Supramolecular self-assembled aggregates formed by pentacosa-10,12-diynyl amidomethyl-β-cyclodextrin

Article abstract of DOI:10.1016/j.carres.2014.03.022

Mono[6-deoxy-6-(pentacosa-10,12-diynyl amidomethyl)]-β-cyclodextrin was successfully synthesized by reacting mono-6-amino-6-deoxy-β- cyclodextrin with N-hydroxysuccinimide ester of 10,12-pentacosadiynoic acid in DMF. The modified β-cyclodextrin self-assembled and aggregated to form a worm-like supramolecular structure, and the novel supramolecular aggregates were studied using 2D nuclear magnetic resonance spectroscopy, X-ray powder diffraction, thermogravimetry, and electron microscopy. Interestingly, the synthesized pentacosa-10,12-diynyl amidomethyl-β-cyclodextrin formed columnar type self-aggregates and it was clearly differentiated from cage-like structure of native β-cyclodextrin.

Full text of DOI:10.1016/j.carres.2014.03.022

Accepted Manuscript
Supramolecular self-assembled aggregates formed by pentacosa-10,12-diynyl
amidomethyl-β-cyclodextrin
Eunae Cho, Hwanhee Kim, Jee Eun Yang, Bong-Hyun Jun, Seung R. Paik,
Seunho Jung
PII:
S0008-6215(14)00126-8
DOI:
http://dx.doi.org/10.1016/j.carres.2014.03.022
CAR 6717
Reference:
To appear in:
Carbohydrate Research
Received Date:
Revised Date:
Accepted Date:
3 February 2014
28 March 2014
31 March 2014
Please cite this article as: Cho, E., Kim, H., Yang, J.E., Jun, B-H., Paik, S.R., Jung, S., Supramolecular self-assembled
aggregates formed by pentacosa-10,12-diynyl amidomethyl-β-cyclodextrin, Carbohydrate Research (2014), doi:
http://dx.doi.org/10.1016/j.carres.2014.03.022
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Supramolecular self-assembled aggregates formed by pentacosa-10,12-
diynyl amidomethyl--cyclodextrin
a
a
b
c
b
Eunae Cho, Hwanhee Kim, Jee Eun Yang, Bong-Hyun Jun, Seung R. Paik and
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a,*
Seunho Jung
a
Department of Bioscience and Biotechnology, Bio/Molecular Informatics Center (BMIC) & Institute for
Ubiquitous Information Technology and Applications (CBRU), Konkuk University, Seoul 143-701,
Republic of Korea
b
School of Chemical & Biological Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu,
Seoul 151-744, Korea
c
Department of Bioscience and Biotechnology, Konkuk University, Seoul 143-701, Republic of Korea
*
Corresponding author:
Seunho Jung, Ph. D.
Mailing address: Department of Bioscience and Biotechnology, Konkuk University, 1
Hwayang-dong Gwangjin-gu, Seoul 143-701, Republic of Korea
Phone: 82-2-450-3520
Fax: 82-2-452-3611
E-mail: shjung@konkuk.ac.kr
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Abstract
Mono[6-deoxy-6-(pentacosa-10,12-diynyl
amidomethyl)]--cyclodextrin
was
successfully synthesized by reacting mono-6-amino-6-deoxy--cyclodextrin with N-
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hydroxysuccinimide ester of 10,12-pentacosadiynoic acid in DMF. The modified -
cyclodextrin self-assembled and aggregated to form a worm-like supramolecular
structure, and the novel supramolecular aggregates were studied using 2D nuclear
magnetic resonance spectroscopy, X-ray powder diffraction, thermogravimetry, and
electron microscopy. Interestingly, the synthesized pentacosa-10,12-diynyl
amidomethyl--cyclodextrin formed columnar type self-aggregates and it was clearly
differentiated from cage-like structure of native -cyclodextrin.
Keywords:
-cyclodextrin;
10,12-pentacosadiynoic
acid;
Self-assembly;
Supramolecular structure.
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1
. Introduction
Supramolecular self-assembly is the spontaneous association of molecules into
patterns or suprastructures by noncovalent bonds. The supramolecular architectures are
ubiquitous in biological systems such as proteins, nucleotides, and polysaccharides.
They exhibit unique properties and functions that are not displayed by their individual
components. Microtubules, flagella, and collagens are helical supramolecular polymers
formed by proteins; their functionality is clearly differentiated from their individual
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polypeptides. In this respect, researchers have mimicked structurally the important
