Nanofibers Produced by Electrospinning of Ultrarigid Polymer Rods Made from Designed Peptide Bundlemers.

Mimicking the hierarchical assembly of natural fiber materials is an important design challenge in the manufacturing of nanostructured materials with biomolecules such as peptides. Here, we produce nanofibers with control of structure over multiple length scales, ranging from peptide molecule assembly into supramolecular building blocks called "bundlemers," to rigid-rod formation through a covalent connection of bundlemer building blocks, and, ultimately, to uniaxially oriented fibers made with the rigid-rod polymers. The peptides are designed to physically assemble into coiled-coil bundles, or bundlemers, and to covalently interact in an end-to-end fashion to produce the rigid-rod polymer. The resultant rodlike polymer exhibits a rigid, cylindrical nanostructure confirmed by transmission electron microscopy (TEM) and, correspondingly, exhibits shear-thinning behavior at low shear rates observed in many nanoscopic rod systems. The rigid-rod chains are further organized into final fiber materials via electrospinning processing, all the while preserving their unique rodlike structural characteristics. Morphological and structural investigations of the nanofibers through scanning electron microscopy, transmission electron microscopy, and X-ray scattering, as well as molecular characterization via Fourier transform infrared (FTIR) and Raman spectroscopy, show that continuous nanofibers are composed of oriented rigid-rod chains constituted by α-helical peptides within bundle building blocks. Mechanical properties of electrospun fibers are also presented. The ability to produce nanofibers from the oriented rigid-rod polymer reveals bundlemer chains as a viable tool for the development of new fiber materials with targeted structure and properties.