A novel polynorbornene-based chemosensor for the fluorescence sensing of Zn2+ and Cd2+ and subsequent detection of pyrophosphate in aqueous solutions

Article abstract of DOI:10.1039/c5dt00542f

A hydroxyquinoline functionlized polynorbornene (P1) was designed and synthesized. In an aqueous solution, P1 shows a "turn-on" fluorescence response for Zn²⁺ and Cd²⁺ with a 50 nm blue shift. Furthermore, both P1-Zn²⁺ and P1-Cd²⁺ complexes were found to respond to pyrophosphate (PPi) over other important biological anions via a fluorescence quenching effect. P1 is also capable of monitoring intracellular Zn²⁺ and PPi in real time.

Full text of DOI:10.1039/c5dt00542f

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A novel polynorbornene-base chemosensor fluorescence sensing of
Zn2+ and Cd2+ and subsequent pyrophosphate in aqueous solution
Pei-Shui Yao, a Qian-Yong Cao, a,* Zhanghua Liu,b Yong Chen,b Jin-Zhu Gea
aDepartment of Chemistry, Nanchang University, Nanchang 330031, P. R. China.
Fax: (+86)791-83969386; E-mail: cqyong@ncu.edu.cn
bInstitute for Advanced Study, Nanchang University, Nanchang 330031, P. R. China
A novel 8-hydroxyquinoline anchored polynobern for fluorescence sensing of
Zn2+/Cd2+ and subsequent pyrophosphate in aqueous solution and its biological
application is introduced.

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A novel polynorborneneꢀbase chemosensor for fluorescence sensing
of Zn2+ and Cd2+ and subsequent pyrophosphate in aqueous solution
PeiꢀShui Yao, a Zhanghua Liu, b JinꢀZhu Ge, a Yong Chen, b QianꢀYong Cao a, *
a Department of Chemistry, Nanchang University, Nanchang 330031, P. R. China.
Fax: (+86)791-83969386; E-mail: cqyong@ncu.edu.cn
b Institute for Advanced Study, Nanchang University, Nanchang 330031, P. R. China
ABSTRACT: A hydroxyquinoline functionlized polynorbornene (P1) was designed and
synthesized. In aqueous solution, P1 shows a “turn–on” fluorescence response of Zn2+ and Cd2+
with a 50 nm blue shift. Further, both the P1ꢀZn2+ and P1ꢀCd2+ complexes were found to respond
pyrophosphate (PPi) over other important biological anions via fluorescence quenching effect.
P1 was also capable of monitoring the intracellular Zn2+ and PPi in real time.
1

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Introduction
The development of fluorescent chemosensors for biologically important metal ions and
anions has received considerable attention because of the simplicity and high sensitivity of
fluorescence assays.1‒6 Among various metal ions, fluorescent chemosensors for zinc and
cadmium ions have received wide attention in the past few decades due to the indispensable role
of zinc ion and deleterious role of the cadmium to the life. 7‒18 Zinc is the second most abundant
transition metal ion in the mammalian body, and plays a critical role in biological processes
including gene expression, apoptosis, and neurotransmission. In contrast, cadmium ion is known
as an extremely toxic and potentially carcinogenic metal, and could cause severe diseases such as
renal dysfunction, calcium metabolism disorders, and certain types of cancers. As the bioproduct
of adenosine triphosphate (ATP) hydrolysis and enzymatic reactions, pyrophosphate anion (PPi)
plays pivotal roles in many biological processes spanning from energy storage, gene regulation,
signal transduction, biosynthesis and muscle contraction. 19, 20 Thus, it is desirable to develop
new chemosensors for detection of Zn2+, Cd2+ and PPi with high selectivity and sensitivity.
