Double-detecting fluorescent sensor for ATP based on Cu2+ and Zn2+ response of hydrazono-bis-tetraphenylethylene

Article abstract of DOI:10.1016/j.saa.2019.117568

Although all kinds of sensors with unique detecting ability for one guest were reported, the fluorescence sensor with multiple detecting abilities was seldom presented. This work designed and synthesized a novel AIE fluorescence probe bearing double detec

Full text of DOI:10.1016/j.saa.2019.117568

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Double-detecting fluorescent sensor for ATP based on Cu2þ and Zn2þ
response of hydrazono-bis-tetraphenylethylene
a
a
a
a
a, b, c, *
Shengjie Jiang , Jiabin Qiu , Shibing Chen , Hongyu Guo , Fafu Yang
a
College of Chemistry and Materials, Fujian Normal University, Fuzhou, 350007, PR China
Fujian Key Laboratory of Polymer Materials, Fuzhou, 350007, PR China
Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fuzhou, PR China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 4 July 2019
Received in revised form
Although all kinds of sensors with unique detecting ability for one guest were reported, the fluorescence
sensor with multiple detecting abilities was seldom presented. This work designed and synthesized a
2þ
2þ
novel AIE fluorescence probe bearing double detecting for ATP based on Cu and Zn response of
hydrazono-bis-tetraphenylethylene (Bis-TPE). Bis-TPE was prepared in 82% yield with simple procedure.
It exhibited strong red AIE fluorescence based on the large conjugated electron effect in aqueous media.
12 September 2019
Accepted 24 September 2019
Available online 17 October 2019
It showed outstanding selective sensing abilities for Cu2 by strong fluorescence quenching and for Zn
þ
2þ
by red-orange fluorescence change. The sensing mechanism of 1:1 stoichiometric ratios was confirmed
Keywords:
1
2þ
by H NMR and MS study. The strong red fluorescence of Bis-TPE þ Cu system could be recovered by
Tetraphenylethylene
Fluorescent sensor
Double detect
ATP
2
þ
2þ
adding ATP. The orange fluorescence of Bis-TPE þ Zn system could be quenched by adding Cu and
then was recovered by adding ATP. These double detecting abilities for ATP with the “off-on” red fluo-
2
þ
2þ
2þ
rescence in Bis-TPE þ Cu system and “allochroic-off-on” orange fluorescence in Bis-TPE þ Zn þCu
2
þ
þ
2þ
2þ
Zn
Cu
system were successfully applied to test Cu , Zn and ATP in test paper and living cell imaging, dis-
2
2þ
2þ
playing the good application prospects for sensing Cu , Zn
and double detecting ATP in the
complicated environment.
©
2019 Elsevier B.V. All rights reserved.
1. Introduction
(AIE) phenomenon, which eliminates effectively the ACQ effect
15]. From then on, AIE molecules had been studied extensively and
[
In the past decades, the fluorescent sensors were paid much
attention in detecting ions and biomolecules due to their obvious
advantages of high sensitivity, low cost, and simple operation [1-6],
avoiding the restriction of huge equipment, long times, high cost,
complicated and professional operation of the other detection
methods such as atomic absorption spectroscopy (AAS), atomic
fluorescence spectrometry (AFS) and inductively coupled plasma
mass spectrometry (ICP-MS) [7,8]. Many traditional dyes, such as
BODIPY, fluorescein, rhodamine and cyanine were modified as
excellent fluorescent probes for sensing anionic ions, cationic ions,
biological molecules, etc. [9-14] However, although these fluores-
cent probes usually possessed high fluorescence in organic sol-
vents, the strong aggregation-caused quenching (ACQ) effect in
aqueous solution seriously limited their practical application. In
exhibited the widely application in numerous fields, such as lu-
minous liquid crystal [16-19], organic light-emitting diodes (OLED)
[20-22], circularly polarized photoluminescence [23,24], as well as
ion detection and biomolecular recognition in aqueous media [25-
33].
It was well known that the contamination of heavy metals is a
kind of serious threat to human health and causes series of diseases
usually [34,35]. For instance, copper leads to Menkes syndrome
[36]. Cobalt induces radiation skin damages, and mercury disturbs
the central neural system [37,38]. The abnormal zinc levels might
result in immune dysfunction diseases such as brain diseases,
diabetes, epilepsy, Alzheimer’s and Parkinson’s disease [39-42]. On
the other hand, phosphates play important roles in biological sys-
tems [43]. Among various phosphate anions, adenosine triphos-
phate (ATP) is one of the most important species due to its pivotal
functions for both intracellular energy supplier and extracellular
signalling mediator in metabolic processes [44,45]. Up to now, all
kinds of fluorescence sensors including AIE sensors had been
applied for detecting heavy metallic ions, ATP and other guests,
respectively [46-55]. Generally, the AIE sensor displayed the
2
001, Tang’s group reported the aggregation induced emission
*
Corresponding author. College of Chemistry and Materials, Fujian Normal
University, Fuzhou, 350007, PR China.
E-mail address: yangfafu@fjnu.edu.cn (F. Yang).
https://doi.org/10.1016/j.saa.2019.117568
1386-1425/© 2019 Elsevier B.V. All rights reserved.

2
S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
detecting ability for one kind of metallic ion, one kind of metallic
3.74; found C 86.66, H 5.33, N 3.69.
2
þ
ion and/or ATP, or two kinds of metallic ions such as for Hg and
þ
2þ
2þ
3þ
2þ
Ag , Zn
and Cd , or Fe
and Hg
[56-58]. Obviously, by
2.4. The tested procedure of the test paper
comparison with the sensor for detecting only one kind of metallic
ion and/or ATP, the sensor for selectively detecting multiple
metallic ions and/or ATP has the advantage of higher efficiency,
cheaper cost and more simplified operation for practical applica-
tion. However, such fluorescence sensor bearing multiple detecting
abilities was seldom prepared so far. In this paper, we wish to report
a novel AIE hydrazono-bridged bis-tetraphenylethylene sensor,
Pieces of filter paper were immersed in THF-H O (5:95) solution
of Bis-TPE (0.1 mM) for 2 min. Then the filter papers were volatil-
ized in air at room temperature. After that, the filter papers were
2
customized as round slices. Three drops of a solution containing
þ
3þ
2þ
2þ
3þ
2þ
3þ
2þ
0.1 mM of different metal ions (none, Ag , Cd , Cr , Fe , Hg ,
þ
þ
2þ
2þ
2þ
2þ
2þ
2þ
K , Na , Pb , Cu , Sr , Mg , Zn , Al , Co , Ni and Ca ) or
ATP were added to the test paper. After drying, the slices were
observed under UV-light (365 nm).
