"covalent-Assembly"-Based Fluorescent Probe for Detection of a Nerve-Agent Mimic (DCP) via Lossen Rearrangement

Article abstract of DOI:10.1021/acs.analchem.9b01006

The highly selective and sensitive fluorescence "light-up" probe, 5′-(dimethylamino)-2′-formyl-N-hydroxy-[1,1′-biphenyl]-2-carboxamide(PTS), has been fabricated for the nerve-agent mimic diethyl chlorophosphate (DCP). The probe is designed by combining tw

Full text of DOI:10.1021/acs.analchem.9b01006

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Article
“Covalent Assembly” Based Fluorescent Probe for the Detection
of a Nerve Agent Mimic (DCP) via Lossen Rearrangement
Baolong Huo, Man Du, Ao Shen, Mengwen Li, Yaru Lai, Xue Bai, Aijun Gong, and Yunxu Yang
Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.9b01006 • Publication Date (Web): 02 Aug 2019
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“
Covalent Assembly” Based Fluorescent Probe for the Detection of a
Nerve Agent Mimic (DCP) via Lossen Rearrangement
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Baolong Huo, Man Du, Ao Shen, Mengwen Li, Yaru Lai, Xue Bai, Aijun Gong*, and Yunxu Yang*
Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Sci-
ence and Technology Beijing, Beijing 100083, China.
ABSTRACT: The highly selective and sensitive fluorescence “light-up” probe, 5'-(dimethylamino)-2'-formyl-N-hydroxy-[1,1'-
biphenyl]-2-carboxamide (PTS), has been fabricated for the nerve agent mimic diethyl chlorophosphate (DCP). The probe is de-
signed by combining two novel strategies of "covalent assembly" and Lossen rearrangement. The formation of a phosphoryl inter-
mediate from DCP and a hydroxamic acid group in PTS yields an isocyanate that quickly undergoes the Lossen rearrangement to
produce an aniline that condenses intramolecularly to a fluorescent phenanthridine system. PTS shows superior properties to probe
2
DCP, such as rapid response (within 100 s), low detection limit (10.4 nM), specificity and excellent linearity (R =0.9993) in range
of 2 μM to 16 μM. More importantly, its application of detecting DCP vapor has also been achieved with satisfying results.
Nerve agents, including Sarin, Soman, and Tabun (Chart 1),
are a class of organophosphate derivatives. Their acute toxici-
ty is mainly attributed to their strong electrophilic ability,
which can easily interact with the important central nervous
enzyme acetylcholinesterase, destroying nerve impulse con-
duction, leading to organ failure, thus causing death in a few
seconds. In World War II, these highly toxic agents served
as chemical warfare agents, killing millions soldiers and civil-
ians. After the war, in view of the cruelty of nerve agents, a
large number of these chemical weapons were destroyed by
many countries. Unfortunately, it was precisely due to the
horrific killing effect of nerve agents that lead terrorists to
tivity, good selectivity, easy operation, low cost, and real-time
3
1-34
situ detection in microenvironment systems.
Usually, di-
ethyl chlorophosphate (DCP) serves as a nerve-agent mimic
due to its low toxicity but similar activity to Sarin (Chart 1).
By utilizing the high chemical reactivity of nerve agents, some
fluorescent probes that detected DCP via directly phosphoryla-
1-8
tion of amino or hydroxyl groups on the probes have been
35-39
fabricated.
However, these sensors still have some short-
9
-13
comings in response time, sensitivity, etc.
In 2010, Han’s group developed a novel approach to detect
DCP via a Lossen rearrangement of rhodamine-hydroxamate
(Scheme 1). As they have claimed, hydroxamic acid was able
to be converted to phosphoryl intermediate and then self-
rearrange into the corresponding isocyanate, for which it was
1
4-19
express a soft spot for nerve agents.
In the past few dec-
ades, nerve agents have been released in the public areas of
some countries for creating panic, which posed a great threat
to social security and human health. Therefore, it is extremely
urgent to detect such highly toxic substances, and thus prevent
40
employed as the target site of DCP. In addition, Yang devel-
oped a sensing reaction via a "covalent-assembly" approach,
41, 42
which results in fluorimetric signal from zero background.
20-22
the occurrence of tragedy.
So, inspired by the research findings of the above-mentioned
two groups, here, our group designed and manufactured an
eye-catching probe PTS for highly specific and sensitive de-
tection of DCP, which combined these two strategies of
Chart 1. Structure of nerve agents and DCP.
