Recyclable Supramolecular Assembly-Induced Emission System for Selective Detection and Efficient Removal of Mercury(II)

Article abstract of DOI:10.1002/chem.202101437

An efficient strategy for simultaneously detecting and removing Hg²⁺ from water is vital to address mercury pollution. Herein a supramolecular assembly G?H with photoluminescent properties is facilely constructed through the self-assembly of a

Full text of DOI:10.1002/chem.202101437

Accepted Article
Accepted Article
Title: Reusable Supramolecular Assembly-Induced Emission System
for Selective Detectionand Efficient Removal of Mercury(II)
Authors: Wei-Ming Wang, Dihua Dai, Jia-Rui Wu, Chun-Yu Wang, Yan
Wang, and Ying-Wei Yang
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Chem. Eur. J. 10.1002/chem.202101437
Link to VoR: https://doi.org/10.1002/chem.202101437
0
1/2020

Chemistry - A European Journal
10.1002/chem.202101437
RESEARCH ARTICLE
Recyclable Supramolecular Assembly-Induced Emission System
for Selective Detection and Efficient Removal of Mercury(II)
[
a]
[a]
[a]
[b]
[a]
[a]
Wei-Ming Wang, Dihua Dai, Jia-Rui Wu, Chun-Yu Wang, Yan Wang,* and Ying-Wei Yang*
[
a]
W.-M. Wang, D. Dai, J.-R. Wu, Prof. Y. Wang, Prof. Y.-W. Yang
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, International Joint Research Laboratory of Nano-Micro Architecture Chemistry,
College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China
E-mail: wangy2011@jlu.edu.cn; ywyang@jlu.edu.cn
[
b]
C.-Y. Wang
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R.
China
Supporting information for this article is given via a link at the end of the document.
Abstract: An efficient strategy for simultaneously detecting and
noncovalent interactions including π−π stacking, hydrogen
bonding, Van der Waals forces, coordination effect, and
electrostatic attraction.[11] Owing to the fascinating stimuli-
responsive properties and reversible monomer-to-polymer
transition of supramolecular assembly, supramolecular
host−guest systems have been extensively investigated for
fabricating intelligent functional materials equipped with advanced
2+
removing Hg from water is vital to address mercury pollution. Herein
a supramolecular assembly G⊂H with photoluminescent properties is
facilely constructed through the self-assembly of
pillar[5]arene bearing two N,N-dimethyldithiocarbamoyl binding sites
H) and an AIE-active tetraphenylethene derivative (G). Remarkably,
a functional
(
2+
the fluorescence of G⊂H can be exclusively quenched by Hg among
the 30 cations due to the formation of non-luminous ground state
complex and only L-cysteine can restore fluorescence in the common
architectures,
prominent
processability,
and
recycling
properties.[12] In particular, conventional macrocyclic hosts, such
as crown ethers,[13] cyclodextrins,[14] cucurbit[n]urils,[15] and
calix[n]arenes[16] have played essential roles via providing
efficient cavities for accommodating multiple guests to construct
supramolecular polymers. Pillar[n]arenes,[17] as a new generation
of macrocyclic hosts, have recently aroused widespread concerns
by virtue of their fascinating characteristics including symmetrical
and rigid framework, electron-rich cavity, and versatile
functionality, satisfying the requirements of selectively interacting
2
0 amino acids. Meanwhile, the probe G⊂H has a considerable
thermal and pH stability, a good anti-interference property from
various cations, and a satisfactory sensitivity. More importantly, G⊂H
2+
exhibits a prominent capability of Hg removal with rapid capture rate
within 1 h) and excellent adsorption efficiency (98%), as well as a
(
highly efficient recyclability without losing any adsorption activity.
with various guests for fabricating multifunctional supramolecular
assembly systems.[18] Thus, self-assembly strategy based on the
Introduction
host-guest properties of pillar[n]arenes has broadened the
application prospects of the resulting systems in drug delivery,[19]
supramolecular gel materials,[20] artificial ion channels,[21]
chemosensors,[22] and so on.
