Sensors and Actuators B 159 (2011) 148153

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Novel pyrazoline-based selective uorescent sensor for Zn2+

in aqueous media
Zhong-Liang Gong, Fei Ge, Bao-Xiang Zhao
Institute of Organic Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, PR China

a r t i c l e

i n f o

Article history:
Received 12 April 2011
Received in revised form 15 June 2011
Accepted 19 June 2011
Available online 24 June 2011
Keywords:
Pyrazoline
Fluorescent sensor
Zinc ion detection
Selective

a b s t r a c t
This work describes the preparation of a novel pyrazoline compound and the properties of its UVvis
absorption and uorescence emission. Moreover, this compound can be used to determine Zn2+ ion with
high selectivity and a low detection limit in the HEPES (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN) buffer
solution. This sensor forms a 1:1 complex with Zn2+ and shows a uorescent enhancement by chelation
enhanced uorescence effect with good tolerance of other metal ions. In addition, this sensor is very
sensitive with uorometric detection limit of 0.12 M.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Transition or heavy metal ion pollution such as Cd2+ , Cr3+ , Cu2+ ,
Hg2+ , Ni2+ , Pb2+ , and Zn2+ poses severe risks for human health and
the environment, due to they tend to accumulate in the food chain
and are usually associated with toxicity. Zinc is one of the most
important metals widely used in electroplating industries and its
toxicity has been found in both acute and chronic forms. In addition, it is well known that zinc ion, the second most abundant
transitionmetal ion in the human body and its highest concentrations occurring in the brain, plays crucial roles in many important
biological processes acting as the structural and catalytic cofactors, neural signal transmitters or modulators, regulators of gene
expression, and apoptosis [14]. Zinc is also known to have a role
in neurological disorders, such as Parkinsons disease, Alzheimers
disease, amyotrophic lateral sclerosis, and epileptic seizures [5,6].
Our increased understanding of the deleterious effects of zinc
exposure has sparked interest in the development of new tools for
detecting Zn2+ in the environment. One major challenge involves
creating Zn2+ sensors that function in water and are highly selective
for Zn2+ against a background of competing analytes. For example,
it is still a challenge to develop chemosensors that can discriminate
Zn2+ from Cd2+ because zinc and cadmium are in the same group of
the periodic table and have similar properties, which usually cause
similar spectral changes after interacting with chemosensors [79].
Therefore, the design and development of a uorescent chemosen-

Corresponding author. Tel.: +86 531 88366425; fax: +86 531 88564464.
E-mail addresses: bxzhao@sdu.edu.cn, sduzhao@hotmail.com (B.-X. Zhao).
0925-4005/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2011.06.064

sor selective to zinc are of considerable interest [10]. Although a

variety of zinc ion selective uorescent probes based on quinoline [1115], uorescein [16,17], coumarin [18,19], indole [20,21],
1,8-naphthalimide [22], thiazole [23], triazole [24,25], xanthene
[26,27], benzoxazole [28], and other uorophores [29,30] have been
developed, chemists still need to design novel ones that are simpler, easier to synthesize, and have better sensitivity, selectivity,
and reliability [31].
1,3,5-Triaryl-2-pyrazolines, with their rigid but only partly
unsaturated central pyrazoline ring, are well-known uorescent
compounds widely used in uorescent dyes emitting blue uorescence with high uorescence quantum yield [32,33] and
electroluminescence elds [3436], However, to the best of our
knowledge, only a few examples have been reported on the
interactions between pyrazoline derivatives and zinc ion [3739]
and most of these systems have their limitations, which include
interference from other metal ions, delayed response to Zn2+ ,
and/or a lack of water solubility. Thus, the development of
chemosensors with high sensitivity and selectivity for detecting
Zn2+ in aqueous media remains a signicant challenge. In our
previous papers, we described synthesis of pyrazoline derivatives [40,41] and application of chemosensor based on pyrazoline
derivative for the detection of Zn2+ [42]. However, it was used
in organic solvent. Hence, in order to detect Zn2+ in aqueous media, we modied the structure of the probe. Herein, we
report the synthesis of 4-chloro-2-(5-phenyl-1-(pyridin-2-yl)-4,5dihydro-1H-pyrazol-3-yl)phenol and the properties of its UVvis
and uorescence. This sensor can be applied in aqueous solution
and will have wider applicable scope than the one reported in our
previous paper [42].

