Cascade reaction-based fluorescent probe for detection of H2S with the assistance of CTAB micelles

Article abstract of DOI:10.1016/j.cclet.2016.04.023

We report a turn-on fluorescent probe for H₂S through a cascade reaction using a new trap group 4-(bromomethyl)benzoate, based on excited-state intramolecular proton transfer (ESIPT) sensing mechanism. The probe showed good selectivity and high

Full text of DOI:10.1016/j.cclet.2016.04.023

G Model
CCLET 3691 1–4
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
1
2
Original article
3
4
Cascade reaction-based fluorescent probe for detection of H2S with the
assistance of CTAB micelles
a
a
a
Q1 Hai-Rong Zheng a,c, Li-Ya Niu a,b, , Yu-Zhe Chen , Li-Zhu Wu , Chen-Ho Tung ,
*
5
6
Qing-Zheng Yang b
7
8
9
a Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b College of Chemistry, Beijing Normal University, Beijing 100875, China
c University of the Chinese Academy of Sciences, Beijing 100049, China
A R T I C L E I N F O
A B S T R A C T
Article history:
We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4-
(bromomethyl)benzoate, based on excited-state intramolecular proton transfer (ESIPT) sensing
mechanism. The probe showed good selectivity and high sensitivity towards H2S and it was capable
of detecting and imaging H2S in living HeLa cells, indicating its potential biological applications.
ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Received 29 March 2016
Received in revised form 25 April 2016
Accepted 28 April 2016
Available online xxx
Keywords:
Hydrogen sulfide
Fluorescent probe
Cascade reaction
ESIPT
Micelles
10
11
1. Introduction
[4,5]. The abnormal level of H2S can resulted in many diseases, 29
such as Alzheimer’s disease, Down’s syndrome, diabetes, and liver 30
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
For centuries, hydrogen sulfide has been recognized as a toxic
molecular. When exposed to this colorless, flammable gas, which
has a distinctive smell of rotten eggs, people may suffer from
respiratory failure, loss of consciousness, sudden cardiac death,
hepatic and olfactory paralysis. However, more recent studies have
challenged this traditional view. H2S is now identified as the third
biological signaling molecular besides nitric oxide (NO) and carbon
monoxide (CO) and plays important roles in maintaining normal
physiology [1]. Endogenous H2S can be produced from sulfur-
containing biomolecules such as cysteine and homocysteine,
which is catalyzed by cystathionine beta synthase (CBS), cysteine
aminotransferase and mercaptopyruvate sulfurtransferase (CAT/
MST) [2,3]. These enzymes are widely spread in human tissues
ranging from the heart and vasculature, brain, kidney, liver, lungs,
indicating the important physiological roles of H2S in the body.
Besides, H2S can also be produced from non-enzymatic processes,
including release from sulfur stores and metabolism of polysulfide
cirrhosis [6–9]. Therefore, methods for monitoring the production, 31
trafficking, and consumption of H2S in living systems are highly 32
desired.
33
Compared with the traditional methods including colorimetric 34
assays [10,11] and gas chromatography [12,13], fluorescent probes 35
present lots of advantages, such as rapid response, high sensitivity 36
and excellent selectivity [14–16]. Recently, several fluorescent 37
probes have been reported for the detection of H2S in living systems 38
[17–20]. Common strategies include: H2S mediated reduction of 39
azide to amine [21,22], H2S trapped by nucleophilic addition [23– 40
25], copper sulfide precipitation [26,27], and thiolysis of dinitro- 41
phenyl ether [28,29]. Among these, H2S trapped by nucleophilic 42
addition strategy has been widely applied. Fluorescent probes based 43
on this strategy usually take advantage of the dual nucleophilicity of 44
H2S. Such probes usually contain a H2S trap group with two 45
electrophilic reaction sites and a fluorescent reporter, which 46
discriminates the H2S from other biothiols.