2
þ
2þ
which possessed the good sensing abilities for Zn , Cu and ATP
with double detecting processes based on the responses of “off-on”
red fluorescence and “allochroic-off-on” orange fluorescence,
respectively. Moreover, it was successfully applied in test paper and
living cell bioimaging, exhibiting the good application prospects in
2
.5. MTT assay
sensing Cu2 , Zn
þ
2þ
and double detecting ATP in complicated
Methylthiazolyldiphenyl-tetrazolium (MTT) trials were done to
environment and living body.
determine the toxicity for MCF-7 cancer cells. The Inoculated MCF-
ꢀ
7
1
2
cancer cells were cultivated at 37 C and 5% CO
2
for 24 h, then
ꢂ5
2
. Experimental section
.0 ꢁ 10 M of Bis-TPE was tracked in the cells after incubating for
4 h. The fostered cells were rinsed by PBS buffer, and continue
2.1. Materials and methods
cultivating for 3 h, in 0.5 mg/mL MTT-PBS buffer. Further, 100 L of
m
DMSO was added into dissolve the generated Formazan crystals,
and detected the absorption intensity at 490 nm.
All chemical reagents were obtained from Aladdin Reagent Co.,
Ltd. and were used directly. The pre-coated glass plates were used
for TLC analysis. Silica gel (100-200 mesh) was applied for column
chromatography. NMR spectra were recorded on a Bruker-ARX 400
2.6. The experiment of living cell imaging. Bis-TPE
ꢀ
instrument at 25 C. MS spectra were measured on Bruker mass
(
3.0 mg) was dissolved in 1 mL of DMSO and then diluted with
spectrometer. PerkinElmer 2400 CHN Elemental Analyzer was used
for elemental analyses. Fluorescent spectra were examined on a
ꢂ5
PBS buffer (pH ¼ 7.4) to concentration of 1.0 ꢁ 10 M for imaging
test. MCF-7 cancer cells were cultivated under the above identical
circumstance of MTT trials for 24 h, and then being tinted by
Hitachi F-4500 spectrometer with conventional quartz cell
ꢀ
(
10 ꢁ 10 ꢁ 45 mm) at 25 C. The fluorescence absolute quantum
ꢂ5
1
.0 ꢁ 10 M of Bis-TPE with 24 h breeding. After rinsing with PBS-
F
yield (F ) was obtained on an Edinburgh Instruments FLS920
buffer, dyed cells were cultivated in solution of metallic ions
Fluorescence Spectrometer with a 6-inch integrating sphere.
Compound 3 was synthesized by reacting 2-hydroxybenzophenone
ꢂ5
2þ
ꢂ5
ꢀ
(
1.0 ꢁ 10 M) or M þATP solution (1.0 ꢁ 10 M) for 1 h at 37 C,
respectively. The cells were imaged by a confocal laser scanning
microscope (CLSM, Zeiss LSM 710, Jena, Germany).
4
and benzophenone in Zn,TiCl /THF system according to the pub-
lished literature [59].
3. Results and discussion
2.2. Synthetic procedure for compound 4
3
.1. Synthesis and characterization
The mixture of compound 3 (0.35 g, 1 mmol) and methenamine
0.84 g, 6 mmol) were stirred and refluxed in 10 mL of HOAc over-
night. TLC detection suggested the disappearance of starting ma-
terial. After reaction, 50 mL of 1 M HCl solution was poured into the
(
The synthetic route was shown as Scheme 1. According to the
reported procedure [59], mono-hydroxy tetraphenylethylene 3 was
synthesized by reacting benzophenone and mono-
hydrobenzophenone in Zn, TiCl /THF system in yield of 32%. Then,
by the classical formylation process under the reaction condition of
HOAc/methenamine, compound 3 was converted to compound 4 in
yield of 54%. Furthermore, the target hydrazono-bridged Bis-TPE
reaction mixture, and then extracted with CHCl
organic phase was collected and concentrated under reduced
3
(20 mL ꢁ 3). The
4
pressure. The residue was purified by column chromatography
(
eluent: CH
2
Cl
2
/hexane ¼ 1/2) to afford compound 4 as pale yellow
1
solid in yield of 54%. H NMR (400 M Hz, CDCl
3
): dppm: 10.92 (s, 1H,
OH), 9.58 (s, 1H, CHO), 7.02e7.19 (m, 17H, ArH), 6.72 (d, J ¼ 8.0 Hz,
1
H, ArH). MALDI-TOF-MS (C27
H
20
O
2
)
Calcd.for m/z ¼ 376.146,
þ
found: m/z ¼ 376.432 (M ).
2.3. Synthesis procedure of Bis-TPE
Compound 4 (0.376 g, 1 mmol) and 0.025 mL of hydrazine hy-
drate were added to 20 mL of absolute ethanol. The mixture was
refluxed and stirred for 12 h under the TLC detection. After the
reaction, the solvents were removed by reduced pressure and the
residue was recrystallized from CHCl
3
/MeOH to afford Bis-TPE as
yellow powder (82% yield). H NMR (400 MHz, CDCl 11.25 (s, 1H,
OH), 8.36 (s, 1H, N¼CH), 7.00e7.26 (m, 16H, ArH), 6.97 (s, 1H, ArH),
1
3
) d
13
6
.74 (d, J ¼ 8.0 Hz, 1H, ArH). C NMR (100 MHz, CDCl
64.52,158.36, 143.60, 143.36, 140.90, 139.33,136.65, 135.32, 131.36,
31.27, 127.95, 127.81, 127.58, 126.66, 126.46, 116.70, 117.47. MALDI-
TOF-MS (C54
Calcd.for m/z ¼ 748.309, found: m/
z ¼ 748.379 (M ). Anal.calcd for C54 : C 86.60, H 5.38, N
3
), dppm:
1
1
40 2 2
H N O )
þ
H
40
N
2
O
2
Scheme 1. The synthetic route for target Bis-TPE.

S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
3
þ
was prepared by refluxing compound 4 with hydrazine hydrate in
yield of 82% after recrystallization. The structure of the Bis-TPE was
characterized by 1H and C NMR spectroscopy, MALDI-TOF mass
spectrometry and elemental analysis (see SI). All the characteriza-
tion data supported its structure. For example, two singlets for
N¼CH and OH appeared at 11.25 and 8.36 ppm, respectively, which
suggested the symmetric trans-structure for C¼N groups of Bis-TPE
as shown in Scheme 1.
UV-vis spectra of Bis-TPE with various ions and Zn2 at different
concentrations. Although these UV-vis spectra exhibited some
fluctuation at maximum absorption, no change for maximum ab-
sorption wavelength and no selectivity for ion were observed
obviously. As to the fluorescence behaviours of Bis-TPE (Fig. 2), the
13
þ
2þ
3þ
fluorescence spectra with different metal ions (Ag , Cd , Cr
,
)
3
þ
2þ
þ
þ
2þ
2þ
2þ
3þ
2þ
2þ
2þ
Fe , Hg , K , Na , Pb , Sr , Mg , Al , Co , Ni and Ca
fluctuated obviously. The maximum deviation percentages of
2
þ
2þ
fluorescence intensities were ꢂ8.6% for Hg and þ29% for Co
.
