Synthesis and crystal structure of a highly selective colorimetric and fluorometric sensor for hydrogen sulfide

Article abstract of DOI:10.1002/bio.3248

A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has been synthesized. The complex and ligand crystals were obtained and the molecular structures were characterized by X-ray diffraction and Electrospray ionization High resolution mass spectrometer (ESI-HRMS). The photophysical and recognition properties were examined. The complex can recognize S^{2 ?}, with an obvious color change from yellow to red based on a copper ion complex displacement mechanism. By contrast, no obvious changes were observed in the presence of other anions (AcO^?, H₂PO₄ ^?, F^?, Cl^?, Br^? and I^?). We present a simple, easily prepared, yet efficient, inorganic reaction-based sensor for the detection of S^{2 ?}. The complex should have many chemical and analytical applications in the sensing of hydrogen sulfide.

Full text of DOI:10.1002/bio.3248

Received: 22 August 2016
DOI 10.1002/bio.3248
Revised: 7 October 2016
Accepted: 8 October 2016
R E S E A R C H A R T I C L E
Synthesis and crystal structure of a highly selective colorimetric
and fluorometric sensor for hydrogen sulfide
Kui Ren1 Xuefang Shang1 Yanmei Chen1 Xueli Zhang2 Jiajia Fu2 Peipei Zhao2
Jinlian Zhang2
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1 Key Laboratory of Medical Molecular Probes,
Abstract
Department of Chemistry, Xinxiang Medical
University, Xinxiang, China
A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has
2 School of Pharmacy, Xinxiang Medical
University, Xinxiang, China
been synthesized. The complex and ligand crystals were obtained and the molecular structures
were characterized by X‐ray diffraction and Electrospray ionization High resolution mass spec-
trometer (ESI‐HRMS). The photophysical and recognition properties were examined. The com-
plex can recognize S2−, with an obvious color change from yellow to red based on a copper ion
complex displacement mechanism. By contrast, no obvious changes were observed in the pres-
ence of other anions (AcO−, H2PO4−, F−, Cl−, Br− and I−). We present a simple, easily prepared,
yet efficient, inorganic reaction‐based sensor for the detection of S2−. The complex should have
many chemical and analytical applications in the sensing of hydrogen sulfide.
Correspondence
Xuefang Shang, Key Laboratory of Medical
Molecular Probes, Department of Chemistry,
School of Basic Medical Sciences, Xinxiang
Medical University, Xinxiang, Henan 453003,
China.
Email: xuefangshang@126.com
Funding information
Fund of Fluorescence Probe and Biomedical
Detection Research Team of Xinxiang City,
Grant/Award Number: CXTD16001; National
Natural Science Foundation of China, Grant/
Award Number: 81301269; Graduate Student
Innovation Project of Xinxiang Medical Univer-
sity, Grant/Award Number: YJSCX201524Y
KEYWORDS
colorimetric chemosensor, copper complex crystal, hydrogen sulfide
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1
INTRODUCTION
including colorimetric, electrochemical, chemiluminescence, chroma-
tography and methylene blue assay have been developed for the detec-
tion of H2S.[17–20] However, use of these methods in living organisms is
generally limited by their invasive and destructive nature. By contrast,
small fluorescent probes confer the advantages of high sensitivity and
good cell permeability, and have attracted much attention for use in
sensing and visualizing analytes in living cells.[21–28] Reduction‐, nucle-
ophilic‐ and metal sulfide‐based strategies are the most frequently
employed.[29] This technology provides real‐time, easy‐to‐use, non‐
destructive detection methods for use in live cells or tissues.
