Self-assembling structures of long-chain sugar-based amphiphiles influenced by the introduction of double bonds

Article abstract of DOI:10.1002/chem.200401288

Nine phenyl glucoside or galactoside amphiphiles possessing a saturated or unsaturated long alkyl-chain group as the self-assembling unit of a highly organized molecular architecture were synthesized. Their self-assembly properties were investigated by using energy-filtering TEM (EF-TEM), SEM, CD, XRD, and FT-IR techniques. Compound 2, possessing one cis double bond in the lipophilic portion, exhibited twisted helical fibers, which formed a bilayered structure with a 3.59 nm period, while 3 exhibited helical ribbons and left-handed nanotubu-lar structures with 150-200 nm inner diameters and a wall thickness of approximately 20 nm. Very interestingly, 4, possessing three cis double bonds, exhibited a nanotubular structure with an inner diameter of approximately 70 nm and a d spacing value of 4.62 nm. On the other hand, 7, possessing two trans double bonds in the lipophilic region, exhibited crystal- or plate-like structures, which formed a bilayer structure with a d spacing value of 3.93 nm. These results indicate that the self-assembly properties are strongly dependent on the type of double bond. Furthermore, 8 and 9, with the galactopyr anose moiety, revealed helical ribbon and well-defined double helical fiber structures, respectively. These findings support the view that the orientation of the intermolecular hydrogen-bonding interaction between the sugar moieties plays a critical role in producing the nanotubular structures. According to CD and powder XRD experiments, the relatively strong intermolecular hydrogen-bonding interaction of the glucopyranoside moiety in 3 and 4 provided a highly ordered chiral packing structure. Even though these compounds formed a weak hydrophobic interaction between lipophilic groups, it led to the formation of the nanotubular structure.

Full text of DOI:10.1002/chem.200401288

DOI: 10.1002/chem.200401288
Self-Assembling Structures of Long-Chain Sugar-Based Amphiphiles
Influenced by the Introduction of Double Bonds
[a, b]
Jong HwaJung,*
Youngkyu Do,[c] Young-A Lee,[d] and Toshimi Shimizu*[a, e]
Abstract: Nine phenyl glucoside or gal-
actoside amphiphiles possessing a satu-
rated or unsaturated long alkyl-chain
group as the self-assembling unit of a
highly organized molecular architec-
ture were synthesized. Their self-as-
sembly properties were investigated by
using energy-filtering TEM (EF-TEM),
SEM, CD, XRD, and FT-IR techni-
ques. Compound 2, possessing one cis
double bond in the lipophilic portion,
exhibited twisted helical fibers, which
formed a bilayered structure with a
3.59 nm period, while 3 exhibited heli-
cal ribbons and left-handed nanotubu-
lar structures with 150–200 nm inner di-
ameters and a wall thickness of approx-
imately 20 nm. Very interestingly, 4,
possessing three cis double bonds, ex-
hibited a nanotubular structure with an
inner diameter of approximately 70 nm
and a d spacing value of 4.62 nm. On
the other hand, 7, possessing two trans
double bonds in the lipophilic region,
exhibited crystal- or plate-like struc-
tures, which formed a bilayer structure
with a d spacing value of 3.93 nm.
These results indicate that the self-as-
sembly properties are strongly depen-
dent on the type of double bond. Fur-
thermore, 8 and 9, with the galactopyr-
anose moiety, revealed helical ribbon
and well-defined double helical fiber
structures, respectively. These findings
support the view that the orientation of
the intermolecular hydrogen-bonding
interaction between the sugar moieties
plays a critical role in producing the
nanotubular structures. According to
CD and powder XRD experiments, the
relatively strong intermolecular hydro-
gen-bonding interaction of the gluco-
pyranoside moiety in 3 and 4 provided
a highly ordered chiral packing struc-
ture. Even though these compounds
formed a weak hydrophobic interaction
between lipophilic groups, it led to the
formation of the nanotubular structure.
Keywords: amphiphiles · carbohy-
drates · lipids · nanotubes · self-
assembly
[a] Dr. J. H. Jung, Prof. Dr. T. Shimizu
Introduction
CREST, Japan Science and Technology Corporation (JST)
Nanoarchitectonics Research Center (NARC)
National Institute of Advanced Industrial Science and Technology
(AIST)
Tsukuba Central 4, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562 (Japan)
E-mail: jonghwa@kbsi.re.kr
Currently, there is tremendous interest in high-axial-ratio
nanostructures (HARNs) formed by the hierarchical self-as-
sembly of amphiphilic molecules into helical ribbons and
nanotubes.[1–6] The need for improved miniaturization and
device performance in the microchip and microelectronics
industry has inspired many investigations into supramolec-
ular chemistry. It is conceivable that the “bottom-up”[7,8]
HARN fabrication approach based on supramolecular
chemistry will provide a solution to the anticipated size limi-
tations of the “top-down” approach, such as photolithogra-
phy,[9] thereby providing the means to fabricate ultrasmall
electronic components.
