Sensors and Actuators B 255 (2018) 3170–3178

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Research paper

A novel turn-on fluorescent probe for cyanide detection in aqueous

media based on a BODIPY-hemicyanine conjugate
Yanhua Yu a,∗ , Tingting Shu a , Bingjie Yu a , Yun Deng a , Cheng Fu a , Yangguan Gao a ,
Changzhi Dong a,c , Yibin Ruan b,∗
a
Institute for Interdisciplinary Research, Jianghan University, Wuhan 430056, China
b
Technology Center of China Tobacco Guizhou Industrial Co. Ltd., Guiyang 550003, China
c
University Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS 7086, 15 rue J-A de Baïf, 75205 Paris Cedex 13, France

a r t i c l e i n f o a b s t r a c t

Article history: A novel BODIPY-hemicyanine based fluorescent probe 1 for cyanide (CN− ) detection was designed and
Received 3 July 2017 synthesized. Among the tested anions, the probe showed high selectivity towards CN− . Only addition
Received in revised form of CN− to probe 1 in aqueous solution (VH2O /VEtOH = 1/1) could result in a remarkable blue shift of the
19 September 2017
absorption band from 385 nm to 265 nm and induce 20-fold fluorescence enhancement at 515 nm. The
Accepted 20 September 2017
sensing mechanism was based on nucleophilic addition between CN− and indolium group, which was
Available online 21 September 2017
confirmed by 1 H NMR and mass spectrum analysis. Plot of fluorescence intensity as a function of CN−
concentrations exhibited a good linear relationship in the range of 0–10 ␮M, with a detection limit to
Keywords:
Cyanide
be 1.53 ppb. Moreover, the proposed sensing approach could work in a wide pH range from 5.0–9.0 and
BODIPY-hemicyanine conjugate reach an equilibrium instantaneously. Finally, probe 1 was successfully applied in detection of CN− in
Fluorescence enhancement natural water samples and on test paper strips with satisfactory results.
Michael addition © 2017 Elsevier B.V. All rights reserved.

1. Introduction injection [9], colorimetric and fluorescent sensors [10–31]. Among

Cyanide compounds are one of the most toxic species to human
health and environment [1], due to their powerful interaction with
ferric iron atoms in metalloenzymes, which can disorder some
important biological processes like cellular respiration and oxida-
tive metabolism [2]. Still they are widely utilized in chemical and
industrial processes, such as plastics production, gold mining, met-
allurgy, synthetic fibers and the resins industry [3]. Any accidental
release of cyanide into the environment could cause serious health
problems. It was reported that in 2015 a large amount of cyanide
was leaked out in Tianjin Port by accident, which was considered
to be a serious environmental disaster. Moreover, according to the
World Health Organization (WHO), the maximum permissive level
of cyanide in the drinking water is 1.9 ␮M [4]. Therefore, it is great
of importance to develop novel approaches for cyanide anion detec-
tion.
The strategies for detecting cyanide include mass spectrometry
[5], electrochemistry [6], ion chromatography [7], headspace sorp-
tive solid phase microextraction with a spectrophotometry [8], flow
∗ Corresponding authors.
E-mail addresses: hpyyh@aliyun.com (Y. Yu), ybruan@xmu.edu.cn (Y. Ruan).
these methods, fluorescent sensors have drawn much attention due
to their various advantages over other techniques, such as sim-
ple operation, versatile adaptation, low-cost, portability, excellent
sensitivity and rapid response. The reported CN− fluorescent sen-
sors were mainly based on metal complex ensemble displacement
[32–39], nucleophilic addition [40], nanoparticles and polymeric
frameworks [41,42]. Among them, nucleophilic-reactions based on
dicyano-vinyl [43–47], pyridinium ring [48], oxazines [49], acri-
dinium [50], aldehyde [51,52], boronic acid [53], indolium groups
[54–61], generally exhibit satisfactory selectivity due to the excep-
tional nucleophilicity of CN− . Indolium has recently emerged as
one of most promising reactive group for CN− because of its pos-
itive charge character which results in a strong attractive force
between indolium group and CN− . The detailed computational cal-
culations further demonstrated that solvation of anions by H2 O
finally give the unique selectivity for CN− [62]. However, many of
them still existed several drawbacks in aqueous environment such
as low sensitivity, narrow pH working range, which cannot fulfill
the requirement for the real sample analysis [63–65].
Borondipyrromethene (BODIPY) derivatives have been widely
used in CN− detection due to its distinct advantages such as large
molar excitation coefficient, high fluorescence quantum yield, nar-
row emission bandwidth, high photostability, small stokes shifts

