Reaction-based fluorescent probe for selective discrimination of thiophenols over aliphaticthiols and its application in water samples

Article abstract of DOI:10.1021/ac300512b

The development of highly sensitive and selective detection techniques for the discrimination of relevant toxic benzenethiols and biologically active aliphatic thiols is of considerable importance in the fields of chemical, biological, and environmental sciences. In this article, we describe a new design of reaction-based fluorescent probe for discrimination of thiophenols over aliphaticthiols through intramolecular charge transfer pathways using N-butyl-4-amino-1,8-naphthalimide as a fluorophore, the strongly electron-withdrawing 2,4-dinitrobenzenesulfonamide group as a recognition unit, and 2,3-dihydroimidazo-[1,2-a] pyridine moiety as a linker. This rational design not only affords finely tunable spectroscopic properties by adding 2,3-dihydroimidazo-[1,2-a] pyridine moiety but also provides the chance to regulate the selectivity and sensitivity of the probe due to the formation of a new type of potentially reversible sulfonamide bond through 4- dimethylaminopyridine-like resonance. The developed probe displayed high off/on signal ratios, good selectivity, and sensitivity with a detection limit of 20 nM and a relative standard deviation of 1.7% for 11 replicate detections of 0.33 μM thiophenol and was successfully applied to the determination of thiophenols in water samples with quantitative recovery (from 94% to 97%) demonstrating its application prospect for thiophenols sensing in environmental and biological sciences.

Full text of DOI:10.1021/ac300512b

Article
pubs.acs.org/ac
Reaction-Based Fluorescent Probe for Selective Discrimination of
Thiophenols over Aliphaticthiols and Its Application in Water
Samples
Zheng Wang,‡ De-Man Han,*,† Wen-Ping Jia,† Qi-Zhong Zhou,† and Wei-Ping Deng*,‡
†Department of Chemistry, Taizhou University, 605 Dongfang Road, Linhai 317000, China
‡School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
S
* Supporting Information
ABSTRACT: The development of highly sensitive and selective detection
techniques for the discrimination of relevant toxic benzenethiols and biologically
active aliphatic thiols is of considerable importance in the fields of chemical,
biological, and environmental sciences. In this article, we describe a new design of
reaction-based fluorescent probe for discrimination of thiophenols over
aliphaticthiols through intramolecular charge transfer pathways using N-butyl-4-
amino-1,8-naphthalimide as a fluorophore, the strongly electron-withdrawing 2,4-
dinitrobenzenesulfonamide group as a recognition unit, and 2,3-dihydroimidazo-
[1,2-a] pyridine moiety as a linker. This rational design not only affords finely
tunable spectroscopic properties by adding 2,3-dihydroimidazo-[1,2-a] pyridine
moiety but also provides the chance to regulate the selectivity and sensitivity of the probe due to the formation of a new type of
potentially reversible sulfonamide bond through 4-dimethylaminopyridine-like resonance. The developed probe displayed high
off/on signal ratios, good selectivity, and sensitivity with a detection limit of 20 nM and a relative standard deviation of 1.7% for
11 replicate detections of 0.33 μM thiophenol and was successfully applied to the determination of thiophenols in water samples
with quantitative recovery (from 94% to 97%) demonstrating its application prospect for thiophenols sensing in environmental
and biological sciences.
hiols are an important class of molecules in biological
systems and chemical science. Aliphaticthiols are found in
charge transfer (ICT) mechanism in spite of the drawbacks of
its relatively weak fluorescence intensity and low sensitivity.8
Recently, several fluorescent probes with high sensitivity and
selectivity toward thiophenols have been reported.9−12
However, to the best of our knowledge, only one fluorescent
probe has been used for detection of thiophenols in real
environmental and biological samples.10 A brighter and more
selective probe for thiophenols is still highly desirable from a
practical application point of view.
Herein, we report a rational fabrication of a novel type of
highly sensitive and selective fluorescent probe toward
thiophenols through ICT pathways by selecting N-butyl-4-
amino-1,8-naphthalimide as a fluorophore, 2,4-dinitrobenzene-
sulfonamide group as a recognition unit, and 2,3-dihydroimi-
dazo-[1,2-a] pyridine (DHIP) moiety as a linker to extend the
fluorophore and reactive sulfonamide bond. The practicality of
this probe was further demonstrated through the detection of
thiophenols in water samples.