tshmz-shimizu@aist.go.jp
[b] Dr. J. H. Jung
Nano Material Team
Korea Basic Science Institute (KBSI)
52 Yeoeun-dong, Yusung-gu, Daejeon 305-333 (Korea)
Fax : (+82)42-865-3619
[c] Prof. Dr. Y. Do
Department of Chemistry
Korea Advanced Institute of Science and Technology (KAIST)
373-1Guseong-dong, Yuseong-gu, Daejeon 305-701(Korea)
In particular, the formation of organic tubular species
from the aggregation of molecular species is an important
nanoscience research field, since it may find applications in
catalysis, selective separations sensors, and conducting devi-
ces in nano-, opto- or ionic electronics. Examples of tubular
structures can be found with several organic systems, for ex-
ample, lipidic,[10] peptidic,[11] and steroidic[1d,12] systems. With
synthetic diacetylene lipidic systems[4] and steroids in
bile,[1c,h] the average diameters of the tubular structures are
[d] Prof. Dr. Y.-A Lee
Department of Chemistry
Chonbuk National University
Jeonju 561-756 (Korea)
[e] Prof. Dr. T. Shimizu
Nanoarchitectonics Research Center (NARC)
National Institute of Advanced Industrial Science and Technology
(AIST)
Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan)
Fax : (+81)298-61-2659
5538
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 5538 – 5544

FULL PAPER
in the micrometer range, while with peptidic systems,[11] the
internal cylindrical cavities are in the molecular range.
Although the evidence is limited, research has re-
vealed[3,4,9] that tube-forming amphiphiles which mediate
helical ribbons require unsaturation in the lipophilic moiety
to impart a bent structure, thereby inducing supramolecular
chirality. However, to the best of our knowledge, there have
never been systematic studies conducted on the influence of
unsaturation, that is, the number and the position of double-
bond units, on the self-assembly of synthetic amphiphiles
into HARNs based on solid chiral bilayers, even though the
tubular structure of amphiphiles has been reported by sever-
al groups.[1,4,5,10]
We provide evidence on the self-assembled morphologies
of a series of long-chain phenyl glucopyranoses, 1–7, and
galactopyranoses, 8–9, which vary in the number of cis and
trans double bonds (0–5) in their lipophilic part. The self-as-
sembled morphologies were strongly dependent on the
number of double bonds in the lipophilic regions, the types
of double bonds, and the sugar moiety. The effects on the
molecular packing and orientation are discussed in relation
to the hydroxy group of the sugar moiety and the number of
double bonds in the lipophilic region. In addition, both cir-
cular dichroism (CD) and powder X-ray diffraction (XRD)
analysis provided useful information about the intermolecu-
lar chiral order. Therefore, on the basis of the CD and
powder XRD experiments, we provide evidence for the
chiral packing structures of self-assembling superstructures
of sugar-based amphiphiles.
Results and Discussion
Self-assembly and morphological observations: A series of
simple sugar-based amphiphiles 1–9 was synthesized by
using a similar method to that reported previously.[13b] For
self-assembly, each sugar-based amphiphile (1mg) was dis-
persed in water (10–30 mL) at temperatures above the cor-
responding melting point, Tm, of the hydrated sample. In
general, heating of the mixture at 958C for 30 min was
enough to get a homogeneous transparent solution. The ob-
tained aqueous solutions were allowed to cool to an incuba-
tion temperature. However, 1 was insoluble in water and
only formed a typical nanofiber structure with a diameter of
100–350 nm and a length of several micrometers in a mix-
ture of water and methanol (1:1). To characterize the resul-
tant morphologies and their size dimensions precisely, we
observed individual self-assembled structures by using
energy-filtering transmission electron microscopy (EF-
TEM) and scanning electron microscopy (SEM). Figure 1
displays SEM and EF-TEM images of the self-assembled
structures of 2–9 in aqueous solution. Compound 2 exhibits
a twisted fiber structure with a width of 50–200 nm and a
length of several micrometers (Figure 1a). Compound 3,
however, exhibits less than 5% of a left-handed coiled tube,
with a 150–200 nm inner diameter and a wall thickness of
approximately 20 nm (Figure 1b), and displays a helical
Figure 1. SEM and TEM images of self-assembled compounds a) 2, b and
c) 3, d and e) 4, f and g) 5, h and i) 6, and j) 7.
ribbon structure (Figure 1c) as the major morphology; these
results show the influence of the number of double bonds
on the final morphology of the self-assembled structures.
On the other hand, 4, possessing three cis double bonds in
the lipophilic region, displays a helical ribbon morphology
with an outer diameter of 80–100 nm as the intermediate
morphology and a nanotubular structure with an inner di-
Chem. Eur. J. 2005, 11, 5538 – 5544
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5539

J. H. Jung, T. Shimizu, et al.
ameter of approximately 70 nm and a wall thickness of 20–
30 nm as the final morphology (Figure 1d and e). As far as
can be determined, all the chiral structures possess a left-
handed helical motif. These observations further support the
view that the unsaturated units are important for producing
nanotubes through self-assembly. Furthermore, 5 and 6 pro-
duced self-assembled solids when they reached room tem-
perature from boiling temperature. They exhibited helical
ribbons with 50–100 nm width (Figure 1 f and h) and tubular
structures with an inner diameter of 80–100 nm and a wall
thickness of 20–30 nm (Figure 1g and i). These results also
provide evidence that the numbers of cis double bonds in
the lipophilic region play an important role in producing
tubular structures.
ate molecular assemblies, which slowly convert into highly
ordered structures. To the best of our knowledge, the pres-
ent finding also gives a unique example of a stable nanome-
ter-sized double-helical structure.
