Highly selective Fe3+ and F?/H2PO4 ? sensor based on a water-soluble cationic pillar[5]arene with aggregation-induced emission characteristic

Article abstract of DOI:10.1016/j.saa.2019.117215

A water-soluble cationic pillar[5]arene (CWP5)without lager conjugated construction was first reported as a novel pillar[5]arene-based aggregation-induced emission luminogen (AIEgen), which showed a remarkable aggregation-induced emission (AIE)with the co

Full text of DOI:10.1016/j.saa.2019.117215

Accepted Manuscript
Highly selective Fe3+ and F−/H2PO4− sensor based on a water-
soluble cationic pillar[5]arene with aggregation-induced emission
characteristic
Hong Yao, Qi Zhou, Jiao Wang, Yan-Yan Chen, Xiao-Tong Kan,
Tai-Bao Wei, You-Ming Zhang, Qi Lin
PII:
S1386-1425(19)30605-5
DOI:
https://doi.org/10.1016/j.saa.2019.117215
Article
Number:
Reference:
117215
SAA 117215
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
To appear in:
Received date:
Revised date:
Accepted date:
13 December 2018
25 April 2019
26 May 2019
Please cite this article as: H. Yao, Q. Zhou, J. Wang, et al., Highly selective Fe3+ and
F−/H2PO4− sensor based on a water-soluble cationic pillar[5]arene with aggregation-
induced emission characteristic, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy, https://doi.org/10.1016/j.saa.2019.117215
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ACCEPTED MANUSCRIPT
-
Highly Selective Fe3+ and F-/H2PO4 Sensor Based on a
Water-soluble Cationic Pillar[5]arene with Aggregation-Induced
Emission Characteristic
Hong Yao*, Qi Zhou, Jiao Wang, Yan-Yan Chen, Xiao-Tong Kan, Tai-Bao Wei*,
You-Ming Zhang, and Qi Lin*
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of
China, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and
Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, PR China
--------------------------------------------------------------------------------------
E-mail: yhxbz@126.com; weitaibao@126.com; linqi2004@126.com.
--------------------------------------------------------------------------------------
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Abstract:
A water-soluble cationic pillar[5]arene (CWP5) without lager conjugated
construction was first reported as a novel pillar[5]arene-based aggregation-induced
emission luminogen (AIEgen), which showed a remarkable aggregation-induced
emission (AIE) with the concentration increasing. The AIE effect of CWP5 has
affected by different solvent, it had the lowest critical aggregation concentration
(CAC) value and highest fluoresence emission intensity in DMSO solution.
Simultaneously, CWP5 can serve as a chemosensor for the successively fluorescent
-
detection of Fe3+ and F-/H2PO4 with high sensitivity and selectivity. A rewritable
portable test kit made from CWP5 provides a possibility to on-site detection and
manufacture of encryption and decryption materials.
Keywords:
chemosensor; AIEgens; self-assembly; ion detection; portable test kit; encryption and
decryption materials
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1. Introduction
Fluorescent sensors with aggregation-induced emission (AIE) attributes have
attracting much attention since the concept of AIE was first proposed [1-2]. AIE is a
phenomenon that AIE luminogens (AIEgens) are weakly or even non-emission when
the luminogens are molecularly dispersed in solvent, but exhibit a robust
augmentation of fluorescent emission in aggregates [3-5] as a result of restriction of
intramolecular motions and relax through radiative pathways [6-7]. AIE-based sensors
for ions [8], organic volatiles [9], toxic gases [10], small molecules [11], biological
molecules [12] and so forth have experienced rapid development by virtue of its fast
responsiveness, superb sensitivity and simple operation [13]. Despite a variety of
AIEgens have been reported, such as derivatives of tetraphenylethene (TPE) [14],
tetraphenylpyrazine (TPP) [15], silole [16], arylbenzene [17-18], pyrrole [19] and
some metal complexes [20], which usually consist of lager conjugated structure.
There are still enthusiastic interest of scientists worldwide in exploring novel sensors
with remarkable AIE feature in recent years.