Environmental contamination arising from toxic heavy metal ions
poses a tremendous threat to the ecosystem and human health.[1]
Mercury(II) is recognized as the most pernicious and ubiquitous
pollutant due to its nonbiodegradable property and extreme
bioaccumulation.[2] Intensive efforts have been made to exploit an
effective strategy for sensitive detection and rapid adsorption of
Hg2+ over the past decades. For instance, various fluorescence
probes including quantum dots (QDs),[3] gels,[4] and metal
nanoclusters[5] have been designed for detection of toxic metal
ions. In addition, a series of functional materials such as metal
organic frameworks (MOFs),[6] covalent organic frame-works
On the other hand, aggregation-induced emission (AIE)
phenomenon, first discovered by Tang and co-workers in 2001,[23]
has conquered the challenge and drawbacks of aggregation-
caused quenching (ACQ).[24] The main mechanism of AIE can be
interpreted as the restriction of intramolecular motion (RIM) or
rotation (RIR), obstructing the dissipation of non-radiative
energy.[25] Inspired by the mechanism of AIE, fluorescent
supramolecular assemblies can be constructed by the
manipulation of AIEgens with macrocycle-based inclusion
(
COFs),[7] conjugated macrocycle polymers (CMPs),[8] porous
organic polymers (POPs),[9] and conjugated microporous
polymers,[10] have shown great promise in adsorbing metal
contamination ions and other pollutants. Nevertheless, most of
the above materials can only represent either the detection or the
removal task separately, and partial developed methods suffer
from expensive regents or complex synthesis routes, restricting
their practical application in the adsorption and removal of
pollutants. Consequently, it is imperative to develop an
economical, simple, and green strategy toward the detection and
removal of Hg2+ in aqueous media simultaneously.
activities.[26]
complexation
The controllable fluorescent
supramolecular assembly relying on their fluorescence
characteristics can be regulated through the appropriate design
and has been successfully applied in optoelectronic devices,[27]
bioimaging,[28] photodynamic therapy,[29] and fluorescence
probes.[30] Nonetheless, constructing powerful fluorescent
materials with prominent performance to address mercury(II)
pollution remains a tough challenge. Considering the appealing
feature of pillar[5]arene including the ideal rigid electron-rich
cavity for interacting with guests and the high yield of synthesis
for further functionalization, an intelligent supramolecular
fluorescence probe can be fabricated by employing a
Supramolecular assemblies or materials have been endowed
with extraordinary properties upon combining diversified
functional monomers by fully taking advantages of the
1
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RESEARCH ARTICLE
Scheme 1. Schematic diagram for the detection and removal of Hg2+ in water based on recyclable supramolecular assembly G⊂H.
2
+
pillar[5]arene derivative modified with specific mercury(II)-
chelated functional entities and functionalized
of Hg , the fluorescence of G⊂H is significantly quenched due to
the formation of non-luminescent ground state complex
a
a
2+
tetraphenylethylene (TPE) derivative to realize the selective
detection and efficient removal of mercury(II) in water.
(G⊂H@Hg ) via the specific tight coordination bonds between
Hg2+ and C=S sulfur atom on H, imparting the fluorescence probe
with selective detection and efficient removal of Hg2+ (Scheme 1).
More importantly, supramolecular assembly G⊂H can be recycled
via simple sodium sulfide treatment, laying a firm foundation for
its practical application. In addition, the sulfhydryl groups on L-
cysteine (L-Cys) can competitively coordinate with Hg2+ in
G⊂H@Hg2+ system to turn on fluorescence and achieve the goal
Here we design and synthesize
a host pillar[5]arene
connecting two N,N-dimethyldithiocarbamoyl binding sites as
flexible arms (H), and a TPE-based tetratopic guest with four
cyano groups (G) through host–guest interactions to obtain a
fluorescent supramolecular polymer (G⊂H), exhibiting strong blue
2
fluorescence emission in DMSO/H O (1:99, v/v). With the addition
2
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Figure 1. (a) 1H NMR spectra (400 MHz, CDCl
3
, 298 K) of (1) H (8.0 mM); (2) H (8.0 mM) + G (2.0 mM) and (3) G (2.0 mM); (b) Variation of fluorescence intensity