Chiral self-assembly involved a helically coiled ribbon
structure as an intermediate. After hot aqueous dispersions
of nanotube-forming amphiphiles are cooled, there are two
routes for nanotube formation. One route proceeds with
shortening of the helical pitch of the ribbon and maintaining
a constant ribbon width, whereas the second involves widen-
ing of the helical width and maintaining a constant helical
pitch. Figure 3 shows the SEM images: self-assembled 4 pos-
To confirm the cis-double-bond effect in the formation of
the nanotubular structure, two trans double bonds were in-
troduced in the lipophilic region of 7, in place of the cis
double bonds of 3. Self-assembled 7 exhibits crystal- and
plate-like structures with a thickness of 160–170 nm (Fig-
ure 1j). This result further supports the view that the mor-
phology formation of sugar-based amphiphiles depends
strongly on the types of double bonds in the long alkyl-
chain group.
We also confirmed the effect of the intermolecular hydro-
gen-bonding interaction by the introduction of a different
type of sugar moiety. Compounds 8 and 9 were synthesized
with a galactose moiety instead of the glucose moiety of 3
and 4. Compound 8 exhibited the helical ribbon structure
with a width of 40–45 nm and a loose, long helical pitch
(Figure 2a and b). However, 9 forms a double-helical fiber
Figure 3. SEM images of the self-assembled helical ribbons obtained
from 4.
sesses the helical ribbon structure with various pitchs (62–
315 nm) and with a constant ribbon width (approximately
80 nm) in the initial stage. Also, as far as can be determined,
all the helicity possesses a left-handed helical motif. The
latter observation is more common in the literature than the
former. These findings strongly suggest that the sugar-based
organic tube formed by self-assembly was produced by a
change of pitch length of the helical ribbon with a constant
ribbon width, as depicted in Figure 4a, rather than by the
mechanism represented in Figure 4b. This mechanism is
quite different from that observed for the crown-appended
cholesterol tube,[14] which formed by the mechanism depict-
ed in Figure 4b. Perhaps the formation mechanisms for tub-
ular structures are related to the formation conditions, cool-
ing times, and deriving forces. However, it is not currently
clear what the main factor is in deciding the mechanism of
tube formation.
Figure 2. TEM images of self-assembled compounds a and b) 8 and c) 9.
d) Schematic representation of the left-handed double-helical fiber struc-
ture of self-assembled 9.
CD measurement: As alternative evidence for the nanotube
formation of 3 and 4 in the microscopic structural view, we
carefully observed the CD spectra of the self-assembled
compounds 2–4 and 7–9 (Figure 5). The CD spectra of the
self-assembled compounds 3 and 4 in aqueous solution
showed a strong negative band at 237 (Figure 5bb) and
225 nm (Figure 5c), respectively, on forming the nanotubu-
lar structures with chiral assembly. They showed only a
weak CD signal at temperatures above a phase-transition
temperature (Figure 5d and e) and this was shifted to a
longer wavelength; this signal probably corresponds to a
monomers or small lipid aggregates, such as micelles or vesi-
structure several micrometers in length and with a diameter
of approximately 11 nm (Figure 2c and d), which exhibits a
three-fold increase in the bilayer structure. All the helicity
also possesses a left-handed helical motif. These findings
suggest that the orientation of the intermolecular hydrogen
bond is important in forming the nanostructure in water. In
addition, only a few reports exist explaining the well-re-
solved double-helical strands or ribbons formed from chiral
amphiphiles[12] and they describe only metastable intermedi-
5540
www.chemeurj.org
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 5538 – 5544

Self-Assembly of Sugar-Based Amphiphiles
FULL PAPER
Table 1. Self-assemblies with different morphologies and their physical
data.
Compound Tgel
[8C][a]
Morphology[b]
d spacing
Molecular
[nm][c]
length [nm][d]
1
2
–
fiber structure
–
–
3.03
90.0 twisted fiber struc- 3.59
ture
3
65.2 helical ribbon struc- 4.62
ture
3.15
3.02
4
5
6
7
8
–
tubular structure
4.62
50.1tubular structure
–
–
–
–
–
tubular structure
–
–
3.20
3.03
plate-like structure 3.93
helical ribbon struc- 3.87
ture
9
–
–
double-helical fiber5 3.813.1
structure
10
twisted fiber struc-
ture
–
–
11
12
13
47.8 tubular structure
–
–
–
–
–
–
17.4
–
–
À25.4
[a] From differential scanning calorimetry (DSC) data. [b] From EF-
SEM observations. [c] From XRD data. [d] From molecular modeling.
Figure 4. Representation of possible tube-formation mechanisms of 4:
a) the tube is formed by a change in the pitch length; b) the tube is
formed by growth in the width of the helical ribbon.
and 4 is enhanced mainly by intermolecular hydrogen-bond-
ing interactions between the amide groups.