https://doi.org/10.1016/j.snb.2017.09.142
0925-4005/© 2017 Elsevier B.V. All rights reserved.
 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178
Scheme 1. Design and synthesis of BODIPY-hemicyanine dye 1.
and tunable fluorescence characteristic [66–74]. In this work, we
herein report a novel fluorescent BODIPY–hemicyanine probe 1 (as
shown in Scheme 1) as a highly selective and sensitive turn-on fluo-
rescent probe for CN− detection in aqueous solution. Hemicyanine
unit containing indolium group which was incorporated to BODIPY
not only acted as the binding unit for CN− , but also promoted the
intramolecular charge transfer (ICT) process and quenched fluores-
cence of BODIPY. When hemicyanine was attacked by CN− through
nucleophilic addition, ICT process was blocked which then led to
turn-on fluorescence. As expected, this BODIPY-hemicyanine based
probe showed excellent selectivity to CN− over other tested anions.
Furthermore, It’s worthy of notice that the BODIPY group was not
a good electron donor, which could lead to a more positive charge
distribution on indolium group and give a fast kinetics and low
detection limit for CN− detection. In our protocol the response time
was within 3 s in aqueous media and the detection limit was cal-
culated to be 59 nM, far lower than the permissive level of WHO
in drinking water. Finally, this probe was successfully applied to
detect CN− in real water samples and on the test paper strips.
2. Materials and methods
2.1. Materials
4-Hydroxymethylbenzaldehyde, 2,4-dimethylpyrrole, 2,3-
dicyano-5,6-dichlorobenzoquinone (DDQ), trifluoroacetic acid
(TFA), boron trifluoride ether complex (BF3 ·OEt2 ) were purchased
from Sigma-Aldrich without further purification. Triethylamine,
manganese dioxide, piperidine and solvents were purchased
from Aladdin (Shanghai, China). In anhydrous reaction, ethanol
was dried by distillation over sodium according to the stan-
dard procedures. Solvents used for extraction treatment and
column chromatography such as petroleum ether, ethyl acetate,
dichloromethane and methanol were purchased from Sinopharm
Chemical Reagent Co., Ltd (Shanghai, China) in commercial grade
and distilled before use. All column chromatography was carried
out using silica gel (200–300 mesh). Thin layer chromatography
(TLC) was performed on silica gel coated on aluminum plates.
Milli-Q water was used in all aqueous analytical experiments. All
anions were prepared from their tetrabutylammonium (TBA+ )
salts.
2.2. Apparatus
Ultraviolet-visible (UV-vis) spectra were measured on a Perkin
Elmer Lambda 25 spectrometer. Fluorescence spectra measure-
ments were performed on a Perkin Elmer LS 55 spectrometer.
Perkin Elmer quartz cells with an inner path length of 10 mm
were used for absorption and fluorescence spectroscopy mea-
3171
surement. 1 H NMR, 13 C NMR spectra were collected on a Bruker
Advance 400 MHz spectrometer in CDCl3 , tetramethylsilane (TMS)
as internal standard, chemical shifts are given in ppm related to
the protonated solvent as internal reference (1 H: CHCl3 in CDCl3 ,
7.26 ppm, 13 CDCl3 in CDCl3 , 77.16 ppm), coupling constants (J) are
given in Hz, the following abbreviations were used to explain
the multiplicities: s = singlet; d = doublet; m = multiplet. MS spectra
were recorded on a Bruker amaZon SL instrument using stan-
dard conditions (ESI). All the measurement experiments were
performed at room temperature.
2.3. Synthesis and characterization
2.3.1. Synthesis of 1,3,5,6-tetramethyl-
8-(4-(hydroxymethyl)phenyl)BODIPY 2
1,3,5,6-tetramethyl- 8-(4-(hydroxymethyl)phenyl)BODIPY 2
was synthesized according to the literature reported pro-
cedures [52]. To a solution of 2,4-dimethylpyrrole (2.2 mL,
20.0 mmol) in deoxygenated CH2 Cl2 (150 mL) was added 4-
hydroxymethylbenzaldehyde (1.4 g, 10.0 mmol) and one drop of
TFA at room temperature. The mixture was stirred over 12 h under
argon, then treated with DDQ (2.3 g, 10.0 mmol), the mixture was
continued stirring for 1 h followed by addition of Et3 N (30 mL).
After stirring for 15 min, the solution was cooled to 0 ◦ C, then
BF3 ·OEt2 (30 mL) was added to the solution, the mixture was
stirred at room temperature for further 3 h. After the completion
of reaction, washed with saturated NaHCO3 solution, the organic
phase was separated, dried over MgSO4, filtered, and concentrated.
The residue was purified by silica gel column chromatography
(CH2 Cl2 /petroleum ether: 1/2) to give compound 2 (0.9 g, 2.5 mmol)
as a red solid in 50% yield. 1 H NMR (400 MHz, CDCl3) ı 7.49 (d,
J = 7.8 Hz, 2H), 7.27 (d, J = 7.8 Hz, 2H), 5.98 (s, 2H), 4.80 (s, 2H), 2.55
(s, 6H), 1.38 (s, 6H). 13 C NMR (101 MHz, CDCl3 )ı155.49, 143.10,
141.89, 141.56, 134.20, 131.48, 128.18, 127.39, 121.22, 64.66, 14.48.
HRMS: calculated for [M + H]+ : 355.1793, measured: 355.1712.
2.3.2. Synthesis of 1,3,5,6-tetramethyl-
8-(4-(formylphenyl))BODIPY 3
To a solution of compound 2 (0.9 g, 2.5 mmol) in CH2 Cl2 (150 mL)
was added MnO2 (5.4 g, 62.5 mmol), the mixture was refluxed
over 12 h. After the completion of reaction, the mixture was fil-
tered through celite, the filtrate was evaporated, then the solid
residue was further purified by silica gel column chromatography
(CH2 Cl2 /petroleum ether: 1/2) to give compound 3 (0.7 g, 2.0 mmol)
as a red solid in 80% yield. 1 H NMR (400 MHz, CDCl3 ) ı 10.14 (s,
1H), 8.03 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 7.8 Hz, 2H), 6.00 (s, 2H), 2.56
(s, 6H), 1.36 (s, 6H). 13 C NMR (101 MHz, CDCl3 ) ı 191.46, 156.26,
142.76, 141.41, 139.69, 136.68, 130.83, 130.34, 129.16, 121.64,
3172 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178