Pillar[n]arenes, as a new class of macrocyclic host compounds, have received
extensive attention. They exhibit intriguing and peculiar properties in fluorescent
supramolecular aggregates [21-22], host-guest recognition [23-24] and biological
applications [25] due to their rigid and symmetrical architecture, facile modification
and existence of multiple self-assembly driving forces: hydrophobic/hydrophilic
interactions, π···π interactions, C-H···π interactions, cation···π interactions, and
H-bond etc [26-27]. These merits may endow pillar[n]arenes with AIE properties
through construction of supramolecular systems. Common construction strategies of
pillar[n]arenes-based AIEgens are on one hand introducing conventional AIEgens,
such as TPE, into pillar[n]arenes structure by modifying the benzene rings on
pillar[n]arenes [28-29], on the other hand utilizing TPE as guest molecules to
assemble with pillar[n]arene [30-31]. Even though pillar[n]arenes possessing AIE
properties without conventional AIEgens have been rarely reported. Our research
group has reported a novel bispillar[5]arene with AIE attribute which can further used
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to mercury (Ⅱ) detection [32], but development of simple pillar[5]-based AIEgens is
still an urgent and important task.
Detection of biologically essential or environmentally related ions is important in
biological study and environment inspection [33]. For example, iron ion (Fe3+) as one
of the most essential trace elements has an important role in biological processes, e.g.,
oxygen transport, DNA synthesis and the growth of biological cells. But the extra of
iron ion will cause vomiting, diarrhea and damage to the intestine, even more
seriously leading Parkinson's and Alzheimer's [34]. Moreover, small amounts of
fluoride (F-) intake may be beneficial for bone strength and prevent dental caries,
while excess fluoride may cause kidney failure, skeletal fluorosis, even death [35].
-
H2PO4 as a central component of nucleic acids (DNA and RNA) plays a crucial role
in life system. Meanwhile phosphate fertilizers are frequently used in agriculture and
drug-related industries [36]. Therefore, exploiting new sensors for the sensitive and
selective detection and developing convenient on-site detection of above mentioned
ions have attracted our attention for a long time.
Based on our previous research and longstanding interest in pillar[5]arene
chemistry and sensors for ions recognition, in order to develop newer AIEgen sensor,
we have designed and synthesized a simple water-soluble cationic pillar[5]arene
(CWP5) by connecting trimethylamine group with bromopillar[5]arene through
nuleophilic substitution reaction [37]. Fortunately, we have surprisingly found that
although CWP5 did not have lager conjugated construction, it exhibited
aggregation-induced emission (AIE) in aggregates with increasing of the
concentration, which suggested that CWP5 is a new kind of pillar[5]arene-based
AIEgen. Interestingly, the AIE effect of CWP5 has affected by different solvent.
Furthermore, this simple water-soluble cationic pillar[5]arene could be used as a
-
AIE-based sensor for successively fluorescence detection of Fe3+ and F-/H2PO4 .
2. Experimental section
2.1 Materials physical methods
All reagents and starting materials were obtained from commercial suppliers and
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used as received unless otherwise noted. All cations (Fe3+, Ca2+, Mg2+, Co2+, Ni2+,
Zn2+, Ba2+, Cd2+, Cu2+, Hg2+, Pb2+, Cr3+, Eu3+, Ag+, Al3+, La3+, perchlorate salts, 0.1 M,
in water) and anions (tetrabutylammonium salt of anions: F-, Cl-, Br-, I-, Ac-, OH-,
-
-
-
-
HSO4 , H2PO4 , ClO4 ; sodium azide salt of anion: N3 ; sodium salt of anion:CN-,
4-
2-
-
P2O7 , CO3 , NO3 , S2- and SCN-, 0.1 M, in water) were purchased from Alfa Aesar
and used as received.
2.2 Physical methods
Nuclear magnetic resonance (NMR) spectra were recorded on Varian Mercury
400 and Varian Inova 600 instruments. The X-ray diffraction analysis (XRD) was
performed in a transmission mode with a Rigaku RINT2000 diffractometer equipped
with graphite monochromated CuKa radiation (λ = 1.54073 Å). The morphologies of
complex were characterized using field emission scanning electron microscopy
(FE-SEM, JSM-6701F) at an accelerating voltage of 8 kV. The infrared spectra were
performed on a Digilab FTS-3000 Fourier transform-infrared spectrophotometer.