Since the gel-to-liquid crystalline phase-transition temper-
ature was near room temperature for self-assembled 5 and
6, we could not obtain enough information on the chiral
packing structures or the number of cis double bonds influ-
encing the formation of the helical ribbon and the tubes by
CD spectrscopy.
The CD spectrum of self-assembled 7, possessing two
trans double bonds, was measured as a reference to confirm
the effect of cis double bonds in the formation of the tubu-
lar structure (Figure 5 f). The CD intensity of self-assembled
7 was much smaller than that of 4. This result indicates that
the sugar moiety of 7 formed loose chiral packing with in-
termolecular hydrogen-bonding interactions between the
glucose moieties, which is due to the relatively strong hydro-
phobic interaction between the linear long alkyl-chain
groups.
Figure 5. CD spectra of self-assembled compounds a) 2, b) 3, c) 4, all at
25.08C, d) 3 at 70.08C, e) 4 at 70.08C, and f) 7 at 25.08C.
The CD spectra of the galactose-based amphiphiles 8 and
9, with two and three cis double bonds, respectively, were
also measured to obtain information regarding chiral molec-
ular packing structures with changed sugar moieties. The
galactose-based amphiphiles 8 and 9 formed helical ribbon
and double-helical fiber structures, which appeared in the
CD spectra as negative bands at 238 nm (Figure 6a and b).
The CD intensities were smaller than those of 3 and 4.
These results continue to support the view that galactose-
based amphiphiles 8 and 9 form disorderly chiral packing
structures with a hydrophobic interaction that is stronger
than those formed by glucose-based amphiphiles 3 and 4.
cles. The CD signal, however, became strong again when the
lipid self-assembled to form nanotubular structures after
several hours. However, the CD spectrum of self-assembled
2 in aqueous solution showed a much weaker negative band
(Figure 5a) in comparison to that of 3 and 4, thereby sug-
gesting that self-assembled 2 forms disordered chiral pack-
ing structures. These CD spectroscopy results provide direct
evidence for the chiral molecular architecture of nanotubes
and for the fact that the molecular packing of 3 and 4 is
loosely chiral at temperatures above the phase-transition
temperature. Furthermore, the phase-transition tempera-
tures of 3 and 4 are much higher (Table 1) than those of glu-
Powder XRD measurement: Recently, an X-ray crystallo-
graphic method for ascertaining the molecular packing of
self-assemblies has been reported,[1d,f,10] and this method was
coside amphiphiles 11–13, which lack the amide group,[10b]
fact indicating that stabilization of self-assembled tubes of 3
a
Chem. Eur. J. 2005, 11, 5538 – 5544
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5541

J. H. Jung, T. Shimizu, et al.
Figure 7. Powder XRD pattern values in the small-angle region of the
freeze-dried nanostructures from a) 4 and b) 2.
Figure 6. CD spectra of self-assembled compounds a) 9 and b) 8 at
25.08C.
used to clarify the self-assembly mechanism. First, the mo-
lecular length of three amphiphiles was calculated by using
Corey–Pauling–Koltun (CPK) modeling based on single-
crystal data for oleic, linoleic, and linolenic acid.[15] The
models showed similar values despite a bending effect.
Second, X-ray diffraction patterns were measured. The d
spacing values of crystalline 2–9 from the self-assembly are
shown in Table 1and Figure 7. The small-angle diffraction
patterns of helical ribbons of 3 and nanotubes of 4 appeared
at 4.62 nm (Figure 7a and Table 1), which is smaller than
twice the extended molecular length of 3 (3.15 nm by using
the CPK molecular modeling) and 4 (3.02 nm) but larger
than the length of one molecule. These results strongly sug-
gest that self-assembled 3 and 4 form a bilayer structure
with a relatively small region interdigitated by hydrophobic
interaction, as shown in Figure 8b and c. On the other hand,
the diffraction diagram of the microcrystalline solid 2
(length of one molecular according to the CPK molecular
modeling: 3.03 nm) indicated a bilayer structure with a d
value of 3.59 nm (Figure 8a), a result supporting the theory
that 2 maintains a much stronger interdigitated bilayer
structure between the lipophilic regions than those of 3 and
4.
Figure 8. Possible molecular arrangements of the self-assembled com-
pounds a) 2, b) 3, c) 4, and d) 7.
hydrogen-bonding interactions of the glucopyranoside
moiety of 3 and 4 provide a highly ordered chiral packing
structure, even though these compounds form a weak hydro-
phobic interaction between the lipophilic groups, which led
to the formation of the nanotubular structure.
Furthermore, the d value (3.93 nm) for self-assembled 7,
possessing trans double bonds in the long alkyl chain, is
much smaller than that of self-assembled 3 (Table 1). This
finding indicates that the molecular packing of the plate-like
structure obtained from 7 forms a relatively stronger hydro-
phobic interaction with the interdigitated bilayer structure
(Figure 8d) between the lipophilic regions than that of 3 or
4.