14.63, 14.52. HRMS: calculated for [M + Na]+ : 375.1456, measured:

375.1475.

2.3.3. Synthesis of BODIPY-hemicyanine conjugate 1

To a solution of compound 3 (0.5 g 1.4 mmol) in anhydrous
ethanol was added compound 4 (0.4 g, 1.4 mmol) and piperidine (3
drops). The mixture was refluxed over 12 h, After cooling the solid
was collected, washed with anhydrous ethanol, then dried, giving
a solid. The solid was purified by silica gel column chromatogra-
phy (CH2 Cl2 /MeOH: 100/1) to give compound 1 (0.5 g, 0.78 mmol)
as a dark purple solid in 56% yield. 1 H NMR (400 MHz, CDCl3 ) ı
8.36-8.23 (m, 3H), 7.96 (d, J = 16.3 Hz, 1H), 7.62-7.59 (m, 4H), 7.49-
7.47 (m, 2H), 5.99 (s, 2H), 4.54 (s, 3H), 2.56 (s, 6H), 1.91 (s, 6H),
1.42 (s, 6H).13 C NMR (101 MHz, CDCl3 ) ı 182.66, 174.25, 156.14,
152.78, 143.08, 142.89, 141.53, 140.51, 139.82, 134.37, 131.70,
130.84, 130.43, 129.86, 129.48, 128.94, 125.39, 122.65, 122.01,
121.57, 115.35, 114.66, 110.90, 105.02, 52.92, 48.86, 37.66, 32.77,
28.11, 26.70, 14.88, 14.66. HRMS: calculated for [M]+ : 508.2730,
measured: 508.2751.
Fig. 1. Absorption spectra of probe 1 (10 ␮M) in aqueous solution (VH2O /VEtOH = 1/1)
with increasing CN− concentrations; inset: the absorption intensity at A385nm versus
2.4. Photophysical property study
concentration of CN− from 0 to 60 ␮M.

