{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/121402"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/121402","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Theory of pattern and pH effects in complex coacervation","abstract":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-12-04 without embargo terms","abstract_html":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-12-04 without embargo terms","abstract_has_math":false,"creators":["Knoerdel, Ashley R"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Biophysics & Quant Biology","degree_department":null,"school":null,"contributors":["Sing, Charles E","Statt, Antonia","Gruebele, Martin","Pogorelov, Taras"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023-08","date_published":"2023-08","updated_at":"2026-07-22T22:24:57Z","subjects":["Ph","Sequence Effects","Complex Coacervation","Hydrophobicity"],"languages":["en","eng"],"rights":["Copyright 2023 Ashley Knoerdel"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/121402","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Sing, Charles E","Statt, Antonia","Gruebele, Martin","Pogorelov, Taras"]},{"key":"dc:creator","label":"Author","values":["Knoerdel, Ashley R"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2023-08","2023-05-30"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Biophysics & Quant Biology"]},{"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":["Ph","Sequence Effects","Complex Coacervation","Hydrophobicity"]}]},{"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 Ashley Knoerdel"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/121402"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-12-04 without embargo terms","The student, Ashley Knoerdel, accepted the attached license on 2023-05-24 at 10:08.","The student, Ashley Knoerdel, submitted this Dissertation for approval on 2023-05-27 at 09:00.","This Dissertation was approved for publication on 2023-05-30 at 12:25.","DSpace SAF Submission Ingestion Package generated from Vireo submission #19391 on 2023-12-04 at 16:59:44","Oppositely-charged polyelectrolytes can undergo an associative phase separation in a process known as polymeric complex coacervation. This phenomenon is driven by the electrostatic attraction between polyanion and polycation species, leading to the formation of a polymer-dense coacervate phase and a coexisting polymerdilute supernatant phase. This phase separation can be influenced by chemical and physical molecular features such as hydrophobicity, charge density, and polyelectrolyte lengths. Lately, there has been intense interest in tuning this phase behavior using chemical and molecular features. A large amount of theoretical modeling of complex coacervation has been performed such as the Voorn-Overbeek theory, random phase approximation, polymer field theory, and the transfer matrix theory. These theories have given many physical insights into coacervation, but most of these approaches are applicable to polymers with low charge density instead of high charge density. My work has led to the expansion of the transfer matrix theory to develop a transfer matrix that works well in the low and high charge regimes as well as describing the affect molecular features have on complex coacervation. This approach maps the complicated three-dimension system to a one-dimension adsorption model, and solves for the adsorption model partition function using a transfer matrix approach. We show that there is good qualitative matching with our theoretical expansion with previously developed simulations of bulk phase separation. We also capture the effects of weak polyelectrolytes, hydrophobicity, chain length asymmetry, and patterned polyelectrolytes on phase separation using this approach. Results suggest that the formation of the coacervate phase is highly sensitive to local electrostatics and system environment. My expansion of the transfer matrix approach is able to capture a wide range of charge densities, sequence effects, chain length asymmetry, and is no longer limited to strong polyelectrolytes. This work provides the necessary building blocks to begin building a single theory capable of describing a sequenced polyelectrolyte system with a dependence on pH, hydrophobicity, and chain length asymmetry. An example of such a system is intrinsically disordered proteins that are able to phase separate inside of the cell to form membraneless compartments. My work has led to the expansion of the transfer matrix theory to develop a transfer matrix that works well in the low and high charge regimes as well as describing the affect molecular features have on complex coacervation. This approach maps the complicated three-dimension system to a one-dimension adsorption model, and solves for the adsorption model partition function using a transfer matrix approach. We show that there is good qualitative matching with our theoretical expansion with previously developed simulations of bulk phase separation. We also capture the effects of weak polyelectrolytes, hydrophobicity, chain length asymmetry, and patterned polyelectrolytes on phase separation using this approach. Results suggest that the formation of the coacervate phase is highly sensitive to local electrostatics and system environment. My expansion of the transfer matrix approach is able to capture a wide range of charge densities, sequence effects, chain length asymmetry, and is no longer limited to strong polyelectrolytes. This work provides the necessary building blocks to begin building a single theory capable of describing a sequenced polyelectrolyte system with a dependence on pH, hydrophobicity, and chain length asymmetry. An example of such a system is intrinsically disordered proteins that are able to phase separate inside of the cell to form membraneless compartments."