Nanozymes,
the enzyme-mimicking nanomaterials, have been developed
to overcome the low stability and high cost of natural enzymes. Unlike
highly active and specific enzymes, however, the catalytic activities
of nanozymes are moderate and lack specificity. To address these issues,
herein we demonstrated an effective and general strategy to specifically
enhance the peroxidase-mimicking activities of carbon nanozymes. By
doping heteroatom nitrogen (N) into reduced graphene oxide (rGO) and
mesoporous carbon (MC), their peroxidase-mimicking activities were
enhanced by over 100- and 60-fold, respectively. Moreover, N-doping
did not significantly affect the oxidase-, superoxide dismutase (SOD)-,
or catalase-mimicking activities of rGO and MC, demonstrating a specific
enhancement of the peroxidase-mimicking activities. To understand
the origin of the specific enhancement, we performed density functional
theory calculations to examine the catalytic reaction mechanisms responsible
for the peroxidase-, catalase-, oxidase-, and SOD-mimicking activities
of N-doped rGO (N-rGO). We revealed that N-rGO selectively activated
H2O2 rather than O2 and •O2
– by forming and stabilizing radical
oxygen species adjacent to the N sites of N-rGO. The radical oxygen
species then oxidized peroxidase substrates, endowing N-rGO with peroxidase-mimicking
activity. This study will aid in the rational design of highly active
and specific peroxidase mimics and help elucidate the catalytic mechanisms
of nanozymes.
Pesticides,
widely used for pest control and plant growth regulation,
have posed a threat to the environment and human health. Conventional
methods to analyze pesticide residues are not applied to resource-limited
areas because of their high cost, complexity, and requirements for
expensive instruments (such as GC/MS and LC/MS). To address these
challenges, herein we fabricated colorimetric nanozyme sensor arrays
based on heteroatom-doped graphene for detection of aromatic pesticides.
The active sites of nanozymes could be differentially masked when
different pesticides were adsorbed on the graphene, which in turn
resulted in the decrease of their peroxidase-mimicking activities.
On the basis of this principle, five pesticides (i.e., lactofen, fluoroxypyr-meptyl,
bensulfuron-methyl, fomesafen, and diafenthiuron) from 5 to 500 μM
were successfully discriminated by the sensor arrays. In addition,
discrimination for different concentrations of each pesticide and
different ratios of two mixed pesticides were also demonstrated. The
practical application of the sensor arrays was further validated by
successfully discriminating the pesticides in soil samples. This work
not only provides a facile and cost-effective method to detect pesticides
but also makes a positive contribution to food safety and environmental
protection.
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