An imine-based colorimetric chemodosimeter for the detection of hypochlorite (ClO -) in aqueous media: its application in test strips and real water samples

Article abstract of DOI:10.1007/s12039-019-1617-6

Abstract: A highly selective colorimetric chemodosimeter ASAD, (E)-2-((4-(diethylamino)-2-hydroxybenzylidene)amino)-5-methoxybenzenesulfonic acid, was readily synthesized and characterized. The probe ASAD could selectively recognize hypochlorite (ClO ^-) through an oxidative cleavage of C=N bond with a color change from yellow to colorless and detected it down to a low concentration of 0.95 μ M. Importantly, ASAD could be employed as a practical and efficient optical sensor for ClO ^- in test strips and water samples. Moreover, the detection process of ASAD to hypochlorite was demonstrated by UV-vis spectroscopy, NMR titration and theoretical calculations. Graphical abstract: A highly selective colorimetric chemodosimeter ASAD was developed to selectively recognize hypochlorite (ClO ^-) through an oxidative cleavage of C=N bond with color change from yellow to colorless and could detect it down to a low concentration of 0.95 μ M.

Full text of DOI:10.1007/s12039-019-1617-6

J. Chem. Sci.
(2019) 131:38
© Indian Academy of Sciences
https://doi.org/10.1007/s12039-019-1617-6
REGULAR ARTICLE
An imine-based colorimetric chemodosimeter for the detection of
−
hypochlorite (ClO ) in aqueous media: its application in test strips
and real water samples
∗
DONGJU YUN, JU BYEONG CHAE and CHEAL KIM
Department of Fine Chemicals, Seoul National University of Science and Technology, Seoul 139-740,
Republic of Korea
E-mail: chealkim@snut.ac.kr
MS received 22 January 2019; revised 11 March 2019; accepted 13 March 2019
Abstract. A highly selective colorimetric chemodosimeter ASAD, (E)-2-((4-(diethylamino)-2-hydroxy-
benzylidene)amino)-5-methoxybenzenesulfonic acid, was readily synthesized and characterized. The probe
−
ASAD could selectively recognize hypochlorite (ClO ) through an oxidative cleavage of C=N bond with a
color change from yellow to colorless and detected it down to a low concentration of 0.95 μM. Importantly,
−
ASAD could be employed as a practical and efficient optical sensor for ClO in test strips and water samples.
Moreover, the detection process of ASAD to hypochlorite was demonstrated by UV-vis spectroscopy, NMR
titration and theoretical calculations.
Keywords. Hypochlorite; colorimetric; chemodosimeter; theoretical calculations.
1
. Introduction
Despite its advantage, it still encounters some problems
suchaspoordetectionlimitandslowreactioninaqueous
media. To surmount the difficulties, we designed sensor
ASAD having readily cleavable imine moiety (C=N),
which could recognize ClO with a low detection limit
and fast reaction time.
Reactive oxygen species (ROS) play a significant role
in pathological and physiological processes.1 ClO
hypochlorite), one of the significant ROS, is ben-
eficial for our health because it has effective anti-
–5
−
−
(
6
–9
inflammatory and antibacterial properties. Moreover,
ClO is largely used as a disinfectant or a bleaching
chemical.
Herein, we present a novel colorimetric chemod-
−
osimeter ASAD to monitor the level of hypochlorite
10–13
−
−
−
However, excessive levels of ClO in
(
ClO ). ASAD showed high selectivity toward ClO
among various anions and ROS with the color change
yellow to colorless). The distinct color change can be
an organism are harmful to cellular components, thus
resulting in several diseases like inflammation and car-
(
diovascular disease.1
4–18
Therefore, the development of
directly visualized through naked-eye and test strip. In
addition, sensor ASAD showed a fast reaction and great
sensitivity to hypochlorite with a low detection limit
practical and selective sensors capable of monitoring
the amount of ClO in both living organisms and envi-
ronment is needed. So, a lot of effort has been devoted
to develop ClO sensors in the past decade, with vari-
−
(
0.95 μM). Moreover, the sensing process of ASAD
−
−
toward ClO was demonstrated with the diverse spec-
troscopic investigations and calculations.
