Supramolecular Assembly-Induced Emission Enhancement for Efficient Mercury(II) Detection and Removal

Article abstract of DOI:10.1021/jacs.9b01546

New strategies that can simultaneously detect and remove highly toxic environmental pollutants such as heavy metal ions are still in urgent need. Herein, through supramolecular host-guest interactions, a fluorescent supramolecular polymer has been facilel

Full text of DOI:10.1021/jacs.9b01546

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Article
Supramolecular Assembly-Induced Emission Enhancement
for Efficient Mercury(II) Detection and Removal
Dihua Dai, Zheng Li, Jie Yang, Chunyu Wang, Jia-Rui Wu, Yan Wang, Dongmei Zhang, and Ying-Wei Yang
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 26 Feb 2019
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Supramolecular Assembly-Induced Emission Enhancement for
Efficient Mercury(II) Detection and Removal
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Dihua Dai,† Zheng Li,† Jie Yang,† Chunyu Wang,§ Jia-Rui Wu,† Yan Wang,† Dongmei Zhang,¶
and Ying-Wei Yang†,‡,*
†State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, International Joint
Research Laboratory of Nano-Micro Architecture Chemistry (NMAC), College of Chemistry,
Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China
‡California NanoSystems Institute and Departments of Chemistry & Biochemistry, University of
California, Los Angeles, California 90095, United States
§State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical
Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China
¶School of Environment, Northeast Normal University, Changchun 130117, P. R. China
KEYWORDS: aggregation-induced emission; sensing; nanoparticles; pillar[n]arenes;
supramolecular polymer
ABSTRACT: New strategies that can simultaneously detect and remove highly toxic
environmental pollutants such as heavy metal ions are still in urgent need. Herein, through
supramolecular host-guest interactions, a fluorescent supramolecular polymer has been facilely
constructed from a newly designed [2]biphenyl-extended pillar[6]arene equipped with two
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thymine sites as arms (H) and a tetraphenylethylene (TPE)-bridged bis(quaternary ammonium)
guest (G) with aggregation-induced emission (AIE) property. Interestingly, supramolecular
assembly-induced emission enhancement (SAIEE) could be switched on upon addition of Hg2+
into the abovementioned supramolecular polymer system to generate spherical-like
supramolecular nanoparticles, owing to the restriction of intramolecular rotation (RIR)-related AIE
feature of G. Significantly, this supramolecular polymer with integrated modalities has been
successfully used for real-time detection and removal of toxic heavy metal Hg2+ ions from water
with quick response, high selectivity, and rapid adsorption rates, which could be efficiently
regenerated and recycled without any loss via a simple treatment with Na2S. The newly developed
supramolecular polymer system combines the inherent rigid and spacious cavity of novel
extended-pillarene host with the AIE characteristics of TPE-based guest, suggesting a great
potential in the treatment of heavy metal pollution and environmental sustainability.
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INTRODUCTION
Water pollution arising from heavy metal ions continues to be one of the major problems of
environmental concerns, which represents a serious threat to human beings and animals
worldwide.1, 2 Among those heavy metal ions, mercury(II) is considered as one of the most harmful
pollutants due to its severe damage to kidney function, immune system, and central nervous
system.3-6 The development of integrative strategy in real-time sensing and rapid removal of
mercury ions is of great importance in materials chemistry, chemical engineering, and
environmental science. Design and synthesis of effective and economical materials to adsorb and
remove mercury ion has attracted numerous attention over the past decades. Notably, a range of
porous materials, which include porous silicas,7 porous organic polymers (POPs),8,9 covalent
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organic frameworks (COFs),10,11 conjugated microporous polymers,12 conjugated macrocycle
polymers,13 porous aromatic frameworks,14 and metal organic frameworks (MOFs),15,16 have been
successfully applied in the adsorption of heavy metal ions by virtue of their considerable porous
nature. Until mercury emissions can be greatly reduced, it is imperative to develop new modern
technologies to decrease and detect the mercury found in the atmosphere and industrial wastewater
run-off to offer enhanced protection to the planet and livings.
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On the other hand, one appealing feature of supramolecular chemistry lies in its excellent ability
in organizing diversified components together for the construction of dynamic and reversible
hybrid materials.17-19 Based on the fascinating directional non-covalent interactions,
supramolecular polymers with advanced architectures and attractive stimuli-responsive properties
have drawn much attention in the fabrication of smart functional materials for applications in
sensing and detection, biomedicine, and organic photoelectronic devices.20-26 Taking advantage of
a wide range of driving forces and upon careful selection of fluorescent building blocks, tailorable
supramolecular polymers with desirable morphologies, optical properties, and unique functions
could be designed and constructed through noncovalent interactions including the special host-
guest inclusion complexation between supramolecular macrocycles and their guests.27-29
Supramolecular host compounds including crown ethers,30 cyclodextrins,31 cucurbit[n]urils,32
calix[n]arenes,28, 33, 34 pillar[n]arenes,35-43 and beyond,44, 45 have been employed as characteristic
building blocks for the construction of multifunctional supramolecular polymeric materials.46-51 In
2016, we reported a new type of macrocyclic arenes, namely [2]biphenyl-extended pillar[6]arene
(BpP6),52 which possesses a larger cavity and less crowded substituents on the ring backbone as
compared with traditional pillar[6]arene, endowing it with favorable binding selectivity towards
petrochemicals such as xylene and toluene in the solid single crystals. More recently, we
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synthesized the first water-soluble derivative of BpP6 as a very promising detection and separation
agent for naphthalene sulfonate substrates in water.53 Along with the abovementioned studies, we
would like to selectively tailor the portals of BpP6 with powerful functionalities for in-depth study
on their structural diversity and expand their versatile applications by precision fabrication.