Recently, a single fluorescent chemosensor for recognition of some metal ions such as
Zn2+/Cd2+ and subsequent PPi have been established, 21‒27 because these metal ions show strong
binding affinity with PPi. PPi can coordinate the center metal ions as the second binding ligand
or displacement the organic flurophore ligand, which leads the original complexes emission
intensity or wavelength changes. However, the reported chemosensors for Zn2+/Cd2+ and PPi are
typically small molecular. The polymer anchored systems are still rare. 28‒ 31 Compared to small
organic compounds, polymer based sensors display several important advantages such as signal
amplification and better water solubility. Herein, we report a polymer based chemosensor for
sensing of Zn2+/Cd2+ metal ions and subsequent PPi anion using a norbornene derived 8ꢀ
2

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hydroxyquinoline motif. 8ꢀHydroxyquinoline (8ꢀHQ) is a wellꢀknown fluorophore, and has been
32‒34
widely used for meal ions recognition.
We found that the 8ꢀHQ anchored polymer P1
(Scheme 1) shows fluorescent turnꢀon recognition of Zn2+/Cd2+ in aqueous solution. In addition,
the P1ꢀZn2+ and P1ꢀCd2+ complexes can be used as the chemosensors for PPi with fluorescence
“turnꢀoff” change. To the best of our knowledge, this is the first fluorescence sensor for PPi
based on polymerꢀbased materials.
Results and discussion
Scheme 1. Synthesis route of P1. a). LiAlH4, THF, 0 oC–rt. b). CHCl3, K2CO3, 0–5 oC, ClCH2COCl. c). 8ꢀ
hydroxyquinoline, K2CO3, acetone, reflux. d). DCM, G1, rt.
O
Cl
O
a
O
b
OH
OH
O
O
O
3
Cl
2
O
4
c
N
n
O
O
O
O
O
O
O
d
O
O
O
N
O
N
O
N
1
P1
The synthesis route of monomer 1 and its homopolymer P1 are shown in Scheme 1. With
commercial available 5ꢀnorborneneꢀendoꢀ2,3ꢀdicarboxylic anhydride and 8ꢀhydroxyquinoline as
starting materials, we firstly prepared the precursor 4 by the literature method.35 Then the
quinolineꢀappended norbornene monomer 1 was easily obtained by condensation of 4 and 8ꢀ
hydroxyquinoline with K2CO3 as a catalyst in acetone solution. The successful formation of 1
1
was confirmed by the H NMR, 13C NMR and ESIꢀMS spectroscopic techniques. The
homopolymer P1 was then obtained by ring opening metathesis polymerization (ROMP) 1 using
3

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1
Grubbs’ first generation catalyst.36 The formation of polymer P1 can be confirmed by the H
NMR spectroscopy: the double bond protons of monomer 1 at 5.99 ppm disappeared with
appearing new peak at 5.22 ppm, and the two unequivalent bridged methylene protons (1.37 and
1.18 ppm) merged to one signal (1.24 ppm in DMSO).
350
a)
CH3CN
b)
DMSO
CH2Cl2
H2O
CH3CN
300
250
200
150
100
50
DMSO
CH2Cl2
H2O
200
150
100
50
0
0
350 400 450 500 550 600
350 400 450 500 550 600
Wavelength/nm
Wavelength/nm
Fig. 1 Normalized emission spectra of 1 (a) and P1 (b) in different solvents (excitation at 315 nm).
With excitation at 315 nm, homopolymer P1 and its monomer 1 show a weak quinolineꢀ
based monomer emission at about 375 nm in organic solutions such as CH3CN, DMSO and
CH2Cl2 (Fig. 1), which may be attributed to the radiationless process from the carbonyl oxygen
lone pair to the 8ꢀHQ fluorophore. 37 On the other hand, P1 shows weak green emission at 475
nm in aqueous solution (Fig. 1), while 1 still shows blue emission at 380 nm. The fluorescence
band at 475 nm can be assigned to the quinoline excimer emission,38, 39 which may be originated
from the aggregation of sideꢀchain quinoline units in P1 in aqueous solution.
