Synthesis of a new pyrene-devived fluorescent probe for the detection of Zn2+

Article abstract of DOI:10.1016/j.tetlet.2018.09.038

A novel pyrene-based receptor bearing benzothiazole was synthesized as a good turn-on fluorescent sensor for the recognition of Zn²⁺. The probe showed an excellent selectivity for Zn²⁺over most other competing ions (eg, Cr³⁺, Li⁺, Cd²⁺, Al³⁺, Pb²⁺, Li⁺, Mg²⁺, Ag⁺, Ca²⁺, Ni²⁺, Mn²⁺, Fe³⁺, Hg²⁺, Ba²⁺, K⁺, Na⁺, Cu²⁺, Fe²⁺) in EtOH-HEPES (65:35, v/v, pH = 7.20), which might be attributed to the photoinduced electron transfer (PET) mechanism. The formation of 1:1 stoichiometric PBZ-Zn²⁺ complex was determined based on the Job's plot, ¹H NMR titration and ESI-MS. The binding constant of the complex was 4.04 × 10⁴ M^?1 with a detection limit of 2.58 × 10^?7 M. The potential application of the PBZ in real water samples for recognizing Zn²⁺ was investigated. Bio-imaging study also revealed that PBZ could be applied to detecting Zn²⁺ in live cells. These results indicated that PBZ could be a favorable probe for Zn²⁺.

Full text of DOI:10.1016/j.tetlet.2018.09.038

Accepted Manuscript
Synthesis of a new pyrene-devived fluorescent probe for the detection of Zn2+
Yanfeng Tang, Yang Huang, Linxia Lu, Chun Wang, Tongming Sun, Jinli Zhu,
Guohua Zhu, Jinyang Pan, Yingli Jin, Ailin Liu, Miao Wang
PII:
S0040-4039(18)31128-6
https://doi.org/10.1016/j.tetlet.2018.09.038
TETL 50277
DOI:
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
24 July 2018
4 September 2018
14 September 2018
Please cite this article as: Tang, Y., Huang, Y., Lu, L., Wang, C., Sun, T., Zhu, J., Zhu, G., Pan, J., Jin, Y., Liu, A.,
2
+
Wang, M., Synthesis of a new pyrene-devived fluorescent probe for the detection of Zn , Tetrahedron Letters
2018), doi: https://doi.org/10.1016/j.tetlet.2018.09.038
(
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Synthesis of a new pyrene-devived fluorescent probe for the detection of Zn2+
a
b
b
b
a
a
Yanfeng Tang , Yang Huang , Linxia Lu , Chun Wang , Tongming Sun , Jinli Zhu , Guohua
a,*
a
a
a
a,
Zhu , Jinyang Pan , Yingli Jin , Ailin Liu and Miao Wang
a. School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, P.R.
China
b. School of Textiles, Nantong University, Nantong 226019, P.R. China
Abstract: A novel pyrene-based receptor bearing benzothiazole was synthesized as a
2
+
good turn-on fluorescent sensor for the recognition of Zn . The probe showed an
2
+
3+
+
2+
3+
excellent selectivity for Zn over most other competing ions (eg, Cr , Li , Cd , Al ,
2
+
+
2+
+
2+
2+
2+
3+
2+
2+
+
+
2+
2+
Pb , Li , Mg , Ag , Ca , Ni , Mn , Fe , Hg , Ba , K , Na , Cu , Fe ) in
EtOH-HEPES (65:35, v/v, pH=7.20), which might be attributed to the photoinduced
electron transfer (PET) mechanism. The formation of 1:1 stoichiometric PBZ-Zn2+
1
complex was determined based on the Job's plot, H NMR titration and ESI-MS. The
4
-1
-7
binding constant of the complex was 4.04×10 M with a detection limit of 2.58×10
M. The potential application of the PBZ in real water samples for recognizing Zn2+
was investigated. Bio-imaging study also revealed that PBZ could be applied to
detecting Zn2+ in live cells. These results indicated that PBZ could be a favorable
2
+
probe for Zn .
2
+
Keywords: Zn detection, pyrene, turn-on fluorescence, live cells
Introduction
Zinc ion, as the second abundant metal ion in the human body after Iron, plays
crucial roles in many biological processes including gene expression, cell growth, cell
division, cellular metabolism, DNA replication and repair [1-4]. Both the deficiency
Corresponding author
1

