Journal Pre-proof A ratiometric fluorescent probe for visualization of thiophenol and its applications
Youming Shen, Lingcong Dai, Youyu Zhang, Xiangyang Zhang, Chunxiang Zhang, Shaoheng Liu, Yucai Tang, Haitao Li PII:
S1386-1425(20)30038-X
DOI:
https://doi.org/10.1016/j.saa.2020.118061
Reference:
SAA 118061
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received date:
22 October 2019
Revised date:
9 January 2020
Accepted date:
10 January 2020
Please cite this article as: Y. Shen, L. Dai, Y. Zhang, et al., A ratiometric fluorescent probe for visualization of thiophenol and its applications, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy(2020), https://doi.org/10.1016/ j.saa.2020.118061
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© 2020 Published by Elsevier.
Journal Pre-proof
A ratiometric fluorescent probe for visualization of thiophenol and its applications Youming Shen, * a,b,c Lingcong Dai, a Youyu Zhang, *b Xiangyang Zhang, a Chunxiang Zhang, *a Shaoheng Liu, a Yucai Tang, a Haitao Li b a
Hunan Province Engineering Research Center of Electroplating Wastewater Reuse Technology,
Hunan Provincial Key Laboratory of Water Treatment Functional Materials,
College of Chemistry
of
and Materials Engineering, Hunan University of Arts and Science, Changde, 415000, PR China
b
ro
E-mail:
[email protected]
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of
Key Laboratory of National Forestry & Grassland Bureau for Plant Fiber Functional Materials,
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c
re
410081, PR China E-mail:
[email protected]
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Education), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha
na
Fujian Agriculture and Forestry University, Fuzhou, 350108, PR China
Abstract
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Thiophenol has a broad application in agriculture and industry. However, thiophenol
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can harm to the environment and health for its high toxicty. Developing an effective method for detection of thiophenol in the field of environmental and biology is valuable. In
this
work,
we
construct
a
reaction-based
ratiometric
fluorescent
probe
(E)-4-(2-(7-(diethylamino)-2-oxo-2H-chromen-3-yl)vinyl)-1-(4-(2,4-dinitrophenoxy)ben zyl)pyridin-1-ium bromide (DCVP-DNP) for probing thiophenol in environment and cells by employing (E)-7-(diethylamino)-3-(2-(pyridin-4-yl)vinyl)-2H-chromen-2-one (DCVP) as the fluorophore and 2,4-dinitrophenyl (DNP) ether as the recognition group for the first time. The probe has high selectivity for thiophenol though
Journal Pre-proof thiophenol-triggered nucleophilic substitution reaction. In additon, the ratio of emission intensities of the probe has linearly with thiophenol concentration in the range of 0-65 μM and the detection limit of thiophenol is as low as 4.8×10-8 M. Moreover, the probe can not only be applied for detection of thiophenol in water samples, but also image thiophenol in living cells, suggesting its potential application in environment and biological system.
Introduction
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1.
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Keywords: Ratiometric; Fluorescent probe; Thiophenol; Bioimaging
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As crucial industrial materials, thiophenol is widely used in organic synthesis including agrochemicals, pharmaceuticals, polymers and pesticides.
[1-3]
However, it is also a class
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of environmental pollutant due to their high toxicity to ecological environment and
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organisms. The experiments results indicated that thiophenols possess the median lethal dose (LC50) for fish (0.01-0.04 mM).
[4]
Besides, long-term contact to thiophenols can
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cause many serious damage to health including shortness of breath, muscle weakness, [5-7]
Therefore,
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headache, burning sensation, increased respiration, laryngitis and nausea.
in view of its undesirable effects, development of the effective method for determining thiophenol in the field of environment and biology is greatly required. Up to now, several ways for the detection of thiophenol have been developed, such as UV-Vis spectroscopy,
[8, 9]
gas chromatographic mass spectrometry
[10]
and high
performance liquid chromatography. [11] Although these methods were satisfactory for the detection of thiophenol in environmental, they are often limited for the analysis of thiophenol in biological system due to complicated operation, costly instrument and
Journal Pre-proof destruction of cell lysates. Compared with the abovementioned methods, fluorescent detection is considered to be a useful tool for monitoring analytes due to its simple pretreatment, convenient visual sensing, high sensitivity and bioimaging analysis. [12-21] Particularly, the colorimetric fluorescent probes for monitoring analytes by naked eyes have received extensive attention due to without any sophisticated and expensive instrumentation.
