The spectrophotometric study of a fluorescence-enhanced inclusion complex Threaded with β-cyclodextrin: Synthesis and characterization

Article abstract of DOI:10.1002/pola.24121

A novel achiral monomer end-capped with a phenyl-[1,3,4]oxadiazolyl group and threaded through β-cyclodextrin was synthesized to investigate the host-guest interactions in the inclusion complex. ¹H NMR studies revealed that one or two eyclodextrin molecules were threaded onto the synthesized achiral monomer, leading to the formation of a fibrous construction of self-assembled inclusion complexes. The formation of a self-assembled inclusion complex was identified using SEM and TEM. The highly ordered alignment of selfassembled supramolecules was confirmed using polarized optical microscopy. We demonstrate an easy process for the fabrication of nano-structured self-assembled inclusion complexes in pyridine/ethanol (1 mL/10 mL) as well as the enhancement of photo-induced fluorescence via monomers end-capped with a phenyl-[1,3,4]oxadiazolyl moiety threaded with β-cyclodextrins.

Full text of DOI:10.1002/pola.24121

The Spectrophotometric Study of a Fluorescence-Enhanced Inclusion
Complex Threaded with b-Cyclodextrin: Synthesis and Characterization
YI-HONG CHIU, JUI-HSIANG LIU
Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan 70101
Received 22 February 2010; accepted 7 May 2010
DOI: 10.1002/pola.24121
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: A novel achiral monomer end-capped with a phe-
nyl-[1,3,4]oxadiazolyl group and threaded through b-cyclodex-
trin was synthesized to investigate the host-guest interactions
in the inclusion complex. 1H NMR studies revealed that one or
two cyclodextrin molecules were threaded onto the synthe-
sized achiral monomer, leading to the formation of a fibrous
construction of self-assembled inclusion complexes. The for-
mation of a self-assembled inclusion complex was identified
using SEM and TEM. The highly ordered alignment of self-
assembled supramolecules was confirmed using polarized op-
tical microscopy. We demonstrate an easy process for the fab-
rication of nano-structured self-assembled inclusion complexes
in pyridine/ethanol (1 mL/10 mL) as well as the enhancement
of photo-induced fluorescence via monomers end-capped with
a phenyl-[1,3,4]oxadiazolyl moiety threaded with b-cyclodex-
C
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trins. 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym
Chem 48: 3368–3374, 2010
KEYWORDS: fluorescence; host-guest systems, inclusion chem-
istry; self-assembly
INTRODUCTION Cyclodextrins (CDs) are known to be highly
water-soluble, essentially nontoxic, and capable of including
various guest molecules in their interiors either in aqueous
solution or in solid state. They are generally regarded as
good molecular receptors for many inorganic, organic, and
biological substrates and are widely applied in various fields,
such as analytical chemistry, enzymology, pharmaceuticals,
the food industry, and so forth.1–5 Furthermore, cyclodextrins
have been successfully applied in the construction of nano-
meter aggregates, especially polyrotaxanes and polypseudor-
otaxanes, owing to their special capability of selectively bind-
ing with a wide variety of model substrates.6–10
the absorbed photon is in the ultraviolet range, and the emit-
ted light is in the visible range, but this depends on the char-
acteristics of the particular fluorescent substance. Many
articles describe metal ion detection in water by selective
chelators using the intrinsic fluorescent of chemosensors, in
which donor atoms of the ligand are incorporated in the
structure of the fluorophore.21 The complexation of a metal
ion results in either an enhanced or decreased fluorescence
of the chemosensor. Intensity modulations also result when
photoinduced electron transfer from a donor atom in a con-
jugate sensor is enhanced or inhibited.22,23 Fluorescence
quantum yield (intensity) can be strongly influenced by the
polarity of the microenvironment. Nonradiative relaxation
