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A multiple-detection-point fluorescent probe for the rapid detection of mercury(II), hydrazine and hydrogen sulphide
Journal Pre-proof A multiple-detection-point fluorescent probe for the rapid detection of mercury(II), hydrazine and hydrogen sulphide Xiaoming Wu, Yanan Li, Shaoxiang Yang, Hongyu Tian, Baoguo Sun PII:
S0143-7208(19)32102-3
DOI:
https://doi.org/10.1016/j.dyepig.2019.108056
Reference:
DYPI 108056
To appear in:
Dyes and Pigments
Received Date: 4 September 2019 Revised Date:
19 October 2019
Accepted Date: 16 November 2019
Please cite this article as: Wu X, Li Y, Yang S, Tian H, Sun B, A multiple-detection-point fluorescent probe for the rapid detection of mercury(II), hydrazine and hydrogen sulphide, Dyes and Pigments (2019), doi: https://doi.org/10.1016/j.dyepig.2019.108056. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier Ltd.
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A multiple-detection-point fluorescent probe for the rapid detection
2
of mercury(II), hydrazine and hydrogen sulphide
3
Xiaoming Wu, Yanan Li, Shaoxiang Yang*, Hongyu Tian and Baoguo Sun
4
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing
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Key laboratory of Flavor Chemistry, Beijing Technology and Business University,
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Beijing 100048, PR China
7
*
8
[email protected] (S. X. Yang)
Corresponding author. Telephone: +86-10-68985382. E-mail:
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1
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Graphical abstract
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A multiple-detection-point fluorescent probe for the rapid detection
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of mercury(II), hydrazine and hydrogen sulphide
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Xiaoming Wu, Yanan Li, Shaoxiang Yang*, Hongyu Tian and Baoguo Sun
30
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing
31
Key laboratory of Flavor Chemistry, Beijing Technology and Business University,
32
Beijing 100048, PR China
33
*
34
[email protected] (S. X. Yang)
Corresponding author. Telephone: +86-10-68985382. E-mail:
35 36
A multiple-detection-point fluorescent probe for the rapid detection of mercury(II),
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hydrazine and hydrogen sulphide
38 39
Highlights
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1. A multiple-detection-point fluorescent probe (Probe 1) was developed for the
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detection of Hg2+, N2H4 and H2S.
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2. Rapid detection of Hg2+, N2H4 and H2S was achieved by a colour change of the test
43
paper of Probe 1.
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3. The test paper turns to dark with Hg2+, yellow with N2H4, and pink with H2S.
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4. Probe 1 could be used to detect Hg2+, N2H4 and H2S in real samples.
2
46
Abstract: A multiple-detection-point fluorescent probe (Probe 1) was developed for
47
the rapid detection of mercury(II) (Hg2+), hydrazine (N2H4) and hydrogen sulphide
48
(H2S). Probe 1 could detect Hg2+, N2H4 and H2S through different reaction sites and
49
mechanisms, i.e. Hg2+ via a desulphurisation reaction, N2H4 via addition-cyclisation,
50
and H2S via a nucleophilic addition reaction. N2H4 and H2S had hardly any effect on
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Hg2+ detection in C2H5OH, but Hg2+ interfered with N2H4 and H2S detection in
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DMSO, and Hg2+ and N2H4 interfered with H2S detection in DMSO. Rapid detection
53
of Hg2+, N2H4 and H2S was achieved by a colour change in the test paper of Probe 1,
54
which gradually turns dark in response to different concentrations of Hg2+, yellow
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with N2H4, and pink with H2S. Furthermore, Probe 1 could be used to detect Hg2+,
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N2H4 and H2S in real samples.
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Keywords: multiple-detection-point; fluorescent probe; rapid detection; test paper
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1. Introduction
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Mercury(II) (Hg2+) is a heavy metal pollutant in manufacturing processes [1] and is
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toxic to human and animals, causing nausea, kidney damage, neurotoxicity and
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abdominal pain [2, 3]. Hg2+ can threaten human health through the food-chain and
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bioaccumulation [4-6]. A limit for mercury content in food has been established by
76
governments worldwide [7, 8]; in China, the Hg2+ content must be below 0.02 mg/kg
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in corn and wheat [9].
78
Hydrazine (N2H4) is used as an engine and rocket fuel, as well as a pharmaceutical
79
raw material [10, 11]. However, N2H4 is a highly toxic compound that can be
80
absorbed through the skin leading to damage to the kidneys, lungs and eyes [12, 13].
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Furthermore, N2H4 is also a carcinogen [14]. N2H4 is very soluble in water and its
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content in water is strictly limited by most countries. In China, the requirement for
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drinking water is <0.001 mg/L N2H4 [15].
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Hydrogen sulphide (H2S) is a colourless, toxic gas and has an odour of bad eggs
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[16]. If wine contains an excess of H2S, it will have a sulphurous taste, which impacts
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the quality of the wine [17-19]. Furthermore, an abnormal content of H2S is
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associated with diseases including ischaemic disease, diabetes, tumours and
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atherosclerosis [20-22].
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Hg2+ can be detected by atomic absorption spectrometry [23], ICP-MS [24] and
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ICP-OES [25] while H2S can be detected by gas chromatography [26], the methylene
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blue method [17] and colourimetry [18, 19]. N2H4 can be detected by gas
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chromatography and electrochemical methods [27]. Hg2+, N2H4 and H2S all
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commonly require detection in, for example, environmental samples. However, as
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their physical and chemical properties differ, it has been hard to develop a single rapid
95
detection method for the detection of Hg2+, N2H4 and H2S. 4
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Fluorescent probes are a simple and fast detection tool [28-34]. Recently,
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fluorescent probes for Hg2+ [35-43], N2H4 [44-48] or H2S [49-57] have been
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developed based on their unique physical and chemical properties. Some
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dual-function fluorescent probes have also been developed [58-61] but the rapid
100
detection of Hg2+, N2H4 and H2S by the same fluorescent probe has not yet been
101
reported.
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A fluorescent probe with multiple detection points is a promising method to detect
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multiple chemicals. Therefore, here, we develop a multiple-detection-point
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fluorescent probe (Probe 1) for the detection of Hg2+, N2H4 and H2S. In Probe 1,
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naphthalene is the fluorophore, phenyl thiobenzoate is the reactive group for Hg2+, a
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carbon-carbon double bond is the reactive group for H2S and an α, β-unsaturated
107
ketone is the reactive group for N2H4. The rapid detection of Hg2+, N2H4 and H2S was
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achieved by a colour change of the test paper.
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2. Materials and methods
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2.1 General Methods
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The Cysteine (Cys, 99%), Phenyl thioxochloroformate (98%), Glutathione (GSH,
112
98%), hydrogen peroxide (H2O2, 30%), Homocysteine (Hcy, 99%), hydarazine
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hydrate (64%), and analytically pure sodium chloride (NaCl), magnesium sulphate
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(MgSO4), ammonium chloride (NH4Cl), cupric sulfate (CuSO4), ferric chloride
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(FeCl3), sodium hydrogen sulfite (NaHSO3), sodium fluoride (NaF), sercury sulfate
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(HgSO4), potassium bromide (KBr), potassium iodide (KI), sodium sulfide (Na2S),
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calcium chloride (CaCl2), ferrous sulfide (FeS), sodium sulfite (Na2SO3), potassium
118
bromide (KBr), N, N-diisopropylethylamine (DIPEA), sodium chloride (NaCl),
119
dichloromethane (DCM) were bought from Yinuokai Co., Ltd.
