Efficient enhancement of fluorescence emission via TPE functionalized cationic pillar[5]arene-based host–guest recognition-mediated supramolecular self-assembly

Article abstract of DOI:10.1016/j.tetlet.2017.12.009

A tetraphenylethene (TPE) functionalized cationic pillar[5]arene (CWP5-TPE) was successfully synthesized, and the intramolecular rotation of the TPE motif was restricted via cationic pillar[5]arene-based host–guest recognition-mediated supramolecular self

Full text of DOI:10.1016/j.tetlet.2017.12.009

Accepted Manuscript
Efficient enhancement of fluorescence emission via TPE functionalized cationic
pillar[5]arene-based host−guest recognition-mediated supramolecular self-as-
sembly
Jifu Sun, Li Shao, Jiong Zhou, Bin Hua, Zhihua Zhang, Qing Li, Jie Yang
PII:
S0040-4039(17)31501-0
https://doi.org/10.1016/j.tetlet.2017.12.009
TETL 49510
DOI:
Reference:
Tetrahedron Letters
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Received Date:
Revised Date:
Accepted Date:
25 October 2017
27 November 2017
2 December 2017
Please cite this article as: Sun, J., Shao, L., Zhou, J., Hua, B., Zhang, Z., Li, Q., Yang, J., Efficient enhancement of
fluorescence emission via TPE functionalized cationic pillar[5]arene-based host−guest recognition-mediated
supramolecular self-assembly, Tetrahedron Letters (2017), doi: https://doi.org/10.1016/j.tetlet.2017.12.009
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Efficient enhancement of fluorescence emission via TPE functionalized cationic
pillar[5]arene-based host−guest recognition-mediated supramolecular self-assembly
Jifu Sun∗, Li Shao, Jiong Zhou, Bin Hua, Zhihua Zhang, Qing Li and Jie Yang∗
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
A tetraphenylethene (TPE) functionalized cationic pillar[5]arene (CWP5-TPE) was successfully
synthesized, and the intramolecular rotation of the TPE motif was restricted via cationic
pillar[5]arene-based host−guest recognition-mediated supramolecular self-assembly in water,
resulting in the efficient enhancement of fluorescence emission based on the aggregation
induced emission (AIE) mechanism. CWP5-TPE self-assembled into nanoribbons while the
host–guest inclusion complex formed into supramolecular amphiphile nanoparticles in water.
Received in revised form
Accepted
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved.
host−guest recognition
supramolecular self-assembly
Supra-amphiphile
TPE functionalized cationic pillar[5]arene
AIE
Pillar[n]arenes, whose repeating units are connected by
methylene bridges at the para-positions of 2,5-dialkoxybenzene
rings, mainly including pillar[5]arenes,1 pillar[6]arenes2 and other
tetraphenylethene (TPE) has been extensively studied. Upon
restriction of intramolecular rotation of the phenyl rings by
increasing the solvent viscosity, lowering the temperature or
applying high pressure, the luminous efficiency of TPE can be
greatly enhanced due to the obstruction of the nonradiative
pathway and activation of radiative decay.17 Moreover, TPE-
based florescence nanoparticles were also widely constructed to
improve their luminous efficiency recently.17f,17j,17k,18 Although
there are a few literatures being reported to modify the TPE
moieties onto neutral pillararenes to construct supramolecular
polymers,17b,17c to the best of our knowledge, the research of
modifying TPE moieties onto water-soluble pillararenes and
further using them to construct fluorescence nanoparticles has not
been reported so far.
high-level pillar[n]arenes (n
≥ a
7),3−6 have stimulated
tremendous upsurge of interest since their first report in 2008.7
Due to their unique symmetric pillar-shaped structures, facile
tunable functionality, as well as intriguing host−guest binding
abilities,1−7,8 pillararenes have been defined as a new generation
of macrocyclic host molecules in supramolecular chemistry after
cyclodextrins,9 crown ethers,10 cucurbiturils11 and calixarenes.12
In recent years, the host−guest properties of pillararenes have
been investigated intensively and also been explored widely in
the construction of numerous supramolecular systems, such as
supramolecular polymers,1k,1p,1s drug-release systems,1r,2a,2c,2g,2h
transmembrane channels1e,1v,1w and other advanced functional
materials.13 Among them, pillararene-based fluorescent materials
have attracted considerable attention owing to their promising
applications in cell imaging,1t drug delivery1r,2c,2g and
chemosensors.1o,2e,14
However, the conventional organic fluorophores have a fatal
drawback that the luminescence in aqueous solution is usually
quenched due to aggregation-caused quenching (ACQ) effect.
Obviously, ACQ effect limits the applications of the
conventional organic fluorophores in practice to
a great
extent.11e,15 In 2001, Tang et al discovered the phenomenon
named aggregation induced emission (AIE),16 which is
completely opposite to ACQ effect. Many scholars have made
great efforts to the development of materials with AIE in recent
years.17
them, as
a
typical AIE luminogen,
——— Among
∗ Corresponding author. Tel.: +86-571-8795-3189; fax: +86-571-8795-3189; e-mail: sunjifu@zju.edu.cn (J. Sun)
∗ Corresponding author. Tel.: +86-571-8795-3189; fax: +86-571-8795-3189; e-mail: jieyang@zju.edu.cn (J. Yang)