1
9
20–22
ous functional moieties like thioether, thioester,
2
3,24
25,26
27,28
29,30
thione,
selenide,
a molecular probe that recognizes analytes with the
p-methoxy,
hydrazide,
oxime,
31,32
and C=N bond.33–35 Chemodosimeter is
2
. Experimental
irrevocable process.3
6–40
It has the advantage of high
selectivity with little interference of other anions, so it
has been frequently studied in anion sensing area.
2.1 Chemicals and instruments
41–45
Chemicals were commercially provided. A LCQTM quadru-
pole ion trap machine and a Varian spectrometer were
*
For correspondence
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-019-1617-6) contains
supplementary material, which is available to authorized users.
0123456789().: V,-vol

38
Page 2 of 8
J. Chem. Sci.
(2019) 131:38
employed to gain ESI-MS, H and 13C NMR spectra. Perkin 2.3e Analysis of ClO : UV-vis analyses of ClO in
1
−
−
Elmer spectrometers (2S UV/Vis and LS45) were employed water samples were performed by adding 24 μL (0.005 M) of
for absorption and fluorescence measurements.
ASAD and 0.60 mL (0.1 M) of a stock PBS buffer to a 5.376
mL sample. Their UV-vis spectra were recorded with UV-vis
spectrometer.
2.2 Synthesis of chemodosimeter ASAD
2
.3f Test strips: ASAD test strips were made by soaking
Methanol (10 mL) was chosen to dissolve 2-amino-5-
−3
−3
filter papers into ASAD (5×10 M), and dried in vacuum.
methoxybenzenesulfonic acid (1×10 mol, 0.203 g). Then,
−
3
ASAD test strips were treated with 3 mM of various oxi-
4
0
-(diethylamino)salicylaldehyde (DAS, 1.2×10
mol,
−
−
−
−
−
−
−
dant and anions (ClO , NO , OH , Cl , CN , OAc , F ,
.232g) was added dropwise to the solution while shaking
2
−
−
−
−
AcOOH, H2PO , Br , BzO , t−BuOOH, N and H2O2).
for 3 h. The yellow powder was filtered and washed with
4
3
After dried at room temperature, the photograph of each test
chilly ethyl alcohol and diethyl ether. ASAD obtained was
0
.273 g (86.8%). 1H NMR (DMF-d7, ppm): δ 13.48 (d,
strip was taken.
J = 15.2 Hz, 1H), 13.15 (s, 1H), 9.13 (d, J = 14.8 Hz,
1
1
H), 8.02 (d, J = 8.8 Hz, 1H), 7.84 (d, J = 9.2 Hz, 2.3g Theoretical calculations for ASAD and DAS:
H), 7.66 (d, J = 2.8 Hz, 1H), 7.30 (m, 1H), 6.84 (d, Energy-optimized structures of ASAD and DAS were calcu-
J = 8.4 Hz, 1H), 6.57 (s, 1H), 4.04 (s, 3H), 3.79 (m, 4H), lated with DFT using Gaussian 09W program. The hybrid
1
3
1
.42 (t, J = 6.8 Hz, 6H), C NMR (DMSO-d6, ppm): functional was 3-parameter, Becke, Lee-Yang-Parr (B3LYP).
The basis set was 6-31G(d,p).4
6–49
Since imaginary fre-
δ 163.66, 157.63, 156.09, 154.59, 139.52, 139.33, 127.82,
1
1
19.70, 116.18, 112.07, 106.98, 105.14, 95.80, 55.70, 44.85, quency was not shown in optimized forms ofASAD and DAS,
+
2.48. ESI-MS (ASAD-H + 2MeOH): calcd, 441.17 (m/z); their geometries displayed local minima. Solvent effect of
water was dealt with CPCM.5
0,51
With the optimized struc-
found, 441.40.
tures of ASAD and DAS, the UV-vis transition investigations
were performed using TD-DFT method with thirty lowest
singlet states.