2
+
and excess of Zn can cause many diseases such as Alzheimer, an increasing
incidence of many types of cancers, epilepsy, ischemic stroke and infantile diarrhea
[
5-9]. Therefore, in order to keep human health, it is of great importance to develop
2
+
the efficient methods for recognizing Zn in drinking water and live cells.
Up till now, many kinds of methods have been applied successfully to detect
2
+
Zn , including atomic absorption spectrometry [10], atomic emission spectrometry
11], inductive coupled plasma-mass microprobe [12], electrochemical methods [13]
[
and fluorescent chemosensors [14]. Along with these various methods, fluorescent
chemosensors have been paid enormous attention to monitor Zn2+ owing to their
excellent selectivity, high sensitivity, quick-response and low cost [15-16]. In the past
few years, numerous fluorescent probes have been reported based on quinolone
[
17-18], coumarin [19-20], BODIPY [21-22] and pyrene fluorescent dyes [23-26].
2
+
They exhibited good performances for the detection of Zn . However, many of them
have complicated synthesis process. And yet, it is relatively challenging to design
fluorescence probes that can discriminate between Cd2+ and Zn because of their
similar electron configurations [27-31]. Thus, it is of great interest to develop a highly
2+
2
+
sensitive fluorescence chemosensors based on pyrene for detecting Zn without the
2
+
interference of Cd .
In this paper, a new turn-on fluorescent sensor (abbreviated as PBZ)based on
pyrene,
synthesized
from
2-hydroxypyreneformaldehyde
and
2
-hydrazinobenzothiazole shown in Scheme 1, exhibited excellent selectivity towards
2
+
environmentally and biologically toxic Zn in EtOH-HEPES (65:35, v/v, pH=7.20)
2
+
with no disturbance from Cd as we expected.
O
O
Br
O
O
OH
a
b
c
S
HN
N
N
e
1
2
3
OH
N
S
NH2
NH
N
S
d
NH2
4
PBZ
2

o
Scheme1. Synthesis of PBZ. a) Na, CuI, MeOH, reflux, 36 h; b) n-butyllithium, 0 C;
3
tetramethylethylenediamine, 4h; DMF, 22 h; c) AlCl , DCM, 6 h, room temperature; d) hydrazine
o
hydrate, ethylene glycol, concentrated sulfuric acid,140 C; e) EtOH, reflux.
Results and Discussion
The fluorescence responses of the PBZ were carried out at 386 nm excitation
2
+
3+
+
2+
3+
2+
+
2+
+
2+
upon the addition of 10 equiv of Zn , Cr , Li , Cd , Al , Pb , Li , Mg , Ag , Ca ,
2
+
2+
3+
2+
2+
+
+
2+
2+
Ni , Mn , Fe , Hg , Ba , K , Na , Cu , Fe in EtOH-HEPES (65:35, v/v, pH =
.20) to investigated the selectivity of PBZ. As shown in Fig.1, the free receptor PBZ
7
showed a weak fluorescence emission at 526 nm with a low fluorescence quantum
yield (Φ= 0.0103). Upon the addition of various metal ions, only the addition of Zn2+
brought a significant fluorescence enhancement at 526 nm and the fluorescence
quantum yield increased to 0.0515, which could be explained by the photoinduced
electron transfer (PET) and -C=N isomerization shown in Scheme 2 [32-33]. Before
complexation with Zn2+ pair electrons of N atom in PBZ can transfer between
excited and ground states under UV light. No obvious fluorescence was observed.
After complexed with Zn2+, PET was inhibited, so the fluorescence emission was
turned on. And fortunately, the probe PBZ was used to detect Zn2+ without the
2
+
2+
interference of Cd , which is possible that the rigid coplanar structure in Zn -PBZ
can inhibit PET and -C=N isomerization, and reduce the probability of non-radiative
transition and obviously increase the probability of radiation transition, leading to
large fluorescence enhancement. However, the pyrene ring and the benzothiazole ring
2
+
of the Schiff base parts in Cd -PBZ becomes non-coplanar and unstable, which may
cause weak fluorescence intensity. In addition, the photograph of PBZ under
hand-held UV lamp with different metal ions also indicated that it has high selectivity
2
+
towards Zn via yellow emission (Fig.2). The competitive experiment was designed
2
+
to further study the specificity of PBZ for recognizing Zn in a complex background
of other competing metal ions. As shown in Fig 3, the fluorescence intensities of the
2
+
PBZ-Zn solution did not appear to have any significant changes after addition of
2
+
2+
other metal ions except in the presence of Cu . The fluorescence of the PBZ-Zn
3