2
reaction was adopted to conjugate the TPE moiety to the cationic
water-soluble pillar[5]arene. All the compounds were obtained
under moderate reaction conditions with satisfactory yields.
Based on the host−guest interactions between the functionalized
cationic pillar[5]arene (CWP5-TPE) and sodium dodecyl
benzene sulfonate (SDBS), we presented a novel strategy to
restrict the intramolecular rotation of the benzene rings of TPE,
resulting in a significant fluorescence emission enhancement
(Scheme 1).
To ensure the formation of a host−guest complex between
CWP5-TPE and SDBS, 1H NMR spectroscopy in D2O was
firstly utilized by using cationic water-soluble pillar[5]arene
CWP5 and sodium benzenesulfonate SBS as model compounds.
1
Figure 1 shows the H NMR spectra of SBS in D2O recorded in
the absence and presence of approximately 1.0 equiv. of CWP5.
Only one set of the peaks was observed, indicating the fast-
exchange complexation on the NMR time scale. Compared with
the spectrum of free SBS, the peaks of protons Ha-c on SBS
shifted upfield significantly (∆δ = −0.17, −1.54 and −2.61 ppm
for Ha, Hb and Hc, respectively, Figure 1) after complexation with
CWP5. Meanwhile, the peaks of protons H1-5 on CWP5 shifted
downfield or upfield slightly (∆δ = −0.09, 0.04, −0.09, −0.07 and
0.03 ppm for H1, H2, H3, H4 and H5, respectively, Figure 1). The
reason is that these protons on the guest located in the cavity of
the pillararene to form an inclusion complex and were shielded
by the electron-rich cavity of pillararene. Moreover, H1 was split
into two separated peaks as a result of the asymmetric structure
of SBS whose anionic sulfonate head group was close to the
cationic quaternary ammonium groups at one end of the CWP5
and formed into a 1:1 inclusion complex.19 2D NOESY NMR
spectrum of the solution of CWP5 and SBS in D2O was also
carried out to prove the formation of host−guest complex (Figure
S13). Nuclear overhauser effect (NOE) correlations were
observed between protons Ha and H1, H2, H3, H4 (A, B, C points,
Figure S13), Hb and H2, H3, H4 (D, E points, Figure S13), Hc and
H1, H4 (F, G points, Figure S13). These results proved that the
negatively charged benzene sulfonate SBS threaded into the
positively charged CWP5 and formed into an inclusion
complex.19
Scheme 1. Top: structures and cartoon representations of
CWP5-TPE, SDBS, CWP5 and SBS; bottom: cartoon
representation of the self-assemblies of CWP5-TPE and
CWP5-TPE⊃SDBS.
Isothermal titration calorimetry (ITC) is a useful method to
study the association constant (Ka) and stoichiometry of a host–
guest complex and its thermo-dynamic parameters (enthalpy
change ∆H° and entropy change ∆S°). From ITC experiments
(Figure S14), the Ka value of CWP5⊃SBS was calculated to be
(8.83 1.05) × 104 M−1. The titration data were well fitted by
computer simulation by using the “one set of binding site” model,
demonstrating 1:1 complexation between CWP5 and SBS
(Figure S14). Moreover, according to the thermodynamic data
listed in Figure S14, the complexation was driven by both
enthalpy and entropy changes (∆H° = −15.27 KJ mol−1; T∆S° =
13.02 KJ mol−1, |∆H°| > |T∆S°|).19 In addition, from the UV-vis
absorption titration spectra (Figure S15), Job plot of complex
CWP5-TPE⊃SDBS showed
a 1:1 stoichiometry between
CWP5-TPE and SDBS which was in accordance with the ITC
results of demonstrating 1:1 complexation between CWP5 and
SBS (Figure S14) by plotting the absorbance difference at 291
nm (a characteristic absorption peak of CWP5-TPE) against the
mole fraction of CWP5-TPE (Figure S15).
Figure 1. Partial 1H NMR (400 MHz, D2O, 298.15 K) spectra: (a) CWP5
(5.0 mM); (b) CWP5 (5.0 mM) and SBS (5.0 mM); (c) SBS (5.0 mM).
Herein we designed and synthesized a novel functionalized
cationic pillar[5]arene which was modified with TPE. A click