phenomena that occur in nature, and much attention has focused on building
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supramolecular structures by designing small molecular building blocks. For example,
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host–guest inclusion complexes made from cyclodextrins and nonpolar chemicals.
Cyclodextrins (CDs) are a series of cyclic oligosaccharides composed of six to
eight glucose units connected through -1,4 linkages. They are called , , and CD,
respectively; because of their complex-forming ability, they are widely used as enzyme
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mimics and drug carriers in the research fields of science and biotechnology. The torus
shape of CDs provides them the ability to incorporate hydrophobic compounds into the
internal cavity; CD is generally used as the enzyme mimic and drug carrier because of
its easy availability and appropriate size. Furthermore, various CD derivatives have
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been synthesized to widen and improve their catalytic and complex-forming abilities.
Recently, the intrinsic conformation and self-assembly properties of the modified CD
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have gained extensive attention for mimicking supramolecular structures. Because
molecular cooperative interactions are highly complicated and poorly understood, more
effort needs to be devoted to their mechanistic study.
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Lipid molecules containing diacetylene moieties in their hydrophobic alkyl
chains are used as another type of building block to form self-assembled
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suprastructure.
For instance, 10,12-pentacosadiynoic acid (PCDA) undergoes
spontaneous molecular assembly in aqueous solution to yield supramolecules,
polymerized via 1,4-addition of diacetylenes under UV irradiation. The resultant
polydiacetylens (PDA) have alternating ene-yne backbone structures and exhibit
distinctive electronic and optical properties because of the highly delocalized π-electron
system of its polymer backbone. External stimuli (pH, heat, solvent, and biological
substances) induce conformational changes in PDA, resulting in blue-to-red color
transition of PDA. Therefore, PDAs have been used as fascinating sensor matrices for
the detection of biologically interesting target molecules. PCDA functionalized with a
specific carbohydrate, antibody, probe DNA, and enzyme has been developed for the
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preparation of a label-free PDA-based chemo/biosensor system.
However, hybrid
materials made of the best known host, CD, and the photonic sensor unit, PCDA, have
not yet been reported.
Herein, we synthesize pentacosa-10,12-diynyl amidomethyl -cyclodextrin
(
PCDACD) using a combination of the functional carbohydrate, CD, and the
functional lipid, PCDA, and propose the modified CD as the neoglycoconjugate
building block for the self-assembled supramolecular structure. Because the long
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aliphatic tail can be threaded into the cavity of CD, PCDACD is expected to form
complicated molecular interactions within the self-assembled structure. The resulting
supramolecular aggregates are studied using various analytical tools such as nuclear
magnetic resonance (NMR) spectroscopy, X-ray powder diffraction (XRD),
Thermogravimetry/differential thermal analysis (TG/DTA), Transmission electron
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microscopy (TEM), and Scanning electron microscopy (SEM).
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. Results and Discussion
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The carbohydrate-lipid hybrid molecule, PCDA-CD, was synthesized from
NHS-PCDA (N-hydroxysuccinimide ester of 10,12-pentacosadiynoic acid) and amino
CD (mono-6-amino-6-deoxy--cyclodextrin), as shown in Scheme 1. NHS-PCDA was
prepared by the reaction between PCDA and NHS in the presence of chloroform
Scheme 1), and its structure was confirmed using FT-IR spectra. The C=O stretch of