Traditionally considered a toxic gas with an unpleasant smell, hydrogen
sulfide (H2S), has been identified as the third member of the
gasotransmitter family, after carbon monoxide (CO) and nitric oxide
(NO).[1,2] It is reported that the typical concentration of H2S in blood
is in the range of 10–600 μM.[3–5] Several studies have shown that
H2S is involved in various physiological processes, including the relaxa-
tion of vascular smooth muscles, mediation of neurotransmission, regu-
lation of inflammation and O2 sensing; it can also protect against
ischemia/reperfusion injury.[6–10] By contrast, its deregulation is corre-
lated with Down syndrome and such diseases as Alzheimer’s, diabetes
and liver cirrhosis.[11–15] Despite the potential therapeutic implications,
our understanding of the biological and pathological roles of this
intriguing gas remains in its infancy.[16] Tracking and quantifying H2S
inside living cells are crucial to understanding the biological and patho-
logical roles of this gas. To date, a variety of detection methods
Using this information, we introduced azo as a colorimetric group
and synthesized a Cu(II) complex to research its anion binding ability, par-
ticularly for Na2S (a commonly employed H2S donor). Fortunately, crys-
tals of the Cu(II) complex and ligand were also obtained. As expected,
the complex could be used as a candidate colorimetric chemosensor for
S2− among the tested anions (S2−, AcO−, H2PO4−, F−, Cl−, Br− and I−).
Abbreviations used: DMSO, Dimethyl sulfoxide; ESI, Electrospray ionization;
HRMS, High resolution mass spectrometer; ESI‐HRMS, Electrospray ionization
High resolution mass spectrometer; MS, Mass spectrometry; NMR, Nuclear
mass resonance; PBS, Phosphate‐buffered saline; TMS, Tetramethylsilane; UV,
Ultraviolet; Vis, Visible.
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2
EXPERIMENTAL
All reagents and solvents used were of analytical grade. Sodium sulfide
hydrate and anions in the form of tetrabutylammonium salts,
Luminescence 2016; 1–7
wileyonlinelibrary.com/journal/bio
Copyright © 2016 John Wiley & Sons, Ltd.
1

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REN ET AL.
e.g. (n‐C4H9)4NCl, (n‐C4H9)4NBr, (n‐C4H9)4NI, (n‐C4H9)4NAcO and
(n‐C4H9)4NH2PO4, were purchased from Aladdin Chemistry Co. Ltd
(Shanghai, China). The anions were stored in a desiccator under vac-
uum and used without further purification. Dimethyl sulfoxide
(DMSO) was distilled under vacuum after being dried with CaH2. 1H
NMR spectra were measured on a Bruker Ascend™ 400 spectrome-
ter, with chemical shifts reported in p.p.m. and using
Tetramethylsilane (TMS) as the internal standard. High resolution
mass spectrometer (HRMS) was performed with a Bruker Microtof‐
QIII spectrophotometer. Ultraviolet–visible (UV–vis) titration experi-
ments were made on a Shimadzu UV2550 spectrophotometer at 298
K. The binding constant, Ks, was obtained using a non‐linear least
squares calculation method for data fitting.
7.38–7.32 (m, 3H, ph‐H), 7.18 (d, J = 8.5 Hz, 1H, ph‐H) (Figure S1).
ESI‐MS (m/z): calc. for 302.1293 (M+H)+, 324.1113 (M+Na)+; found:
302.1293 (M+H)+, 324.1087 (M+Na)+ (Figure S2).
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2.3
Synthesis of bis(5‐(azo‐benzene)‐salicylidene‐
aniline) Cu(II)
In accordance with the literature,[31] copper acetate hydrate (110 mg,
0.5 mmol) was added to a stirred solution of 5‐(azo‐benzene)‐
salicylidene‐aniline (301 mg, 1 mmol) in 40 ml of ethanol. The mixture
was stirred for 6 h at 78°C, and then left to stand for 2 days at room
temperature. A suitable single brown crystal for X‐ray crystal structural
analysis was obtained, separated by filtration, washed with cyclohex-
ane and water. Yield: 71%. ESI‐HRMS (m/z): calc. for 686.1467 (M
+Na)+; found: 686.1433 (M+Na)+ (Figure S3).
The compound was synthesized according to the route shown in
Scheme 1.