47
Recently, excited state intramolecular proton transfer (ESIPT) 48
compounds have been widely used in designing sensors for anions 49
[30,31], cations [32,33], amino acids [34–36] and small neutral 50
molecules [37,38], because of their intrinsic properties, ultra-fast 51
reaction rate and huge bathochromic shift in the emission signal. 52
*
Corresponding author at: Technical Institute of Physics and Chemistry, Chinese
Academy of Sciences, Beijing 100190, China.
E-mail address: niuly@mail.ipc.ac.cn (L.-Y. Niu).
http://dx.doi.org/10.1016/j.cclet.2016.04.023
1001-8417/ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: H.-R. Zheng, et al., Cascade reaction-based fluorescent probe for detection of H2S with the assistance of
CTAB micelles, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.023

G Model
CCLET 3691 1–4
2
H.-R. Zheng et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
3000
2500
2000
1500
1000
500
53
54
55
56
57
58
59
60
61
62
Herein, we reported a fluorescent probe using 2-2(hyroxyphe-
nyl)benzothiazole (HBT), a typical ESIPT molecule, as fluorescent
reporter, and 4-(bromomethyl)benzoate as trap group, which
showed fast response to H2S through cascade reaction. As the
hydroxyl group was protected by 2-(bromomethyl)benzoate, the
HBT moiety of the probe showed enol-like fluorescence. The initial
nucleophilic attack of H2S towards bromomethyl group would lead
to an intermediate thiol, which was followed by a cyclization
cascade reaction towards the adjacent ester carbonyl to release the
HBT with keto emission. Thus, the detection of H2S was realized.
0
10 min
20 min
30 min
40 min
50 min
60 min
70 min
80 min
63
2. Experimental
0
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
Probe 1 was synthesized using a simple procedure with HBT
and 2-(bromomethyl)benzoic acid as starting materials, 1-ethyl-3-
(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) as a
coupling reagent, and 4-dimethylaminopyridine (DMAP) as cata-
lyst (Scheme 1).
2-(20-Hydroxy-30-methoxyphenyl)benzothiazole (HMBT): A solu-
tion of 2-aminothiophenol (0.3 mL, 4.2 mmol) and o-vanillin
(0.48 g, 3.15 mmol) in EtOH (10 mL), aq. H2O2 (30%, 18.9 mmol)
and aq HCl (37%, 9.45 mmol) was stirred at rt for 90 min. The
solution was quenched by 10 mL H2O. The precipitate was filtered,
dried under vacuum and recrystallized from EtOH to afford the
desired product as a light brown solid (0.64 g, 79% yield). 1H NMR
350
400
450
500
550
600
Wavelength (nm)
Fig. 2. Time-dependent fluorescence response of probe 1 (10
of NaHS (200 mol/L) in HEPES buffer (20 mmol/L, pH 7.4, containing 1 mmol/L
CTAB). ex = 310 nm, em = 484 nm. Slits: 5/5 nm.
mmol/L) upon addition
m
l
l
3. Results and discussion
95
The proposed sensing mechanism is shown in Fig. 1. As the
hydroxyl group is protected by 2-(bromomethyl)benzoate, the
excited state intramolecular proton transfer (ESIPT) process was
forbidden. As a result, the HBT moiety of probe 1 shows enol-like
fluorescence. The initial nucleophilic attack of H2S towards
bromomethyl group would lead to an intermediate thiol, which
is followed by a cyclization cascade reaction towards the adjacent
ester carbonyl to release the HBT. Upon irradiation, the resulting
HBT generated the excited state intramolecular proton transfer
(ESIPT) tautomer, which shows keto emission. To identify the
proposed sensing mechanism, probe 1 was treated with excess
NaHS and Et3N in CH3CN. After the reaction, the HBT was released,
with the formation of cyclization product 4. All products were
separated and confirmed with 1H NMR (Figs. S1 and S2 in
Supporting information).
