Self-Assembly of PEGylated Diphenylalanines into Photoluminescent Fibrillary Aggregates

Diphenylalanine (FF) represents one of the most studied self-assembling peptides. As a consequence of non-covalent interactions (aromatic stacking and hydrogen bonds), FF is able to generate different nanoarchitectures, proposed in the last years as innovative tools for several applications. The identification of the relationship between the chemical building block composition and the supramolecular structure of final material is the objective of intense research. Different FF analogues were synthetized and studied. At the state of art, in the high number of FF derivatives, PEGylation has not been studied yet, notwithstanding its role has been demonstrated for longer poly-phenylalanine peptides. Herein, we describe the synthesis and the supramolecular behavior of two PEGylated-FF derivatives, PEG2-FF and PEG6-FF, in which the zwitterionic FF has been derivatized at the N-terminus with two or six ethoxylic moieties, respectively. Spectroscopic methodologies (fluorescence, circular dichroism, Fourier transform infrared) allowed the identification of their secondary structure and the calculation of the critical aggregation concentration. PEGylation of the dipeptide induces a modification of the conformational organization from nanotubes with hexagonal symmetry to β-sheet rich fibrils. This structural organization confers photoluminescence features to the supramolecular structures.