of H, G and G⊂H (Experimental conditions: solution: DMSO/H
µM G with 40 µM H); (c) Partial spectrum of 2D ROESY (600 MHz, CDCl
600 MHz, CDCl , 298 K) of H (20 mM).
2
O (1:99, v/v); λex = 310 nm; slit widths: Ex. 5 nm, Em. 1.5 nm; [H] = 40 µM, [G] = 10 µM, [G⊂H] = 10
3
, 298 K) of a mixture of G (5.0 mM) and H (20.0 mM); (d) Full spectrum of 2D ROESY
(
3
1
of specific sensing L-Cys. We envisage that the functional
material G⊂H constructed under the guidance of the
supramolecular assembly-induced emission enhancement
by H NMR in deuterated chloroform. As demonstrated in Figure
1a, once four equivalents of H were added into the solution of G,
1 3
the proton signals of H -H assigned to alkyl chains of G were
(
SAIEE)[17a,25b] strategy will not only possess high quantum yield,
broadened and shifted upfield significantly compared with pure G
(Δδ = −2.02, −2.87, −4.54 ppm for the NMR peaks corresponding
but also sense and sequester Hg2+ stably, conveniently,
sensitively, and selectively, providing an efficient and practical
approach for the treatment of mercury(II) ions pollution.
1 3
to H '–H ') on account of the shielding effect of the electron-rich
cavity of H, indicating the high affinities between the nitrile
moieties of G and the cavities of H. Besides, the downfield shift of
a
phenyl protons H assigned to H further confirmed the host-guest
Results and Discussion
interactions, which resulted in the formation of supramolecular
assembly G⊂H.
Subsequently, 2D ROESY experiment of the 4:1 mixture of H
Construction of Supramolecular Host–Guest Assembly.
and G in CDCl
guest interaction. As shown in Figure 1c and Figure S12, the ROE
correlations were clearly observed between the phenyl protons H
and H ' of H and the alkyl chains protons H -H and H '-H ' of G,
3
was also conducted to further confirm the host-
A N,N-dimethyldithiocarbamoyl-derived copillar[5]arene (H)
2
was facilely synthesized from P5-Br via nucleophilic substitution
a
in a good yield of 60%. Cyano-functionalized TPE guests (G and
G') were synthesized for host-guest assembly due to their strong
binding abilities to pillar[5]arene in most organic solvents, whether
low polar chloroform or high polar DMSO.[31] The synthetic routes
to H, G, and model guest G' were illustrated in Figure S1. The
a
1
3
1
3
suggesting that the alkyl chains of G penetrated into the cavities
of H to form a supramolecular complex by the strong electrostatic
interactions. 2D diffusion-ordered NMR experiments (DOSY)
were also carried out to verify the structure of G⊂H assembly on
macromolecular level (Supporting Information, Figure S11). The
weight-average diffusion coefficient (D) of H was estimated to be
1
structure of new compound H has been characterized by H NMR,
13C
NMR, and MALDI-TOF-MS spectroscopy (Supporting
Information, Figures S4-S6).
.54×10−10 m s , and the value diminished to 3.09×10 m s
2
−1
−10
2
−1
4
The association and combination between the macrocyclic
host (H) and the neutral nitrile guest (G) were firstly investigated
with the addition of G, demonstrating the formation of
supramolecular assembly. To exclude the self-assembly
3
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RESEARCH ARTICLE
Figure 2. (a) Fluorescence changes at 462 nm (b) The photo under 365nm UV lamp of G⊂H with the addition of 10 equiv. of 30 different metal ions; (c) Fluorescence
quenching degrees at 462 nm in competition experiments of G⊂H with 1 equiv. of Hg2+ and 10 equiv. of other metal ions; (d) Plot of the fluorescence intensity of
G⊂H at 462 nm against the concentration of Hg2+; Fluorescence spectrum of G⊂H with Hg2+ toward the variation of (e) HCl aqueous solution and (f) NaOH aqueous
2
solution (0-50 equiv.) (Experimental conditions: solution: DMSO/H O (1:99, v/v); λex = 310 nm; slit widths: Ex. 5 nm, Em. 1.5 nm; 298 K; [G] = 10 µM, [H] = 40 µM).
