights":["Copyright 2016 Ying Li"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/90531","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steven C.","Gewirth, Andrew A.","van der Donk, Wilfred A.","Murphy, Catherine J."]},{"key":"dc:creator","label":"Author","values":["Li, Ying"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2016-07-07T19:53:43Z","2016-04-14","2016-05"]},{"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":["stimuli-responsive"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2016 Ying Li"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/90531"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This thesis reports studies in three separate contexts that show how responsiveness can be introduced or tuned in different molecular systems thus providing desirable control over material properties. In Chapter 2, we designed a new quadruple hydrogen-bonding module (eDAN). The binding affinity of this molecule towards its partner (DeUG) was specifically controlled by redox reactions without affecting other hydrogen-bonding recognition pairs in the system. This orthogonal switch was successfully applied to tune supramolecular polymer blends (Scheme 0.1). In Chapter 3, we developed a scalable and general synthetic approach to solubilize and stabilize different classes of organic fluorophores, which may be useful in bioimaging. The crosslinked dendronized polymeric structure obtained by ring opening metathesis polymerization and intra-molecular ring close metathesis reduced the responsiveness of dyes toward reactive excited species (Scheme 0.2). In Chapter 4, we designed the first synthetic photoresponsive proton gate incorporated in a lipid layer. The new proton carrier features a boronic acid head-group for proton transfer, a stiff stilbene body for photoresponsiveness, and an alkyl tail for lipid incorporation. The light-induced cross-membrane proton transfer was quantified by the activity of an O2 reduction catalyst buried under the lipid layer by electrochemistry. This molecular switch mimics the natural system allowing precise control of proton relocation without perturbing the proton thermodynamics (Scheme 0.3).","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2016-07-07 without embargo terms","The student, Ying Li, accepted the attached license on 2016-04-13 at 13:09.","The student, Ying Li, submitted this Dissertation for approval on 2016-04-13 at 13:25.","This Dissertation was approved for publication on 2016-04-14 at 08:53.","DSpace SAF Submission Ingestion Package generated from Vireo submission #9205 on 2016-07-07 at 13:30:01","Made available in DSpace on 2016-07-07T19:53:43Z (GMT). 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Photoresponsive proton gate for cross-membrane transfer"]}]}],"canonical_facts":{"dc:contributor":["Zimmerman, Steven C.","Gewirth, Andrew A.","van der Donk, Wilfred A.","Murphy, Catherine J."],"dc:creator":["Li, Ying"],"dc:date":["2016-07-07T19:53:43Z","2016-04-14","2016-05"],"dc:description":["This thesis reports studies in three separate contexts that show how responsiveness can be introduced or tuned in different molecular systems thus providing desirable control over material properties. In Chapter 2, we designed a new quadruple hydrogen-bonding module (eDAN). The binding affinity of this molecule towards its partner (DeUG) was specifically controlled by redox reactions without affecting other hydrogen-bonding recognition pairs in the system. This orthogonal switch was successfully applied to tune supramolecular polymer blends (Scheme 0.1). In Chapter 3, we developed a scalable and general synthetic approach to solubilize and stabilize different classes of organic fluorophores, which may be useful in bioimaging. The crosslinked dendronized polymeric structure obtained by ring opening metathesis polymerization and intra-molecular ring close metathesis reduced the responsiveness of dyes toward reactive excited species (Scheme 0.2). In Chapter 4, we designed the first synthetic photoresponsive proton gate incorporated in a lipid layer. The new proton carrier features a boronic acid head-group for proton transfer, a stiff stilbene body for photoresponsiveness, and an alkyl tail for lipid incorporation. The light-induced cross-membrane proton transfer was quantified by the activity of an O2 reduction catalyst buried under the lipid layer by electrochemistry. This molecular switch mimics the natural system allowing precise control of proton relocation without perturbing the proton thermodynamics (Scheme 0.3).","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2016-07-07 without embargo terms","The student, Ying Li, accepted the attached license on 2016-04-13 at 13:09.","The student, Ying Li, submitted this Dissertation for approval on 2016-04-13 at 13:25.","This Dissertation was approved for publication on 2016-04-14 at 08:53.","DSpace SAF Submission Ingestion Package generated from Vireo submission #9205 on 2016-07-07 at 13:30:01","Made available in DSpace on 2016-07-07T19:53:43Z (GMT). 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Crosslinked dendronized polyols for brighter and more stable dyes 3. Photoresponsive proton gate for cross-membrane transfer"],"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":"2026-07-22T22:26:32Z"}