A Mechanistic and Kinetic Study of the Formation of Metal Nanoparticles by Using Synthetic Tyrosine-Based Oligopeptides

Synthetic oligopeptides containing redox‐active tyrosine residues have been employed to prepare gold and silver nanoparticles. In this reduction process an electron from the tyrosinate ion of the peptide is transferred to the metal ion at basic pH through the formation of a tyrosyl radical, which is eventually converted to its dityrosine form during the reaction. This reaction mechanism was confirmed from UV‐visible, fluorescence, and EPR spectroscopy and was found to be pH‐dependent. Transmission electron microscopy measurement shows that the average size and the monodispersity of gold nanoparticles increase as the number of tyrosine residues in the peptide increases. The kinetic study, based on spectrophotometric measurements of the surface plasmon resonance optical property, shows that the rate of formation of gold nanoparticles was much faster at higher pH than at lower pH and was also dependent on the number of tyrosine residues present in the peptide. The dityrosine form of the peptide was found to retain reducing properties like those of tyrosine in basic medium. Redox‐active tyrosine‐based peptides have been employed to prepare gold and silver nanoparticles. An electron from the tyrosinate ion of the peptide is transferred to the metal ion at basic pH through the formation of a tyrosyl radical, which is eventually converted to the dityrosine form during the reaction (see graphic) and was confirmed by UV‐visible, fluorescence, and EPR spectroscopy. The kinetic studies show that the rate of formation of gold nanoparticles was much faster at higher pH than at lower pH and was also dependent on the number of tyrosine residues present in the peptide.