from S1 states can be effected via fluorescence resonance
energy transfer. The covalent interaction between a guest
and the fluorophore substructure might also give rise to a
new fluorescing species.24–26
It is well known that cyclodextrins and their derivatives can
incorporate appropriately sized guest molecules selectively
through weak interactions like hydrophobic interactions, van
der Waals forces, and hydrogen bonding. Depending on the
relative sizes of the cyclodextrins and the guest molecules,
more than one guest can be accommodated inside a single
CD cavity. If the guest molecule is long enough, several cyclo-
dextrins can be threaded along its length. Formation of com-
pound-induced cyclodextrin nanotubes or nanorods has been
the topic of interest for many groups in the applied field of
chemical research.11–15 Recently, various types of cyclodex-
trin aggregates, inclusion complexes, and their aggregates of
cyclodextrin rotaxanes and polyrotaxanes, cyclodextrin nano-
tubes and their secondary assembly were reported.16–20
Molecules derived from [1,3,4]oxadiazolyl were widely used
for molecular design of chromophores.27–30 To investigate
host-guest interaction, a new achiral monomer end-capped
with phenyl-[1,3,4]oxadiazolyl group and threaded with b-
cyclodextrin was synthesized. In our previous article, we
described the synthesis of inclusion complexes and the self-
assembled helical constructions formed from the inclusion
complex clusters.31,32 Interestingly, a significant enhancement
of photoinduced luminance of inclusion complexes threaded
with b-cyclodextrin was found in this investigation. Depend-
ing on exciting wavelength, various strengths of fluorescence
Fluorescence is the emission of visible light by a substance
that has absorbed light of a different wavelength. Sometimes
Additional Supporting Information can be viewed in the online version of this article. Correspondence to: J.-H. Liu (E-mail: jhliu@mail.ncku.edu.tw)
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were achieved. In this article, we demonstrate strengthen
effect of photoinduced fluorescence due to molecular interac-
tion in host-guest molecules as well as appearances of self-
assembled inclusion complexes in pyridine/ethanol mixture.
the reaction mixture to room temperature, it was poured
into distilled water and the crude product was collected by
filtration and dried under vacuum to result in white powder
of p-(5-Phenyl-1,3,4-oxadiazole-2-yl) phenol (5). Yield: 42%.
1H NMR (DMSO-d6, ppm): d 10.36 (s, 1H, OH), 8.10-8.06 (m,
2H, Ar H), 7.97-7.92 (d, 2H, Ar H), 7.64-7.58 (m, 3H, Ar H),
6.99-6.93 (m, 2H, Ar H).
EXPERIMENTAL
Instruments
All new compounds were characterized by 1H NMR, FTIR,
and elemental analysis (EA). FTIR spectra were recorded in
a KBr disk on a Jasco VALOR III (Tokyo, Japan) FTIR spectro-
Synthesis of 11-[4-(5-Phenyl-[1,3,4]oxadiazol-2-yl)-
phenoxy]-undecan-1-ol (6)
1
photometer. H NMR (400 MHz) spectra were recorded on a
p-(5-Phenyl-1,3,4-oxadiazole-2-yl) phenol (5) (3.57 g, 15
mmol) was dissolved in a mixture of ethanol (42 mL) and
water (18 mL), and a solution of potassium hydroxide (1.01
g, 18 mmol) dissolved in ethanol (50 mL) was added drop-
wise. 11-Bromo-1-undecanol (165 mmol) was then added,
and the solution was heated at reflux for 24 h. The resulting
mixture was poured into water and extracted with ethyl
ether. The aqueous solution was acidified with hydrochloric
acid diluted with water until it was weakly acidic. The
resulted precipitate was filtered and washed five times with
water. The crude product of 11-[4-(5-Phenyl-[1,3,4]oxadia-
zol-2-yl)-phenoxy]-undecan-1-ol (6) was then recrystallized
from ethanol/water (4/1). Yield: 82%s.
Bruker AMX-400 (Darmstadt, Germany) high-resolution NMR
spectrometer, and chemical shifts were reported in ppm with
tetramethylsilane (TMS) as an internal standard. Elemental
analyses were carried out on a Heraeus CHN-O (Darmstadt,
Germany) rapid elemental analyzer. UV/Vis absorption spec-
tra were measured with a Jasco V-550 spectrophotometer.