of H in the construction of G⊂H, the related association and the
geometry of H were studied by 2D ROESY and the results
Information, Figures S13a, b). For comparison, a TPE derivative
(G') with single cyano group was selected as a control entity.
According to the Job's plot analysis of H and G' (Supporting
Information, Figures S13c, d), the stoichiometric ratio was
determined to be 1:1, supporting the 4:1 binding mode between
H and G. Furthermore, we carried out the fluorescence titration
showed obvious ROE correlations between the phenyl protons H
and methyl protons H , H , H of H due to the C−H···π as well
as π−π interactions (Figure 1d). However, no distinct interaction
between alkyl chain protons H and phenyl protons H was
a
,
H
e
b
c
d
e
a
discovered, illustrating that no self-inclusion structure existed in H. experiments in DMSO/H
2
O (1:99, v/v) at 298 K to determine the
Afterwards, the binding mode between H and G was
association constant (K ). Through the nonlinear curve-fitting
a
determined as 4:1 through the analysis of Job's plot (Supporting
4
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RESEARCH ARTICLE
Figure 3. (a) Fluorescence variation at 462 nm of G⊂H@Hg2+ with the addition of 10 equiv. of 20 different amino acids; (b) Fluorescence spectra of G⊂H@Hg in
2+
2+
the presence of increasing amounts of L-Cys; (c) Fluorescence opening degrees at 462 nm in competition experiments of G⊂H@Hg with 1 equiv. of L-Cys and
1
3
0 equiv. of other amino acids; (d) Absolute fluorescence quantum yield of G⊂H@Hg2+ with L-Cys. (Experimental conditions: solution: DMSO/H
10 nm; slit widths: Ex. 5 nm, Em. 1.5 nm; 298 K; [G] = 10 µM, [H] = 40 µM and [Hg2+] = 1 equiv.).
2
O (1:99, v/v); λex =
was calculated to be (3.0±0.5)×106 M−1
(1.56×10 s and 9.64×10 s , respectively). The results and
phenomena further supported the mechanism of SAIEE that the
structure of G⊂H restricted the intramolecular rotation of phenyl
7
−1
8
−1
method, the
K
a
(
Supporting Information, Figure S14).
rings of G resulting in the nonradiative relaxation pathway and
populated excitons that underwent radiative decay.[24b,26]
Fluorescent Properties of Supramolecular Assembly G
⊂
H.
The emission of individual H and G in dilute solutions is
negligible, while the mixed system of H and G exhibited intense
blue fluorescence emission (under the 365 nm UV lamp),
reflecting the formation of supramolecular assembly G⊂H (Figure
Detection of Hg2+ with G
⊂
H.