−
2.3 Chromogenic sensing of ClO
2
.3a UV-vis titration: DMF (N,N-dimethylformamide,
−6
1
.0 mL) was chosen to dissolve ASAD (5×10 mol, 1.9
−3
3
. Results and discussion
mg). 12.0 μL (5×10 M) of ASAD was diluted in 2.988
mL of PBS buffer (10 mM, pH 7.4) to give 0.02 mM. NaClO
−4
ASAD was readily produced by the condensation
(
5×10 mol, 256 μL) was dissolved in distilled water (5.0
−
mL). 0.3–11.4 μL (0.1 M) of the ClO were added to separate of 2-amino-5-methoxybenzenesulfonic acid with 4-
ASAD solutions (0.02 mM, 3 mL). UV-vis spectra of the (diethylamino)salicylaldehyde in methanol (yield
1
solutions were recorded with UV-vis spectrometer.
86.8%), as depicted in Scheme 1. It was identified by H
13
NMR, ESI-MS and C NMR (Figure S1, Supplemen-
.3b Competition experiment: 10.8 μL (0.1 M) of a tary Information).
2
−
ClO stock solution was diluted in 2.966 mL of PBS to give
1
8 equiv. 10.8 μL (100 mM) of diverse oxidants and anions
3
ClO
.1 Colorimetric and spectral studies of ASAD with
−
−
−
−
−
−
−
−
(
NO , OH , Cl , CN , OAc , F , AcOOH, H2PO , Br ,
−
2
4
−
−
−
BzO , t−BuOOH, N and H2O2) was transferred to ClO
3
−3
solution. 12.0 μL (5×10 M) of the ASAD was added into
the solution above prepared to make 20 μM. UV-vis spectra
of the solutions were recorded with UV-vis spectrometer.
To investigate the sensing properties of ASAD toward
various anions including some oxidants (ClO , NO ,
OH , Cl , CN , OAc , F , AcOOH, H PO , Br ,
−
−
−
2
−
−
−
−
−
−
−
2
4
−
BzO , t−BuOOH, N and H O ), we conducted selec-
3
2
2
2
.3c pH effect: Buffers of pH = 6−8 were provided by
tivity test in PBS buffer (Figure 1). Some oxidants
mixing HCl and NaOH in the PBS buffer. Sensor DMF (2
such as AcOOH, t−BuOOH and H O were also tested
2
2
−2
mL) was chosen to dissolve ASAD (1×10 mol, 3.8 mg).
−
because ClO can act as an anion as well as an oxidant.
−3
1
2.0 μL (5×10 M) of ASAD was diluted in 2.988 mL of
−
−
Addition of 18 equiv. of ClO induced a great spec-
PBS buffer to give 20 μM. Then 10.8 μL (0.1 M) of a ClO
stock was added to each ASAD (0.02 mM). UV-vis spectra
of the solutions were recorded with UV-vis spectrometer.
tral change with the disappearance of the absorbance
at 413 nm, accompanied by a noticeable color change
from yellow to colorless. On the other hand, none of the
other oxidants and anions led to any significant change.
These observations signified that ASAD had outstand-
1
2
.3d H NMR titration: To three NMR cuvettes of
ASAD (0.0025 mmol, 0.95 mg) dissolved in DMF-d7 (500
−
ing selectivity to ClO over various anions and oxidants.
μL) were added three different equivalents (0, 1 and 5)
of NaClO dissolved in D2O. Their H NMR spectra were
−
1
UV-vis titrations of ASAD toward ClO were con-
recorded with a Varian spectrometer.
ducted to understand the photophysical properties.

J. Chem. Sci.
(2019) 131:38
Page 3 of 8
38
SO3H
NH2
HO
SO3H
in MeOH
O
HO
N
O
N
O
H3C
N
at R.T. for 3 hr
H3C
DAS
ASAD
Scheme 1. Synthesis of ASAD.
Figure 1. (a) Absorbance and (b) color changes of ASAD
(
(
0.02 mM) with the addition of diverse oxidants and anions
18 equiv.).
The reaction of ASAD with varied concentrations of
hypochlorite was shown in Figure 2, which exhibited
the two-step change in the spectra (Figure 2(a)). In the
first step, the absorbance band around 413 nm decreased
consistently, and then the absorbance of 500 nm con-
tinuously increased with a redshift of 87 nm, resulting
in a color change from yellow to orange (Figure 2(b)).
