Recently, magnetic beads (MBs) are moving toward chemiluminescence
(CL) functional magnetic nanomaterials with a great potential for
constructing label-free immunosensors. However, most of the CL-functionalized
MBs suffer from scarce binding sites, easy aggregation, and leakage
of CL reagents, which will ultimately affect the analytical performance
of immunosensors. Herein, by using core–shell Fe3O4@Au/Ag magnetic nanomaterials as a nanoplatform, a novel N-(4-aminobutyl)-N-ethylisopropanol (ABEI)
and Co2+ dual-functionalized magnetic nanomaterial, namely,
Fe3O4@Au/Ag/ABEI/Co2+, with strong
and stable CL emission was successfully synthesized. Its CL intensity
was 36 and 3.5 times higher than that of MB@ABEI-Au/Co2+ and ABEI and Co2+ dual-functionalized chemiluminescent
MBs previously reported by our group, respectively. It was found that
the excellent CL performance of Fe3O4@Au/Ag/ABEI/Co2+ could be attributed to the enrichment effect of the Au/Ag
shell and the synergistic enhance effect of the Au/Ag shell and Co2+. A related CL mechanism has been proposed. Afterward, based
on the intense and stable CL emission of Fe3O4@Au/Ag/ABEI/Co2+, a sensitive and effective label-free
CL immunosensor for exosome detection was established. It exhibited
excellent analytical performance with a wide detection range of 3.1
× 103 to 3.1 × 108 particles/mL and
a low detection limit of 2.1 × 103 particles/mL, which
were better than the vast majority of the reported CL immunosensors.
Moreover, the proposed label-free CL immunosensor was successfully
used to detect exosomes in human serum samples and enabled us to distinguish
healthy persons and lung cancer patients. It has the potential to
be a powerful tool for exosome study and early cancer diagnosis.