Catalyzed and Electrocatalyzed Oxidation of L-Tyrosine and L-Phenylalanine to Dopachrome by Nanozymes

Catalyzed oxygen insertion into C-H bonds represents a continuous challenge in chemistry. Particularly, driving this process at ambient temperature and aqueous media represents a "holy grail" in catalysis. We report on the catalyzed cascade transformations of L-tyrosine or L-phenylalanine to dopachrome in the presence of L-ascorbic acid/H2O2 as oxidizing mixture and CuFe-Prussian Blue-like nanoparticles, Fe3O4 nanoparticles or Au nanoparticles as catalysts. The process involves the primary transformation of L-tyrosine to L-DOPA that is further oxidized to dopachrome. The transformation of L-phenylalanine to dopachrome in the presence of CuFe-Prussian Blue-like nanoparticles and L-ascorbic acid/H2O2 involves in the first step the formation of L-tyrosine and, subsequently, the operation of the catalytic oxidation cascade of L-tyrosine to L-DOPA and dopachrome. Electron spin resonance experiments demonstrate that ascorbate radicals and hydroxyl radicals play cooperative functions in driving the different oxygen-insertion processes. In addition, the aerobic elecrocatalyzed oxidation of L-tyrosine to dopachrome in the presence of naphthoquinone-modified Fe3O4 nanoparticles and L-ascorbic acid is demonstrated. In this system, magnetic-field attraction of the naphthoquinone-modified Fe(3)O(4 )nanoparticles onto the electrode allows the quinone-mediated electrocatalyzed reduction of O-2 to H2O2 (bias potential -0.5 V vs SCE). The electrogenerated H2O2 is then utilized to promote the transformation of L-tyrosine to dopachrome in the presence of L-ascorbic acid and Fe3O4 catalyst.