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RESULTS AND DISCUSSION
2.1
Synthesis of 5‐(azo‐benzene)‐salicylidene
5‐(Azo‐benzene)‐salicylidene was synthesized in accordance with the
literature.[30] HCl (37%, 10 ml) was added slowly to phenylamine
(5 mmol, 465 mg) in 2 ml of water at 0–5°C. Then, NaNO2 (20%, 20
ml) was added to the above‐mentioned mixture and the solution was
stirred for 1 h to give a bright yellow solution. Salicylaldehyde (5 mmol)
dissolved in 150 ml of a saturated aqueous solution of Na2CO3 was
added dropwise to the bright yellow solution for 1 h. After stirring
for 4 h, the reaction mixture was neutralized with HCl. The deep‐red
crude solid was filtered and recrystallized from ethanol to afford a pure
product. Yield: 75%. m.p. 124–126°C. 1H NMR, δ 11.53 (s, 1H, −OH),
10.38 (s, 1H, −CH), 8.19 (d, J = 2.4 Hz, 1H, ph‐H), 8.12 (d, J = 2.4 Hz,
1H, ph‐H), 8.09 (d, J = 2.4 Hz, 2H, ph‐H), 7.87 (d, 2H, J = 6.6 Hz,
ph‐H), 7.57 (t, 1H, J = 7.8 Hz, ph‐H), 7.21 (d, J = 8.7 Hz, 1H, ph‐H).
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3.1
X‐Ray crystal structure
A brown single crystal of complex was obtained at room temperature
from the solvent of CH3CH2OH solution by slow evaporation. To con-
firm the chemical structure of the complex, single crystal X‐ray analysis
was used to determine the structure of the copper complexes. An
ORTEP view of the copper Schiff base complex with its atom number-
ing scheme is given in Figure 1. A summary of the crystal data, data col-
lection and refinement details are given in Table 1. Selected bond
lengths and bond angles are listed in Table 2. The bond angles all fit
with the ideal value of 180°. The crystallographic data revealed that
the metal center was four‐coordinated by two phenolate oxygen and
two imine nitrogen atoms of two Schiff base ligands. The Cu–O bonds
are in the trans configuration and Cu–O distances are shorter than
Cu–N distances. The Schiff base loses a proton from the hydroxyl
group and acts as a single charged bidentate ligand coordinating to
Cu(II). The ligands coordinate to the Cu(II) center in the trans orienta-
tion with respect to each other. The geometry around the metal center
was a distorted square‐planar, with a P21/c space group. These param-
eters are in close agreement with those reported for square‐planar Cu
(II) compounds.[32–35]
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2.2
Synthesis of ligand (5‐(azo‐benzene)‐
salicylidene‐aniline)
5‐(Azo‐benzene)‐salicylidene‐aniline was synthesized in accordance
with the literature.[31] It was obtained by refluxing an ethanol solution
(40 ml) of 5‐(azo‐benzene)‐salicylidene (10 mmol) and phenylamine
(10 mmol) for 4 h and the red precipitate was recrystallized by ethanol,
washed with water and dried under vacuum. A suitable single red crys-
tal for X‐ray crystal structural analysis was obtained. Yield: 73%. m.p.
126–128°C. 1H NMR (400 MHz, CDCl3) δ 13.90 (s, 1H, −OH), 8.79
(s, 1H, −CH=N‐), 8.13–8.02 (m, 2H, ph‐H), 7.92 (d, J = 7.3 Hz, 2H,
ph‐H), 7.55 (t, J = 7.4 Hz, 2H, ph‐H), 7.51–7.45 (m, 3H, ph‐H),
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3.2
UV–vis titration
The binding ability of the copper complex with anions was investi-
gated using UV–vis absorption spectra in DMSO and DMSO–H2O
SCHEME 1 Synthesis route for ligand and copper complex

REN ET AL.
