Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.
","abstract_html":"<p>Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.</p>","abstract_has_math":false,"creators":["Tran-Math, Carolyn"],"institution":null,"degree_name":"Master of Science (M.S.)","degree_level":"Thesis - Pacific Access Restricted","degree_discipline":"Pharmaceutical and Chemical Sciences","degree_department":null,"school":null,"contributors":["Qinglang Zhao"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-01-01T08:00:00Z","date_published":"2014-01-01T08:00:00Z","updated_at":"2026-07-24T05:36:09Z","subjects":["Inorganic chemistry","Polymer chemistry","Pure sciences","Cross-linked pnipam","Metallopolymer","Photonic properties","Polypyridyl ligands","Ru and ni monomers","Size-uniform microspheres","Chemicals and Drugs","Chemistry","Medical Pharmacology","Medicinal-Pharmaceutical Chemistry","Medicine and Health Sciences","Pharmaceutical Preparations","Pharmacy and Pharmaceutical Sciences","Physical Sciences and Mathematics"],"languages":[],"rights":[],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9781321400083"],"render_values":[{"text":"9781321400083","href":null,"code":true}]}]},"links":{"outbound_url":"https://scholarlycommons.pacific.edu/uop_etds/271","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Qinglang Zhao"]},{"key":"dc:creator","label":"Author","values":["Tran-Math, Carolyn"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2018-06-29T09:07:47Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Pharmaceutical and Chemical Sciences"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis - Pacific Access Restricted"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science (M.S.)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Inorganic chemistry","Polymer chemistry","Pure sciences","Cross-linked pnipam","Metallopolymer","Photonic properties","Polypyridyl ligands","Ru and ni monomers","Size-uniform microspheres","Chemicals and Drugs","Chemistry","Medical Pharmacology","Medicinal-Pharmaceutical Chemistry","Medicine and Health Sciences","Pharmaceutical Preparations","Pharmacy and Pharmaceutical Sciences","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9781321400083","https://scholarlycommons.pacific.edu/uop_etds/271"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.
"]},{"key":"dc:source","label":"Dc Source","values":["124"]},{"key":"dc:title","label":"Title","values":["Synthesis of poly(NIPAM-co-vmbpy) microspheres and transition metal monomers for metallopolymeric material construction"]}]}],"canonical_facts":{"dc:contributor":["Qinglang Zhao"],"dc:creator":["Tran-Math, Carolyn"],"dc:date.available":["2018-06-29T09:07:47Z"],"dc:description.abstract":["Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.
"],"dc:identifier":["9781321400083","https://scholarlycommons.pacific.edu/uop_etds/271"],"dc:rights":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:source":["124"],"dc:subject":["Inorganic chemistry","Polymer chemistry","Pure sciences","Cross-linked pnipam","Metallopolymer","Photonic properties","Polypyridyl ligands","Ru and ni monomers","Size-uniform microspheres","Chemicals and Drugs","Chemistry","Medical Pharmacology","Medicinal-Pharmaceutical Chemistry","Medicine and Health Sciences","Pharmaceutical Preparations","Pharmacy and Pharmaceutical Sciences","Physical Sciences and Mathematics"],"dc:title":["Synthesis of poly(NIPAM-co-vmbpy) microspheres and transition metal monomers for metallopolymeric material construction"],"thesis:degree_discipline":["Pharmaceutical and Chemical Sciences"],"thesis:degree_level":["Thesis - Pacific Access Restricted"],"thesis:degree_name":["Master of Science (M.S.)"]},"updated_at":"2026-07-24T05:36:09Z"}