(
-1
the carboxylic acid disappeared at 1693 cm and new peaks were observed. The ketone
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C=O stretching vibrations of NHS were observed at 1819 and 1787 cm , whereas the
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ester C=O and CO stretching bands by linkage were observed at 1725 and 1071 cm ,
respectively.
Amino CD (mono-6-amino-6-deoxy--cyclodextrin) was synthesized from
tosyl CD (mono-6-O-p-toluenesulfonyl--cyclodextrin). Tosyl CD is the most
important intermediate that is required for modifying one of the 6-hydroxy groups of
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
CD into other functional groups on the primary side. Accordingly, the mono-
pentacosa-10,12-diynyl amidomethyl group was attached to CD through mono-
tosylation, azidation and amination, as described in Section 3.2.1. Although the
selective functionalization of the primary hydroxyl groups within the cyclic
oligosaccharides is difficult and low yielding, monosubstitution at the primary hydroxyl
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group is important because it has expanded the research scope of CD.
The desired product synthesized from NHS-PCDA and amino CD was
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analyzed using MALDI TOF mass spectrometry and NMR spectroscopy (Figure 1). The
chemical structure of PCDA-CD is shown in Figure 1A, and the mass difference of
m/z 355, obtained by added mono-pentacosa-10,12-diynyl amidomethyl group, is shown
in Figure 1B. Furthermore, the mono-functionalized CD was obtained without any
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reactants and was confirmed by integrating the H-NMR spectra (Figure 1C). The
obtained PCDA-CD shows self-assembly behavior due to its structural characteristics.
The analysis of the binding mode among the PCDA-CDs is useful to understand the
remarkable complexity of the assembled supramolecular structure. In fact, the binding
processes between artificial molecules, complexes, or aggregates within
multicomponent mixtures have been investigated to understand the complexity of
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supramolecular systems.
To gain insight into the molecular geometry of PCDA-CD, nuclear
Overhauser enhancement spectroscopy (NOESY) experiments in D O were carried out.
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Figure 2 shows the NOE cross-peaks between the H2-H6 protons of CD and 3–6 and
11–19 protons of PCDA. It is highly probable that the 11–19 protons of PCDA group
are located in another CD cavity. With regard to the correlation of H2 and H4 protons
outside the cavity, we speculate that 3–6 protons of the PCDA substituent are located
between CDs, but not inside the cavities. Most of the studies so far have described
supramolecular polymers made from CD substituted with aromatic rings such as 6-O-
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(4-formyl-phenyl), 6-deoxy-6-anilino, and 6-O-hydrocinnamoyl groups.
Because
the size of substituents fits to the CD cavity, consecutive and ordered three-
dimensional suprastructures are obtained. However, the present substituent PCDA has a
long alkyl chain with a diacetylene, and six carbons of the aliphatic chain can be
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inserted in the CD cavity. Therefore, PCDA-CD forms a novel self-assembled
structure under aqueous condition, and the intermolecular association is expected to be
more complicated.
To study the thermal behavior of the supramolecular structure, TG/DTA was
performed with the PCDA, CD, PCDA, andCD physical mixture, and the
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synthesized PCDA-CD. The TGA and DTA curves of each of these are shown in
Figure 3. PCDA began to decompose at around 282 °C with a slow-down curve;
however, the curve dropped more sharply when the temperature was increased to
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33 °C. CD began to decompose at 310 °C, with dehydration being observed at 73 °C.
The TGA of the physical mixture of PCDA and CD showed two curves characteristic
of the individual components. However, the synthesized PCDA-CD began to
decompose at 317 °C, with a pattern different from that of PCDA or CD. Additionally,
DTA traces of each compound are shown in Figure 3B. The DTA curve for PCDA
showed an endothermic peak at 69.1 °C and an exothermic peak at 322.9 °C relating to
the melting point and crystallization of PCDA, respectively. Both peaks are also present
in the DTA graph of the PCDA and CD physical mixture; however, the DTA graph of
PCDA-CD shows no characteristic peaks of PCDA or CD. These results suggest that
the self-assembled PCDA-CD structure forms through inclusion phenomena in the
solid state.
The crystal structures of PCDA-CD and CD were compared using X-ray
powder diffraction (XRD) (Figure 4A). CD showed strong peaks at 10.6° and 12.4°
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with many small sharp peaks, indicating a cage-like structure (Figure 4B). However,
the XRD pattern of PCDA-CD showed a smooth curve with three main peaks (2θ =
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.6°, 11.5°, and 17.7°). This pattern is assigned to a columnar structure; the
supramolecular structure of PCDA-CD might be self-assembled and aggregated in a
certain ordered structure by noncovalent bonds formed via hydrophobic interactions and
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hydrogen bonding.
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Transmission electron microscopy (TEM) was also carried out to gain an
insight into the size and shape of the aggregates in the aqueous environment. In contrast
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to the micrometer planar aggregates formed by the original CD (Figure 5A), the
worm-like supramolecular structure was formed by the self-assembly of PCDA-CD
(
Figure 5B). The morphology of the novel nanostructure appeared to be similar to that
of Staphylococcus aureus, and the length of the irregular supramolecules ranged from
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0 to 400 nm with a width of ~20 nm. Considering that the outer diameter and height of
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CD are 1.5 and 0.8 nm, respectively, the supramolecules are joined longitudinally
through 50–500 units and are intertwined. The PCDA-CD formed intermolecular
complexes to give supramolecular polymers.
Furthermore, the surface morphologies of CD, PCDA, and PCDA-CD were
compared (Figure 6). Scanning electron microscopy (SEM) images of each (Figure 6A-
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C) provided macrostructure information in the solid state. CD and PCDA are
characterized by their rod shape and plate piece shape, respectively. As shown in Figure
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C, the PCDA-CD assembled macrostructure is an aggregated structure, distinct from
the respective components. Such a difference in surface morphology clearly indicates
the formation of a supramolecular structure.
In conclusion, we have synthesized mono[6-deoxy-6-(pentacosa-10,12-diynyl
amidomethyl)]--cyclodextrin, which forms a novel self-assembled supramolecular
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structure. The supramolecules were characterized using NMR, TG/DTA, XRD, TEM,
and SEM. The structure showed worm-like nano-aggregates made of columnar-type
units. Further studies are in progress to investigate the applicability of the present PCDA-