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2. Materials and methods

149

108.5, 60.7, 42.7. HRMS: calcd for [M+H]+ C20 H17 ClN3 O: 350.1060;
found: 350.1052.

2.1. Apparatus
Thin-layer chromatography (TLC) was conducted on silica gel
60 F254 plates (Merck KGaA). 1 H NMR spectra were recorded on a
Bruker Avance 400 (400 MHz) spectrometer, using CDCl3 as solvent
and tetramethylsilane (TMS) as internal standard. Melting points
were determined on an XD-4 digital micro melting point apparatus.
IR spectra were recorded with an IR spectrophotometer VERTEX
70 FT-IR (Bruker Optics). HRMS spectra were recorded on a QTOF6510 spectrograph (Agilent). UVvis spectra were recorded on
a U-4100 (Hitachi). Fluorescent measurements were recorded on a
PerkinElmer LS-55 luminescence spectrophotometer. All pH measurements were made with a Model PHS-3C pH meter (Shanghai,
China) and operated at room temperature about 298 K.
2.2. Reagents
Deionized water was used throughout the experiment. All
the reagents were purchased from commercial suppliers and
used without further purication. The salts used in stock
aqueous solutions of metal ions were CoCl2 6H2 O, ZnCl2 ,
CaCl2 , NaCl, CuCl2 2H2 O, NiCl2 6H2 O, KCl, CdCl2 2H2 O, HgCl2 ,
FeCl3 6H2 O, AgNO3 , Mg(ClO4 )2 . HEPES (4-(2-hydroxyethyl)-1piperazineethanesulfonic acid) buffer solution (pH = 7.2) was
prepared using 20 mM HEPES, and proper amount of aqueous
sodium hydroxide under adjustment by a pH meter.
2.3. Synthesis of 4-chloro-2-(5-phenyl-1-(pyridin-2-yl)-4,5dihydro-1H-pyrazol-3-yl)phenol
3
The synthetic route of the proposed compound 3 is shown in
Scheme 1. Starting materials chalcone (1) and 2-hydrazinylpyridine
(2) were prepared according to literatures [4345]. To a stirred
solution of chalcone (1) (0.258 g, 1.0 mmol) in ethanol (15 mL)
was added 2-hydrazinylpyridine (2) (0.131 g, 1.2 mmol) and NaOH
(0.12 g, 3.0 mmol). The reaction mixture was reuxed for 4 h. The
progress of the reaction was monitored by TLC. After completion,
the reaction mixture was cooled to room temperature and diluted
with chilled water, and then hydrochloric acid was added to neutralize it. The crude product was obtained as yellow precipitates.
The precipitates were ltered, washed with water and ethanol,
and consequently recrystallized from ethanol to afford 3. Yellow
crystal; yield: 36.0%; mp: 172173 C; IR (KBr, cm1 ): 3066.0,
3031.5, 1588.9, 1476.0, 1443.9, 1255.9, 1145.2, 760.4, 692.9; 1 H
NMR (400 MHz, CDCl3 ): 3.28 (dd, 1H, J = 5.6, 17.4 Hz, 4-Htrans ), 3.89
(dd, 1H, J = 12.4, 17.4 Hz, 4-Hcis ), 5.81 (dd, 1H, J = 5.6, 12.4 Hz, 5-H of
pyrazoline), 6.70 (dd, 1H, J = 5.3, 6.7 Hz, pyridine-H), 6.99 (d, 1H,
J = 8.8 Hz, Ar-H), 7.12 (d, 1H, J = 2.5 Hz, Ar-H), 7.22 (dd, 1H, J = 2.5,
8.8 Hz, Ar-H), 7.257.32 (m, 6H, Ar-H + pyridine-H), 7.56 (m, 1H,
pyridine-H), 8.07 (d, 1H, J = 4.2 Hz, pyridine-H), 10.61 (s, 1H, OH);
13 C NMR (100 MHz, CDCl ): 155.8, 154.4, 150.6, 147.9, 142.4, 137.4,
3
130.4, 128.8 (2C), 127.4, 126.9, 125.8 (2C), 124.2, 118.0, 117.5, 115.4,