T
several biologically important molecules, including cysteine,
homocysteine, and glutathione,1−3 which are associated with a
wide range of biological functions, whereas thiophenols, as
widely used chemical intermediate for pesticides, pharmaceut-
icals, and amber dyes, are a class of highly toxic and pollutant
compounds with a median lethal dose (LC 50) of 0.01−0.4
mM for fish.4,5 Long-term exposure to thiophenols can cause
severe damage to the central nervous and other nervous
systems including shortness of breath, muscular weakness,
paralysis of the hind limbs, coma, and even death. Therefore, a
number of analytical methods such as high-performance liquid
chromatography- (HPLC) based methods have been reported
for determination of thiols.6a Nevertheless, a simple method
that can selectively differentiate toxic thiophenols over
biologically important aliphaticthiols is still of considerable
significance.
Recently, great efforts have been directed toward the
development of fluorescent probes for thiols.6b However,
these previous fluorescent probes are designed mainly for
discrimination of aliphaticthiols such as cysteine, glutathione,
and homocysteine from other amino acids, and in general they
exhibit poor selectivity for aliphatic thiols over thiophenols.7 A
probe capable of distinguishing aliphatic thiols and thiophenols
had not been realized until Wang et al. developed the first
fluorescent probe for thiophenols based on an intramolecular
EXPERIMENTAL SECTION
Materials and Chemicals. All reagents and solvents were
of the highest available purity and at least of analytical grade. 2-
■
Received: February 21, 2012
Accepted: April 26, 2012
Published: April 26, 2012
© 2012 American Chemical Society
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Scheme 1. Synthesis Route of Probe 1
chloro-4-nitropyridine was purchased from TCI Development
Co. Ltd. (Shanghai, China). Palladium 10% on carbon, 4-
methylthiophenol, thiohydracrylic acid, propylmercaptan, cys-
teine, acetylcysteine, homocysteine, glutathione and histidine
were from Aladdin Reagent Corporation (Shanghai, China).
Pd(OAc)2, 2,2′-bis(diphenylphosphino)-1,1′-binaph-thalene,
tetrabutylammonium fluoride were from Alfa Aesar. Triethyl-
amine was from Sigma-Aldrich. Pd2(dba)3, 2,4-dinitrobenzene-
1-sulfonyl chloride were from J&K Scientific Ltd. (Shanghai,
China). Thiophenol was from Shoufu Chemical Co. (Zhejiang,
China). Milli-Q ultrapure water was used in all experiments.
compound 3 in MeOH was hydrogenated over 10% Pd/C at a
1 bar H2 pressure for 3 h to afford compound 4. Under
nitrogen, the reaction of compound 4 with 6-bromo-2-butyl-
1H-benzo[de]-isoquinoline-1,3(2H)-dione afforded compound
5. Next, 1 M solution of tetrabutylammonium fluoride (TBAF)
in tetrahydrofuran (THF) was dropped to a solution of
compound 5 in THF, the reaction mixture was extracted and
then treated with Et3N followed with methanesulfonyl chloride
(MsCl). The crude product was purified by preparative thin
layer chromatography (silica gel) to give the compound 2 as a
dark red solid.
1
Instrumentation. H nuclear magnetic resonance (NMR)
A solution of compound 2 in anhydrous CHCl3 was added to
2,4-dinitrobenzene-1-sulfonyl chloride under N2. After being
stirred at room temperature overnight, the reaction mixture was
treated with Et2O. The precipitate was collected to afford probe
spectra were recorded on the Bruker AVANCE DPX-400 NMR
Spectrometer (400 MHz) using an internal deuterium lock for
the residual protons in CDCl3 (δH = 7.26) at ambient
temperatures. Data were presented as follows: Chemical shift
(in ppm on the scale relative to δTMS = 0), integration,
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, and
m = multiplet), coupling constant (J/Hz), and interpretation.