Fluorescence spectra were recorded on a Shimadzu RF–5301spectrofluorophotometer.
2.3 Synthesis of CWP5 and reference compound R.
The water-soluble cationic pillar[5]arene (CWP5) was synthesized using a
method described in our previous work [35, 37]. Meanwhile, we also synthesized
compound R as a control (Scheme S1). Moreover, the target compound were
characterized by 1H NMR, 13C NMR, and ESI-MS (Fig. S1-S3).
3. Results and Discussion
3.1 Critical Aggregation Concentration (CAC) Determination of CWP5
The fluorescence (FL) emission behaviour of CWP5 in different solvent that
include DMSO, DMF, EtOH, H2O and MeCN were examined by the fluorescence
emission spectra. As the Fig. 1a shown, CWP5 shows the relatively highest
fluorescence emission intensity in DMSO solution.
(Insert Fig. 1)
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To further investigate the impact of solvent on aggregation effect of CWP5,
concentration depended fluorescence emission spectra was used to determine the
critical aggregation concentration (CAC) of CWP5 [38] in H2O, DMSO, and EtOH
(Fig. S4). A double logarithmic plot of specific fluorescence intensity versus
concentration was obtained, presenting a fluorescence intensity transition. With the
increase of the concentration, a remarkable uprush in the fluorescence intensity was
observed, indicating that CWP5 may self-assemble into supramolecular system to
produce aggregation-induced emission (AIE). Using the increased slope, the CAC
values of CWP5 in H2O, DMSO, and EtOH were calculated as 0.20 mg/mL, 0.07
mg/mL and 0.10 mg/mL, respectively (Fig. 1b, c, d). These results demonstrated that
CWP5 have lowest CAC value in DMSO solution. In light of these, we selected
DMSO as the solvent for the next experiments due to CWP5 have highest
fluorescence emission intensity and lowest CAC value in DMSO, and the quantum
yield of the probe in DMSO was calculated to be 0.49 (Eq. S1).
Meanwhile, we also found that the reference compound R had no obvious
fluorescence emission at the same condition (Fig. S6), which revealed that the
aggregation-induced emission of CWP5 was related to the columnar structure of
pillar[5]arene.
3.2 Fluorescent response behavior of CWP5 towards cations
In order to investigate application of pillar[5]arene-based AIEgen as sensors, we
primarily investigated the sensing properties of CWP5 towards cations by adding 10
equiv. of various cations into the CWP5. Interestingly, as shown in Fig. 2, only Fe3+
could induce the fluorescence of CWP5 completely to quench, and the other tested
cations could not induce a similar response. It was also essential to explore the
selectivity of CWP5 towards Fe3+ by performing interference studies. Negligible
interference with any of the coexisting cations showed CWP5 can highly selectively
sense for Fe3+ (Fig. 3).
(Insert Fig. 2)
(Insert Fig. 3)
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To further investigated the performance of the CWP5 for Fe3+ detection, the
fluorescence emission profile of the CWP5 was monitored in the presence of
increasing concentrations of Fe3+ ions (0 - 9.5 equiv.). A completely quenching of the
fluorescence could be evidently perceived from Fig. 4. The detection limit for Fe3+
was estimated to be 7.49×10-8 M based on 3δ/S method (Fig. S8), indicating CWP5
has high sensitivity for Fe3+ than other sensing systems (Table S1). Moreover, the
association constant (Ka) of CWP5 with Fe3+ was about 1.11 × 106 M-1 and the
stoichiometry between CWP5 and Fe3+ 1:2, which was obtained from the intercept
and slope of the linear fit of fluorescence titration experiment as shown in (Fig. S9).
Simultaneously, the obtained Job’s plot (Fig. S10) also proved that CWP5 and Fe3+
exhibit a 1:2 binding mode.