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2.2 Instruments 5
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Fluorescence spectra was performed at Rili F-4600 fluorescence spectrometer.
122
NMR spectra were performed at a Bruker AV 300 MHz NMR. HRMS was performed
123
at a Bruker Apex IV FTMS.
124
2.3 Preparation of Probe 1
125
Compound 1 (0.20g，0.63 mmol), dichloromethane (10 mL), DIPEA (0.35 mL) and
126
compound 2 (0.14g，8.14 mmol) were stirred together at 25 °C for 8.5 h (Scheme 1).
127
Probe 1 was purified by column chromatography.
128
1
H NMR (300 MHz, DMSO) δ 8.47 (s, 1H), 8.42 (s, 4H), 8.23 (s, 1H), 8.15 (d, J =
129
6.9 Hz, 1H), 8.12 – 8.05 (m, 2H), 8.00 (s, 1H), 7.96 (d, J = 2.3 Hz, 1H), 7.61 (dd, J =
130
8.9, 2.3 Hz, 1H), 7.57 – 7.50 (m, 2H), 7.39 (dd, J = 7.4, 5.4 Hz, 3H). 13C NMR (75
131
MHz, DMSO) δ 194.66, 188.81, 153.65, 152.31, 150.35, 145.69, 142.80, 135.00,
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133.02, 131.89, 131.59, 131.13, 130.43, 128.96, 127.54, 125.87, 124.38, 122.97,
133
122.68, 122.23, 119.51. HRMS (MALDI): calcd for [M+H]+ 456.090020, found
134
456.089226.
135
2.4 Preparation of samples
136
20 µL sample was used to detect the level of Hg2+, N2H4 and H2S. Different level of
137
Hg2+, N2H4 and H2S was added.
138
2.5 The detection settings of Hg2+, N2H4 and H2S
139
The preparation of test system: 0.02 mL probe solution was dissolved in 0.48 mL
140
H2O, added to the ion solution, then the capacity to 2 mL in cuvette with buffer
141
solution. After mixture, it was mixed to test the spectrum, the fluorescence signal was
142
recorded [62, 63]. Slit widths = 5 nm, 5 nm, λex = 300 nm, λem = 278 nm, temperature
143
= 25 °C, and voltage = 600 V.
144
2.6 Preparation of test strips
145
The test strips were prepared using waterman filter paper (1 cm × 1 cm pieces). 6
146
Dropping a DMSO solution of Probe 1 (10 µM, 10 µL) to filter paper and then baking
147
for 5 minutes in an oven at 70 oC.
148
3. Results and Discussion
149
3.1 Probe synthesis
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The key intermediate compound 1 was synthesised in our previous work [64].
151
Probe 1 was produced through a nucleophile substitution reaction of compound 1 with
152
compound 2. Probe 1 was purified by column chromatography and characterised by
153
HRMS and NMR (Figs. S1–S3).
154
3.2 Fluorescence properties of Probe 1 in response to Hg2+
155
The fluorescence response of Probe 1 (10 µM) to Hg2+ in DMSO, H2O, C2H5OH
156
and CH3CN solutions at 25oC was investigated (Fig. 1a). After 300 µM Hg2+was
157
added, the fluorescence intensity of Probe 1-Hg2+ in DMSO, H2O and C2H5OH
158
solutions at 311 nm decreased, but this change was not obvious in CH3CN. The
159
maximum difference between Probe 1 and Probe 1-Hg2+ was about three-fold in
160
C2H5OH and so C2H5OH was selected to be the solvent for Hg2+ detection.
161
The time-dependence of Probe 1 to Hg2+ in C2H5OH was determined by recording
162
the emission peak at 1-min intervals (Fig. 1b). The fluorescence intensity of Probe 1
163
showed little difference after 9 min. After adding Hg2+ (150 and 300 µM), the
164
fluorescence intensity at 311 nm decreased with increasing time until 6 min, after
165
which it remained stable. These results show that detecting Hg2+ only requires 6
166
minutes.
167
The concentration-dependence of Probe 1 (10 µM) to Hg2+ was determined. The
168
peak intensity at 311 nm decreased from 0 to 400 µM (Fig. 2a) with a good linear
169
relationship with the Hg2+ concentration in the range 0–300 µM (y = 1342.9 - 3.0281
170
x; R2 = 0.9951; Fig. 2b). The limit of detection (LOD) for Hg2+ was 1.10 µM, based 7
171
on LOD = 3σ/k.
172
The Hg2+ selectivity of Probe 1 in C2H5OH was investigated. Various competitive
173
species were tested (Mg2+, Na+, Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-,
174
Hcy, SO32-, Cl-, Cys, I-, H2O2, Br-, GSH and F; Fig. 3a). When the competitors were
175
added to solutions of Probe 1, the fluorescence intensity was similar to the Probe 1
176
without a competitor, except for Cu2+, Fe3+ and GSH in which the fluorescence
177
intensity of Probe 1 decreased to varying degrees. The Cu2+, Fe3+ and GSH group
178
have an obvious fluorescence quenching. That may be due to the weak intermolecular
179
interactions, include coordination bonds of metal ions, hydrogen bonds and so on.
180
However, when Hg2+ was added to the abovementioned solutions, the fluorescence
181
intensity of Hg2+ and Hg2++competitors were similar.
182
When H2S and N2H4 were added to the solution of Probe 1, the fluorescence
183
intensity was almost identical to that of Probe 1. The fluorescence intensity of Probe
184
1-Hg2+, Probe 1-H2S +Hg2+ and Probe 1-H2S +N2H4 were similar (Fig. 3b). Therefore,
185
the effect of competing species for the recognition of Hg2+ by Probe 1 can be ignored
186
in C2H5OH.
187
The mechanism of Hg2+ detection by Probe 1 was confirmed by 13C NMR (Fig. S4).
188
After the addition of Hg2+, the peak of the thiocarbonyl group (C=S) at 194.66 ppm
189
disappeared and the carbon peak of compound 1 appeared. Next, mass spectrometry
190
was used (Fig. S5). A peak at m/z 318.25 (M-H) appeared, which is consistent with
191
compound 1. The peak at m/z 232.90 indicates the existence of HgS and implies that
192
Probe 1 could react with Hg2+ to form mercury sulphide and compound 1 (Scheme 2).
193
Probe 1 (Fig. S6) and compound 1 (Fig. S7) were not stable in the buffer solution at
194
different pH values.
195
3.4 Fluorescence properties of Probe 1 in response to N2H4 8
196
The fluorescence response of Probe 1 (10 µM) to N2H4 in DMSO, H2O, C2H5OH
197
and CH3CN solutions at 25oC was investigated (Fig. 4a). After 300 µM N2H4 was
198
added, the fluorescence intensity of Probe 1-N2H4 in DMSO and CH3CN solutions at
199
305 nm increased but this change was not significant in C2H5OH and H2O. The
200
maximum difference between Probe 1 and Probe 1-N2H4 was about three-fold in
201
DMSO and so DMSO was selected to be the solvent for N2H4 detection.