96
97
98
99
(CDCl3, 400 MHz, ppm): d 12.75 (s, 1H), 8.01 (d, 1H, J = 7.6 Hz), 7.91
(d, 1H, J = 7.2 Hz), 7.51 (t, 1H, J = 6.8 Hz), 7.42 (t, 1H, J = 7.2 Hz), 7.33
(dd, 1H, J1 = 1.2 Hz, J2 = 8.0 Hz), 6.99 (dd, 1H, J1 = 1.2 Hz,
J2 = 8.0 Hz), 6.91 (t, 1H, J = 8.0 Hz), 3.96 (s, 1H).
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
Probe 1: To a solution of EDCI (0.346 g, 1.5 mmol) in CH2Cl2
(20 mL) was added 2-bromodomethylbenzoic acid (0.312 g,
1.5 mmol) followed by DMAP (0.012 g, 0.1 mmol) and HMBT
(0.346 g, 1 mmol). The mixture was stirred at room temperature
for 12 h and then filtered, washed with water. The filtrate was
concentrated to afford the crude product, then purified by silica
gel column chromatography (PE:CH2Cl2 = 1:1) to afford com-
pound 1 as a white solid (0.24 g, 40%). 1H NMR (400 MHz, CDCl3,
ppm):
d 8.41 (d, 1H, J = 4.0 Hz), 7.93–7.99 (m, 2H), 7.83 (d, 1H,
We first tested the absorption spectra of probe 1 in HEPES
buffer. However, the obvious variation of the absorption spectra of
1 in 12 h suggested that it was unstable in HEPES buffer, probably
due to its poor solubility in pure water (Fig. S3 in Supporting
information). Then we used 50% ethanol as co-solvent, and the
stability of 1 was improved (Fig. S4 in Supporting information). As
J = 4.0 Hz), 7.34–7.56 (m, 6H), 7.15 (d, 1H, J = 4.0 Hz,), 4.94–5.14
(d, 2H), 3.90 (s, 3H). 13C NMR (100 MHz,CDCl3): 164.2, 162.3,
153.0, 152.1, 140.0, 139.8, 138.1, 135.5, 134.0, 133.3, 132.3, 132.0,
130.9,129.0, 128.7, 128.5, 128.2, 127.7, 126.9, 126.3, 125.8, 125.3,
123.4, 122.1, 121.1, 121.5, 121.4, 114.2, 69.6, 56.4, 44.1,
31.0. HRMS: calcd: 454.010, found: 454.011.
Scheme 1. Synthesis of probe 1 for detection of H2S.
S
S
N
HS-
S
N
S- O
O
+
BrO
O
S
O
N
O
HO
O
O
Probe 1
4
3
2
Fig. 1. The proposed sensing mechanism of probe 1 for H2S.
Please cite this article in press as: H.-R. Zheng, et al., Cascade reaction-based fluorescent probe for detection of H2S with the assistance of
CTAB micelles, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.023

G Model
CCLET 3691 1–4
H.-R. Zheng et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
3
0
5000
4000
3000
2000
1000
0
(b)
2500
2000
1500
1000
500
10 μmol/L
25 μmol/L
50 μmol/L
75 μmol/L
100 μmol/L
150 μmol/L
200 μmol/L
300 μmol/L
400 μmol/L
(a)
0
0
20
40
60
80
100
350
400
450
500
550
600
-
Wavelength (nm)
HS (μmol/L)
Fig. 3. (a) Fluorescence spectra of probe 1 (10
Fluorescence response of probe 1 at 484 nm to NaHS concentration (0–100
ex = 310 nm, em = 484 nm. Slits: 5/5 nm.
m
mol/L) upon addition of NaHS (0–400
mmol/L) in HEPES buffer (20 mmol/L, pH 7.4, containing 1 mmol/L CTAB). (b)
mmol/L). Spectra were recorded after incubation with different concentrations of NaHS for 1 h.
