Insights into diphenylalanine peptide self-assembled nanostructures for integration as nanoplatforms in analytical...

New insights on the self-assembling process of diphenylalanine (FF) into nanostructures in view of its application as an alternative nanomaterial for bioanalytical and biomedical systems are presented in the frame of the present work. Experimental conditions, such as peptide concentration and solubilization medium pH, were explored to understand the hierarchical process involved in the formation of self-assembled nanostructures arising from the simple and short diphenylalanine peptide. Optical microscopic and TEM images supported by DLS data authenticated the hierarchical self-assembly outcoming from the original nature of the first nanostructures, showing individual nanotubes and vesicles stacking to grow well-defined microtubes. Moreover, the influence of metal cations on peptide self-assembly was evaluated for the first time in the presence of Mg²⁺ and compared with other ions, such as Na⁺, K⁺, and Ca²⁺. The results evidenced a tendency of Mg²⁺ to interact with diphenylalanine peptides to form self-assembled nanostructures showing vesicle- and ellipse-like morphologies. FF solubilization in water prepared under sonication in a bath at 65-68°C followed by dilution into chloride metal cation solutions at 50 mmol.L^-1 proved to be optimal conditions to obtain metal-coordinated self-assembled FF structures. Besides, the latter revealed fluorescence features and electron-transfer properties on carbon-based electrode surfaces, that can be further explored in analytical and bioanalytical devices for fully integrated platforms. In this context, self-assembled nanostructures achieved in the presence of Mg²⁺ and Ca²⁺ were implemented for the surface modification of carbon screen-printed electrodes and proved to increase the electrochemical response toward a redox probe. This proof of concept is particularly interesting for further use of these peptide-based nanoarchitectures as nanoplatforms for clinical imaging, therapeutic and diagnosis purposes.