In
this work, fluorescent copper nanoclusters (CuNCs) have been
fabricated with ascorbic acid (AA) as reductant and polyvinyl pyrolidone
(PVP) as scaffold in aqueous solution for the on-site detection of
hypochlorous acid (HClO) with high sensitivity and selectivity. The
CuNCs showed a specific fluorescence quenching toward HClO compared
with other reactive oxygen species and ions that are found widely
in the environment. The CuNCs also exhibited a good linear fluorescence
quenching effect on HClO with a limit of detection at 55 nM. The mechanism
has been investigated and was attributed to the oxidation of reduced
Cu on the surface of CuNCs by HClO. Surprisingly, the fluorescence
intensity of the probe was more responsive to HClO in the presence
of excessive iodide ions (I–), with a lower detection
limit of 19 nM. In acidic conditions, iodine (I2) was generated
by HClO oxidation and subsequently reacted with Cu atoms on the surface
of CuNCs to form cuprous iodide (CuI) precipitation. This resulted
in surface defects on the CuNCs, which further significantly reduced
the fluorescence intensity of the CuNCs. Under the influence of the
reaction mechanism, the order of excessive I– and
HClO addition affects the linear range and detection limit of the
probe. Because these CuNCs have shown excellent performance as a fluorescent
probe, they have been further successfully applied for real-time quantitative
detection of HClO in practical samples, and I– can
also be used as a “sensitizer” in HClO sensing.
Hydrogen sulfide reacts to NBD-based derivatives and quenches the fluorescence, while the fluorescence of CDs is enhanced, leading to a distinct ratiometric fluorescence signal.
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