In the second step, the absorbance of the visible region
−
gradually decreased up to 18 equiv. of ClO with a color
change from orange to colorless. Based on these results,
−
we assumed that ASAD would react with ClO through
two-step mechanisms. In the first process, there was the
−
oxidative addition of ClO to the C=N bond and in the
second process, the imine bond was cleaved to produce
DAS (Scheme 2).
To obtain a quantitative appraisal of ASAD toward
−
ClO , a calibration experiment was carried out in the
scope of 0–40 μM and a suitable linear relationship
2
was observed (R = 0.9994, n = 3, Figure 3). The
detection limit of 0.95 μM was obtained on the basis of
5
2
3
σ/slope, which is the second lowest among those for
−
formerly addressed colorimetric sensors for ClO in a
near-perfect aqueous media, to date (Table S1, Supple-
mentary Information). To assess the feasibility of ASAD
Figure 2. (a) Absorbance changes of ASAD (0.02 mM)
−
with ClO (0–19 equiv). (b) Absorbance changes of ASAD
(
−
with ClO in water samples, drinking and tap samples
−
0.02 mM), extracted from the range of 0–4 equiv. of ClO in
were selected and analyzed three times (Table 1). Suit-
able numbers for relative standard deviations (R.S.D.) from the range of 5–19 equiv. of ClO in (a).
(
a). (c) Absorbance changes of ASAD (0.02 mM), extracted
−

38
Page 4 of 8
J. Chem. Sci.
(2019) 131:38
OH
SO3H
SO3H
H
SO H
3
HO
HO
ClO-
H2O
HO
O
N
O
N
O
NH
H3C
N
H3C
N
3
H C
N
ClO-
Cl
O
-OH
ASAD
SO3H
NH-
HO
SO3H
O
O
HO
H3C
N
H
O
O
NH2
N
H3C
ClO
DAS
−
Scheme 2. Probable sensing mechanism of ClO by ASAD.
decreased and the new H7 peak (10.5 ppm) began to
ꢀ
appear. The result indicated that the imine bond (C=N)
−
was cleaved by strong oxidizing agent ClO to produce
DAS, which was proved by ESI-MS (Figure 5). Positive-
−
ion MS of ASAD with ClO showed that the peak (m/z
+
=
2
257.10) is assignable to DAS + Na + MeCN [m/z =
1
57.13, calcd]. Based on the UV-visible and H NMR
titrations, and ESI-MS, the conceivable detecting pro-
−
cess of ClO was proposed (Scheme 2).
−
The selectivity of ASAD for ClO with the various
oxidants and anions was examined through competitive
studies (Figure S2, Supplementary Information). Most
of the oxidants and anions did not interfere with the
sensing of hypochlorite by ASAD. However, AcOOH
−
inhibited about 50% of the absorbance, and H PO ,
2
4
−
−
2
Figure 3. Detection limit based on the intensity (413 nm)
H O , CN and NO showed inhibition of more than
2
2
−
of ASAD as a function of the concentration of ClO .
8
0%.
−
[
ASAD] = 20μM and [ClO ] = 0−40 μM.
Moreover, the pH effect on sensing capability for
−
ClO was studied in a pH scope of 6–8 (Figure S3,
Supplementary Information). ASAD with ClO showed
a prominent color change between pH 6 and 8. These
consequences indicated that ClO can be obviously
−
and recoveries were obtained. These outcomes indicated
that ASAD had a good potential for determination of
hypochlorite levels in the environment.
−
detected by the UV-visible measurements or naked eye
using ASAD over physiological pH range. For practi-
cable application, test strips were prepared by coating
filter paper with ASAD (Figure 6). When the strips were
exposed to diverse oxidants and anions, an evident color
In order to explore the sensing process of ASAD
−
1
toward ClO , H NMR titrations were performed (Fig-
−
ure 4). Upon the addition of ClO (1.0 equiv.) to ASAD,
the H signal of the diethyl group and H signal of the
3
7
imine moiety diminished, and the new H3
ꢀ
signal (1.2
−
−
change appeared only with ClO in PBS buffer. To our
surprise, this observation is the first case that a sensor
ppm) began to appear. With further addition of ClO
(
5.0 equiv.) to ASAD, the H peak (9.1 ppm) gradually
7
Table 1. Determination of ClO a.