13C NMR spectra were recorded on the Bruker AVANCE
DPX-400 NMR Spectrometer (100.6 MHz) by broadband spin
decoupling using an internal deuterium lock for CDCl3 (δ =
77.2) at ambient temperatures. Chemical shift values were
given in ppm on the scale (δTMS = 0). FTIR spectra (4000−400
cm−1) were collected on a Varian Excalibur 3100 FTIR
spectrometer. HRMS (EI) spectra were obtained on a Finigann
MAT8401 instrument. All pH measurements were made with a
Sartorius basic pH meter PB-10. Fluorescence spectra were
determined on a Varian Cary Eclipse Fluorescence Spectropho-
tometer with a 1 cm quartz cell.
Comparative analysis was performed on a FULI 9790 gas
chromatograph equipped with a flame photometric detector
(GC-FPD). A KB-5 (30 m × 0.53 mm ID × 0.50 μm) capillary
column was used for the analysis under the following
conditions: Initial temperature 100 °C for 1 min, then
programmed from 100 to 250 °C at 30 °C/min; injection
and detector temperature were set at 250 and 220 °C,
respectively; nitrogen was used as carrier gas; injections were
carried out in the splitless mode, and the injection volume was
1 μL.
1
1 as a yellow solid. H NMR (400 MHz, CDCl3) for major
isomer: δ 12.79 (s, 1H), 9.16 (s, 1H), 8.64−7.89 (m, 5H), 7.62
(brs, 2H), 7.50−7.02 (m, 6H), 6.92 (brs, 2H), 5.88 (brs, 1H),
4.88 (brs, 1H), 4.51 (brs, 1H), 4.06 (brs, 2H), 1.63 (brs, 2H),
1.39 (brs, 2H), 0.94 (brs, 3H); 13C NMR (100 MHz, CDCl3):
δ 163.4, 163.1, 156.1, 156.0, 150.4, 147.7, 147.2, 146.3, 143.4,
140.2, 139.0, 138.7, 133.9, 133.3, 131.2, 128.9, 128.6, 127.3,
126.7, 126.1, 125.6, 125.4, 122.5, 122.2, 121.1, 120.7, 119.4,
119.0, 118.3, 105.3, 89.1, 64.1, 59.1, 57.3, 52.8, 40.2, 30.0, 20.4,
13.8; HRMS (ESI, m/z): Calcd for C35H26N6O8S+: 693.1762,
found: 693.1763; IR ν 2958, 1701, 1655, 1586, 1540, 1389,
1353, 1237, 788, 754 cm−1.
Measurement Procedures. To a 6 mL calibrated test
tube, phosphate buffer solution (0.01 M, 1 mL, pH 8.0),
aqueous solution of probe 1 (0.2 mM, 0.1 mL), and certain
amounts of thiophenol standard solution (0.2 mM) or other
various testing species (2.0 equiv) were sequentially added at
room temperature. After 20 min, the reaction solution was
diluted to volume with ultrapure water, mixed thoroughly, and
sampled for fluorescence measurements at an excitation
wavelength of 481 nm and an emission wavelength of 590 nm.
Real Samples. Water samples were collected from Linjiang
River and Chemical Factory wastewater near Linhai city,
respectively. The water samples were filtered through 0.2 μm
cellulose acetate membranes (Whatman, UK) prior to use. The
pretreated samples (3 mL) were then subjected to the
determination of the concentrations of thiophenol by using
probe 1.
Synthesis of Probe 1. Probe 1 was prepared in five steps
according to the route shown in Scheme 1. Reaction of 2-
chloro-4-nitropyridine with (S)-2-(tert-butyl-dimethylsilyloxy)-
1-phenylethanamine afforded compound 3. A suspension of
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We hypothesized that the reaction of the nucleophilic
nitrogen of DHIP derivatives with an electron-withdrawing 2,4-
dinitrobenzenesulfonyl chloride would give rise to a non-
fluorescent molecule. In principle, the resulting sulfonamide
can be readily cleaved by nucleophile such as thiophenol under
basic conditions (Scheme 3), and the removal of 2,4-
dinitrobenzenesulfonyl group should recover the highly
fluorescent compound. By taking advantage of the unique
reactivity profile, a new highly selective fluorescent probe 1 for
thiophenols based on an ICT mechanism with improved
features of water solubility and high sensitivity was designed
and synthesized.
