A γ-ray and dual redox-responsive supramolecular polymer constructed by a selenium containing pillar[5]arene dimer and a neutral guest

Article abstract of DOI:10.1039/c5cc02886h

The first γ-radiation responsive linear supramolecular via pillararene-based host-guest recognition polymer was built successfully. What is more, this supramolecular polymer exhibited dual redox responsiveness.

Full text of DOI:10.1039/c5cc02886h

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COMMUNICATION
A -ray and dual redox-responsive supramolecular polymer constructed
by a selenium containing pillar[5]arene dimer and a neutral guest†
Yujuan Zhou, Kecheng Jie, Bingbing Shi, Yong Yao*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/c0xx00000x
we designed and synthesized a selenium-bridged A-A type
pillar[5]arene dimer 1 having two recognition sites. And to the
50 best of our knowledge, this is the first report of a pillar[5]arene
dimer containing a diselenide group. Beyond that, in order to
obtain supramolecular polymers with a high molecular weight, a
high asscociation constant between the repeating units is
prerequisite. The most special host–guest properties of
55 pillararenes are their strong affinities towards neutral guests in
organic media,6c since crown ethers, calixarenes and resorcarenes
generally interact strongly with cationic guests.10 From previous
studies, we know that the associtation constants of a series of
efficient neutral molecular recognition motifs based on
60 pillar[5]arenes were high enough for the formation of
supramolecular polymers.11 Thus, a symmetric B-B type guest 2
possessing two cyano sites and triazole sites at its ends was also
synthesized to connect pillar[5]arene dimer 1 (Scheme 1). As a
result, a linear supramolecular polymer was successfully prepared
65 in the A2B2 form. Interestingly, it not only exhibited -radiation
responsiveness but also showed dual redox responsiveness.
The first -radiation responsiveness linear supramolecular
polymer was built successfully. What is more, this
supramolecular
responsivenesses.
polymer
exhibited
dual
redox
10 Supramolecular polymers1 based on hostguest recognition
motifs have shown unique and interesting properties, such as
gelation,1d adaptibity, degradability, self-healing property1g
and responsiveness to environmental stimuli due to the
dynamic nature of hostguest interactions.1c,h In view of this,
15 stimuli-responsive supramolecular polymers have developed
more rapidly in recent years as a result of their prospective
applications in biotechnology and drug delivery systems.2
Among various external stimuli, irradiation has been widely
used because it requires no other chemical additives to the
20 system. In addition, high-energy rays, such as -rays, have
been used clinically for antitumor chemo- and radiotherapy.3
However,
-ray
responsive
materials
especially
supramolecular polymers are comparatively rare due to the
difficulty in the introduction of -ray responsive groups. It is
25 well-known that selenium containing compounds was selected
to be the candidates of stimuli-responsive materials due to
their sensitivity in the presence of low radiation dose -rays or
oxidants or reductants.4,5 Hence, selenium containing
compounds could be applied to construct supramolecular
30 polymers whose morphology could be tuned by -radiation.
Pillar[n]arenes6 are a new class of macrocyclic hosts and
appeared in the supramolecular world since 2008. It is a
macrocyclic molecule made up of hydroquinone units linked by
methylene bridges at the 2 and 5 positions. Pillararenes have
35 captured more and more attention of scientists in recent years not
only because they are easy to be functionalized but also because
of their adjustable inclusion property.7 These features make them
excellent candidates of stimuli-responsive molecular recognition
and enable their various applications, such as nanomaterials,
40 supramolecular polymers, self-assembly systems and so forth.8
However, pillararene dimers which can be regarded as the A-A
type monomers in constructing supramolecular polymers have
been rarely reported due to their tedious synthetic procedure. 9
Based on these, we want to explore whether organoselenium
45 can be introduced appended upon macrocyclic host, and whether
-ray-responsive linear supramolecular polymer based on a
selenium containing pillar[5]arene dimer can be created. Herein,
Scheme 1. Cartoon representations of selenium-bridged
pillar[5]arene dimer 1, neutral guest 2 and multi-responsive
70 supramolecular polymer.
The synthesis of Selenium containing pillar[5]arene dimer 1
was included in the ESI (Scheme S1, ESI†). 1 was characterized
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by H NMR spectroscopy, 77Se NMR spectroscopy, 13C NMR
To further investigate the supramolecular aggregates, a double
logarithmic representation of specific viscosity versus monomer
spectriscopy, LRESIMS and HRESIMS (Fig. S1S5, ESI†).12
Neutral guest 2 was synthesized according to previous reports 40 concentration for equimolar mixtures of 1 and 2 in CHCl3 was
(Fig. S6S10, ESI†).1h,9a It is worth noting that the binding
behaviour of 1 and 2 has been reported by Li and co-workers and
the association constant can be as high as (1.2  0.2)  104 M1 in
chloroform.9b,11 The main driving forces for the molecular