“
Lossen rearrangement” and "covalent-assembly". We sup-
posed that once the hydroxamic acid group in PTS bound with
DCP, the new formed phosphoryl intermediate would undergo
Lossen rearrangement swiftly to afford the corresponding iso-
cyanate that was inclined to further react with water to release
NH
2
group, and then covalently assembled with formyl to
afford the strongly fluorescent phenanthridine derivative
Traditional analytical methods of nerve agents mainly con-
(Scheme 3).
23-25
sist of electrochemistry , gas chromatography-mass spec-
trometry , interferometry and enzymatic bio-sensing tech-
nology . However, cumbersome sample pretreatment, com-
plicated operation, and requirement for large instruments that
greatly handicap their further application.
2
6
27
2
8
EXPERIMENTAL SECTION
Materials and Measurements. All chemicals were pur-
chased from commercial sources and were used directly. Sol-
vent (Analytical Grade) was purchased from Beijing chemical
2
9, 30
The fluorescent
probe technology, which is rapidly developed in recent years,
has been widely used by researchers because of its high sensi-
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Scheme 1. Detection of DCP via Lossen rearrangement.
Scheme 4. Synthetic routes of PTS and compound 4.
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Scheme 2. The “Covalent Assembly” approach.
UV-vis Absorption and Fluorescence Properties. The
characteristics of UV-vis absorption and fluorescence emis-
sion of PTS (10 μM) before and after addition of DCP were
carried out in acetonitrile solution containing TEA (20 μM).
As shown in Figure. 1A, upon binding PTS to DCP (0-20
μM), the absorption signals of PTS at 248 nm decreased and
that at 338 nm increased as a function of the increasing DCP
concentration. For fluorescence emission, a proportionate in-
Scheme 3. Proposed recognition process of PTS for DCP.
Free
DCP
crease of emission at 418 nm (Ф =0.0001, Ф =0.2533)
was measured (Figure. 1B), and a remarkable color change of
the detection system from colorless to blue-violet was ob-
served after exciting at 365 nm with a UV lamp (Figure. 1B,
inset).
Regent Co. NMR and HRMS were recorded on a Bruker AM-
00 Nuclear Magnetic Instrument and Mass Spectrometer,
respectively. Shimadzu UV-1800 Spectrophotometer and Hi-
tachi F-4500 Fluorescence Spectrophotometer were used to
measure the UV-vis and fluorescence spectra, respectively.
4
Synthesis of PTS. The synthetic procedure of probe PTS
and its related compounds were shown and outlined in Scheme
, and their chemical structures were all confirmed by NMR
and HRMS (SI, Figure. S1-S9).
4
Fluorometric Assay Studies. Fluorescence assays were
performed in solutions containing PTS (10 μM), triethylamine
TEA 20 μM) in acetonitrile. Fluorescence response was
measured (λex = 330 nm) upon addition of aliquots of a solu-
tion of DCP in acetonitrile.
(
RESULTS AND DISCUSSION
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Figure 1. Absorption (A) and emission (B) of PTS toward
Figure 3. Time-dependent photoluminescence of PTS to-
ward to DCP in acetonitrile, the spectra were recorded every
20 s (0 to 300 s), [PTS] = 10 μM, [DCP] = 20 μM, [TEA] = 20
μM, λex = 330 nm, λem = 418 nm.
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to DCP (0 to 20 μM) in acetonitrile. [PTS] = 10 μM, [TEA]
=20 μM, λex = 330 nm, λem = 418 nm. Inset: Fluorescence color
change of PTS in absence and presence of DCP, λex = 365 nm.
Sensory Properties. To ascertain the sensing ability of PTS
(10 μM), we plotted the fluorescence emission intensity at 418
nm toward different concentrations of DCP (0-20 μM) and
performed a linear fit. As shown in Figure. 2, with the addition
of DCP (0-20 μM), the fluorescence intensity at 418 nm in-
Selectivity is another important factor of the sensing per-
formance. We employed some possible liquid interferents,
such as phosphorus oxychloride (POCl
(C Cl ), phosphorus trichloride (PCl
(AcCl), hydrochloric acid (HCl) and thionyl chloride (SOCl
3
), oxalyl chloride
), acetyl chloride
).
2
O
2
2
3
2
2
creased smoothly, and a good linear relationship (R =0.9993)
Upon binding PTS with these interferents and DCP at the
same condition, we could find that only DCP could cause the
fluorescence emission at 418 nm, and none of these inter-
ferents casused the same fluorescence change as DCP did
(Figure. 4). These results indicated that PTS exhibited good
specificity toward DCP over other species at 418 nm with ex-
citation at 330 nm.
was obtained by fitting the fluorescence intensity towards
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DCP (2 μM to 16 μM). Meanwhile, in accordance with
43
3
δ/slope , the corresponding detection limit (LOD) was calcu-
lated as low as 10.4 nM.
