Amphiphilic Organic Cages: Self-Assembly into Nanotubes and Enhanced Anion-π Interactions

Article abstract of DOI:10.1002/cplu.202000143

An amphiphilic organic cage was synthesized and used as self-assembly synthon for the fabrication of novel functional supramolecular structures in solution. The transmission electron microscopy (TEM) results showed that this amphiphilic cage self-assemble

Full text of DOI:10.1002/cplu.202000143

A Multidisciplinary Journal Centering on Chemistry
Accepted Article
Title: Amphiphilic Organic Cages: Self-Assembly into Nantubes and
Enhanced Anion-Pi Interactions
Authors: Shaodong Zhang, Zi-Ying Li, Chuanlong Li, Pan Li, Yong Zuo,
Xiaoning Liu, Lingyi Zou, Qixin Zhuang, Shan Gao, Xiaoyun
Liu, and Shijun Xu
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To be cited as: ChemPlusChem 10.1002/cplu.202000143
Link to VoR: https://doi.org/10.1002/cplu.202000143
01/2020

10.1002/cplu.202000143
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Amphiphilic Organic Cages: Self-Assembly into Nantubes and
P
Enhanced Anion- Interactions
Zi-Ying Li+,[a] Chuanlong Li+,[b] Pan Li,[b] Yong Zuo,[b] Xiaoning Liu,[b] Shijun Xu,[a] Lingyi Zou,[b] Qixin
Zhuang,[a] Shan Gao,*[c] Xiaoyun Liu*[a] and Shaodong Zhang*[b]
[a]
[b]
Z.-Y. Li, Prof. Dr. Q. Zhuang, Prof. Dr. X. Liu
Key Laboratory of Specially Functional Polymeric Materials and Related Technology (ECUST), Ministry of Education
East China University of Science and Technology
130 Meilong Road, Shanghai 200237, China
E-mail: liuxiaoyun@ecust.edu.cn
Dr. C. Li, Dr. P. Li, Y. Zuo, X. Liu, L. Zou, Prof. Dr. S. Zhang
Frontiers Science Centre for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, School of Chemistry and
Chemical Engineering
Shanghai Jiao Tong University
800 Dongchuan Road, Shanghai 200240, China
E-mail: sdzhang@sjtu.edu.cn
[c]
[+]
Dr. S. Gao
Neurological Department
Shanghai Jiao Tong University affiliated the Sixth People Hospital, South Campus
Shanghai 200240, China
E-mail: 15921515971@163.com
These authors contributed equally.
Supporting information for this article is given via a link at the end of the document.
Abstract: In this work, a new amphiphilic organic cage was
synthesized and used as self-assembly synthon for the fabrication of
novel functional supramolecular structures in solution. The
transmission electron microscopy (TEM) results showed that this
amphiphilic cage self-assembled in aqueous solution into unilamellar
nanotubes with a diameter of 29 ± 4 nm at a concentration of 0.05 mg
mL-1. Interestingly, the self-assembly of this cage significantly
enhanced the anion-π interactions as indicated by a remarkable
increasement of association constant (Ka) between Cl- and this
amphiphilic cage after self-assembly. In specific, Ka was increased
from 223 M-1 for discrete state cages in methanol to 6800 M-1 for
aggregated cages after self-assembly in water at the same
concentration of 2.26 × 10-5 M. In order to explain this self-assembly
enhanced anion-π interactions phenomenon, a synergistic effect
mechanism was proposed.
Anion-π interaction is the non-covalent interaction
between an anion and an electron-deficient π-arene
species.[9] To data, it has been employed as the key driving
force to prepare various fascinating supramolecular
structures with different morphologies and dimensions.[10]
However, what is the influence of a given self-assembly on
anion-π interactions? This question has been overlooked
and remains elusive.
As a novel type of porous materials, organic cages have
recently attracted increasing interest.[1] They exhibit a three-
dimensional cavity with relatively rigid framework and several
windows, which are effective to encapsulate various guest
molecules. When they self-assemble in bulk, extra porosity
can be created by the formation of intermolecular channels.
The unique characteristics of organic cages with intrinsic and
extrinsic voids have been widely applied to sensing,[2]
catalysis,[3] selective adsorption and separation,[4] etc.
However, their self-assembly in solution has been
underexplored. The building blocks of solution self-assembly
are amphiphiles, which typically include small molecules,[5]
dendrimers[6] and various types of copolymers.[7] When
organic cages are rendered amphiphilic,[8] the marriage with
their porous feature should be of great interest for the search
of novel functional nanomaterials.
Figure 1. (a) Cartoon illustration of self-assembly of Cage 1 into nanotubes and
their unilamellar membrane structure. (b) Synergistic effect of self-assembly
leading to enhanced anion-π interactions between chloride ion and Cage 1.
1
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Herein, we report the construction of amphiphilic organic
Cage 1, which is used as a novel type of building blocks that
self-assemble into nanotubes in aqueous solution (Figure 1).
downfield from 5.85 ppm to 6.58 ppm compared to the
hydrophilic precursor (Figure 2a and Figure S1 in Supporting
Information). The peak arisen from H4 is also shifted