CD as an effective sensor system for detecting biological targets by using its dual
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function as a well-known receptor and a sensor matrix.
3
. Experimental
3.1. Materials
CD and 1-(p-toluenesulfonyl)imidazole were obtained from Tokyo Chemical Industry

Co., Ltd. CD was recrystallized from distilled water and dried in vacuo for 12 h. NHS
was obtained from Fluka. PCDA, ammonium chloride, and chloroform were purchased
from Sigma Aldrich. N,N-dimethylformamide (DMF) was obtained from Alfa Aesar, a
Johnson Matthey Company. 1-(3-Dimethylaminopropyl)-3-ethyl carbodiimide
hydrochloride (EDC) was purchased from Acros Organics, New Jersey, USA. Organic
solvents such as hexane, ethyl acetate, acetone, and diethyl ether were of
chromatographic purity, and the water used was triply distilled.
3
.2. Synthesis of mono[6-deoxy-6-(pentacosa-10,12-diynyl amidomethyl)]--
cyclodextrin (PCDA-CD)
3
.2.1. N-hydroxysuccinimide ester of 10,12-pentacosadiynoic acid (NHS-PCDA)
PCDA (1 g, 2.7 mmol) was dissolved in 10 mL of chloroform. To the organic
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solvent, NHS (337.5 mg, 2.9 mmol) and EDC (615 mg, 3.2 mmol) were added. The
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resulting solution was stirred at room temperature for 3 h. After removing the solvent in
vacuo, the product was extracted with ethyl acetate and washed with water. The organic
layer was dried with magnesium sulfate and filtered, and the solvent was removed in
vacuo. The product was then recrystallized and a clean product was obtained in 70.3%
yield. The product was confirmed using thin-layer chromatography (TLC, hexane:ethyl
acetate 3:1) and FT-IR spectra.
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6
3
.2.2. Mono-6-amino-6-deoxy--cyclodextrin (amino CD)
In a 250-mL three-necked round-bottomed flask, CD (5.0 g, 4.4 mmol) was
2
8
dissolved in 112.5 mL of water by heating to 60 ºC under vigorous stirring. After
cooling to room temperature, finely powdered 1-(p-toluenesulfonyl)imidazole (3.9 g,
1
7.7 mmol) was added to the suspension. After 6 h, a solution of sodium hydroxide (2.3
g, 56.3 mmol) in 6.3 mL of water was added over 20 min. After 10 min, unreacted 1-(p-
toluenesulfonyl)imidazole was removed by filtration. To the filtrate was added
ammonium chloride (6.1 g, 112.5 mmol) to quench the reaction. The resulting mixture
was concentrated by blowing a stream of air across the mixture and the product began to
precipitate out of the solution. The suspension was filtered, and the solid was washed
with ice water and acetone. The vacuum-dried tosyl CD was obtained in 28.2% yield.
The mono-tosylated CD was treated with an equivalent amount of sodium azide in 16
29
mL of water at 80 °C for 5 h. After cooling, the solution was precipitated with acetone
and then lyophilized. Lyophilized azido CD and triphenylphosphine (PPh ) (224 mg,
3
8
48 mol) were dissolved in DMF (8 mL) and stirred for 2 h at room temperature. After
adding 1.6 mL of water, the solution was stirred for 3 h at 90 °C, and the resulting
10