−
−
−
Sample
ClO added (μM) ClO found (μM) Recovery (%) R.S.D. (n=3) (%)
Tap water
0.0
0.00
0.0
0.0
19.82
0.0
-
-
2
99.09
-
1.35
-
Drinking water
20.00
20.02
100.08
0.50
a
Conditions: [ASAD] = 20 μmol/L in PBS buffer.

J. Chem. Sci.
(2019) 131:38
Page 5 of 8
38
Figure 4. 1H NMR titrations of ASAD with ClO (0, 1.0 and 5.0 equiv).
−
Figure 5. Positive ESI-MS of ASAD (1×10− M) with ClO (1 equiv).
4
−

38
Page 6 of 8
J. Chem. Sci.
(2019) 131:38
Figure 6. Photographs of ASAD-test strips immersed in various oxidants and anions.
Figure 7. Optimized forms of (a) ASAD and (b) DAS.
−
could detect ClO via the test strip in a near-perfect and S6, Supplementary Information). The electron den-
aqueous media, to date (Table S1, Supplementary Infor- sity of both HOMO and LUMO was evenly scattered
mation). These results meant that the strip might have over the DAS showing ICT. Moreover, the increased
practical application for rapid and easy detection of energy gap of DAS was consistent with the blue shift
−
ClO .
of the UV-visible spectrum (Figure S5, Supplementary
Information). Since the blue-shifted spectrum was not
observed in the visible region, this calculation was con-
sistent with the color change from yellow to colorless.
The results of the theoretical calculations further con-
firmed the conceivable detection process in Scheme 2.
3
.2 Theoretical calculations
To demonstrate the detection mechanism of ASAD
to hypochlorite, calculations were achieved. The opti-
mized forms of ASAD and DAS were calculated using
B3LYP as a hybrid functional and 6-31G(d,p) as a basis
set (Figure 7). The oscillator strengths and major transi-
4
. Conclusions
tion energies of the two compounds are shown in Figures A new selective colorimetric probe ASAD was readily
S4 and S5, Supplementary Information. The MO of synthesized based on the combination of 2-amino-
ASAD turned out to be the HOMO → LUMO transi- 5-methoxybenzenesulfonic acid and 4-(diethylamino)
tion at the first lowest excited state (417.41 nm, Figures salicylaldehyde. Sensor ASAD exhibited the outstand-
S4 and S6, Supplementary Information). This transition ingdetectiontohypochloritewiththelowdetectionlimit
showed ICT (intramolecular charge transfer). The MO (0.95 μM), which is the second lowest among those for
−
of DAS also showed the HOMO → LUMO transition at formerly addressed colorimetric sensors for ClO in a
the second lowest excited state (299.75 nm, Figures S5 near-perfect aqueous media. Oxidative cleavage of the

J. Chem. Sci.
(2019) 131:38
Page 7 of 8
38
C=N bond in ASAD by hypochlorite resulted in colori- 10. Chen H, Sun T, Qiao X G, Tang Q O, Zhao S C and
Zhou Z 2018 Red-emitting fluorescent probe for detect-
ing hypochlorite acid in vitro and in vivo Spectrochim.
Acta A 204 196
metric sensing from yellow to colorless. Its excellent
sensing ability could be applied in real samples and
test strips. Importantly, ASAD could, for the first time,
1
1. Zhang Y, Ma L, Tang C, Pan S, Shi D, Wang S, Li M
and Guo Y 2018 A highly sensitive and rapidly respond-
ing fluorescent probe based on a rhodol fluorophore
for imaging endogenous hypochlorite in living mice J.
Mater. Chem. B 6 725
−
detect ClO via the test strip in a near-perfect aqueous
media, to date. Therefore, ASAD has a great potential
−
application for recognizing ClO .