IR measurement: Compound 2 shows a highly ordered
structure in the aliphatic region, possibly due to hydrocar-
bon crystallization, an observation which is further support-
ed by the Fourier transformation infrared (FT-IR) spectros-
À1
À
copy studies showing C H stretching values of 2855 cm
for 3/4 and 2851cm À1 for 2 (Table 2). It is reasonable to
The d values of galactose-based amphiphiles 8 and 9 were
also smaller than those of glucose-based amphiphiles 3 and
4, a result indicating again that amphiphiles 8 and 9 form a
relative strong hydrophobic interaction with a large region
of interdigitated bilayer structure in the lipophilic section.
Once again, according to CD spectroscopy and powder X-
ray diffraction results, the relatively strong intermolecular
Table 2. FT-IR results of the self-assembled compounds 1–4.
compound
CH2 [cmÀ1
]
C=O [cmÀ1
]
1
2
3
4
657
656
28511
28511
2855
1649
1649
2855
5542
www.chemeurj.org
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 5538 – 5544

Self-Assembly of Sugar-Based Amphiphiles
FULL PAPER
aqueous dispersions of the nanotube (0.1mgmL À1) were dripped onto
the prism and dried under a nitrogen stream prior to measurement.
argue that the lipophilic groups of 3 and 4, possessing three
cis double bonds, formed a more disordered structure than
that of 2. Also, the C=O (amide I) stretching patterns of the
three compounds 2–4 are different: the signals for 3 and 4
appeared at 1649 cmÀ1, whereas that for 2 appeared at
1656 cmÀ1. This suggests that 3 and 4 maintain a well-or-
dered structure of the glucopyranoside head group by inter-
molecular hydrogen-bonding interactions between the
amide groups.
XRD measurements: The XRD pattern of a freeze-dried sample was
measured with a Rigaku type 4037 diffractometer by using graded d-
space elliptical side-by-side multilayer optics, monochromated CuKa ra-
diation (40 kV, 30 mA), and an R-Axis IV imaging plate. The typical ex-
posure time was 10 min with a 150 mm camera length. Freeze-dried sam-
ples of 2–9 were vacuum dried to constant weight and then put into capil-
lary tubes, without being powdered.
1-Octadecanecarboxylic chloride: A mixture of 1-octadecanecarboxylic
acid (0.15 g, 0.58 mmol), oxalic chloride (0.50 g, 3.96 mmol), and dime-
thylformamide (DMF; 1–2 drops) was dissolved in dichloromethane
(5.0 mL), and the reaction mixture was then stirred for 10 h at room tem-
perature. The residual oxalic chloride and solvent were removed by
vacuum. The product was directly used for the coupling reaction without
further purification.
Conclusion
The present study has demonstrated that long-chain phenyl
glucosides form twisted nanofiber, helical ribbon, and nano-
tubular structures, depending on the double-bond unsatura-
tion. Long-chain phenyl galactosides revealed that their heli-
cal ribbon and double-helical fiber structures depended on
the number of double bonds. cis double bonds in the lipo-
philic region of long-chain phenyl glucosides more efficient-
ly induce the tubular structure, compared to trans double
bonds. To the best of our knowledge, these results are the
first example of a systematic study of the influence of cis
double-bond units in a hydrophobic portion on self-assem-
bled morphologies. Based on the CD results, the self-assem-
bled nanotubular structure showed a relatively stronger in-
tensity than that of the twisted fiber structure, a fact indicat-
ing that the nanotubes formed relatively well-ordered chiral
packing structures compared to the twisted fiber structures.
Furthermore, the XRD experiments indicated that the rela-
tively weak hydrophobic interactions of the glucopyranoside
moiety of 3 and 4 formed bilayer structures between the lip-
ophilic groups, which led to the formation of the nanotubu-
lar structure.
Related carboxylic chlorides were synthesized according to a similar
method.
p-Aminophenyl-b-d-glucopyranoside and p-Aminophenyl-b-d-galactopyr-
anoside: p-Nitrophenyl-b-d-glucopyranoside (1.0 g, 2.54 mmol) or p-ni-
trophenyl-b-d-galactopyranoside (1.0 g, 2.54 mmol) was dissolved in
methanol (150 mL). 10% Pd/C (1.0 g) was then added to the solution.
Hydrogen gas was introduced into the mixed solution for 10 h at room
temperature under a nitrogen atmosphere. The reaction mixture was fil-
tered to remove Pd/C, and the filtrate was evaporated in vacuo to dry-
ness. The residue was purified by column chromatography on silica gel
with tetrahydrofuran (THF)/chloroform (1/1): Yields 80–90%; 1H NMR
(600 MHz, [D6]DMSO): d=3.4–4.1(s, 2H), 5.2–5.3 (m, 3H), 5.6 (s, 1H),
6.7 (d, 2H), 7.37–7.46 ppm (m, 5H); FT-IR (KBr): n˜ =3312, 2909, 1635,
1510, 1364, 1217, 1089, 1005, 1035, 999, 806, 706 cmÀ1; MS (p-nitrobenzoic
acid (NBA)): m/z: 360 [M+H]+; elemental analysis calcd (%) for
C19H21NO6: C 63.50, H 5.89, N 3.90; found: C 63.18, H 6.04, N 3.78.