202
The time-dependence of 10 µM Probe 1 in DMSO to N2H4 in Probe 1 was
203
determined (Fig. 4b). The fluorescence intensity of Probe 1 without N2H4 remained
204
similar during the 10-min experiment. After adding 150 µM N2H4, the fluorescence
205
intensity at 305 nm increased with increasing time. The fluorescence intensity stopped
206
increasing after 8 min and remained stable, which shows that N2H4 detection requires
207
only 8 minutes.
208
The concentration-dependence of Probe 1 (10 µM) to N2H4 was investigated. The
209
peak intensity at 305 nm increased from 0 to 120 µM (Fig. 5a) and had a good linear
210
relationship with N2H4 in the range 0–120 µM (y = 4.7748 x + 316.6333; R2 = 0.9951;
211
Fig. 5b). The LOD for N2H4 was 0.11 µM based on LOD = σ/k. When the various
212
levels of N2H4 were added to Probe 1 solution, the colourless solution gradually
213
changed to yellow under natural light (Fig. 5c).
214
The N2H4 selectivity of Probe 1 in DMSO was investigated using various
215
competitive species (Mg2+, Na+, Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-,
216
Hcy, SO32-, Cl-, Cys, I-, H2O2, Br-, GSH and F-; Fig. 6a). When the competitors were
217
added to the solution of Probe 1, the fluorescence intensity was similar to that of
218
Probe 1 alone. When N2H4 was added to the abovementioned solutions, the
219
fluorescence intensities of N2H4 and N2H4+competitors were similar. When H2S or
220
Hg2+ were added to the solution of Probe 1, the fluorescence intensity of Probe 1-Hg2+ 9
221
was almost identical to that of Probe 1 alone and there was an obvious increase in the
222
fluorescence of Probe 1-H2S. When N2H4 was added, the fluorescence intensities of
223
Probe 1-N2H4 and Probe 1-H2S+N2H4 were similar; however, the fluorescent intensity
224
of Probe 1+Hg2++N2H4 was almost identical to that of Probe 1 and Probe 1-Hg2+ (Fig.
225
6b). Therefore, Probe 1 can detect N2H4 in complex samples unless Hg2+ is present.
226
The mechanism of N2H4 detection by Probe 1 was investigated by 1H NMR (Fig.
227
S8). After the addition of N2H4, 1H peaks at 2.94–3.03 ppm were assigned to the
228
C-CH2-C=N group and the peak at 5.07 ppm was assigned to the C-CH-N group.
229
These data indicate that Probe 1 could detect N2H4 through the addition-cyclisation of
230
N2H4 with the α, β-unsaturated ketone (Scheme 2). Compound 5 (Fig. S9) was not
231
stable in the buffer solution at different pH values.
232
3.5 Fluorescence properties of Probe 1 in response to H2S
233
The fluorescence response of Probe 1 (10 µM) to H2S in DMSO, H2O, C2H5OH
234
and CH3CN solutions at 25oC was investigated (Fig. 7a). After 300 µM H2S was
235
added, the fluorescence intensity of Probe 1-H2S in DMSO at 305 nm increased but
236
there was no change in C2H5OH, CH3CN or H2O. The maximum difference between
237
Probe 1 and Probe 1-H2S was about 0.5-fold in DMSO and so DMSO was selected to
238
be the solvent for H2S detection.
239
The time-dependence of Probe 1 to H2S in DMSO was determined (Fig. 7b). After
240
adding 80 µM H2S, the fluorescence intensity at 305 nm increased with increasing
241
time. The fluorescence intensity stopped increasing after 10 min and remained stable,
242
which indicates that only 10 min is required to detect H2S.
243
When various levels of H2S were added, the peak intensity at 305 nm increased
244
from 0 to 120 µM (Fig. 8a) and had a good linear relationship with H2S in the range
245
0–100 µM (y = 1.6601 x + 359.46; R2 = 0.9963; Fig. 8b). The LOD for H2S was 0.96 10
246
µM based on LOD= 3σ/k. When the various levels of H2S were added to the Probe 1
247
solution, the colourless solution gradually changed to purple-red under natural light
248
(Fig. 8c).
249
The H2S selectivity of Probe 1 was investigated. Competitive species (Mg2+, Na+,
250
Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-, Hcy, SO32-, Cl-, Cys, I-, H2O2,
251
Br-, GSH and F-; Fig. 9a) were added to the solution of Probe 1. The fluorescence
252
intensities of Probe 1+competitors were similar to that of Probe 1. When H2S was
253
added to the abovementioned solutions, the fluorescence intensity of H2S and
254
H2S+competitors were similar. When N2H4 and Hg2+ were added to the solution of
255
Probe 1, there was an obvious difference compared to Probe 1-N2H4 and Probe 1-Hg2+
256
(Fig. 9b). Therefore, Probe 1 can detect H2S in complex samples that do not contain
257
N2H4 and Hg2+.
258
The detection mechanism of Probe 1 to H2S was determined by 1H NMR (Fig. S10).
259
After H2S was added, a new peak at 2.46 ppm appeared, which was assigned to the
260
-CH2-C=O of Probe 1-H2S. These data indicate that Probe 1 can recognise H2S by the
261
nucleophilic addition reaction of a carbon-carbon double bond with H2S (Scheme 2).
262
Compound 6 (Fig. S11) was not stable in the buffer solution at different pH values.
263
3.6 Application of Probe 1
264
Probe 1 can be used to detect Hg2+ in complex samples, N2H4 in complex samples
265
without Hg2+, and H2S in complex samples without N2H4 and Hg2+. Seawater, tap
266
water and mineral water were used to determine the detection capability of Probe 1.
267
Water samples (20 µL) were added to 10 µM Probe 1 in C2H5OH for Hg2+ detection
268
and 10 µM Probe 1 in DMSO for N2H4 or H2S detection. Various concentrations of
269
Hg2+ (150, 300 µM), N2H4 (40, 80 µM) or H2S (40, 80 µM) were added. The recovery
270
of Hg2+ ranged from 93.82% to 98.15% (Table 1), N2H4 from 97.35% to 107.50% 11
271
(Table 2), and H2S from 90.28% to 105.58% (Table 3). The results indicated that
272
Probe 1 is suitable for Hg2+, N2H4 and H2S detection in real samples based on different
273
test conditions.
274
In addition, test strips of Probe 1 could be used for Hg2+, N2H4 and H2S detection.
275
The test strips were prepared by the previous method [54]. After various
276
concentrations of Hg2+ were added, the colour of the test strips gradually changed to
277
dark under 254-nm UV light (Fig. 10a). After various concentrations of N2H4 were
278
added, the colour of the test strips gradually changed to yellow under natural light
279
(Fig. 10b). After various concentrations of H2S were added, the colour of the test
280
strips gradually changed to pink under natural light (Fig. 10c). Thus, rapid detection
281
of Hg2+, N2H4 and H2S could be achieved by the colour change of the test paper.
