Construction of Vesicles, Micro/Nanorods and Ultralong Nanotubes through the Self-Assembly of Non-Classical Amphiphiles with Rigid Conformation

Article abstract of DOI:10.1002/cjoc.201600906

Amphiphilic molecules have long been regarded as an important class of supramolecular building blocks for the fabrication of nanomaterials. While most previous researches have mainly focused on amphiphlies with flexible structures, in this work, four novel amphiphiles possessing wholly-rigid skeletons have been designed and synthesized. These molecules were built by using 4,4’-bipyridin-1-ium or viologen as hydrophilic moieties and phenyl or biphenyl as hydrophobic segments, bridged by a pyridazine unit. Their self-assembly behavior has been investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM), which revealed they could self-assemble into well-ordered nanoarchitectures with various morphologies such as vesicles, micro/nanorods and nanotubes in water or methanol, depending on their hydrophilic/hydrophobic fraction ratios.

Full text of DOI:10.1002/cjoc.201600906

FULL PAPER
DOI: 10.1002/cjoc.201600906
Construction of Vesicles, Micro/Nanorods and Ultralong
Nanotubes through the Self-Assembly of Non-Classical
Amphiphiles with Rigid Conformation
Feng Lin,a Rongran Liang,a Qiaoyan Qi,a Tianguang Zhan,a Zhanting Li,b and Xin Zhao*,a
a Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
b Department of Chemistry, Fudan University, Shanghai 200433, China
Amphiphilic molecules have long been regarded as an important class of supramolecular building blocks for the
fabrication of nanomaterials. While most previous researches have mainly focused on amphiphlies with flexible
structures, in this work, four novel amphiphiles possessing wholly-rigid skeletons have been designed and synthe-
sized. These molecules were built by using 4,4'-bipyridin-1-ium or viologen as hydrophilic moieties and phenyl or
biphenyl as hydrophobic segments, bridged by a pyridazine unit. Their self-assembly behavior has been investigated
by scanning electron microscopy (SEM), atomic force microscopy (AFM) and transmission electron microscopy
(TEM), which revealed they could self-assemble into well-ordered nanoarchitectures with various morphologies
such as vesicles, micro/nanorods and nanotubes in water or methanol, depending on their hydrophilic/hydrophobic
fraction ratios.
Keywords amphiphiles, self-assembly, hydrophobic-lipophilic interaction, aromatic stacking, rigid conformation
Introduction
extremely rich self-assembly behavior which leads to
the fabrication of a variety of functional materials. The
typical structure of an amphiphile consists of a hydro-
philic head and a hydrophobic tail which are covalently
connected. Thus, the self-assembly of amphiphiles is
mainly driven by HLI and usually their aggregating be-
havior can be predicated according to the packing pa-
rameters theory.[13] The classic amphiphiles are simple
molecules possessing a cationic or anionic head group
and a hydrophobic tail such as lipids and surfactants.[14]
In recent years, supramolecular amphiphiles, in the
structures of which hydrophilic parts and hydrophobic
parts are connected by noncovalent bonds, particularly,
host-guest interactions, have been developed by Zhang
group.[15] In addition to small organic molecules, poly-
meric amphiphiles such as amphiphlic block copoly-
mers have been extensively studied in the past dec-
ade.[16] The progress largely enriches the family of am-
phiphiles and makes self-assembly of amphiphiles ac-
tive research fields in supramolecular chemistry and soft
materials. However, it should be pointed out that, those
amphiphilic molecules, although their structures are
diverse, still have a common feature, that is, flexible
conformation. In this context, developing amphiphilic
molecules with unusual structures might bring in exotic
features. Very recently, we developed a new type of
As a “bottom up” approach which pieces together
small parts to generate united ones, molecular self-as-
sembly is a powerful tool to fabricate well-ordered ob-
jects with nano/microscale.[1] In the process of a
self-assembly, aggregation of building blocks sponta-
neously occurs under certain conditions driven by non-
covalent interactions such as hydrogen bonding,[2] coor-
dination,[3] aromatic stacking,[4] host-guest recognition,[5]
static interaction,[6] cation…π,[7] anion…π,[8] C－H…
π,[9] dimerization of radicals,[10] and hydrophobic-lipo-
philic interaction (HLI).[11] To facilitate this process,
building blocks must be constructed in a way that
bonding information has been pre-stored in their struc-
tures. Directed by the information encoded, building
blocks hierarchically self-assemble into well-ordered
nano/micro-scale aggregates. To this end, over the past
decades a myriad of organic molecules have been cre-
ated as building blocks, from which multifarious su-
pramolecular architectures have been fabricated.
