title: Aggregation of poly(acrylic acid)-containing elastin-mimetic copolymers.
abstract: Polymer-peptide conjugates were produced via the copper-catalyzed azide-alkyne cycloaddition of poly(tert-butyl acrylate) (PtBA) and elastin-like peptides. An azide-functionalized polymer was produced via atom transfer radical polymerization (ATRP) followed by conversion of bromine end groups to azide groups. Subsequent reaction of the polymer with a bis-alkyne-functionalized, elastin-like peptide proceeded with high efficiency, yielding di- and tri-block conjugates, which after deprotection, yielded poly(acrylic acid) (PAA)-based diblock and triblock copolymers. These conjugates were solubilized in dimethyl formamide, and addition of phosphate buffered saline (PBS) induced aggregation. The presence of polydisperse spherical aggregates was confirmed by dynamic light scattering and transmission electron microscopy. Additionally, a coarse-grained molecular model was designed to reasonably capture inter- and intramolecular interactions for the conjugates and its precursors. This model was used to assess the effect of the different interacting molecular forces on the conformational thermodynamic stability of the copolymers. Our results indicated that the PAA's ability to hydrogen-bond with both itself and the peptide is the main interaction for stabilizing the diblocks and triblocks and driving their self-assembly, while interactions between peptides are suggested to play only a minor role on the conformational and thermodynamic stability of the conjugates.
authors.affiliation: Department of Materials Science and Engineering, Delaware Biotechnology Institute, University of Delaware, Newark, DE 19716, USA. kiick@udel.edu.
authors.forename: Bradford A
authors.initials: BA
authors.lastname: Paik
authors.forename: Marco A
authors.initials: MA
authors.lastname: Blanco
authors.forename: Xinqiao
authors.initials: X
authors.lastname: Jia
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Roberts
authors.forename: Kristi L
authors.initials: KL
authors.lastname: Kiick
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D032701:Biomimetics; D004549:Elastin / Q000737:chemistry*; D058105:Polymerization; D013816:Thermodynamics
chemical_list: D000179:Acrylates; C532460:poly(tert-butyl acrylate); D004549:Elastin