282
4. Conclusions
283
In summary, a multiple-detection-point fluorescent probe (Probe 1) was developed
284
for the detection of Hg2+, N2H4 and H2S. Probe 1 could recognise Hg2+, N2H4 and H2S
285
through different reaction sites, i.e. Hg2+ via a desulphurisation reaction with phenyl
286
thiobenzoate, N2H4 via the addition-cyclisation of N2H4 with the α, β-unsaturated
287
ketone, and H2S via a nucleophilic addition reaction with the carbon-carbon double
288
bond. Probe 1 could be used to detect Hg2+ in complex samples, N2H4 in complex
289
samples without Hg2+, and H2S in complex samples without N2H4 and Hg2+. Deferent
290
concentrations of Hg2+, N2H4 and H2S led to different colour change responses in the
291
test strips of Probe 1. After adding different concentrations of Hg2+, the test paper
292
gradually turns dark, to yellow with N2H4, and to pink with H2S. In summary, rapid
293
detection of Hg2+, N2H4 and H2S was achieved by the colour change of the Probe 1
294
test paper and Probe 1 was used to detect Hg2+, N2H4 and H2S in real samples.
295
Acknowledgements 12
296
Thank you for the National Natural Science Foundation of China (31901770).
297
Appendix A. Supplementary data
298
Supplementary data related to this article can be found at
299
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300
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493 494 495 20
496
Lists of Figures and Tables
497
Scheme 1. Synthesis of Probe 1.
498
Scheme 2. The mechanism for reaction of Probe 1 with Hg2+, N2H4 and H2S.
499
Figure 1. (a) Fluorescence spectra of Probe 1 (10 µM) added to Hg2+ (300 µM) in
500
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
501
fluorescence spectra of Probe 1 (10 µM) in the presence of Hg2+ (150, 300 µM) in
502
C2H5OH at 25°C.
503
Figure 2. (a) Fluorescence spectra of Probe 1 (10 µM) with Hg2+ (0, 50, 100, 150, 200,
504
250, 300, 400 µM). (b) Plot of fluorescence intensity differences with 0–300 µM Hg2+.
505
Tests were performed in triplicate.
506
Figure 3. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of
507
various species (300 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
508
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
509
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 300 µM for Hg2+). Tests were
510
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
511
Hg2+, N2H4, H2S, N2H4+Hg2+ and H2S+Hg2+ (300 µM for each).
512
Figure 4. (a) Fluorescence spectra of Probe 1 (10 µM) added to N2H4 (300 µM) in
513
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
514
fluorescence spectra of Probe 1 (10 µM) in the presence of N2H4 (150 µM) in DMSO
515
at 25°C.
516
Figure 5. (a) Fluorescence spectra of Probe 1 (10 µM) with N2H4 (0, 10, 20, 40, 60,
517
80, 100, 120, 150 µM). (b) Plot of fluorescence intensity differences with 0–120 µM
518
N2H4. Tests were performed in triplicate. (c) Photograph of Probe 1 (10 µM) with
519
N2H4 (0, 1, 10, 20, 40, 60, 80 µM) under natural light.
520
Figure 6. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of 21
521
various species (100 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
522
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
523
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 100 µM for N2H4). Tests were
524
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
525
Hg2+, N2H4, H2S, Hg2++N2H4 and H2S+N2H4 (100 µM for each).
526
Figure 7. (a) Fluorescence spectra of Probe 1 (10 µM) added to H2S (300 µM) in
527
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
528
fluorescence spectra of Probe 1 (10 µM) in the presence of H2S (80 µM) in DMSO.
529
Figure 8. (a) Fluorescence spectra of Probe 1 (10 µM) with H2S (0, 10, 20, 30, 40, 60,
530
80, 100 µM). (b) Plot of fluorescence intensity differences with 0–100 µM H2S.
531
Tests were performed in triplicate. (c) Photograph of Probe 1 (10 µM) with H2S (0, 10,
532
100, 200, 250, 300, 600 µM) under natural light.
533
Figure 9. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of
534
various species (100 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
535
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
536
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 100 µM for H2S). Tests were
537
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
538
Hg2+, N2H4, H2S, Hg2++H2S and N2H4+H2S (100 µM for each).
539
Figure 10. (a) Photograph of the test strips with Hg2+ (0, 1, 10, 100, 300 µM)
540
under UV light at 254 nm. (b) Photograph of the test strips with N2H4 (0, 10, 100, 200,
541
300, 400, 600 µM) under natural light. (c) Photograph of the test strips with H2S (0,
542
10, 100, 200, 300, 400, 600 µM) under natural light.
543
Table 1. Determination of Hg2+ concentrations in real sample
544
Table 2. Determination of N2H4 concentrations in real sample
545
Table 3. Determination of H2S concentrations in real sample 22
546 547
Scheme 1
548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568 569 23
570 571
Scheme 2
572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588
24
589 590
Figure 1.
591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 25
609 610
Figure 2.
611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628
26
629 630
Figure 3.
631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648
27
649 650
Figure 4.
651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 28
670 671
Figure 5.
672 673 674 675 676 677 678 679 680 681 682 683 684 685 686 687 29
688 689
Figure 6.
690 691 692 693 694 695 696 697 698 699 700 701 702 703 704 705 706 707
30
708 709
Figure 7.
710 711 712 713 714 715 716 717 718 719 720 721 722 723 724 725 726 727
31
728 729
Figure 8.
730 731 732 733 734 735 736 737 738 739 740 741 742 743 744 32
745 746
Figure 9.
747 748 749 750 751 752 753 754 755 756 757 758 759 760 761 762 763 764 765 33
766 767
Figure 10.
768 769 770 771 772 773 774 775 776 777 778 779 34
780
Table 1 Sample
Hg2+ level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
150.00
144.28
95.17
0.1675
300.00
294.20
98.07
0.5640
150.00
143.34
0.9070
300.00
294.50
93.82 97.30
150.00
148.82
300.00
281.91
98.15 95.80
0.5273 0.3948 0.2543
781 782 783 784 785 786 787 788 789 790 791 792 793 794 795 796 797 798 799 800 801 802 803 804 35
805
Table 2 Sample
N2H4 level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
40.00
42.02
102.80
0.2860
80.00
87.00
107.50
0.4800
40.00
39.80
0.0500
80.00
83.28
97.35 103.03
40.00
42.23
80.00
84.57
102.48 104.16
0.6840 0.4706 0.5990
806 807 808 809 810 811 812 813 814 815 816 817 818 819 820 821 822 823 824 825 826 827 828 829 830 831 832 833 834 835 836 837 36
838
Table 3 Sample
H2S level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
40.00
38.40
91.67
0.4267
80.00
86.20
105.58
0.7704
40.00
39.22
0.3570
80.00
79.36
95.00 96.40
40.00
37.21
80.00
79.79
90.28 99.61
0.2451 0.0480 0.2129
839 840
37
Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
S0143-7208(19)32102-3
DOI:
https://doi.org/10.1016/j.dyepig.2019.108056
Reference:
DYPI 108056
To appear in:
Dyes and Pigments
Received Date: 4 September 2019 Revised Date:
19 October 2019
Accepted Date: 16 November 2019
Please cite this article as: Wu X, Li Y, Yang S, Tian H, Sun B, A multiple-detection-point fluorescent probe for the rapid detection of mercury(II), hydrazine and hydrogen sulphide, Dyes and Pigments (2019), doi: https://doi.org/10.1016/j.dyepig.2019.108056. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier Ltd.