Fluorescence Property and Optimal Measurement
Conditions. The fluorescence property of probe 1 was
examined in the absence and presence of a thiol and the
optimal measurement conditions was established. Its water
solubility enables us to perform the investigation in an aqueous
phosphate buffer solution containing probe 1 at room
temperature in the absence and presence of a thiophenol
with different concentrations. After 20 min, the reaction
solution was diluted with ultrapure water (the total
concentration of probe 1 was 3.3 × 10−6 M) for emission
measurement (λex = 481 nm). As expected, probe 1 exhibited
RESULTS AND DISCUSSION
■
Design of the Fluorescent Probe. Conjugation of a well-
established and efficient recognition site with a suitable
signaling moiety is the most popular and rewarding approach,
which has been widely used for the design of selective and
sensitive probes for discrimination between chemically closely
related analysts.11 As a signaling unit, fluorophores generally
have many desirable characteristics in both high sensitivity and
ease of signal transduction. Among many of the fluorophores,
naphthalimide fluorescent dyes have been recognized as the
promising ones for the construction of molecular probes
because of their excellent characteristics, such as intense
fluorescence quantum yields, high photo- and chemo-stability,
and ease of modification.13 However, to our knowledge, no
reports have been published concerning naphthalimide as a
signaling unit for discrimination of thiophenols and aliphatic-
thiols so far. Recently, DHIP has emerged as a core structure of
acylation catalysts for asymmetric kinetic resolution.14 With the
inspiration from Wang’s design8 and high nucleophilic property
of DHIP core (Scheme 2), we envisaged that the incorporation
Scheme 2. Design of a Fluorescent Probe for Thiophenols
almost no fluorescence in the absence of a thiophenol at λem
=
590 nm (Figure 1). When thiophenol (6.6 × 10−6 M, 2.0 equiv)
was added, a dramatic increase in fluorescence intensity (>60
times) was observed. The reaction product was monitored and
confirmed by a comparison study with a standard pure
1
compound 2 through H NMR analysis. The quantum yield
of fluorescence for the product 2 was determined to be 0.36.
Kinetic studies indicate that probe 1 reacted rapidly with
thiophenol in aqueous solution (pH 8.0) at room temperature
(Figure S1 of the Supporting Information). A pronounced
intensity increase was obtained even after 5 min. The reaction
completed after around 15 min. A limited change of
fluorescence intensity was observed when longer reaction
time was examined. Therefore, a reaction time of 20 min was
selected to explore the selectivity of probe 1 toward thiols.
Next, we evaluated the effect of reaction pH on probe 1. As
designed, no fluorescence intensity enhancement of probe 1
of DHIP moiety into fluorophore 1,8-naphthalimide would
generate a new probe not only affording finely tunable
spectroscopic properties by adding DHIP moiety but also
providing the chance to regulate the selectivity and sensitivity
of the probe due to the formation of a new type of potentially
reversible sulfonamide bond through DMAP-like resonance.15
Scheme 3. Reaction Mechanism of the Fluorescent Probe for Thiophenols
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Figure 1. Fluorescence emission spectra of the probe 1 in the absence
and presence of a thiophenol with different concentrations. Probe 1
was studied in a phosphate buffer solution at room temperature in the
absence and presence of a thiophenol with different concentrations.
After 20 min, the reaction solution was diluted with ultrapure water
(the total concentration of probe 1 was 3.3 × 10−6 M) for emission
measurement (λex = 481 nm).
was observed for either thiophenol or aliphatic thiols at pH <6
(Figure S2 of the Supporting Information) as these analytes
exist as less nucleophilic neutral forms. It is expected that a
large increase in fluorescence intensity would be observed at
pH 7.8 to 9.0 as a result of the strong ionization of thiophenol.
However, we found that probe 1 was not stable at high pH
values. The probe 1 itself can generate obvious fluorescent
signals at pH >11.