Among the numerous building blocks created so far,
amphiphilic molecules, which possess both hydrophilic
and hydrophobic moieties in one molecule, have drawn
particular attention.[12] It is not only because the crucial
roles amphiphiles play in living systems (for example,
the formation of cell membranes), but also because their
*
E-mail: xzhao@sioc.ac.cn; Tel.: 0086-021-54925023; Fax: 0086-021-64166128
Received December 22, 2016; accepted February 12, 2017; published online XXXX, 2017.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201600906 or from the author.
Dedicated to Professor Xikui Jiang on the occasion of his 90th birthday.
Chin. J. Chem. 2017, XX, 1—X
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156.61, 151.79, 144.56, 143.13, 135.60, 132.52, 130.48,
129.58, 128.75, 127.18, 124.55, 123.87; MS (ESI) m/z:
311.0 [MCl]＋; HRMS (MALDI) calcd for C20H15N4
311.1291, found 311.1290.
amphiphilic molecules, which were constructed by cou-
pling hydrophilic 4,4'-bipyridine or viologen with hy-
drophobic phenyl, biphenyl or para-tert-phenyl. As a
result, these amphiphiles possess unusual rigid rod-like
conformation.[17] These non-classic amphiphiles exhib-
ited interesting self-assembly behavior. In this article,
we report the synthesis and self-assembly behavior of
another series of wholly rigid amphiphiles. Unlike the
previous work, an pyridazine unit is inserted between
4,4'-bipyridine and phenyl/biphenyl segments to intro-
duce hydrophilicity at the lateral part of the molecules
(Scheme 1, T1 － T4). A variety of well-ordered
nanostructures including vesicles, nanorods and ultra-
long nanotubes have been obtained from the self-as-
sembly of these non-classic amphiphiles in water or in
methanol. Moreover, it was also found that the rigid
conformation of the amphiphiles resulted in an en-
hancement of the stability of the as-prepared soft mate-
rials, demonstrating an intriguing property of these
unique amphiphilic structures.
Synthesis of compound T2
Compound T1 (90 mg, 0.3 mmol) and methyl iodide
(2.7 mL, 43.4 mmol) were dissolved with dry acetoni-
trile (2 mL) in a sealed tube. The mixture was heated at
70 ℃ for 3 d. Upon being cooled to room temperature,
the resulting precipitate was filtered and thoroughly
washed with chloroform, and dried in vacuo to yield T2
1
as a brownish-red powder (126 mg, 86%). H NMR
(400 MHz, CD3OD) δ: 10.02 (d, J＝7.1 Hz, 2H), 9.28
(d, J＝6.7 Hz, 2H), 8.99 (d, J＝7.1 Hz, 2H), 8.81 (d,
J＝6.7 Hz, 2H), 8.68 (d, J＝9.3 Hz, 2H), 8.34－8.25 (m,
2H), 7.71－7.61 (m, 3H), 4.58 (s, 3H); 13C NMR (100
MHz, DMSO-d6) δ: 160.85, 155.45, 151.40, 147.53,
146.66, 144.12, 134.07, 131.37, 129.42, 127.98, 127.51,
126.49, 124.42, 48.21; MS (ESI) m/z: 326.1 [MClI]＋,
＋
163.2 [MClI]2 ; HRMS (MALDI) calcd for C21H18N4
326.1526, found 326.1520.
Scheme 1 Structures of T1－T4
Synthesis of compound 4
A solution of 4-bromodiphenyl (9.3 g, 40 mmol) in
anhydrous THF (100 mL) was cooled to 78 ℃ and
then n-BuLi (17 mL, 2.4 mol•L1 in n-hexane) was
slowly added over 30 min under an argon atmosphere.