1
A multiple-detection-point fluorescent probe for the rapid detection
2
of mercury(II), hydrazine and hydrogen sulphide
3
Xiaoming Wu, Yanan Li, Shaoxiang Yang*, Hongyu Tian and Baoguo Sun
4
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing
5
Key laboratory of Flavor Chemistry, Beijing Technology and Business University,
6
Beijing 100048, PR China
7
*
8
[email protected] (S. X. Yang)
Corresponding author. Telephone: +86-10-68985382. E-mail:
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1
26
Graphical abstract
27
A multiple-detection-point fluorescent probe for the rapid detection
28
of mercury(II), hydrazine and hydrogen sulphide
29
Xiaoming Wu, Yanan Li, Shaoxiang Yang*, Hongyu Tian and Baoguo Sun
30
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing
31
Key laboratory of Flavor Chemistry, Beijing Technology and Business University,
32
Beijing 100048, PR China
33
*
34
[email protected] (S. X. Yang)
Corresponding author. Telephone: +86-10-68985382. E-mail:
35 36
A multiple-detection-point fluorescent probe for the rapid detection of mercury(II),
37
hydrazine and hydrogen sulphide
38 39
Highlights
40
1. A multiple-detection-point fluorescent probe (Probe 1) was developed for the
41
detection of Hg2+, N2H4 and H2S.
42
2. Rapid detection of Hg2+, N2H4 and H2S was achieved by a colour change of the test
43
paper of Probe 1.
44
3. The test paper turns to dark with Hg2+, yellow with N2H4, and pink with H2S.
45
4. Probe 1 could be used to detect Hg2+, N2H4 and H2S in real samples.
2
46
Abstract: A multiple-detection-point fluorescent probe (Probe 1) was developed for
47
the rapid detection of mercury(II) (Hg2+), hydrazine (N2H4) and hydrogen sulphide
48
(H2S). Probe 1 could detect Hg2+, N2H4 and H2S through different reaction sites and
49
mechanisms, i.e. Hg2+ via a desulphurisation reaction, N2H4 via addition-cyclisation,
50
and H2S via a nucleophilic addition reaction. N2H4 and H2S had hardly any effect on
51
Hg2+ detection in C2H5OH, but Hg2+ interfered with N2H4 and H2S detection in
52
DMSO, and Hg2+ and N2H4 interfered with H2S detection in DMSO. Rapid detection
53
of Hg2+, N2H4 and H2S was achieved by a colour change in the test paper of Probe 1,
54
which gradually turns dark in response to different concentrations of Hg2+, yellow
55
with N2H4, and pink with H2S. Furthermore, Probe 1 could be used to detect Hg2+,
56
N2H4 and H2S in real samples.
57 58
Keywords: multiple-detection-point; fluorescent probe; rapid detection; test paper
59 60 61 62 63 64 65 66 67 68 69 70 3
71
1. Introduction
72
Mercury(II) (Hg2+) is a heavy metal pollutant in manufacturing processes [1] and is
73
toxic to human and animals, causing nausea, kidney damage, neurotoxicity and
74
abdominal pain [2, 3]. Hg2+ can threaten human health through the food-chain and
75
bioaccumulation [4-6]. A limit for mercury content in food has been established by
76
governments worldwide [7, 8]; in China, the Hg2+ content must be below 0.02 mg/kg
77
in corn and wheat [9].
78
Hydrazine (N2H4) is used as an engine and rocket fuel, as well as a pharmaceutical
79
raw material [10, 11]. However, N2H4 is a highly toxic compound that can be
80
absorbed through the skin leading to damage to the kidneys, lungs and eyes [12, 13].
81
Furthermore, N2H4 is also a carcinogen [14]. N2H4 is very soluble in water and its
82
content in water is strictly limited by most countries. In China, the requirement for
83
drinking water is <0.001 mg/L N2H4 [15].
84
Hydrogen sulphide (H2S) is a colourless, toxic gas and has an odour of bad eggs
85
[16]. If wine contains an excess of H2S, it will have a sulphurous taste, which impacts
86
the quality of the wine [17-19]. Furthermore, an abnormal content of H2S is
87
associated with diseases including ischaemic disease, diabetes, tumours and
88
atherosclerosis [20-22].
89
Hg2+ can be detected by atomic absorption spectrometry [23], ICP-MS [24] and
90
ICP-OES [25] while H2S can be detected by gas chromatography [26], the methylene
91
blue method [17] and colourimetry [18, 19]. N2H4 can be detected by gas
92
chromatography and electrochemical methods [27]. Hg2+, N2H4 and H2S all
93
commonly require detection in, for example, environmental samples. However, as
94
their physical and chemical properties differ, it has been hard to develop a single rapid
95
detection method for the detection of Hg2+, N2H4 and H2S. 4
96
Fluorescent probes are a simple and fast detection tool [28-34]. Recently,
97
fluorescent probes for Hg2+ [35-43], N2H4 [44-48] or H2S [49-57] have been
98
developed based on their unique physical and chemical properties. Some
99
dual-function fluorescent probes have also been developed [58-61] but the rapid
100
detection of Hg2+, N2H4 and H2S by the same fluorescent probe has not yet been
101
reported.
102
A fluorescent probe with multiple detection points is a promising method to detect
103
multiple chemicals. Therefore, here, we develop a multiple-detection-point
104
fluorescent probe (Probe 1) for the detection of Hg2+, N2H4 and H2S. In Probe 1,
105
naphthalene is the fluorophore, phenyl thiobenzoate is the reactive group for Hg2+, a
106
carbon-carbon double bond is the reactive group for H2S and an α, β-unsaturated
107
ketone is the reactive group for N2H4. The rapid detection of Hg2+, N2H4 and H2S was
108
achieved by a colour change of the test paper.
109
2. Materials and methods
110
2.1 General Methods
111
The Cysteine (Cys, 99%), Phenyl thioxochloroformate (98%), Glutathione (GSH,
112
98%), hydrogen peroxide (H2O2, 30%), Homocysteine (Hcy, 99%), hydarazine
113
hydrate (64%), and analytically pure sodium chloride (NaCl), magnesium sulphate
114
(MgSO4), ammonium chloride (NH4Cl), cupric sulfate (CuSO4), ferric chloride
115
(FeCl3), sodium hydrogen sulfite (NaHSO3), sodium fluoride (NaF), sercury sulfate
116
(HgSO4), potassium bromide (KBr), potassium iodide (KI), sodium sulfide (Na2S),
117
calcium chloride (CaCl2), ferrous sulfide (FeS), sodium sulfite (Na2SO3), potassium
118
bromide (KBr), N, N-diisopropylethylamine (DIPEA), sodium chloride (NaCl),
119
dichloromethane (DCM) were bought from Yinuokai Co., Ltd.
120
2.2 Instruments 5
121
Fluorescence spectra was performed at Rili F-4600 fluorescence spectrometer.
122
NMR spectra were performed at a Bruker AV 300 MHz NMR. HRMS was performed
123
at a Bruker Apex IV FTMS.
