Colorimetric signaling of hydrogen sulfide by reduction of a phenylseleno-nitrobenzoxadiazole derivative

Article abstract of DOI:10.1016/j.dyepig.2013.06.018

A new reaction-based probe for the colorimetric signaling of hydrogen sulfide was developed. Reduction of the nitro group of a nitrobenzoxadiazole moiety to an amino group resulted in pronounced chromogenic signaling in the form of a yellow to pink color change. The transformation of the nitro group to amino group was confirmed by the ¹H NMR spectroscopy. The seleno derivative showed more efficient signaling behavior than the phenylthio and phenoxy analogues. Hydrogen sulfide signaling of phenylseleno- nitrobenzoxadiazole probe was fast and completed immediately after sample preparation. Selective signaling of hydrogen sulfide was possible in the presence of commonly encountered metal ions and anions with a detection limit of 2.1 × 10^-6 M.

Full text of DOI:10.1016/j.dyepig.2013.06.018

Dyes and Pigments 99 (2013) 748e752
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Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Colorimetric signaling of hydrogen sulfide by reduction of a
phenylseleno-nitrobenzoxadiazole derivative
*
Jihee Bae, Myung Gil Choi, Jiyoung Choi, Suk-Kyu Chang
Department of Chemistry, Chung-Ang University, Seoul 156-756, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
A new reaction-based probe for the colorimetric signaling of hydrogen sulfide was developed. Reduction
of the nitro group of a nitrobenzoxadiazole moiety to an amino group resulted in pronounced chro-
mogenic signaling in the form of a yellow to pink color change. The transformation of the nitro group to
amino group was confirmed by the 1H NMR spectroscopy. The seleno derivative showed more efficient
signaling behavior than the phenylthio and phenoxy analogues. Hydrogen sulfide signaling of
phenylseleno-nitrobenzoxadiazole probe was fast and completed immediately after sample preparation.
Selective signaling of hydrogen sulfide was possible in the presence of commonly encountered metal ions
and anions with a detection limit of 2.1 ꢀ 10ꢁ6 M.
Received 10 April 2013
Received in revised form
13 June 2013
Accepted 16 June 2013
Available online 24 June 2013
Keywords:
Hydrogen sulfide
Colorimetry
Ó 2013 Elsevier Ltd. All rights reserved.
Probe
Reduction
Nitrobenzoxadiazole derivative
Selenoether
1. Introduction
of quantification [11]. Representative examples are colorimetry
using the Cu(II) complex of 1,10-phenanthroline [12], fluorometry
Hydrogen sulfide (H2S) is widely used in industrial activities, such
as production of organosulfur compounds, as a precursor to metal
sulfides, modification of catalysts, and the delignification of pulp [1]. It
is generated as a by-product in many industrial processes, such as
wastewater treatment, coke production, and petroleum-related pro-
cesses [2]. On the other hand, hydrogen sulfide is produced in small
amounts by some cells of the mammalian body and has a number of
biological signaling functions [3]. It also acts as an important gaseous
regulator inplants and its sodium salt (Na2S) is usedin the preservation
of food and beverages [4]. However, hydrogen sulfide is poisonous to
several different systems in the human body, with the nervous system
being the most significantly affected [5]. Therefore, easy and conve-
nient signaling of toxic H2S is very important for the rapid assessment
of this widely used and environmentally important species.
using fluorescein mercuric acetate [13e15], phosphorescence of the
ZnO/SiO2 nanocomposite [16], and surface plasmon resonance ab-
sorption resulting from the stripping of gold nanorods [17]. More
recently, reaction-based hydrogen sulfide or sulfide ion signaling
using reduction of azides to fluorescent amines [18,19], a Michael
additionecyclization sequence [20], and pyryliumꢁthiopyrylium
transformation [21] were reported. In addition, the high affinity of
sulfide for Cu(II) ion is the basis of the signaling [22] in azama-
crocycliceCu(II) [23] and dipicolylamineeCu(II) complexes [24,25],
while nucleophilic reaction of sulfide ions is the design strategy in
dinitrobenzenesulfonate derivatives of fluorescein [26].
