Development of Nanoscale Hybrids from Ionic Liquid-Peptide Amphiphile Assemblies as New Functional Materials

Over the years, ionic liquids (ILs) have gained tremendous importance because of their unique properties and plethora of applications. In this work, we have developed a new nanoscale hybrid gel consisting of 1-ethyl-3-methylimidazolium dimethyl phosphate, [C₂mim][dmp], and self-assembled peptide nanoassemblies. The peptide nanoassemblies were formed by self-assembly of a newly synthesized peptide bolaamphiphile bis(N-α-amido-threonine) 1,7 heptane dicarboxylate (ThrC7). Upon mild heating and sonication of the IL and ThrC7 nanoassemblies, ThrC7-IL nanocomposites were formed. We explored the formation of nanohybrids by varying the ratio of IL to ThrC7 assemblies. While at lower IL ratios, a gelatinous matrix was formed, at higher IL ratios, highly ordered multilayered structures were observed by atomic force microscopy (AFM) imaging. The interactions between the ThrC7 nanofibers and [C₂mim][dmp] IL were probed by Fourier transform infrared spectroscopy, transmission electron microscopy, and AFM imaging. Differential scanning calorimetry and thermogravimetric analysis showed that the nanohybrids illustrated distinct thermal phase changes due to changes in hydrogen bonding interactions and unfolding of the nanoassemblies. The viscoelastic behavior of the nanohybrids indicated that the materials displayed higher storage modulus upon incorporation of the ThrC7 nanoassemblies when compared to the IL. Furthermore, the nanohybrids were found to adhere to and promote proliferation of human dermal fibroblasts, while cytotoxicity was observed toward MCF-7 breast cancer cells. Thus, for the first time, we have developed peptide-based nanohybrids with an imidazolium-based IL with unique structural properties that may open new avenues for exploring potential biological applications.