124
2.3 Preparation of Probe 1
125
Compound 1 (0.20g，0.63 mmol), dichloromethane (10 mL), DIPEA (0.35 mL) and
126
compound 2 (0.14g，8.14 mmol) were stirred together at 25 °C for 8.5 h (Scheme 1).
127
Probe 1 was purified by column chromatography.
128
1
H NMR (300 MHz, DMSO) δ 8.47 (s, 1H), 8.42 (s, 4H), 8.23 (s, 1H), 8.15 (d, J =
129
6.9 Hz, 1H), 8.12 – 8.05 (m, 2H), 8.00 (s, 1H), 7.96 (d, J = 2.3 Hz, 1H), 7.61 (dd, J =
130
8.9, 2.3 Hz, 1H), 7.57 – 7.50 (m, 2H), 7.39 (dd, J = 7.4, 5.4 Hz, 3H). 13C NMR (75
131
MHz, DMSO) δ 194.66, 188.81, 153.65, 152.31, 150.35, 145.69, 142.80, 135.00,
132
133.02, 131.89, 131.59, 131.13, 130.43, 128.96, 127.54, 125.87, 124.38, 122.97,
133
122.68, 122.23, 119.51. HRMS (MALDI): calcd for [M+H]+ 456.090020, found
134
456.089226.
135
2.4 Preparation of samples
136
20 µL sample was used to detect the level of Hg2+, N2H4 and H2S. Different level of
137
Hg2+, N2H4 and H2S was added.
138
2.5 The detection settings of Hg2+, N2H4 and H2S
139
The preparation of test system: 0.02 mL probe solution was dissolved in 0.48 mL
140
H2O, added to the ion solution, then the capacity to 2 mL in cuvette with buffer
141
solution. After mixture, it was mixed to test the spectrum, the fluorescence signal was
142
recorded [62, 63]. Slit widths = 5 nm, 5 nm, λex = 300 nm, λem = 278 nm, temperature
143
= 25 °C, and voltage = 600 V.
144
2.6 Preparation of test strips
145
The test strips were prepared using waterman filter paper (1 cm × 1 cm pieces). 6
146
Dropping a DMSO solution of Probe 1 (10 µM, 10 µL) to filter paper and then baking
147
for 5 minutes in an oven at 70 oC.
148
3. Results and Discussion
149
3.1 Probe synthesis
150
The key intermediate compound 1 was synthesised in our previous work [64].
151
Probe 1 was produced through a nucleophile substitution reaction of compound 1 with
152
compound 2. Probe 1 was purified by column chromatography and characterised by
153
HRMS and NMR (Figs. S1–S3).
154
3.2 Fluorescence properties of Probe 1 in response to Hg2+
155
The fluorescence response of Probe 1 (10 µM) to Hg2+ in DMSO, H2O, C2H5OH
156
and CH3CN solutions at 25oC was investigated (Fig. 1a). After 300 µM Hg2+was
157
added, the fluorescence intensity of Probe 1-Hg2+ in DMSO, H2O and C2H5OH
158
solutions at 311 nm decreased, but this change was not obvious in CH3CN. The
159
maximum difference between Probe 1 and Probe 1-Hg2+ was about three-fold in
160
C2H5OH and so C2H5OH was selected to be the solvent for Hg2+ detection.
161
The time-dependence of Probe 1 to Hg2+ in C2H5OH was determined by recording
162
the emission peak at 1-min intervals (Fig. 1b). The fluorescence intensity of Probe 1
163
showed little difference after 9 min. After adding Hg2+ (150 and 300 µM), the
164
fluorescence intensity at 311 nm decreased with increasing time until 6 min, after
165
which it remained stable. These results show that detecting Hg2+ only requires 6
166
minutes.
167
The concentration-dependence of Probe 1 (10 µM) to Hg2+ was determined. The
168
peak intensity at 311 nm decreased from 0 to 400 µM (Fig. 2a) with a good linear
169
relationship with the Hg2+ concentration in the range 0–300 µM (y = 1342.9 - 3.0281
170
x; R2 = 0.9951; Fig. 2b). The limit of detection (LOD) for Hg2+ was 1.10 µM, based 7
171
on LOD = 3σ/k.
172
The Hg2+ selectivity of Probe 1 in C2H5OH was investigated. Various competitive
173
species were tested (Mg2+, Na+, Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-,
174
Hcy, SO32-, Cl-, Cys, I-, H2O2, Br-, GSH and F; Fig. 3a). When the competitors were
175
added to solutions of Probe 1, the fluorescence intensity was similar to the Probe 1
176
without a competitor, except for Cu2+, Fe3+ and GSH in which the fluorescence
177
intensity of Probe 1 decreased to varying degrees. The Cu2+, Fe3+ and GSH group
178
have an obvious fluorescence quenching. That may be due to the weak intermolecular
179
interactions, include coordination bonds of metal ions, hydrogen bonds and so on.
180
However, when Hg2+ was added to the abovementioned solutions, the fluorescence
181
intensity of Hg2+ and Hg2++competitors were similar.
182
When H2S and N2H4 were added to the solution of Probe 1, the fluorescence
183
intensity was almost identical to that of Probe 1. The fluorescence intensity of Probe
184
1-Hg2+, Probe 1-H2S +Hg2+ and Probe 1-H2S +N2H4 were similar (Fig. 3b). Therefore,
185
the effect of competing species for the recognition of Hg2+ by Probe 1 can be ignored
186
in C2H5OH.
187
The mechanism of Hg2+ detection by Probe 1 was confirmed by 13C NMR (Fig. S4).
188
After the addition of Hg2+, the peak of the thiocarbonyl group (C=S) at 194.66 ppm
189
disappeared and the carbon peak of compound 1 appeared. Next, mass spectrometry
190
was used (Fig. S5). A peak at m/z 318.25 (M-H) appeared, which is consistent with
191
compound 1. The peak at m/z 232.90 indicates the existence of HgS and implies that
192
Probe 1 could react with Hg2+ to form mercury sulphide and compound 1 (Scheme 2).
193
Probe 1 (Fig. S6) and compound 1 (Fig. S7) were not stable in the buffer solution at
194
different pH values.
195
3.4 Fluorescence properties of Probe 1 in response to N2H4 8
196
The fluorescence response of Probe 1 (10 µM) to N2H4 in DMSO, H2O, C2H5OH
197
and CH3CN solutions at 25oC was investigated (Fig. 4a). After 300 µM N2H4 was
198
added, the fluorescence intensity of Probe 1-N2H4 in DMSO and CH3CN solutions at
199
305 nm increased but this change was not significant in C2H5OH and H2O. The
200
maximum difference between Probe 1 and Probe 1-N2H4 was about three-fold in
201
DMSO and so DMSO was selected to be the solvent for N2H4 detection.
202
The time-dependence of 10 µM Probe 1 in DMSO to N2H4 in Probe 1 was
203
determined (Fig. 4b). The fluorescence intensity of Probe 1 without N2H4 remained
204
similar during the 10-min experiment. After adding 150 µM N2H4, the fluorescence
205
intensity at 305 nm increased with increasing time. The fluorescence intensity stopped
206
increasing after 8 min and remained stable, which shows that N2H4 detection requires
207
only 8 minutes.