Reduction of nitro groups by hydrogen sulfide is a well-known
process and has been successfully used for the reduction of nitro-
phthalocyanine [27], dinitroaniline herbicides [28], 6-nitroisatoic
anhydride [29], aromatic/aliphatic nitro groups [30], and resin-
bound o-nitroimine [31]. Furthermore, reduction of nitro groups by
hydrogen sulfide was recently used for the construction of nitro-
naphthalimide and cyanine-based hydrogen sulfide probes by
modulating the photoinduced electron transfer process [32,33].
Visualization of hydrogen sulfide in biological systems has
attracted much research interest [18,19]. However, there are few
convenient signaling systems targeting hydrogen sulfide in chemical
and environmental systems. In this current study we have explored a
Various analytical techniques for the detection of hydrogen
sulfide were recently reviewed [6,7]. Analysis of H2S has been most
frequently carried out by gas chromatography [8], atomic absorp-
tion spectrometry [9], and electrochemical techniques [10]. Optical
signaling is also attractive due to its simplicity, sensitivity, and ease
* Corresponding author. Tel.: þ82 2 820 5199; fax: þ82 2 825 4736.
E-mail address: skchang@cau.ac.kr (S.-K. Chang).
0143-7208/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2013.06.018

J. Bae et al. / Dyes and Pigments 99 (2013) 748e752
749
new, structurally simple colorimetric probe based on the nitro-
benzoxadiazole (NBD) chromophore to achieve H2S signaling. The
hydrogen sulfide signaling is based on the reduction of the nitro
group of the NBD framework to amine expecting a significant change
in the absorption profile. We reasoned that reduction of the nitro
group into an amino group should induce a change in the electronic
properties and thus the absorption properties of the NBD moiety.
Based on this reasoning, we synthesized a series of NBD-derivatives
1e3 having oxygen, sulfur, and selenium atoms. Reduction of the
NBD nitro group resulted in a selective colorimetric signal toward the
hydrogen sulfide that was discernible by eye.
was stirred at room temperature for 2 h, and the precipitates were
filtered and washed with ethanol. The solid product was crystal-
lized from dichloromethane/hexane solution (1:1, v/v) and dried
under vacuum to give compound 3 (75% yield) as brown crystals;
mp: 135.0e135.4 ꢂC. 1H NMR (600 MHz, DMSOed6)
d 8.44 (d,
J ¼ 7.8 Hz, 1H), 7.85e7.68 (m, 2H), 7.68e7.52 (m, 3H), 7.02 (d,
J ¼ 7.8 Hz, 1H); 13C (150 MHz, DMSOed6)
d 150.26, 142.99, 136.93,
134.19, 132.52, 131.16, 131.06, 127.71, 124.17; HRMS (FAB); m/z calcd
for C12H8N3O3Se [M þ H]þ: 321.9731, found 321.9728.
2.5. Time course plot of signaling
2. Experimental section
Time course of the H2S signaling of 1e3 was followed by
monitoring the absorbance of the measuring solution at 551 nm.
The concentrations of the probes 1e3 and H2S were 10 mM and
2.1. General
0.1 mM, respectively, in a mixture of DMSO and acetate buffer so-
lution (pH 4.8, 10 mM), (1:1, v/v).
NBDeCl (4-chloro-7-nitrobenzofurazan), benzeneselenol, thio-
phenol, phenol, and sodium sulfide were purchased from Aldrich
Chemical Co. All solvents were obtained from Aldrich Chemical
Co. as ‘spectroscopic grade’. 1H NMR (600 MHz) and 13C NMR
(150 MHz) spectra were measured on a Varian VNS spectrometer
and referenced to the residual solvent signal. UVeVis spectra were
recorded with a Jasco V-550 spectrophotometer equipped with a
Peltier temperature controller. Fluorescence spectra were
measured with a PTI QuantaMaster steady-state spectrofluorom-
eter. Mass spectra were obtained on a Micromass Autospec mass
spectrometer.