l
l
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
shown in Fig. S5 in Supporting information, with the addition of
200 mol/L NaHS in ethanol/HEPES buffer (1:1, v/v, 20 mmol/L, pH
indicated that ESIPT process was greatly enhanced with the 132
assistance of CTAB micelles. Therefore, the following studies were 133
carried out in HEPES buffer (20 mmol/L, pH 7.4, containing 134
m
7.4), the emission at 350 nm (which is attributed to the enol form)
decreased, followed by a new peak appearing at 484 nm (which is
attributed to the keto form). However, the fluorescence at 484 nm
was quite weak, as the intramolecular hydrogen bond is strongly
disturbed in polar solvents [39]. We speculated that the ESIPT
would be enhanced in the nonpolar core of CTAB micelles. Probe 1
was stable in HEPES buffer (20 mmol/L, pH 7.4) containing
1 mmol/L CTAB (Fig. S6 in Supporting information). As we
expected, upon addition of NaSH to probe 1, the original emission
at 350 nm decreased, and a significant fluorescence enhancement
at 484 nm of approximately 60-fold was observed (Fig. 2). In
contrast, an enhancement of only 5-fold was observed in ethanol/
HEPES buffer (1:1, v/v, 20 mmol/L, pH 7.4) (Fig. S5). The results
1 mmol/L CTAB). The probe 1 (10
mmol/L) upon reaction with 135
NaHS (2 mmol/L) in HEPES buffer (20 mmol/L, pH 7.4, containing 136
1 mmol/L CTAB) exhibited a pseudo first order reaction kinetics 137
with rate constant k = 0.59 minꢀ1 (t1/2 = 1.17 min), indicating the 138
fast response of 1 towards H2S (Fig. S7 in Supporting information). 139
Subsequently, quantitative response of probe 1 in HEPES buffer 140
(20 mmol/L, pH 7.4, containing 1 mM CTAB) towards H2S was 141
estimated. As shown in Fig. 3a, with the increasing concentrations 142
of NaHS, the original emission at 350 nm decreased, and a 143
significant fluorescence enhancement at 484 nm was observed. 144
Moreover, the fluorescence intensity of 484 nm showed linear 145
relationship with NaHS concentrations ranging from
100 mol/L, suggesting the potential application for quantitative 147
determination of H2S (Fig. 3b). The detection limit for HSꢀ was 148
estimated to be 0.50 mol/L (S/N = 3), which is much lower than 149
the concentration required to cause physiological response [40]. 150
0 to 146
m
2500
2000
1500
1000
500
m
To evaluate the selectivity of the probe to H2S, emission spectra 151
changes upon addition of 20 equivalents of different interfering 152
species, such as cysteine (Cys), glutathione (GSH), homocysteine 153
(Hcy), sodium acetate (CH3COONa), sodium fluoride (NaF), sodium 154
persulfate (Na2S2O4), sodium dihydrogen phosphate (NaH2PO4), 155
sodium sulfate (Na2SO4), sodium chloride (NaCl), sodium tartrate 156
(C4H4Na2O6), sodium gluconate (C6H11NaO7), sodium carbonate 157
(Na2CO3), sodium bicarbonate (NaHCO3), sodium nitrate (NaNO3), 158
sodium bromide (NaBr), sodium hydrogen sulfite (NaHSO3) were 159
studied. As shown in Fig. 4, in most cases, little change in emission 160
intensity was observed. In contrast, a great enhancement in 161
emission intensity was only observed when adding NaHS. Thus, 162
these results demonstrated that probe 1 has a high selectivity 163
0
towards H2S.
We further examined the capability of probe 1 to H2S in living 165
cells (Fig. 5). After incubated with probe 1 (20 mol/L) for 45 min 166
164
Fig. 4. Fluorescence response of probe 1 (10
species in HEPES buffer (20 mmol/L, pH 7.4, containing 1 mmol/L CTAB).
ex = 310 nm, em = 484 nm. Slits: 5/5 nm.
mmol/L) upon addition of various
m
l
l
in culture medium, HeLa cells showed almost no fluorescence in 167
Fig. 5. Images of H2S in HeLa cells using probe 1 (20
m
mol/L) at 37 8C. (a) Fluorescence and (b) bright-field images of HeLa cells incubated with probe 1 for 45 min. (c)
Fluorescence and (d) bright-field images of HeLa cells incubated with NaHS (200
mmol/L) for 30 min and further incubated with probe 1 for 45 min. Scale bar: 50 mm.