After completing the addition of n-BuLi, the mixture
was stirred at 78 ℃ for 2 h and then triisopropyl bo-
rate (13.8 mL, 60 mmol) was added dropwise. The reac-
tion mixture was allowed to warm to room temperature
and stirred for 2 h at room temperature. The resulting
mixture was acidified with 10% HCl (60 mL) and ex-
tracted with diethyl ether (30 mL×3). The combined
organic phase was washed with water and brine and
then dried over anhydrous MgSO4. Upon removal of the
solvent with a rotavapor, the crude product was purified
by column chromatography (silica gel, petroleum
ether/ethyl acetate, V∶V＝3∶1) to give compound 4 as
a white solid (6.69 g, 85%). 1H NMR (400 MHz,
acetone-d6) δ: 7.97 (d, J＝8.0 Hz, 2H), 7.65－7.59 (m,
4H), 7.47 (t, J＝7.2, 8.0 Hz, 2H), 7.37 (t, J＝7.6 Hz,
1H), 7.12 (s, 2H); MS (MALDI) m/z: 197.0 [MH].
Experimental
General methods
All the reactions were carried out under a dry nitro-
gen atmosphere. The starting materials were obtained
from commercial suppliers and were used without fur-
ther purification. The H and 13C NMR spectra were
1
recorded on 300 or 400 MHz spectrometers in the indi-
cated solvents.
Synthesis of compound T1
Synthesis of compound 6
A mixture of 3-chloro-6-phenylpyridazine (250 mg,
1.3 mmol) and 4,4'-dipyridine (1.02 g, 6.6 mmol) in
anhydrous DMF was heated at 120 ℃ for 3 d under an
argon atmosphere. Upon being cooled to room temper-
ature, dichloromethane (10 mL) was added. The result-
ing precipitate was filtered and the solid was thoroughly
washed with dichloromethane to afford T1 as a brown
solid after being dried in vacuo (0.20 g, 48%). 1H NMR
(400 MHz, CD3OD) δ: 9.85 (d, J＝7.0 Hz, 2H), 8.92 (d,
J＝6.1 Hz, 2H), 8.84 (d, J＝7.0 Hz, 2H), 8.69 (d, J＝
9.3 Hz, 1H), 8.59 (d, J＝9.3 Hz, 1H), 8.29 (dd, J＝6.6,
2.9 Hz, 2H), 8.14 (d, J＝6.2 Hz, 2H), 7.69－7.60 (m,
3H); 13C NMR (100 MHz, CD3OD) δ: 163.20, 157.79,
To a mixture of compound 4 (2.33 g, 11.8 mmol),
3,6-dichloropyridazine (2.64 g, 17.7 mmol) and K2CO3
(2.44 g, 17.7 mmol) in dioxane (40 mL) and water (10
mL), Pd(PPh)4 (408 mg, 0.35 mmol) was added under
an argon atmosphere. The mixture was heated under
refluxing for 7 h. Upon being cooled to room tempera-
ture, the solvent was removed under vacuum and the
residue was passed through a neutral alumina column
with dichloromethane as eluent to give crude product as
a white solid, which was further purified by column
chromatography (silica gel, petroleum ether/dichloro-
methane, V∶V＝1∶1) to afford compound 6 as a white
2
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Construction of Vesicles, Micro/Nanorods and Ultralong Nanotubes through the Self-Assembly
solid (1.83 g, 58%). 1H NMR (400 MHz, CDCl3) δ: 8.14
(d, J＝8.8 Hz, 2H), 7.88 (d, J＝8.8 Hz, 1H), 7.77 (d,
J＝8.4 Hz, 2H), 7.66 (d, J＝7.2 Hz, 2H), 7.58 (d, J＝
8.4 Hz, 1H), 7.48 (t, J＝7.6 Hz, 2H), 7.40 (t, J＝7.2 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ: 158.42, 155.71,
143.56, 140.26, 134.06, 129.11, 128.63, 128.12, 128.00,
127.68, 127.31, 126.12; MS (ESI) m/z: 267.3 [M＋H]＋;
HRMS (MALDI) calcd for C16H12N2Cl [M ＋ H]
267.0684, found 267.0684.
by methylation of T3 with iodomethane.