The stock solution of probe 1 (1 mM) was prepared in ethanol.

The UV–vis absorption spectra of the solutions were measured in
a 1 cm quartz cell from 250 nm to 600 nm at room temperature.
The fluorescence spectra were measured from 475 nm to 625 nm
at room temperature using an excitation wavelength at 385 nm.
The spectra were acquired from 10 ␮M solutions, diluted from the
stock solution with their respective solvents.
2.5. UV–vis absorption and fluorescence spectra study
All the UV–vis absorption and fluorescence spectra were
acquired from ethanol and water (V/V = 1/1). The stock solutions
of the tested anions (F− , Cl− , Br− , I− , ClO4 − , AcO− , H2 PO4 − , NO3 − ,
HSO4 − , CN− ) (5 mM) were prepared by dissolving their tetrabuty-
lammonium (TBA+ ) salts in Milli-Q water. For selectivity study, the
volumes of the mixtures were adjusted to 2.5 mL by ethanol and
water (V/V = 1/1) to afford the final concentration of 10 mM for the
fluorophores and 80 mM for the anions. The mixture was shaken for
3 s before recording absorption and fluorescence spectra. For CN−
titration study, to a solution of probe 1 (10 ␮M) was added CN− (0.1
equiv.) and the mixture was shaken for 3 s before recording absorp-
tion and fluorescence spectra. This step was repeated until reaching
the desired amount of CN− . The fluorescence quantum yield (ФF )
was calculated by the standard method using Rhodamine 6G in
ethanol as a reference.
2.6. Job’s plot measurements
A series of solutions containing probe 1 and CN− in the mixture
of ethanol and water (V/V = 1/1) were prepared, which the sum of
the concentrations remained constant (10 ␮M). The molar fraction
of probe 1 was varied from 0 to 1. After measuring fluorescent
intensity of each solution,F(F = F(probe 1) − F(probe 1 + CN− ))
was plotted against the molar fractions of probe 1.
2.7. Paper-based sensor
The solution of probe 1 (0.1 mM, 20 ␮L) in aqueous solution
(VH2O /VEtOH = 1/1) was pipetted onto the filter paper and then dried
by air. Various anions and CN− at different concentrations (20 ␮L)
were pipetted onto the surface of the spots of probe 1. After air
drying, the images of the filter paper under 365 nm UV lamp were
photographically recorded.
3. Results and discussions
3.1. Design and synthesis of probe 1
Synthesis of probe 1 was illustrated in Scheme 1.
BODIPY 2 was synthesized through a condensation of 4-
hydroxymethylbenzaldehyde and 2,4-dimethylpyrrole in the
presence of trifluoroacetic acid (TFA) as catalyst in CH2 Cl2 solution,
followed by oxidation with 2,3-dicyano-5,6-dichlorobenzoquinone
(DDQ). The boron difluoride bridge was formed by treatment with
boron trifluoride diethyl etherate (BF3 ·Et2 O) and triethylamine.
Hydroxyl group was oxidized by MnO2 to afford BODIPY 3 in 80%
yields. BODIPY-hemicyanine conjugate 1 was prepared in 56%
yields from a Knoevenagel condensation between BODIPY 3 with
1-methyl-2,3,3-trimethyl-3H-indolium, which was synthesized
according to the reported procedures [53]. Compounds 2, 3 and 1
were well characterized by 1 H NMR, 13 C NMR and HRMS.
3.2. Optical properties of probe 1
With probe 1 in hand, we firstly examined its sensing ability
towards CN− in aqueous solution (VH2O /VEtOH = 1/1) by UV–vis and
fluorescence spectroscopy. As shown in Fig. 1, probe 1 exhibits
three main absorption bands peaked at 385 and 502, 545 nm, which
are respectively attributed to intramolecular charge transfer from
BODIPY to hemicyanine and BODIPY’s typical absorption. With the
incremental additions of CN− , the absorption band of probe 1 at
385 nm decreases progressively with appearance of a new band at
256 nm; and the absorption bands at 502 nm and 545 nm decreased
slightly. An isosbestic point at 295 nm was observed, which indi-
cated formation of a new species. Plot of change in the absorption
band at 385 nm of probe 1 as a function of the added CN− con-
centrations ranging from 0 to 11 mM gave a good linear regression
(R2 = 0.991) and reached a plateau in the presence of 2.0 equiv. of
CN− (Fig. 2).
Fluorescence response of probe 1 towards CN− was also inves-
tigated. As shown in Fig. 3, probe 1 exhibits an emission band
centered at 515 nm upon excitation at 385 nm, which could be
attributed to emission of BODIPY moiety. With increasing addi-
tion of CN− , fluorescence intensity at 515 nm increased gradually
and reached a plateau in the presence of 20 ␮M CN− . Meanwhile,
the fluorescence quantum yield (ФF ) increased from 0.015 to 0.33
(SI). The initial weak fluorescence emission of probe 1 was proba-
 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178 3173