2
+
was completely quenched by Cu because of its paramagnetic property [34], causing
the electron or charge transfers from photoinduced metal to pyrene fluorophore. These
results also indicated that PBZ could be used to detect Zn2+ in the co-existence of
most metal ions.
5000
4500
4000
3500
3000
2500
2000
1500
1000
2+
Zn
3
+
+
2+
3+
2+
2+
PBZ, Cr , Li , Cd , Al , Pb ,Co ,
2
+
+
2+
2+
2+
3+
2+
Mg , Ag , Ca , Ni , Mn , Fe , Hg ,
2
+
+
+
2+
2+
Ba , K , Na , Cu and Fe .
500
0
4
50
500
550
600
650
700
Wavelength(nm)
Fig.1. The fluorescence spectra of PBZ (10 μM) in the presence of various metal ions (100 μM) in
EtOH-HEPES buffer (65:35,v/v, pH = 7.20) at 526 nm, λex= 386 nm.
Fig.2.A photograph of fluorescence change of PBZ（10 μM）under hand-held UV lamp with
various metal ions in EtOH-HEPES buffer(65:35, v/v, pH = 7.20), where [metal ions]= 100 μM.
4

S
S
N
HN
N
N
HN
N
T
Zn2+
E
T
P
Zn2+
E
P
OH
O
Scheme 2.Proposed binding mechanism between PBZ and Zn2+
n+
2+
PBZ + M + Zn
6000
5000
4000
3000
2000
1000
0
n+
PBZ + M
Fig.3. Fluorescence intensities of PBZ(10 μM) at 458 nm upon addition of various metal ions
3+
+
2+
3+
2+
+
2+
+
2+
2+
2+
3+
2+
2+
+
(
100 μM) ( Cr , Li , Cd , Al , Pb , Li , Mg , Ag , Ca , Ni , Mn , Fe , Hg , Ba , K ,
+
2+
2+
Na , Cu , Fe ) in EtOH-HEPES buffer (65:35, v/v, pH = 7.20) (black bars). Red bars represent
2
+
the intensities after the subsequent addition of Zn (10 μM), at λex= 386 nm.
To study the detecting properties of PBZ, the fluorescence titration was performed
2
+
with varying concentration of Zn （Fig.4A). A good linear relationship between the
fluorescence intensity of PBZ and the amount of Zn2+ was maintained in the
concentration range 0-20 μM（Fig.4B), indicating that PBZ could be used to detect
2
+
-7
Zn quantitatively. The detection limit was found to be 2.58×10 M according to the
following equation [35]: detection limit =3σ/κ, where σ is the standard deviation of
blank measurements, and κ is the slope between the fluorescence intensity versus
5

sample concentration (Fig.4C). The detection limit was low enough to recognize a
2
+
submicromolar concentration of Zn . In addition, the association constant was
4
-1
calculated to be 4.04×10 M by the Benesi-Hildebrand analysis of the titration
profiles based on a 1:1 binding model confirmed by Job's plot study（Fig.4D, Fig.5).
3
3
2
2
1
1
500
000
500
000
500
000
3500
3000
2500
2000
1500
1000
500
0
A
B
3
.8 eq
2+
Zn
0 eq
5
00
0
4
50
500
550
600
650
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
2
+
-5
Wavelength(nm)
[Zn ] 10 M
30
25
20
15
10
5
0
D
3
2
2
1
1
000
500
000
500
000
C
y = 2.10607 + 52.1718 x
y = 364.63 + 1109.9 x
2
2
R = 0.997
5
00
R = 0.987
00
.0
0.5
1.0
1.5
2.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
2
+
-5
2+
6
-1
[
Zn ] 10
M
1/[Zn ] (10 M )
Fig.4. (A) Fluorescence emission changes of PBZ (10 μM) in EtOH-HEPES buffer (65:35, v/v,
2+
pH = 7.20) upon the addition of different amount of Zn (0-38 μM). (B) a plot of fluorescence
2+
intensity changes versus the concentrations of Zn in EtOH-HEPES buffer(65:35, v/v, pH = 7.20).
2
+
(
C) The limit of detection of PBZ for Zn in EtOH-HEPES buffer (65:35, v/v, pH = 7.20): the
2
+
solid line stands for a linear fit to the data. (D) Benesi-Hidebrand plot for PBZ to Zn in
EtOH-HEPES buffer (65:35, v/v, pH = 7.20): I represents fluorescence intensity of PBZ solution
0
2+
(
10 μM) upon addition of different amount of Zn . I represents fluorescence intensity of free PBZ
solution.
6

