10.1002/anie.201814507
Angewandte Chemie International Edition
COMMUNICATION
Plasticizers are mainly detected by chromatography and
chromatography-mass spectrometry.[21] Owing to the issues of
volatilization, instability, and low plasticizer content, the existing
methods have some shortcomings such as a poor separation
for compounds with similar polarities, the difficulties in the
choice of the solvent and fixed phase, and low sensitivity. ECL
analysis has been proven to be highly selective and sensitive
and may avoid the analytical shortcomings described above.[2,4]
The HPS/K2S2O8 ECL system can also produce the excited
state intermediates: silole radical anions that could be
quenched by an ester: DNBP via electron transfer reactions[19]
(Scheme 2). As shown in Figure S17, the ECL intensity
decreased linearly when DNBP was added to the HPS/K2S2O8
system, suggesting a potential application of the ECL system to
the sensing of DNBP. Figure S18 shows a linear correlation
between the decrease in the cathodic ECL intensity and
increase in the DNBP concentration in the range of the plot of
ln(I0/I) versus the DNBP concentration, where I0 and I represent
the ECL intensities in the absence and presence of DNBP,
respectively. The linear range was 5 ~ 2500 nM and the limit of
detection was 0.15 nM (S/N = 3), with a good correlation
coefficient R2 = 0.9946 (n = 3). To demonstrate the selectivity,
we examined the effect of other plastic residues (Mg2+, Al3+, Cl−,
Ti4+ and phenols)[19]. The results are shown in Figure S19, and
it is clear that only DNBP responded to the HPS/K2S2O8 system.
This may be due to the electron transfer of the silole
intermediate radical anions being very specific to the carbonyl
compounds (Figure S20). The new analysis method was very
sensitive and selective for the detection of DNBP compared to
This work was supported by the Natural Science Foundation of
China (Grant Nos. 21575115 and 21705117); and the Program
of Gansu Provincial Higher Education Research Project (Grant
No. 2017-D-01).
Keywords: electrochemiluminescence • siloles •
heterogeneous • aggregation-induced • plasticizer
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In summary, we developed
a facile and feasible
silole/K2S2O8 ECL system named HAIE-ECL. Both experiments
and theoretical calculations revealed the inherently electronic
and non-coplanar structure of this system, and it was shown
that the HOMO and LUMO levels of the system affected by the
substituents at 2,5 and 1,1-postions played the dominant role in
the HAIE-ECL emissions. The new system is simple design,
convenient to use, environment friendly, low interference to
analytes, and the detection of the widely used DNBP industrial
plasticizer by the HPS/K2S2O8 ECL system showed high
sensitivity and selectivity. This work not only introduced AIE
luminophores for the first time to solve the water-insolubility and
aggregation-caused quenching (ACQ) problems found for
organic-based molecule probe systems but also established a
highly efficient electrochemical method for analysis of the
DNBP industrial plasticizer.
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Experimental Section
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