Inspired by the above strong fluorescence of the
supramolecular assembly G⊂H, we explored the application of
the G⊂H in sensing different cations. The properties of selective
cation detection were elaboratively investigated by corresponding
real-time fluorescence response after adding 30 different metal
1
b). The reasonable explanation was that the individual TPE
derivative G showed no fluorescence in the dispersed state due
to the unrestricted free rotation of the phenyl group, generating a
non-radiative energy decay. However, with the addition of H, the
intramolecular rotation of phenyl rings of G was restricted by
cavities of H, which could be described as the process of
supramolecular assembly-induced emission enhancement
+
2+
3+
3+
2+
3+
2+
ions (10 equiv) including Na , Mg , Fe , Cr , Zn , Al , Fe ,
2
+
2+
2+
2+
+
+
2+
+
3+
3+
3+
3+
4
Co , Cd , Ca , Cu , Cu , K , Ni , NH , Ce , Pr , Nd , Sm ,
3+
3+
3+
3+
3+
3+
3+
3+
3+
2+
Eu , Gd , Tb , Dy , Ho , Er , Tm , Yb , Lu , and Hg ,
respectively (Cl− as the counterions) into the dilute DMSO/H
(
SAIEE). Further fluorescent experiments were carried out to
2
O
investigate the fluorescence quantum yield and fluorescence
lifetime of G⊂H. As illustrated in Figure S15 and Table S1, the
photoluminescence decay profile displayed that the fluorescence
lifetime of G⊂H was 4.793 ns, which was more durable than
individual G (1.021 ns). The absolute fluorescence quantum yield
of G⊂H was measured at 41.48%, which was much higher than
G. Intriguingly, G⊂H showed 5 times bigger radiative decay rate
(1:99, v/v) solution of G⊂H under identical conditions. Notably,
only Hg2+ revealed a conspicuous fluorescence quenching and
the fluorescence intensity decreased by 20 times as well as the
material quantum yield was reduced to 1.25% (Figure 2a;
Supporting Information, Figures S16 and S17). More importantly,
the fluorescence emission change could be rapidly and
conveniently observed with naked eyes when the test solution
was irradiated and excited with a UV light of 365 nm (Figure 2b).
7
−1
constant (8.65×10 s ) as well as 8 times smaller nonradiative
decay rate constant (1.22×108 s−1) in comparison with G
5
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For the sake of substantively researching the probe G⊂H
to fluorescence titration experiments (Figure 3b). Simultaneously,
the LOD for L-Cys was determined to be 4.7×10−7 M via the 3σ/s
method, indicating a highly detection sensitivity (Supporting
Information, Figure S25). It is worth mentioning that the absolute
quantum yield of G⊂H@Hg2+ with L-Cys returned to 36.61%,
demonstrating that L-Cys could effectively recover the
fluorescence of G⊂H@Hg2+ from another perspective (Figure 3d).
Moreover, controlled experiments were employed to investigate
the anti-interference ability of G⊂H@Hg2+ for L-Cys with the
coexistence of acids, bases and other amino acids. The
subsequent results showed that various competitive factors could
not induce any interference for sensing L-Cys (Figure 3c;
Supporting Information, Figures S23, S24), which sufficiently
suggested that the supramolecular complex G⊂H@Hg2+ could
serve as a considerable probe for detecting L-Cys through
fluorescence “turn-on” response.
2+
applied in specific detection of Hg , the competition experiments
were conducted to test the fluorescence change in the presence
of interfering metal cations. The results exhibited that coexisting
competition cations had no interference on the fluorescence
quenching of Hg2+ (Figure 2c). Furthermore, as shown in Figure
2
d and Figure S19, the decrease of fluorescence emission
intensity was linear with the increase of Hg2+ concentration in the
range of 0−40 μM as well as the quenching reached the maximum
extent when the addition amount of Hg2+ was equal to H,
suggesting that the binding ratio between the H and Hg2+ was 1:1.
Subsequently, the limit of detection (LOD) was calculated to be
4
.1×10−7 M through utilizing the fluorescent titration and 3σ/s
2+
method, indicating a satisfactory sensitivity toward Hg . Besides,
we performed a series of fluorescence experiments under
different temperatures and pH conditions (Supporting Information,
Figure S18; Figures 2e, 2f), and the results identified that the
fluorescence remained in the quenched state, demonstrating that
Rapid Adsorption and Efficient Removal of Hg2+ in Water.
G H had an excellent performance for stable detection of toxic
⊂
To demonstrate that the probe G⊂H has an excellent
Hg2+ in potential applications. The specific coordination of carbon-
sulfur double bonds with Hg2+ endowed the fluorescence probe
G⊂H based on supramolecular assembly with the characteristics
of selective, sensitive, and anti-interference detection of Hg2+ in
complicated environmental systems.