4

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1000
800
600
400
200
0
10
8
0
6
10%
4
2
0
0
2
4
6
8
10
Water fraction (vol%)
350
400
450
500
550
600
Wavelength/nm
Fig. 2 Normalized emission spectra of 1 (20 ꢁM) toward Cd2+ (5 equiv added) with increasing the content
of H2O in CH3CN solution. Inset : The I/I0 ratio changes at 423 nm versus the content of H2O
Fig. 3 a) Fluorescent color changes of P1 (20 ꢁM) upon addition of various metal ions on excitation at 365 nm
using a handheld UV lamp. b) Emission spectra of P1 (20 ꢁM) before and after the addition of 5 equiv of
metal ions in TrisꢀHCl solution (pH = 7.4). c) Emission titration of P1 (20 ꢁM) upon the addition of various
Zn2+ ions in TrisꢀHCl solution (pH = 7.4). Inset: emission intensity at 425 nm upon titration with Zn2+.
5

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The fluorescence recognition abilities of P1 and 1 toward various metal ions (Li+, Na+, K+,
Rb+, Cs+, Ag+, Mg2+, Ca2+, Ba2+, Sr2+, Cd2+, Hg2+, Pb2+, Fe2+, Fe3+, Al3+, Cu2+, Co2+ and Ni2+)
were then investigated in CH3CN and aqueous solutions. In CH3CN solution, both P1 and 1
showed similar large fluorescence enhancement response to Zn2+ and Cd2+ with a red shift from
375 nm to 425 nm (Fig. S1 and S2), a moderate response to Hg2+, and weak or almost no change
to other metal ions. However, the recognition abilities of P1 and 1 toward metal ions in H2Oꢀ
CH3CN solution were different. 1 showed little fluorescence changes to Zn2+ and Cd2+ when the
H2O content is larger than 5% (Fig. 2). This implies that H2O can dissociate 1ꢀZn2+ and 1ꢀCd2+
complexes, since H2O are also strong binding ligand for some transition metal ions. In contrast,
P1 still exhibited good fluorescence enhancement response to Zn2+ and Cd2+ even in pure
aqueous solution (Fig. 3). The solubility of P1 in TrisꢀHCl (20 mM, pH = 7.4) buffer solution
was estimated to be more than 400 ꢁM by serial dilution from a concentrated stock solution (100
mM in DMSO). In TrisꢀHCl (20 mM, pH = 7.4) buffer solution, the addition of Zn2+ or Cd2+
disrupted the quinolineꢀbased excimer at 475 nm, and a strong blue emission at 425 nm was
observed. This process can be detected by the naked eyes with the emission color changing from
green to blue (Fig. 3a). The above results revealed that P1 may provide a hydrophobic scaffold
for interaction between the quinoline ligand and the metal ions, and can retain the same binding
mode with Zn2+/Cd2+ in competitive aqueous solution as that in CH3CN solution. Polymerꢀbased
chemosensors often exhibit higher binding ability than small molecular analog in competitive
solvent.40‒42 Little emission spectra changes were observed upon the addition of other metal ions
to P1 in aqueous solution, such as Li+, K+, Rb+, Cs+, Ag+, Hg2+, Co2+, Ni2+, Zn2+, Ba2+, Mg2+,
Ca2+ and Fe2+, even at a large amount.
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The emission titrations of P1 with Zn2+ and Cd2+ were carried out (Figs. 3c and S4), which
exhibited that P1 shows stronger binding ability with Zn2+ than that of Cd2+. The addition of
about 10 equiv of Zn2+ can saturate P1’s emission, with 32 fold enhancement at 425 nm.