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FIGURE 1 Molecular structure of ligand (left) and copper complex (right)
TABLE 1 Crystal Data and Structure Refinement for Complexes
Empirical formula
C19 H15 N3O
C38 H28 Cu N6 O22
Formula weight
301.34
296 (2)
664.20
293 (2)
T (K)
λ (Å)
0.71073
0.71073
Monoclinic
P21/c
Crystal system
Monoclinic
P21/c
Space group
Crystal color
Colorless
0.325 × 0.219 × 0.098
10.3339 (4)
12.5776 (5)
12.3764 (6)
90
Brown
Crystal size (mm × mm × mm)
0.750 × 0.400 × 0.080
10.0455 (10)
19.644 (2)
8.2552 (7)
90
a (Å)
b (Å)
c (Å)
α (°)
β (°)
100.3830 (10)
90
100.667 (3)
90
γ (°)
V (Å3)
μ (mm−1
1582.29 (12)
0.081
1600.9 (3)
0.727
)
Dcalc (g·ml−1
)
1.265
1.378
Z
4
2
F (0 0 0)
632
686
θ range for data collection (°)
3.24 to 25.00
2.926 to 27.102
Index ranges
−11 · h · 12
−14 · k · 14
−14 · l · 14
−12 · h · 12
−25 · k · 25
−10 · l · 10
Refinement method
Full‐matrix least‐squares on F2
Full‐matrix least‐squares on F2
Goodness‐of‐fit on F2
1.052
1.076
R1 and wR2 indices [I > 2σ(I)]
R1 and wR2 indices (all data)
Largest difference in peak and hole (e Å−3
R1 = 0.0485, wR2 = 0.1209
R1 = 0.0595, wR2 =0.1341
0.150 and −0.230
R1 = 0.0424, wR2 = 0.0981
R1 = 0.0602, wR2 = 0.01054
0.297 and −0.255
)
TABLE 2 Selected Bond Lengths (Å) and Angles (°) for the Complex
(4 : 1, v/v) at 298 K. UV–vis spectral changes in the copper complex
(4.0 × 10−5 mol·L−1 in DMSO) are shown in Figure 2. It was clear that
the maximal absorption band of the complex at 391 nm red‐shifted grad-
ually with increasing amounts of S2−. Two processes were shown in the
titration with S2−. The valley at 328 nm changed to a peak when 1.2
equiv. of S2− was added, and two clear isosbestic points at 363 and
Cu(1)‐O(1)
1.8739 (16)
1.8739 (16)
1.9934 (17)
1.9934 (17)
180.0
Cu(1)‐O(1)#1
Cu(1)‐N(1)
Cu(1)‐N(1)#1
O(1)#1‐Cu(1)‐O(1)
N(1)‐Cu(1)‐N(1)#1
O(1)‐Cu(1)‐N(1)
O(1)#1‐Cu(1)‐N(1)#1
O(1)#1‐Cu(1)‐N(1)
O(1)‐Cu(1)‐N(1)#1
462 nm suggested a strong interaction between the complex and S2−
.
180.00 (11)
91.83 (7)
When 20 equiv. of S2− was added, the maximal absorption band red‐
shifted to 430 nm with one clear isosbestic point at 392 nm. A new
shoulder peak appeared at ~ 525 nm with 16 times enhanced absor-
bance. For an excellent chemosensor, high selectivity is very important.
Analogous investigations were carried out on other normal anions. Addi-
tion of H2PO4− and F− to the complex induced a blue shift from 392 to
91.83 (7)
88.17 (7)
88.17 (7)
Symmetry transformations used to generate equivalent atoms: #1 –x + 1,
−y + 1, −z + 2.

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FIGURE 2 UV–vis spectral changes of Cu(II) complex upon the addition of S2−. [complex] = 4.0 × 10−5 mol·L−1 in DMSO: (a) [S2−] = 0–5.4 × 10−4
mol·L−1; (b) [S2−] = 0–3.2 × 10−5 mol·L−1; (c) [S2−] = 3.2–54 × 10−5 mol·L−1. Arrows indicate the direction of increasing anion concentration
FIGURE 3 UV–vis spectral changes of Cu(II) complex (1) upon the addition of various anions. [complex] = 4.0 × 10−5 mol·L−1 in DMSO: (a) H2PO4
0–6.2 × 10−4 mol·L−1; (b) F− 0–6.2 × 10−4 mol·L−1. Arrows indicate the direction of increasing anions concentration
−

REN ET AL.