(Insert Fig. 4)
3.3 Fluorescent response behavior of CWP5-Fe3+ for anions
From those above results, the AIE-active CWP5 could act as a detector for Fe3+
with high selectivity and sensitivity. Then, the recognition property of CWP5-Fe3+ for
anions has been further investigated by adding 20 equiv. various anions into
CWP5-Fe3+ solution. As a result (Fig. 5), the fluorescence of CWP5-Fe3+ turned on
-
again upon adding F- or H2PO4 into the CWP5-Fe3+. Moreover, we also carried out
-
fluorescence emission titration experiment, with an increasing amount of F- or H2PO4 ,
and found emission peak at 446 nm gradually increased (Fig. S11a, S13a). The
-
detection limit of CWP5-Fe3+ for F-/H2PO4 was 2.53 × 10-8 M and 5.04 × 10-8 M,
respectively (Fig. S11b, S13b), which was also calculated by 3δ/S method. The Job’s
-
plot between CWP5-Fe3+ and F-/H2PO4 showed 1:3 and 1:2 stoichiometry,
respectively (Fig. S12, S14). Given the above, CWP5-Fe3+ achieved high sensitivity
during successively detection for anions, and superior than most previous sensors
(Table S1).
(Insert Fig. 5)
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3.4 The possible self-assembly and recognition mechanism of CWP5
As a proof of ion detection properties of this pillar[5]arene-based AIEgen, the
self-assembly
mechanism
of
CWP5
was
first
investigated
using
concentration-dependent 1H-NMR, 2D-NOESY NMR, concentration-dependent
UV-Vis experiment, XRD and SEM. To begin with, the concentration-dependent
1H-NMR of CWP5 were carried out (Fig. S15). The resonance signals of Ha and Hb
shifted downfield and Hb became broadened. Besides, the signals of proton Hf and Hg
displayed slightly upfield shifts. Then, 2D-NOESY NMR of the CWP5 was
performed to investigate the relative spatial positions of protons. When the
concentration of CWP5 was 5 mM, there was no correlation signals observed (Fig.
S16 a). As the concentration of CWP5 increased to 80 mM, correlation signals (A, B,
C, D in Fig. 6) appeared between protons Ha, Hb and Hf, Hg. These results indicated
that the partial positively charged trimethylammonium head of CWP5 threaded into
the cavity of the other CWP5, and further self-assembled into supramolecular system,
while the intramolecular motion is restricted in the self-assembly system and an
aggregation-induced emission (AIE) was observed. To further justify the aggregation
of CWP5 was occurred, the concentration-dependent UV-Vis absorption spectra of
CWP5 was also measured. As Fig. S5 shown, a neatly linear relationship between
absorbance (A) and the concentration was obtained with a slope of 0.12 at low
concentration, which neatly fitted the beers law and manifested no obvious
aggregation between the solute molecules. However, with the concentration increased,
a remarkable change in the absorbance was observed as the slope of the curve
increased to 2.02, indicating the foramtion of CWP5 aggregates and the CAC value
reached 10-5 M. The XRD pattern of CWP5 showed peaks at 2θ = 21.98º, 25.02º,
32.72º corresponding to the d-spacing 4.04, 3.56 and 2.73 Å (Fig. S17a), which
confirmed that the exo-wall π-π stacking and C-H···π interaction existed [39].
Meanwhile, the morphological features of CWP5 were studied by SEM, showing a
curving ribbon-like structure (Fig. 7a). These above results indicated that the CWP5
self-assembled into supramolecular system and leaded to aggregation-induced
emission (AIE) at relatively high concentration.
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(Insert Fig. 6)
(Insert Fig. 7)
Then the recognition mechanism of CWP5 for Fe3+ was verified by IR
spectroscopy, XRD and SEM. Comparing the IR spectrum of CWP5-Fe3+ and CWP5
(Fig. S17b), we found that the stretching vibration absorption peaks of =C-H, C=C on
benzene ring of CWP5 were changed into the 3023, 2966 and 2926 cm-1 respectively
after addition of Fe3+ into CWP5. Besides, the vibration absorption peaks of the
C-O-C and CH2 adjacent to benzene ring of CWP5 were also obviously changed. In
addition, Fe3+ is easy to bind with the π electrons of pillar[5]arene groups through
cation-π interactions due to Fe3+ ion has odd electron and high ionic strength [40].