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product was precipitated with acetone. Amino CD was purified by cation-exchange
chromatography (CM-Sephadex C25) using 0.5-M ammonium bicarbonate as a solvent
1
and desalted with Bio-gel P2. The product was confirmed using H-NMR spectra.
1
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3
.2.3. Synthesis of mono[6-deoxy-6-(pentacosa-10,12-diynyl amidomethyl)]--
cyclodextrin (PCDA-CD)
First, amino CD (100 mg, 88.3 mol) was dissolved in 3.1 mL of DMF, and
then NHS-PCDA (56 mg, 118.7 mol) was added. After stirring at 45 °C for 24 h, the
product was washed and precipitated with ether. The dried product was afforded in
76.3% yield. The product was analyzed using MALDI TOF mass spectrometry and
NMR spectroscopy.
3
.3. Fourier-transform infrared (FT-IR) spectroscopy
FT-IR spectra were obtained using a KBr matrix with a Bruker IFS-66
spectrometer (AMX, Germany). The samples were recorded at wavenumbers ranging
-1
from 4000 to 500 cm .
3
.4. Matrix-assisted desorption/ionization time-of-flight mass spectrometry
(MALDI-TOF MS)
The mass spectrum was obtained using a MALDI-TOF mass spectrometer
TM
(Voyager-DE
STR BioSpectrometry, PerSeptive Biosystems, Framingham, MA,
USA) using the positive-ion mode. 2,5-Dihydroxybenzoic acid (DHB) was used as the
matrix.
11

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.5. Nuclear magnetic resonance (NMR) spectroscopy
For the NMR spectroscopic analysis, a Bruker Avance 500 spectrometer was
1
used to record the H–NMR and NOESY spectra. The NOESY spectra were recorded
with 256/2048 complex data points using a pulse train to achieve a spin-lock field with
a mixing time of 800 ms for the complex. NMR analyses were performed in D O or d –
1
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2
6
DMSO at room temperature.
3
.6. Thermogravimetry/differential thermal analysis (TG/DTA)
TGA and DTA were determined using a thermogravimetric analyzer (SEICO,
Seiko Exstar 6000 (TG/DTA6100), Japan). The samples were put inside the platinum
pans, which were hanging in the heating furnace. The weight percentage of the
remaining material was recorded while the furnace was heated from 25 to 630 ºC.
Nitrogen was used as the purge gas and a heating rate of 10 ºC/min was employed.
3
.7. X-ray powder diffraction (XRD)
Powder X-ray diffraction patterns were recorded with D8 FOCUS (Bruker
Corp., Germany) X-ray diffractometer by using a Ni-filtered CuKλ radiation (λ =
1.5406 Å) in the 5° ≤ 2 ≥ 60° range. The measurement conditions were as follows:
voltage of 40 kV, current of 100 mA, step size of 0.02°, scan speed of 5 °/min.
3
.8. Transmission electron microscopy (TEM)
First, 100 L of distilled water was added to 1.5 mg of PCDACD. To agitate
the particles in a sample, 30-s sonication and 1-min voltex were carried out. The
12

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aqueous suspension (10 L) containing the supramolecular aggregates formed by
PCDACD was adsorbed onto a carbon-coated copper grid (300-mesh) and air-dried
for 1 min. The equivalent concentration of CD was loaded onto a carbon-coated grid
and air-dried. For clear negative staining, we used the supernatant of 2% uranyl acetate
following centrifugation at 13,200 rpm for 2 min. Then, the aggregates were examined
using transmission electron microscopy (JEOL, JEM 1010, Tokyo, Japan).
1
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6
3.9. Scanning electron microscopy (SEM)
The samples were mounted onto stubs using double-sided adhesive tape and
then made electrically conductive by coating with a thin layer of gold. The surface
morphologies of the materials were examined using scanning electron microscopy
(JEOL, JSM 6380, Tokyo, Japan).
Acknowledgements
This work was supported by the National Research Foundation of Korea Grant
funded by the Korean Government (NRF-2011-619-E0002) and the Priority Research
Centers Program through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education, Science and Technology (2012-0006686). SDG.
13