2
þ
3.2. AIE property
One the other hand, the fluorescence spectra of Bis-TPE with Cu
2
þ
and Zn
exhibited dramatically changes. The fluorescence was
2þ
2þ
Tetraphenylethylene (TPE) is a typical AIE group. Thus, the AIE
completely quenched by the addition of Cu . When Zn was
added, the fluorescence enhanced remarkably and exhibited
obvious blue shift (from 626 nm to 602 nm), accompanying by the
color change from red to orange under ultraviolet lamp (as shown
in Fig. 2). These results suggested that Bis-TPE possessed the good
sensing ability for Cu and Zn simultaneously with the obvious
phenomena of fluorescence quenching and color change,
respectively.
property of Bis-TPE was firstly investigated in the THF-H
solution. The changes of fluorescence spectra and intensities of Bis-
TPE with O solutions were
ex ¼ 360 nm in a series of THF-H
exhibited in Fig. 1 and Fig. S5. It can be seen that the changes of
fluorescence intensities from f
¼ 0% to 50% were negligible. But
the emission intensities increased rapidly when f > 60%, reaching
its maximum value at f
¼ 95%. By comparison with that in pure
THF solution, the fluorescence intensity of Bis-TPE increased by 6.4
times in THF-H O solution with 95% water content. The fluores-
cence quantum yield was 0.56 in THF-H O solution with 95% of
O. The fluorescence spectrum of Bis-TPE at solid state was also
2
O mixture
l
2
2þ
2þ
w
w
w
2
þ
2þ
3
.4. Fluorescence titration for Cu2 and Zn
2
H
2
In order to further investigate the sensing properties of Bis-TPE
for Cu and Zn , the fluorescence titration experiments were
performed by varying the concentrations of Cu and Zn ions
0e3.0 equiv) in THF-H O (5:95) mixtures. As shown in Fig. 3a, with
the increase of the concentration of Cu , the intensities of the
investigated as shown in Fig. S6. It displayed the strong solid
fluorescence with fluorescence quantum yield of 0.63. All these
results suggested the excellent AIE fluorescence for Bis-TPE at
aggregated state. On the other hand, the fluorescence wavelength
appeared at 550-700 nm with red color, which exhibited huge red
shift than that of normal TPE derivatives (450-550 nm usually). This
phenomenon could be attributed to the favorable influence of the
conjugated electron effect of the structure of hydrazono-bridged
Bis-TPE. This characteristic is an obvious advantage for the probe
in living body, because the long wavelength emission benefits for
the deep tissue permeation, minimum self-absorption and low
2
þ
2þ
2
þ
2þ
(
2
2
þ
emission of Bis-TPE gradually decreased and the fluorescence was
almost quenched completely when 2.0 equiv Cu added. In Fig. 3b,
2
þ
2
þ
with the increasing of concentrations of Zn , the fluorescence
intensities increased gradually and the maximum fluorescence
wavelength exhibited blue shift. Based on these changes of fluo-
rescence spectra, the corresponding plot of fluorescence intensities
versus concentrations of metal ions was presented in Fig. S10. Both
Fig. S10a and S10b displayed a good linear relationship for the
systems with 0.0 to 1.0 equivalent concentrations of metal ions (as
shown in insetting part). According to the calculation formula
DL ¼ K ꢁ Sb1/S (where K ¼ 2 or 3, in this case the value ¼ 2, Sb1 is
the standard deviation of the blank solution, S is the value of the
slope of the regression line), the detection limits can be calculated
background noise, etc. Moreover, Bis-TPE in THF-H
had good fluorescence stability in 24 h under normal daylight lamp
Fig. S7). As the highest fluorescence appeared in THF-H O with
¼ 95%, this solution system was chosen for the further investi-
gation on sensing guests.
2
O with f
w
¼ 95%
(
2
f
w
3.3. The sensing abilities for metal ions
ꢂ7
2þ
ꢂ7
2þ
as DL ¼ 2.51 ꢁ 10
M
for Cu
and 4.85 ꢁ 10
M
for Zn
,
respectively. The linear relationships also indicated the 1:1 binding
As a useful probe, it is essential to achieve a selective and sen-
2
þ
2þ
stoichiometric ratios for Bis-TPE with Cu and Zn , which were
further confirmed by the Job’s plots as shown in Figure S11. It can be
sitive response to the target analytes. Therefore, the selective
response of Bis-TPE to different metal ions was investigated by UV-
vis spectra and fluorescence spectra. Figs. S8 and S9 displayed the
Fig. 1. The emission spectra of Bis-TPE in THF/H
O (1 M,
ex ¼ 360 nm).
2
O solutions with different fractions of
Fig. 2. Fluorescence spectra of Bis-TPE (1
O solution (5:95, V/V).
ex ¼ 360 nm.
mM) with different metal ions (3 mM) in THF-
H
2
m
l
H
2
l

4
S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
sensing stabilities of Bis-TPE for Cu2 and Zn were investigated at
different pH conditions. As shown in Fig. S13, Bis-TPE has good
fluorescence stability over a wide pH range of 4-10. As to Bis-TPE
þ
2þ
2
þ
with Cu , its fluorescence quenched remarkably and the good
fluorescence stabilities were observed between pH ¼ 4-10. The
2
þ
fluorescence intensities of Bis-TPE with Zn increased obviously
and exhibited wider stable ranges at pH ¼ 2-11. These data indi-
2
þ
2þ
cated that Bis-TPE had good sensing stabilities for Cu and Zn in
wide ranges of pH values, which were favorable for the practical
application on analyzing samples.
3.7. The crystal data and sensing mechanism
A single crystal of Bis-TPE for X-ray diffraction analysis was
obtained by slowly evaporating in dichloromethane. As shown in
Fig. 4, tetraphenylethylene units adopted a highly distorted
conformation. The dihedral angles between the four phenyl moi-
ꢀ
ꢀ
eties of the TPE unit and the C¼C double bond were 56.68 , 57.91 ,
ꢀ ꢀ
5
5.94 and 59.24 , respectively. The two phenyl moieties bridged
by hydrazono group were coplanar structure and the trans-struc-
ture was observed for C¼N bonds.
1
2þ
2þ
The H NMR spectra of Bis-TPE with Cu
and Zn
were
investigated as shown in Fig. 5. The protons of both OH and N¼CH
displayed obvious shifts and no split appeared, suggesting that the
two OH groups and C¼N groups were involved the sensing metal
ions equally. Fig. S14 illustrated the MS spectra of Bis-TPE with
2
þ
2þ
excess Cu and Zn , in which the 1:1 stoichiometric peaks at
8
2
þ
2þ
11.266 for Cu and 813.393 for Zn were observed and no other
stoichiometric peak was detected. These 1:1 stoichiometric ratios
were in accordance with the previous fluorescence Job’s plots in
2
þ
Fig. S11. The fluorescence changes of Bis-TPE þ Cu (1:1, 1
mM) at
ꢀ
2
5, 30, 35, 40 C were investigated and the results were shown in
Figure S15. The fluorescence increased gradually with the increase
of the temperature. These phenomena also supported the forma-
2
þ
Fig. 3. Fluorescence spectra of Bis-TPE (1
m
M) upon gradual addition of increasing
tion of Bis-TPE þ Cu
complex since the higher temperature
2þ
2þ
amounts of (a) Cu (0e3.0 equiv), (b) Zn (0e3.0 equiv). Inset: Fluorescence images
resulted in the dissociation of weakly bound complexes. Thus,
of Bis-TPE without and with Cu 2 and Zn (1
mM), respectively.
