Artificial
enzymes with modulated enzyme-mimicking activities of
natural systems represent a challenge in catalytic applications. Here,
we show the creation of artificial Cu metalloenzymes based on the
generation of Cu nanoparticles in an enzyme matrix. Different enzymes
were used, and the structural differences between the enzymes especially
influenced the controlled the size of the nanoparticles and the environment
that surrounds them. Herein, we demonstrated that the oxidase-like
catalytic activity of these copper nanozymes was rationally modulated
by enzyme used as a scaffold, with a special role in the nanoparticle
size and their environment. In this sense, these nanocopper hybrids
have confirmed the ability to mimic a unique enzymatic activity completely
different from the natural activity of the enzyme used as a scaffold,
such as tyrosinase-like activity or as Fenton catalyst, which has
extremely higher stability than natural mushroom tyrosinase. More
interestingly, the oxidoreductase-like activity of nanocopper hybrids
was cooperatively modulated with the synergistic effect between the
enzyme and the nanoparticles improving the catalase activity (no peroxidase
activity). Additionally, a novel dual (metallic and enzymatic activity)
of the nanozyme made the highly improved catechol-like activity interesting
for the design of 3,4-dihydroxy-
l
-phenylalanine (
l
-DOPA) biosensor for detection of tyrosinase. These hybrids also
showed cytotoxic activity against different tumor cells, interesting
in biocatalytic tumor therapy.