1
2. Xiong K, Huo F, Yin C, Chao J, Zhang Y and Xu M
2015 A highly selective fluorescent bioimaging probe
for hypochlorite based on 1,8-naphthalimide derivative
Sens. Actuat. B Chem. 221 1508
Supplementary Information (SI)
Supplementary data (Table S1 and Figures S1–S6) associated
with this article is available at www.ias.ac.in/chemsci.
1
3. Zhang J and Yang X 2013 A simple yet effective chro-
mogenic reagent for the rapid estimation of bromate and
hypochlorite in drinking water Analyst 138 434
Acknowledgements
1
4. Yang Y, Yin C, Huo F, Chao J, Zhang Y and Jin
S 2014 Simple 1,8-diaminonaphthalene-based fluores-
cence chemosensor for hypochlorites and its practical
application Sens. Actuat. B Chem. 199 226
We acknowledge KEITI (Korea Environment Industry &
Technology Institute) (2016001970001) and NRF (National
Research Foundation of Korea) (2018R1A2B6001686).
1
5. Goswami S, Aich K, Das S, Pakhira B, Ghoshal K, Quah
C K, Bhattacharyya M, Fun H-K and Sarkar S 2015
A triphenyl amine-based solvatofluorochromic dye for
−
the selective and ratiometric sensing of OCl in human
References
blood cells Chem. - An Asian J. 10 694
1
6. Chen W C, Venkatesan P and Wu S P 2015 A highly
selective turn-on fluorescent probe for hypochlorous
acid based on hypochlorous acid-induced oxidative
intramolecular cyclization of boron dipyrromethene-
hydrazone Anal. Chim. Acta 882 68
1
. Ji R, Qin K, Liu A, Zhu Y and Ge Y 2018 A simple and
fast-response fluorescent probe for hypochlorite in living
cells Tetrahedron Lett. 59 2372
2
. Jiang Y, Zheng G, Duan Q, Yang L, Zhang J, Zhang
H, He J, Sun H and Ho D 2018 Ultra-sensitive flu-
orescent probes for hypochlorite acid detection and
exogenous/endogenous imaging of living cells Chem.
Commun. 54 7967
1
1
1
2
2
7. Zhu B, Xu Y, Liu W, Shao C, Wu H, Jiang H, Du B and
Zhang X 2014 A highly selective colorimetric probe for
fast and sensitive detection of hypochlorite in absolute
aqueous solution Sens. Actuat. B Chem. 191 473
8. Sasikumar T and Ilanchelian M 2017 Colorimetric detec-
tion of hypochlorite based on the morphological changes
of siver nanoprisms to spherical nanoparticles Anal.
Methods 9 3151
9. Chang C, Wang F, Qiang J, Zhang Z, Chen Y, Zhang W,
Wang Y and Chen X 2017 Benzothiazole-based fluores-
cent sensor for hypochlorite detection and its application
for biological imaging Sens. Actuat. B Chem. 243 22
0. Chen X, Lee K-A, Ren X, Ryu J-C, Kim G, Ryu J-H,
Lee W-J and Yoon J 2016 Synthesis of a highly HOCl-
selective fluorescent probe and its use for imaging HOCl
in cells and organisms Nat. Protoc. 11 1219
3
. Wang L, Chen X, Xia Q, Liu R and Qu J 2018 Deep-Red
AIE-active fluorophore for hypochlorite detection and
bioimaging in live cells Ind. Eng. Chem. Res. 57 7735
. Chen X, Wang F, Hyun J Y, Wei T, Qiang J, Ren X, Shin
I and Yoon J 2016 Recent progress in the development
of fluorescent, luminescent and colorimetric probes for
detection of reactive oxygen and nitrogen species Chem.