However, these values for Cd2+ were 20 equiv and 23 fold, respectively. The binding constants
between P1 and Zn2+ and Cd2+ were obtained according to the emission titration data. The 1:1
stoichiometry binding between P1 and Zn2+/Cd2+ was confirmed by the fluorescence Job’s plot
(Fig. S4). From the fluorescent titration data, the binding constants of P1ꢀZn2+ and P1ꢀCd2+ were
calculated to be (2.9 ± 0.2) × 105 M‒1 and (1.7 ± 0.5) × 104 M‒1 (Fig. S5 and S6), respectively.
And the detection limits were also measured to be 2.04×10‒7 M and 3.55 × 10ꢀ6 M, respectively.
The stronger binding ability of P1ꢀZn2+ than that of P1ꢀCd2+ may make P1 distinguish zinc from
cadmium. Also, cadmium is an ultratrace element, and has extremely low concentration in
human bodies.
1
Fig. 4 H NMR titration of 1 upon the addition of Zn2+ in CD3CN solution. ▲ denotes the H2O peak. The top
structure shows the possible binding mechanism between 1 and Zn2+ in CD3CN solution.
Motivated by the fluorescence response, we then wanted to make clear the binding
1
mechanisms between P1 and Zn2+/Cd2+. The H NMR titrations of 1 with Zn2+ were conducted
7

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in CD3CN solution (Fig. 4), since both compounds show similar binding mechanism in this
solution. Upon the addition of Zn2+, the protons of 1 in the quinoline ring (7‒9 ppm) showed
large downꢀfield (H2 and H3) or upꢀfield (H1) changes upon interaction, which indicates that the
N atoms take part in binding with Zn2+. The upꢀfield shift of H1 may be attributed to the
restricting bond rotation and/or πꢀ stacking interaction between the pendant quinoline moieties in
1 for coordination.43 In addition, the protons of the two methylenes also exhibited a downꢀfield
shift (ꢂδ = ‒0.34 ppm for H4, and ꢂδ = –0.39 ppm for H5, respectively), implying that the ether
O and the carbonyl O atom may also take part in binding. The proposed binding mode of 1ꢀZn2+
shown in Fig. 4 was also proved by the density functional theory (DFT) calculation (see below).
Fig. 5 Optimized conformation of 1ꢀZn2+ by DFT calculation. Selected distances (Å): Zn‒N1, 2.103; Zn‒N2,
2.133; Zn‒O1, 2.289; Zn‒O2, 2.316; Zn‒O3, 2.391; Zn‒O4, 2.122.
The optimized configuration of 1ꢀZn2+ is shown in Fig. 4, which showed that Zn2+ ion binds to
1 very well through six coordination sites: two N atoms, two ether O atoms and two carbonyl O
atoms. The Zn–O bond length is ranged from 2.12 Å to 2.39 Å, and the Zn–N bond length is 2.12
Å, respectively. These data indicate that 1 could provide suitable space to better accommodate
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corresponding ions. Similar binding mode is also observed in 1ꢀCd2+ complex (Fig. S7).
Noting the selective fluorescence enhancement due to Zn2+, the competition experiments of
P1ꢀZn2+ with other concomitant metal ions were investigated (Fig. S8). The presence of most
other metal ions except Cd2+ had not induced any noticeable spectral change compared to Zn2+
alone. Furthermore, the sensing ability of P1 with Zn2+ was also investigated at different pH
values (Fig. S9). P1 exhibited satisfactory sensing abilities when the pH was ranged from 4 to 11,
indicating that P1 could act as a fluorescent probe for Zn2+ under physiological pH conditions.
800
800
a)
b)
P1-Zn2+ and
other anions
800
600
400
200
0
600
400
200
0
800
600
400
200
0
600
400
200
0
0
5
10
15
20
0 1 2 3 4 5 6 7 8 910111213
[PPi]/[P1]
PPi
350
400
450
500
550
600
350 400 450 500 550 600
Wavelength/nm
Wavelength/nm
Fig. 6 a) The emission spectra of P1ꢀZn2+ upon the addition of various anions (10 equiv) in aqueous solution
.