[22, 23]
However, there is challenging to construct fluorescent probes for
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selectively detection of thiophenols because of similar chemical properties between
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thiophenol and thiols. [24-26] Fortunately, Wang et al reported a selective fluorescent probe
thiophenol
fluorescent
probes
have
been
developed
[27]
Since then,
though
utilizing
re
many
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toward thiophenol base on 2‚4-dinitrobenzenesulfonate recognition unit.
2,4-dinitrobenzenesulfonyl, pyrimidine and dinitrophenyl ethers as recognition group. However, many reported thiophenol fluorescent probes are fluorescence intensity
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[28-37]
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changes in a single-emission window and are interfered by factors such as solvent polarity, probe concentration, instrumental parameters and excitation intensity, which is
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unfavourable for reliable analysis. Ratiometric fluorescent probes are an alternative
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approach for solving this problem by selfcalibration at two emission bands. [38, 39] In order to overcome the limitation of intensity-base probes and improve the precise detection of the probes, many ratiometric fluorescent probes have developed. But unfortunately, very few ratiometric fluorescent probes for detecting thiophenol were synthesized up till now. Meanwhile, some of them were not used for bio-imaging in living cells. one was small emission wavelength shift (41 nm).
[45]
[40-44]
The other
Ratiometric fluorescent probes
with severe overlap in two emission peaks are disadvantageous for accurate ratiometric detection [46] Hence, developing a suitable ratiometric fluorescent probe for quantitative
Journal Pre-proof detection thiophenol with excellent sensitivity and high selectivity in environmental and biological systems is still demanded. Herein,
we
designed
and
synthesized
(E)-4-(2-(7-(diethylamino)-2-oxo-2H-chromen-3-yl)vinyl)-1-(4-(2,4-dinitrophenoxy)ben zyl)pyridin-1-ium bromide (DCVP-DNP) as colorimetric and ratiometric fluorescent probe for detecting thiophenol by the protection-deprotection strategy (scheme 1).
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(E)-7-(diethylamino)-3-(2-(pyridin-4-yl)vinyl)-2H-chromen-2-one (DCVP) was used as
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fluorophore owning to its excellent fluorescence properties such as good photostability, a
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high quantum yield and modulation of fluorescence emission wavelength by change
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electronic features. In probe DCVP-DNP, pyridine salt would cause strong ICT process, resulting in red fluorescence emission. However, the 1,6-elimination of pyridine salt
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mediated by thiophenol-triggered nucleophilic substitution reaction could remove
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pyridine salt to pyridine and thus reduced its ICT process, which would lead to green emission. Notably, the probe DCVP-DNP was found to be a significant color changed
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from red to green with the naked eye after addition of thiophenol, which was a very
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promising colorimetric of sensor for detction thiophenol. Most importantly, probe DCVP-DNP was used for monitoring thiophenol in water samples and in living cells with good satisfactory results. Compared with most reported fluorescent probes (Table S1), probe DCVP-DNP has its advantage for thiophenol. 2. Experimental section 2.1. Apparatus and materials NMR spectra were implemented on a Bruker AVB-500 spectrometer. Fluorescence spectra were measured on a Hitachi F-7000. UV-vis spectra were recorded using a
Journal Pre-proof UV-2600 spectrophotometer. The mass spectra were performed by using a Agilent 6530 Accurate-Mass Q-TOF spectrometer. 4-(Diethylamino)salicylaldehyde, diethyl malonate, 4-picoline, 4-dinitrofluorobenzene were obtained from Sinopharm Chemical Reagent Company. All other reagents were analytical grade, which was purchased from commercial suppliers and directly used. 2.2 Synthesis of probe DCVP-DNP
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DCVP was prepared according to the literature. [47] DCVP (1.2 mmol, 0.3204 g) and
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1-(4-(bromomethyl)phenoxy)-2,4-dinitrobenzene (1.2 mmol, 0.4236 g) were dissolved in
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10 mL CH3CN. After being stirred and refluxed for 12 h, the mixture was filtered to afford DCVP-DNP( 0.4917 g, 72% yield) as a purplish red solid. 1H NMR (500 MHz,
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DMSO-d6) δ(ppm): 9.06 (d, 2H, J = 6.5 Hz), 8.91 (d, 1H, J = 2.5 Hz), 8.47 (dd, 1H, J = 3
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Hz, J = 9.0 Hz), 8.27 (s, 1H), 8.23 (d, 2H, J = 7.0 Hz,), 7.89 (d, 1H, J = 16.0 Hz), 7.74 (d,
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2H, J = 8.5 Hz), 7.70 (d, 1H, J = 16 Hz), 7.56 (d, 1H, J = 9.0 Hz), 7.37 (d, 2H, J = 8.5 Hz), 7.23 (d, 1H, J = 9.0 Hz), 6.81 (d, 1H, J = 9.0 Hz), 6.61 (s, 1H), 5.79 (s, 2H), 3.50 (q, 13
C NMR (125 MHz, DMSO-d6) δ(ppm): 160.1, 156.9, 155.0, 154.7,
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4H), 1.15 (t, 6H);
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154.3, 152.6, 146.1, 144.5, 142.3, 140.2, 138.0, 132.7, 131.8, 131.3, 130.1, 124.2, 123.0, 122.4, 121.1, 120.5, 114.1, 110.6, 108.9, 96.8, 61.7, 44.8, 12.9; HRMS calcd for C33H29BrN4O7 [M-Br]+ 539.6060, found 539.2030.