Scheme 1. Synthesis of compound 3.

2.4. Analytical procedure and Quantum yield

A 5.0 104 M of stock solution of compound 3 was prepared
in CH3 CN. The cationic stocks were all in H2 O with a concentration
of 102 M for UVvis absorption and uorescence spectra analysis. For all measurements of uorescence spectra, excitation was
at 350 nm with 10.0 nm of excitation slit width and scan speed
was set at 800 nm min1 . UVvis and uorescence titration experiments were performed using 5 105 M and 105 M of compound
3 in the HEPES buffer (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN),
respectively. For Zn2+ ion absorption and uorescence titration
experiments, a 3 mL solution of compound 3 (5 105 M) and a
3 mL solution of compound 3 (105 M) were lled in the quartz
cell of 1 cm optical path length, and each time 1.5 L solution of
Zn2+ (102 M) and 1.0 L solution of Zn2+ (3 103 M) were added
into the quartz cell gradually by using a micro-syringe, respectively.
After each addition of Zn2+ ion, the solution was stirred for 3 min.
The volume of cationic stock solution added was less than 100 L
with the purpose of keeping the total volume of testing solution
without obvious change. The ability of the molecules to emit the
absorbed light energy is characterized quantitatively by the uorescence quantum yield (F ). Quantum yields were determined
by the relative comparison procedure, using quinine sulfate dihydrate (99.0%) in 0.1 N H2 SO4 as the main standard. The corrected
emission spectra were measured for the quinine sulfate dihydrate
standard (ex = 380 nm; A (absorption) < 0.01; F = 0.510 [46] and
for compound 3 as well as complex of compound 3 with Zn2+
(ex = 380 nm; A < 0.05). The general equation used in the determination of relative quantum yields from earlier research was given
in Eq. (1) [47].
Fu =

(FS )(FAu )(As )(2u )

(FAs )(Au )(2s )

(1)

where F = uorescence quantum yield; FA = integrated area under

the corrected emission spectrum; A = absorbance at the excitation
wavelength;  = the refractive index of the solution; and the subscripts u and s refer to the unknown and the standard, respectively.
3. Results and discussion
3.1. UVvis studies
The absorption spectrum of compound 3 exhibits a broad band
at 347 nm at room temperature in the HEPES buffer solution
(20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN). Binding afnities of
compound 3 toward metal ions, Ag+ , Mg2+ , Hg2+ , Cd2+ , Co2+ , Cu2+ ,
Ni2+ , Zn2+ and Fe3+ ions were evaluated by UVvis spectroscopy
measurements. Upon addition of these metal ions, the absorption
spectrum changes in different manner as shown in Fig. 1. In the
case of Ag+ or Mg2+ , absorption curve did not change, whereas
in the case of Hg2+ , Fe3+ , Cd2+ , Co2+ , Cu2+ , Ni2+ and Zn2+ ions, the
addition of metal ions caused a decrease of absorption intensity to
some extent at 347 nm, accompanied by an new absorption peak
appeared obviously at the range of 400420 nm.
To investigate the binding property of compound 3 toward
Zn2+ , we measured the UVvis absorption spectra of compound 3
(5 105 M) in the presence of various concentrations of Zn2+ ion
(02 104 M), as shown in Fig. 2. The absorbance of compound
3 at 347 nm gradually decreases with an increasing concentration of Zn2+ ion. Moreover, isobestic point appears at 378 nm and
a new absorption peak appears at the range of 400420 nm, and
its absorption intensity gradually increases with the addition of

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Fig. 1. UVvis spectral changes of compound 3 (5 105 M) in the HEPES buffer

solution (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN) upon additions of various metal
ions (5 105 M).