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References
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2
. Amos, L. A.; Baker, T. S. Nature 1979, 279, 607–612.
. Lehn, J.-M. Supramolecular Chemistry: Concepts and perspectives; VCH:
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. Miyauchi, M.; Takashima, Y.; Yamaguchi, H.; Harada, A. J. Am. Chem. Soc. 2005,
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Langmuir 2003, 19, 5233-5239.
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6. Tripodo, G.; Wischke, C.; Neffe, A. T.; Lendlein, A. Carbohydr. Res. 2013, 381, 59-
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1
1
8. Liu, Y.; Li L.; Fan, Z.; Zhang, H-Y.; Wu, X.; Guan, X-D.; Liu, S-X. Nano Lett. 2002,
, 257-261.
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9. Taib, N.; Aimé, A.; Moreau, L.; Camplo, M.; Houmadi, S.; Desbat, B.; Laquerre,
M.; Grinstaff, M. W.; Bestel, I.; Barthélémy, P. J. Colloid Interface Sci. 2012, 377,
122–130.
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4. Bojinova, T.; Coppel, Y.; Lauth-de Viguerie N.; Milius, A.; Rico-Lattes, I.; Lattes, A.
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Langmuir 2006, 22, 1478-1484.
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Figure legends
Scheme 1. Synthesis of pentacosa-10,12-diynyl amidomethyl -cyclodextrin
(PCDACD).
1
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1
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1
Figure 1. Chemical structure (A), MALDI-TOF mass spectrum (B), and H-NMR
spectrum (d –DMSO) of PCDACD (C). The mass shows m/z 1512.8 ([mono-
6
+
pentacosa-10,12-diynyl amidomethyl CD + Na] ). Peaks designated with H or OH
represent signals by CD moiety, and only numerically designated peaks denote protons
of the attached pentacosa-10,12-diynyl amidomethyl group.
Figure 2. Partial NOESY spectrum (500 MHz) of PCDACD, in D O at 298 K with a
2
mixing time of 800 ms. The signals in the F1 and F2 chemical shift are attributed to
pentacosa-10,12-diynyl amidomethyl group and CD moieties, respectively.
Figure 3. TGA (A) and DTA (B) graphs of 10,12-pentacosadiynoic acid (PCDA), CD,
PCDA+CD physical mixture, and PCDACD.
Figure 4. X-ray diffraction patterns (A) and proposed structures (B) of PCDACD and

CD.
Figure 5. TEM images of CD (A) and supramolecular assembly by PCDACD (B).
16

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Figure 6 SEM images of CD (A), PCDA (B), and PCDACD (C).
1
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ChemDraw/IsisDraw files
Scheme 1.
O
O
EDC
2
O O
O N
O
+
HON
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
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6
6
6
6
6
OH
CH Cl2
O
NHS
NHS-PCDA
PCDA
DMF
O
OH
OTs
N3
NH2
HN
TsIm
H2O
NaN3
H2O
PPh3
DMF

CD
Tosyl CD
Azido CD
Amino CD
PCDA-CD
18

Figure 1
(
A)
B)
(
(C)
3-6, 11-19
DMSO
H O
2
H1
H3,H5,H6
H2,H4
8,9
20
OH3
OH2
OH6
2,7,10
1
7.00
3.01
6
5
4
Chemical Shift (ppm)
3
2
1

Figure 2
HDO
H3,H6
H 2,H4
H 1
H5
0
1
1
2
2
.5
.0
.5
.0
.5
2
0
3-6, 11-19
2
,7,10
1
,8,9
5
.0
4.5
4.0
3.5
F2 Chemical Shift (ppm)

Figure 3
(
A)
(B)

Figure 4
340
280
220
160
100
(
A)
(B)
PCDA-bCD
bCD
Columnar type
PCDA-bCD)
Cage type
0
10
20
30
40
50
60
(
(bCD)
2
θ

Figure 5
(
A)
(B)
1
mm
2 mm
200 nm
500 nm

Figure 6
(
A)
(
B)
(C)

Supramolecular self-assembled aggregates formed by pentacosa-10,12-diynyl
amidomethyl -cyclodextrin
Eunae Cho, Hwanhee Kim, Jee Eun Yang, Bong-Hyun Jun, Seung R. Paik, and Seunho
*
Jung

Highlights.
•
•
A pentacosa-10,12-diynyl amidomethyl--cyclodextrin was newly synthesized.
Self-assembled supramolecular aggregates were formed by the modified -
cyclodextrin.
A novel supramolecular structure showed worm-like nano-aggregates of columnar-
type.
•