Although the utilization of fluorescent supramolecular polymers based on macrocyclic arenes in
the detection and removal of heavy metal ions especially mercury in wastewaters still remains
challenging,50 we envision that, by a rationale design of proper supramolecular polymer systems
that are capable of selectively sequestering and detecting mercury(II) simultaneously with the aid
of synthetic macrocyclic arene chemistry, we could satisfy the different demands and complicated
requirements in the control of mercury pollution, hopefully with much lower detection limit,
quicker response, and better anti-interference ability.
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Inspired by the discovery of tight covalent bonds between thymine (T) and mercury ion (T-
Hg2+-T bonds) by Ono in 2006,54 and the recent employment of T-Hg2+-T pairing for ion detection
and molecular sensing in DNA,55, 56 herein, we design and synthesize a new BpP6 derivative
bearing two thymine binding sites as flexible arms (H), followed by supramolecular assembly with
a tetraphenylethylene (TPE)-bridged bis(quaternary ammonium) guest (G) capable of
aggregation-induced emission (AIE)57 to give a fluorescent linear supramolecular polymer (G⊂H,
Figure 1). Upon addition of Hg2+, this supramolecular polymer could eventually self-assemble
into spherical nanoparticles through the formation of supramolecular network induced by the T-
Hg2+-T pairing between Hg2+ ions and the arms of H, which exhibit strong AIE fluorescence
attributing to supramolecular-assembly induced emission enhancement (SAIEE).47, 58-62 Therefore,
a simple supramolecular assembled module strategy has been utilized in the construction of a
sensitive "switch-on" fluorescent probe for Hg2+ with highly efficient removal performance.
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Figure 1. Schematic illustration of the sensing and removal of Hg2+ from water based on the
"switch-on" fluorescence of the supramolecular polymers (G⊂H) and the regeneration-recycling
process.
RESULTS AND DISCUSSION
Synthesis of the functional supramolecular macrocycle (H).
The synthetic route to the targeted compound H is shown in Scheme 1. The starting macrocycle
(BpP6) was synthesized according to our published procedure.52 To realize the tailored terminal
functionalization, we first conducted partial oxidation towards single methoxy group within the
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cyclic ring of BpP6 to give a synthetic intermediate QBpP6 containing one benzoquinone unit,
followed by the hydrogenated reduction to afford HBpP6 in a quantitative yield. Thereafter,
bromo-functionalized DBBpP6 was obtained through a nucleophilic substitution between HBpP6
and excess 1,4-dibromo butane in the presence of K2CO3 with a satisfactory yield. Furthermore,
the obtained DBBpP6 was treated with sodium azide in dimethylformamide (DMF) to generate
AZBpP6 via nucleophilic substitution in a high yield of 90%, followed by further reduction by
PPh3 through the Staudinger reaction in the mixture solution of tetrahydrofuran and water to
produce the intermediate AMBpP6 with a good yield of 50%. Finally, the target H was facilely
synthesized in a yield of 68% through the condensation of AMBpP6 and thymine derivative as
catalyzed by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI). All the
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obtained compounds have been verified and fully characterized by H NMR, 13C NMR, and
MALDI-TOF-MS spectroscopy (Figure S2-26).
Scheme 1. Synthetic route to the thymine-functionalized BpP6 derivative H and the chemical
structure of the TPE-bridged bis(quaternary ammonium) guest G.
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Supramolecular assembly of H and G mediated by Hg2+.
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To rule out the roles of host-guest interactions in the construction of supramolecular polymers, we
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investigated the related association and binding between macrocyclic H and cationic G by H
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NMR spectroscopy. As shown in Figure 2a, a fast exchange process on the NMR timescale did
take place due to the supramolecular complexation of H and G in CDCl3 according to the proton
NMR spectra of H, G, and the mixture of G and 1.0 equiv. H. Upon the addition of H, alkyl
protons signals of G displayed clear upfield shift in sharp contrast with pure G (Δδ = -0.12, -0.14,
-0.11, -0.13, -0.11 ppm for protons Ha, Hb, Hc, Hd, He, respectively), indicating the shielding effect
of macrocyclic cavity and the existence of inclusion complexation. With regard to the proton NMR
spectrum of H, obvious upfield shifts of protons H1, H2, H4 in biphenyl and phenyl and downfield
shifts of protons H3, H5 further confirmed the host-guest inclusion complexation between the
electron-deficient quaternary ammonium groups of G and the electron-rich cavity of H via
electrostatic interactions.
In addition, 2D ROESY NMR spectroscopy was also performed to demonstrate the geometry
of H. As in Figure 2b and Figure S27, the ROE correlations were clearly observed due to the π-
π and C-H···π interactions of the protons Ha, Hb, Hc, Hd, He, Hf and Hg at high concentration.
However, no ROE correlation between the protons of biphenyl or phenyl and the protons of alkyl
chain of H has been found, strongly suggesting that no self-inclusion structure existed in H. And
1
the same conclusion was also reached based on the H NMR spectra of H at different
concentrations (Figure S28).
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Figure 2. (a) H NMR spectra (500 MHz, CDCl3, 298 K) of (1) G (5.0 mM); (2) the equimolar
mixture of G and H (5.0 mM each); (3) H (5.0 mM); and (b) Partial 2D ROESY spectrum (400
MHz, CDCl3, 298 K) of H (20 mM) with a mixing time of 300 ms.