Zn2+ ion. This absorption peak is likely due to the coordination

of compound 3 with Zn2+ ion. Under comparable experimental
conditions, the UVvis spectrum of Zn2+ displayed no appreciable absorption between 220 and 600 nm within the appropriate
concentration range. According to the above phenomena, we can
observe the transformation from free compound 3 to the Zn2+ coordinated species. In addition, the coordination stoichiometry
between 3 and Zn2+ ion was estimated to be 1:1 by a nonlinear
curve tting of the UVvis titration results (inset) similar to Jobs
plot as depicted in Fig. S1.
3.2. Effect of pH on the uorescence and 1 H NMR spectra studies
The effect of pH (6.38.5) on the uorescence of the sensor 3
with Zn2+ ion was also evaluated. As depicted in Fig. S2, the uorescence intensity slightly increased with increasing pH and reached
its maximum at pH around 7.0 and then uorescence intensity
sharply decreased with continuing to increase pH.
The 1 H NMR spectra of sensor 3 (Fig. S3) indicate that upon coordination to Zn2+ ion in acetonitrile-d3 the protons of the pyridine
slightly shift downeld and the hydroxyl proton shifts upeld. The

Fig. 3. Fluorescence emission spectra of compound 3 (105 M) was titrated with

Zn2+ (05 105 M) in the HEPES buffer solution (20 mM HEPES, pH = 7.2, 50% (v/v)
CH3 CN). Emission slit width was 2.5 nm. Inset: variations of uorescence intensity
of compound 3 (105 M) at 460 nm vs. equivalents of [Zn2+ ] [3] (I and I0 denote
uorescence intensity of compound 3 at 460 nm in the presence and absence of
Zn2+ , respectively).

changes of proton peaks suggested the interaction of nitrogen of

pyridine and oxygen of hydroxyl with Zn2+ ion. We also tried to
obtain more evidence for the interaction position between Zn2+ ion
and sensor 3 by 1 H NMR spectroscopy in the solution of CD3 CN/D2 O
(1/1, v/v), but failed due to the low solubility of sensor 3 in the
solution of CD3 CN/D2 O (1/1, v/v).
3.3. Fluorescence titration studies
The titration of Zn2+ ion was carried out by adding small aliquots
of ZnCl2 stock aqueous solution (102 M) into the solution of 3
(105 M) in the HEPES (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN)
buffer solution. As shown in Fig. 3, the uorescence quantum yield
of compound 3 in the absence of Zn2+ was calculated to be 0.12. As
Zn2+ ion was gradually titrated, the uorescence intensity of compound 3 gradually enhanced, and when the amount of Zn2+ ion
added was about 10 M, the uorescence intensity almost reached
maximum. The quantum yield of 3 was calculated to be 0.53 in
the presence of Zn2+ ion (10 M) and almost enhanced 3.5-fold.
When more ZnCl2 ethanol solution was titrated, the uorescence
intensity showed negligible changes. The nonlinear curve tting
of the uorescence titration (inset) also gives a 1:1 stoichiometric
ratio between compound 3 and Zn2+ similar to UVvis spectra as
shown in Fig. 2 and the association constant (Ka ) between compound 3 and Zn2+ ion in the HEPES buffer (20 mM HEPES, pH = 7.2,
50% (v/v) CH3 CN) was calculated to be 2.87 106 M1 according to
the literature [48].
3.4. Interference from other ions

Fig. 2. UVvis titration of compound 3 (5 105 M) in the HEPES buffer solution (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN) with increasing amount of Zn2+ .
Inset: Absorption changes of compound 3 at 400 nm upon the addition of Zn2+
(02 104 M).