208
The concentration-dependence of Probe 1 (10 µM) to N2H4 was investigated. The
209
peak intensity at 305 nm increased from 0 to 120 µM (Fig. 5a) and had a good linear
210
relationship with N2H4 in the range 0–120 µM (y = 4.7748 x + 316.6333; R2 = 0.9951;
211
Fig. 5b). The LOD for N2H4 was 0.11 µM based on LOD = σ/k. When the various
212
levels of N2H4 were added to Probe 1 solution, the colourless solution gradually
213
changed to yellow under natural light (Fig. 5c).
214
The N2H4 selectivity of Probe 1 in DMSO was investigated using various
215
competitive species (Mg2+, Na+, Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-,
216
Hcy, SO32-, Cl-, Cys, I-, H2O2, Br-, GSH and F-; Fig. 6a). When the competitors were
217
added to the solution of Probe 1, the fluorescence intensity was similar to that of
218
Probe 1 alone. When N2H4 was added to the abovementioned solutions, the
219
fluorescence intensities of N2H4 and N2H4+competitors were similar. When H2S or
220
Hg2+ were added to the solution of Probe 1, the fluorescence intensity of Probe 1-Hg2+ 9
221
was almost identical to that of Probe 1 alone and there was an obvious increase in the
222
fluorescence of Probe 1-H2S. When N2H4 was added, the fluorescence intensities of
223
Probe 1-N2H4 and Probe 1-H2S+N2H4 were similar; however, the fluorescent intensity
224
of Probe 1+Hg2++N2H4 was almost identical to that of Probe 1 and Probe 1-Hg2+ (Fig.
225
6b). Therefore, Probe 1 can detect N2H4 in complex samples unless Hg2+ is present.
226
The mechanism of N2H4 detection by Probe 1 was investigated by 1H NMR (Fig.
227
S8). After the addition of N2H4, 1H peaks at 2.94–3.03 ppm were assigned to the
228
C-CH2-C=N group and the peak at 5.07 ppm was assigned to the C-CH-N group.
229
These data indicate that Probe 1 could detect N2H4 through the addition-cyclisation of
230
N2H4 with the α, β-unsaturated ketone (Scheme 2). Compound 5 (Fig. S9) was not
231
stable in the buffer solution at different pH values.
232
3.5 Fluorescence properties of Probe 1 in response to H2S
233
The fluorescence response of Probe 1 (10 µM) to H2S in DMSO, H2O, C2H5OH
234
and CH3CN solutions at 25oC was investigated (Fig. 7a). After 300 µM H2S was
235
added, the fluorescence intensity of Probe 1-H2S in DMSO at 305 nm increased but
236
there was no change in C2H5OH, CH3CN or H2O. The maximum difference between
237
Probe 1 and Probe 1-H2S was about 0.5-fold in DMSO and so DMSO was selected to
238
be the solvent for H2S detection.
239
The time-dependence of Probe 1 to H2S in DMSO was determined (Fig. 7b). After
240
adding 80 µM H2S, the fluorescence intensity at 305 nm increased with increasing
241
time. The fluorescence intensity stopped increasing after 10 min and remained stable,
242
which indicates that only 10 min is required to detect H2S.
243
When various levels of H2S were added, the peak intensity at 305 nm increased
244
from 0 to 120 µM (Fig. 8a) and had a good linear relationship with H2S in the range
245
0–100 µM (y = 1.6601 x + 359.46; R2 = 0.9963; Fig. 8b). The LOD for H2S was 0.96 10
246
µM based on LOD= 3σ/k. When the various levels of H2S were added to the Probe 1
247
solution, the colourless solution gradually changed to purple-red under natural light
248
(Fig. 8c).
249
The H2S selectivity of Probe 1 was investigated. Competitive species (Mg2+, Na+,
250
Cu2+, K+, Fe2+, Ca2+, Fe3+, NH4+, HSO3-, NH3, SO42-, Hcy, SO32-, Cl-, Cys, I-, H2O2,
251
Br-, GSH and F-; Fig. 9a) were added to the solution of Probe 1. The fluorescence
252
intensities of Probe 1+competitors were similar to that of Probe 1. When H2S was
253
added to the abovementioned solutions, the fluorescence intensity of H2S and
254
H2S+competitors were similar. When N2H4 and Hg2+ were added to the solution of
255
Probe 1, there was an obvious difference compared to Probe 1-N2H4 and Probe 1-Hg2+
256
(Fig. 9b). Therefore, Probe 1 can detect H2S in complex samples that do not contain
257
N2H4 and Hg2+.
258
The detection mechanism of Probe 1 to H2S was determined by 1H NMR (Fig. S10).
259
After H2S was added, a new peak at 2.46 ppm appeared, which was assigned to the
260
-CH2-C=O of Probe 1-H2S. These data indicate that Probe 1 can recognise H2S by the
261
nucleophilic addition reaction of a carbon-carbon double bond with H2S (Scheme 2).
262
Compound 6 (Fig. S11) was not stable in the buffer solution at different pH values.
263
3.6 Application of Probe 1
264
Probe 1 can be used to detect Hg2+ in complex samples, N2H4 in complex samples
265
without Hg2+, and H2S in complex samples without N2H4 and Hg2+. Seawater, tap
266
water and mineral water were used to determine the detection capability of Probe 1.
267
Water samples (20 µL) were added to 10 µM Probe 1 in C2H5OH for Hg2+ detection
268
and 10 µM Probe 1 in DMSO for N2H4 or H2S detection. Various concentrations of
269
Hg2+ (150, 300 µM), N2H4 (40, 80 µM) or H2S (40, 80 µM) were added. The recovery
270
of Hg2+ ranged from 93.82% to 98.15% (Table 1), N2H4 from 97.35% to 107.50% 11
271
(Table 2), and H2S from 90.28% to 105.58% (Table 3). The results indicated that
272
Probe 1 is suitable for Hg2+, N2H4 and H2S detection in real samples based on different
273
test conditions.
274
In addition, test strips of Probe 1 could be used for Hg2+, N2H4 and H2S detection.
275
The test strips were prepared by the previous method [54]. After various
276
concentrations of Hg2+ were added, the colour of the test strips gradually changed to
277
dark under 254-nm UV light (Fig. 10a). After various concentrations of N2H4 were
278
added, the colour of the test strips gradually changed to yellow under natural light
279
(Fig. 10b). After various concentrations of H2S were added, the colour of the test
280
strips gradually changed to pink under natural light (Fig. 10c). Thus, rapid detection
281
of Hg2+, N2H4 and H2S could be achieved by the colour change of the test paper.
