Year: 2026
Type: article
Abstract: ABSTRACT Biological nanocomposites, such as spider silk and bamboo, employ sacrificial dynamic interactions across multiple length scales to build hierarchical structures with tunable and robust mechanics. Inspired by these systems, we programmed non‐covalent matrix‐filler interactions within an active polymer–peptide hybrid to achieve mechanically‐ and architecturally‐tunable nanocomposites. Self‐assembling poly(β‐benzyl‐ l ‐aspartate) (PBLA) blocks are grafted onto cellulose nanocrystals (CNCs) and incorporated into a non‐chain extended peptide−polyurea (PPU) hybrid, in which ordered PBLA blocks, coupled to a hydrophobic poly(dimethylsiloxane) (PDMS) block, direct matrix‐filler interactions to the soft domain. This design enables control of the self‐assembled morphology and mechanical performance. We explore PPU/CNC self‐assembly as a function of CNC surface chemistry by comparing peptide‐grafted and non‐grafted CNCs. Incorporation of peptide‐grafted CNCs redirects interactions to the PBLA blocks within the PPU. At 5 wt% CNC content, urea ordering is maintained, and dynamic peptide–matrix interactions lead to a pseudo‐dual network, preserving elastic modulus with enhanced extensibility (∼300% vs. 175%) and toughness (0.54 vs. 0.21 MJ/m 3 ) relative to the PPU. Hysteresis and fractography experiments reveal improved stress transfer and energy storage through targeted PBLA interactions. Overall, this work demonstrates how this active‐matrix strategy can program assembly pathways in scalable polymer nanocomposites for applications ranging from coatings to biomedicine.
Source: Advanced Functional Materials
Institution: University of Delaware
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: bronze
Funders: National Science Foundation, U.S. Department of Energy, University of Delaware, National Institutes of Health, Office of Science, National Institute of General Medical Sciences, Division of Materials Research, Office of International Science and Engineering, Division of Chemistry, Basic Energy Sciences
Awards: G1177608224, MRI: Acquisition of an X-Ray Photoelectron Spectrometer, G1451002057, G1703205069, G1705962760, G1880822571, G2302630240, G2902092823, G3115553707, CENTER FOR PLASTICS INNOVATION (CPI), G3350574766, Discovery of Chemical Probes and Therapeutic Leads, Phase II, G3983532892, G4129942005, G4444685404, G501384772, PIRE: Bio-Inspired Materials and Systems, G545157245, Acquisition of a 400 MHz NMR Spectrometer, CENTER FOR PLASTICS INNOVATION (CPI), Delaware INBRE, G6192324953, G6217188618, G6345397415, G6359476556, G6718912342, G6772302223, University of Delaware MRSEC - Center for Hybrid, Active, and Responsive Materials (CHARM), G8414554082, Molecular Design of Advanced Biomaterials, G9000004818, G9000014540, G9000019295, G9000042617, G9000093202, G9000125231, Discovery of Chemical Probes and Therapeutic Leads, Phase 3
OpenAlex ID: W7129752901