2+
performance for removing Hg in water, we performed the
2+
adsorption experiments in Hg aqueous solution. The aqueous
solution (10 mL) containing 40 ppm Hg2 was firstly added to the
DMSO solution of G⊂H (5 μM, 0.5 mL), as shown in Figure 4a.
Visible white suspension was observed immediately in the
solution, indicating the strong interaction between Hg2 and sulfur-
containing functional groups of G⊂H. The mixture was stirred for
+
+
H@Hg2+ with L-Cys.
2+
Turn on Fluorescence of G
⊂
1 h in order to guarantee that Hg completely coordinated with
G⊂H. Subsequently, inductively coupled plasma spectrometer
(
in the mother liquor after getting rid of the precipitation by
It is universally acknowledged that amino acids, as the
building blocks of proteins, have a close relationship with
biological life activities. In order to explore the sensing properties
of supramolecular polymer G⊂H@Hg2+ toward amino acids, 20
common amino acids including L-Lys, L-Trp, L-Arg, L-Ala, L-Asn,
L-Asp, L-Glu, L- Gly, L-Leu, L-Met, L-Phe, L-His, L-Pro, L-Ser, L-
Thr, L-Tyr, L-Val, L-Ile, L-Gln, and L-Cys were selected to add into
ICP) analysis was applied to analyze the content of residual Hg2+
centrifugation. The result illustrated that the concentration of
2+
residual Hg
was only 0.71 ppm, suggesting that the
supramolecular assembly G⊂H has an excellent removal
efficiency of Hg2 up to 98% in a single treatment. On the basis of
the outstanding Hg2 adsorption capacity, we further evaluated
the recycling property of G⊂H. The isolated white precipitate was
+
+
2+
the solution of G⊂H@Hg , respectively. As a result, the
fluorescence of G⊂H@Hg2+ could be selectively turned on by L-
2
redispersed in DMSO, upon the addition of Na S, the suspended
black precipitation of HgS was generated instantly. Ultimately, the
probe G⊂H was completely recovered via centrifugation and
another five cycles were conducted in the identical removal
procedures, showing negligible loss of activities in the adsorption
of Hg2 (Figure 4b). All of the features proved that G⊂H
Cys and the fluorescence emission intensity increased tenfold
(
Figure 3a; Supporting Information, Figure S21). Furthermore, the
fluorescence intensity increased rapidly and reached the
maximum value when L-Cys was added to 1 equivalent according
+
Figure 4. (a) Diagrammatic sketch of G⊂H in the efficient removal of Hg2+ and material recycling in water; (b) Reusability of G⊂H in removing Hg2+ in water.
6
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RESEARCH ARTICLE
Figure 5. (a) 1H NMR spectra (400 MHz, DMSO-d
, 298 K) of (1) H (5.0 mM) + Hg2+ (5.0 mM) and (2) H (5.0 mM); (b) Fluorescence decay profile of G⊂H@Hg2+
6
(
(
solution: DMSO/H
d) G⊂H@Hg2+ and (e) G⊂H@Hg with L-Cys ([G] = 1 mM, [H] = 4 mM, [Hg2+] and [L-Cys] = 1 equiv.).
2
O (1:99, v/v); λex = 310 nm; 298 K; [G] = 10 µM, [H] = 40 µM and [Hg2+] = 1 equiv.) ; 2D DOSY spectra (600 MHz, DMSO-d
6
, 298K) of (c) G⊂H;
2+
achieved simultaneous detection and removal of the toxic heavy
ppm for protons a and b in the methyl groups of N(CH3)2 with
2+
metal Hg in water. More importantly, our study also provided a
considerable and applicable strategy toward dealing with
pollutants in the practical application via the construction of
supramolecular polymers with desirable recyclability.
2+
different chemical environments. After combining with Hg , the
two groups of protons shifted downfield to 3.65 ppm and 3.49 ppm
respectively, owing to the de-shielding effect caused by
2+
coordination with electron-withdrawing Hg . These results were
consistent with the literature that the C=S sulfur atom in the N,N-
dimethyldithiocarbamoyl group acts as the ligand of Hg2+ instead
of the C-S-C sulfur atom.[33] Inspired by the dipole-cation
Detection Mechanism of Fluorescence Probe.