Moreover, we investigated the binding mode between synthetic macrocycle H and quaternary
ammonium G assisted by the analysis of Job’s plot (Figure S29a).63 We anticipate that the larger
cavity of H holds great potential in stabilizing more than one guest. For the sake of comparison, a
counterpart guest molecule G', with only one quaternary ammonium moiety, was synthesized as a
control entity. As illustrated in Figure S29b, the experimental results of Job’s plot analysis support
the 1:2 binding mode between H and G', so that the related 2:2 binding mode between H and G
could be concluded. Furthermore, 1H NMR titration experiments were carried out to calculate the
related association constant (Ka) between H and G', which was determined to be 2×103 M-1
according to the nonlinear least-squares analysis (Figure S29c,d).
In the readily prepared linear polymer G⊂H, the thymine arms in H possess the binding ability
towards Hg2+, which allows the further formation of crosslinked supramolecular network. The
related connections could be ascribed to the unique T−Hg2+−T pairings between thymine and Hg2+.
In this regard, upon the addition of Hg2+, the host-guest complex underwent an assembled process
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and afforded the resulting supramolecular assembly (G⊂H@Hg2+). Scanning electron microscopy
(SEM), transmission electron microscope (TEM) and dynamic light scattering (DLS)
measurements have been conducted to characterize the morphology of G⊂H@Hg2+ (Figure 3a
and Figure S33). The observed spherical assemblies have an average diameter of around 164 nm,
reflecting that the crosslinked aggregates have been created due to the tight binding of T-Hg2+-T
pairings in an almost perpendicular direction with respect to the host-guest interactions between
H and G. Herein, we found that the T-Hg2+-T pairings not only connect the pseudorotaxane
structures in G⊂H, but also cooperatively pull the supramolecular polymer into nanoscaled
spherical assemblies. The 2D diffusion-ordered NMR spectroscopy (DOSY) experiments (Figure
S34) showed that the weight-average diffusion coefficient (D) of H (2 mM), G⊂H (2 mM), and
G⊂H@Hg2+ (2 mM) were 5.99×10-10 m2 s-1, 5.82×10-10 m2 s-1, and 3.78×10-10 m2 s-1, respectively,
revealing the formation of supramolecular polymer G⊂H and the supramolecular assembly of
G⊂H@Hg2+.
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Figure 3. (a) SEM image of G⊂H@Hg2+. The insert is the DLS analysis of G⊂H@Hg2+; (b)
Fluorescence emission (at 388 nm) of G⊂H in a mixed solvent of chloroform and acetone (15 μM)
with the addition of the aqueous solutions of 1.0 equiv. of different metal ions (15 μM). Conditions:
CHCl3/acetone/H2O (v/v/v = 1:4:495) as solvent; λex = 312 nm; slit widths: Ex. 3 nm, Em. 5 nm.
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Switch-on fluorescence of supramolecular assembly G⊂H@Hg2+.
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Fluorescent experiments were carried out to investigate the proposed mechanism for fluorescent
sensing of G⊂H toward Hg2+. Both the TPE derivative G and the supramolecular polymer G⊂H
exhibited negligible or very weak fluorescence in the state of dispersion on account of the free
rotation of peripheral phenyl rings and the concomitant nonradiative energy decay in accordance
with the pioneer work by Tang and coworkers.64-67 Regardless of the addition of H, G⊂H also
displayed weak fluorescence. However, once the aqueous solution of HgCl2 was introduced,
spherical-shaped supramolecular assembly G⊂H@Hg2+ was formed and the obvious fluorescence
enhancement was switched on upon the irradiation of 312 nm UV light. As shown in Figure 4a,5a,
the strong fluorescence emission and white solid could be observed just by naked eyes. In
particular, the formation of spherical-shaped supramolecular assembly G⊂H@Hg2+ renders the
intramolecular rotations within the TPE entities to be restricted, resulting in the switch-on
fluorescence due to the effect of SAIEE. Along with the addition of Hg2+, the emission intensity
increased sharply and reached the maximum value when the equivalent of Hg2+ reached 1.0. These
findings strongly support that the supramolecular polymer G⊂H could serve as considerable
fluorescent probe for sensing toxic heavy metal ion Hg2+.
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Moreover, in order to study the anti-interference ability of G⊂H against the variation of pH and
temperature in response to Hg2+, we preformed the fluorescence measurement experiments under
different conditions as presented in Figure 4b-d. With an elevated temperature, no obvious change
of emission was observed. Similarly, with that case of temperature, the fluorescence emission of
G⊂H@Hg2+ also remained at almost maximum value under different acidic environment. In
contrast, significant fluorescence quenching of G⊂H@Hg2+ was discovered under alkaline
conditions, most likely due to the generation of mercuric oxide coming from the reaction between
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OH- and Hg2+ and the destruction of the crisscrossed network. Next, the selectivity and specificity
of G⊂H sensing towards Hg2+ was investigated by assessing the fluorescence intensity change by
the addition of various metal ions of 1.0 equiv. into the system of G⊂H including Na+, Mg2+, K+,
Cr3+, Fe2+, Fe3+, Co2+, Ni2+, Cu+, Cu2+, Zn2+, Cd2+, and Hg2+, respectively. Other metal ions, despite
under identical conditions, were still unfavorable for the switch-on fluorescence as shown in
Figure 3b. The specific coordination of thymine with Hg2+ was recognized as the dominating
reason for the formation of crossed-linked network, which endowed G⊂H with unique ability in
sensing Hg2+.