2.6. Detection limit
Detection limit for the signaling of H2S was estimated from the
concentration-dependent absorption spectra by plotting the
absorbance changes at 551 nm of 3 as a function of log[H2S]
following the reported procedure [35]. For the intermediate values
of the resulting sigmoidal plot, a linear regression curve was ob-
tained. The point at which this line crossed the ordinate axis was
taken as the detection limit.
2.2. Preparation of 1 [34]
2.7. pH effect on sulfide signaling
Phenol (0.28 g, 3.0 mmol) was added to a solution of NBDeCl
(0.20 g, 1.0 mmol) in ethanol (10 mL), after which triethylamine
(0.42 mL, 3.0 mmol) was added dropwise. The reaction mixture was
stirred at room temperature for 12 h, diluted with water and
extracted with dichloromethane. The organic layer was separated
and washed with water, and then evaporated. The crude product
was purified by column chromatography (silica gel, dichloro-
methane) to give compound 1 as an orange solid. The product was
crystallized from dichloromethane/hexane solution (1:1, v/v) to
give 1 (25% yield) as orange crystals; mp: 121.1e121.5 ꢂC (lit. mp:
The effects of pH on the sulfide signaling of 1e3 were tested by
using different buffer solutions. Sulfide signaling in the pH range
between 3.6 and 8.1 was measured (acetate buffer for 3.6 to 5.6,
hepes buffer for 7.1, and tris buffer for 8.1). Final concentrations of
probes 1e3, sulfide, and each buffer solution were 10 mM, 0.1 mM,
and 10 mM, respectively, under the same measurement conditions.
2.8. Hydrogen sulfide signaling for practical samples
Hydrogen sulfide signaling for tap water and simulated
wastewater samples was performed to confirm the practical ability
of the probe 3. The changes in the signaling of 3 for the ‘distilled
water’, ‘tap water’, and ‘simulated wastewater’ were measured as a
function of H2S concentrations. Stock solutions of hydrogen sulfide
(1.0 mM) were prepared in distilled water, tap water, and simu-
lated wastewater. Stock solution of 3 (5.0 ꢀ 10ꢁ4 M) in DMSO was
prepared. Acetate buffer solution (1.0 M) in distilled water, tap
water, and simulated wastewater was also prepared. Calculated
amounts of hydrogen sulfide, 3, and acetate buffer were added to a
vial and the resulting solution was diluted to 3.0 mL with DMSO
and distilled water, tap water, or simulated wastewater to make
121 ꢂC [34]). 1H NMR (600 MHz, DMSOed6)
1H), 7.63e7.54 (m, 2H), 7.50e7.30 (m, 3H), 6.67 (d, J ¼ 8.4 Hz, 1H);
13C (150 MHz, DMSOed6)
153.75, 153.28, 145.86, 144.82, 136.02,
d
8.63 (d, J ¼ 8.4 Hz,
d
131.28, 130.68, 127.44, 121.30, 109.92; LRMS (FAB); m/z calcd for
C
12H8N3O4 [M þ H]þ: 258.1, found 258.1.
2.3. Preparation of 2 [34]
Thiophenol (0.33 g, 3.0 mmol) was added to a solution of NBDe
Cl (0.20 g, 1.0 mmol) in ethanol (10 mL). The reaction mixture was
stirred at room temperature for 12 h, and the yellow precipitates
were filtered and washed with ethanol. The solid product was
crystallized from dichloromethane/hexane solution (1:1, v/v) and
dried under vacuum to give compound 2 (23% yield) as orange
crystals; mp: 157.5e158.0 ꢂC (lit. mp: 157e158 ꢂC [34]). 1H NMR
a
final composition of 1:1 (v/v). Final concentrations of 3
and acetate buffer were 1.0 ꢀ 10ꢁ5 M and 1.0 ꢀ 10ꢁ2 M,
(600 MHz, DMSOed6)
d
8.49 (d, J ¼ 8.0 Hz, 1H), 7.81e7.68 (m, 2H),
7.68e7.58 (m, 3H), 6.81 (d, J ¼ 8.0 Hz,1H); 13C (150 MHz, DMSOed6)
d
149.01, 143.27, 140.44, 135.74, 133.32, 132.99, 131.64, 131.23,
126.37, 123.77; LRMS (FAB); m/z calcd for C12H8N3O3S [M þ H]þ:
274.0, found 274.0.