1200
1100
1000
900
800
700
600
500
400
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
2
+
2+
[
Zn ]/([Zn ]+[PBZ])
Fig.5.The Job's plot of fluorescence intensity response of PBZ at 526 nm to the mole fraction of
2
+
Zn in EtOH-HEPES buffer (65:35, v/v, pH = 7.20), λex= 386 nm.
0
eq
0.6
0.5
0.4
0.3
0.2
0.1
0.0
2
+
Zn
9
eq
9
0
eq
2+
Zn
eq
250
300
350
400
450
500
550
Wavelength(nm)
Fig.6. Absorption spectra changes of PBZ (10 μM) in EtOH-HEPES buffer (65:35, v/v, pH = 7.20)
2+
upon the addition of different amount of Zn (0-90μM).
Fig.6 showed the UV- absorption spectra changes of PBZ upon the addition of
2
+
Zn , the intensity of the absorption bands of PBZ enhanced at 478 nm and 445 nm
and decreased at 353 nm and 263 nm. The presence of three isosbestic points at 364
nm, 302 nm and 271 nm inferred that the formation of complex between PBZ and
Zn2+ has occurred. To better understand the binding site of the receptor PBZ with
2
+
1
Zn ， H NMR titration experiments were carried out in DMSO-d6. Fig.7A (1)
1
showed H NMR spectrum of receptor PBZ. The peak observed at 12.29 ppm was an
overlapping peak assigned to the phenolic -OH (Ha) and the imine -NH (Hc) in PBZ,
7

which can be confirmed from the integral area of the peak at 12.29 in Fig. S12. Upon
2
+
the addition of Zn with 0.5-4.0 equiv concentrations shown in Fig 7B, the peak of
Ha at 12.29 ppm disappeared, indicating that -OH (Ha) was involved in the
2
+
complexation of Zn and PBZ. At the same time, the peak of Hc shifts from 12.29
ppm to 12.08 ppm instead of disappearing, In addition, the peak of -CH=N- (Hb)
2
+
shifts from 8.92 ppm to 8.90 ppm while Zn existed. These results might confirm that
2
+
PBZ may chelate Zn by coordination of the oxygen atom of the phenolic -OH and
the nitrogen atom of the imine -NH on thiazole and the nitrogen atom of -CH=N-.
2
+
When 2.0 equiv of Zn was added, there were no obvious differences between Fig.7B
3) and Fig.7B (4), which verifies the formation of 1:1 complex between PBZ and
(
2
+
2+
+
Zn . The peak m/z at 493.2 (calculated for [PBZ+Zn +2H O-H ] = 493.2) further
2
2
+
indicated a 1:1 complex formed between PBZ and Zn (Fig. 8), which are consistent
with the Job's plot results.
8

1
2+
1
Fig.7 A. H NMR spectra in DMSO-d6 of (1) PBZ only, (2) PBZ with 4 equiv of Zn ; B. H
2
+
NMR spectra in DMSO-d6 of (1) PBZ only, (2) PBZ with 0.5 equiv of Zn , (3) PBZ with 1
2+
2+
2+
equiv of Zn , (4) PBZ with 2 equiv of Zn , (5) PBZ with 4 equiv of Zn .
2+
Fig. 8. ESI Mass spectrum ofPBZ-Zn -H O complex.
2
Optimization of pH on the practical application of fluorescence probe under
2
+
physiological conditions is essential. The pH dependency of PBZ for Zn detection
was recorded in EtOH-HEPES (65:35, v/v). As shown in Fig.9, it was found that the
2
+
fluorescence intensity of PBZ-Zn could almost remain in the range of pH 7-13. In
addition, the optical stability of the probe PBZ for the detecting of Zn2+ was also
investigated in EtOH-HEPES (65:35, v/v, pH = 7.20). As shown in Fig.S13, under the
9