Please cite this article in press as: H.-R. Zheng, et al., Cascade reaction-based fluorescent probe for detection of H2S with the assistance of
CTAB micelles, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.023

G Model
CCLET 3691 1–4
4
H.-R. Zheng et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
[14] L.Y. Niu, Y.Z. Chen, H.R. Zheng, et al., Design strategies of fluorescent probes for
selective detection among biothiols, Chem. Soc. Rev. 44 (2015) 6143–6160.
[15] X. Zhou, S. Lee, Z.C. Xu, J. Yoon, Recent progress on the development of chemo-
sensors for gases, Chem. Rev. 115 (2015) 7944–8000.
[16] L.Y. Niu, Y.S. Guan, Y.Z. Chen, et al., BODIPY-based ratiometric fluorescent sensor
for highly selective detection of glutathione over cysteine and homocysteine, J.
Am. Chem. Soc. 134 (2012) 18928–18931.
[17] V.S. Lin, C.J. Chang, Fluorescent probes for sensing and imaging biological hydro-
gen sulfide, Curr. Opin. Chem. Biol. 16 (2012) 595–601.
[18] C.C. Zhao, X.L. Zhang, K.B. Li, et al., Fo¨rster resonance energy transfer switchable
self-assembled micellar nanoprobe: ratiometric fluorescent trapping of endoge-
nous H2S generation via fluvastatin-stimulated upregulation, J. Am. Chem. Soc.
137 (2015) 8490–8498.
[19] X. Wang, J. Sun, W.H. Zhang, et al., A near-infrared ratiometric fluorescent probe
for rapid and highly sensitive imaging of endogenous hydrogen sulfide in living
cells, Chem. Sci. 4 (2013) 2551–2556.
[20] Z.S. Wu, Y.L. Feng, B. Geng, J.Y. Liu, X.J. Tang, Fluorogenic sensing of H2S in blood
and living cells via reduction of aromatic dialkylamino N-oxide, RSC Adv. 4 (2014)
30398–30401.
[21] H.J. Peng, Y.F. Cheng, C.F. Dai, et al., A fluorescent probe for fast and quantitative
detection of hydrogen sulfide in blood, Angew. Chem. Int. Ed. 50 (2011) 9672–9675.
[22] S. Chen, Z.J. Chen, W. Ren, H.W. Ai, Reaction-based genetically encoded fluores-
cent hydrogen sulfide sensors, J. Am. Chem. Soc. 134 (2012) 9589–9592.
[23] K.J. Wu, G.Q. Li, Y. Li, L.X. Dai, S.L. You, Reaction-based genetically encoded
fluorescent hydrogen sulfide sensors, Chem. Commun. 47 (2011) 493–495.
[24] C.R. Liu, J. Pan, S. Li, et al., Capture and visualization of hydrogen sulfide by a
fluorescent probe, Angew. Chem. Int. Ed. 50 (2011) 10327–10329.
[25] C.R. Liu, B. Peng, S. Li, et al., Reaction based fluorescent probes for hydrogen
sulfide, Org. Lett. 14 (2012) 2184–2187.
[26] K. Sasakura, K. Hanaoka, N. Shibuya, et al., Development of a highly selective
fluorescenceprobeforhydrogensulfide,J.Am. Chem.Soc. 133(2011)18003–18005.
[27] F.P. Hou, L. Huang, P.X. Xi, et al., A retrievable and highly selective fluorescent
probe for monitoring sulfide and imaging in living cells, Inorg. Chem. 51 (2012)
2454–2460.
[28] X.W. Cao, W.Y. Lin, K.B. Zheng, L.W. He, A near-infrared fluorescent turn-on probe
for fluorescence imaging of hydrogen sulfide in living cells based on thiolysis of
dinitrophenyl ether, Chem. Commun. 48 (2012) 10529–10531.
[29] T.Y. Liu, Z.C. Xu, D.R. Spring, J.N. Cui, A lysosome-targetable fluorescent probe for
imaging hydrogen sulfide in living cells, Org. Lett. 15 (2013) 2310–2313.
[30] S.D. Liu, L.W. Zhang, P.P. Zhou, et al., HBT-based chemosensors for the detection of
fluoride through deprotonation process: experimental and DFT studies, RSC Adv.
5 (2015) 19983–19988.
[31] L.H. Geng, X.F. Yang, Y.G. Zhong, Z. Li, H. Li, ‘‘Quinone–phenol’’ transduction
activated excited-state intramolecular proton transfer: a new strategy toward
ratiometric fluorescent probe for sulfite in living cells, Dyes Pigm. 120 (2015)
213–219.
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
168
169
170
171
green channel. By contrast, when HeLa cells were pretreated with
NaHS (200 mol/L) before incubated with probe 1 (20 mol/L) for
45 min, the obvious fluorescence was observed. It revealed that
m
m
probe 1 has potential for visualizing H2S levels in living cells.
172
4. Conclusion
173
174
175
176
177
178
179
180
181
182
183
184
In conclusion, we designed and synthesized a novel fluorescent
probe 1 for the detection of H2S based on ESIPT mechanism with
the assistance of CTAB. As the hydroxyl group is protected by 2-
(bromomethyl)benzoate, probe 1 showed weak enol-like fluores-
cence at 350 nm. The 2-(bromomethyl)benzoate group showed
fast response to H2S through cascade reaction and released free
HBT, which showed strong fluorescence at 484 nm in CTAB
micelles. The emission at 484 nm showed linear relationship with
the H2S concentration at 0–100
mmol/L with the detection limit of
0.50 mol/L. The high selectivity and sensitivity of our probe to
m
H2S may give new insights for the development of fluorescent
probe to selectively detect H2S in biological systems.
185
186
Acknowledgments
We thank Prof. Z. Niu and Dr. Y. Tian for providing HeLa cells.
187 Q2 This work was financially supported by the 973 Program (no.
188
189
190
191
2013CB933800), National Natural Science Foundation of China
(nos. 21525206, 21402216, 21272243), the Fundamental Research
Funds for the Central Universities and Beijing Municipal Commis-
sion of Education.
192
References
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
[1] C. Szabo´, Hydrogen sulphide and its therapeutic potential, Nat. Rev. Drug. Discov.
6 (2007) 917–935.
[2] M. Ishigami, K. Hiraki, K. Umemura, et al., A source of hydrogen sulfide and a
mechanism of its release in the brain, Antioxid. Redox Signal. 11 (2009) 205–214.
[3] G.A. Benavides, G.L. Squadrito, R.W. Mills, et al., Hydrogen sulfide mediates the
vasoactivity of garlic, Proc. Natl. Acad. Sci. U.S.A. 104 (2007) 17977–17982.
[4] S. Singh, D. Padovani, R.A. Leslie, T. Chiku, R. Banerjee, Relative contributions of
cystathionine b-synthase and g-cystathionase to H2S biogenesis via alternative
trans-sulfuration reactions, J. Biol. Chem. 284 (2009) 22457–22466.
[5] S. Singh, R. Banerjee, PLP-dependent H2S biogenesis, Biochim. Biophys. Acta 1814
(2011) 1518–1527.
[6] K. Eto, T. Asada, K. Arima, T. Makifuchi, H. Kimura, Brain hydrogen sulfide is
severely decreased in Alzheimer’s disease, Biochem. Biophys. Res. Commun. 293
(2002) 1485–1488.
[7] P. Kamoun, M.-C. Belardinelli, A. Chabli, K. Lallouchi, B. Chadefaux-Vekemans,
Endogenous hydrogen sulfide overproduction in Down syndrome, Am. J. Med.
Genet. A 116 (2003) 310–311.
[8] W. Yang, G.D. Yang, X.M. Jia, L.Y. Wu, R. Wang, Activation of KATP channels by H2S
in rat insulin-secreting cells and the underlying mechanisms, J. Physiol. (Lond.)
569 (2005) 519–531.
[9] S. Fiorucci, E. Antonelli, A. Mencarelli, et al., The third gas: H2S regulates perfusion
pressure in both the isolated and perfused normal rat liver and in cirrhosis,
Hepatology 42 (2005) 539–548.
[10] L.M. Siegel, A direct microdetermination for sulfide, Anal. Biochem. 11 (1965)
126–132.
[11] E. Fischer, Formation of methylene blue in response to hydrogen sulfide, Ber.
Dtsch. Chem. Ges. 16 (1983) 2234–2236.
[32] S. Sahana, G. Mishra, S. Sivakumar, P.K. Bharadwaj, A 2-(2[Prime or minute]-
hydroxyphenyl)benzothiazole (HBT)-quinoline conjugate: a highly specific fluo-
rescent probe for Hg2+ based on ESIPT and its application in bioimaging, Dalton
Trans. 44 (2015) 20139–20146.
[33] S. Goswami, A. Manna, S. Paul, et al., FRET based ‘red-switch’ for Al3+ over ESIPT
based ‘green-switch’ for Zn2+: dual channel detection with live-cell imaging on a
dyad platform, RSC Adv. 4 (2014) 34572–34576.
[34] X.F. Yang, Q. Huang, Y.G. Zhong, et al., A dual emission fluorescent probe enables
simultaneous detection of glutathione and cysteine/homocysteine, Chem. Sci. 5
(2014) 2177–2183.
[35] Q.S. Liu, C.L. Zhang, X.Q. Wang, et al., Benzothiazole-pyimidine-based BF2 com-
plex for selective detection of cysteine, Chem. Asian J. 11 (2016) 202–206.
[36] C.C. Zhao, X.A. Li, F.Y. Wang, Target-triggered NIR emission with a large stokes
shift for the detection and imaging of cysteine in living cells, Chem. Asian J. 9
(2014) 1777–1781.
[37] S. Goswami, S. Das, K. Aich, et al., A chemodosimeter for the ratiometric detection
of hydrazine based on return of ESIPT and its application in live-cell imaging, Org.
Lett. 15 (2013) 5412–5415.
[38] D.P. Murale, H. Kim, W.S. Choi, D.G. Churchill, Highly selective excited state
intramolecular proton transfer (ESIPT)-based superoxide probing, Org. Lett. 15
(2013) 3946–3949.
[39] S.M. Aly, A. Usman, M. AlZayer, et al., Solvent-dependent excited-state hydrogen
transfer and intersystem crossing in 2-(20-Hydroxyphenyl)-Benzothiazole, J.
Phys. Chem. B 119 (2015) 2596–2603.
[40] A.R. Lippert, E.J. New, C.J. Chang, Reaction-based fluorescent probes for selective
imaging of hydrogen sulfide in living cells, J. Am. Chem. Soc. 133 (2011) 10078–
10080.
[12] U. Hannestad, S. Margheri, B. So¨rbo, A sensitive gas chromatographic method for
determination of protein associated sulfur, Anal. Biochem. 178 (1989) 394–398.
[13] J. Furne, A. Saeed, M.D. Levitt, Whole tissue hydrogen sulfide concentrations are
orders of magnitude lower than presently accepted values, Am. J. Physiol. Regul.
Integr. Comp. Physiol. 295 (2008) 1479–1485.
225
Please cite this article in press as: H.-R. Zheng, et al., Cascade reaction-based fluorescent probe for detection of H2S with the assistance of
CTAB micelles, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.023