Scanning electron microscope (SEM) images were taken with
a JEOL HR-FESEM JSM-6700F (Osaka, Japan) instrument. The
morphology of the colloidal spheres and the surface micro-
phase separation were characterized by the transmission
electron microscopy (TEM). Differential scanning calorimetry
(DSC) was conducted with a Perkin–Elmer DSC 7 at a heat-
ing and cooling rate of 10 K minꢀ1, under a nitrogen atmos-
phere. The phase transitions were investigated with an
Olympus BH-2 polarized light microscope (POM) equipped
with Mettler hot stage FP-82, and the temperature scanning
1H NMR (DMSO-d6, ppm): d 10.36 (s, 1H, OH), 8.10-8.06 (m,
2H, Ar H), 7.97-7.92 (d, 2H, Ar H), 7.64-7.58 (m, 3H, Ar H),
6.599-6.93 (m, 2H, Ar H), 4.32-4.29 (t, 2H, AArOCH2), 4.08-
4.05 (t, 2H, AOCH2), 1.31-1.20 (s, 14H, ACH2).
rate was determined to be 10 K minꢀ1
.
Synthesis of 11-[4-(5-Phenyl-[1,3,4]oxadiazol-2-yl)-
phenoxy]-undecyl Ester (7)
Monomer Preparation
Synthesis of 1-(p-Anisoyl)-2-benzoyl Hydrazide (3)
A mixture of 4-methoxybenzoyl chloride (1: 4.077 g, 23.9
mmol) and NMP (100 mL) was stirred at 0 ꢁC, and a solu-
tion of benzoyl hydrazide (2: 3.200 g, 23.5 mmol) in 20 mL
pyridine was added. The reaction mixture was stirred at
40 ꢁC for 4 h, after which the reaction mixture was poured
into 200 mL distilled water. The precipitated product of
3 was collected by filtration. Yield: 81%.
1H NMR (DMSO-d6, ppm): d 7.91-7.98 (d, 4H, Ar H), 7.59-
7.48 (m, 3H, Ar H), 7.05-7.02 (d, 2H, Ar H), 3.82 – (s, 3H,
AOCH3).
A mixture of 11-[4-(5-phenyl-[1,3,4]oxadiazol-2-yl)-phenoxy]-
unsdecan-1-ol (6) (4.53 g, 10 mmol), methacryloyl chloride
(3.135 g, 30 mmol), N,N-dimethyl aniline (1.331 g, 11
mmol), and 2,6-di-t-buthyl-4-methylphenolꢁ (inhibitor) in
dioxane (100 ppm, 50 mL) was heated at 65 C for 3 h. After
cooling, the solution was poured into cold water and the pre-
cipitate was filtered. The crude product of 2-methyl-acrylic
acid 11-[4-(5-phenyl-[1,3,4]-oxadiazol-2-yl)-phenoxy]undecyl
ester (7) was washed five times with water and then puri-
fied by silica-gel column chromatography with ethyl acetate/
n-hexane (1/4) and the product was recrysstallized twice
from ethanol. Yield: 53%.
Synthesis of 2-(p-Anisyl)-5-phenyl-1,3,4-oxadiazole (4)
A mixture of 1-(p-anisoyl)-2-benzoyl hydrazide (3) (4.526 g,
16.8 mmol) in 90 mL POCl3 was stirred at 120 ꢁC for 7 h.
After cooling to room temperature, the mixture was poured
into ice water. The precipitate was collected by filtration and
washed twice with de-ionized water to afford a white pow-
der of 2-(p-Anisyl)-5-phenyl-1,3,4-oxadiazole (4). Yield: 91%.
1H NMR (d6-acetone, ppm): d 8.10-8.06 (m, 2H, Ar H), 7.97-
7.92 (d, 2H, Ar H), 7.64-7.58 (m, 3H, Ar H), 6.99-6.93 (m,
2H, Ar H), 6.03 (s, 1H, AC¼¼CH2), 5.59 (s, 1H, AC¼¼CH2),
4.14-4.09 (m, 4H,-ArOCH2, AOCH2), 1.89 (s, 3H, ACH3), 1.31-
1.20 (s, 14H, ACH2). 13C NMR of the synthesized monomer
was submitted in Supporting Information.
1H NMR (DMSO-d6, ppm): d 8.12-8.06 (m, 4H, Ar H), 7.64-
7.61 (m, 3H, Ar H), 7.19-7.15 (d, 2H, Ar H), 3.86 (s, 3H,
AOCH3).