obtained. As presented in Fig. 2, the linear supramolecular
polymer assembled from monomers 1 and 2 exhibited viscosity
transitions. In the low concentration range, the slope of the curve
was 0.64, indicating a linear relationship between the specific
5
recognition includes the multiple CH··· interactions and 45 viscosity and the concentration, which demonstrated the presence
CH···N/CH···O hydrogen bonds between the 1 and 2.11
The supramolecular polymer formation was characterized by
various techniques including 1H NMR spectroscopy, DOSY,
specific viscosity and SEM. The concentration-dependent 1H
of cyclic oligomers in dilute solutions. As the concentration
increased, a sharp increase in the viscosity was observed (slope =
1.24 at 298 K), manifesting the formation of supramolecular
polymers of increasing sizes. The critical polymerization
10
NMR studies of 1 and 2 complexes provided clear evidence for 50 concentration of 1 and 2 in CHCl3 was about 60 mM.
the formation of large supramolecular polymers. As shown in Fig.
15 1, 1H NMR spectra of 1 and 2 were recorded over a concentration
range of 1.00 up to 200 mM. As the concentration increased, the
signals of protons He, Hf, Hd, Hc and Hb became broad, which
demonstrated the formation of high molecular weight aggregates
driven by hostguest interactions between 1 and 2.11a,13
Fig. 2 Specific viscosity of equimolar monomers 1 and 2 in
CHCl3 at 298 K versus monomer concentration.
The formation of linear supramolecular polymer was also
55 proved by SEM. A rod-like fiber was drawn from a high
concentration solution of equimolar 1 and 2 and observed by
SEM (Fig. 3a). It is well known that compounds containing
diselenide groups are particularly sensitive to -radiation or redox
stimuli. Based on this, we wondered whether this linear
60 supramolecular polymer could be disrupted by using -radiation,
or adding peroxides or reduced gluthione (GSH). As confirmed
by SEM, rod-like fibers could not be drawn and only spherical
assemblies were observed upon -ray irradiation of 50 Gy for 1
hour (Fig. 3b). Meanwhile, the diffusion coefficient (D) of 1 and
65 2 at 88 mM increased from 6.76  1011 m2s1 to 2.69  1010
20
Fig. 1 1H NMR spectra (500 MHz, 298 K) of 1 and 2 in CDCl3 at
various concentrations: (a) 1.00 mM; (b) 5.50 mM; (c) 11.0 mM;
(d) 22.0 mM; (e) 44.0 mM; (f) 60.0 mM; (g) 88.0 mM; (h) 123
mM; (i) 160 mM; (j) 200 mM.
1
m2s1. Moereover, the H NMR spectra (Fig. S13, ESI†) showed
that the signals of protons He, Hf, Hd, Hc and Hb were no longer
broad and became sharp after -radiation, which is in good
agreement with the result of SEM and DOSY. These results
70 indicated the destruction of supramolecular polymers. Besides,
rod-like fibers were also broken after the addition of H2O2 or
GSH (Fig. S12cS12d, ESI†).
25
Supramolecular assemblies formed by 1 and 2 were also
probed by 2D diffusion-ordered NMR (DOSY). The measured
weight-average diffusion coefficient (D) of 1 and 2 in CDCl3
decreased gradually from 3.31  1010 m2s1 to 1.86  1011 m2s1
upon increasing the concentrations of 1 and 2 from 11.0 up to 200
30 mM (Fig. S11, ESI†). It is implied that the increase of average
aggregation size led to the transition from supramolecular
oligomer species to supramolecular polymers. From previous
studies, we know that a significant decrease in the diffusion
coefficient was resulted from a high polymerization degree value.
35 Therefore, the experiments mentioned above indicated that 1 and
2
formed extended and high-molecular-weight polymeric
structures in chloroform.
Fig. 3 SEM images of rod-like fibers drawn from a highly
2
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In summary, we have prepared a novel linear supramolecular
polymer by self-assembly of a selenium containing pillar[5]arene
dimer 1 and a neutral guest 2. Through 1H NMR, DOSY and
specific viscosity, we found that the formation of the
supramolecular polymer was mainly dependent on the monomer
concentration. On the other hand, rod-like fibers could be drawn
10 from a highly concentrated chloroform solution, which provided
direct evidence for the formation of supramolecular polymer.
Interestingly, the supramolecular polymer could be disrupted by
-radiation or adding peroxides or GSH due to the damage of a
diselenide group in the pillararene dimer. As far as concerned,
15 this is the first pillararene-based -ray-responsive supramolecular
polymer, which may have potential to fabricate supramolecular
materials with more complex structures and functions.
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Acknowledgements
7
This work was supported by the Fundamental Research Funds
20 for the Central Universities.
Notes and references
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R.
China; Fax: +86-571-8795-3189; Tel: +86-571-8795-3189; E-mail:
yaoyong@zju.edu.cn
25 † Electronic Supplementary Information (ESI) available: Synthetic
procedures, characterizations, 2D NOSEY spectra and other materials.
See DOI: 10.1039/c0xx00000x.
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Colour Graphic：
A novel linear supramolecular polymer was fabricated by self-
assembly of a selenium containing pillar[5]arene dimer 1 and a
neutral guest 2. This supramolecular polymer can be destroyed by
irradiating -radiation , or adding H2O2 or GSH.
5
4
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]