þ
2þ
1
based on the analyses of H NMR spectra and MS spectra, the
sensing mechanism of Bis-TPE for Cu and Zn was proposed as
2þ
2þ
2
þ
Figure S16. The similar spectra changes for ligands with Cu and
seen that the break points for the change of fluorescence intensities
2
þ
Zn
was also observed in other fluorescence sensor system
were 0.5, implying strongly the 1:1 binding stoichiometric ratios of
2
þ
Bis-TPE for Cu2 and Zn
þ
2þ
[60,61]. The fluorescence quenching after adding Cu could be
ascribed to the chelation-enhanced quenching (CHEQ) derived
from the ligand-to-metal charge transfer (LMCT) based on its
strong paramagnetic property. The fluorescence enhancement after
.
3.5. Interference experiments
2þ
The sensing selectivity of Bis-TPE for Cu2þ and Zn2þ were
further studied by competition experiments with other metal ions.
The results were shown in Figure S12. It can be seen that the values
adding Zn can be attributed to the chelation-enhanced fluores-
cence (CHEF) effect, which suppressed effectively the photoinduced
electron transfer (PET) process.
o
of I/I (indicating the changes of maximum fluorescence intensities
2
þ
of Bis-TPE with Cu before and after adding interfering metal ions)
were close to 1 (0.95e1.05, Figure 12a), suggesting the little influ-
ence of the competing metal ions on the sensing abilities of Bis-TPE
3.8. Off-on and allochroic-off-on responses for double detecting
of ATP
2
þ
for Cu . These values suggested that the fluorescence of Bis-TPE
It had been confirmed that ATP has excellent binding abilities of
2
þ
with Cu were almost not interfered by other ions. On the other
hand, as to Zn2 , the values of I/I
þ
were near 1 in presence of all
o
2
þ
2þ
kinds of metallic ions except Cu (I/I
o
¼ 0.068 for Cu , Figure 12b),
2
þ
implying that the fluorescence of Bis-TPE with Zn was quenched
by adding Cu2 . This phenomenon might indicate that the
þ
2
þ
complexation ability of Bis-TPE for Cu was stronger than that for
2
þ
2þ
2þ
2þ
Zn , resulting in the substitution of Zn by Cu after adding Cu
2
þ
in Bis-TPE þ Zn solution.
.6. pH influence on sensing stabilities for Cu2þ and Zn2þ
3
The sensing stabilities under different pH are important for
evaluating sensor performance in practical application. Thus, the
Fig. 4. (a) The ORTEP crystal diagram of a Bis-TPE, (b) The unit cell of Bis-TPE (see
CCDC 1910867).

S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
5
with Cu2 (2
mM) or Bis-TPE (1 mM) with Zn (2 mM) and Cu
þ
2þ
2þ
(2 mM) were prepared beforehand. Then ATP (0e3.0 equiv) was
added and the fluorescence changes were measured as shown in
Fig. 6. It could be seen that the quenched fluorescence in these two
systems were recovered gradually. The red fluorescence for system
2þ
of Bis-TPE with Cu (Fig. 6a) and the orange fluorescence for
2
þ
2þ
system of Bis-TPE with Zn and Cu (Fig. 6b) were turned on
obviously with the increase of ATP. Moreover, based on Fig. 6, the
corresponding plot of fluorescence intensities versus concentra-
tions of ATP were displayed in Figure S17. Both Figure S17a and S17b
exhibited a good linear relationship for the systems with 0.0 to 2.0
equivalent concentrations of ATP. According to the calculation for-
mula DL ¼ K ꢁ Sb1/S (where K ¼ 2 or 3, the value ¼ 2 in this case,
Sb1 is the standard deviation of the blank solution, S is the value of
the slope of the regression line), the detection limits of ATP could be
ꢂ7
2þ
counted as DL ¼ 4.23 ꢁ 10 M for system of Bis-TPE with Cu and
ꢂ7
2þ
2þ
1
.04 ꢁ 10 M for system of Bis-TPE with Zn and Cu , respec-
Fig. 5. 1H NMR spectral changes of Bis-TPE upon the addition of 1.0 equiv of Cu2þ and
tively, revealing the good application prospect for the quantitative
detection of ATP.
2
þ
Zn , respectively.
Based on the above fluorescence recovery of system of Bis-TPE
with Cu and Bis-TPE with Zn and Cu , the multiple detecting
2
þ
2þ
2þ
Cu2þ based on the multiple complexed sites [53]. Thus, the sensing
systems of Bis-TPE for Cu and Zn were applied for further
2
þ
2þ
sensing ATP. In a typical experiment, the solution of Bis-TPE (1 mM)
Fig. 7. The processes of double response for detecting ATP.
Fig. 8. Photographs of test slices with different ions under UV light (365 nm).
Fig. 9. Photographs of test slices of Bis-TPE for double detecting ATP with off-on and
allochroic-off-on response under UV light (365 nm).
Table 1
Determination of Cu2 and Zn in real samples using Bis-TPE and ICP-MS.
þ
2þ
M) with Cu2 (2
þ
mM) upon gradual
Fig. 6. (a) Fluorescence spectra of Bis-TPE (1
m
Sample
Using Bis-TPE
Using ICP-MS
addition of increasing amounts of ATP (0e3.0 equiv), (b) Fluorescence spectra of Bis-
2þ
2þ
Cu
Zn
91
86
m
m
g/L
g/L
88
88
m
m
g/L
g/L
2þ
2þ
TPE (1
m
M) with Zn (2
m
M) and Cu (2
mM) upon gradual addition of increasing
amounts of ATP (0e3.0 equiv).

6
S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
process for Cu2 , Zn and ATP could be summarized in Fig. 7. Bis-
þ
2þ
Pb , Cu , Sr , Mg , Zn , Al , Co , Ni and Ca ) were added
to the test paper. Fig. 8 showed that no obvious color change was
2þ
2þ
2þ
2þ
2þ
3þ
2þ
2þ
2þ
2
þ
TPE not only possessed the good sensing abilities for Cu and
Zn , but also had the sensing abilities for ATP through double
2
þ
þ
2þ
observed for the photographs of the test papers with Ag , Cd
,
3
þ 3þ 2þ þ þ 2þ 2þ 2þ 3þ 2þ 2þ
detecting processes with the “off-on” fluorescence for system of
Cr , Fe , Hg , K , Na , Pb , Sr , Mg , Al , Co , Ni and
2
þ
þ
2þ
2þ
Bis-TPE þ Cu and “allochroic-off-on” fluorescence for system of
Ca . But the color of the test paper with Cu was very faint and
2
2þ
2þ
Bis-TPE þ Zn þCu , respectively.
that with Zn turned into yellow. These results were in accordance
with the fluorescence experiment in solution and indicated the
good prospect for detecting Cu and Zn in practical applications.