Figure 2. (A) Fluorescence responses of probe 1 toward thiols and
other substances (2.0 equiv) in a phosphate buffer solution at room
temperature. After 20 min, the reaction solution was diluted and
sampled for fluorescence measurement at λex = 481 nm (the total
concentration of probe 1 was 3.3 × 10−6 M). The fluorescence
intensity at λem = 590 nm was plotted versus substances: (1) 4-methyl
thiophenol, (2) thiophenol, (3) glutathione, (4) cysteine, (5)
homocysteine, (6) acetylcysteine, (7) thiohydracrylic acid, (8)
propylmercaptan, (9) histidine, (10) glucose, (11) vitamin C, (12)
phenol, (13) aniline, (14) alanine, (15) blank. (B) Fluorescence
response of probe 1 toward thiophenol in the presence of other
substances (2.0 equiv): (1) thiophenol, (2) thiophenol + glutathione,
(3) thiophenol + cysteine, (4) thiophenol + homocysteine, (5)
thiophenol + acetylcysteine, (6) thiophenol + thiohydracrylic acid, (7)
thiophenol + glucose, (8) thiophenol + vitamin C, (9) thiophenol +
phenol, (10) thiophenol + aniline, (11) thiophenol + alanine.
Probe 1 was treated with a variety of thiols including
thiophenol, 4-methylthiophenol, thiohydracrylic acid, cysteine,
propylmercaptan, acetylcysteine, homocysteine, glutathione,
and other nucleophile such as histidine to evaluate the
selectivity. As shown in Figure 2, the fluorescence intensity of
probe 1 was highly enhanced by adding thiolphenols, whereas it
did not change noticeably by adding representative aliphatic
thiols, such as propylmercaptan, cysteine, glutathione. This
phenomenon can be explained as follows: In a pH 8.0 reaction
medium, the high degree of dissociation of thiophenols resulted
in the predominant generation of the corresponding thiolate,
which could effectively react with 2,4-dinitrobenzenesulfona-
mide. However, under the same reaction conditions, the
aliphatic thiols remained as a less reactive neutral form and thus
the cleavage of the sulfonamide was very slow. Furthermore,
the nucleophilic capacity of thiophenols is stronger than that of
aliphaticthiols. More significantly, adding the same amount of
any other nucleophiles (such as cysteine, glutathione) to the
thiophenol solution resulted in a similar fluorescence intensity
increase to that of a pure thiophenol, which indicates that probe
1 is particularly selective toward thiophenol without any
obvious interference.
An interference test was carried out to further demonstrate
the selectivity of probe 1. The results show that no significant
change in the fluorescence response of probe 1 toward
thiophenol was observed in the presence of other substances
(2.0 equiv) such as amino acids, sugar, vitamins, aromatic
alcohols and amines, or aliphatic thiols (part B of Figure 2)
indicating no interference from these substances.
The sensitivity of probe 1 was then examined by the
fluorescence response of the probe toward different concen-
trations of thiophenol under the same reaction conditions
described above (Figure 3). The increase in fluorescence
intensity was displayed in a concentration dependent manner.
However, when more than 2 equiv of thiophenol were used, the
enhancement of fluorescence intensity reached a maximum
Figure 3. Enhanced fluorescence intensity of probe 1 versus the
concentration of added thiophenol at λem = 590 nm. The inner panel
displays the fluorescence enhancement of probe 1 toward thiophenol
from 3.3 × 10−8 M to 3.3 × 10−6 M.