The selectivity and tolerance of compound 3 for zinc ion over

other metal cations such as Co2+ , Cu2+ , Fe3+ , and Ni2+ ions were
investigated by adding metal cations (105 M) to the solution of
compound 3 (105 M). As depicted in Fig. 4, the uorescence of
compound 3 (105 M) was either partially or completely quenched
by Co2+ , Cu2+ , Fe3+ , and Ni2+ ions; whereas it showed enhancement after additions of Ag+ and Zn2+ ions, especially with 10 M
Zn2+ ion, the uorescence quantum yield increased almost 3.5-fold.
This means that sensor 3 has a high selectivity to Zn2+ ion. The
uorescence quenching resulted from the additions of the paramagnetic transitionmetal ions Co2+ , Cu2+ , Fe3+ , and Ni2+ suggests

Z.-L. Gong et al. / Sensors and Actuators B 159 (2011) 148153

151

Fig. 4. Fluorescence intensity changes ((I I0 )/I0 ) of free compound 3 (105 M) at

460 nm in the HEPES buffer solution (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN)
upon additions of various metal ions (105 M). Emission slit width was 3 nm. (I
and I0 denote uorescence intensity of compound 3 in the presence and absence of
Zn2+ , respectively.) Photograph of compound 3 in the HEPES buffer (20 mM HEPES,
pH = 7.2, 50% (v/v) CH3 CN) without (left) and with (right) addition of 10 M Zn2+ ion
under the irradiation of UV light at 365 nm (inset).

Fig. 6. Fluorescence emission spectra of free compound 3 (105 M) in the HEPES

buffer solution (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN) upon additions of various
zinc salts (105 M). Emission slit width was 2.5 nm.

that these ions occupy open shell d-orbitals and provide a very fast
and efcient non-radiative decay of the excited states due to the
electron or energy transfer between the metal ions and compound
3 [23]. Whereas Zn2+ ion, which has close shell d-orbitals, does not
introduce low-energy metal-centered or charge-separated excited
states energy and electron transfer processes cannot take place
[10]; at the same time, the uorescence intensity of compound 3 at
460 nm increased after addition of 10 M Zn2+ ion can be attributed
to chelation enhanced uorescence (CHEF) of compound 3 with
Zn2+ ion. And from the photo shown in Fig. 4 (inset), we can see the
stronger blue emission of compound 3 with addition of 10 M Zn2+
ion under the irradiation at 365 nm than without addition of Zn2+
ion. To further gauge selectivity for zinc ion over other metal ions,
the competition experiments of Zn2+ ion mixed with other metal
ions were carried out and the results were shown in Figs. 5 and
S4. When 10 M Co2+ , Cu2+ or Ni2+ ion was added, respectively,
the uorescence of compound 3 in the presence of Zn2+ ion was
quenched in different degrees, and the uorescence can be completely quenched when 30 M Co2+ , Cu2+ or Ni2+ ion was added.
But Fe3+ ion almost had no inuence on the uorescence even when