Table 1
Comparison of CN− detection limit of probe 1 with other reported sensors.

Sensors Solvent Detection limit Ref.

Coumarin-based MeCN/buffer (V/V = 1/1) 9.37 ␮M [58]

Naphthaldehyde-based EtOH/H2 O (V/V = 95/5) 1.6 ␮M [75]
Benzofurazan-based CH3 CN/H2 O (V/V = 95/5) 1.5 ␮M [76]
Indanedione-based THF/H2 O (V/V = 1/9) 0.94 ␮M [16]
BODIPY-salicylaldehyde-based DMSO/buffer (V/V = 9/1) 0.88 ␮M [51]
Diketopyrrolopyrrole-based THF 0.36 ␮M [77]
Gold nanodots-based Water 0.15 ␮M [18]
Dicyanovinyl-based DMSO/H2 O (V/V = 2/8) 0.14 ␮M [78]
Carbazole-based CH3 CN/H2 O (V/V = 95/5) 0.13 ␮M [79]
BODIPY-hemicyanine conjugate EtOH/H2 O (V/V = 1/1) 0.059 ␮M present work

Fig. 2. Plot of change in absorption band of probe 1 at 358 nm as a function of Fig. 4. Linear relationship between fluorescence intensity ratio (I/I0 ) of probe
concentrations of CN− from 0 to 11 ␮M in aqueous solution (VH2O /VEtOH = 1/1). 1 and the low concentrations of CN− from 0 to 10 ␮M in aqueous solution
(VH2O /VEtOH = 1/1).

(1.53 ppb) according to the equation 3s/k, where s is the standard

deviation of the blank measurements and k is the slope of the inten-
sity ratio versus the sample concentration plot. The detection limit
in present work is much lower than other reported CN− -selective
sensors (Table 1) and three times lower than maximum permissi-
ble level of CN− in drinking water proposed by the World Health
Organization (WHO).

