title: Molecular Design: Network Architecture and Its Impact on the Organization and Mechanics of Peptide-Polyurea Hybrids.
abstract: Nature has achieved controlled and tunable mechanics via hierarchical organization driven by physical and covalent interactions. Polymer-peptide hybrids have been designed to mimic natural materials utilizing these architectural strategies, obtaining diverse mechanical properties, stimuli responsiveness, and bioactivity. Here, utilizing a molecular design pathway, peptide-polyurea hybrid networks were synthesized to investigate the role of architecture and structural interplay on peptide hydrogen bonding, assembly, and mechanics. Networks formed from poly(β-benzyl-l-aspartate)-poly(dimethylsiloxane) copolymers covalently cross-linked with a triisocyanate yielded polyurea films with a globular-like morphology and parallel β-sheet secondary structures. The geometrical constraints imposed by the network led to an increase in peptide loading and ∼7x increase in Young's modulus while maintaining extensibility (∼160%). Thus, the interplay of physical and chemical bonds allowed for the modulation of resulting mechanical properties. This investigation provides a framework for the utilization of structural interplay and mechanical tuning in polymer-peptide hybrids, which offers a pathway for the design of future hybrid biomaterial systems.
authors.affiliation: Department of Macromolecular Science and Engineering, Case Western Reserve University , 2100 Adelbert Road, Cleveland, Ohio 44106-7202, United States.
authors.forename: Lindsay
authors.initials: L
authors.lastname: Matolyak
authors.affiliation: Center for Nanophase Materials Sciences and Chemical and Engineering Materials Division, Oak Ridge National Laboratory , 1 Bethel Valley Rd, Oak Ridge, Tennessee 37831, United States.
authors.forename: Jong
authors.initials: J
authors.lastname: Keum
authors.affiliation: Department of Macromolecular Science and Engineering, Case Western Reserve University , 2100 Adelbert Road, Cleveland, Ohio 44106-7202, United States.
authors.forename: LaShanda T J
authors.initials: LT
authors.lastname: Korley
mesh_terms: D001672:Biocompatible Materials / Q000737:chemistry*; D055119:Elastic Modulus; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D010446:Peptide Fragments / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D017433:Protein Structure, Secondary
chemical_list: D001672:Biocompatible Materials; D010446:Peptide Fragments; D011108:Polymers; C045786:polyurea