These results indicated that the CWP5 coordinated with Fe3+ via the cation-π
interactions [26]. Moreover, the peaks at 2θ = 21.98º, 25.02º (d = 4.04, 3.56 Å) was
disappeared after adding Fe3+ into CWP5 (Fig. S17a), which confirmed that the tight
exo-wall π-π stacking was destroyed and the aggregates of CWP5 disassembled
because Fe3+ combined with CWP5 by cation-π interaction. The SEM characterized
that the morphological of CWP5 transformed from a curving ribbon-like structure to a
short rod-like structure in the present of Fe3+ (Fig. 7), this phenomenon further proof
the above point. These above experimental phenomenon turned out that CWP5
combined with Fe3+ and generated CWP5-Fe3+ via the cation-π interactions, and
exo-wall π-π stacking between CWP5 was destroyed. The disassembly process of
CWP5 supramolecular system reduced the AIE fluorescence of CWP5 and even
-
completely quenching. As we know, both F- and H2PO4 have a strong binding ability
3-
with Fe3+ to form compounds [Fe(H2PO4)3] and [FeF6 ], respectively. In consequence,
the aggregation-induced emission (AIE) of CWP5 was recovered when the added F-/
-
H2PO4 competed Fe3+ with CWP5 and the supramolecular system of CWP5
restructured.
(Insert Scheme 1)
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3.5 Practical Application
Finally, we investigated the practical application of this novel pillararene-based
AIE sensor. As shown in Fig. 8, an untreated silica gel plate can be served as a
rewritable portable test kit, when we writing on this test kit using a writing brush
inked with DMSO solution of CWP5(1.0 mM), a significant blue handwriting can be
observed under UV lamp at 365 nm. In addition, the handwriting can be erased by
-
Fe3+ water solution (1.0 × 10-4 M) and reappeared by F-/H2PO4 aqueous solution (1.0
× 10-4 M), which is very convenient for on-site detection. The rewritable portability of
CWP5 can be used to achieve novel encryption and decryption materials.
(Insert Fig. 8)
4. Conclusion
A novel simple water-soluble cationic pillar[5]arene-based AIEgen (CWP5) was
reported, which showed aggregation-induced emission (AIE) with the increase of
concentration. The AIE principle was explained as that partial positively charged
trimethylammonium groups of CWP5 threaded into the cavity of the other CWP5
and further self-assembled into supramolecular system through exo-wall π-π stacking
and C-H···π interaction. This novel pillar[5]arene-based AIEgen can be used as
-
fluorescence sensor for sensitive and selective detection for Fe3+ and F-/H2PO4 . A
rewritable portable test kit was fabricated with CWP5 for on-site detection and
encryption and decryption technology.
Acknowledgments
This work was supported by the National Natural Science Foundation of China
(No. 21661028; 21662031; 21574104), the Program for Changjiang Scholars and
Innovative Research Team in University of Ministry of Education of China (IRT
15R56).
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List of Figures and Schemes:
Fig. 1. (a) Fluorescence emission spectra of CWP5 (1.0 mM) in various solvent. A double
logarithmic plot of fluorescence intensity versus concentration of CWP5 in (b) H2O, (c) DMSO,
and (d) EtOH (λex = 380 nm).
Fig. 2. (a) Fluorescence emission spectra of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380 nm) upon
addition of 10.0 equiv. various cations. (b) photograph showing the corresponding color changes
of CWP5 with various cations under UV lamp (365 nm).
Fig. 3. Changes in fluorescence emission spectra of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380
nm, λem = 446 nm) upon addition of 10.0 equiv. various cations (0.1 M, in water) in the presence of
10.0 equiv. Fe3+ (0.1 M, in water).
Fig. 4. Fluorescent spectrum of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380 nm) in the presence of
different concentration of Fe3+. Inset: A plot of fluorescent intensity depending on the
concentration of Fe3+ in the range from 0 to 9.5 equivalents.
