title: Amphiphilic graft copolymers from end-functionalized starches: synthesis, characterization, thin film preparation, and small molecule loading.
abstract: End-functionalized macromolecular starch reagents, prepared by reductive amination, were grafted onto a urethane-linked polyester-based backbone using copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry to produce novel amphiphilic hybrid graft copolymers. These copolymers represent the first examples of materials where the pendant chains derived from starch biopolymers have been incorporated into a host polymer by a grafting-to approach. The graft copolymers were prepared in good yields (63-90%) with high grafting efficiencies (66-98%). Rigorous quantitative spectroscopic analyses of both the macromolecular building blocks and the final graft copolymers provide a comprehensive analytical toolbox for deciphering the reaction chemistry. Due to the modular nature of both the urethane-linked polyester synthesis and the postpolymerization modification, the starch content of these novel hybrid graft copolymers was easily tuned from 28-53% (w/w). The uptake of two low molecular weight guest molecules into the hybrid polymer thin films was also studied. It was found that binding of 1-naphthol and pterostilbene correlated linearly with amount of starch present in the hybrid polymer. The newly synthesized graft copolymers were highly processable and thermally stable, therefore, opening up significant opportunities in film and coating applications. These results represent a proof-of-concept system for not only the construction of starch-containing copolymers, but also the loading of these novel polymeric materials with active agents.
authors.affiliation: Department of Chemistry and Biochemistry, University of San Diego , San Diego, California 92110, United States.
authors.forename: Lisa M
authors.initials: LM
authors.lastname: Ryno
authors.forename: Cassandra
authors.initials: C
authors.lastname: Reese
authors.forename: McKenzie
authors.initials: M
authors.lastname: Tolan
authors.forename: Jeffrey
authors.initials: J
authors.lastname: O'Brien
authors.forename: Gabriel
authors.initials: G
authors.lastname: Short
authors.forename: Gerardo
authors.initials: G
authors.lastname: Sorriano
authors.forename: Jason
authors.initials: J
authors.lastname: Nettleton
authors.forename: Kayleen
authors.initials: K
authors.lastname: Fulton
authors.forename: Peter M
authors.initials: PM
authors.lastname: Iovine
mesh_terms: D008567:Membranes, Artificial; D009284:Naphthols / Q000737:chemistry*; D011091:Polyesters / Q000138:chemical synthesis / Q000737:chemistry; D013213:Starch / Q000138:chemical synthesis / Q000737:chemistry; D013267:Stilbenes / Q000737:chemistry*
chemical_list: D008567:Membranes, Artificial; D009284:Naphthols; D011091:Polyesters; D013267:Stilbenes; C107773:pterostilbene; C029350:1-naphthol; D013213:Starch