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Figure 4. (a) The variation of fluorescence intensity of G ⊂ H, H and G (15 μM) with the
increasing concentration of Hg2+ (from 0 to 22 μM); slit width: Ex. 3 nm, Em. 5 nm. The inset
shows the emission of (1) Hg2+; (2) Hg2+ + H; (3) Hg2+ + G; (4) G⊂H; (5) G⊂H@Hg2+ under 365
nm UV light irradiation; (b) Fluorescence spectral responses of G⊂H + Hg2+ (15 M) towards the
variation of temperature; slit width: Ex: 1.5 nm, Em: 3 nm. And the fluorescence spectra of
G⊂H@Hg2+ (15 μM) upon the addition of different amounts of (c) NaOH and (d) HCl aqueous
solution (from 0 to 50 equiv.); slit widths: Ex: 3 nm, Em: 5 nm. Conditions: CHCl3/acetone/H2O
(v/v/v = 1:4:495) as solvent; λex = 312 nm.
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Application in the rapid removal of Hg2+.
In addition to fluorescence sensing toward Hg2+, we also evaluated the performance of G⊂H in
the applicable removal of Hg2+. Since the supramolecular polymer G⊂H exhibited excellent
solubility in a mixed solvent of chloroform and acetone, the aqueous solution of Hg2+ (30 ppm in
10 mL water) was added into the mixture of G⊂H and 0.5 mL chloroform/acetone (v/v = 1:4) (4.5
M). The apparent white precipitate emerged immediately, indicating the formation of
supramolecular assembly G⊂H@Hg2+. By virtue of the strong binding of T−Hg2+−T pairings
between thymine groups and Hg2+, the supramolecular polymer G⊂H tends to form a much
hypercross-linked network, which has rendered the obtained materials as versatile absorbents for
Hg2+. The mixture was stirred for another 12 h to guarantee the complete adsorption of Hg2+ ion,
followed by further centrifugation to separate the precipitate from the mother liquid. Then the
remaining solution was analyzed by inductively coupled plasma (ICP) for the analysis of residual
Hg2+. With the considerable selectivity and strong binding, the supramolecular polymer G⊂H
displayed remarkable Hg2+ removal efficiency that was found to be over 90% and only 2.9 ppm
detectable Hg2+ existed in the remaining solution. In a simple regeneration treatment, the separated
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white precipitate G⊂H@Hg2+ was dissolved in 10 mL chloroform/acetone (v/v = 1:4), followed
by the addition of excessive amount of Na2S, and black HgS solid was produced. After stirring the
mixture for another 12 h, the absorbent G⊂H was fully regenerated and recycled with
centrifugation (Figure 5a). Furthermore, another five cycles have been performed within the
identical removal procedures, showing that G⊂H possesses excellent recyclability (Figure 5d).
Besides, as shown in Figure 5b, with the increasing concentration of Hg2+, the emission exhibited
a linear relationship with Hg2+ in the range of 0-15 M. Meanwhile, the detection limit of Hg2+
was determined to be 3×10-7 M based on 3σ/s, where σ was coming from the standard deviation in
10 blank measurements in Figure 5c and s was the slope in Figure 5b. All the experimental results
clearly demonstrated that supramolecular polymer G⊂H could serve as an applicable fluorescence
probe and a good absorbent material for sensing and removing Hg2+ in water and provided a
considerable method in the treatment of mercury ion pollutants with desirable recyclability.
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Figure 5. (a) Representative photos during the process of sensing and removal of Hg2+ and
regeneration of absorbent material (G⊂H). (b) The plot of the fluorescence intensity of G⊂H at
388 nm against the concentration of Hg2+. λex = 312 nm; slit width: Ex. 3 nm, Em. 5 nm; (c) The
fluorescence spectra of ten blank measurements of G⊂H (15 μM) in CHCl3/acetone/H2O;
Conditions: CHCl3/acetone/H2O (v/v/v = 1:4:495) as solvent; λex = 312 nm; slit widths: Ex: 3 nm,
Em: 5 nm; (d) Recyclable performance of G⊂H towards the removal of Hg2+.
CONCLUSION
In summary, we reported on the construction of the first fluorescent supramolecular polymer based
on a thymine modified [2]biphenyl-extended version of pillarene host by a simple supramolecular
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assembly with the aid of an AIEgen-bridged quaternary ammonium guest, and addressed its facile
application not only for fluorescent detection of heavy metal ion Hg2+ with quick response and
high selectivity, but also for efficient removal of Hg2+ with rapid adsorption rate and high
adsorption capacity. Based on the SAIEE mechanism, the fluorescent emission emerged instantly
with the addition of Hg2+ due to the tight T-Hg2+-T paring between thymine groups in H and Hg2+
in the environment and the corresponding formation of the spherical-shaped crosslinked
supramolecular assembly G⊂H@Hg2+. This work thus combined the AIE effect and the
supramolecular module strategy in delivering an applicable method for the selective detection and
rapid removal of toxic Hg2+, offering perspective potential in tackling the problem of heavy metal
ions pollution for environmental remediation and stimulating new thinking for the sorbent
materials design.
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ASSOCIATED CONTENT
Supporting Information.