Soc. Rev. 45 2976
4
5
6
7
8
. Lohar S, Patra A, Roy P and Babu P S 2018 A highly
selective fluorescence turn-on probe for the sensing and
bioimaging of hypochlorite anion in aqueous media
ChemistrySelect 3 6707
. Hu Q, Qin C, Huang L, Wang H, Liu Q and Zeng L 2018
Selective visualization of hypochlorite and its fluctuation
in cancer cells by a mitochondria-targeting ratiometric
fluorescent probe Dyes Pigm. 149 253
. ShenS L, Zhang X F, GeY Q, Zhu Y and Cao X Q 2017A
mitochondria-targeting ratiometric fluorescent probe for
the detection of hypochlorite based on the FRET strategy
RSC Adv. 7 55296
1. Zhou J, Li L, Shi W, Gao X, Li X and Ma H 2015
HOCl can appear in the mitochondria of macrophages
during bacterial infection as revealed by a sensitive
mitochondrial-targeting fluorescent probe Chem. Sci. 6
4
884
2. Xu Q, Lee K-A, Lee S, Lee K M, Lee W-J and Yoon J
013 A highly specific fluorescent probe for hypochlor-
2
2
ous acid and its application in imaging microbe-induced
HOCl production J. Am. Chem. Soc. 135 9944
. Xu X and Qian Y 2017 A novel (3,6-di-tert-
butylcarbazol-9-yl)
triphenylamine-BODIPY-
2
3. Xu Q, Heo C H, Kim J A, Lee H S, Hu Y, Kim D, Swamy
K M K, Kim G, Nam S-J, Kim H M and Yoon J 2016
A selective imidazoline-2-thione-bearing two-photon
fluorescent probe for hypochlorous acid in mitochondria
Anal. Chem. 88 6615
tricyanofuran conjugated dye: Synthesis and rapid
naked-eye detection of hypochlorite New J. Chem. 41
9607
9
. Lou X, Zhang Y, Qin J and Li Z 2012 Colorimetric
hypochlorite detection using an azobenzene acid in pure
aqueous solutions and real application in tap water Sens.
Actuat. B Chem. 161 229
2
4. Xu Q, Heo C H, Kim G, Lee H W, Kim H M and Yoon J
2015 Development of imidazoline-2-thiones based two-

38
Page 8 of 8
J. Chem. Sci.
(2019) 131:38
photon fluorescence probes for imaging hypochlorite 37. Xu S, Chen K and Tian H 2005 A colorimetric and flu-
generation in a co-culture system Angew. Chem. Int. Ed.
4 4890
5. Sun Z-N, Liu F-Q, Chen Y, Tam P K H and Yang D
orescent chemodosimeter: Fluoride ion sensing by an
axial-substituted subphthalocyanine J. Mater. Chem. 15
2676
5
2
2
2
2
2
3
2
008 A highly specific BODIPY-based fluorescent probe 38. Fu L, Jiang F-L, Fortin D, Harvey P D and Liu Y 2011
for the detection of hypochlorous acid Org. Lett. 10
A reaction-based chromogenic and fluorescent chemod-
osimeter for fluoride anions Chem. Commun. 47 5503
2171
6. Cui K, Zhang D, Zhang G and Zhu D 2010 A highly 39. Venkatesan P and Wu SP 2015 A turn-on fluorescent
selective naked-eye probe for hypochlorite with the
p-methoxyphenol-substituted aniline compound Tetra-
hedron Lett. 51 6052
probe for hypochlorous acid based on the oxidation of
diphenyl telluride Analyst 140 1349
40. Quang D T and Kim J S 2010 Fluoro- and chromogenic
chemodosimeters for heavy metal ion detection in solu-
tion and biospecimens Chem. Rev. 110 6280
7. Jin X, Jia Y, Chen W, Chui P and Yang Z 2016 A
reaction-based fluorescent probe for rapid detection of
hypochlorite in tap water, serum, and living cells Sens. 41. Jiménez D, Martínez-Máñez R, Sancenón F, Ros-Lis
Actuat. B Chem. 232 300
8. Long L, Zhang D, Li X, Zhang J, Zhang C and Zhou L
J V, Benito A and Soto J 2003 A New chromo-
chemodosimeter selective for sulfide anion J. Am. Chem.
Soc. 125 9000
2
013 A fluorescence ratiometric sensor for hypochlorite
based on a novel dual-fluorophore response approach 42. Goswami S, Maity S, Maity A C and Das A K 2014
Anal. Chim. Acta 775 100
Fluorometric and naked-eye detectable dual signaling
chemodosimeter for hypochlorite Sens. Actuat. B Chem.
