A new dibenzothiophene-based dual-channel chemosensor for cyanide with aggregation induced emission

Article abstract of DOI:10.1016/j.jphotochem.2020.112993

Based on dibenzothiophene fluorophore, a new colorimetric and fluorescent sensing material 2-(dibenzothiophenyl-4-ethenylidenyl)-1,3-indanedione (DTI) was developed, which was a favorable turn-off fluorescent sensor of monitoring CN– ion at extremely low detection limit (0.14 μM) in 99 % aq. DMSO solution. The response mechanism of DTI towards CN– could put down to nucleophilic attack of cyanide group (CN–) toward the double-bond between the dibenzothiophene and the 1,3-indanedione units, which breaking intramolecular charge transfer (ICT) process. This mechanism was proposed by ¹H NMR, Job's titration and DFT calculation, leading to a significant fluorescence attenuation and a visual color change. The absorption and emission experiments demonstrated that it showed highly sensitive, selective and good stability for CN– in DMSO/H₂O (1:99, v/v). Moreover, DTI displayed high effectiveness in monitoring the CN– in test strips achieved to conveniently determinate CN– by naked-eye without any instruments.

Full text of DOI:10.1016/j.jphotochem.2020.112993

Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Contents lists available at ScienceDirect
Journal of Photochemistry & Photobiology, A: Chemistry
journal homepage: www.elsevier.com/locate/jphotochem
A new dibenzothiophene-based dual-channel chemosensor for cyanide with
aggregation induced emission
Qiqi Zou, Jinhao Du, Chuanfeng Gu, Datong Zhang, Furong Tao, Yuezhi Cui*
School of Chemical and Pharmaceutical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, PR China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Based on dibenzothiophene fluorophore, a new colorimetric and fluorescent sensing material 2-(dibenzothio-
Colorimetric
phenyl-4-ethenylidenyl)-1,3-indanedione (DTI) was developed, which was a favorable turn-off fluorescent sensor
Fluorescent turn-off sensor
Dibenzothiophene
1,3-indanedione
CN–
of monitoring CN– ion at extremely low detection limit (0.14 μM) in 99 % aq. DMSO solution. The response
mechanism of DTI towards CN– could put down to nucleophilic attack of cyanide group (CN–) toward the
double-bond between the dibenzothiophene and the 1,3-indanedione units, which breaking intramolecular
charge transfer (ICT) process. This mechanism was proposed by 1H NMR, Job’s titration and DFT calculation,
leading to a significant fluorescence attenuation and a visual color change. The absorption and emission ex-
periments demonstrated that it showed highly sensitive, selective and good stability for CN– in DMSO/H2O
(1:99, v/v). Moreover, DTI displayed high effectiveness in monitoring the CN– in test strips achieved to
conveniently determinate CN– by naked-eye without any instruments.
1. Introduction
Hence, efficient, simple and rapid detection method of cyanide is
essential to prevent human poisoning from contaminated environment
Anions are commonly found in nature and play a vital important role
in the fields of life science, medicine, catalysis and the environment [1].
CNꢀ is a highly toxic anionic, even at a lower concentration, which could
cause great harm to human, animal and environment. Cyanide com-
bined with iron ions of the cytochrome oxidase, causing the process of
metastatic electron from cytochrome oxidase to oxygen become more
and more retardation, decreasing the production of ATP in cell, and
brought about the biological system unable to provide energy to central
nervous system, heart and other important organs ultimately [2,3]. By
the way, according to the statistics, at least 2650 species of plants and
microorganism contain cyanide, such as cassava, bitter seeds and
sprouting potatoes and so on [4]. Human englobed CNꢀ into the body
through the lungs, gastrointestinal tract, and skin, causing vomiting, loss
of livestock, loss of consciousness, and even death. In addition, the
World Health Organization (WHO) stipulates, the concentration of CNꢀ
and food.
Different approaches, involving titrimetric analysis, voltammetry,
potentimetric method, chromatography of ions and so on [13–22].
