{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/83831"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/83831","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Formulation and Surface Analysis of Perfluoropolyether-Modified Poly-Hydroxyethyl Methacrylate Hydrogel","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["Quinn, Austin; 0000-0003-2467-693X"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Gardella, Joseph","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-06-17T19:54:31Z","date_published":"2022-06-17T19:54:31Z","updated_at":"2026-07-27T19:05:28Z","subjects":["chemistry","materials science"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/83831","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gardella, Joseph","Chemistry"]},{"key":"dc:creator","label":"Author","values":["Quinn, Austin; 0000-0003-2467-693X"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-06-17T19:54:31Z","2020"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Text","Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["chemistry","materials science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/83831"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","A medical device is defined, materials formulated, the design was then prototyped, A series of graft copolymers were made having a hydrophilic poly(2-hydroxyethyl methacrylate) [poly(HEMA)] and a “less-hydrophilic” cross-linker trimethylolopropane-trimethacrylate (TMPTMA) with a chloroform soluble surfactant, which was a telechelic copolymer of methacrylic-perfluoropolyether-ε-polycaprolactone (TX2-CL5-MA).This was acquired for formulating a hydrogel to be used for construction of the aforementioned medical device and also create a model to examine the hydrogel surface using time of flight secondary ion mass spectrometry in loading and delivery conditions of relevant biomolecules. The direct free radical copolymerization of the hydrophobic TX2-CL5-MA macromer with HEMA and TMPTMA generated crosslinked copolymers of the structure: p(HEMA-g- TX2-CL5-MA-g-HEMA), some having well defined surface properties. For constructing a medical device, the free-radical copolymerization of (HEMA) with TX2-CL5-MA macromers, was carried out to make this well-defined device with a hydrophilic p(HEMA) surface opposite to a hydrophobic PFPE surface was carried out secondarily. First, graft copolymers consisting of a poly(HEMA) backbone and TMPTMA crosslinker were cast into a mold to create a smooth flat film. Without removing the new p(HEMA) film the surface of the newly made hydrogel was coated with p(HEMA) and MA –PCL-PFPE-PCL-MA in the presence of a trace amount of chloroform, TMPTMA, glycerol, and benzoin methyl ether. This was accomplished using bulk free radical polymerization in the same injection mold. Using the technique angle-dependent X-ray photoelectron spectroscopy (XPS), the surface compositions of copolymerized graft copolymers were measured under dry vacuum conditions. The relative effects of total surfactant concentration on fluorine concentration at the surface and in the bulk, surface segregation, and composition were investigated. It was found that, for poly(HEMA-g- TX2-CL5-MA-g-HEMA) graft copolymers, the PFPE surface concentration increases with increasing TX2-CL5-MA, up to about 2.5% surfactant in the total formula. For surfactant concentrations higher than 2.5 % in the bulk content, a greater amount of fluorine is detected in the bulk. Beyond 5% the bulk content increases linearly. The effect is greatest between 0.1%-4.5% surfactant in the bulk. The effect on air (free) surface composition does not account for reorganization upon exposure to water. However, the backbone hydrophilicity has a great effect on the PFPE segregation to the surface in the unreacted and cured hydrogel, and the surface composition difference between p(HEMA) and poly(HEMA-g- TX2-CL5-MA-g-HEMA) graft copolymers. Not surprisingly, the formula with more hydrophilic content exhibited more fluorine concentration at the lower free interface and the surface becomes saturated at about 85-90% of fluorine (atomic w/w %). A less expectable outcome was the lack of an observable surface rearrangement upon exposure to water. This process has engineered a device with distinct surface properties that remain stable in both wet and dry conditions.","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Formulation and Surface Analysis of Perfluoropolyether-Modified Poly-Hydroxyethyl Methacrylate Hydrogel"]}]}],"canonical_facts":{"dc:contributor":["Gardella, Joseph","Chemistry"],"dc:creator":["Quinn, Austin; 0000-0003-2467-693X"],"dc:date":["2022-06-17T19:54:31Z","2020"],"dc:description":["Ph.D.","A medical device is defined, materials formulated, the design was then prototyped, A series of graft copolymers were made having a hydrophilic poly(2-hydroxyethyl methacrylate) [poly(HEMA)] and a “less-hydrophilic” cross-linker trimethylolopropane-trimethacrylate (TMPTMA) with a chloroform soluble surfactant, which was a telechelic copolymer of methacrylic-perfluoropolyether-ε-polycaprolactone (TX2-CL5-MA).This was acquired for formulating a hydrogel to be used for construction of the aforementioned medical device and also create a model to examine the hydrogel surface using time of flight secondary ion mass spectrometry in loading and delivery conditions of relevant biomolecules. The direct free radical copolymerization of the hydrophobic TX2-CL5-MA macromer with HEMA and TMPTMA generated crosslinked copolymers of the structure: p(HEMA-g- TX2-CL5-MA-g-HEMA), some having well defined surface properties. For constructing a medical device, the free-radical copolymerization of (HEMA) with TX2-CL5-MA macromers, was carried out to make this well-defined device with a hydrophilic p(HEMA) surface opposite to a hydrophobic PFPE surface was carried out secondarily. First, graft copolymers consisting of a poly(HEMA) backbone and TMPTMA crosslinker were cast into a mold to create a smooth flat film. Without removing the new p(HEMA) film the surface of the newly made hydrogel was coated with p(HEMA) and MA –PCL-PFPE-PCL-MA in the presence of a trace amount of chloroform, TMPTMA, glycerol, and benzoin methyl ether. This was accomplished using bulk free radical polymerization in the same injection mold. Using the technique angle-dependent X-ray photoelectron spectroscopy (XPS), the surface compositions of copolymerized graft copolymers were measured under dry vacuum conditions. The relative effects of total surfactant concentration on fluorine concentration at the surface and in the bulk, surface segregation, and composition were investigated. It was found that, for poly(HEMA-g- TX2-CL5-MA-g-HEMA) graft copolymers, the PFPE surface concentration increases with increasing TX2-CL5-MA, up to about 2.5% surfactant in the total formula. For surfactant concentrations higher than 2.5 % in the bulk content, a greater amount of fluorine is detected in the bulk. Beyond 5% the bulk content increases linearly. The effect is greatest between 0.1%-4.5% surfactant in the bulk. The effect on air (free) surface composition does not account for reorganization upon exposure to water. However, the backbone hydrophilicity has a great effect on the PFPE segregation to the surface in the unreacted and cured hydrogel, and the surface composition difference between p(HEMA) and poly(HEMA-g- TX2-CL5-MA-g-HEMA) graft copolymers. Not surprisingly, the formula with more hydrophilic content exhibited more fluorine concentration at the lower free interface and the surface becomes saturated at about 85-90% of fluorine (atomic w/w %). A less expectable outcome was the lack of an observable surface rearrangement upon exposure to water. This process has engineered a device with distinct surface properties that remain stable in both wet and dry conditions.","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/83831"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["chemistry","materials science"],"dc:title":["Formulation and Surface Analysis of Perfluoropolyether-Modified Poly-Hydroxyethyl Methacrylate Hydrogel"],"dc:type":["Text","Dissertation"]},"updated_at":"2026-07-27T19:05:28Z"}