Scheme 2 Synthesis of T1－T4
Synhthesis of compound T3
This compound was prepared in 63% yield as a solid
from the reaction of compound 6 and 4,4'-dipyridine
according to a procedure similar to that described for
compound T1. 1H NMR (400 MHz, CD3OD) δ: 9.84 (d,
J＝6.8 Hz, 2H), 8.90 (d, J＝5.2 Hz, 2H), 8.81 (d, J＝
6.0 Hz, 2H), 8.71 (d, J＝9.2 Hz, 1H), 8.60 (d, J＝9.6 Hz,
1H), 8.36 (d, J＝8.4 Hz, 2H), 8.13 (d, J＝5.2 Hz, 2H),
7.89 (d, J＝8.4 Hz, 2H), 7.73 (d, J＝7.6 Hz, 2H), 7.49 (t,
J＝7.2, 8.4 Hz, 2H), 7.40 (t, J＝7.2 Hz, 1H); 13C NMR
(100 MHz, CD3OD) δ: 163.14, 158.33, 156.65, 152.09,
144.55, 143.12, 141.10, 134.49, 130.12, 129.32, 128.97,
128.11, 127.15, 124.23, 123.68; MS (ESI) m/z: 387.2
＋
[MCl] ; HRMS (MALDI) calcd for C26H19N4
The self-assembly behavior of T1 in water was
firstly investigated by scanning electron microscopy
(SEM). It was found that T1 gave rise to ill-defined ag-
gregates in water (Figure 1a). It might be attributed to
an improper hydrophilic/hydrophobic ratio of T1, which
bears a large hydrophilic part but a small hydrophobic
part. Therefore, methanol was used to decrease the po-
larity of the solvent. SEM investigation revealed that T1
self-assembled into spherical entities in methanol. Their
sizes varied from several hundred nanometers to around
one micrometer and some of them were partly fusing
each other (Figure 1b). Transmission electron micros-
copy (TEM) study further revealed that the spheres were
hollow inside by demonstrating a clear contrast between
the periphery and central part of the spheres (Figure 1c),
which is typically produced by the projection of hollow
sphere,[18] suggesting that the spheres are vesicles. The
TEM image also gave the wall thickness of a selected
vesicle to be approximately 2.0 nm. Since the length of
T1 was estimated to be 1.6 nm from its CPK model, the
wall of the vesicle was proposed to be an interdigitated
bimolecular layer, in which the phenyl ring overlaps
with pyridazine unit in a head-to-head manner while
dipyridine segments point outside. The formation of
spherical structures by T1 in methanol was further
demonstrated by tapping-mode atomic force microscopy
(AFM). Cross-section analysis of a selected sphere re-
vealed that it had a diameter of 597 nm and a height of
154 nm (Figure 1d). In contrast to the vesicles fabricat-
ed from conventional amphiphiles with flexible struc-
tures which usually exhibit flattened shapes under AFM,
as the results of the high local force applied by the AFM
tip and evaporation of the solvent molecules encapsu-
lated in vesicles,[19] the vesicles assembled from T1 just
exhibit modest ratio of diameter over height (3.9), sug-
387.1604, found 387.1598.