Compared with the method mentioned above for detecting CNꢀ , color-
imetric and fluorescent sensors are of great preference to detect CNꢀ in
virtue of their convenience, simple synthesis method, high sensitivity
and tenability and rapid response. Nevertheless, some sensors displayed
flaws (intricate structure, poor solubility in water, lasting response time,
low sensitivity) in the existing reports, restricted the practical applica-
tion of sensors to detect CNꢀ [23–30]. Therefore, it is of urgent demand
to design and synthesize new structure of fluorescence sensor that could
more efficient and simpler detect more micro trace of cyanide anion in
pure and/or partial aqueous medium.
With the time went by, oligothiophene-based oligomers has been
found to detect CNꢀ [31], Hg2+ and so on [32–35], attributed to its
remarkable coplanarity, powerful electron-donating properties, benign
crystallization properties and excellent photophysical properties
[36–39]. The fluorogen of fluorescent probe intramolecular charge
transfer (ICT) mechanism was linked to recognition group via conju-
gated bond under the emission of light, which caused charge transfer
between fluorogen and recognition group. So far, with the
in drinking water must be less than 1.9 μM [5,6]. If the content of the
CNꢀ in 1 kg of organism reaches the 3.5ꢀ 5 mg, it will have a fatal harm
to the human body [7]. Although CNꢀ has a very strong toxicity, it is still
widely used in the fields of metallurgy, fiber, herbicide, resin, nylon and
polypropane acid [8–12]. In recent years, with the increase of cyanide
poisoning events, cyanide has attracted more and more attention.
* Corresponding author.
E-mail address: yuezhicui@163.com (Y. Cui).
https://doi.org/10.1016/j.jphotochem.2020.112993
Received 17 February 2020; Received in revised form 24 September 2020; Accepted 19 October 2020
Available online 21 October 2020
1010-6030/© 2020 Elsevier B.V. All rights reserved.

Q. Zou et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Scheme 1. The synthesis route of DTI.
intramolecular charge transfer (ICT) mechanism developed, plenty of
typical donor- -acceptor (D- -A) type sensor have been reported to
detect trace ions, which cut off the ICT process [40–49] and it contained
π
π
–
–
–
the subunits (such as C C and C N) that can be attacked by nucleo-
–
philic ions that causes distinct color and spectral changes. Bearing the
unique nucleophilicity of cyanide ions in mind, CNꢀ can be detected by
the D-
π-A type sensor that served as a colorimetric and fluorimetric
sensor.
We herein have successfully synthesized DTI (Scheme 1) as a new
dual-modal colorimetric and fluorescent sensor for cyanide ions detec-
tion, which based on ICT mechanism and displayed high sensitivity and
selectivity in 99 % aqueous DMSO solution. The sensing mechanism
could be attributed to the nucleophilic attack of CNꢀ to
π-conjugation so
that interrupted the ICT process to led to a obvious spectroscopic
response. The overt color change could be lightly distinguished by
naked-eye in the ambient light as well as under UV lamp. For the
detection of CNꢀ probe DTI revealed preeminent uniqueness, fast time
response and low limit of detection (0.14 μM). In addition, DTI was
successfully applied to filter paper strip for detecting CNꢀ .
2. Experimental
2.1. Materials and apparatus
Unless noted otherwise, all chemicals and solvents were obtained as
analytical grade and used without further purification. NMR spectra
were measured on Bruker AvanceII 400 spectrometer in DMSO–d6.
Infrared spectra of DTI and DTI-CNꢀ were recorded on Bruker ALPHA
FT–IR spectrometer using KBr pellets. HRMS analysis was performed on
Agilent 6510 Accurate–Mass Q–TOF LC/MS system. UV–vis and fluo-
rescent spectra were carried out on a Shimadzu UV–2600 and Hitachi
F–4600 fluorescence spectrophotometer, respectively. Anions anions
(Fꢀ , Clꢀ , AcOꢀ , NOꢀ3 , SCNꢀ , CO23ꢀ , HCOꢀ3 , HSOꢀ4 , SO24ꢀ , H2PO4ꢀ , HPO42ꢀ
and CNꢀ ) were purchased from Sigma–Aldrich, which was diluted to
1 × 10–3 M by deionized water (throughout all experiments) to obtain
the stock solution. Compound 1 was purchased from Sigma–Aldrich. All
the analytical solutions were prepared in DMSO/H2O (1:99, v/v)
solution.