without further alteration. Notably, a pronounced change in the
fluorescence signal was observed when the thiophenol
concentration was 3.3 × 10−7 M (0.1 equiv). The detection
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Table 1. Comparison of Fluorescent Probes for Thiophenols
Table 2. Analytical Results for the Determination of Thiophenols in Real Water Samples
sample
the proposed method
GC-FPD method
thiophenol spiked (M) thiophenol determined (mean s, n = 3) (M) thiophenol spiked (M) thiophenol determined (mean s, n = 3) (M)
Linjiang river
0
not detected
0
not detected
3.96 × 10−8
3.96 × 10−7
3.96 × 10−6
0
(3.75 0.08) × 10−8
(3.85 0.06) × 10−7
(3.83 0.05) × 10−6
(5.77 0.12) × 10−8
(9.47 0.12) × 10−8
(4.35 0.07) × 10−7
(3.85 0.06) × 10−6
3.96 × 10−8
3.96 × 10−7
3.96 × 10−6
0
(3.64 0.11) × 10−8
(3.65 0.08) × 10−7
(3.73 0.06) × 10−6
(5.42 0.18) × 10−8
(9.04 0.18) × 10−8
(4.20 0.08) × 10−7
(3.77 0.07) × 10−6
wastewater
3.96 × 10−8
3.96 × 10−7
3.96 × 10−6
3.96 × 10−8
3.96 × 10−7
3.96 × 10−6
limit was estimated to be 2.0 × 10−8 M based on a signal-to-
noise ratio of 3, which was much lower than that of the ICT
probe reported by Wang et al.,8 and a good precision (relative
standard deviation) of 1.7% was obtained for 11 replicate
detections of 3.3 × 10−7 M thiophenol. A summary of the
comparison of recently developed fluorescent probes for
thiophenols is given in Table 1. The probe 1 showed its
excellent analytical performance.
Detection of Thiophenols in Water Samples. To
validate the practicality of this new method, probe 1 was
employed to determine thiophenols concentrations in water
samples from Linjiang River and Chemical Factory wastewater.
The water samples were directly determined first, and then
spiked with thiophenol at different levels of 3.96 × 10−8, 3.96 ×
10−7, and 3.96 × 10−6 M. The recoveries of thiophenol ranged
from 94% to 97%. To validate the proposed method, a GC-
FPD Method was used as a reference method. The analytical
results obtained by the proposed method were in good
agreement with those obtained by the GC-FPD method. The
above results show that the thiophenol in the water samples
could be accurately measured with good recovery, indicating
that probe 1 is effective for quantitative detection of
benzenethiols in water samples.
CONCLUSIONS
■
We have successfully developed a novel, sensitive, and highly
selective fluorescence probe 1 for thiophenols based on the
analyte reactivity profile and reaction conditions through ICT
process. Dramatic fluorescence intensity enhancement in the
presence of thiophenol was observed as a result of effective
nucleophilic cleavage of the electron withdrawing 2,4-
dinitrobenzenesulfonyl moiety from nonfluorescent probe 1
to generate highly fluorescent reagent 2 in an aqueous weakly
basic buffer solution in very short reaction time. Moreover, its
excitation and emission wavelength were 481 and 590 nm
respectively, which would have less background interferences.
These good features of the probe warranted its practical
application for the determination of highly toxic thiophenols in
environmental samples with satisfactory results.
ASSOCIATED CONTENT
■
S
* Supporting Information
Detailed description of the synthesis and additional information
as noted in the text. This material is available free of charge via
the Internet at http://pubs.acs.org.
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Article
(10) Lin, W. Y.; Long, L. L.; Tan, W. Chem. Commun. 2010, 46,
1503−1505.
AUTHOR INFORMATION
■
Corresponding Author
*Fax: (86)576-85137029, e-mail: hdm@tzc.edu.cn.
(11) (a) Zhao, C. C.; Zhou, Y.; Lin, Q. N.; Zhu, L. Y.; Feng, P.;
Zhang, Y. L.; Cao, J. J. Phys. Chem. B 2011, 115, 642−647. (b) Chen,
W. B.; Elfeky, S. A.; Nonne, Y.; Male, L.; Ahmed, K.; Amiable, C.; Axe,
P.; Yamada, S.; James, T. D.; Bull, S. D.; Fossey, J. S. Chem. Commun.
2011, 47, 253−255. (c) Ma, X.; Wang, J.; Shan, Q. L.; Tan, Z. W.;
Wei, G. H.; Wei, D. B.; Du, Y. G. Org. Lett. 2012, 14, 820−823.
(12) Zhao, W.; Liu, W.; Ge, J.; Wu, J.; Zhang, W.; Meng, X.; Wang,
P. J. Mater. Chem. 2011, 21, 13561−13568.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by Natural Science Foundation of
China (21172068, 21172166), and Natural Science Foundation
of Zhejiang Province (Y4090166).
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