Mn(II)-based electron spin resonance (ESR) spectroscopy
was used
for detecting butyrylcholinesterase (BChE) and organophosphorus pesticides
(OPs). MnO2 nanosheets were synthesized with manganese
chloride and hydrogen peroxide. With the catalysis of BChE, S-butyrylthiocholine
iodide (BTCh) was hydrolyzed into thiocholine which has a reducing
−SH group. In the presence of thiocholine, MnO2 nanosheets
were broken down and Mn(IV) in MnO2 nanosheets was reduced
into Mn(II). Mn2+ is a paramagnetic ion and gives a good
ESR signal. In contrast, MnO2 nanosheets have no ESR signal
and need not be separated from Mn2+. Mn2+ can
be determined directly by ESR spectroscopy, and no further sensing
probe is needed. ESR spectroscopy based on directly detecting Mn2+ is much simpler than those using other probes besides MnO2. The ESR signal of Mn2+ is proportional to the
catalytic activity of BChE. OPs which inhibit the activity of BChE
can also be detected by probing the ESR signal of Mn2+.
Since there is no ESR signal of MnO2 nanosheets, the background
signal in the absence of BChE was close to zero. The limit of detection
(LOD) of BChE was as low as 0.042 U L–1. The standard
curve for determining the OP paraoxon was established by measuring
the inhibition of BChE by paraoxon, and the LOD of paraoxon was found
to be 0.076 ng mL–1. The spiked Chinese cabbage
extract samples were analyzed, and the experimental results indicated
that the recoveries were from 96.5 to 102.8%. The planted Chinese
cabbage was sprayed with the paraoxon solution, and the residue amount
of paraoxon in the extract was estimated by the method. The result
obtained by the present method was consistent with that obtained by
HPLC, which proved the practicability of this new method.