3.3. Selectivity of probe 1 for CN− detection

Selectivity of probe 1 to CN− was evaluated by screening a series

Fig. 3. Fluorescence spectra of probe 1 (10 ␮M) in aqueous solution
(VH2O /VEtOH = 1/1) as a function of CN− concentration; inset: fluorescence
intensity ratio (I/I0 ) versus concentration of CN− from 0 to 60 ␮M.
bly due to the ICT from BODIPY unit to the strong electron acceptor
indolium group through its ␲-conjugated bridge. After nucleophilic
attack of CN− to indolium group, the electron accepting ability
of indolium group was strongly reduced and the ICT process was
blocked, which then led to turn-on fluorescent signal of BODIPY.
Plot of fluorescence intensity (I/I0 ) as a function of the concentra-
tions of CN− also exhibited a good linear relationship (R2 = 0.993)
in the range of 0–10 ␮M (Fig. 4). The limit of detection for CN−
based on fluorescence spectral changes was calculated to be 59 nM
of anions such as F− , Cl− , Br− , I− , ClO4 − , AcO− , H2 PO4 − , NO3 − ,
HSO4 − , CN− in aqueous solution (VH2O /VEtOH = 1/1). As shown in
Figs. 5 and 6, only addition of CN− can lead to a considerable absorp-
tion spectral change and turn-on fluorescence emission, while
other tested anions show no influence. This demonstrated that
probe 1 showed excellent selectivity for CN− over the other tested
anions. Emission color changes from blank to green were easily
observed by the naked-eye under the illumination with a 365 nm
UV-lamp (Fig. 7). While color changes from orange to pink under
daylight could be only be observed with increasing the solution
concentration to 0.1 mM (Fig. S1)
3.4. Competition studies of probe 1 for CN− detection
To further confirm practical applicability of probe 1 for CN−
detection, a competition experiment was carried out. As shown in
Fig. 8, introducing the interfering anions including F− , Cl− , Br− , I− ,
ClO4 − , AcO− , H2 PO4 − , NO3 − , HSO4 − , CN− to the solution of probe
1 did not cause any fluorescence emission changes. A significant
fluorescence enhancement was observed after the addition of CN−
3174 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178

Fig. 5. Absorption spectra of probe 1 (10 ␮M) in aqueous solution (VH2O /VEtOH = 1/1)
in the presence of 8 equiv. different anions.
Fig. 8. Fluorescence intensity ratio (I/I0 ) of probe 1 (10 ␮M) in aqueous solution
(VH2O /VEtOH = 1/1) in the presence of different anions (80 ␮M) without/with CN−
(40 ␮M).

Fig. 6. Fluorescence spectra of probe 1 (10 ␮M) in aqueous solution

(VH2O /VEtOH = 1/1) in the presence of 8 equiv. different anions. (lex = 385 nm,
slit: 5 nm/5 nm).
in all the interfering samples. This phenomenon demonstrated that
probe 1 had excellent selectivity for CN− detection over the other
anions even in the complicated environment.
3.5. pH influence
It’s well known that the existing forms of CN− are highly pH-
dependent, which would then strongly affect the nucleophilic
addition reaction. Therefore, pH influence on spectral response of
probe 1 to CN− was investigated at different pH values (10 mM
NaH2 PO4 -citric acid buffer for pH 2.2–8.0 and 10 mM glycine-
Fig. 9. Fluorescence intensity at 515 nm of probe 1 (10 ␮M) in the absence and
presence of CN− (80 ␮M) as a function of pHs.
hydroxide buffer for pH 9.0–10.6). As depicted in Fig. 9, no
significant fluorescence changes could be observed at pH values
lower than 9 in the absence of CN− , while a 4-fold fluorescence
enhancement was detected when pH was higher than 10. This
might be attributed to the nucleophilic attack of OH− to probe 1. In
presence of CN−, almost no spectral change could be observed at pH
below 4, which indicated that no reaction occurred between probe
1 and HCN. While in the pH range from 5 to 9, the fluorescence
intensity at 515 nm of probe 1 increased remarkably in presence

Fig. 7. A visual fluorescence changes of probe 1 (10 ␮M) in aqueous solution (VH2O /VEtOH = 1/1) in the presence of 8 equiv. different anions under illumination with a 365 nm
UV lamp.
 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178 3175

Scheme 2. The proposed mechanism of probe 1 for CN− detection.

Table 2
Recovery data for CN− detection in spiked water samples.

Samples Spiked (␮M) Found (␮M) Recovery (%) RSD (%)

Lake water 5.0 5.23 ± 0.11 104.05 ± 2.03 1.81

8.0 7.87 ± 0.12 98.39 ± 1.51 1.35

Minerals water 5.0 5.13 ± 0.18 102.56 ± 3.73 3.64

8.0 8.17 ± 0.20 102.16 ± 2.28 2.79

Drinking water 5.0 5.27 ± 0.19 105.46 ± 3.67 1.67

8.0 7.83 ± 0.14 97.93 ± 1.81 1.68

shift of the absorption spectrum and fluorescence enhancement.