Inset shows the emission intensity at 425 nm upon the addition of various anions (0‒P1ꢀCd2+, 1‒F‒, 2‒Cl‒,
‒
‒
3‒Br‒, 4‒I‒, 5‒NO3 , 6‒CH3COO–, 7‒CO32–, 8‒HSO4 , 9‒Pi, 10‒ATP, 11‒AMP, 12‒ADP, 13‒PPi). b) The
emission spectra of P1ꢀZn2+ upon the addition of PPi. Inset show the emission intensity at 425 nm upon the
addition of PPi.
To evaluate the selectivity and sensitivity of P1ꢀZn2+ and P1ꢀCd2+ for anions, fluorescence
changes upon addition of excess amounts of various anions were measured. The P1ꢀZn2+ and P1ꢀ
Cd2+ complexes were prepared in situ by mixing P1 with Zn2+/Cd2+ (1:5 for Zn2+ and 1:10 for
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Cd2+) in 100% TrisꢀHCl (20 mM, pH = 7.4) buffer solution (Fig. 6 and S10). Upon the addition
of PPi, the strong fluorescence of P1ꢀZn2+ and P1ꢀCd2+ quenched largely. In contrast, little
fluorescence changes were observed upon the addition of other anions, such as F–, Cl–, Br–, I–,
–
2–
–
NO3 , CH3COO–, CO3 , HSO4 , Pi, ATP, AMP, ADP, even at a large amount. Therefore, P1ꢀ
Zn2+ and P1ꢀCd2+ can function as fluorescent turnꢀoff PPi sensors from other investigated anions,
including some other phosphate anions.
The fluorescence titrations of P1ꢀZn2+ and P1ꢀCd2+ to PPi in aqueous solution were shown in
Fig. 5 and S11. With increasing the concentration of PPi, the emission of P1ꢀZn2+ at 425 nm
gradually decreased. When 10 equiv of PPi was added to the solution, the fluorescence intensity
reached saturation. This PPi induced fluorescence recovery almost reverted to the initial state of
free probe P1, which suggests that PPi dissociates P1ꢀZn2+ completely. The detection limits of
P1ꢀZn2+ and P1ꢀCd2+ to PPi were measured to be 2.8 × 10‒5 M and 3.5 × 10‒5 M (Fig. S12),
respectively, indicating that P1ꢀZn2+ shows stronger binding ability to PPi than that of P1ꢀCd2+.
C
D
A
B
B1
D1
A1
C1
Fig. 6 Imaging of P1 before and after addition Zn2+ and PPi in living cells. Top: brightfield images. (A) HepGꢀ
2 cells. (B) HepGꢀ2 cells were incubated with P1 (20 ꢁM) for 60 min. (C) HepGꢀ2 cells were preincubated
with P1 (20 ꢁM) for 60 min and then treated with 200 ꢁM Zn2+. (D) HepGꢀ2 cells were preincubated with P1
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(20 ꢁM) for 60 min and then added Zn2+ (200 ꢁM) for another 30 min then added PPi (200 ꢁM). Bottom: A1,
B1, C1 and D1 are fluorescence images of A, B, C and D, respectively.
To demonstrate the biological application of P1 to detect Zn2+ and PPi in live cells, HepGꢀ2
cells have been used for cell imaging studies (Fig. 6). Brightfield image shows that the HepGꢀ2
cells were healthy and available throughout the experiment. The cells itself shows no
fluorescence (A1), when it treated with P1 for an hour, a weak green fluorescence were observed
(B1), then Zn2+ was added for another 30 min, it exhibited strong blue fluorescence (C1). With
the subsequent addition of PPi to those cells, the blue fluorescence backed to the original weak
green fluorescence. This indicated that the polymer P1 is permeable to HepGꢀ2 cells and can be
used for bioimaging of Zn2+, its P1ꢀZn2+ complex can also distinguish PPi from other anions in
living cells.