2
+
tungsten lamp (0-120 minutes), the fluorescence intensities of the Zn -PBZ had
almost no changes, which indicating that the PBZ has good optical stability for
2
+
2+
detecting Zn . These results clearly suggested that PBZ is suitable as Zn sensor for
biological applications.
PBZ
1
1
2000
0000
2+
PBZ+Zn
8
6
4
2
000
000
000
000
0
2
3
4
5
6
7
8
9
10 11 12 13
pH
Fig.9. Effect of pH on fluorescence intensity of the PBZ (10 μM) and PBZ with 10 equiv of Zn2+
in EtOH-HEPES buffer (65:35, v/v, pH = 7.20), λem= 526 nm, λex= 386 nm.
In order to examine the practical application of PBZ, the fluorescence
2
+
quantitative experiments for detecting Zn were carried out in three real water
samples including distilled water, lake, and river water, collected from our laboratory,
Tongda lake in Nantong university and Haohe River in Nantong, respectively (Fig.10).
2
+
Upon increasing the concentration of Zn (0-14 μM)，the fluorescence intensity of
2
+
PBZ and the amount of Zn exhibited good linear properties in these water samples,
indicating that the probe PBZ can be used for recognizing Zn2+ in environmental
analysis.
10

River
4
4
3
3
2
2
1
500
000
500
000
500
000
500
Lake
Distilled water
0
.4
0.6
0.8
2
1.0
-5
1.2
1.4
+
[
Zn ] 10 M
2+
Fig.10. The fluorescence intensities changes of PBZ (10 μM) upon the addition of Zn (0-14 μM)
in distilled water, lake and river water samples.
2
+
To further investigate the application of PBZ to detect Zn in live cells, firstly,
the cytotoxicity of the probe PBZ by MTT assay on the HepG-2 cells [36-37]. Fig.11
showed the viability of the HepG-2 cells is still over 80%, even at higher
concentration of the PBZ at 20 μM，indicating the probe PBZ has low cytotoxicity
and could be used as detect Zn2+ in live cells. The fluorescence bio-imaging
experiments were also carried out in the HepG-2 cells [38].As shown in Fig.12 (a),
the probe PBZ in the cell nucleus showed no detectable fluorescence emission. After
2
+
further incubation with fresh RPMI-1640 containing 100 mM Zn for 15 min, a
bright yellow fluorescence inside the HepG-2 cell nucleus was observed significantly
by dual photon confocal microscope (Fig.12 (c)). Additionally, An overlay of the
bright field and the fluorescence images suggested that the probe PBZ could go
2
+
through cell membrane into nucleus and binds to intracellular Zn , resulting in large
fluorescence emission intensity (Fig.12 (b) and (c)) [39-40] . These results indicated
2
+
that the PBZ could be applied potentially to recognize intracellular Zn .
11

1
00
8
6
4
2
0
0
0
0
0
0
5
10
15
20
-5
Concentration (10 M)
Fig.11. Cell viability of HepG-2 cell nucleus treated with different concentration (0-200μM).
Fig.12. (a) fluorescence images of HepG-2 cell nucleus treated with probe PBZ (10 mM); (b)
bright field images after presence of Zn2+ (100 mM); (c) fluorescence images after presence of
2
+
Zn (100 mM).
Conclusions
In summary, a new pyrene-based fluorescence probe PBZ was developed to
2
+
recognize Zn with a turn-on fashion based on PET. PBZ displayed high selectivity
for Zn2+ comparing to other competing metal ions, and high sensitivity with the
-7
detection limit reaching 10 level in EtOH-HEPES buffer (65:35,v/v, pH = 7.20).
Furthermore, the complex formation, stoichiometry and binding mode was well
1
determined by Job's plot, H NMR titration and ESI-MS, which showed the
configuration of a 1:1 PBZ-Zn2+ complex. Moreover, PBZ also demonstrated its
2
+
potential ability to recognize Zn in real water samples. Finally, Bio-imaging study
2
+
also showed PBZ could be suitable for monitoring Zn in live cells. These results
2
+
indicated that PBZ could be a promising fluorescent probe for detection of Zn in
environmental and biological diagnostics analysis.
12

Acknowledgements
This work was supported by National Natural Science Foundation of China
(
No. 21476117, 21776140, 21501100) and High-level Talents in Six Industries
of Jiangsu Province (XCL-062). We also thanked Analysis and Testing Center
of Nantong University for their testing support.
Supporting information
Detailed the experimental methods and characterizations can be found in the
supporting information.
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+
1
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3
. A novel pyrene-based fluorescence sensor for Zn was designed and synthesized.
2
+
2+
. This sensor was of good selectivity and sensitivity for Zn without the interference of Cd .
. This sensor can be used in live cells.
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