The synthetic routes to H, G and G'. 1H NMR, 13C NMR and MALDI-TOF-MS spectra of the
obtained products. Job’s plots of H with G and H with G'. The NMR titration experiment and
association constant figures of H with G. Fluorescence experiment figures of H with Hg2+ and G
with Hg2+. SEM and TEM images of H with Hg2+ and G with Hg2+. The following files are
available free of charge. This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: ywyang@jlu.edu.cn
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Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENT
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We thank the National Natural Science Foundation of China (21871108, 51673084); Jilin
Province-University Cooperative Construction Project-Special Funds for New Materials
(SXGJSF2017-3), Jilin University Talents Cultivation Program, and the Fundamental Research
Funds for the Central Universities for financial support.
REFERENCES
(1) Alsbaiee, A.; Smith, B. J.; Xiao, L.; Ling, Y.; Helbling, D. E.; Dichtel, W. R. Rapid Removal
of Organic Micropollutants from Water by a Porous Beta-Cyclodextrin Polymer. Nature 2016,
529, 190-194.
(2) Banerjee, D.; Kim, D.; Schweiger, M. J.; Kruger, A. A.; Thallapally, P. K. Removal of
TcO4(-) Ions from Solution: Materials and Future Outlook. Chem. Soc. Rev. 2016, 45, 2724-
2739.
(3) Li, X.; Bian, C.; Meng, X.; Xiao, F. Design and Synthesis of an Efficient Nanoporous
Adsorbent for Hg2+ and Pb2+ Ions in Water. J. Mater. Chem. A 2016, 4, 5999-6005.
(4) Tchinda, A. l. J.; Ngameni, E.; Kenfack, I. T.; Walcarius, A. One-Step Preparation of Thiol-
Functionalized Porous Clay Heterostructures: Application to Hg(II) Binding and
Characterization of Mass Transport Issues. Chem. Mater. 2009, 21, 4111-4121.
(5) Das, R.; Vecitis, C. D.; Schulze, A.; Cao, B.; Ismail, A. F.; Lu, X.; Chen, J.; Ramakrishna, S.
Recent Advances in Nanomaterials for Water Protection and Monitoring. Chem. Soc. Rev. 2017,
46, 6946-7020.
ACS Paragon Plus Environment
16

Page 17 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
(6) Li, J.; Wang, X. X.; Zhao, G. X.; Chen, C. L.; Chai, Z. F.; Alsaedi, A.; Hayat, T.; Wang, X.
K. Metal-Organic Framework-Based Materials: Superior Adsorbents for the Capture of Toxic
and Radioactive Metal Ions. Chem. Soc. Rev. 2018, 47, 2322-2356.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(7) Feng, X.; Fryxell, G. E.; Wang, L. Q.; Kim, A. Y.; Liu, J.; Kemner, K. M. Functionalized
Monolayers on Ordered Mesoporous Supports. Science 1997, 276, 923-926.
(8) Aguila, B.; Sun, Q.; Perman, J. A.; Earl, L. D.; Abney, C. W.; Elzein, R.; Schlaf, R.; Ma, S.
Q. Efficient Mercury Capture Using Functionalized Porous Organic Polymer. Adv. Mater. 2017,
29, 1700665.
(9) Li, B. Y.; Zhang, Y. M.; Ma, D. X.; Shi, Z.; Ma, S. Q. Mercury Nano-Trap for Effective and
Efficient Removal of Mercury(II) from Aqueous Solution. Nat. Commun. 2014, 5, 5537.
(10) Ding, S. Y.; Dong, M.; Wang, Y. W.; Chen, Y. T.; Wang, H. Z.; Su, C. Y.; Wang, W.
Thioether-Based Fluorescent Covalent Organic Framework for Selective Detection and Facile
Removal of Mercury(II). J. Am. Chem. Soc. 2016, 138, 3031-3037.
(11) Sun, Q.; Aguila, B.; Perman, J.; Earl, L. D.; Abney, C. W.; Cheng, Y.; Wei, H.; Nguyen, N.;
Wojtas, L.; Ma, S. Q. Postsynthetically Modified Covalent Organic Frameworks for Efficient
and Effective Mercury Removal. J. Am. Chem. Soc. 2017, 139, 2786-2793.
(12) Jiang, J. X.; Su, F.; Trewin, A.; Wood, C. D.; Campbell, N. L.; Niu, H.; Dickinson, C.;
Ganin, A. Y.; Rosseinsky, M. J.; Khimyak, Y. Z.; Cooper, A. I. Conjugated Microporous
Poly(Aryleneethynylene) Networks. Angew. Chem., Int. Ed. 2007, 46, 8574-8578.
(13) Li, X.; Li, Z.; Yang, Y. W. Tetraphenylethylene-Interweaving Conjugated Macrocycle
Polymer Materials as Two-Photon Fluorescence Sensors for Metal Ions and Organic Molecules.
Adv. Mater. 2018, 30, 1800177.
ACS Paragon Plus Environment
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Journal of the American Chemical Society
Page 18 of 25
1
2
3
4
5
6
7
8
9
(14) Ben, T.; Ren, H.; Ma, S.; Cao, D.; Lan, J.; Jing, X.; Wang, W.; Xu, J.; Deng, F.; Simmons,
J. M.; Qiu, S.; Zhu, G. S. Targeted Synthesis of a Porous Aromatic Framework with High
Stability and Exceptionally High Surface Area. Angew. Chem., Int. Ed. 2009, 48, 9457-9460.