30 M Fe3+ ion was added. In addition, the uorescence intensity

of compound 3 with Zn2+ ion in the presence of 30 M Cd2+ ion
was slightly enhanced as shown in Fig. S4. Whereas excess other
transition metal ions Ag+ and Hg2+ ions, alkali metal ions K+ , Na+
ions as well as alkali earth metal ions Mg2+ , Ca2+ ions and even
mixture of them all showed no obvious inuence on the uorescence of compound 3 in the presence of Zn2+ ion. Compound 3
can form complexes with these cations and the complexes possess
different association constants. The difference in association constants results in different interference capacity to the uorescence
selectivity of compound 3 to Zn2+ ion.
Additionally, in order to explore the effects of anionic counterions on the sensing behavior of compound 3 to Zn2+ ion, uorescence
responses of compound 3 to acetate, chloride, and nitrate salts of
zinc were conducted in the HEPES buffer (20 mM HEPES, pH = 7.2,
50% (v/v) CH3 CN). As can be seen from Fig. 6, there were no obvious
changes in the uorescence responses of compound 3 to Zn(AcO)2 ,
ZnCl2 , and Zn(NO3 )2 . To gain further insight into the uorescent signaling behavior of compound 3 toward Zn2+ ion, the effect of EDTA
on the uorescence signaling of the 3Zn2+ system was investigated. When 10 M EDTA was added into the 3Zn2+ system, the
uorescence intensity decreased to the uorescence intensity of
compound 3 without Zn2+ ion as shown in Fig. S5. This may be

Fig. 5. Fluorescence emission spectra of compound 3 (105 M) and 3Zn2+ in the

presence of Ag+ , Fe3+ , Co2+ , Ni2+ , Cu2+ , Cd2+ and Hg2+ (105 M) and Mg2+ , Ca2+ , K+
and Na+ (5 104 M) in the HEPES buffer solution (20 mM HEPES, pH = 7.2, 50% (v/v)
CH3 CN). Emission slit width was 3 nm.

Fig. 7. Fluorescence intensity of compound 3 (105 M) at 460 nm vs. Zn2+ concentrations.

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Z.-L. Gong et al. / Sensors and Actuators B 159 (2011) 148153

attributed to the stronger complexation of Zn2+ ion with EDTA than

with sensor 3.
3.5. Quantitative studies
The quantitative response of compound 3 toward Zn2+ ion was
studied by the uorescence titration and the linear calibration plots
as shown in Fig. 7. The dynamic range for the determination of Zn2+
was determined to be linear up to 07 M with correlation coefcient (R2 ) of 0.973 [49]. The limit of detection (LOD) is evaluated
using 3 bi /m [50], where  bi is the standard deviation of the blank
signals and m is the slope of the linear calibration plot. The LOD for
determination of Zn2+ was thus calculated to be 0.12 M.
4. Conclusions
In summary, a new highly selective uorescent sensor based
on pyrazoline unit was synthesized and used for the determination of Zn2+ ion with high selectivity and a low detection limit
in the HEPES buffer (20 mM HEPES, pH = 7.2, 50% (v/v) CH3 CN).
This sensor formed a 1:1 complex with Zn2+ and showed a uorescent enhancement by CHEF effect with good tolerance of other
metal ions. Moreover, this sensor is very sensitive with uorometric
detection limit of 0.12 M.
Acknowledgements
This study was supported by 973 Program (2010CB933504) and
the National Natural Science Foundation of China (20972088).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.snb.2011.06.064.
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Biographies
Zhong-Liang Gong received his B.Sc. in chemistry from Zao Zhuang University
(Zaozhuang, China) in 2008. At present, he is a M.Sc. student in Institute of Organic
Chemistry, School of Chemistry and Chemical Engineering, Shandong University
(Jinan, China). His current research interest involves the synthesis of the uorescence materials and the application of uorescent sensors.
Fei Ge received his B.Sc. in chemistry from Shandong University (Jinan, China).
At present, he is a M.Sc. student in the Institute of Organic Chemistry, School of
Chemistry and Chemical Engineering, Shandong University (Jinan, China). His current research interest involves the chemosensor and polymer modied magnetic
nanoparticles used for the detection or removal of heavy metal ions and organic
dyes.
Dr. Bao-Xiang Zhao is a professor in organic chemistry at Institute of Organic Chemistry, School of Chemistry and Chemical Engineering, Shandong University (Jinan,
China), since 2000. Currently his research interests include synthesis of uorescent
probe for detecting ions in water and in living cells; preparation of polymer modied magnetic nanoparticles used for the detection and removal of heavy metal ions
and organic dyes; design and synthesis of diversity small molecules for chemical
biology research.