Figure 2. Linear relationship between emission and DCP
ranging from 0 to 20 μM. All measurements were taken ace-
Figure 4. Fluorescence responses of PTS to DCP as well as
other species in acetonitrile, [PTS] = 10 μM, [TEA] = 20 μM,
tonitrile, [PTS] = 10 μM, [TEA] = 20 μM, λex= 330 nm, λem
18 nm.
Rapid response is a critical index for reactive-type fluores-
=
4
[
DCP] = 20 μM, [other species] = 20 μM for each, λex = 330
nm, λem = 418 nm.
cent probes, especially of significant importance for such a
Nerve-agent-Probe. Therefore, time course for signaling of
PTS with DCP was carried out. By recording fluorescence
intensity change at different time intervals (20 s), a time titra-
tion curve was obtained (Figure. 3). It could be seen that the
fluorescence emission enhanced swiftly and leveled off within
Moreover, some reported nerve agent mimic probes have
been summarized to make a comparison with PTS, and the
results were depicted in Table 1. PTS displayed better proper-
ties in both response time and detection limit than other probes.
Therefore, PTS was more capable of detecting low-level nerve
agent.
1
00 s, and remained almost unchanged even the time was ex-
tended to 5 minutes, which suggest PTS was an effective can-
didate for rapidly monitoring DCP.
Mechanism Investigations. Control experiments were car-
ried out to confirm the probe design hypotheses. The recogni-
tion mechanism was discussed through NMR and HRMS. By
performing the reaction of PTS and DCP, we afforded com-
pound X, which showed the same proton shifts as compound 4
1
(
C) in H NMR titration spectra (Figure. S10). In addition,
+
compound X showed m/z 223.1229 (M+H ), which was con-
sistent with compound 4 (223.1227 M+H ) in HRMS spectra
+
(
Figure. S11). All the above results indicated that PTS con-
versed to compound 4 during the process. In summary, based
on covalent assembly and Lossen rearrangement, we made a
feasible point for the recognition mechanism that shown in
Scheme 5.
Practical Sensing Application. Finally, the action of DCP
vapor on probe PTS was investigated. To make a comparison,
we added PTS (10 μM) in acetonitrile solution containing
TEA (20 μM) in two flasks, and a small bottle containing DCP
was hanged up in one of them, avoiding any contact of liquid
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DCP with PTS. Both flasks were sealed from air and kept at
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room temperature. Once DCP fumes get into touch with the
Table 1. Comparisons of proposed method with recently
reported strategies for nerve agent mimic.
Figure 5. Display of vapour phase sensing of DCP using
PTS coated paper strips at different times under a UV lamp.
CONCLUSION
Probe Response
Dynamic
range
Detection
limit
Response
time
To conclude, a novel probe PTS, which shows a significant
code
type
fluorescence “light-up” response to nerve agent mimic (DCP),
has been developed by combining “Lossen rearrangement”
and "covalent-assembly". PTS features outstanding recogni-
tion capability, fast response (within 100 s) and low detection
limit (10.4 nM) toward DCP. More importantly, the detection
of DCP in gas state has also succeeded. Based on the above,
we are confident that PTS will be an innovative probe for
sensing nerve agents.
12
off-on
on-off
off-on
0 to 3 mg/L
0 to 3 mM
0.71 μg/L
372.7 μM
44 nM
10 min
—
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315
50 to 500 μM
﹤1 min
417
ratiometric
ratiometric
0 to 8 μM
0 to 8 μM
0 to 60 μM
10 nM
18.86 nM
1.87 ppb
﹥60 min
﹤1 min
10 min
—
520
ASSOCIATED CONTENT
Supporting Information
644
off-on
off-on
off-on
722
The Supporting Information is available free of charge on the
ACS Publications website.
0.2 to 1.5 mM 142 nM
0 to 16 μM 10.4 nM
PTS
﹤2 min
Synthesis details, table listing detailed comparison with
some of other chemosensors, and additional figures show-
ing NMR spectra, HRMS spectra, method for determining
quantum yield (PDF).
“
—” Not mentioned
Scheme 5. Recognition mechanism of PTS for DCP.
AUTHOR INFORMATION
Corresponding Author
*
*
(Y.Y.) Email: yxyang@ustb.edu.cn.
(A.G.) Email: gongaijun@ustb.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank National Science Foundation of China (No. 21575012)
and Natural Science Foundation of Beijing (No. 2151003) for
funding this research.
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