Fig. 5. Fluorescent spectra of CWP5-Fe3+ (2.0 × 10-4 M, with 10 equiv. Fe3+, in DMSO at λex = 380
-
-
-
nm) in the presence of 20 equiv. various anions (F-, Cl-, Br-, I-, Ac-, OH-, HSO4 , H2PO4 , ClO4 ,
-
4-
2-
-
N3 , CN-, P2O7 , CO3 , NO3 , S2- and SCN-, 0.1 M, in water).
Fig. 6. 2D NOESY NMR spectrum (600 MHz, 298K) of 80 mM CWP5 in DMSO-d6 solution.
Fig. 7. Representative SEM images of (a) CWP5 and (b) CWP5-Fe3+ .
Fig. 8. Writing and erasing experiment on silica gel plate. The photographs were taken under UV
lamp (365 nm) at room temperature.
Scheme 1. The possible self-assembly and recognition mechanism of CWP5.
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Figures
Fig. 1 (a) Fluorescence emission spectra of CWP5 (1.0 mM) in various solvent. A double
logarithmic plot of fluorescence intensity versus concentration of CWP5 in (b) H2O, (c) DMSO,
and (d) EtOH (λex = 380 nm).
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Fig. 2 (a) Fluorescence emission spectra of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380 nm) upon
addition of 10.0 equiv. various cations. (b) photograph showing the corresponding color changes
of CWP5 with various cations under UV lamp (365 nm).
Fig. 3 Changes in fluorescence emission spectra of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380 nm,
λem = 446 nm) upon addition of 10.0 equiv. various cations (0.1 M, in water) in the presence of
10.0 equiv. Fe3+ (0.1 M, in water).
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Fig. 4 Fluorescent spectrum of CWP5 (2.0 × 10-4 M, in DMSO at λex = 380 nm) in the presence of
different concentration of Fe3+. Inset: A plot of fluorescent intensity depending on the
concentration of Fe3+ in the range from 0 to 9.5 equivalents.
Fig. 5 Fluorescent spectra of CWP5-Fe3+ (2.0 × 10-4 M, with 10 equiv. Fe3+, in DMSO at λex = 380
-
-
-
nm) in the presence of 20 equiv. various anions (F-, Cl-, Br-, I-, Ac-, OH-, HSO4 , H2PO4 , ClO4 ,
-
4-
2-
-
N3 , CN-, P2O7 , CO3 , NO3 , S2- and SCN-, 0.1 M, in water).
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Fig. 6 2D NOESY NMR spectrum (600 MHz, 298K) of 80 mM CWP5 in DMSO-d6 solution.
Fig. 7 Representative SEM images of (a) CWP5 and (b) CWP5-Fe3+ .
Fig. 8 Writing and erasing experiment on silica gel plate. The photographs were taken under UV
lamp (365 nm) at room temperature.
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Scheme 1. The possible self-assembly and recognition mechanism of CWP5.
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Graphical Abstract:
In this paper, a water-soluble cationic pillar[5]arene (CWP5) without large
conjugation construction was first reported as a new pillar[5]arene-based
aggregation-induced emission luminogen (AIEgen). CWP5 exhibited bright blue
fluorescence emission in aggregate state due to self-assembly of CWP5 driving by
exo-wall π-π stacking and C-H···π interaction. Simultaneously, CWP5 could
-
successively fluorescent detection of Fe3+ and F-/H2PO4 with high sensitivity and
selectivity. We also prepared a rewritable portable test kit using CWP5 that provides a
possibility to on-site detection and manufacture of encryption and decryption
materials.
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Research Highlights:
1 A novel water-soluble pillar[5]arene-based AIEgen (CWP5) was reported.
2 CWP5 without large conjugation construction exhibited strong AIE fluorescence.
-
3
4
5
AIE-active CWP5 could successively detect Fe3+ and F-/H2PO4 .
A portable test kit made from CWP5 could achieve convenient on-site detection.
CWP5 give a possibility for manufacture encryption and decryption materials.
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Figure 1

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Figure 4

Figure 5

Figure 6

Figure 7