Fabrication
of high-performance artificial antioxidant enzyme (AAE)
systems based on a single nanozyme possessing multi-enzymatic activities
is fascinating but challenging. Here, polyvinylpyrrolidone (PVP)–platinum–copper
nanoparticle clusters (PVP-PtCuNCs) are prepared by a facile one-pot
chemical coreduction method. PVP-PtCuNCs possess efficient superoxide
dismutase (SOD)-like, peroxidase (POD)-like, and catalase (CAT)-like
activities, and the multi-enzymatic activities depend on the bimetal
component and cluster structure. Compared with individual platinum
nanoparticle clusters (PVP-PtNCs), PVP-PtCuNCs can effectively eliminate
reactive oxygen species (ROS) including superoxide anions, hydrogen
peroxide, and hydroxyl radicals. The doping of copper not only reduces
the usage of Pt content but also improves the catalytic efficiency
and versatility effectively through the synergistic effect of bimetal
components and the nanocluster structure. The results not only demonstrate
that a single bimetallic nanozyme has the potential as an efficient
AAE system in the biomedical application but also demonstrate that
traditional concepts of structure–activity relationships can
be used to fabricate nanozymes with the desired multi-enzymatic activities.
The single function and weak catalytic activity of nonprecious
metal nanozymes distinctly hinder their practical applications, so
it is intriguing to develop multifunctional nanozymes via a facile
and green route. Here, for the first time, “bottom–up”
strategies were used to realize the efficient synthesis of MnO2 quantum dots (QDs) with simple operation and mild reaction
conditions based on proteins, avoiding the operation complexity of
the traditional “up–down” approach. More interestingly,
MnO2 QDs exhibit extraordinarily outstanding catechol oxidase-like
activity. QD nanozymes can catalyze the oxidation of dopamine (DA)
into DA quinone in just 2 min, and then DA quinone polymerizes to
form PDA in more than 10 min at 37 °C over a broad pH range (above
pH 7.4). Based on the catechol oxidase-like activity and the interaction
between QDs with a DA quinone-induced passivation effect, a “turn-on”
fluorescence sensor based on two sequential recognitions for DA with
self-signal output is developed without using the commonly used chromogenic
reactions. The dual recognition provides the sensor with extremely
good selectivity, which removes the interference from common reducible
substances and metal ions. The detection limit can reach 0.038 μM,
and the sensor has good specificity and a short detection time (just
2 min) under mild conditions. This offers a flexible guide for rational
design and fabrication of FL turn-on biosensors for redox-active dopamine
and enriches our understanding of QD nanozymes in bioanalytical fields.
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