{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/108117"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/108117","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Single-chain nanoparticle based catalysts","abstract":"Enzymes achieve their excellent catalytic properties by surrounding the catalytic sites with a polypeptide scaffold. The three-dimensional structure of the peptide chains creates a local environment that supramolecularly binds substrates to facilitate the catalysis. In this dissertation, synthetic polymers are used to serve a similar role, binding substrates and creating an optimal environment for performing efficient catalysis. Several single-chain nanoparticle (SCNP) catalysts have been developed to perform copper(I)-mediated alkyne–azide cycloaddition (CuAAC), “click” reactions, or the photoreduction of azido groups to amines. The nanoparticles are shown to have significantly higher activity when compared to analogous small molecule catalysts. Structure-activity relationships and reaction mechanisms are studied with SCNPs of different structures. The polymeric scaffolds are found to bind substrates in an enzyme-like manner. The catalysts operate in two modes: an “uptake mode” where small molecule substrates bind inside the polymer pockets and an “attach mode” that involves surface binding of protein substrates. The versatility and high efficiency of the nanoparticles lead to applications in protein and cell surface modification. In addition, another SCNP was shown to co-deliver an exogenous enzyme inside cells. The enzyme and SCNP reside and stay active in the endosomes, in essence engineering the endosome into an artificial organelle. The SCNP-enzyme complex can perform both concurrent and tandem reactions performing organic synthesis intracellularly. The combination of SCNP and enzymatic catalysts provides a versatile tool for intracellular organic synthesis with applications in chemical biology.","abstract_html":"Enzymes achieve their excellent catalytic properties by surrounding the catalytic sites with a polypeptide scaffold. The three-dimensional structure of the peptide chains creates a local environment that supramolecularly binds substrates to facilitate the catalysis. In this dissertation, synthetic polymers are used to serve a similar role, binding substrates and creating an optimal environment for performing efficient catalysis. Several single-chain nanoparticle (SCNP) catalysts have been developed to perform copper(I)-mediated alkyne–azide cycloaddition (CuAAC), “click” reactions, or the photoreduction of azido groups to amines. The nanoparticles are shown to have significantly higher activity when compared to analogous small molecule catalysts. Structure-activity relationships and reaction mechanisms are studied with SCNPs of different structures. The polymeric scaffolds are found to bind substrates in an enzyme-like manner. The catalysts operate in two modes: an “uptake mode” where small molecule substrates bind inside the polymer pockets and an “attach mode” that involves surface binding of protein substrates. The versatility and high efficiency of the nanoparticles lead to applications in protein and cell surface modification. In addition, another SCNP was shown to co-deliver an exogenous enzyme inside cells. The enzyme and SCNP reside and stay active in the endosomes, in essence engineering the endosome into an artificial organelle. The SCNP-enzyme complex can perform both concurrent and tandem reactions performing organic synthesis intracellularly. The combination of SCNP and enzymatic catalysts provides a versatile tool for intracellular organic synthesis with applications in chemical biology.","abstract_has_math":false,"creators":["Chen, Junfeng"],"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","Cheng, Jianjun","Lu, Yi","Murphy, Catherine J"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2020,"date_issued":"2020-08-26T23:54:35Z","date_published":"2020-08-26T23:54:35Z","updated_at":"2026-07-22T22:24:47Z","subjects":["Single-Chain Nanoparticle, catalyst, click chemistry, crosslinking"],"languages":["en"],"rights":["Chapter 1 Copyright 2020 ACS, Chapter 2 Copyright 2018 ACS, Chapter 3 Copyright 2019 ACS, Chapter 4 Copyright 2020 ACS"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/108117","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steven C","Cheng, Jianjun","Lu, Yi","Murphy, Catherine J"]},{"key":"dc:creator","label":"Author","values":["Chen, Junfeng"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2020-08-26T23:54:35Z","2022-08-26T23:58:55Z","2020-04-23","2020-05"]},{"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":["Single-Chain