Synhthesis of compound T4
This compound was prepared in 76% yield as a solid
from the reaction of compound T3 and methyl iodine
according to a procedure similar to that described for
compound T2. 1H NMR (400 MHz, CD3CN) δ: 9.65 (d,
J＝6.3 Hz, 2H), 8.91 (d, J＝6.2 Hz, 2H), 8.69 (d, J＝
6.3 Hz, 2H), 8.62 (d, J＝9.4 Hz, 1H), 8.50 (d, J＝5.9 Hz,
2H), 8.38 (t, J＝9.0 Hz, 3H), 7.95 (d, J＝7.9 Hz, 2H),
7.79 (d, J＝7.6 Hz, 2H), 7.55 (t, J＝7.5 Hz, 2H), 7.47 (d,
J＝7.1 Hz, 1H), 4.58 (s, 3H); 13C NMR (100 MHz,
CD3CN) δ: 162.69, 153.81, 147.62, 144.73, 140.48,
134.13, 130.10, 129.33, 129.27, 129.15, 128.86, 128.42,
128.11, 128.05, 124.27, 49.73; MS (ESI) m/z: 402.3
[MClI] ＋ ; HRMS (MALDI) calcd for C27H22N4
402.1839, found 402.1844.
Results and Discussion
The synthesis of these unique amphiphiles is straight
forward. As illustrated in Scheme 2, compound T1 was
obtained in 48% yield by heating a mixture of
3-chloro-6-phenylpyridazine (1) and 4,4'-dipyridine (2)
in DMF, which was further methylated by iodomethane
to give compound T2 in 86% yield. For the preparation
of compounds T3 and T4, 4-bromobiphenyl was first
converted to 4-biphenyllithium, which further reacted
with triisopropyl borate followed by hydrolysis with
aqueous HCl to generate 4-biphenylboronic acid (4).
Compound 4 was then coupled with 3,6-dichloro-
pyridazine (5) to give compound 6. With this key inter-
mediate available, compound T3 was obtained in 63%
yield by the reaction of 6 with 4,4'-dipyridine. Follow-
ing the above procedure, compound T4 was synthesized
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Lin et al.
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gesting that the vesicles are robust enough to keep their
shape after the solvent molecules are evaporated, albeit
the walls of the vesicles are extremely thin. It might be
attributed to the rigid structures of the building blocks,
which greatly enhance the stability of the vesicles.
Figure 2 (a) SEM and (b) TEM images of T2 in water (1.0
mg/mL for SEM and 0.2 mg/mL for TEM), and (c) SEM, (d)
TEM and (e) AFM images of T2 in methanol (0.05 mg/mL) after
the solvents were evaporated.
Figure 1 (a) SEM image of T1 in water (1.0 mg/mL) and (b)
SEM, (c) TEM and (d) AFM images of T1 in methanol (0.2
mg/mL) after the solvents were evaporated.
Compared to compounds T1 and T2, compounds T3
and T4 have longer hydrophobic parts. The SEM image
revealed that T3 gave rise to wire-like structures in wa-
ter (Figure 3a). The length of these wires was estimated
to be at least several hundred micrometers, for no ends
of the wires could be observed in the scope of the SEM
image. High resolution TEM investigations revealed
that these wires were hollow inside, which suggested
that they were nanotubes (Figure 3b). The diameters of
these nanotubes were found to be around 150－180 nm
and their wall thicknesses were estimated to be less than
3 nm, also suggesting that the walls of the tubes consist
of a head-to-head interdigitated bimolecular layer (T3
has a length of 2.0 nm estimated by CPK modeling).
These tubular entities were also characterized by AFM,
which revealed a width of 218 nm and a height of 66 nm
for a selected tube (Figure 3c). The value of width is a
little bit larger than the diameters obtained from TEM. It
is reasonable if one considers the nanotubes with ex-
tremely thin walls may flatten a little bit under the local
force applied by the AFM tip. The small width over
height ratio (3.3) again suggests the robustness of the
nanotube which should be beneficial from the rigid
structure of T3. The self-assembly of T3 in methanol
was also investigated. Nanospheres were observed by
SEM and the shells of some of the spheres were cracked,
T2 exhibits different self-assembly behavior in water
from T1. As shown in Figure 2a, rod-like structures
with dozens of microns in length and around one micron
in diameter were observed. Furthermore, TEM experi-
ment revealed that these microrods were solid inside
(Figure 2b). Its self-assembly behavior in methanol was
also investigated, which revealed that compound T2
displayed similar behavior in methanol as T1. It was
found that it also self-assembled into discrete spherical
structures (Figure 2c), which were further confirmed to
be vesicles by TEM investigation, for contrast between
the shell and the inner part was observed (Figure 2d).