(15) Abney, C. W.; Gilhula, J. C.; Lu, K.; Lin, W. Metal-Organic Framework Templated
Inorganic Sorbents for Rapid and Efficient Extraction of Heavy Metals. Adv. Mater. 2014, 26,
7993-7997.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(16) Yee, K. K.; Reimer, N.; Liu, J.; Cheng, S. Y.; Yiu, S. M.; Weber, J.; Stock, N.; Xu, Z.
Effective Mercury Sorption by Thiol-Laced Metal-Organic Frameworks: in Strong Acid and the
vapor phase. J. Am. Chem. Soc. 2013, 135, 7795-7798.
(17) Lehn, J. M. Toward Self-Organization and Complex Matter. Science 2002, 295, 2400-2403.
(18) Behr, J. P.; Lehn, J. M.; Dock, A. C.; Moras, D. Crystal Structure of a Polyfunctional
Macrocyclic K+ Complex Provides a Solid-State Model of a K+ Channel. Nature 1982, 295, 526-
527.
(19) Koert, U.; Harding, M. M.; Lehn, J. M. DNH Deoxyribonucleohelicates: Self Assembly of
Oligonucleosidic Double-Helical Metal Complexes. Nature 1990, 346, 339-342.
(20) Wang, H.; Ji, X. F.; Li, Z. T.; Huang, F. H. Fluorescent Supramolecular Polymeric
Materials. Adv. Mater. 2017, 29, 1606117.
(21) Guan, Y.; Ni, M.; Hu, X.; Xiao, T.; Xiong, S.; Lin, C.; Wang, L. Y. Pillar[5]arene-Based
Polymeric Architectures Constructed by Orthogonal Supramolecular Interactions. Chem.
Commun. 2012, 48, 8529-8531.
(22) Hu, X. Y.; Wu, X.; Duan, Q. P.; Xiao, T. X.; Lin, C.; Wang, L. Y. Novel Pillar[5]arene-
Based Dynamic Polyrotaxanes Interlocked by the Quadruple Hydrogen Bonding
Ureidopyrimidinone Motif. Org. Lett. 2012, 14, 4826-4829.
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Page 19 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
(23) Sun, R.; Xue, C.; Ma, X.; Gao, M.; Tian, H.; Li, Q. Light-Driven Linear Helical
Supramolecular Polymer Formed by Molecular-Recognition-Directed Self-Assembly of Bis(p-
Sulfonatocalix[4]arene) and Pseudorotaxane. J. Am. Chem. Soc. 2013, 135, 5990-5993.
(24) Yan, X.; Cook, T. R.; Pollock, J. B.; Wei, P.; Zhang, Y.; Yu, Y.; Huang, F. H.; Stang, P. J.
Responsive Supramolecular Polymer Metallogel Constructed by Orthogonal Coordination-
Driven Self-Assembly and Host/Guest Interactions. J. Am. Chem. Soc. 2014, 136, 4460-4463.
(25) Krieg, E.; Bastings, M. M.; Besenius, P.; Rybtchinski, B. Supramolecular Polymers in
Aqueous Media. Chem. Rev. 2016, 116, 2414-2477.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(26) Yu, G. C.; Zhao, X. L.; Zhou, J.; Mao, Z. W.; Huang, X. L.; Wang, Z. T.; Hua, B.; Liu, Y.
J.; Zhang, F. W.; He, Z. M.; Jacobson, O.; Gao, C. Y.; Wang, W. L.; Yu, C. Y.; Zhu, X. Y.;
Huang, F. H.; Chen, X. Y. Supramolecular Polymer-Based Nanomedicine: High Therapeutic
Performance and Negligible Long-Term Immunotoxicity. J. Am. Chem. Soc. 2018, 140, 8005-
8019.
(27) Harada, A.; Takashima, Y.; Yamaguchi, H. Cyclodextrin-Based Supramolecular Polymers.
Chem. Soc. Rev. 2009, 38, 875-882.
(28) Guo, D. S.; Liu, Y. Calixarene-Based Supramolecular Polymerization in Solution. Chem.
Soc. Rev. 2012, 41, 5907-5921.
(29) Zheng, B.; Wang, F.; Dong, S.; Huang, F. H. Supramolecular Polymers Constructed by
Crown Ether-Based Molecular Recognition. Chem. Soc. Rev. 2012, 41, 1621-1636.
(30) Cram, D. J. The Design of Molecular Hosts, Guests, and Their Complexes. Angew. Chem.,
Int. Ed. 1988, 27, 1009-1112.
ACS Paragon Plus Environment
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Journal of the American Chemical Society
Page 20 of 25
1
2
3
4
5
6
7
8
9
(31) Wang, Y.; Ma, N.; Wang, Z.; Zhang, X. Photocontrolled Reversible Supramolecular
Assemblies of an Azobenzene-Containing Surfactant with Alpha-Cyclodextrin. Angew. Chem.,
Int. Ed. 2007, 46, 2823-2826.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(32) Ma, D.; Hettiarachchi, G.; Nguyen, D.; Zhang, B.; Wittenberg, J. B.; Zavalij, P. Y.; Briken,
V.; Isaacs, L. Acyclic Cucurbit[n]uril Molecular Containers Enhance the Solubility and
Bioactivity of Poorly Soluble Pharmaceuticals. Nat. Chem. 2012, 4, 503-510.
(33) Baldini, L.; Casnati, A.; Sansone, F.; Ungaro, R. Calixarene-Based Multivalent Ligands.
Chem. Soc. Rev. 2007, 36, 254-266.
(34) Nimse, S. B.; Kim, T. Biological Applications of Functionalized Calixarenes. Chem. Soc.