Nanoparticle, catalyst, click chemistry, crosslinking"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Chapter 1 Copyright 2020 ACS, Chapter 2 Copyright 2018 ACS, Chapter 3 Copyright 2019 ACS, Chapter 4 Copyright 2020 ACS"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/108117"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Enzymes achieve their excellent catalytic properties by surrounding the catalytic sites with a polypeptide scaffold. The three-dimensional structure of the peptide chains creates a local environment that supramolecularly binds substrates to facilitate the catalysis. In this dissertation, synthetic polymers are used to serve a similar role, binding substrates and creating an optimal environment for performing efficient catalysis. Several single-chain nanoparticle (SCNP) catalysts have been developed to perform copper(I)-mediated alkyne–azide cycloaddition (CuAAC), “click” reactions, or the photoreduction of azido groups to amines. The nanoparticles are shown to have significantly higher activity when compared to analogous small molecule catalysts. Structure-activity relationships and reaction mechanisms are studied with SCNPs of different structures. The polymeric scaffolds are found to bind substrates in an enzyme-like manner. The catalysts operate in two modes: an “uptake mode” where small molecule substrates bind inside the polymer pockets and an “attach mode” that involves surface binding of protein substrates. The versatility and high efficiency of the nanoparticles lead to applications in protein and cell surface modification. In addition, another SCNP was shown to co-deliver an exogenous enzyme inside cells. The enzyme and SCNP reside and stay active in the endosomes, in essence engineering the endosome into an artificial organelle. The SCNP-enzyme complex can perform both concurrent and tandem reactions performing organic synthesis intracellularly. The combination of SCNP and enzymatic catalysts provides a versatile tool for intracellular organic synthesis with applications in chemical biology.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2022-05-01","The student, Junfeng Chen, accepted the attached license on 2020-04-21 at 15:27.","The student, Junfeng Chen, submitted this Dissertation for approval on 2020-04-21 at 15:53.","This Dissertation was approved for publication on 2020-04-23 at 10:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #15024 on 2020-08-25 at 17:27:49","Made available in DSpace on 2020-08-26T23:54:35Z (GMT). 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The three-dimensional structure of the peptide chains creates a local environment that supramolecularly binds substrates to facilitate the catalysis. In this dissertation, synthetic polymers are used to serve a similar role, binding substrates and creating an optimal environment for performing efficient catalysis. Several single-chain nanoparticle (SCNP) catalysts have been developed to perform copper(I)-mediated alkyne–azide cycloaddition (CuAAC), “click” reactions, or the photoreduction of azido groups to amines. The nanoparticles are shown to have significantly higher activity when compared to analogous small molecule catalysts. Structure-activity relationships and reaction mechanisms are studied with SCNPs of different structures. The polymeric scaffolds are found to bind substrates in an enzyme-like manner. The catalysts operate in two modes: an “uptake mode” where small molecule substrates bind inside the polymer pockets and an “attach mode” that involves surface binding of protein substrates. The versatility and high efficiency of the nanoparticles lead to applications in protein and cell surface modification. In addition, another SCNP was shown to co-deliver an exogenous enzyme inside cells. The enzyme and SCNP reside and stay active in the endosomes, in essence engineering the endosome into an artificial organelle. The SCNP-enzyme complex can perform both concurrent and tandem reactions performing organic synthesis intracellularly. The combination of SCNP and enzymatic catalysts provides a versatile tool for intracellular organic synthesis with applications in chemical biology.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2022-05-01","The student, Junfeng Chen, accepted the attached license on 2020-04-21 at 15:27.","The student, Junfeng Chen, submitted this Dissertation for approval on 2020-04-21 at 15:53.","This Dissertation was approved for publication on 2020-04-23 at 10:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #15024 on 2020-08-25 at 17:27:49","Made available in DSpace on 2020-08-26T23:54:35Z (GMT). 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