The wall thickness of a selected vesicle was estimated
to be ca. 3.5 nm, which is almost double of the molecu-
lar length of T2 (1.8 nm estimated by CPK modeling),
suggesting a bimolecular layer. AFM study on a selected
vesicle indicated that the vesicles possessed a low ratio
of diameter over height (1.7), reflecting its robustness
(Figure 2e). Furthermore, collapse in the centers of
some spheres was observed under AFM, which might be
attributed to break of the hollow spheres induced by the
high local force of the AFM tip, indicating again the
hollow nature of the spheres. This result suggests that
the polarity of solvent has dramatic influence on the
self-assembly behavior of this type of amphiphiles.
4
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Construction of Vesicles, Micro/Nanorods and Ultralong Nanotubes through the Self-Assembly
which revealed that T3 self-assembled into vesicles
(Figure 3d). The result again suggests that the polarity
of solvent has a dramatic influence on the self-assembly
behavior of this type of non-classic amphiphiles.
Figure 4 (a) SEM, and (b) TEM images of T4 in water (1.0
mg/mL for SEM and 0.4 mg/mL for TEM) after the solvent was
evaporated.
these well-ordered nanostructures, UV-vis spectroscopy
and powder X-ray diffraction (XRD) experiments were
carried out. UV-vis spectra indicated that they exhibited
significant hypochromic effects at higher concentrations
(Figure S1, Supporting Information). This result strong-
ly suggests the existence of aromatic stacking between
the amphiphiles. Moreover, the XRD patterns of the
self-assembled entities described above all display dif-
fraction peaks in the range of 0.35－0.43 nm, which can
be attributed to π-π stacking of the aromatic rings (Fig-
ure S2, Supporting Information), confirming again that
aromatic stacking makes a significant contribution to
the formation of the nano/microstructures. Therefore,
driven by aromatic stacking and HLI (or solvophobic
effect when methanol was employed as solvent), the
amphiphiles hierarchically self-assemble to generate
micro/nanoscale architectures of various morphologies.
Conclusions
In summary, four novel non-classic amphiphiles
possessing wholly rigid conformation have been de-
signed and synthesized. Their assembly properties have
been investigated, which revealed that they self-assem-
bled into various well-ordered architectures of different
morphologies. While the previous researches are mainly
focused on amphiphiles with flexible structures, this
work discloses that rigid amphiphilic molecules also
exhibit rich assembly properties. Furthermore, an inter-
esting property, that is, enhancement of the robustness
of the aggregates, which originates from the rigid con-
formation of their unique structures, has also been ob-
served. This work demonstrates that this unique type of
amphiphilic molecules deserve to be further exploited as
building blocks, from which construction of supramo-
lecular systems of multilevel and high complexity can
be expected. In this context, developing more rigid am-
phiphilic molecules of various structures is highly de-
sired in future.
Figure 3 (a) SEM, (b) TEM and (c) AFM images of T3 in wa-
ter (0.1 mg/mL), and (d) SEM image of T3 in methanol (0.1
mg/mL) after the solvents were evaporated.
Compound T4 also self-assembled into one dimen-
sional microstructure in water. Its SEM image revealed
the formation of rod-like architectures with diameters
ranging from several hundred nonometers to around one
micrometer, depending on the concentration of T4 (Fig-
ure 4a). Unlike the tubular structure generated from
compound T3 above, the as-prepared rod-like structures
from T4 were confirmed to be solid (Figure 4b). How-
ever, when methanol was used as solvent, no well-de-
fined aggregates were obtained.
It has been generally accepted that the driven force
for the self-assembly of amphiphiles is mainly HLI. In
the case of compounds T1－T4, since they consist of
aromatic rings, we anticipated that, in addition to HLI,
aromatic stacking between the aromatic moieties should
also make a significant contribution to drive their ag-
gregation. To understand the aggregation mechanism of
Acknowledgement
We thank the National Natural Science Foundation
of China (No. 21502216) and the Technology Commis-
sion of Shanghai Municipality (No. 15ZR1449500) for
the financial support.
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