Fig. 9 exhibited the colour changes of test slices after adding
sequentially Cu -ATP and Zn -Cu -ATP for double detecting
ATP, respectively. It can be seen that the fluorescence of Bis-TPE
was quenched by Cu and then the red fluorescence was recov-
ered by the addition of ATP. On the other hand, the red fluorescence
of Bis-TPE turned to yellow by adding Zn . This yellow fluores-
cence was further quenched by adding Cu and was lightened
2
þ
2þ
3
.9. Application in test paper and real samples
2
þ
2þ
2þ
Test strip is a convenient way to evaluate the real application
prospect for sensor. Therefore, the test paper of Bis-TPE was pre-
pared by immersing the neutral filter paper in a 0.1 mM solution of
Bis-TPE for 2 min. Then the dried filter paper was obtained by
volatilization at room temperature and was further customized as
round slices. Three drops of a solution containing 0.1 mM of
2
þ
2
þ
2
þ
þ
2þ
3þ
3þ
2þ
þ
þ
again by adding ATP with strong yellow fluorescence. These results
different metal ions (none, Ag , Cd , Cr , Fe , Hg , K , Na ,
ꢂ5
Fig. 10. Confocal fluorescence images of MCF-7 cells before and after incubated with Bis-TPE (1.0 ꢁ 10 M), metallic ions and ATP. (A)e(C) MCF-7 cells with Bis-TPE; (D)e(F) MCF-
2
þ
2þ
2þ
2þ
2þ
7
cells with Bis-TPE and Zn ; (G)e(I) MCF-7 cells with Bis-TPE, Zn and Cu ; (J)e(L) MCF-7 cells with Bis-TPE, Zn , Cu and ATP. Left images were bright field images, middle
images were fluorescence images, and right images were the merged images of fluorescence and bright field. (
K).
lex ¼ 405 nm). The same scale bar for all images (as shown for image

S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
7
also supported that Bis-TPE possesses excellent off-on and
on fluorescence response.
allochroic-off-on fluorescence response for double detecting ATP in
practical applications. On the other hand, the practical applications
Acknowledgment
of detecting Cu2 and Zn were also investigated (ATP detection in
practical samples was not performed because there is no ideal
method available on hand for detecting ATP in controlled trials).
þ
2þ
Financial support from the National Natural Science Foundation
of China (No: 21406036), Fujian Science and Technology Project
(No. 2019N0010), Fuzhou science and technology project (2018-G-
44), and Undergraduate innovation program of FJNU (2019) were
greatly acknowledged.
Some Cu2 and Zn were added in real water sample of Minjiang
River. Then these samples were analyzed by the fluorescence
method of this work and ICP-MS, respectively. The results were
summarized in Table 1. The obtained data of these two methods
were almost identical with a deviation of less than 3%, suggesting
again the potential of Bis-TPE for detecting practical samples.
þ
2þ
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.saa.2019.117568.
3.10. Application in living cell imaging
Recently, the fluorescent probe exhibited the broad application
References
prospects for living cell imaging. Therefore, the sensing abilities of
2
þ
2þ
Bis-TPE were used for the detecting Zn , Cu and ATP in living
biologic cells by confocal laser scanning microscopy (CLSM). Usu-
ally, the AIE-active polymeric nanoparticles were used in biological
imaging to avoiding organic solvents [62-70]. In this work, DMSO/
[1] E.K. Feuster, T.E. Glass, Detection of amines and unprotected amino acids in
aqueous conditions by formation of highly fluorescent iminium ions, J. Am.
Chem. Soc. 125 (2003) 16174e16175.
[
2] Y. Takagai, Y. Nojiri, T. Takase, W.L. Hinze, M. Butsugan, S. Igarashi, Turn-on’’
fluorescent polymeric microparticle sensors for the determination of
ammonia and amines in the vapor state, Analyst 135 (2010) 1417e1425.
3] A.R. Longstreet, M. Jo, R.R. Chandler, K. Hanson, N. Zhan, J.J. Hrudka,
H. Mattoussi, M. Shatruk, D.T. Mcquade, Ylidenemalononitrile enamines as
fluorescent "turn-on" indicators for primary amines, J. Am. Chem. Soc. 136
(2014) 15493e15496.
2
H O system was chosen as solution due to the low toxicity of DMSO
[
and good solubility of DMSO for Bis-TPE. According to the pub-
lished method of metabolic activity with MTT assay, Bis-TPE dis-
played low biotoxicity with above 82% of the alive MCF-7 cell at
ꢂ5
ꢀ
[4] L. Dong, C. Deng, C. He, L. Shi, Y. Fu, D. Zhu, H. Cao, Q. He, J. Cheng, Highly
sensitive vapor detection of amines with fluorescent conjugated polymer: a
novel lasing turn-on sensory mechanism, Sens. Actuators, B 180 (2013) 28e34.
[5] M. Venkateswarulu, P. Gaur, R.R. Koner, Sensitive molecular optical material
for signaling primary amine vapors, Sens. Actuators, B 210 (2015) 144e148.
concentration of 1.0 ꢁ 10 M for 24 h at 37 C (Figure S18). Then,
Bis-TPE was tracked in MCF-7 cells by incubation for 1 h. A red
fluorescence was seen in the cells (Fig. 10 B), indicating the good
living cell imaging performance of Bis-TPE. With the addition of
[
6] P.L. McGrier, K.M. Solntsev, S. Miao, L.M. Tolbert, O.R. Miranda, V.M. Rotello,
U.H.F. Bunz, Hydroxycruciforms: amine-responsive fluorophores, Chem. Eur J.
14 (2018) 4503e4510.
2
þ
Zn in Bis-TPE-MCF-7 system, the red fluorescence changed to
2þ
bright yellow, and was then quenched by adding Cu . After further
adding ATP, the yellow fluorescence was recovered again (Fig. 10).
Also, the red fluorescence in the cells with Bis-TPE was quenched
[
7] M.T. Salazar, T.K. Smith, A. Harris, High-performance liquid chromatographic
method for determination of biogenic amines in feedstuffs, complete feeds,
and animal tissues, J. Agric. Food Chem. 48 (2000) 1708e1712.
by adding Cu2 and recovered by further adding ATP (The fluo-
rescence images were similar with Fig. 10H and B). All these
experimental results suggested that Bis-TPE not only could sense
þ
[8] Y. Zhang, C. Peng, X. Ma, Y. Che, J. Zhao, Fluorescent and photoconductive
nanoribbons as a dual-mode sensor for selective discrimination of alkyl
amines versus aromatic amines, Chem. Commun. 51 (2015) 15004e15007.