5
356 nm (Figure 3), indicating that the Cu(II) complex also interacted with
the above anions. By contrast, the addition of AcO−, Cl−, Br− and I− did
not induce any spectral responses. The above results indicated that Cu
(II) complex showed almost no binding ability toward these anions. It
was found that S2− could lead to a color change in the complex from yel-
low to red, whereas other tetrabutylammonium salts did not induce any
obvious color change (Figure 4) or spectral changes in the complex at
525 nm (Figure S6). Thus, the complex can be used to detect S2− selec-
tively using the naked eye.
on increasing the concentration of S2−, the fluorescence emission
intensity gradually strengthened at ~ 340 nm, because added S2− could
coordinate with Cu2+ and release the free ligand. Fluorescence titra-
tion of the chemosensor with various anions was conducted to exam-
ine the selectivity of the sensor. As shown in Figure 5(b), addition of
AcO−, H2PO4−, F−, Cl−, Br− and I− (4.0 × 10−4 mol·L−1) produced a nom-
inal change in the fluorescence spectra of the probe. These results sug-
gest that the complex is a practical probe for the detection of S2− with
high selectivity. In order to test the real‐world applicability of the
probe, we studied the S2− recovery rate of the sensor in tap water. A
ninefold enhancement in the fluorescence suggested that the probe
would be a good candidate for the detection of S2− in tap water
(Figure 5d). In order to exclude the effect of pH, we then evaluated
the fluorescence of the sensor in DMSO–phosphate‐buffered saline
(PBS) (4 : 1, v/v, pH 7.4). The fluorescence intensity of the emission
band centered at 340 nm increased significantly. These results sug-
gested that the complex was a practical candidate sensor for the
detection of S2− with high selectivity.
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3.3
Fluorescent response
The fluorescence spectrum of the ligand in DMSO was characterized
by strong emission at 341 nm (λex = 296 nm). Upon interaction with
Cu2+, the system exhibited significant quenching in the fluorescence
intensity (Figure S8). The fluorescence properties of the Cu(II) complex
were investigated in DMSO–H2O (4 : 1, v/v). The free probe displayed
weak fluorescence upon excitation at 296 nm. As shown in Figure 5,
FIGURE 4 Photographic images of the
complex sensor solution and the sensor solution
upon the addition of different anions (20
equiv.). Left to right: free complex, S2−, H2PO4
,
−
AcO−, F−, Cl−, Br− and I−). The concentration of
the sensor is 4.0 × 10−5 mol·L−1
FIGURE 5 (a) Fluorescence response (λex = 296 nm; slit widths = 5/5 nm) of copper probe (4.0 × 10−5 mol·L−1) upon the addition of S2−
(0–1.4 × 10−3 mol·L−1). Spectra were acquired in DMSO–H2O (4 : 1, v/v). (b) Fluorescence spectra (λex = 296 nm; slit widths = 5/5 nm) of
probe (4.0 × 10−5 mol·L−1) upon the addition of anions (8.0 × 10−4 mol·L−1) in DMSO–H2O (4 : 1, v/v). (c) Na2S (0–7.2 × 10−4 mol·L−1), in
DMSO–tap water (4 : 1, v/v). (d) Na2S (0–3.2 × 10−4 mol·L−1), in DMSO–PBS (4 : 1, v/v) at pH 7.4

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FIGURE 6 Non‐linear fitting curves of Cu(II) complex in DMSO (a, b, c) or DMSO–H2O(d, e, f, 4 : 1) upon the addition of anions
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tested. This is probably due to the displacement reaction, in which
3.4
Binding constant
the Cu2+ was captured by S2− and free ligand was released from the
complex; the other anions could only be coordinated with the complex.
The above results indicate that the synthesized copper complex could
be used as a chemosensor for the detection of S2− in environmental or
pharmaceutical samples.