Octadecanoyl-p-aminophenyl-b-d-glucopyranoside (1): A mixture of p-
aminophenyl-b-d-glucopyranoside (0.30 g, 1.10 mmol), dodecanoyl cho-
ride (0.24 g, 1.10 mmol), and triethylamine (0.536 g, 5.50 mmol) in dry
THF (50 mL) was heated to reflux for 3 h under a nitrogen atmosphere.
The solution was filtered after cooling to room temperature, and the fil-
trate was concentrated to dryness by a vacuum evaporator. The residue
was purified by column chromatography on silica gel with methanol/
1
chloroform (1:6): Yield 40%; H NMR (600 MHz, [D6]DMSO): d=0.9 (t,
3H), 1.2–2.0 (m, 24H), 2.3 (m, 2H), 3.2–4.7 (m, 19H), 7.25 (d, 2H), 7.65
(d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3340, 2912, 1630, 1510, 1364,
1217, 1089, 1005, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z: 538.27
[M+H]+; elemental analysis calcd (%) for C30H51NO7: C 67.01, H 9.56, N
2.60; found: C 67.20, H 9.25, N 2.55.
Experimental Section
General: The 1H and 13C NMR spectra were recorded with a JEOL 600
(600 MHz) or a JEOL GSX 270 (270 MHz) NMR spectrometer. Prepara-
tive column chromatography was performed on silica gel. The chromato-
graphic purity of the intermediates was monitored by thin-layer chroma-
tography (Kiesel gel F 254, Merck). The compounds were visualized by
spraying the plates with 5% sulfuric acid in methanol and then charring
them on a hot plate. The molecular lengths were estimated by molecular
mechanics calculations performed with the CONFLEX-MM2 force field
as implemented in the CAChe program, version 4.1.1 (Fujitsu Co. Ltd.,
Japan).
Related compounds (2–9) were synthesized according to
a similar
method. Their analytical data are described below.
n-(11’Z)-Octadecanyl-(p-aminophenyl-b-d-glucopyranoside) (2): Yield
50%; m.p. 127.58C; 1H NMR (600 MHz, [D6]DMSO): d=0.9 (t, 3H),
1.2–2.5 (m, 20H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d, 2H), 7.65 (d,
2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3410, 3340, 2915, 1630, 1513,
1357, 1217, 1090, 1005, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z: 536.55
[M+H]+; elemental analysis calcd (%) for C30H49NO7: C 67.26, H 9.22, N
2.61; found: C 67.52, H 9.40, N 2.52.
n-(9’Z,12’Z)-Octadecadienyl-(p-aminophenyl-b-d-glucopyranoside) (3):
Yield 50%; m.p. 120.78C; 1H NMR (600 MHz, [D6]DMSO): d=0.9 (t,
3H), 1.2–3.0 (m, 18H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d, 2H), 7.65
(d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3410, 3342, 2912, 1628, 1513,
1364, 1219, 1089, 1005, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z: 534.73
[M+H]+; elemental analysis calcd (%) for C30H47NO7: C 67.51, H 8.88, N
2.62; found: C 67.31, H 8.50, N 2.57.
TEM observations: The aqueous dispersions of the nanostructures
(0.1mgmL À1) were dripped onto an amorphous carbon grid and excess
water was blotted with filter paper. TEM was performed with a Carl-
Zeiss LEO912 instrument operated at 50 keV. Images were recorded on
an imaging plate (Fuji Photo Film Co. Ltd. FDL5000 system) with 20 eV
energy windows at 3000–250000” and were digitally enlarged.
FT-IR measurements: The FT-IR spectra of the self-assembled nano-
structures were measured with a JASCO FT-620 FT-IR spectrometer op-
erated at 4 cmÀ1 resolution with an unpolarized beam and attenuated
total reflection (ATR) accessory system (Diamond Miracle horizontal
ATR accessory with a diamond crystal prism, PIKE Technologies, USA)
and a mercury cadmium telluride (MCT) detector. Several drops of the
n-(6’Z,9’Z,12’Z)-Octadecatrienyl-(p-aminophenyl-b-d-glucopyranoside)
(4): Yield 63%; m.p. 105.58C; 1H NMR (600 MHz, [D6]DMSO): d=0.9
(t, 3H), 1.2–2.5 (m, 20H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d, 2H),
7.65 (d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3410, 3342, 2912, 1630,
1511, 1367, 1217, 1089, 1007, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z:
Chem. Eur. J. 2005, 11, 5538 – 5544
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5543

J. H. Jung, T. Shimizu, et al.
532.80 [M+H]+; elemental analysis calcd (%) for C30H45NO7: C 67.77, H
8.53, N 2.63; found: C 67.25, H 8.55, N 2.50.
dek, F. M. Konikoff, J. M. Donovan, Proc. Natl. Acad. Sci. USA
1993, 90, 11341.
[2] a) J. D. Hartgerink, E. Beniash, S. I. Stupp, Science 2001, 294, 1684;
b) S. I. Stupp, V. LeBonheur, K. Walker, L. S. Li, K. E. Huggins, M.
Keser, A. Amstutz, Science 1997, 276, 384.
[3] a) J. S. Cheng, S. Kopta, R. C. Stevens, J. Am. Chem. Soc. 2001, 123,
3205; b) Q. Cheng, M. Yamamoto, R. C. Stevens, Langmuir 2000,
16, 5333.
n-(5’Z,8’Z,11’Z,14’Z-Dosocatetraenyl-(p-aminophenyl-b-d-glucopyrano-
side) (5): Yield 55%; m.p. 65.78C; 1H NMR (600 MHz, [D6]DMSO): d=
0.9 (t, 3H), 1.2–2.5 (m, 20H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d,
2H), 7.65 (d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3412, 3341, 2912,
1633, 1512, 1365, 1215, 1089, 1003, 1035, 999, 806, 706 cmÀ1; MS (NBA):
m/z: 558.75 [M+H]+; elemental analysis calcd (%) for C32H47NO7: C
68.91, H 8.49, N 2.51; found: C 69.05, H 8.53, N 2.47.
[4] a) M. S. Spector, A. Singh, P. B. Messersmith, J. M. Schnur, Nano
Lett. 2001, 1, 375; b) M. S. Spector, J. V. Selinger, A. Singh, J. M. Ro-
driguez, R. R. Price, J. M. Schnur, Langmuir 1998, 14, 3493; c) M. S.
Spector, R. R. Price, J. M. Schnur, Adv. Mater. 1999, 11, 337; d) J. M.
Schnur, B. R. Ratna, J. V. Selinger, A. Singh, G. Jyothi, K. R. Eas-
waran, Science 1994, 264, 945; e) M. S. Spector, K. R. Easawaran, G.
Jyothi, J. V. Seliger, A. Singh, J. M. Schnur, Proc. Natl. Acad. Sci.
USA 1996, 93, 12943; f) J. M. Schnur, Science 1993, 262, 1669.
[5] G. John, M. Mason, P. M. Ajayan, J. S. Dordick, J. Am. Chem. Soc.
2004, 126, 15012.
[6] a) B. K. Mishra, B. N. Thomas, J. Am. Chem. Soc. 2002, 124, 6866;
b) B. N. Thomas, C. R. Safinya, R. J. Plano, N. A. Clark, Science
1995, 267, 1635; c) B. N. Thomas, R. C. Cororan, C. L. Cotant, C. M.
Lindeman, J. E. Kirsch, P. J. Persichini, J. Am. Chem. Soc. 2002, 124,
1227; d) S. Pakhomov, R. P. Hammer, B. K. Mishra, B. N. Thomas,
Proc. Natl. Acad. Sci. USA 2003, 100, 3040.
n-(5’Z,8’Z,11’Z,14’Z,17’Z)-Dosocapentaenyl-(p-aminophenyl-b-d-gluco-
pyranoside) (6): Yield 57%; m.p. 52.58C; 1H NMR (600 MHz,
[D6]DMSO): d=0.9 (t, 3H), 1.2–2.5 (m, 20H), 3.2–4.7 (m, 21H), 4.82 (d,
2H), 7.25 (d, 2H), 7.65 (d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3412,
3345, 2913, 1630, 1510, 1364, 1217, 1089, 1007, 1035, 999, 806, 707 cmÀ1
;
MS (NBA): m/z: 556.55 [M+H]+; elemental analysis calcd (%) for
C32H45NO7: C 69.16, H 8.16, N 2.52; found: C 69.15, H 8.73, N 2.42.
n-(trans,trans-9’,11’)-Octadecadienyl-(p-aminophenyl-b-d-glucopyrano-
side) (7): Yield 50%; m.p. 170.58C; 1H NMR (600 MHz, [D6]DMSO):
d=0.9 (t, 3H), 1.2–3.0 (m, 18H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d,
2H), 7.65 (d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3413, 3341, 2913,
1630, 1512, 1365, 1217, 1089, 1005, 1035, 999, 806, 706 cmÀ1; MS (NBA):
m/z: 534.73 [M+H]+; elemental analysis calcd (%) for C30H47NO7: C
67.51, H 8.88, N 2.62; found: C 67.45, H 8.65, N 2.54.
n-(9’Z,12’Z)-Octadecadienyl-(p-aminophenyl-b-d-galactopyranoside) (8):
Yield 60%; m.p. 150.58C; 1H NMR (600 MHz, [D6]DMSO): d=0.9 (t,
3H), 1.2–3.0 (m, 18H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d, 2H), 7.65
(d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3410, 3340, 2912, 1630, 1510,
1364, 1217, 1089, 1005, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z: 534.73
[M+H]+; elemental analysis calcd (%) for C30H47NO7: C 67.51, H 8.88, N
2.62; found: C 67.01, H 9.01, N 2.54.
[7] a) O. Gronwald, S. Shinkai, Chem. Eur. J. 2001, 7, 4329; b) S. Sakur-
ai, S. Shinkai, J. Am. Chem. Soc. 2000, 122, 4520; c) K. Yoza, N.
Amanokura, Y. Ono, T. Akao, H. Shinmori, M. Takeuchi, S. Shinkai,
D. N. Reinhoudt, Chem. Eur. J. 1999, 5, 2722; d) N. Amanokura, Y.
Kanekiyo, S. Shinkai, D. N. Reinhoudt, J. Chem. Soc. Perkin Trans. 2
1999, 1995.