downfield from 3.95-4.00 ppm to 4.12-4.19 ppm. MALDI-TOF
MS provides further evidence for the formation of Cage 1. As
shown in Figure 2b, three peaks were found at m/z= 2217.01,
2239.00 and 2254.98, assigned to [M+H]+ (calcd. 2217.01),
[M+Na]+ (calcd. 2238.99) and [M+K]+ (calcd. 2254.96),
respectively. We tried in vain to grow single crystals of Cage
By comparing the anion-π binding of anion Cl- and Cage 1
,
in discrete and self-assembled form of the latter,
respectively, we aim to demonstrate how this non-covalent
interaction is enhanced by the formation of superstructure of
1
, likely due to the conformational flexibility introduced by
three hydrophilic arms to Cage 1
.
nanotube.
Scheme 1. Synthesis of Cage 1. (a) Cyanuric chloride, diisopropylethylamine
(DIPEA), THF, 0 oC, 75 %; (b) Phloroglucinol, DIPEA, Acetone, rt, 35 %; (c) R-
Ts, K2CO3, KBr, CH3CN, 80 oC, 75 %; (d) aqueous NH3, MeOH, rt, 12 h, 60 %;
(e) Br2, KOH, 12 h, 90 oC, 63 %; (f) THF, K2CO3, 0 oC~reflux, 50 %.
Cage 1 was synthesized by grafting three hydrophilic
moieties onto
a hydrophobic organic cage precursor
bis(tetra-oxacalix[2]arene[2]triazine) (Scheme 1). This cage
precursor was chosen as it has a rigid skeleton and three V-
shaped electron-deficient clefts, which works as efficient
Figure 2. (a) 1H NMR and (b) experimental and calculated MALDI-TOF MS
spectra of Cage 1.
anion receptor.[10e,11] Typically, half cage
1 was first prepared
via the reaction of phloroglucinol with excessive amount of
Self-assembly of Cage 1 was triggered by injection of its
THF solution into water. Typically, 100 µL of THF solution of
Cage 1 (1 mg mL-1) was injected into 2 mL of deionized water
(VTHF:VH2O = 1:20), followed by 10 s vortexing to yield the self-
assembled superstructures with a concentration of 0.05 mg
mL-1, higher than the critical aggregation concentration (CAC)
of Cage 1 (ca. 0.02 mg mL-1, Figure S5 in Supporting
Information). The morphology of the assemblies was
examined by transmission electron microscopy (TEM). As
shown in Figure 3a, the TEM image reveals that nanosized
tubular superstructures were formed, as evidenced by the
clear contrast between the dark periphery and the lighter
inner cavity. The length of these nanotubes ranges from tens
to hundreds of microns with an average diameter and
polydispersity index (PDI) of 29 ± 4 nm and 0.14, respectively
(Figure 3b). The wall thickness of the nanotubes is 4-5 nm.
The self-assembly mechanism of Cage 1 includes two
aspects: one is the driving force of the self-assembly, and
another is the molecular packing in the wall of nanotubes.
Considering its amphiphilic nature and the parallel benzene-
cyanuric chloride in the presence of diisopropylethylamine
o
(DIPEA) at 0 C. Further treatment of the half cage
1 with
phloroglucinol in acetone at room temperature afforded the
hydrophobic cage precursor
was synthesized through
2
[11b and d]. The hydrophilic part
three-step procedure[12]
5
a
.
Commercially available trihydroxymethyl benzoate was first
reacted with tosylated monomethoxy-triethylene glycol, the
product of which
corresponding amide
Hoffman’s degradation, the hydrophilic moiety
3
was subsequently converted to the
with ammonia. After a subsequent
was
4
5
obtained. Three hydrophilic precursors were then grafted
onto one hydrophobic cage through aromatic nucleophilic
substitution, yielding the amphiphilic Cage 1 (50% yield). The
structure of Cage 1, hydrophobic cage precursor and
1
hydrophilic part were characterized by H NMR, 13C NMR
and matrix-assisted laser desorption/ionization-time of flight
mass spectrum (MALDI-TOF MS) spectroscopies (Figure 2
and Figure S1-S4 in Supporting Information). Simple
resonances of Cage 1 are presented in its 1H NMR spectrum
(Figure 2a). The signal attributed to H3 is remarkably shifted
2
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ring panels, hydrophobic and π-π interactions provide the
main driving forces of the self-assembly. A tentative
unilamellar model for the molecular packing in the wall of
nanotube is shown in Figure 3c. Cage 1 molecules are very
probably packed into a monolayer with a continuous array of
alternating Y- and inverse Y-shaped conformations, in which
the hydrophilic glycol groups form the coronae, and the
hydrophobic cage moieties are buried inside. This packing
pattern is in line with the optimized conformation of Cage 1
(Figure S6 in Supporting Information), as the distance
between two amphiphilic chain ends was measured to be ca.
4.5 nm. The nanotubes were stable, as monitored by TEM
analysis with time ranging from 1 h to 24 h. It is also worth
noting that vesicles were also accessible by varying the
concentration of Cage 1 in the aqueous solution (Figure S7
in Supporting Information), in line with the concentration-
discrete. The characteristic proton signal H1 of Cage 1 was
employed to monitor the binding process. Upon addition of
NaCl to the solution of discrete Cage 1, the H1 signal
gradually shifted downfield (Figure S8 in Supporting