204 741
9. Kang J, Huo F, Yue Y, Wen Y, Chao J, Zhang Y and Yin C
2
017 A solvent depend on ratiometric fluorescent probe
for hypochlorous acid and its application in living cells 43. Goswami S, Paul S and Manna A 2013 Highly reactive
Dyes Pigm. 136 852
(<1 min) ratiometric “naked eye” detection of hypochlo-
rite with real application in tap water Dalton Trans. 42
10097
0. Li D, Feng Y, Lin J, Chen M, Wang S, Wang X,
Sheng H, Shao Z, Zhu M and Meng X 2016 A
mitochondria-targeted two-photon fluorescent probe for 44. Fan J, Mu H, Zhu H, Wang J and Peng X 2015 Light up
−
highly selective and rapid detection of hypochlorite and
ClO in live cells using an aza-coumarin based fluores-
cent probe with fast response and high sensitivity Analyst
140 4594
its bio-imaging in living cells Sens. Actuat. B Chem. 222
483
3
1. Mulay S V, Choi M, Jang YJ, Kim Y, Jon S and Churchill 45. Jung H S, Han J H, Kim Z H, Kang C and Kim J S
D G 2016 Enhanced fluorescence turn-on imaging of
hypochlorous acid in living immune and cancer cells
Chem. - A Eur. J. 22 9642
2011 Coumarin-Cu(II) ensemble-based cyanide sensing
chemodosimeter Org. Lett. 13 5056
46. Becke AD 1993 Density-functional thermochemistry.
III. The role of exact exchange J. Chem. Phys. 98 5648
3
2. LiuS-RandWuS-P2013Hypochlorousacidturn-onflu-
orescent probe based on oxidation of diphenyl selenide 47. Lee C, Yang W and Parr R G 1998 Development of the
Org. Lett. 15 878
3. Wang B, Chen D, Kambam S, Wang F, Wang Y, Zhang
Colle–Salvetti correlation-energy formula into a func-
tional of the electron density Phys. Rev. B 37 785
3
W, Yin J, Chen H and Chen X 2015 A highly specific 48. Hariharan P C and Pople J A 1973 The influence of
fluorescent probe for hypochlorite based on fluorescein
derivative and its endogenous imaging in living cells
Dyes Pigm. 120 22
polarization functions on molecular orbital hydrogena-
tion energies Theor. Chim. Acta 28 213
49. Francl M M, Pietro W J, Hehre W J, Binkley J S, Gordon
M S, DeFrees D J and Pople J A 1982 Self-consistent
molecular orbital methods. XXIII. A polarization-type
basissetforsecond-rowelementsJ. Chem. Phys. 77 3654
50. Barone V and Cossi M 2001 Quantum calculation of
molecular energies and energy gradients in solution by
a conductor solvent model J. Phys. Chem. A 102 1995
3
3
3
4. Wu W L, Zhao Z M, Dai X, Su L and Zhao B X 2016
A fast-response colorimetric and fluorescent probe for
hypochlorite and its real applications in biological imag-
ing Sens. Actuat. B Chem. 232 390
5. Zang L, Liang C, Wang Y, Bu W, Sun H and Jiang S
2
015 A highly specific pyrene-based fluorescent probe
for hypochlorite and its application in cell imaging Sens. 51. Cossi M and Barone V 2001 Time-dependent density
Actuat. B Chem. 211 164
functional theory for molecules in liquid solutions J.
Chem. Phys. 115 4708
6. Lee J J, Lee S Y, Bok K H and Kim C 2015 A new
dual-channel chemosensor based on chemodosimeter 52. TsuiYK, DevarajSandYenYP2012Azodyesfeaturing
approach for detecting cyanide in aqueous solution: A
combination of experimental and theoretical studies J.
Fluoresc. 25 1449
with nitrobenzoxadiazole (NBD) unit: A new selective
chromogenic and fluorogenic sensor for cyanide ion
Sens. Actuat. B Chem. 161 510