Scheme 1 Synthesis of DCVP-DNP.
Journal Pre-proof 2.3 Analytical procedure Stock solutions of DCVP-DNP, PhSH, p-CH3-PhSH, p-NH2-PhSH, p-CH3O-PhSH, aniline and phenol (1.0 × 10-3 M) were prepared in DMSO. The other analytes were prepared in double distilled water. The testing solutions consisted of DCVP-DNP (10 μL) stock solutions, proper amounts of PhSH stock solutions and an appropriate volume of DMSO. The solutions were diluted to 2 mL with phosphate buffered saline (containing
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50% DMSO, pH 7.4). The fluoresce were recorded with excitation wavelength of 490
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2.4 Thiophenols detection in water sample
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nm.
As descried previously, [48] the standard addition method was employed to investigate
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the ability of DCVP-DNP to detect thiophenol in water samples. The water samples were
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collected from Yuanjiang River and Tap water and were pretreated through a
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microfiltration membrane before using. Theose water samples were sequentially spiked in thiophenol (0, 8.0, 16.0 and 24.0 μM) and DCVP-DNP (10.0 μM). Each samples were
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2.5 Cell Imaging
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measured three times.
The HepG2 cells were cultrured in 96-well plates in the culture medium and maintained for overnight at 37°C. The cells were initially pretreated DCVP-DNP (10 μM) for 30 min at 37°C and imaged. Then the cells were incubated with thiophenol (65 μM) for another 30 min after washing with PBS and imaged again. The fluorescence imaging were collected using a confocal microscope (Olympus FV1000). 3 Results and discussion 3.1 Sensing properties of DCVP-DNP toward thiophenol To verify the sensing ability of DCVP-DNP, we investigated the optical response of
Journal Pre-proof DCVP-DNP toward thiophenol in 50 mM PBS buffer (containing 50% DMSO, pH 7.4). Fig. 1 shown the UV absorption of DCVP-DNP solution could be observed at 505 nm without addition of thiophenol. However, upon additon of thiophenol, the absorption spectrum of DCVP-DNP solution displayed a blue-shifted to 450 nm. Meanwhile, the color of DCVP-DNP solution changed from red to green, which could be due to DCVP-DNP reacting with thiophenol, indicating that DCVP-DNP was indicator for
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visual detection of thiophenol. The fluorescence spectrum of DCVP-DNP to thiolphenol
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was then studied. Fig. 2 shown the free DCVP-DNP exhibited an intense fluorescence
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emission at 645 nm owning to the strong ICT process arising from the pyridine salt. In
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the presence of thiophenol, the fluorescence emission band dispeared at 645 nm and a blue-shifted fluorescence emission band at 542 nm appeared, and was accompanied by
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the emssion of DCVP-DNP solution change from red to green. Due to the emssion
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colour change, DCVP-DNP could serve as a ratiometric detector for thiophenol. When the concentration of thiophenol enhanced, the fluorescence emission intensity of
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DCVP-DNP solution at 645 nm graddually decreased concurrent with increase of
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fluorescence intensity at 542 nm. The ratio of emission intensities (I645/I542) of DCVP-DNP solution reached a maximum value where a 125 folds enhancement upon treament with 6.5 equiv of thiophenol. The ratio of emission intensities displayed prominent linearity with the concentrations of thiophenol (0-65 μM) and a low detection limit (4.8×10-8 M), which suggested that DCVP-DNP is suitable for sensing the thiophenol in environmental and biological samples.