The structure−property relationship of the supramolecular
H in the efficient detection of Hg2+ and L-Cys
2+
assembly probe G
⊂
coordination between C=S of H and Hg , we deduce that the
was further investigated through a series of experiments. The
fluorescence quenching mechanisms of analyte toward sensor
can be mainly classified according to three aspects: (i) the
structure destruction of fluorescence sensor; (ii) dynamic
quenching of energy transfer between sensor and analyte; (iii)
static quenching (also referred to as contact quenching) of the
non-luminescent ground state complex formed by the sensor and
the analyte.[32] However, the negative field region of G⊂H@Hg2+
could still distinctly observe identical chemical shifts in
consistency with G⊂H in the 1H NMR experiments (Supporting
Information, Figure S26), reflecting the structure of the
fluorescence probe G⊂H remained intact due to electrostatic
interaction. UV−vis spectroscopy showed that no overlap
between the emission peak of G with AIE properties and the
absorption peak of H after adding Hg2+ (Supporting Information,
Figure S27a), indicating that dynamic quenching based on energy
transfer could not reasonably explain the quenching mechanism.
To better rule out the mechanism of selective quenching of
quenching mechanism should be a static quenching process due
to the formation of non-luminescent ground state complex,
0
exhibiting significant characteristics: (i) τ /τ = 1; (ii) the absorption
spectrum of the detector changed after adding the quenching
agent; (iii) the stability of the ground state complex deteriorated,
resulting in a decrease in quenching efficiency with increasing
temperature.[34] Accordingly, the fluorescence lifetimes of G⊂H
(τ
0
) and G⊂H@Hg2+ (τ) were measured to be 4.793 ns and 4.807
ns, respectively by fluorescence decay experiments (Supporting
Information, Figure S15a; Figure 5b), implying the presence of
Hg2+ hardly affected the excited state lifetime of the probe, which
was recognized as the dominating indicator of static quenching.
Afterwards, the UV-vis absorption spectrum of G⊂H@Hg2+
displayed a red shift and decreased intensity compared with G⊂H
(Supporting Information, Figure S27b), which strongly suggested
the generation of ground state complex during static quenching.
The trend graph of fluorescence quenching constant with
temperature explicitly illustrated that the quenching efficiency
reduced with increasing temperature on account of the decrease
in the stability of the ground state complex (Supporting
Information, Figure S28).
2+ 1
fluorescence probe by Hg , H NMR experiments were used to
evaluate the coordination effect between H and Hg2+ (Figure 5a).
Free H exhibited two sharp singlet peaks at δ 3.46 ppm and 3.35
7
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To further confirm the conclusion, scanning electron
microscopy (SEM) and 2D DOSY experiments were conducted to
gain direct evidence. G⊂H@Hg2+ represented a larger particle
size in the SEM images and a lower value of D calculated from
and the Fundamental Research Funds for the Central Universities
for financial support.
Keywords: aggregation-induced emission • supramolecular
2
D DOSY spectra than G⊂H (Figures 5c, d; Supporting
assembly • pillar[n]arene • sensing and detection • fluorescence
Information, Figures S29a, b), indicating that the non-luminous
ground state complex was generated with a larger diameter and
higher molecular weight. The EDX experiment results also
showed that almost all Hg2+ are distributed in spherical assembly
[
1]
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(
Supporting Information, Figure S29c), suggesting the structure of
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Entry for the Table of Contents
A supramolecular functional system with appreciable photoluminescent properties on the basis of the supramolecular assembly-
induced emission enhancement (SAIEE) mechanism is successfully constructed through host-guest interactions, which shows great
potentials in simultaneously selective detection and efficient removal of Hg2+ from water owing to the formation of non-luminous
ground state complexes. This system also possesses excellent regeneration ability without the loss of adsorption activity.
1
0
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