[
9] R. Lincoln, L.E. Greene, W. Zhang, Louisia, G. Cosa, Mitochondria alkylation and
cellular trafficking mapped with a lipophilic BODIPY-acrolein fluorogenic
probe, J. Am. Chem. Soc. 139 (2017), 16273-12261.
the Cu2 and Zn in living cell system with obviously fluorescence
þ
2þ
changes, but also possessed the ability of double detecting ATP in
2þ
[10] J. Shie, Y. Liu, Y. Lee, C. Lim, J. Fang, C. Wong, An azido-BODIPY probe for
glycosylation: initiation of strong fluorescence upon triazole formation, J. Am.
Chem. Soc. 136 (2014) 9953e9961.
[11] G. Sivaraman, M. Iniya, T. Anand, N.G. Kotla, O. Sunnapu, S. Singaravadivel,
A. Gulyani, D. Chellappa, Chemically diverse small molecule fluorescent che-
mosensors for copper ion, Coord. Chem. Rev. 357 (2018) 50e104.
living cells by sequentially adding Cu -ATP with off-on red fluo-
2þ
2þ
rescence response and sequentially adding Zn -Cu -ATP with
allochroic-off-on red-yellow fluorescence response, respectively.
This kind of double detecting ATP based on organic sensor was
observed for the first time, which was obviously better than the
mode of single fluorescence response and might bring the more
extensive application prospects.
[12] J. Rosenthal, S.J. Lippard, Direct detection of nitroxyl in aqueous solution using
a
tripodal copper(II) BODIPY complex, J. Am. Chem. Soc. 132 (2010)
5536e5537.
[
13] X. Zhao, C. Ji, L. Ma, Z. Wu, W. Cheng, M. Yin, An aggregation-Induced emis-
sion-based “turn-on” fluorescent probe for facile detection of gaseous form-
aldehyde, ACS Sens. 3 (2018) 2112e2117.
4
. Conclusion
[
14] A. JI, Y. Fan, W. Ren, S. Zhang, H.W. Ai, A sensitive near-infrared fluorescent
sensor for mitochondrial hydrogen sulfide, ACS Sens. 3 (2018) 992e997.
15] J. Luo, Z. Xie, J.W. Lam, L. Cheng, H. Chen, C. Qiu, H.S. Kwok, X. Zhan, Y. Liu,
D. Zhu, B.Z. Tang, Aggregation-induced emission of 1-methyl-1,2,3,4,5-
pentaphenylsilole, Chem. Commun. 14 (2001) 1740e1743.
In summary, this paper prepared a hydrazono-bridged bis-tet-
[
raphenylethylene (Bis-TPE) in 82% yield with simple procedure.
Bis-TPE exhibited good AIE fluorescence at 550-700 nm based on
the large conjugated electron effect. It possessed outstanding se-
[
[
16] X. Yu, H. Chen, X. Shi, P. Albouy, J. Guo, J. Hu, M. Li, Liquid crystal gelators with
photo-responsive and AIE properties, Mater. Chem. Front
2245e2249.
17] S. Jiang, J. Qiu, Y. Chen, H. Guo, F. Yang, Luminescent columnar liquid crystals
based on AIE tetraphenylethylene with hydrazone groups bearing multiple
alkyl chains, Dyes Pigm 159 (2018) 533e541.
2 (2018)
2
þ
lective sensing abilities for Cu by strong fluorescence quenching
and for Zn2 by blue shift of fluorescence wavelength among 16
kinds of tested metal ions. Furthermore, the strong red fluorescence
þ
2
þ
in Bis-TPE þ Cu system could be recovered by adding ATP. On the
[18] L. Lin, H. Guo, X. Fang, F. Yang, Novel AIE columnar liquid crystals: the in-
fluence of the number of diphenylacrylonitrile groups on the mesomorphic
and fluorescence properties, RSC Adv. 7 (2017) 20172e20176.
2
þ
other hand, the orange fluorescence of Bis-TPE þ Zn system
2þ
could be quenched by Cu and then was recovered again by adding
ATP. These results suggested that Bis-TPE possessed the double
detecting abilities of ATP with the off-on red fluorescence for sys-
[
19] H. Guo, L. Lin, J. Qiu, F. Yang, Phenylacrylonitrile-bridging triphenylene di-
mers: the columnar liquid crystals with high fluorescence in both solid state
and solution, RSC Adv. 7 (2017) 53316e53319.
2þ
[20] H. Nie, B. Chen, J. Zeng, Y. Xiong, Z. Zhao, B. Tang, Excellent n-type light
emitters based on AIE-active silole derivatives for efficient simplified organic
light-emitting diodes, J. Mater. Chem. C 6 (2018) 3690e3698.
[21] W.W.H. Lee, Z. Zhao, Y. Cai, Z. Xu, Y. Yu, Y. Xiong, R.T.K. Kwok, Y. Chen,
N.L.C. Leung, D. Ma, J.W.Y. Lam, A. Qin, B. Tang, Facile access to deep red/near-
infrared emissive AIEgens for efficient non-doped OLEDs, Chem. Sci. 9 (2018)
tem of Bis-TPE þ Cu and allochroic-off-on orange fluorescence
2
þ
2þ
for Bis-TPE þ Zn þCu system. The 1:1 stoichiometric ratios of
Bis-TPE with Cu2 and Zn were confirmed by H NMR and MS
þ
2þ
1
spectra. Moreover, this sensor was also successfully used to detect
2
þ
2þ
Cu , Zn and ATP in test paper and living cell imaging, exhibiting
good double detecting for ATP based on off-on and allochroic-off-
6118e6125.
[22] H. Shi, X. Zhang, C. Gui, S. Wang, L. Fang, Z. Zhao, S. Chen, B.Z. Tang, Synthesis,

8
S. Jiang et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 227 (2020) 117568
aggregation-induced emission and electroluminescence properties of three
new phenylethylene derivatives comprising carbazole and (dimesitylboranyl)
aggregation-induced emission micelle (AIE micelle) as interfacial fluorescence
probe for sequential recognition of Cu2 and ATP in water, Sens. Actuators, B
þ
phenyl groups, J. Mater. Chem. C 5 (2017) 11741e11750.
255 (2018) 440e447.
[
[
[
23] D.D. La, S.V. Bhosale, L.A. Jones, S.V. Bhosale, Tetraphenylethylene-based AIE-
active probes for sensing applications, ACS Appl. Mater. Interf. 10 (2018)
[51] L.C. Mao, Y.Z. Liu, S.J. Yang, Y.X. Li, X.Y. Zhang, Y. Wei, Recent advances and
progress of fluorescent bio-/chemosensors based on aggregation-induced
emission molecules, Dyes. Pigm. 162 (2019) 611e623.
12189e12216.