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Theory of pattern and pH effects in complex coacervation"]}]}],"canonical_facts":{"dc:contributor":["Sing, Charles E","Statt, Antonia","Gruebele, Martin","Pogorelov, Taras"],"dc:creator":["Knoerdel, Ashley R"],"dc:date":["2023-08","2023-05-30"],"dc:description":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-12-04 without embargo terms","The student, Ashley Knoerdel, accepted the attached license on 2023-05-24 at 10:08.","The student, Ashley Knoerdel, submitted this Dissertation for approval on 2023-05-27 at 09:00.","This Dissertation was approved for publication on 2023-05-30 at 12:25.","DSpace SAF Submission Ingestion Package generated from Vireo submission #19391 on 2023-12-04 at 16:59:44","Oppositely-charged polyelectrolytes can undergo an associative phase separation in a process known as polymeric complex coacervation. This phenomenon is driven by the electrostatic attraction between polyanion and polycation species, leading to the formation of a polymer-dense coacervate phase and a coexisting polymerdilute supernatant phase. This phase separation can be influenced by chemical and physical molecular features such as hydrophobicity, charge density, and polyelectrolyte lengths. Lately, there has been intense interest in tuning this phase behavior using chemical and molecular features. A large amount of theoretical modeling of complex coacervation has been performed such as the Voorn-Overbeek theory, random phase approximation, polymer field theory, and the transfer matrix theory. These theories have given many physical insights into coacervation, but most of these approaches are applicable to polymers with low charge density instead of high charge density. My work has led to the expansion of the transfer matrix theory to develop a transfer matrix that works well in the low and high charge regimes as well as describing the affect molecular features have on complex coacervation. This approach maps the complicated three-dimension system to a one-dimension adsorption model, and solves for the adsorption model partition function using a transfer matrix approach. We show that there is good qualitative matching with our theoretical expansion with previously developed simulations of bulk phase separation. We also capture the effects of weak polyelectrolytes, hydrophobicity, chain length asymmetry, and patterned polyelectrolytes on phase separation using this approach. Results suggest that the formation of the coacervate phase is highly sensitive to local electrostatics and system environment. My expansion of the transfer matrix approach is able to capture a wide range of charge densities, sequence effects, chain length asymmetry, and is no longer limited to strong polyelectrolytes. This work provides the necessary building blocks to begin building a single theory capable of describing a sequenced polyelectrolyte system with a dependence on pH, hydrophobicity, and chain length asymmetry. An example of such a system is intrinsically disordered proteins that are able to phase separate inside of the cell to form membraneless compartments. My work has led to the expansion of the transfer matrix theory to develop a transfer matrix that works well in the low and high charge regimes as well as describing the affect molecular features have on complex coacervation. This approach maps the complicated three-dimension system to a one-dimension adsorption model, and solves for the adsorption model partition function using a transfer matrix approach. We show that there is good qualitative matching with our theoretical expansion with previously developed simulations of bulk phase separation. We also capture the effects of weak polyelectrolytes, hydrophobicity, chain length asymmetry, and patterned polyelectrolytes on phase separation using this approach. Results suggest that the formation of the coacervate phase is highly sensitive to local electrostatics and system environment. My expansion of the transfer matrix approach is able to capture a wide range of charge densities, sequence effects, chain length asymmetry, and is no longer limited to strong polyelectrolytes. This work provides the necessary building blocks to begin building a single theory capable of describing a sequenced polyelectrolyte system with a dependence on pH, hydrophobicity, and chain length asymmetry. An example of such a system is intrinsically disordered proteins that are able to phase separate inside of the cell to form membraneless compartments."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/121402"],"dc:language":["en","eng"],"dc:rights":["Copyright 2023 Ashley Knoerdel"],"dc:subject":["Ph","Sequence Effects","Complex Coacervation","Hydrophobicity"],"dc:title":["Theory of pattern and pH effects in complex coacervation"],"dc:type":["text"],"thesis:degree_discipline":["Biophysics & Quant Biology"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:57Z"}