The binding constant (K) of the complex derived from the fluorescence
titration data was found to be 1.07 × 102 using a Bensi–Hildebrand
plot (Figure S9), suggesting that the ligand showed greater binding
capacity than sulfide with Cu2+. Cu(II) complex interacted with S2− at
a ratio of 1 : 2 according to the non‐linear fitting curves and Job’s plot
(Figure S10 and Figure 6). However, the complex interacted with other
anions at a ratio of 1 : 1. The corresponding coefficients were all >
0.99. The binding constants were obtained and are listed in Table 3
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3.5
Mechanism
based on the UV–vis data.[36,37] The anion binding constants (Ks) of
A full understanding of the principles that govern anion recognition has
not yet been achieved. Similar to previously reported metal‐based H2S
probes,[38–40] the red shift in the absorbance was most likely due to the
much higher binding constant between sulfide and copper ions which
the Cu(II) complex were in the order: H2PO4 > F− > S2− >> AcO−
~
−
Cl− ~ Br− ~ I−. From Table 3, it can be seen that the Cu(II) complex
highlighted the different binding ratio between S2− and other anions
TABLE 3 Binding Constants of Cu(II) Complex with Various Anions
S2−
H2PO4
F−
AcO−, Br−, Cl− or I−
−
Anions
Ks
(2.36 0.04) × 104a
(1.74 0.04) × 104a
(2.92 0.09) × 104b
(2.27 0.09) × 104b
(2.77 0.08) × 104b
(2.12 0.08) × 104b
NDc
NDc
Ks DMSO–H2O (4:1, v/v)
aThe binding ratio of host–guest is 1 : 2.
bThe binding ratio of host–guest is 1 : 1.
cThe binding constant could not be determined.
SCHEME 2 Possible binding mode for the sensing of anions

REN ET AL.
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enabled the added S2− to snatch copper ions from the complex
(Scheme 2). Direct evidence of the displacement mechanism came
from ESI‐MS. The copper complex itself exhibited a dominant peak
at m/z = 686.1433 (Figure S3), however, after the addition of 0.5
equiv. of S2−, this peak decreased and a new peak was seen at m/z =
302.1282 (Figure S4), corresponding to the developed ligand. By con-
trast, comprehensive UV–vis analysis shows that the other anions
could only coordinate with the complex to form five‐coordinated com-
plexes. The binding ratio and binding constants also illustrate this. As
shown in Table 3, the copper complex interacted with S2− at the ratio
of 1 : 2 in DMSO solution, which indicates that copper atoms were
released from the complex.
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4
CONCLUSION
In summary, we designed and synthesized a novel, effectively selective
and sensitive colorimetric and fluorometric chemosensor for Na2S based
on a Schiff base copper complex. The complex acts as a colorimetric
chemosensor for S2− in DMSO solution and allows the naked‐eye detec-
tion of S2− at room temperature. These properties make the complex
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suitable for the direct and rapid detection of biologically important S2−
.
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Radic. Biol. Med. 2011, 50, 1021.
The advantages of the above method are the simplicity of the analysis
and the low cost of the starting material. The complex has great potential
in the environmental analysis of HS−, S2− and H2S, although its use in bio‐
analysis remains a challenge. The preparation of a highly fluorescent
copper complex is currently under investigation.
[28] C. Gao, X. Liu, X. Jin, J. Wu, Y. Xie, W. Liu, X. Yao, Y. Tang, Sensor
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[29] A. R. Lippert, J. Inorg. Biochem. 2014, 133, 136.
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[31] K. Ren, X. Shang, J. Fu, P. Zhao, J. Zhang, Polyhedron 2016, 104, 99.
ACKNOWLEDGMENTS
[32] C. Zou, L. Gao, T. Liu, Z. Xu, J. Cui, J. Incl. Phenom. Macrocycl. Chem.
2014, 80, 383.
This work was supported by the National Natural Science Foundation
of China (81301269), Graduate Student Innovation Project of Xinxiang
Medical University (YJSCX201524Y), Fund of Fluorescence Probe and
Biomedical Detection Research Team of Xinxiang City (CXTD16001)
and Program for Science & Technology Innovation Talents in Universi-
ties of Henan Province (15HASTIT039).
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