Figure 2. (a) Fluorescence emission spectra of CWP5-TPE (1.0 × 10−4 M) in
the presence of SDBS from 0.0 equiv to 2.0 equiv in water. The inset
photograph shows the corresponding fluorescence of CWP5-TPE alone (left)
and CWP5-TPE⊃SDBS (right, molar ratio 1:2) in water upon excitation at
365 nm using a UV lamp at 298.15 K. (b) Fluorescence emission spectra of
CWP5-TPE⊃SDBS (molar ratio 1:1) aqueous solution at different
concentrations (from 1.0 × 10−5 M to 1.0 × 10−4M). The inset photograph
shows the corresponding fluorescence of CWP5-TPE⊃SDBS (molar ratio
Figure 3. TEM images: (a) CWP5-TPE (1.0 × 10−3 M) and (b) CWP5-
TPE⊃SDBS (1.0
10−3 M). (c) Amplified TEM image of CWP5-
TPE⊃SDBS (1.0 × 10−3 M). (d) DLS study and Tyndall effect of the
host−guest complex CWP5-TPE⊃SDBS (1.0 × 10−3 M).
×
1:1) in water at the concentrations of 1.0 × 10−5 M (left) and 1.0 × 10−4
M
(right), respectively, upon excitation at 365 nm using a UV lamp at 298.15 K.
Although the average diameter of CWP5-TPE⊃SDBS
increased slightly upon its concentration increasing, the average
diameter of CWP5-TPE⊃SDBS was still approximately 100 nm
(Figure S21),1t which was consistent with the TEM results
(Figure 3b and Figure 3c) as a result of the nanoparticles
composed of multiple layers structures self-assembled by
CWP5-TPE⊃SDBS (Scheme 1). CWP5-TPE self-assembled
Then, we utilized fluorescence titration experiments to
confirm the formation of host−guest complex between CWP5-
TPE and SDBS. As shown in Figure 2a, a very weak
fluorescence emission of CWP5-TPE was observed at 461 nm,
while upon addition of SDBS from 0.1 equiv to 2.0 equiv, the
emission intensity of the supramolecular aggregates increased
significantly and a new emission band centered at 477 nm
appeared in the fluorescent spectra as a result of the host−guest
interactions between CWP5-TPE and SDBS. The fluorescence
emission intensity of CWP5-TPE increased approximately 11-
fold by addition of 2.0 equiv of SDBS. Furthermore,
concentration-dependent fluorescent emission spectra of CWP5-
TPE⊃SDBS (molar ratio 1:1, Figure 2b) was conducted. As a
result of the stoichiometry of host–guest complex was 1:1
according to the ITC experiments (Figure S14) and the UV-vis
absorption titration experiments (Figure S15), additionally, in
order to keep in line with the molar ratio of host-guest in critical
aggregation concentration (CAC) experiments (Figure S17), we
adopted the same molar ratio of host-guest (1:1) in the
investigation of concentration-dependent fluorescent emission
−π
into nanoribbons driven by hydrophobic interactions and π
interactions of the TPE moieties with very weak emission in
water (Figure 2a) and its fluorescence quantum yield (ΦF) was
1.23 % (Table S1), therefore, it can be acted as a macrocycle
amphiphile molecule. However, after adding SDBS, the
nanoribbons transformed into nanoparticles as a result of the
formation of suprarmolecular amphiphile between CWP5-TPE
and SDBS driven by hydrophobic interactions, π−π interactions
and electrostatic interactions of the CWP5-TPE and SDBS. The
rotation of the benzene rings of TPE was further restricted in the
amphiphile nanoparticles formed by CWP5-TPE⊃SDBS so that
the nonradiative pathway was obstructed and the radiative decay
was activated, therefore the emission intensity of the
suprarmolecular amphiphile nanoparticles (ΦF was 11.84 %,
Table S1) was more stronger than the nanoribbon formed by