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Fig. 1 The absorption spectrum of DCVP-DNP with (a) and without (b) PhSH in 50 mM
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PBS buffer (containing 50% DMSO, pH 7.4). Inset: photographs of DCVP-DNP with
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and without PhSH.
Fig. 2 (a) Fluorescence emission spectra of DCVP-DNP (10 μM) uopn addition of different PhSH (0, 0.5, 1.0, 1.5, 2.5, 3.5, 4.5, 5.5, 6.5, 7.5 μM) in 50 mM PBS buffer (containing 50% DMSO, pH 7.4). (b) The linear correlation of ratio of emission intensities (I645/I542) and the PhSH concentration. λex = 490 nm. 3.2 Selectivity To view the selectivity of DCVP-DNP for thiophenol, we investigated the fluorescence response of DCVP-DNP in the presence of some potentially competing
Journal Pre-proof species, including thiophenols (PhSH, p-CH3-PhSH, p-NH2-PhSH, p-CH3O-PhSH), Cys, GSH, Hcy, Gly, aniline, phenol, NaHS, NaN3, NaHSO3, KI, NaBr, NaNO2, KSCN, H2O2 and NaClO. As shown in Fig. 3, the ratio of emission intensities (I645/I542) of DCVP-DNP showed an obvious enhancement upon addition of thiophenol, whereas other analytes did not trigger a significant ratio of emission intensities (I645/I542) change, which was due to relatively low local softness (Ssulfur-) value of thiophenols.
[49]
These experimental
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of
results suggested that DCVP-DNP was excellent selectivity for thiophenol.
Fig. 3 The selectivity of DCVP-DNP (10 μM) towards PhSH over other analytes in 50
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mM PBS buffer (containing 50% DMSO, pH 7.4). (1) Bank, (2) PhSH, (3) p-CH3-PhSH, (4) p-NH2-PhSH, (5) p-CH3O-PhSH, (6) Cys, (7) GSH, (8) Hcy, (9) Gly, (10) aniline, (11) phenol, (12) NaHS, (13) NaN3, (14) NaHSO3, (15) KI, (16) NaBr, (17) NaNO2, (18) KSCN, (19) H2O2, (20) NaClO. λex = 490 nm. 3.3 Reaction time In order to explore the fluorescence changes of DCVP-DNP for detection of thiophenol, the time-dependent ratio of emission intensities (I645/I542) was studied. As depicted in Fig. 4, The DCVP-DNP had negligible effect on the ratio of emission
Journal Pre-proof intensities (I645/I542) without thiophenol. Hovever, with addition of thiophenol, the ratio of emission intensities (I645/I542) of DCVP-DNP increased gradually to a plateau about 7 min. Those results indicated that DCVP-DNP for detection of thiophenol is rapid and can
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be used as a real-time detector for thiophenol.
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Fig. 4 The ratio of emission intensities (I645/I542) changes with different incubation time
λex = 490 nm.
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3.4 Response of pH
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with (a) and without (b) PhSH in 50 mM PBS buffer (containing 50% DMSO, pH 7.4).
pH is vival impact for reaction indicator due to its effection on the proceeding of chemical reaction. Thus, we studied the fluorescence response of DCVP-DNP along with various pH before/after thiophenol. As shown in Fig. 5, there was almost invariant in the ratio of emission intensities (I645/I542) of DCVP-DNP toward pH range from 1.0 to 12.0 in the absence of thiophenol, which indicated that DCVP-DNP was hardly affected by pH. However, between pH 5.0 and 12.0, the ratio of emission intensities had a remarkable change in presce of thiophenol, maintained a relative high plateau at pH over 7.0, which could be attributed to the strong ionization of thiophenol at pH greater than 6.5.
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Theose results implied that DCVP-DNP could monitor thiophenol over a wide pH range.
Fig. 5 The the ratio of emission intensities (I645/I542) changes in various pH with (a) and
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3.5 Recognition Mechanism
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without (b) PhSH. λex = 490 nm.
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To verify the sensing mechanism of DCVP-DNP for thiophenol, the sensing reaction product of DCVP-DNP and thiophenol was separated and recorded by 1H NMR
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spectroscopy. In the 1H NMR spectra, DCVP-DNP itself displayed at the peak 5.79 ppm
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corresponds to the methylene proton signal between pyridimium salt and phenyl goup (Figure S1). Nevertheless, the signal of the methylene of DCVP-DNP at 5.79 ppm disappeared in prescent of thiophenol (Figure S4), in a good agreement with that of DCVP. In addition, thiophenol-triggered the cleavage product was confirmed by HRMS spectrum. After treatment with thiophenol, a peak at 321.1592 m/z appeared in the HRMS spectrum (Figure S5), which was attributed to DCVP (calcd. C20H20N2O2 [M+H]+, 321.1525). Based on these evidences, the proposed sensing mechanism DCVP-DNP with thiophenol was as shown in Scheme 2.