282
4. Conclusions
283
In summary, a multiple-detection-point fluorescent probe (Probe 1) was developed
284
for the detection of Hg2+, N2H4 and H2S. Probe 1 could recognise Hg2+, N2H4 and H2S
285
through different reaction sites, i.e. Hg2+ via a desulphurisation reaction with phenyl
286
thiobenzoate, N2H4 via the addition-cyclisation of N2H4 with the α, β-unsaturated
287
ketone, and H2S via a nucleophilic addition reaction with the carbon-carbon double
288
bond. Probe 1 could be used to detect Hg2+ in complex samples, N2H4 in complex
289
samples without Hg2+, and H2S in complex samples without N2H4 and Hg2+. Deferent
290
concentrations of Hg2+, N2H4 and H2S led to different colour change responses in the
291
test strips of Probe 1. After adding different concentrations of Hg2+, the test paper
292
gradually turns dark, to yellow with N2H4, and to pink with H2S. In summary, rapid
293
detection of Hg2+, N2H4 and H2S was achieved by the colour change of the Probe 1
294
test paper and Probe 1 was used to detect Hg2+, N2H4 and H2S in real samples.
295
Acknowledgements 12
296
Thank you for the National Natural Science Foundation of China (31901770).
297
Appendix A. Supplementary data
298
Supplementary data related to this article can be found at
299
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300
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493 494 495 20
496
Lists of Figures and Tables
497
Scheme 1. Synthesis of Probe 1.
498
Scheme 2. The mechanism for reaction of Probe 1 with Hg2+, N2H4 and H2S.
499
Figure 1. (a) Fluorescence spectra of Probe 1 (10 µM) added to Hg2+ (300 µM) in
500
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
501
fluorescence spectra of Probe 1 (10 µM) in the presence of Hg2+ (150, 300 µM) in
502
C2H5OH at 25°C.
503
Figure 2. (a) Fluorescence spectra of Probe 1 (10 µM) with Hg2+ (0, 50, 100, 150, 200,
504
250, 300, 400 µM). (b) Plot of fluorescence intensity differences with 0–300 µM Hg2+.
505
Tests were performed in triplicate.
506
Figure 3. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of
507
various species (300 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
508
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
509
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 300 µM for Hg2+). Tests were
510
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
511
Hg2+, N2H4, H2S, N2H4+Hg2+ and H2S+Hg2+ (300 µM for each).
512
Figure 4. (a) Fluorescence spectra of Probe 1 (10 µM) added to N2H4 (300 µM) in
513
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
514
fluorescence spectra of Probe 1 (10 µM) in the presence of N2H4 (150 µM) in DMSO
515
at 25°C.
516
Figure 5. (a) Fluorescence spectra of Probe 1 (10 µM) with N2H4 (0, 10, 20, 40, 60,
517
80, 100, 120, 150 µM). (b) Plot of fluorescence intensity differences with 0–120 µM
518
N2H4. Tests were performed in triplicate. (c) Photograph of Probe 1 (10 µM) with
519
N2H4 (0, 1, 10, 20, 40, 60, 80 µM) under natural light.
520
Figure 6. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of 21
521
various species (100 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
522
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
523
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 100 µM for N2H4). Tests were
524
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
525
Hg2+, N2H4, H2S, Hg2++N2H4 and H2S+N2H4 (100 µM for each).
526
Figure 7. (a) Fluorescence spectra of Probe 1 (10 µM) added to H2S (300 µM) in
527
different solvents (CH3CN, DMSO, C2H5OH, H2O) at 25°C. (b) Time-dependent
528
fluorescence spectra of Probe 1 (10 µM) in the presence of H2S (80 µM) in DMSO.
529
Figure 8. (a) Fluorescence spectra of Probe 1 (10 µM) with H2S (0, 10, 20, 30, 40, 60,
530
80, 100 µM). (b) Plot of fluorescence intensity differences with 0–100 µM H2S.
531
Tests were performed in triplicate. (c) Photograph of Probe 1 (10 µM) with H2S (0, 10,
532
100, 200, 250, 300, 600 µM) under natural light.
533
Figure 9. (a) Fluorescence intensity change of Probe 1 (10 µM) upon addition of
534
various species (100 µM for each. 1, blank; 2, Mg2+; 3, Na+; 4, Cu2+; 5, K+; 6, Fe2+; 7,
535
Ca2+; 8, Fe3+; 9, NH4+; 10, HSO3-; 11, SO42-; 12, SO32-; 13, Cl-; 14, Br-; 15, I-; 16,
536
H2O2; 17, Cys; 18, GSH; 19, Hcy; 20, F-; 21, NH3. 100 µM for H2S). Tests were
537
performed in triplicate. (b) Fluorescence spectra of Probe 1 (10 µM) upon addition of
538
Hg2+, N2H4, H2S, Hg2++H2S and N2H4+H2S (100 µM for each).
539
Figure 10. (a) Photograph of the test strips with Hg2+ (0, 1, 10, 100, 300 µM)
540
under UV light at 254 nm. (b) Photograph of the test strips with N2H4 (0, 10, 100, 200,
541
300, 400, 600 µM) under natural light. (c) Photograph of the test strips with H2S (0,
542
10, 100, 200, 300, 400, 600 µM) under natural light.
543
Table 1. Determination of Hg2+ concentrations in real sample
544
Table 2. Determination of N2H4 concentrations in real sample
545
Table 3. Determination of H2S concentrations in real sample 22
546 547
Scheme 1
548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568 569 23
570 571
Scheme 2
572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588
24
589 590
Figure 1.
591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 25
609 610
Figure 2.
611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628
26
629 630
Figure 3.
631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648
27
649 650
Figure 4.
651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 28
670 671
Figure 5.
672 673 674 675 676 677 678 679 680 681 682 683 684 685 686 687 29
688 689
Figure 6.
690 691 692 693 694 695 696 697 698 699 700 701 702 703 704 705 706 707
30
708 709
Figure 7.
710 711 712 713 714 715 716 717 718 719 720 721 722 723 724 725 726 727
31
728 729
Figure 8.
730 731 732 733 734 735 736 737 738 739 740 741 742 743 744 32
745 746
Figure 9.
747 748 749 750 751 752 753 754 755 756 757 758 759 760 761 762 763 764 765 33
766 767
Figure 10.
768 769 770 771 772 773 774 775 776 777 778 779 34
780
Table 1 Sample
Hg2+ level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
150.00
144.28
95.17
0.1675
300.00
294.20
98.07
0.5640
150.00
143.34
0.9070
300.00
294.50
93.82 97.30
150.00
148.82
300.00
281.91
98.15 95.80
0.5273 0.3948 0.2543
781 782 783 784 785 786 787 788 789 790 791 792 793 794 795 796 797 798 799 800 801 802 803 804 35
805
Table 2 Sample
N2H4 level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
40.00
42.02
102.80
0.2860
80.00
87.00
107.50
0.4800
40.00
39.80
0.0500
80.00
83.28
97.35 103.03
40.00
42.23
80.00
84.57
102.48 104.16
0.6840 0.4706 0.5990
806 807 808 809 810 811 812 813 814 815 816 817 818 819 820 821 822 823 824 825 826 827 828 829 830 831 832 833 834 835 836 837 36
838
Table 3 Sample
H2S level found (µmol)
Sea water
0
Tap water Mineral water
0
0
Added
Found
Recovery/
RSD/%
(µmol/L)
(µmol/L)
%
(n=3)
40.00
38.40
91.67
0.4267
80.00
86.20
105.58
0.7704
40.00
39.22
0.3570
80.00
79.36
95.00 96.40
40.00
37.21
80.00
79.79
90.28 99.61
0.2451 0.0480 0.2129
839 840
37
Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: