Construction of Supramolecular Assemblies from Self-Organization of Amphiphilic Molecular Isomers

Article abstract of DOI:10.1002/asia.201600683

Amphiphilic coil-rod-coil molecules, incorporating flexible and rigid blocks, have a strong affinity to self-organize into various supramolecular aggregates in bulk and in aqueous solutions. In this paper, we report the self-assembling behavior of amphiphilic coil-rod-coil molecular isomers. These molecules consist of biphenyl and phenyl units connected by ether bonds as the rod segment, and poly(ethylene oxide) (PEO) with a degree of polymerization of 7 and 12 as the flexible chains. Their aggregation behavior was investigated by differential scanning calorimetry, thermal optical polarized microscopy, small-angle X-ray scattering spectroscopy, and transmission electron microscopy. The results imply that the molecular structure of the rod building block and the length of the PEO chains dramatically influence the creation of supramolecular aggregates in bulk and in aqueous solutions. In the bulk state, these molecules self-organize into a hexagonal perforated lamellar and an oblique columnar structure, respectively, depending on the sequence of the rod building block. In aqueous solution, the molecule with a linear rod segment self-assembles into sheet-like nanoribbons. In contrast, its isomer, with a rod building block substituted at the meta-position of the aryl group, self-organizes into nanofibers. This is achieved through the control of the non-covalent interactions of the rod building blocks.

Full text of DOI:10.1002/asia.201600683

DOI: 10.1002/asia.201600683
Full Paper
Self-Assembly
Construction of Supramolecular Assemblies from Self-
Organization of Amphiphilic Molecular Isomers
Zhaohua Li+,[a] Yuntian Yang+,[a] Yanqiu Wang,[b] Tie Chen,[a] Long Yi Jin,*[a] and
Myongsoo Lee*[b]
Abstract: Amphiphilic coil-rod-coil molecules, incorporating
flexible and rigid blocks, have a strong affinity to self-organ-
ize into various supramolecular aggregates in bulk and in
aqueous solutions. In this paper, we report the self-assem-
bling behavior of amphiphilic coil-rod-coil molecular iso-
mers. These molecules consist of biphenyl and phenyl units
connected by ether bonds as the rod segment, and poly(-
ethylene oxide) (PEO) with a degree of polymerization of 7
and 12 as the flexible chains. Their aggregation behavior
was investigated by differential scanning calorimetry, ther-
mal optical polarized microscopy, small-angle X-ray scatter-
ing spectroscopy, and transmission electron microscopy. The
results imply that the molecular structure of the rod building
block and the length of the PEO chains dramatically influ-
ence the creation of supramolecular aggregates in bulk and
in aqueous solutions. In the bulk state, these molecules self-
organize into a hexagonal perforated lamellar and an obli-
que columnar structure, respectively, depending on the se-
quence of the rod building block. In aqueous solution, the
molecule with a linear rod segment self-assembles into
sheet-like nanoribbons. In contrast, its isomer, with a rod
building block substituted at the meta-position of the aryl
group, self-organizes into nanofibers. This is achieved
through the control of the non-covalent interactions of the
rod building blocks.
Introduction
lecular electronics, biomimetic chemistry, and materials sci-
ence.[3] Rod-coil molecules have a strong tendency to form ani-
sotropic and orientational nanostructures that arise from mi-
crophase separation of the rod and coil segments. These mole-
cules are spontaneously held together by non-covalent molec-
ular interactions, including hydrophobic and hydrophilic
effects, p–p stacking, hydrogen bonding, and electrostatic in-
teractions.[4] We have previously reported that dumbbell-
shaped rod-coil molecules with conjugated rod building blocks
and hydrophilic dendrons can form helical nanostructures in
aqueous solutions.[5] This is achieved through steric repulsion
interactions between the parallel arrangement of the conjugat-
ed rod block and the bulky dendritic poly(ethylene oxide)
(PEO) coil chains. In subsequent work, we synthesized laterally
grafted and elliptical macrocycle rod-coil molecules, and con-
structed 2D porous, closed porous sheets and helical fibers, re-
spectively.[6] Recently, we have reported that depending on the
PEO chain lengths in the solid state and aqueous solutions,
bent-shaped amphiphilic molecules (consisting of a diben-
zo[a,c]phenazine unit as the rigid segment and PEO flexible
chains) self-assemble into oblique columnar structures, and cy-
lindrical micelles and helical fibers, respectively.[7] More recent-
ly, we have reported the self-assembling behavior of coil-rod-
coil molecules incorporating lateral hydroxy or methoxy
groups in the center rod segments, and PEO as the coil seg-
ments.[8] These molecules aggregate into nanoribbons and
vesicles, depending on their lateral groups and oligo(ethylene
oxide) chain lengths in aqueous solutions. The above results
The spontaneous organization of organic molecules or block
polymers by the orchestrated interplay of various non-covalent
interactions has been one of the major research topics in the
field of supramolecular chemistry.[1] Among the polymer scaf-
folds, amphiphilic block copolymers consisting of hydrophobic
and hydrophilic blocks can self-assemble into various core-
shell nanoaggregates such as spheres, cylinders, fibers, rib-
bons, and vesicles through aqueous self-assembly.[2] These ag-
gregates incorporate a specific building block with desired
functions and act as novel functional nanomaterials. Thus, they
have remarkable potential in fields such as biochemistry, mo-
[a] Z. Li,+ Y. Yang,+ T. Chen, Prof. L. Y. Jin
Key Laboratory for Organism Resources of the Changbai Mountain
and Functional Molecules, Ministry of Education
Department of Chemistry
Yanbian University
Yanji 133002 (China)
E-mail: lyjin@ybu.edu.cn
[b] Y. Wang, Prof. M. Lee
State Key Lab of Supramolecular Structure and Materials
College of Chemistry
Jilin University
Changchun 130012 (China)
E-mail: mslee@jlu.edu.cn
[+] These authors contributed equally to this work.
Supporting information for this article can be found under http://
dx.doi.org/10.1002/asia.201600683.
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indicated that the shape of the rod building block and the lat-
eral groups in the center of the rod segments significantly in-
fluence the self-assembly of the rod-coil molecular system in
the bulk state and in aqueous solution. This is achieved
through the tuning of the driving force of the molecular ag-
gregation.
small-angle X-ray scattering (SAXS), ultraviolet-visible and fluo-
rescence (UV/Vis and FL, respectively) spectroscopy, and trans-
mission electron microscopy (TEM).
To our knowledge, the synthesis and self-assembly of coil- Results and Discussion
rod-coil molecular isomers, based on sequence of the rod
Molecular Design and Synthesis
building block and the length of the oligo(ethylene oxide)
chain in aqueous solution, has not been reported to date.
Therefore, it is of great interest to investigate the self-assembly
of rod-coil molecular isomers in the bulk state and in aqueous
solution to construct various supramolecular nanoaggregates
that can be applied to drug delivery systems and nanomateri-
als science.
Coil-rod-coil triblock molecules 1a,b and 2a,b, incorporating
phenyls, biphenyls, and a p-phenyl or an m-phenyl unit linked
together with ether bonds as the rod segment, and PEO with
a DP of 7 and 12 as the coil segments were synthesized. Poly(-
ethylene glycol) methyl ether; 1,4-benzenediol; or 1,3-benze-
nediol were used as the starting materials. Molecules 1a,b and
2a,b were afforded from a substitution reaction of compound
4a,b with 1,4-benzenediol or 1,3-benzenediol in the presence
of potassium carbonate. The structures of these molecules
With this in mind, we have designed and synthesized coil-
rod-coil molecules 1a,b and 2a,b, consisting of biphenyl and
phenyl units linked together with ether bonds as the rod seg-
ments, and PEO with a degree of polymerization (DP) of 7 and
12 as the coil segments (Scheme 1). The rod building blocks of
molecules 1a,b, consist of a p-phenyl unit at the center of the
rod segment and another two p-phenyl groups connected to
biphenyl units through ether bonds. The isomers of 1a,b,
namely, meta-position substituted molecules 2a,b (conforma-
tion-stable bent-shaped molecules 2a,b determined by energy
minimized molecular structures through the simulation (Gaus-
sian 09-TD-DFT-B3LYP/6-31G(d)) of 2a–2b, see Figure S1), are
composed of an m-phenyl unit at the center of the rod seg-
ments, and p-phenyl and biphenyl units, respectively. The self-
assembling behavior of these molecules in bulk and in aque-
ous solution was investigated by using differential scanning
calorimetry (DSC), thermal optical polarized microscopy (POM),
1
were characterized by H NMR spectroscopy and matrix-assist-
ed laser desorption ionization time-of-flight (MALDI-TOF) mass
spectroscopy (Figures S2 and S3, respectively). All the results
were in full agreement with the structures presented in
Scheme 1.
Structure Analysis of 1a,b and 2a,b in Bulk State
The self-assembling behavior of coil-rod-coil triblock molecules
1a,b and 2a,b was investigated by means of DSC, POM, and
SAXS. The transition temperatures of these molecules, deter-
mined from the DSC heating and cooling traces (Figure 1), de-
crease as the PEO coil length increases (Table S1).
Figure 1. DSC traces (108CminÀ1) recorded during the heating and cooling
scans of 1a,b and 2a,b (Colo: oblique columnar; HPL: hexagonal perforated
lamella; i: isotropic phase).
Scheme 1. Synthetic route to molecules 1a,b and 2a,b.
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Interestingly, the transition temperatures of linear molecules
1a,b are significantly higher than those of meta-position sub-
stituted molecules 2a,b. This is indicative of loose stacking of
the molecules 2a,b when compared to the linear molecules.
On slow cooling of 1a,b and 2a,b from isotropic liquid to
room temperature, POM displayed a focal conical fan texture
with arced striations, or a spherulitic fan texture. The DSC
curves, together with the optical textures, preliminarily con-
firmed the presence of an ordered columnar phase or hexago-
nal perforated layer phase (Figure 2 and Figure S4).[9]
Figure 2. Representative optical polarized micrographs (40ꢂ) of the textures
exhibited by a) the hexagonal perforated lamellar structure for 1a at 1758C
and b) the oblique columnar structure for 1b at 1558C.
Figure 3. SAXS diffraction patterns of 1a,b and 2a,b measured at different
temperatures: a) hexagonal perforated lamellar structure for 1a at 1908C;
b) oblique columnar structure for 1b at 1608C; c) oblique columnar struc-
ture of 2a at 1308C; and d) oblique columnar structure of 2b at 968C.
To identify the detailed self-organizing structures of mole-
cules 1 and 2, SAXS experiments were performed in the crys-
talline phases. The SAXS patterns of 1a display four sharp re-
flections that can be indexed as the (100), (002), (200), and
(300) reflections of a 2D hexagonal perforated lamellar phase
with lattice parameters a=9.5 nm, c=12.3 nm. An interesting
point is that the peak intensity associated with the (002) reflec-
tion of molecule 1a appears to be the most intense, implying
that the fundamental structure is lamellar. Therefore, we con-
firm that molecule 1a self-organizes into a hexagonally perfo-
rated lamellar structure in the crystalline phase.
result demonstrates that these molecules are highly packed
within the rod segments of the rod-coil molecules.
Notably, molecules 1a and 1b, having the same rod seg-
ment but a different PEO coil length, self-organize into a hexag-
onal perforated lamellar or an oblique columnar structure
(Figure 4), depending on the coil-chain length. On the other
hand, meta-position substituted 2a and 2b self-assemble into
oblique columnar structures in the solid state. Clearly, the di-
verse volume fractions of the flexible chains and the sequence
of the rod segments lead to the construction of different
supramolecular nanostructures. This is mainly due to the rela-
tively loose packing of molecules 2a and 2b (when compared
to that of their corresponding linear isomers 1a and 1b), and
is caused by steric hindrance of the bent-shaped rod building
blocks and the coil-chain length.
The result of SAXS analysis is consistent with POM experi-
ment (Figure S4). Meanwhile, the WAXS pattern of molecule
1a shows four clear peaks at q-spacings of 9.55, 11.91, 14.24,
and 17.15 nmÀ1, which appear due to crystal packing of the
rod segments within the aromatic domain. The molecules pack
in a rectangular lattice with unit cell dimensions of a=8.8 ꢁ
and b=6.5 ꢁ (Figure S5). For molecule 1b, the SAXS patterns
display four sharp reflections that can be indexed as the (100),
(010), (210), and (310) reflections with lattice parameters a=
8.8 nm, b=5.2 nm, and g=74.58. These characteristic peaks,
together with the POM images, imply the existence of a hexag-
onal perforated lamellar phase and an oblique columnar phase
as the crystalline mesophase of molecules 1a and 1b, respec-
tively.[10] Similarly, coil-rod-coil molecules 2a and 2b, based on
a bent-shaped rod segment, display an oblique columnar
structure with lattice parameters a=8.0 nm, b=3.9 nm, g=
838 and a=7.4 nm, b=3.8 nm, g=828, respectively (Figure 3
and Table S2).[11] Similar to molecule 1a, the WAXS pattern of
molecules 1b, 2a, and 2b also exhibit three clear reflections,
which can be assigned as a rectangular structure with lattice
parameters a=8.9 ꢁ, b=6.7 ꢁ for 1b, a=9.0 ꢁ, b=6.8 ꢁ for
2a and a=9.2 ꢁ, b=6.9 ꢁ for 2b, respectively (Figure S5).This
Figure 4. Schematic representation of self-assembly of 1a,b in bulk state.
a) A hexagonal perforated lamellar structure of 1a. b) An oblique columnar
structure of 1b. PEO chains are not shown.
Aggregation Behavior in Aqueous Solution
Molecules 1a,b and 2a,b consist of a hydrophilic flexible PEO
chain and a hydrophobic rigid aromatic segment. When dis-
solved in water, they can self-assemble into an ordered aggre-
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compound 1a (5ꢂ10À5 m) and negatively stained with sodium
phosphotungstate displayed sheet-like nanoribbons with an
average width and length of ~40 and ~200 nm, respectively.
Interestingly, 1b, with a longer PEO chain than 1a, exhibits
short nanofibers with lengths up to ~300 nm and a uniform di-
ameter of ~13.0 nm. The fully extended molecular length of
1b, estimated by CPK modeling to be 14.1 nm, is similar to the
measured length. Thus, we deduced that the cylindrical entity,
formed from aqueous solution, consists of a rigid rod building
block and a hydrophilic PEO chain that are surrounded by rod
segments and are fully interdigitated with each other. This
result indicates that an increase in the length of the hydrophil-
ic PEO chain increases the interfacial curvature. Thus, com-
pound 1b favors self-organization into the relatively more dy-
namically stable nanofibers over the formation of nanoribbons.
This construction of various supramolecular nanostructures can
also be explained by considering the relative volume fraction
of the hydrophobic rod segments to hydrophilic PEO head
groups.
Figure 5. Absorption and emission spectra of 2a,b in methylene chloride
(MC) and aqueous solution (2ꢂ10À5 m) a) 2a; b) 2b.
gate due to their amphiphilic characteristics.[12] The aggrega-
tion behavior of these molecules was subsequently studied in
dichloromethane and aqueous solutions by UV/Vis and FL
spectroscopy. The absorption spectra of 2a and 2b in aqueous
solution (5ꢂ10À5 m) exhibit a red-shift in the absorption
maxima compared to those in dichloromethane solution. This
is a result of the conjugated rod block (Figure 5).
These observations may be caused by the cooperative effect
between the hydrophilic and hydrophobic interactions, and
the p–p stacking interactions between the aromatic seg-
ments.[13] The fluorescence spectrum of 2a in dichloromethane
solution (Figure 5) exhibits a strong emission maximum at
348 nm. However, the emission maximum in aqueous solution
is blue-shifted with respect to that observed in the chloroform
solution, and the fluorescence is significantly quenched. This
implies an aggregation of the conjugated rod segments. The
same phenomena were also observed in the UV/Vis and FL
spectra of 1a,b (Figure S6). The dynamic light scattering(DLS)
experiments further corroborated this; the DLS data show that
molecules 1 and 2 self-assemble into nano-aggregates with
average hydrodynamic diameters ranging from 35 to 142 nm
(Figure S7).[13c]
In contrast to molecules 1a,b, the TEM images of bent-
shaped molecules 2a,b, with an m-phenylene unit at the
center of the rod segment, display supramolecular nanofibers
and cylindrical micelles, depending on the length of the PEO
chains. Molecule 2a, with a PEO DP of 7, spontaneously self-as-
sembles into nanofibers with a uniform diameter of ~6.5 nm
and average lengths up to several micrometers. To further cor-
roborate the construction of nanofibers of molecule 2a in
aqueous solution, we performed a cryo-TEM investigation. As
shown Figure S8, the micrograph shows the nanofiber with
uniform diameters against the vitrified aqueous solution back-
ground. On the other hand, molecule 2b, with a longer PEO
chain, self-organizes into short-length cylindrical micelles with
a uniform diameter of ~10.0 nm and a length of ~120 nm (Fig-
ure 6d). The fully extended molecular lengths of both rod and
coil blocks of molecules 2a,b (estimated to be 7.1 and
11.9 nm, respectively, by CPK modeling) are less than those of
the observed diameters. These results indicate that the cylin-
drical entities consist of hydrophobic aromatic inner cores sur-
rounded by hydrophilic flexible PEO segments that are ex-
posed to the aqueous environment (Figure 6). Similar to the
construction of various molecular aggregates of molecules
1a,b, the volume fraction of the hydrophilic PEO head groups
of 2a,b significantly influences the formation of the ordered
nanoentities by the tuning of the interfacial area between the
hydrophilic and hydrophobic domains. Therefore, the effective
hydrophilic coil ratio of the rod-coil amphiphilic molecules
gives rise to the formation of ordered supramolecular nanoas-
semblies.
Evidence for the creation of supramolecular aggregates in
dilute aqueous solution was also provided by TEM (Figure 6).
The micrograph of a sample cast from an aqueous solution of
It should be pointed out that molecules 1a and 2a have the
same molecular weight and PEO coil segments, but a different
sequence of rod building blocks. Molecule 1a, with a linear-
shaped rod segment, self-assembles into sheet-like nanorib-
bons in dilute aqueous solutions. However, molecule 2a, with
a meta-position substituted aromatic rod segment, self-organ-
izes into nanofibers. A similar tendency of the self-organization
of 1b and 2b into short nanofibers and cylindrical micelles
was also observed by TEM experiments. The results of the self-
Figure 6. TEM images of negatively stained nanoaggregates a) 1a; b) 1b;
c) 2a; d) 2b (obtained from 5ꢂ10À5 m aqueous solution).
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assembling behavior of these isomers imply that the sequence
of the rod building block is also the main parameter that influ-
ence the creation of supramolecular nanoassemblies of rod-
coil molecular systems in an aqueous environment. This is con-
sistent with the self-assembling behavior of the linear rod-coil
isomers reported by our team in bulk state. The variation of
aggregate morphology might be partly explained by the se-
quence of the individual molecules and the effective cross sec-
tional area of the hydrophilic head groups. Although molecule-
s 1a and 2a have the same effective hydrophilic domains,
a second driving force of linear 1a might be responsible for
the strong p–p interactions between the aromatic segments
down the perpendicular surface of the sheet-like ribbons, dem-
onstrated in bulk state. Thus, the interface of 1a between the
hydrophilic rod segment and the hydrophobic coil domains is
flatter than that of 2a. This causes a small interfacial area and
results in the formation of more dynamic stable sheet-like as-
semblies.
ed lamellar and an oblique columnar structure, respectively,
depending on the sequence of the rod building block. In aque-
ous solution, molecule 1a, with a linear rod segment, self-as-
sembles into sheet-like nanoribbons, whereas the isomer of
molecule 1a (2a) with meta substitution of the central C6H4
group, self-organizes into nanofibers through the control of
the non-covalent interactions of the rod building blocks. The
experimental results described herein imply that the sequence
of the rod building block and the length of the PEO chains
dramatically influence the creation of supramolecular aggre-
gates in bulk and aqueous solutions. Notably, the non-covalent
driving force of the molecular architecture of differently
shaped rod-coil molecules can be tuned precisely to construct
diverse supramolecular functional materials. These materials
can be applied to drug delivery systems and biomolecular sen-
sors.
On the basis of the above discussion, we have concluded
that molecules 1a and 2a self-assemble into nanosheet-like
aggregates and long nanofibers in aqueous solution, respec-
tively (Figure 7). However, molecules 1b and 2b, with longer
Experimental Section
General Materials: Poly(ethylene glycol) methyl ether (MW =
350,550), toluene-p-sulfonyl chloride (99%), 4,4’-biphenol, 1-(dibro-
momethyl)-4-methylbenzene, 1,4-benzenediol (99%), 1,3-benzene-
diol, pyridine, potassium carbonate (Aldrich, TCI, and Alfa Aesar,
etc.) and conventional reagents were used as received. Com-
pounds 3 and 4 were prepared according to the references de-
scribed elsewhere (see the Supporting Information).[14]
Characterization: Flash column chromatography was performed
1
using silica gel (200–300 mesh). H NMR(300 MHz) was recorded in
CDCl3 on Bruker AM-300 instruments. Chemical shifts were de-
scribed in parts per million (ppm, d units) downfield of tetrame-
thylsilane (TMS) as an internal standard. MALDI-TOF-MS was per-
formed on a PerSeptive Biosystems Voyager-DESTR using 2-cyano-
3-(4-hydroxyphenyl) acrylic acid (CHCA) as the matrix. A PerkinElm-
er Pyris Diamond differential scanning calorimeter was used to de-
termine the thermal transitions, which were reported as the
maxima and minima of their endothermic or exothermic peaks;
the heating and cooling rates were controlled to 108CminÀ1 under
a N2 atmosphere. An Olympus optical polarized micro scope,
equipped with a Mettler FP 82 hot-stage and a Mettler FP 90 cen-
tral processor, was used to observe the thermal transitions and to
analyze the anisotropic texture. The SAXS measurements were per-
formed in transmission mode with synchrotron radiation at the
1W2A X-ray beam line at Beijing Accelerator Laboratory.[15] The UV/
Vis and fluorescence spectra were obtained from a Shimadzu UV-
1650PC spectrometer and a Hitachi F-4500 fluorescence spectrom-
eter, respectively. Transmission electron microscopy (TEM) was per-
formed with a JEOL JEM-2100F microscope.
Figure 7. Schematic representation of the proposed self-assembly of mole-
cules in aqueous solution: a) nanoribbons for 1a; b) short nano-fibers for
1b; c) nano-fibers 2a; d) cylindrical micelles for 2b. PEO chains are not
shown.
PEO chains, self-assemble into short nanofibers and cylindrical
micelles, respectively, in a dilute aqueous environment. Al-
though these molecules have the same rod and coil segments,
they have a different rod shape and sequence of rod building
blocks. This is caused by the cooperative effect between the
hydrophilic and hydrophobic interactions, and the p–p stack-
ing interactions between the aromatic segments. This effect is
the driving force for the self-assembly of the rod segments
into ordered nanostructures.
General Synthetic Procedure for 1 and 2: Coil-rod-coil mole-
cules 1a,b and 2a,b were synthesized with similar procedures. A
representative example is described here for 1a. Compound 4a
(0.3 g, 0.43 mmol) and potassium carbonate (98 mg, 0.71 mmol)
were dissolved in 40 mL acetone. Next, 1,4-benzenediol (0.016 g,
0.14 mmol) was added dropwise to the mixture and heated at
reflux for 24 h. The resulting solution was filtered and concentrat-
ed, and the crude product was purified by column chromatogra-
phy (silica gel, CH2Cl2, ethyl acetate and CH2Cl2:CH3OH=20:1) to
yield 0.14 g (74.0%) white solid.
