{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/27714"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/27714","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Photo-reactive Surfactant and Macromolecular Supramolecular Structures","abstract":"For the first time nonwoven fibrous scaffolds were electrospun from a low molar mass gemini ammonium surfactant, N,N–-didodecyl-N,N,N–,N–-tetramethyl-N,N–-ethanediyl-di-ammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing.","abstract_html":"For the first time nonwoven fibrous scaffolds were electrospun from a low molar mass gemini ammonium surfactant, N,N–-didodecyl-N,N,N–,N–-tetramethyl-N,N–-ethanediyl-di-ammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing.","abstract_has_math":false,"creators":["Cashion, Matthew Paul"],"institution":"Virginia Tech","degree_name":"Ph. 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Richard","Davis, Richey M.","Madsen, Louis A."],"year":2009,"date_issued":"2009-04-30","date_published":"2009-04-30","updated_at":"2026-07-24T05:56:14Z","subjects":["photo-curing","gemini surfactants","n-butyl acrylate","2-hydroxyethyl acrylate","cinnamate","hydrogen bonding","adhesives","electrospinning","photo-rheology"],"languages":[],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-05142009-143351"],"render_values":[{"text":"etd-05142009-143351","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/27714","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Long, Timothy E."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Moore, Robert Bowen","Turner, S. 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Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:title","label":"Title","values":["Photo-reactive Surfactant and Macromolecular Supramolecular Structures"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Long, Timothy E."],"dc:contributor.committeemember":["Moore, Robert Bowen","Turner, S. Richard","Davis, Richey M.","Madsen, Louis A."],"dc:contributor.department":["Chemistry"],"dc:creator":["Cashion, Matthew Paul"],"dc:date.accessioned":["2014-03-14T20:12:03Z"],"dc:date.available":["2014-03-14T20:12:03Z","2012-03-30"],"dc:date.issued":["2009-04-30"],"dc:description.abstract":["For the first time nonwoven fibrous scaffolds were electrospun from a low molar mass gemini ammonium surfactant, N,N–-didodecyl-N,N,N–,N–-tetramethyl-N,N–-ethanediyl-di-ammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing."],"dc:description.degree":["Ph. D."],"dc:identifier.other":["etd-05142009-143351"],"dc:identifier.uri":["http://hdl.handle.net/10919/27714"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:subject":["photo-curing","gemini surfactants","n-butyl acrylate","2-hydroxyethyl acrylate","cinnamate","hydrogen bonding","adhesives","electrospinning","photo-rheology"],"dc:title":["Photo-reactive Surfactant and Macromolecular Supramolecular Structures"],"dc:type":["Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-24T05:56:14Z"}