2.4. Preparation of 3
Benzeneselenol (0.47 g, 3.0 mmol) was added to a solution of
NBDeCl (0.20 g, 1.0 mmol) in ethanol (10 mL). The reaction mixture
Scheme 1. Preparation of NBDebased H2S probes 1e3.

750
J. Bae et al. / Dyes and Pigments 99 (2013) 748e752
180
0.3
0.2
0.1
0
3
3 + S2
+ H2
S
-
3 only,
150
120
90
60
30
0
other metal ions
3
+
300
400
500
600
700
Wavelength (nm)
Fig. 2. Absorbance ratio (A/Ao) of 3 at 551 nm in the presence of various metal ions.
Inset: UVevis absorption spectra of
3 in the presence of common metal ions.
[3] ¼ 1.0 ꢀ 10ꢁ5 M, [H2S] ¼ [Mnþ] ¼ 1.0 ꢀ 10ꢁ4 M in a mixture of DMSO and acetate
buffer solution (pH 4.8, 10 mM), (1:1, v/v).
DMSO and acetate buffer (pH 4.8, 10 mM) (1:1, v/v) was charac-
terized by a strong absorption band at 440 nm. Upon treatment
with 10 equiv of various anions, a strong band at 551 nm appeared
exclusively with H2S (Fig. 1) [37]. The solution color changed
dramatically from yellow to pink. Other anions surveyed
ðFꢁ; Clꢁ; Brꢁ; Iꢁ; HPO42ꢁ; P2O74ꢁ; HSOꢁ3 ; SO24ꢁ; NOꢁ3 ; HCOꢁ3 ; N3ꢁ;
OAcꢁ; and ClOꢁ4 Þ did not induce a response. The absorbance ratio of
3 in the presence and absence of anions (A/Ao) at 551 nm ranged
between 0.59 for Fe and 1.51 for Nꢁ3 ion (Fig. S1, Supplementary
Data). PhenylselenoeNBD 3 also exhibited no significant response
toward commonly encountered metal ions (Fig. 2). Meanwhile, the
fluorescence of 3 was very weak as has been reported for oxo and
thio analogues, 1 and 2 [34]. Furthermore, the fluorescence changes
of 1e3 induced by H2S were insignificant to provide any useful
information (Fig. S2, Supplementary Data).
Signaling was due to reduction of the NBD nitro group of 3 to an
amine functional group (Scheme 2). The hydrogen sulfide signaling
process of 3 depicted in Scheme 2 was confirmed by 1H NMR
spectroscopy (Fig. 3). The spectrum 3 in the presence of Na2S was
obtained directly without any purification from the solution of 3
(1.0 ꢀ 10ꢁ2 M) in the presence of 3 equiv of Na2S (3.0 ꢀ 10ꢁ2 M) in
DMSOed6. Upon treatment of 3 with 3 equiv of Na2S, a pair of
Fig. 1. (a) UVevis absorption spectra of 3 in the presence of various anions. (b)
Photograph of
3
in the presence of various anions. [3]
¼
1.0
ꢀ
10ꢁ5 M,
[H2S] ¼ [Anꢁ] ¼ 1.0 ꢀ 10ꢁ4 M in a mixture of DMSO and acetate buffer solution (pH 4.8,
10 mM), (1:1, v/v).
respectively. Simulated wastewater was prepared according to the
composition of the literature wastewater [36]: [Naþ] ¼ 2.39 ꢀ 10ꢁ3
M, [Kþ]
¼
2.81
ꢀ
10ꢁ4 M, [Mg2þ
]
¼
2.88
ꢀ
10ꢁ4 M,
[Ca2þ] ¼ 2.50 ꢀ 10ꢁ4 M, [Fe] ¼ 1.60 ꢀ 10ꢁ5 M, [Cle] ¼ 9.87 ꢀ 10ꢁ4
M, ½PO34ꢁꢃ ¼ 1:05 ꢀ 10ꢁ4 M; ½SO42ꢁꢃ ¼ 2:08 ꢀ 10ꢁ4 M; ½NOꢁ3 ꢃ ¼
4:84 ꢀ 10ꢁ4 M; ½HCOꢁ3 ꢃ ¼ 1:23 ꢀ 10ꢁ3 M:
3. Results and discussion
doublets at
are characteristic of the two protons of nitrobenzofurazan, shifted
up-field to 8.05 and 6.98, respectively.
d 8.46 and 7.03 (marked by blue and red stars), which
Phenyl ether derivative 1 was prepared by the reaction of
4-chloro-7-nitrobenzofurazan (NBDeCl) with phenol (Scheme 1).
Thioether and selenoether analogues 2 and 3 were also prepared
similarly by the reaction of NBDeCl with thiophenol and benze-
neselenol, respectively.
The NBD-based probes 1e3 showed dramatic chromogenic
signaling behavior toward hydrogen sulfide in mixed aqueous so-
lutions of DMSO (Fig. 1 and Fig. S1, Supplementary Data). However,
the colorimetric behavior of 3 was found to be superior to that of 1
and 2 (vide infra). Therefore, seleno derivative 3 was chosen as a
signaling probe for H2S. The UVevis spectrum of 3 in a mixture of
d
The potential for hydrogen sulfide signaling using similarly
structured oxo and thio analogues 1 and 2 was also assessed. Thio
derivative 2 exhibited similar H2S-selective colorimetric signaling
via a pronounced color change from yellow to pink under the same
signaling conditions of DMSO and acetate buffer solution (pH 4.8,
10 mM) (1:1, v/v) (Figs. S1 and S3, Supplementary Data). Upon
interaction with H2S, the absorption band at 425 nm of 2 decreased
while a new strong band at 551 nm was observed. On the other
Scheme 2. Hydrogen sulfide signaling by phenylselenoeNBD 3.

J. Bae et al. / Dyes and Pigments 99 (2013) 748e752
751
0.4
0.4
0.3
0.3
0.2
0.1
0
0.2
0.1
0
[H2S]
0
1
2
3
4
5
6
Equiv. of H2S
Fig. 3. Partial 1H NMR spectra of
3 alone and 3 in the presence of Na2S.
[3] ¼ 1.0 ꢀ 10ꢁ2 M, [Na2S] ¼ 3.0 ꢀ 10ꢁ2 M in DMSOed6.
300
400
500
Wavelength (nm)
600
700
hand, oxo analogue 1 showed different chromogenic behavior in
that the solution color went from colorless to pink toward H2S.
Under the conditions of DMSO and acetate buffer solution (pH 4.8,
10 mM) (1:1, v/v), the absorption band at 378 nm decreased, and a
new band at 551 nm was evolved (Figs. S1 and S3, Supplementary
Data). However, the signaling efficiency of 1 and 2 assessed by
changes in absorbance with respect to the two characteristic ab-
sorption maxima was significantly inferior to that of seleno deriv-
ative 3. In addition to this, hydrogen sulfide signaling of 3 was
completed immediately after sample preparation, while the
signaling of 1 and 2 required about 40 min (Fig. S4, Supplementary
Data). The large difference in the signaling behavior of NBD-based
probes 1e3 might be due to the different electronic effects of the
oxygen, sulfur, and selenium atoms of bridging ether moiety on the
hydrogen sulfide-induced reduction of the nitro group of nitro-
benzoxadiazole moiety [28].
Competition experiments were carried out in order to test the
practical applicability of 3 in hydrogen sulfide signaling (Fig. 4 and
Fig. S5, Supplementary Data). In the presence of common anions as
background, the H2S signaling of phenylselenoeNBD 3 was not
considerably affected. The absorbance ratio of 3-H2S system in the
presence and absence of anions at 551 nm varied in a narrow range
between 0.97 for chloride and 1.0 for perchlorate ions. In addition
to the common anions, the possible interference from environ-
mental interfering species, particularly sulfur species, was assessed
for 1e3. Among the tested species, S2O23ꢁ and thiophenol exhibited
minor responses under the same signaling conditions (Fig. S6,
Supplementary Data). To have more information on the signaling
Fig. 5. Changes in UVevis spectrum of 3 as a function of H2S concentration. The inset
shows the absorbance changes at 551 nm [3] ¼ 1.0 ꢀ 10ꢁ5 M in a mixture of DMSO and
acetate buffer solution (pH 4.8, 10 mM), (1:1, v/v).
behavior, effects of pH on the hydrogen sulfide signaling of 1e3
were measured. The pH of the measuring solution was adjusted by
using acetate, hepes, and tris buffer solutions. For probe 3, the
signaling of hydrogen sulfide was not affected by the solution pH
between 3.6 and 8.1 (Fig. S7, Supplementary Data). On the other
hand, probes 1 and 2 showed increasing response with increases in
solution pH up to 4.8, and thereafter revealed constant signaling
between pH 4.8 and 8.1.
Concentration-dependent signaling of 3 toward hydrogen sul-
fide was measured in aqueous DMSO solution (Fig. 5). Upon addi-
tion of H2S to the solution of 3, the intensity of the absorption band
at 440 nm decreased steadily while that of the new band at 551 nm
increased. From the concentration-dependent signaling behavior,
the detection limit for the determination of H2S in 50% aqueous
DMSO solution was estimated to be 2.1 ꢀ 10ꢁ6 M [35].
Finally, to confirm the practical ability of the probe 3, the
hydrogen sulfide signaling in the tap water and simulated waste-
water was tested (Fig. 6). The changes in the signaling of 3 for
distilled water, tap water, and simulated wastewater [36] were
measured for a series of H2S concentrations in aqueous DMSO so-
lution. As shown in Fig. 6, the responses of 3 at 551 nm for H2S in
0.3
Distilled water
Tap water
Simulated wastewater
0.2
0.1
0
0
1
2
3
4
[
3
[H2S] / [
Fig. 6. UVevis signaling of H2S in ‘distilled water’, ‘tap water’, and ‘simulated
wastewater’ by 3. In a mixture of DMSO and acetate buffer solution (pH 4.8, 10 mM),
(1:1, v/v). [3]
¼
1.0
ꢀ
10ꢁ5 M. Simulated wastewater: [Naþ
]
¼
2.39
ꢀ
10ꢁ3 M,
Fig. 4. Competitive signaling of H2S by
3
in the presence of common anions.
[Kþ] ¼ 2.81 ꢀ10ꢁ4 M, [Mg2þ] ¼ 2.88 ꢀ 10ꢁ4 M, [Ca2þ] ¼ 2.50 ꢀ 10ꢁ4 M, [Fe] ¼ 1.60 ꢀ 10ꢁ5
M, [Cle] ¼ 9.87 ꢀ 10ꢁ4 M, ½PO34ꢁꢃ ¼ 1:05 ꢀ 10ꢁ4 M; ½SO42ꢁꢃ ¼ 2:08 ꢀ 10ꢁ4 M; ½NO3ꢁꢃ ¼
4:84 ꢀ 10ꢁ4 M; and ½HCO3ꢁꢃ ¼ 1:23 ꢀ 10ꢁ3 M:
[3] ¼ 1.0 ꢀ 10ꢁ5 M, [H2S] ¼ [Anꢁ] ¼ 1.0 ꢀ 10ꢁ4 M in a mixture of DMSO and acetate
buffer solution (pH 4.8, 10 mM), (1:1, v/v).

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J. Bae et al. / Dyes and Pigments 99 (2013) 748e752
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hydrogen sulfide in chemical and environmental applications.
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4. Conclusion
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online analysis of sulfide based on the red shifts of longitudinal surface
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10078e80.
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A new reaction-based hydrogen sulfide signaling probe based
on phenylselenoeNBD was investigated. Reduction of the nitro
group of the NBD framework by H2S resulted in selective colori-
metric signaling behavior in 50% aqueous DMSO solution. Signaling
was not affected by the presence of common anions or metal ions.
The designed probe, which is based on reduction of the nitro group
of the NBD moiety, could be useful for the construction of selective
switching or signaling systems for other important reducing agents.
Acknowledgments
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This work was supported by the ChungeAng University
Research Scholarship Grant in 2012 (JB).
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Appendix A. Supplementary data
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Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2013.06.018.
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