24] J. Jiang, J. Qiu, L. Lin, H. Guo, F. Yang, Circularly polarized luminescence based
on columnar self-assembly of tetraphenylethylene with multiple cholesterol
units, Dyes Pigm 163 (2019) 363e370.
25] A. Chatterjee, M. Banerjee, D.G. Khandare, R.U. Gawas, S.C. Mascarenhas,
A. Ganguly, R. Gupta, H. Joshi, Aggregation-induced emission-based chemo-
dosimeter approach for selective sensing and imaging of Hg(II) and methyl-
mercury species, Anal. Chem. 89 (2017) 12698e12704.
[52] M. Pannipara, A.G. Al-Sehemi, A. Irfan, M. Assiri, A. Kalam, Y.S. Al-Sehemi, AIE
2þ
2þ
active multianalyte fluorescent probe for the detection of Cu , Ni , and
Hg ions, Spectrochim. Acta. A 201 (2018) 54e60.
2
þ
[53] Z.H. Xu, Y. Wang, Y. Wang, J.Y. Li, W.F. Luo, W.N. Wu, Y.C. Fan, AIE active
3
þ
salicylaldehyde-based hydrazone: a novel single-molecule multianalyte (Al
or Cu2
146e154.
[54] H.Y. Huang, D.Z. Xu, M.Y. Liu, R.M. Jiang, L.C. Mao, Q. Huang, Q. Wan, Y.Q. Wen,
X.Y. Zhang, Y. Wei, Direct encapsulation of AIE-active dye with -cyclodextrin
þ
)
sensor in different solvents, Spectrochim. Acta. A 212 (2019)
[
26] F. Hu, D. Mao, X. Cai, W. Wu, D. Kong, B. Liu, A light-up probe with
aggregation-induced emission for real-time bio-orthogonal tumor labeling
and image-guided photodynamic therapy, Angew. Chem. Int. Ed. 57 (2018)
b
terminated polymers: self-assembly and biological imaging, Mat. Sci. Eng. C-
Mater. 78 (2017) 862e867.
10182e10184.
[
27] J. Qiu, Y. Chen, S. Jiang, H. Guo, F. Yang, A fluorescent sensor based on
aggregation-induced emission: highly sensitive detection of hydrazine and its
application in living cell imaging, Analyst 143 (2018) 4298e4305.
[55] J.W. Tian, R.M. Jiang, P. Gao, D.Z. Xu, L.C. Mao, G.J. Zeng, M.Y. Liu, F.J. Deng,
X.Y. Zhang, Y. Wei, Synthesis and cell imaging applications of amphiphilic AIE-
active poly(amino acid)s, Mat. Sci. Eng. C-Mater. 79 (2017) 563e569.
[56] L. Lan, Q. Niu, Z. Guo, H. Liu, T. Li, Highly sensitive and fast responsive "turn-
[
28] J. Qiu, Y. Chen, S. Jiang, H. Guo, F. Yang, An AIE and FRET-based BODIPY sensor
2
-
3þ
2þ
with large Stoke shift: novel pH probe exhibiting application in CO
3
detection
on" fluorescent sensor for selectively sensing Fe and Hg in aqueous media
based on an oligothiophene derivative and its application in real water
samples, Sens. Actuators, B 244 (2017) 500e508.
and living cell imaging, Dyes Pigm 157 (2018) 351e358.
[
[
29] J. Mei, Y. Huang, H. Tian, Progress and trends in AIE-based bioprobes: a brief
overview, ACS Appl. Mater. Interf. 10 (2018) 12217e12261.
30] M. Kang, X. Gu, R.T.K. Kwok, C.W.T. Leung, J.W.Y. Lam, F. Li, B.Z. Tang, A near-
infrared AIEgen for specific imaging of lipid droplets, Chem. Commun. 52
[57] Y. Li, Y. Liu, H. Zhou, W. Chen, J. Mei, J. Su, Ratiometric Hg2 /Ag Probes with
orange red-white-blue fluorescence response constructed by integrating
vibration-induced emission with an aggregation-induced emission motif,
Chem. Eur J. 23 (2017), 9280-0287.
þ
þ
(
2016) 5957e5960.
[
31] M. Donnier-Mar eꢀ chal, S. Abdullayev, M. Bauduin, Y. Pascal, M. Fu, X. He,
E. Gillon, A. Imberty, E. Kipnis, R. Dessein, S. Vida, Tetraphenylethylene-based
glycoclusters with aggregation-induced emission ( AIE) properties as high-
affinity ligands of bacterial lectins, Org. Biomol. Chem. 16 (2018) 8804e8809.
32] R.T.K. Kwok, C.W.T. Leung, J.W.Y. Lam, B.Z. Tang, Biosensing by luminogens
with aggregation-induced emission characteristics, Chem. Soc. Rev. 4 (2015)
[58] J.L. Vinkenborg, S.M.J. Van, Duijnhoven, M. Merkx, Reengineering of a fluo-
rescent zinc sensor protein yields the first genetically encoded cadmium
probe, Chem. Commun. 47 (2011) 11879e11881.
[59] W.Z. Yuan, Z.Q. Yu, P. Lu, C. Deng, J.W.Y. Lam, Z. Wang, E.Q. Chen, Y. Ma,
B.Z. Tang, High efficiency luminescent liquid crystal: aggregation-induced
emission strategy and biaxially oriented mesomorphic structure, J. Mater.
Chem. 22 (2012) 3323e3326.
[60] Q. Niu, T. Sun, T. Li, Z. Guo, H. Pang, Highly sensitive and selective colori-
metric/fluorescent probe with aggregation induced emission characteristics
for multiple targets of copper, zinc and cyanide ions sensing and its practical
[
[
4228e4238.
33] W. Wu, D. Mao, F. Hu, S. Xu, C. Chen, C.J. Zhang, X. Cheng, Y. Yuan, D. Ding,
D. Kong, B. Liu, A highly efficient and photostable photosensitizer with near-
infrared aggregation-induced emission for image-guided photodynamic
anticancer therapy, Adv. Mater. 29 (2017) 1700548.
application in water and food samples, Sens. Actuators,
B 266 (2018)
[
[
[
34] F.R. Siegel, Environmental Geochemistry of Potentially Toxic Metals, Springer,
Berlin Heidelberg, Berlin, 2002.
730e743.
[61] S. Goswami, S. Paul, A. Manna, A differentially selective chemosensor for
aratiometric response to Zn2 and Al in aqueous media with applications
þ
3þ
35] P.A. Kobielska, A.J. Howarth, O.K. Farha, S. Nayak, Metal-organic frameworks
for heavy metal removal from water, Coord. Chem. Rev. 358 (2018) 92e107.
36] A. Navas-Acien, E. Selvin, A.R. Sharrett, E. Calderon-Aranda, E. Silbergeld,
E. Guallar, Lead, cadmium, smoking, and increased risk of peripheral arterial
disease, Circulation 109 (2014) 3196e3201.
formolecular switches, RSC Adv. 3 (2013) 25079e25085.