Conclutions
To summarize, a new hydroxyquinoline functionlized polynobern (P1) was investigated as a
“turnꢀon” fluorescence sensor for Zn2+ and Cd2+ in aqueous solution. The in situ generated P1ꢀ
Zn2+ and P1ꢀCd2+ complexes displays high selectivity to PPi over other anions based on metal
ions displacement approach. As the biological application, P1 is successfully applied to monitor
the intracellular Zn2+ and PPi staining experiments in HepGꢀ2 cells. The cell study also
confirmed that the fluorescence of P1 enhances with Zn2+ ion followed by quenching in the
presence of PPi.
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Experimental section
General methods. Unless otherwise noted, materials were obtained from commercial suppliers
and were used without further purification. Flash chromatography was carried out on silica gel
(230ꢀ400 mesh). NMR spectra were recorded using Varian instruments (400 MHz). Chemical
shifts were expressed in ppm and coupling constants (J) in Hz.
Calculation details. 1ꢀZn2+ and 1ꢀCd2+ were optimized using Density Functional Theory (DFT)
at B3LYP/6ꢀ31G(d) level of theory. No imaginary frequencies were available after vibration
analysis of the optimized structures, which implied that each of the optimized structures was at
the real minimum on the potential energy surfaces (PES). Basis set superposition error (BSSE)
has been corrected by counterpoise correction method applied on an optimized geometry while
calculating binding energy. All calculations were performed using Gaussian 09 W program
package.44
Calculation of the association constants and the detection limits. The binding constants of
the inclusion complex were obtained from the fluorescence titration data. According to the
BenesiꢀHildebrand method, 45 the equations for 1:1 host:guest complexes are given below:
1
1
1
ꢀ
ꢀ
ꢀ
ꢀ
2+
=
+
ꢀ
ꢀ
ꢀ
I − I0
I' − I0 K(I' − I0 )[M ]
In the equations, I0 is the intensity of fluorescence of
1
or P1 without M2+, I is the intensity with
a particular concentration of Hg2+, I' is the intensity of the fully complexed form at the highest
concentration of M2+, and K is the binding constant.
The detection limits (DLs) were calculated with the following equation: 46
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3
σ
ꢀ
DL =
K
Which σ is the standard deviation of blank measurement and is 0.02 here, and K is the binding
constant.
General UVꢀvis and fluorescence spectra measurements. Stock solutions of metal ions
(perchlorate salts, 0.1 M) and anions (sodium or potassium salts, 0.1 M) were prepared in
aqueous solution. Stock solutions of
concentration of and P1 in the UVꢀvis and emission titrations was 0.02 mM in CH3CN solution
or in aqueous solution, respectively. During the titration, ions solution ware added into a solution
of or P1 (2 mL) using a micro injector and the whole volume of the final system can be
1 and P1 (0.1 M) were prepared in DMSO solution. The
1
1
considered constant because the volume of ions solution added is negligible compared to that of
ligand’s solution.
Synthesis of the 5ꢀnorborneneꢀ2ꢀexo, 3ꢀexodimethanol (3). Under argon, 16.41 g (0.1 mol)
2
was dissolved in 300 mL dry THF solution, and cooled at 0 ºC. Then which LiAlH4 (8.34 g, 0.13
mol) was added slowly to the mixture in several portions and allowed to react for 14 hours at
room temperature. The reaction was then quenched by adding NaSO4·10H2O until gas evolution
subsided at 0ºC. The resulting precipitate was then filtered through a celite plug followed by
several washes with EtOAc. The mother liquor was dried over MgSO4, filtered through celite,
and concentrated in vacuo. The crude exodiol
3 was purified recrystallization with
dichloromethane and hexane, give pure (13.3 g, 86 mmol, 81% yield) as a colorless crystal.