Rev. 2013, 42, 366-386.
(35) Chen, W.; Zhang, Y.; Li, J.; Lou, X.; Yu, Y.; Jia, X.; Li, C. J. Synthesis of a Cationic
Water-Soluble Pillar[6]arene and Its Effective Complexation towards Naphthalenesulfonate
Guests. Chem. Commun. 2013, 49, 7956-7958.
(36) Chi, X.; Ji, X.; Xia, D.; Huang, F. H. A Dual-Responsive Supra-Amphiphilic
Polypseudorotaxane Constructed from a Water-Soluble Pillar[7]arene and an Azobenzene-
Containing Random Copolymer. J. Am. Chem. Soc. 2015, 137, 1440-1443.
(37) Cui, W.; Tang, H.; Xu, L.; Wang, L.; Meier, H.; Cao, D. R. Pillar[5]arene-
Diketopyrrolopyrrole Fluorescent Copolymer: A Promising Recognition and Adsorption
Material for Adiponitrile by Selective Formation of a Conjugated Polypseudorotaxane.
Macromol. Rapid Commun. 2017, 38, 1700161.
(38) Hu, X. B.; Chen, Z.; Chen, L.; Zhang, L.; Hou, J. L.; Li, Z. T. Pillar[n]arenes (n = 8-10)
with Two Cavities: Synthesis, Structures and Complexing Properties. Chem. Commun. 2012, 48,
10999-11001.
ACS Paragon Plus Environment
20

Page 21 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
(39) Kakuta, T.; Yamagishi, T.; Ogoshi, T. Supramolecular Chemistry of Pillar[n]arenes
Functionalised by a Copper(i)-Catalysed Alkyne-Azide Cycloaddition "Click" Reaction. Chem.
Commun. 2017, 53, 5250-5266.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(40) Ogoshi, T.; Ueshima, N.; Sakakibara, F.; Yamagishi, T. A.; Haino, T. Conversion from
Pillar[5]arene to Pillar[6-15]arenes by Ring Expansion and Encapsulation of C60 by
Pillar[n]arenes with Nanosize Cavities. Org. Lett. 2014, 16, 2896-2899.
(41) Ogoshi, T.; Yamagishi, T. A.; Nakamoto, Y. Pillar-Shaped Macrocyclic Hosts
Pillar[n]arenes: New Key Players for Supramolecular Chemistry. Chem. Rev. 2016, 116, 7937-
8002.
(42) Tan, L. L.; Li, H.; Qiu, Y. C.; Chen, D. X.; Wang, X.; Pan, R. Y.; Wang, Y.; Zhang, S. X.;
Wang, B.; Yang, Y. W. Stimuli-Responsive Metal–Organic Frameworks Gated by Pillar[5]arene
Supramolecular Switches. Chem. Sci. 2015, 6, 1640-1644.
(43) Zhang, Z.; Luo, Y.; Chen, J.; Dong, S.; Yu, Y.; Ma, Z.; Huang, F. H. Formation of Linear
Supramolecular Polymers That is Driven by C-Hpi Interactions in Solution and in the Solid
State. Angew. Chem., Int. Ed. 2011, 50, 1397-1401.
(44) Wu, J. R.; Mu, A. U.; Li, B.; Wang, C. Y.; Fang, L.; Yang, Y. W. Desymmetrized Leaning
Pillar[6]arene. Angew. Chem., Int. Ed. 2018, 57, 9853-9858.
(45) Wu, J. R.; Yang, Y. W. New Opportunities in Synthetic Macrocyclic Arenes. Chem.
Commun. 2019, 55, 1533-1543.
(46) Guo, D. S.; Wang, K.; Wang, Y. X.; Liu, Y. Cholinesterase-Responsive Supramolecular
Vesicle. J. Am. Chem. Soc. 2012, 134, 10244-10250.
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Journal of the American Chemical Society
Page 22 of 25
1
2
3
4
5
6
7
8
9
(47) Song, N.; Chen, D. X.; Qiu, Y. C.; Yang, X. Y.; Xu, B.; Tian, W.; Yang, Y. W. Stimuli-
Responsive Blue Fluorescent Supramolecular Polymers Based on a Pillar[5]arene Tetramer.
Chem. Commun. 2014, 50, 8231-8234.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
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36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(48) Yu, G. C.; Zhao, R.; Wu, D.; Zhang, F. W.; Shao, L.; Zhou, J.; Yang, J.; Tang, G. P.; Chen,
X. Y.; Huang, F. H. Pillar[5]arene-Based Amphiphilic Supramolecular Brush Copolymer:
Fabrication, Controllable Self-Assembly and Application in Self-Imaging Targeted Drug
Delivery. Polym. Chem. 2016, 7, 6178-6188.
(49) Chen, J. F.; Lin, Q.; Zhang, Y. M.; Yao, H.; Wei, T. B. Pillararene-Based Fluorescent
Chemosensors: Recent Advances and Perspectives. Chem. Commun. 2017, 53, 13296-13311.
(50) Cheng, H. B.; Li, Z. Y.; Huang, Y. D.; Liu, L.; Wu, H. C. Pillararene-Based Aggregation-
Induced-Emission-Active Supramolecular System for Simultaneous Detection and Removal of
Mercury(II) in Water. ACS Appl. Mater. Interfaces 2017, 9, 11889-11894.