Information), indicating the formation of Cage 1·Cl- complex
with the anion hosted in the V-cleft of the cage.[10e,11] UV-Vis
experiments were then performed to quantify the
stoichiometric ratio and binding constant (Ka) between Cage
1
and Cl- in MeOH. The Job’s plot shows that the maximum
value was achieved when the molar fraction of [Cl-]/([Cage1
]
+ [Cl-]) was 0.5, indicating that the stoichiometric ratio
between discrete Cage 1 and Cl- was 1:1 (Figure S10 in
Supporting Information). Based on UV-Vis titration profiles
measured at 278 nm (Figure S12 in Supporting Information
and Figure 4a) and the modified Hildebrand-Benesi equation,
the association constant (Ka) between Cage 1 and Cl- was
223 M-1 (Figure 4b).
morphology
dependence
of
other
self-assembling
amphiphiles[13]. The morphological effect on the binding of
anion is currently under investigation.
Figure 3. (a) TEM image of the nanotubes. (b) Diameter histogram of the
nanotubes, based on statistical analysis of ca. 150 randomly selected cross-
sections of the nanotubes in the TEM images. (c) A tentative unilamellar
membrane model of the nanotubes with the packing pattern of Cage 1.
Figure 4. (a) UV-Vis titration of discrete Cage 1 with addition of NaCl (0-25 eq.)
in MeOH ([Cage 1] = 2.26 × 10-5 M), (b) the Hildebrand-Benesi plot based on
UV-Vis titration, and (c) the corresponding cartoon illustration of complex Cage
1·Cl-. (d) UV-Vis titration of Cage 1 in the form of nanotubes with addition of
NaCl (0-13 eq.) in H2O ([Cage 1] = 2.26 × 10-5 M), (e) the Hildebrand-Benesi
plot based on UV-Vis titration, and (f) the corresponding cartoon illustration of
the proposed complexation mode between Cage 1 and Cl- in the self-assembled
nanotubes.
In order to study the effect of self-assembly on anion-π
interactions, we compared the binding between an anion and
Cage 1, before and during self-assembly of the latter,
respectively. As reported by Wang and coworkers,[11d]
halogenated anions, such as F-, Cl- and Br- can bind with the
cage precursor
2 (Scheme 1). Their single-crystal X-ray
For investigating the complexation of Cage 1 in the form of
nanotube and Cl-, the self-assembly of Cage 1 was prepared
by injection of 100 µL of THF solution of Cage 1 (1 mg mL-1)
into 2 mL of NaCl aqueous solution with predetermined
concentrations, followed by 10 s vortexing. The TEM imaging
shows that the morphology of nanotubes was retained upon
addition of NaCl (Figure S9 in Supporting Information). UV-
Vis experiments were then performed to quantify the binding
ratio and association constant (Ka). The Job’s plot shows that
diffraction (SC-XRD) analysis unambiguously revealed that
one anion is hosted in each V-cleft of the cage via anion-π
interaction. In order to examine the impact of self-assembly
of amphiphilic Cage 1, Cl- was selected herein as a proof-of-
1
concept anion. We first conducted H NMR measurements
to probe the complexation of molecular Cage 1 and anion Cl-
in CD3OD. Since CD3OD is a good solvent for both
hydrophilic and hydrophobic segments of Cage
1,
aggregation of Cage 1 was avoided so as to render Cage 1
3
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ratio between host Cage 1 and guest Cl- was also 1:1 (Figure
S11 in Supporting Information). Based on the UV-Vis titration
profiles measured at 278 nm (Figure S13 in Supporting
Information and Figure 4d) and the modified Hildebrand-
Benesi equation, the association constant (Ka) was 6800 M-1
(Figure 4e), which was 30 times higher compared to that of
discrete Cage 1 before self-assembly (223 M-1). This means
the anion-π interaction was considerably enhanced by the
formation of self-assembled superstructure.
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.
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Acknowledgements
This work was supported by National Natural Science
Foundation of China (key program 21890733), the Shanghai
Natural Science Foundation (18ZR1420800), and the
Innovation Fund from Joint Research Centre for Precision
Medicine set up by Shanghai Jiao Tong University &
Affiliated Sixth People's Hospital South Campus
(IFPM2017A002). The authors thank Dr. Le Li for her help
with 3D Max drawing.
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Conflict of interest
The authors declare no conflict of interest.
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Keywords: amphiphiles, anion-π interactions, organic cages,
nanotubes, self-assembly
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Entry for the Table of Contents
Unilamellar nanotubes were self-assembled from novel amphiphilic organic cages. With three electron deficient V-Clefts working as
anion-receptors, these cages could bind Cl- in both discrete and self-assembled states through anion-π interactions. A remarkable
self-assembly enhanced anion-π interactions phenomenon was observed via a comparison of the association constant of the
amphiphilic cage and Cl- between these two states.
6
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