3
Synthesis of 4. Compound
3
(1.0 g, 6.48 mmol) and K2CO3 (0.62 g, 4.5 mmol) were added to 30
o
mL dry CH2Cl2 solution, and cooled to 0−5 C. Then chloroacetyl chloride (1.35 mL, 15 mmol)
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dissolved in 10 mL DCM for several minutes. The reaction mixture was stirred for 2 h. After
completion of the reaction, 20 mL of water was added. The organic layer was separated and
washed with 10 mL of saturated NaHCO3 aqueous solution and then with brine (15 mL). The
dichloromethane layer was dried over anhydrous Na2SO4, filtered, and evaporated completely to
1
give a yellow viscous liquid (1.23 g, 62% yield). HꢀNMR (CDCl3, 400 MHz, TMS): 6.17 (2H,
−CH=CH−), 4.05 (4H, −CH2Cl), 3.97 (2H, −COCH2), 3.90 (2H, −COCH2), 2.92 (2H, =CHꢀ
CH−), 2.61 (2H, OCH2−CH−), 1.54 (1H, CH2−bridge), 1.34 (1H, CH2−bridge).
Synthesis of the monomer 1. Compound
4 (0.342 g, 1.11 mmol), K2CO3 (0.61g, 4.4 mmol) and
8ꢀhydroxyquinoline (0.363g, 2.5 mmol) were dissolved in 30 mL dry acetone, and the reaction
mixture was stirred at 70 oC for 10 hours. After completion of the reaction, the product was
filtered and the solvent was removed under reduced pressure. The crude product was further
purified by column chromatography (CH2Cl2:CH3OH, 99:1) to get pure
1 (337.7 mg, 0.64 mmol,
1
58% yield). HꢀNMR (CDCl3, 400 MHz, TMS): δ (ppm): 8.94 (2H, d, J = 8.0), 8.13 (2H, d, 2),
7.43 (6H, m, 3), 6.96 (2H, d, J =4.0), 5.98 (2H, −CH=CH−), 4.95 (4H, −COCH2), 3.88 (4H,
−OCH2), 2.67 (2H, =CHꢀCH−), 2.20 (2H, OCH2−CH−), 1.37 (1H, CH2−bridge), 1.18 (1H,
CH2−bridge). 13C NMR (100 MHz, CDCl3), δ (ppm): 168.63, 153.54, 149.47, 140.05, 135.95,
135.33, 129.57, 126.34, 121.81, 120.97, 109.41, 66.09, 65.32, 48.88, 45.27, 40.40.
Synthesis of the polymer P1. Mononer
1 (131.1 mg, 0.25 mmol) and the first generation Grubbs
catalyst (41.5 mg, 0.05 mmol) were dissolved in 3 mL dry dichloromethane under nitrogen. The
mixture was stirred at room temperature for 24 h. Ethylꢀvinyl ether was added to quench the
polymerization. The resulting polymer was isolated by precipitating in cold ether and
1
concentrated under vacuum. (54.4 mg, 41.5% yield). H NMR (DMSOꢀd, 400 MHz,): δ (ppm):
8.74−8.83 (2H), 8.16−8.25 (2H), 7.30−7.48 (6H), 7.00−7.09 (2H), 5.18−5.30 (2H new peaks
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were observed), 3.93−4.13 (4H), 3.93−4.13 (4H), 2.05−2.20 (2H), 1.50−1.80 (2H), 1.15−1.33
(2H new peaks were observed).
Associated content
Supporting Information
NMR and MS spectra of
1
and P1, extra fluorescence studies, Job’s plot of P1 with Zn2+ and
ꢀZn2+ and ꢀCd2+, and the calculation data of the binding
Cd2+, the optimized structures of
1
1
constants. See DOI: 10.1039/b000000x.
AUTHOR INFORMATION
Corresponding Authors
Eꢀmail: cqyong@ncu.edu.cn
Acknowledgments
This work was supported by the National Nature Science Foundation of China (nos. 21162017
and 21462027).
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