(51) Lin, Q.; Zhong, K.; Zhu, J. H.; Ding, L.; Su, J. X.; Yao, H.; Wei, T. B.; Zhang, Y. M. Iodine
Controlled Pillar[5]arene-Based Multiresponsive Supramolecular Polymer for Fluorescence
Detection of Cyanide, Mercury, and Cysteine. Macromolecules 2017, 50, 7863-7871.
(52) Gao, B.; Tan, L. L.; Song, N.; Li, K.; Yang, Y. W. A High-Yield Synthesis of [m]Biphenyl-
Extended Pillar[n]arenes for an Efficient Selective Inclusion of Toluene and m-Xylene in the
Solid State. Chem. Commun. 2016, 52, 5804-5807.
(53) Wu, J. R.; Wang, C. Y.; Tao, Y. C.; Wang, Y.; Li, C. J.; Yang, Y. W. A Water-Soluble
[2]Biphenyl-Extended Pillar[6]arene. Eur. J. Org. Chem. 2018, 2018, 1321-1325.
(54) Miyake, Y.; Togashi, H.; Tashiro, M.; Yamaguchi, H.; Oda, S.; Kudo, M.; Tanaka, Y.;
Kondo, Y.; Sawa, R.; Fujimoto, T.; Machinami, T.; Ono, A. MercuryII-Mediated Formation of
Thymine-HgII-Thymine Base Pairs in DNA Duplexes. J. Am. Chem. Soc. 2006, 128, 2172-2173.
ACS Paragon Plus Environment
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Page 23 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
(55) Maiti, S.; Pezzato, C.; Garcia Martin, S.; Prins, L. J. Multivalent Interactions Regulate
Signal Transduction in a Self-Assembled Hg2+ Sensor. J. Am. Chem. Soc. 2014, 136, 11288-
11291.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(56) Wen, S.; Zeng, T.; Liu, L.; Zhao, K.; Zhao, Y.; Liu, X.; Wu, H. C. Highly Sensitive and
Selective DNA-Based Detection of Mercury(II) with Alpha-Hemolysin Nanopore. J. Am. Chem.
Soc. 2011, 133, 18312-18317.
(57) Mei, J.; Leung, N. L.; Kwok, R. T.; Lam, J. W.; Tang, B. Z. Aggregation-Induced Emission:
Together We Shine, United We Soar! Chem. Rev. 2015, 115, 11718-11940.
(58) Song, N.; Chen, D. X.; Xia, M. C.; Qiu, X. L.; Ma, K.; Xu, B.; Tian, W.; Yang, Y. W.
Supramolecular Assembly-Induced Yellow Emission of 9,10-Distyrylanthracene Bridged
Bis(Pillar[5]arene)s. Chem. Commun. 2015, 51, 5526-5529.
(59) Wang, Y.; Lv, M. Z.; Song, N.; Liu, Z. J.; Wang, C. Y.; Yang, Y. W. Dual-Stimuli-
Responsive Fluorescent Supramolecular Polymer Based on a Diselenium-Bridged Pillar[5]arene
Dimer and an AIE-Active Tetraphenylethylene Guest. Macromolecules 2017, 50, 5759-5766.
(60) Jin, X. Y.; Song, N.; Wang, X.; Wang, C. Y.; Wang, Y.; Yang, Y. W.
Monosulfonicpillar[5]arene: Synthesis, Characterization, and Complexation with
Tetraphenylethene for Aggregation-Induced Emission. Sci. Rep. 2018, 8, 4035.
(61) Lou, X. Y.; Yang, Y. W. Manipulating Aggregation-Induced Emission with Supramolecular
Macrocycles. Adv. Opt. Mater. 2018, 6, 1800668.
(62) Song, N.; Lou, X. Y.; Hou, W.; Wang, C. Y.; Wang, Y.; Yang, Y. W. Pillararene-Based
Fluorescent Supramolecular Systems: The Key Role of Chain Length in Gelation. Macromol.
Rapid. Commun. 2018, 39, 1800593.
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Page 24 of 25
1
2
3
4
5
6
7
8
9
(63) Yang, H.; Han, C.; Zhu, X.; Liu, Y.; Zhang, K. Y.; Liu, S.; Zhao, Q.; Li, F.; Huang, W.
Upconversion Luminescent Chemodosimeter Based on NIR Organic Dye for Monitoring
Methylmercury In Vivo. Adv. Funct. Mater. 2016, 26, 1945-1953.
10
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(64) Hong, Y.; Lam, J. W.; Tang, B. Z. Aggregation-Induced Emission: Phenomenon,
Mechanism and Applications. Chem. Commun. 2009, 4332-4353.
(65) Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Aggregation-Induced Emission. Chem. Soc. Rev.
2011, 40, 5361-5388.
(66) Wang, J.; Gu, X.; Zhang, P.; Huang, X.; Zheng, X.; Chen, M.; Feng, H.; Kwok, R. T. K.;
Lam, J. W. Y.; Tang, B. Z. Ionization and Anion-pi(+) Interaction: A New Strategy for Structural
Design of Aggregation-Induced Emission Luminogens. J. Am. Chem. Soc. 2017, 139, 16974-
16979.
(67) Han, T.; Deng, H.; Qiu, Z.; Zhao, Z.; Zhang, H.; Zou, H.; Leung, N. L. C.; Shan, G.;
Elsegood, M. R. J.; Lam, J. W. Y.; Tang, B. Z. Facile Multicomponent Polymerizations toward
Unconventional Luminescent Polymers with Readily Openable Small Heterocycles. J. Am.
Chem. Soc. 2018, 140, 5588-5598.
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