Divalent metal ion modulation of a simple peptide-based hydrogel: self-assembly and viscoelastic properties

Abstract

Peptide self-assembly has been highly studied to understand the pathways in forming higher order structures along with the development and application of resulting hydrogel materials. Driven by noncovalent interactions, peptide hydrogels are stimuli-responsive to any addition to its gelling conditions. Here, a Phe-His based peptide, C₁₄-FH(Trt)-OH, was synthesized and characterized with ¹H NMR, FT-IR, MS, UV-vis spectroscopies and elemental analysis. Based on SEM imaging, the dipeptide conjugate was capable of forming a nanofibrous, interconnected network encapsulating buffer to produce a supramolecular hydrogel. Through the addition of Zn²⁺ and Cu²⁺, there is a clear change in the self-assembled nanostructures characterized through SEM. With this effect on self-assembly follows a change in the viscoelastic properties of the material, as determined through rheological frequency sweeps, with 2 and 3 orders of magnitude decreases in the elastic modulus G′ in the presence of Zn²⁺ and Cu²⁺ respectively. This highlights the tunability of soft material properties with peptide design and self-assembly, through metal ions and N^δ-directed coordination.