CWP5-TPE alone (Figure 2a). Additionally, the solution of
CWP5-TPE⊃SDBS exhibited a clear Tyndall effect (Figure 3d),
indicating the formation of regular aggregates of nanopaiticles.
spectra. At low concentration (1.0
×
10−5 M), CWP5-
TPE⊃SDBS had very weak emission, while with the
concentration increasing, the luminescence intensity increased
gradually. When the concentration of CWP5-TPE⊃SDBS
increased to be 9.0 × 10−5 M, which is approximately in
accordance with the CAC value of CWP5-TPE⊃SDBS (8.0 ×
10−5 M, Figure S17), the fluorescence intensity reached the
highest value, which is approximately 8-fold of that at 1.0 × 10−5
M. Notably, the fluorescence emission of CWP5-TPE⊃SDBS
could be clearly visualized under UV light (excited at 365 nm) by
naked eyes (the inset photographs in Figure 2). We speculated
that the reason for the fluorescence intensity enhancement may
be that the negatively charged SDBS threaded into the cavity of
CWP5-TPE to form a supramolecular amphiphile and further
self-assembled in solution which made TPE moiety stack more
tightly so that the intramolecular rotation of the benzene rings of
TPE was further restricted.
In summary, novel AIE-active nanoparticles were fabricated
by utilizing CWP5-TPE⊃SDBS as the self-assembly building
block. In contrast to the nanoribbons self-assembled from
CWP5-TPE alone, CWP5-TPE ⊃ SDBS self-assembled into
nanoparticles and the average diameter of the nanoparticles was
approximately 100 nm. The nanoribbons showed very weak
fluorescence emission, while the nanoparticles showed much
more stronger fluorescence emission at the same concentrations
because the intramolecular rotation of the benzene rings of the
TPE group was restricted significantly and the nonradiative
decay pathway was blocked by the formation of a supramolecular
amphiphile. Therefore, we developed
a new strategy for
fabricating the AIE-emissive nanoparticles based on host−guest
chemistry of CWP5-TPE and SDBS. These research results
indicated that functionalized cationic pillar[5]arene-based
host−guest complexes will be significant for the development of
many fields such as biological and pharmaceutical fields,
including cell imaging, drug delivery and biosensors, etc.
Finally, in order to verify the self-assembly behaviours of
CWP5-TPE and CWP5-TPE⊃SDBS. Transmission electron
microscopy (TEM) and dynamic light scattering (DLS) were
investigated (Figure 3 and Figure S21). The TEM images
revealed that the aggregates of CWP5-TPE were ribbon-like
assemblies (Figure 3a) while the aggregates of CWP5-
TPE⊃SDBS were spherical assemblies (Figure 3b and Figure 3c).
Acknowledgments

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Graphical Abstract
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Efficient enhancement of fluorescence emission
via TPE functionalized cationic pillar[5]arene-
based host−guest recognition-mediated
supramolecular self-assembly
Leave this area blank for abstract info.
Jifu Sun∗, Li Shao, Jiong Zhou, Bin Hua, Zhihua Zhang, Qing Li and Jie Yang∗
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6
Research highlights
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Cationic pillar[5]arene modified with TPE was
synthesized for the first time.
Host−guest interactions were confirmed by NMR,
UV−vis absorption spectra and ITC.
The fluorescence emission was efficiently
enhanced by host−guest complexion.
The self-assemblies of host−guest complexes were
verified by TEM and DLS.