Hydrogen peroxide (H2O2), a double-edged
sword, exists at all stages of proliferation, invasion, and metastasis
of tumor cells; thus, it has become one of the most important markers
for the diagnosis and treatment of cancer. Owing to its fast diffusion,
natural decomposition, and ultralow level in the extracellular microenvironment,
it still poses many challenges in distinguishing and quantifying H2O2 released from tumor cells. Therefore, it is
of great importance to establish a fast-response and ultrasensitive
method for real-time monitoring of intracellular H2O2 dynamic balance for the study of cancer mechanisms. In this
study, a dual-mode electrochemical and electrochemiluminescence (ECL)
biosensor was prepared using peroxidase-like N-doped carbon nanotubes
loaded with NiCo-layered double-hydroxide (N-CNTs@NiCo-LDH) hollow
tubular nanoflowers, which were synthesized using hollow N-CNTs as
templates and ultrathin NiCo-LDH nanosheets (Ni/Co = 1:2) grown in
situ on their surfaces. The thin and uniform nanopetals with the synergistic
effect of Ni and Co make its catalytic performance comparable to that
of noble-metal catalysts. Moreover, peroxidase mimics of N-CNTs@NiCo-LDHs
serve not only as a redox mediator to H2O2 but
also as a scaffold carrier to immobilize luminol to form a solid-state
luminophore, which accelerates the generation of reactive oxygen species
and decreases the distance between the luminophore and electrode.
Furthermore, an electrochemical response speed of 4 s is consistent
with the short half-life of H2O2. The experimental
results show that electrochemistry with a wide detection range (2.5–187.5
and 187.5–16987.5 μM) can distinguish abundant cancer
cells from normal cells, while ultrasensitive ECL (limit of detection
of 8.72 nM) can detect H2O2 released from as
low as 59 cancer cells per mL.