Supramolecular Gelation Based on Native Amino Acid Tyrosine and Its Charge-Transfer Complex Formation

Abstract

Self-assembly of amino acids and short-peptide derivatives attracted significant curiosity worldwide due to their unique self-assembly process and wide variety of applications. Amino acid is considered one of the important synthons in supramolecular chemistry. Self-assembly processes and applications of unfunctionalized native amino acids have been less reported in the literature. In this article, we are first-time reporting the self-assembly process of tyrosine (Tyr), an aromatic amino acid, in dimethyl sulfoxide (DMSO) solvent. Most of the studies related to Tyr self-assembly were reported in different aqueous solutions. In our work, we studied the self-assembly in several common organic solvents and found that Tyr could self-assemble into a supramolecular gel in dimethyl sulfoxide (DMSO) solvent. The self-assembly process was investigated by several techniques, such as UV–vis, fluorescence, FTIR, and NMR spectroscopy. Morphological features on the nanoscale were investigated through scanning electron microscopy (SEM). SEM images indicated the formation of nanofibrils with high aspect ratios. The supramolecular gel property was investigated by different rheological experiments. Computational study on the self-assembly process of Tyr in DMSO medium suggested that noncovalent interactions like hydrogen bonding and π–π stacking among the Tyr molecules played a prominent role. Finally, the charge-transfer complex formation ability of electron-rich Tyr with electron-deficient 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was studied. In the presence of DDQ due to the charge-transfer complex formation, the supramolecular gel converted into a reddish color solution, and their fibrillar nanoscale morphologies collapsed.