In this study, we rationally combined target-induced
nanoprobe
deactivation with a static headspace microextraction strategy for
highly selective and sensitive colorimetric/SERS dual-mode sensing
of trimethylamine N-oxide (TMAO). Prussian blue–polyacrylic
acid–gold (PB-PAA-Au) nanohybrids were elaborately constructed
as excellent peroxidase-like and SERS-active nanoprobes owing to the
synergistic effect between PB and Au nanoparticles, which, however,
could be deactivated by trimethylamine (TMA), the reduction product
of TMAO. Accordingly, the nonvolatile TMAO in sample solution was
catalytically reduced to volatile TMA, which could be headspace extracted
and in turn cause the deactivation of PB-PAA-Au in the extracting
droplet. The deactivation degree was totally dependent on TMA concentration
and could be indicated by the catalytic efficiency of PB-PAA-Au toward
chromogenic reaction of H2O2–3,3′,5,5′-tetramethylbenzidine,
as well as the SERS intensity of PB-PAA-Au. Thus, the quantitative
determination of TMAO could be realized by tracking the changes in
colorimetric and SERS signals. Under the optimal conditions, the
proposed sensing strategy exhibited a limit of detection down to 1.57
μM in colorimetric mode and 5.33 μM in SERS mode. Furthermore,
the dual-mode system was successfully applied for TMAO detection in
real samples with satisfactory outcomes. This work provides an efficient
strategy for clinical monitoring of TMAO and holds great promise for
further evaluation of the impact of dietary and environmental factors
on TMAO levels.