Fig. 10. Time-dependent fluorescence intensity at 515 nm of probe 1 (10 ␮M) in
aqueous solution (VH2O /VEtOH = 1/1) in the presence CN− (20 ␮M).
of CN− . The results indicated that the probe 1 was stable in the pH
range from 2 to 9 and could successfully detect CN− in a range of
pH values from 5 to 9.This is more applicable in real sample when
compared with other reported results.
3.6. Effect of reaction time
Using chemodosimeters as a sensing approach usually takes
minutes or hours to complete the reactions, which restricts their
applications in the real-time detection. As shown in Fig. 10, we use
fluorescence spectroscopy to monitor the reaction between probe 1
and CN− in aqueous solution (VH2O /VEtOH = 1/1). Quite surprisingly,
this reaction was very fast and reached a plateau instantaneously,
which might be attributed to the poor electron-donating ability of
BODIPY unit in probe 1. Due to this fast kinetics, it showed promis-
ing applications in real-time detection for CN− .
3.7. Mechanism study
Based on the data collected from the absorption and fluores-
cence spectra, it’s deduced that nucleophilic addition between CN−
and hemicyanine moiety in probe 1 was responsible for the blue
To confirm this plausible mechanism, 1 H NMR titration with CN−
was carried out in CDCl3 . As illustrated in Scheme 2 and Fig. 11,
upon addition of TBACN to probe 1, the vinyl protons (Ha and
Hb ) displayed upfield shifts from 8.25 ppm, 8.00 ppm to 6.62 ppm,
6.33 ppm and the N-methyl protons (He ) displayed an upfield shift
from 4.55 ppm to 3.36 ppm. Moreover, the singlet peak correspond-
ing to C-methyl protons (Hc and Hd ) in probe 1 shifted from
1.90 ppm (s, 6H) to 1.58 ppm (s, 3H) and 1.33 ppm (s, 3H), which
indicated C-methyl was adjacent to a chiral center. All these infor-
mation supported the above assumption that nucleophilic attack
of CN− to hemicyanine moiety of probe 1 led to formation of 1–CN
adduct, in which the positive charged indolium group changed
into a neutral indole group with poor electron-withdrawing prop-
erty. Job’s plot analysis also revealed that the probe 1 formed a 1:
1 adduct with CN− (Fig. S2). Furthermore, 1–CN adduct was fur-
ther confirmed by mass spectrometry analysis, where a peak at
m/z 573.73 was observed, corresponding to [1-CN-K]+ (Fig. S3). All
these results strongly support the proposed mechanism that CN−
attacks the hemicyanine moiety of probe 1.
3.8. CN− detection in spiked water samples
To investigate the practical application of probe 1 for CN− detec-
tion in complicated environment, probe 1 was applied to determine
CN− in the real water samples, such as lake water, mineral water
and drinking water. The water samples were spiked with set
amount of CN− (5 and 8 ␮M). As shown in Table 2, CN− was tested
with a satisfactory analytical accuracy and precision (RSD < 4%).
3176 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178

Fig. 11. 1
H NMR spectra of probe 1 in CDCl3 in the absence and presence of CN− (1.0 equiv.).

Fig. 12. The photos of the filter paper containing probe 1 after exposure to different anions under UV light (365 nm).

Fig. 13. The photos of the filter paper containing probe 1 after exposure to CN− solution at different concentrations under UV light (365 nm).