[8] a) M. Schmutz, B. Michels, P. Marie, M. P. Krafft, Langmuir 2003,
19, 4889; b) S. Wang, R. Lunn, M. P. Krafft, R. M. Leblanc, Lang-
muir 2000, 16, 2882; c) S. M. Bertilla, J.-L. Thomas, P. Marie, M. P.
Krafft, Langmuir 2004, 20, 3920; d) M. Maaloum, P. Muller, M. P.
Krafft, Langmuir 2004, 20, 2261.
n-(6’Z,9’Z,12’Z)-Octadecatrienyl-(p-aminophenyl-b-d-galactopyranoside)
(9): Yield 55%; m.p. 125.98C; 1H NMR (600 MHz, [D6]DMSO): d=0.9
(t, 3H), 1.2–2.5 (m, 20H), 3.2–4.7 (m, 21H), 4.82 (d, 2H), 7.25 (d, 2H),
7.65 (d, 2H), 9.1ppm (s, 1H); FT-IR (KBr): n˜ =3410, 3345, 2917, 1630,
1517, 1364, 1215, 1088, 1007, 1035, 999, 806, 706 cmÀ1; MS (NBA): m/z:
532.80 [M+H]+; elemental analysis calcd (%) for C30H45NO7: C 67.77, H
8.53, N 2.63; found: C 68.25, H 8.55, N 2.50.
[9] Y. Xia, G. M. Whitesides, Angew. Chem. 1998, 110, 568; Angew.
Chem. Int. Ed. 1998, 37, 550.
[10] a) G. John, M. Masuda, Y. Okada, K. Yase, T. Shimizu, Adv. Mater.
2001, 13, 715; b) G. John, J. H. Jung, H. Minamikawa, K. Yoshida, T.
Shimizu, Chem. Eur. J. 2002, 8, 5494; c) B. Yang, S. Kamiya, H. Yui,
M. Masuda, T. Shimizu, Chem. Lett. 2003, 32, 1146; d) J. H. Jung, G.
John, K. Yoshida, T. Shimizu, J. Am. Chem. Soc. 2002, 124, 10674.
[11] a) D. T. Bong, T. D. Clark, J. R. Granja, M. R. Ghadiri, Angew.
Chem. 2001, 113, 1 01 6A; ngew. Chem. Int. Ed. 2001, 40, 988; b) S.
Ferandez-Lopez, H.-S. Kim, E. C. Choi, M. Delgado, J. R. Granja,
A. Khasanov, K. Krehenbuehl, G. Long, D. A. Weinberger, K. M.
Wilcoxen, M. R. Ghadiri, Nature 2001, 412, 452.
Acknowledgements
We thank the CREST of JST (Japan Science and Technology) for finan-
cial support. In addition, J.H.J. is grateful to KOSEF for partial financial
support.
[12] a) P. Terech, Y. Talmon, Langmuir 2002, 18, 7240; b) P. Terech, A.
de Geyer, B. Sernd, Y. Talmon, Adv. Mater. 2002, 14, 495.
[13] a) R. Iwaura, K. Yoshida, M. Masuda, M. Ohnish-Kameyama, M.
Yoshida, T. Shimizu, Angew. Chem. 2003, 115, 1039; Angew. Chem.
Int. Ed. 2003, 42, 1009; b) J. H. Jung, K. Yoshida, T. Shimizu, Lang-
muir 2003, 19, 8724.
[14] J. H. Jung, S.-H. Lee, J. S. Yoo, K. Yoshida, T. Shimizu, S. Shinkai,
Chem. Eur. J. 2003, 9, 5307.
[15] J. Ernst, W. S. Sheldrick, J.-H. Fuhrhop, Z. Natuforsch. 1979, 34b,
706.
[1] a) T. Kunitake, Angew. Chem. 1992, 104, 692; Angew. Chem. Int. Ed.
Engl. 1992, 31, 709; b) J.-H. Fuhrhop, W. Helfrich, Chem. Rev. 1993,
93, 1562; c) J.-H. Fuhrhop, J. Koning, Membranes and Molecular As-
sembles: The Synkinetic Approach (Ed.: J. F. Stoddart), The Royal
Society of Chemistry Cambridge, 1994; d) J. H. Jung, H. Kobayashi,
M. Masuda, T. Shimizu, S. Shinkai, J. Am. Chem. Soc. 2001, 123,
8795; e) T. Shimizu, Macromol. Rapid Commun. 2002, 23, 31 1 ; f) R.
Oda, I. Huc, M. Schmutz, S. J. Candau, F. C. Mackintosh, Nature
1999, 399, 566; g) G. Li, W. Fudickar, M. Skupin, A. Klyszcz, C.
Draeger, M. Lauer, J.-H. Fuhrhop, Angew. Chem. 2002, 114, 1906;
Angew. Chem. Int. Ed. 2002, 41, 1828; h) D. S. Chung, G. B. Bene-
Received: December 16, 2004
Published online: July 11, 2005
5544
www.chemeurj.org
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 5538 – 5544