Conclusions
Amphiphilic coil-rod-coil triblock molecules 1a,b and 2a,b, in-
corporating biphenyl and phenyl units connected together
with ester bonds as a rod segment and PEO with a DP of 7
and 12, were synthesized. Their self-assembling behavior was
investigated in bulk state and in aqueous solution. In the bulk
state, these molecules self-organize into a hexagonal perforat-
1H NMR (300 MHz,CDCl3): d=7.47–7.62 (m,16Ar-H, o to phenyl-
OCH2CH2O, o to phenylOCH2, o to CH2Ophenyl), 6.96–7.16 (m,
12Ar-H,
m to phenylOCH2CH2O, m to phenylOCH2, o to
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OCH2phenyl), 5.14 (s, 8H,OCH2phenyl), 4.16 (t, 4H, phenyl-
OCH2CH2O), 3.87(t, 4H, phenyl-OCH2CH2O), 3.55–3.72(m,48H,
-OCH2CH2O-), 3.37 ppm (s, 6H, OCH3). MALDI-TOF-MS m/z [M]+
1331, [M+Na]+ 1354.
1b: white solid (75.0%).1H NMR (300 MHz, CDCl3): d=7.47–7.62
(m,16Ar-H,
o to phenylOCH2CH2O, o to phenylOCH2, o to
CH2Ophenyl), 6.96–7.16 (m, 12Ar-H, m to phenylOCH2CH2O, m to
phenylOCH2, o to OCH2phenyl), 5.14 (s, 8H,OCH2phenyl), 4.16 (t,
4H, phenyl-OCH2CH2O), 3.87 (t, 4H, phenyl-OCH2CH2O), 3.55–3.72
(m,88H, -OCH2CH2O-), 3.37 ppm (s, 6H, OCH3). MALDI-TOF-MS m/z
[M]+ 1772, [M+Na]+ 1795.
2a: white solid (72.0%). 1H NMR (300 MHz,CDCl3): d=7.47–7.62
(m,16Ar-H,
CH2Ophenyl), 7.23 (t,1Ar-H) 6.96–7.16 (m, 8Ar-H, m to phenyl-
OCH2CH2O, to phenylOCH2), 6.35–6.60 (3Ar-H), 5.14 (s,
o to phenylOCH2CH2O, o to phenyl OCH2, o to
m
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8H,OCH2phenyl), 4.16 (t, 4H, phenyl-OCH2CH2O), 3.87 (t, 4H,
phenyl-OCH2CH2O), 3.55–3.72 (m,48H, -OCH2CH2O-), 3.37 ppm (s,
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2b: white solid (71.0%). 1H NMR (300 MHz,CDCl3): d=7.47–7.62
(m,16Ar-H,
o to phenylOCH2CH2O, o to phenyl OCH2, o to
CH2Ophenyl, 7.23 (t, 1Ar-H), 6.96–7.16 (m, 8Ar-H, m to phenyl-
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OCH2CH2O), 3.55–3.72 (m, 88H, -OCH2CH2O-), 3.37 ppm (s, 6H,
OCH3). MALDI-TOF-MS m/z [M]+ 1772.
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This work was supported by the National Natural Science
Foundation of China (grant number: 21562043, 21564016,
21164013), the Open Projects of the State Key Laboratory of
Supramolecular Structure and Materials (sklssm201430), Jilin
University, China. We are grateful to Bejing Synchrotron Radia-
tion Facility (BSRF), Institute of High Energy Physics, Chinese
Academy of Sciences for help with the X-ray scattering meas-
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Keywords: amphiphiles · coil-rod-coil structures · nanofibers ·
nanostructures · self-assembly
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Manuscript received: May 17, 2016
Accepted Article published: June 27, 2016
Final Article published: && &&, 0000
&
&
Chem. Asian J. 2016, 00, 0 – 0
www.chemasianj.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
FULL PAPER
Self-Assembly
Hot rods: Self-assembling behavior of
amphiphilic coil-rod-coil molecular iso-
mers, consisting of biphenyl and phenyl
units, incorporating p-aryl or m-aryl
groups in the middle of the rod seg-
ments was investigated in bulk and in
aqueous solutions. The experimental re-
sults suggest that the sequence of the
rod building block dramatically influen-
ces self-assembly of the rod-coil molec-
ular system.
Zhaohua Li, Yuntian Yang, Yanqiu Wang,
Tie Chen, Long Yi Jin,* Myongsoo Lee*
&& – &&
Construction of Supramolecular
Assemblies from Self-Organization of
Amphiphilic Molecular Isomers
Chem. Asian J. 2016, 00, 0 – 0
www.chemasianj.org
7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