3.9. CN− detection on filter paper
To verify if this approach could be utilized as a portable sens-
ing device, the paper test strips were constructed. As shown in
Fig. 12, after dropping the solution of probe 1 (100 ␮M) on the neu-
tral filter paper and drying them by air, no fluorescence emission
was observed under UV light (365 nm). The filter paper contain-
ing probe 1 were carefully exposed to different anions solutions
(100 ␮M), such as F− , Cl− , Br− , I− , ClO4 − , AcO− , H2 PO4 − , NO3 − ,
HSO4 − , CN− . Only CN− could switch on the emission color from dark
to green. Moreover, CN− at different concentrations were tested by
the paper-based sensor. As depicted in Fig. 13, dropping the solu-
tion of CN− at different concentrations from 5 ␮M to 100 ␮M on the
filter paper containing probe 1, the green emission can be clearly
observed, the more concentrated of the CN− solutions, the brighter
colors are observed on the filter paper. These results demonstrated
that probe 1 could selectively detect CN− based on a portable device
by naked eye.
 Y. Yu et al. / Sensors and Actuators B 255 (2018) 3170–3178
4. Conclusions
In summary, a BODIPY-hemicyanine based turn-on fluorescent
probe 1 has been designed and easily synthesized for sensitive and
selective CN− detection. The detection limit was calculated to be
59 nM in aqueous media. Nucleophilic addition of CN− to indolium
interrupted the ␲-conjugation system and restore fluorescence of
BODIPY unit. Combined its fast kinetics and wide pH range, probe
1 could be a good approach for the real-time, on-spot, selective
and sensitive detection of CN− in the complicated systems. More-
over, probe 1 was successfully applied to detect CN− in real water
samples and on paper test strips with satisfactory results.
Acknowledgement
This research work was financially supported by National Nat-
ural Science Foundation of China (No. 21708015).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.snb.2017.09.142.
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Biographies
Dr. Yanhua Yu has earned her MS degree under the supervision of Prof. Jie Tang at
East China Normal University in 2010 and PhD degree under the supervision of Prof.
Joanne Xie at École normale supérieure de Cachan (France) in 2013. She then moved
to Jianghan University as Assistant Researcher. Her research field refers to analyt-
ical chemistry and organic chemistry. Her research subject of PhD focused on the
rational design and synthesis of fluorescent molecules based on benzothiadiazole,
coumarin, BODIPY and DCM with click reaction and investigation on their applica-
tions in biology and analytical chemistry. In Jianghan University, her research work
is focused on fluorescent probes and fluorescent peptide synthesis.
Dr. Yibin Ruan, currently a staff of Technology Center of China Tobacco Guizhou
Industrial Co. Ltd., worked with Prof. Yun-Bao Jiang at Xiamen University for his MS
degree. He received his PhD degree under the supervision of Dr. Isabelle Leray and
Prof. Joanne Xie at École normale supérieure de Cachan (France). And then he spent 6
months as a post-doc to work in Laboratoire de Spectrochimie Infrarouge et Raman
with Dr. Stéphane Aloïse. His research interests are the development of molecular
sensors for anionic and cationic species and photophysics of metal-complex in the
excited state.
Prof. Changzhi Dong has earned his BS and MS degrees from Beijing University in
1983 and 1986 respectively. He moved then to Yantai University as Assistant Pro-
fessor. In 1990, he was awarded of an one-year scholarship from the French Atomic
Energy Commissariat (CEA) to work as a visiting scholar in CEA Cadarache Research
Centre. He pursued then in France his education and defended successfully his PhD
thesis in 1996 in the School of Pharmacy, Paris V University with the major in medic-
inal chemistry under the supervision of Dr. Bernard P. Roques. He spent then one
year as a post-doc to work in Dr. Marc Julia’s lab in the Chemistry Department of
“Ecole Normale Supérieure de Paris (ENS Paris)”. He was appointed as assistant pro-
fessor in 1997 and full professor in 2011 in Paris VII University. From 2001–2003,
he has worked as a research associate in Ziwei Huang’s lab in UIUC, USA.S ince
2011, he has been the PI of the Peptide and Protein Chemistry Center of the Institute
for Interdisciplinary Research, Jianghan University. The research interests of Prof.
Dong mainly focus on two domains: drug development and peptide/protein chem-
istry. In the first one, he has worked on design, synthesis and SAR study of small
organic compounds for the treatment of different diseases, such as AIDS, AD, cancer
and inflammation.In the second one, he has performed total chemical synthesis of
certain small proteins with full biological activities and their derivatives and these
works provided powerful tools for the structure-function relationship study of these
proteins. He is recently interested also in the development of chemical sensors for
detecting ions, small molecules or peptides.