Fig. 1. (a) The FL spectra of probe DTI (10 μM) in DMSO/H2O (v/v) mixtures
with different water fraction (ƒw) at λex = 400 nm; (b) Plot of relative FL in-
tensity (blue) and wavelength (green) of DTI as the fw.
DTI upon gradual addition of CNꢀ .
DL = 3δ/S
where δ was the standard deviation of blank sample, S represented the
absolute value of the slope between fluorescence intensity and CNꢀ
concentration.
2.2. Synthesis of the sensor DTI (compound 2)
The synthesis of the compounds are showed in Scheme 1. Compound
1
(0.5 g, 2.4 mmol) was mixed with 1,3-indanedione (0.344 g,
2.4. Computational procedures for HOMO-LUMO energy gap
1.9 mmol) in absolute ethanol (10 mL) and refluxed overnight, then the
mixture was cooled and simple filtered, which followed by washing with
ethanol to remove impurities, and finally vacuum dried to give a bright
yellow solid (0.737 g, yield 92 %). m.p: 277~279 ◦C. 1H NMR:
(400 MHz, DMSO-d6) δ = 9.57 (s, 1 H), 8.80 (d, J =12.0 Hz, 1 H), 8.45
(d, J =8.0 Hz, 1 H), 8.27 (d, J =8.0 Hz, 1 H), 8.14 (d, J =8.0 Hz, 1 H),
8.09 (s, 1 H), 8.03–8.06 (m, 2 H), 7.98–8.01 (m, 2 H), 7.59–7.66 (m,
The HOMO–LUMO energy gap for DTI and its complexes were
calculated by density functional theory (DFT) using Gaussian 09 W. The
DFT based B3LYP/6-31G* model was performed for C, N, O, S, H atoms.
The binding pattern of DTI with CN– were further proposed the calcu-
lation results using DFT.
2 H); FT-IR: (KBr, cm–1)
ν = 1719 (C = O), 1686 (C = C); HRMS (ESI): m/
3. Results and discussion
z [M+H]+ calcd for: C22H12NaO2S: 363.0450, found: 363.0456.
3.1. Synthesis and characterization
2.3. The determination of DL
DTI was synthesized via 1,3-indanedione with dibenzothiophene-2-
The detection limits (DL) was confirmed by emission data of sensor
carbaldehyde in dry EtOH under refluxing for 6 h as shown in Scheme
2

Q. Zou et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Fig. 2. The photography of DTI in DMSO/H2O mixture with different fw (0 % ~ 99 %) under 365 nm UV light.
Fig. 3. (a) Visual solution color change in DTI in the presence of various anions in the sun light. (b) Fluorescence color changes upon anions added to sensor DTI
under 365 nm UV lamp.
1, which was characterized by 1H NMR, FT–IR, HRMS (Figs. S1–S3).
3.2. AIE activity of sensor DTI
increases from 0 % to 99 %, the emission peak of DTI shifts from 523 nm
to 615 nm. When DTI molecules aggregate under high water content, the
large red shift can be attributed to the π-π conjugate (Fig. 1(b)).
It was studied how the AIE effect be affected with the concentration
of DTI. The optimal DTI concentration was determined in the range from
AIE activity of DTI was investigated by fluorescence (FL) spectra.
Since water is a poor solvent, the addition of water to DMSO causes the
aggregation of DTI, which increases emissions. Therefore, the changes in
fluorescence intensity and wavelength of DTI with different percentages
of water (fw) in DMSO/H2O mixture were recorded. As shown in Fig. 1
1 μM to 50 μM. In this range, the AIE factors, which were defined as the
ratio of the highest FL intensity of aggregation solution to that in pure
DMSO, were relatively higher than those in other concentrations, which
changed from 2.8 to 3.9. In this work, the DTI concentration of 10 μM
was selected to study in detail, due to this concentration corresponded to
the highest AIE factor of 3.9 (Fig. 2).