[62] X.Y. Zhang, K. Wang, M.Y. Liu, X.Y. Zhang, L. Tao, Y.W. Chen, Y. Wei, Polymeric
AIE-based nanoprobes for biomedical applications: recent advances and
perspectives, Nanoscale 27 (2015) 11486e11508.
[
37] D. Mozaffarian, P. Shi, J.S. Morris, D. Spiegelman, P. Grandjean, D.S. Siscovick,
W.C. Willett, E.B. Rimm, Mercury exposure and risk of cardiovascular disease
in two U.S. cohorts, N. Engl. J. Med. 364 (2011) 1116e1125.
[63] Q. Wan, Q. Huang, M.Y. Liu, D.Z. Xu, H.Y. Huang, X.Y. Zhang, Y. Wei, Aggre-
gation-induced emission active luminescent polymeric nanoparticles: non-
covalent fabrication methodologies and biomedical applications, Appl.
Mater. Today 06 (2017) 145e160.
[64] Z. Long, M.Y. Liu, R.M. Jiang, Q. Wan, L.C. Mao, Y.Q. Wan, F.J. Deng, X.Y. Zhang,
Y. Wei, Preparation of water soluble and biocompatible AIE-active fluorescent
organic nanoparticles via multicomponent reaction and their biological im-
aging capability, Chem. Eng. J. 308 (2017) 527e534.
[65] Z. Long, M.Y. Liu, Q. Wan, L.C. Mao, H.Y. Huang, G.J. Zeng, Y.Q. Wan, F.J. Deng,
X.Y. Zhang, Y. Wei, Ultrafast preparation of AIE-active fluorescent organic
nanoparticles via a “one-pot” microwave-assisted KabachnikeFields reaction,
Polym. Chem-UK 37 (2016) 5644e5654.
[66] Z. Long, M. Liu, K. Wang, F.J. Deng, D.H. Xu, L.J. Liu, Y.Q. Wan, X.Y. Zhang,
Y. Wei, Facile synthesis of AIE-active amphiphilic polymers: self-assembly
and biological imaging applications, Mat. Sci. Eng. C-Mater. 66 (2016)
215e220.
[67] L. Huang, S.J. Yang, J.Y. Chen, J.W. Tian, Q. Huang, H.Y. Huang, Y.Q. Wen,
F.J. Deng, X.Y. Zhang, Y. Wei, A facile surface modification strategy for fabri-
cation of fluorescent silica nanoparticles with the aggregation-induced
emission dye through surface-initiated cationic ring opening polymeriza-
tion, Mat. Sci. Eng. C-Mater. 94 (2018) 270e278.
[68] R. Jiang, M.Y. Liu, H.Y. Huang, L.C. Mao, Q. Huang, Y.Q. Wen, Q.Y. Cao, J.W. Tian,
X.Y. Zhang, Y. Wei, Facile fabrication of organic dyed polymer nanoparticles
with aggregation-induced emission using an ultrasound-assisted multicom-
ponent reaction and their biological imaging, J. Colloid Interface Sci. 519
(2018) 137e144.
[69] H. Huang, M.Y. Liu, R.M. Jiang, J.Y. Chen, L.C. Mao, Y.Q. Wen, J.W. Tian,
N.G. Zhou, x. y. Zhang, Y. Wei, Facile modification of nanodiamonds with
hyperbranched polymers based on supramolecular chemistry and their po-
tential for drug delivery, J. Colloid Interface Sci. 513 (2017) 198e204.
[70] X.Y. Zhang, X.Q. Zhang, B. Yang, W.Y. Liu, Y.W. Chen, Y. Wei, Fabrication of
aggregation induced emission dye-based fluorescent organic nanoparticles
via emulsion polymerization and their cell imaging applications, Polym.
Chem-UK 5 (2013) 399e404.
[
[
[
38] T.W. Clarkson, L. Magos, G.J. Myers, The toxicology of mercury - current ex-
posures and clinical manifestations, N. Engl. J. Med. 349 (2003) 1731e1737.
39] B.J. Grattan, H.C. Freake, Zinc and cancer: implications for LIV-1 in breast
cancer, Nutrients 4 (2012) 648e675.
40] P. Huang, L. Feng, E.A. Oldham, M.J. Keating, W. Plunkett, Superoxide dis-
mutase as a target for the selective killing of cancer cells, Nature 407 (2000)
390e395.
[
[
[
41] S.L. Sensi, P. Paoletti, A.I. Bush, I. Sekler, Zinc in the physiology and pathology
of the CNS, Nat. Rev. Neurosci. 10 (2009) 780e791.
42] M.D. Pluth, E. Tomat, S.J. Lippard, Biochemistry of mobile zinc and nitric oxide
revealed by fluorescent sensors, Annu. Rev. Biochem. 80 (2011) 333e355.
43] E.M. Farr eꢀ , P. Geigenberger, L. Willmitzer, R.N. Trethewey, A possible role for
pyrophosphate in the coordination of cytosolic and plastidial carbon meta-
bolism within the potato tuber, Plant Physiol. 123 (2000) 681e688.
44] Y. Chen, R. Corriden, Y. Inoue, L. Yip, N. Hashiguchi, A. Zinkernagel, V. Nizet,
P.A. Insel, W.G. Junger, ATP release guides neutrophil chemotaxis via P2Y2 and
A3 receptors, Science 314 (2006) 1792e1795.
[
[
45] A.V. Gourine, E. Llaudet, N. Dale, K.M. Spyer, ATP is a mediator of chemo-
sensory transduction in the central nervous system, Nature 436 (2005)
108e111.
[
46] S. Farshbaf, P. Anzenbacher Jr., Fluorimetric sensing of ATP in water by an
imidazolium hydrazone based sensor, Chem. Commun. 55 (2019) 1770e1773.
47] X. Jin, X. Wu, B. Wang, P. Xie, Y. He, H. Zhou, B. Yan, J. Yang, W. Chen, X. Zhang,
[
2þ
A reversible fluorescent probe for Zn and ATP in living cells and in vivo,
Sens. Actuators, B 261 (2018) 127e134.
[
[
[
48] Y. Liu, D. Lee, D. Wu, K.M.K. Swamy, J. Yoon, A new kind of rhodamine-based
fluorescence turn-on probe for monitoring ATP in mitochondria, Sens. Actu-
ators, B 265 (2018) 429e434.
49] L.Y. Geng, Y. Zhao, E. Kamya, J.T. Guo, B. Sun, Y.K. Feng, M.F. Zhu, X.K. Ren,
2þ
Turn-off/on fluorescent sensors for Cu and ATP in aqueous solution based
on a tetraphenylethylen derivative, J. Mater. Chem. C 7 (2019) 2640e2645.
50] A.X. Ding, Y.D. Shi, K.X. Zhang, W. Sun, Z.L. Tan, Z.L. Lu, L. He, Self-assembled