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Scheme 2 The possible mechanism DCVP-DNP for detection of thiophenol.
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3.6 Application of DCVP-DNP in water samples
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To interrogate the ability of DCVP-DNP for the practical application, we measured
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thiophenol in Yuanjiang river water and Tap water samples by a standard addition
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method to validate its practical utility in environmental science. The results were showed in Table 1. It was seen that there were good recoveries (97.6%-103.0%) in both
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Yuanjiang river water and tap water samples, which suggested that the proposed method
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could be applied for determination of thiophenol in water samples. Table 1 Determination of PhSH in water samples
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Sample
Yuangjiang river
Tap water
3.7 Cellular imaging
Spiked (μM)
Recovered (μM)
Recovery (%)
0
Not detected
--
8
7.81±0.11
97.6
16
15.76±0.06
98.5
24
24.17±0.03
100.7
0
Not detected
--
8
8.24±0.07
103.0
16
16.35±0.06
102.1
24
23.83±0.14
99.2
Journal Pre-proof In order to inquire into the application of DCVP-DNP, the fluorescence imaging thiophenol by DCVP-DNP was studied in living cells. The cytotoxicity tests of HepG2 cells were investigated by an MTT assay (Fig. S6). The results indicated that the DCVP-DNP had little cytotoxicity to cells in our experiment. As displayed in Fig. 6, HepG2 cells pretreated with DCVP-DNP (10 μM) alone displayed a red fluorescence. However, when the above cells were further pretreated with thiophenol, remarkable green
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fluorescence could be observed. These results demonstrated that DCVP-DNP was
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cell-permeable and was able to monitor intracellular thiophenol in living cells.
Fig. 6. Imaging of DCVP-DNP with incubated PhSH in HeLa cells. Bright-field (A), fluorescence image of the cells at the green channel (scan range of 500-570 nm) with excitation at 488 nm (B) and at the red channel
(scan range of 600-700 nm) with
excitation at 546 nm (C) after stained with 10 μM DCVP-DNP for 30 min. Bright-field (D), fluorescence image of the cells at the green channel (E) and at the red channel (F) incubated with DCVP-DNP for 30 min and then pretreated PhSH for another 30 min. 4 Conclusion
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We have successfully developed a novel colorimetric and ratiometric probe for thiophenol recognition via thiophenol-triggered cleaving reaction based on ICT process. The probe exhibited highly selective and sensitive toward thiophenol with ratiometric fluorescence signal and distinct color changes. Moreover, the probe had low cytotoxicity so that it could be applied to imaging thiophenol in living cells. Not only that, the probe
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also could be used for thiophenol detection in water samples. Taken together, this work provides potential method for detecting thiophenol in environmental and biological
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systems.
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Acknowledgment
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We thank Key Laboratory of National Forestry & Grassland Bureau for Plant Fiber
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Functional Materials, Fujian Agriculture and Forestry University (No. 2019KFJJ14), the National Natural Science Foundation of China (51909090, 21675051), Scientific
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Research Fund of Hunan Provincial Education Department (17B181) and the Natural
References
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support.
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Science Foundation of Hunan Provincial (2017JJ2195, 2019JJ50409) for financial
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Journal Pre-proof Author contributions section Author Contributions: Youyu Zhang and conceived the idea; Lingcong Dai Xiangyang Zhang and Chunxiang Zhang analysed the data; Lingcong Dai provided the data; Shaoheng Liu, Yucai Tang and Haitao Li interpreted the results; Youming Shen wrote the paper; all
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authors discussed the results and revised the manuscript.
Journal Pre-proof Declaration of interest statement: The authors declare that we do not have any commercial or associative interest that
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represents a conflict of interest in connection with the work submitted.
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Graphical abstract
Journal Pre-proof Highlights a) A coumarin fluorescent probe for detection of thiophenol was synthesized. b) The probe exhibited ratiometric emission and a large pseudo-Stokes shift with a low detection limit. c) The probe has been successfully used for thiophenol detection in real water samples
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and in living cells.