(a), the FL intensity of DTI (10 μM) in pure DMSO (fw = 0 %) is very
weak. The FL intensity of DTI gradually increases with increasing water
content and reaches its maximum at fw = 99 %, which is a 3.9-fold in-
crease compared to the FL intensity (fw = 0 %) in pure DMSO solvent.
These data prove that DTI is a molecule with AIE activity. when fw
Fig. 4. (a) UV–vis absorption spectra of sensor DTI (10
μ
M) towards 1.0 equiv. various anions (Fꢀ , Clꢀ , AcOꢀ , NOꢀ3 , SCNꢀ , CO32ꢀ , HCOꢀ3 , HSOꢀ4 , SO42ꢀ , H2POꢀ4 ,
HPO24ꢀ , CNꢀ ) in DMSO/H2O (1:99, v/v) solution; (b) Changes in the emission spectra of DTI (10
μM) upon addition of different anions (1.0 equiv.) in DMSO/H2O
(1:99, v/v) solution.
3

Q. Zou et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Fig. 7. The time-dependent FL spectrum of DTI toward CN¡.
Fig. 5. Absorption spectra of DTI (10 μM) in 99 % aq. DMSO solution upon the
addition of various concentrations of CN– (0–2.0 equiv.) ions.
peak at 317 nm exhibits red-shift of 5 nm while that at 370 nm shows
blue-shift of 10 nm. However, when adding the other anions but CNꢀ ,
the absorption spectra remains almost unchanged relative to that of pure
DTI. These spectral results are in well agreement with the phenomenon
shown in Fig. 3(a).
3.3. Sensing performance of DTI
3.3.1. Selectivity and anti-interference of anions
To conveniently observe the sensing properties of sensor DTI, the
absorption spectral experiments of recognition and sensing ability to-
wards various anions (Fꢀ , Clꢀ , AcOꢀ , NO3ꢀ , SCNꢀ , CO32ꢀ , HCO3ꢀ , HSOꢀ4 ,
SO42ꢀ , H2POꢀ4 , HPO42ꢀ , CNꢀ ) in DMSO/H2O (1:99, v/v) solution were
examined at room temperature. As displayed in Fig. 3(a), upon addition
of CN– solution, the sensor DTI instantaneously interacts with CN- along
with the solution color changes from yellow to light yellow. Further-
more, a intense bright blue fluorescence is clearly investigated by naked-
eye under 365 nm UV lamp upon addition of CN– solution, which is
remarkable different from those yellow fluorescence upon addition
other anions (Fig. 3(b)).
The emission spectra of DTI shows fluorescence peak at 610 nm
under the excitation wavelength of 400 nm, which is ascribed to ICT
process (Fig. 4(b)). Upon addition of each tested anions (1.0 equiv.)
except for CN–, only negligible change is observed in the emission
spectra. However, the emission intensity remarkably decreased upon
addition of CN–, which indicates the ICT process is interrupted due to
the nucleophilic attack by CNꢀ . These results revealed that DTI can be
severed as a simple ‘turn off’ sensor for naked-eye and fluorescent
monitoring CN– in 99 % aq. DMSO.
Fig. 4 shows the absorption and emission spectra of DTI upon addi-
tion of various anions. As observed in Fig. 4(a), there are three ab-
sorption bands in the absorption spectrum of DTI, with peak
wavelengths at 236 nm, 317 nm and 380 nm, respectively. The peaks at
3.3.2. Detection performance of sensor DTI to CN–
The variation in the absorption of DTI after addition of CN– of
various concentration were carried out in 99 % aq. DMSO solution
(Fig. 5).
236 and 317 nm are assigned to the local π-π* electronic transition of
In the absorption spectral, It can be clearly found that the absorption
bands at 380 nm, 317 nm and 236 nm gradually attenuate along with a
progressive enhancement of new absorption peak at 287 nm upon
addition of concentration-increasing of CN– (0–2.0 equiv.).
DTI shows strong emission peak at 610 nm (λex = 400 nm) due to
intramolecular charge transfer (ICT). Upon successive addition of CN–
benzene, dibenzothiophene and 1,3-indanedione units, while that at
380 nm may be attributed to the intramolecular charge transfer (ICT)
from the dibenzothiophene to the indanedione units.With addition of
CNꢀ , all the three peaks at 236, 317 and 380 nm are decreased,
accompanied by the appearing of a new peak at 278 nm. Moreover, the
Fig. 6. (a) Fluorescence titration of DTI (10
CN– (right).
μM) with the gradually increasing of CN– (0–2.0 equiv.) concentration (left); (b) The detection limit of DTI for
4

Q. Zou et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Fig. 8. Competitive experiments of DTI (10 μM) for CN– (10.0 equiv.) in the
Fig. 10. The Job’s plot for DTI (10
μ
M) towards CNꢀ in 99 % aqueous
presence of common anions (10.0 equiv.) in DMSO/H2O (1:99, v/v).
DMSO solution.
equiv.) in DMSO/H2O (1:99, v/v). As noticed in Fig. 8, It is unaffected in
CN–-induced emission intensity in the presence of coexistence ions,
which showed the efficient signaling and higher anti-interference ability
of DTI-CN– system.
3.4. Detection mechanism
The interaction mechanism of DTI towards CN– may be attributed to
nucleophilic cyanide attacking the π-conjugated position of the 1,3-inda-
nedione, which was confirmed by 1H NMR (Fig. 9). In the 1H NMR
spectrum, the proton signal of aromatic on free DTI appears at around
7.65–8.82 ppm (7 H), whereas these protons clearly exhibited an upshift
to 7.05–8.22 ppm (7 H) after addition of 1.0 equiv. of CN–, due to the
breaking of conjugation between vinyl and thiophene units. It is also be
observed that the compound DTI displays a single peak at 9.59 ppm
Fig. 9. 1H NMR spectra (400 Hz, DMSO–d6) of sensor DTI in the absence and
presence of CN– (1.0 equiv.).
–
corresponding to the proton of C C (H ). However, the presence of CN–
–
a
with the amount from 0 to 2.0 equiv., the fluorescence emission band at
610 nm decreases gradually together with a 14 nm blue-shift, indicating
that DTI could be used as a potential candidate to quantitatively monitor
CN–. The linear regression equation (R2 = 0.99186) was performed ac-
cording to fluorescence intensity against concentration of CN– (Fig. 6
(b)) to determine the slope. The limit of detection (LOD) was calculated
to be 2.26 × 10ꢀ 7 M using the equation (3δ/S); where δ was the standard
deviation of DTI, and S represented the slope of linear fitting. This LOD
value is much lower than the limit maximum of CN– in drinking water
resulted in the complete disappearance of the vinyl Ha proton together
with the observation of a new upfield signal (Hb) at around 4.60 ppm.
The results of 1HNMR spectra indicate that the proposed sensing
mechanism (Scheme 2) is the nucleophilic attack of CNꢀ to vinyl unit
with the formation of a new specie (DTI-CN¡), which efficiently blocks
the intramolecular charge transfer (ICT) process and causes both the
fluorescence attenuation and absorption spectral blue shift.
Additionally, the Job’s titration was researched, which indicated
that the stoichiometric ratio of reaction between DTI and CN– was 1:1
(Fig. 10). This stoichiometric ratio is in well agreement with the
mechanism proposed in Scheme 2
(～1.9 μM) set by the WHO. In addition, the rapid decrease of the
emission intensity at 610 nm is observed in fluorescence spectral in the
presence of CN– (0–2.0 equiv.), which achieves the intensity minimum
and stable value within 15 s (Fig. 7). These data clearly demonstrate that
CN– can result in both the color change of DTI solution and the atten-
uation of emission intensity, indicating DTI may be a potential candidate
to be used in portable device for rapid CN– detection.
This mechanism can also be proved by the absorption and emission
spectral changes of DTI after adding CNꢀ to DTI (seen in Figs. 4 and 5).
Due to the ICT process is blocked by CNꢀ , the absorption peak at 380 nm
and the emission band and 610 nm, both of which are ascribed to ICT
process, decreased remarkably, while a new absorption peak at 278 nm
To further confirm the specifically selective attenuation of DTI to
CN–, a competition experiment was investigated upon addition of 10-
fold CN– to DTI solution containing other common anions (10.0
that is ascribed to a local π–π* electron transition arises. Furthermore,
with the increase of CNꢀ concentration, the new absorption peak gets
stronger.
Scheme 2. Proposing the sensing mechanism between DTI and CN–.
5

Q. Zou et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
Fig. 11. DFT calculated optimized structure of DTI and DTI-CN–.
Fig. 12. Colour changes of test strip containing sensor DTI for CN– detection under sunlight and 365 nm UV light.
3.5. Theoretical calculations
eyes only when CN– was added to DTI-based test strips. Hence, sensor
DTI exhibited excellent colorimetric and fluorimetric response proper-
ties in the solid state, and DTI could be made into simple paper strips to
conveniently sense CNꢀ in water by naked eyes without requiring any
expensive equipment.
The density functional theory (DFT) calculations were performed to
be aware of the changes of colorimetric and fluorescence of DTI with the
addition of CNꢀ at the B3LYP/6-31G* level using the Gaussian 09
package. Fig. 11 states the optimized geometries of DTI and DTI-CN¡. It
is clearly observed that compound DTI is nearly in the same planar via
4. Conclusions
2
–
–
the formation of a
π
-conjugation bridge (C C, sp ), resulting in intra-
molecular charge transfer (ICT) from electron-donating (dibenzothio-
A novel dibenzothiophene-based dual-channel fluorometric/colori-
metric senor DTI that exhibited CN– selective fluorescence ‘on-off’
behavior was designed and synthesized. The sensor DTI showed highly
selectivity, excellent sensitivity, rapid interaction time (within 15 s) and
phene) to electron-accepting (1,3-indanedione). However, introducing
the CNꢀ to
π
-conjugation bridge (C C) undergoes an obvious twist on
–
–
DTI-CN¡, causing the formation of a nearly sp3-hybridized carbon bond
and V-shaped conformation. The apparent structure twist results in the
low LOD (0.14 μM) for CN– detection in DMSO/H2O (1:99, v/v) with
interruption of the
π
-conjugation which blocks the ICT process, thus a
visual color change from yellow to colourless over other competitive
anions. The phenomenon of fluorescence ‘on-off’ of sensor DTI in the
presence of CN– was observed by strong nucleophilic of cyanide
new absorption band around 278 nm appeared in Fig. 5.
resulting in interruption of π-conjugation and blocking the ICT. The
3.6. Test strips for CNꢀ detection in 100 % aqueous DMSO
sensing mechanism was evidenced by absorption and emission spec-
1
troscopic analysis, H NMR titration, and DFT calculations. Moreover,
Test strips of sensor DTI in the presence and absence of CN– were
prepared by immersing filter papers in its DMSO/H2O (1:99, v/v) so-
lution and drying them in the air to explore its application by the
colorimetric and fluorimetric methods in the solid state. These test strips
containing DTI were illustrated in Fig. 12 to monitor CN– in water. An
obvious color change under visible light (from yellow-green to light
yellow) and 365 nm (from green to blue) was clearly observed by naked
the excellent fluorescence response in the solid sate were clearly
confirmed by test strips containing sensor DTI to conveniently detect
CN– without any additional equipment.
6

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Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112993
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Declaration of Competing Interest
The authors reported no declarations of interest.
Acknowledgments
This work was financially supported by the Natural Science Foun-
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