The synthesis, characterization, self-assembly, and gel formation of poly(γ-benzyl-l-glutamate) (PBLG) in a molecular weight range from ca. 7,000-100,000 g/mol and with narrow molecular weight distribution are described. The PBLG is synthesized by the nickel-mediated ring-opening polymerization and is characterized by size-exclusion chromatography coupled with multiple-angle laser light scattering, NMR, and Fourier transform infrared spectroscopy. The self-assembly and thermoreversible gel formation in the helicogenic solvent toluene is investigated by transmission electron microscopy, atomic force microscopy, small-angle X-ray scattering, and synchrotron powder X-ray diffraction. At concentrations significantly below the minimum gelation concentration, spherical aggregates are observed. At higher concentrations, gels are formed, which show a 3D network structure composed of nanofibers. The proposed self-assembly mechanism is based on a distorted hexagonal packing of PBLG helices parallel to the axis of the nanofiber. The gel network forms due to branching and rejoining of bundles of PBLG nanofibers. The network exhibits uniform domains with a length of 200 ± 42 nm composed of densely packed PBLG helices.
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