Preparation of Monomer Threaded with b-Cyclodextrin
To synthesize the inclusion complex, b-cyclodextrin (b-CD)
was dissolved in water at 60 C. A solution of the monomer
ꢁ
(M) in tetrahydrofuran (THF) was then added dropwise and
ꢁ
Synthesis of p-(5-Phenyl-1,3,4-oxadiazole-2-yl) Phenol (5)
the resulting reaction mixture was stirred at 60 C for 24 h.
A
mixture of 2-(p-anisyl)-5-phenyl-1,3,4-oxadiazole (4)
The turbid solution was ultrasonically agitated at room tem-
perature for 15 min, and the clear solution was allowed to
stand at room temperature for 2 days. The precipitate was
(1.001 g, 4.0 mmol) and 57 wt % HI(aq) (30 mL) was stirred
at 120 ꢁC for 7 h under nitrogen atmosphere. After cooling
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
SCHEME 1 Synthesis of mono-
mer 11-[4-(5-phenyl-[1,3,4]oxa-
diazol-2-yl)-phenoxy]-undecyl
ester.
collected, washed thoroughly with THF and then with water
to remove the free CAHB and b-CD, and dried at 60 C under
and the monomer (b-CD/M ¼ 1.6:1) was seen. The peaks
appearing at 310 nm and 330 nm could be due to the
shorter and longer conjugation length of the methacryloyl
group and the phenyl-[1,3,4]-oxadiazolyl group, respectively.
However, as seen in Figure 3(a), the inclusion complex pro-
duced a significantly different absorption spectrum. A single
maximum absorption peak was observed at 310 nm. The
results suggest that a strong host-guest interaction occurred
in inclusion complex. The hydroxyl groups from the b-CD
molecules may coordinate with polar sites at the phenyl-
[1,3,4]oxadiazolyl group in the monomer leading to the
decrease in the absorption at 330 nm. To investigate the sta-
bility of inclusion complex in pyridine, UV-vis spectra of the
inclusion complex were acquired at various temperatures
and are shown in Figure 3(b). These results show that the
host-guest interaction in the inclusion complex is stable even
ꢁ
vacuum. To further purify the inclusion complex, 2 mg of the
inclusion complex was dissolved in 1 mL pyridine and then
was added to 10 mL ethanol. The mixture was stirred slowly
at ambient temperature for 5 h and was then allowed to
stand for one day. The precipitated samples were collected
and dried on substrates ready for TEM, SEM, and POM
analysis.
RESULTS AND DISCUSSION
Synthesis of Inclusion Complex
To investigate the effect of molecular interactions on fluores-
cence, a functional monomer with a phenyl-[1,3,4]oxadiazolyl
group was synthesized as shown in Scheme 1. The molecular
structure of the monomer was confirmed using NMR, FTIR,
ꢁ
1
when the temperature of the solution is increased to 80 C.
and elemental analysis. H NMR spectrum of the synthesized
monomer end-capped with a phenyl-[1,3,4]oxadiazolyl group
can be seen in Supporting Information. The synthesized
monomer was then threaded with b-cyclodextrin according
to the process outlined in the experimental section. As seen
A significant change in the molecular host-guest interactions
in the inclusion complex may cause variation of both the UV-
vis and the fluorescence spectra. Both the absorption and
fluorescence spectra of inclusion complex were measured
and are summarized in Figure 4. Fluorescence occurs when
a molecule relaxes to its ground state after being electrically
excited. For excitation: S0 þ hvex ! S1; and for fluorescence
(emission): S1 ! S0 þ hvem, where hm is a generic term for
photon energy with h is Planck’s constant and m is the fre-
quency of light. (The specific frequencies of exciting and
emitted light are dependent on the particular system.) The
S0 state is called the ground state of the fluorophore (fluo-
rescent molecule) and S1 is its first (electronically) excited
state. From the intersection of both spectra at 335 nm
shown in Figure 4, the energy gap between HOMO and
LUMO of the inclusion complex was calculated to be 6 ꢂ
10ꢀ19 J (3.7 eV).
1
in Figure 1, from the integrated H NMR spectrum of specific
proton in the molecules, it was found that on average 1.6 b-
CDs were threaded onto each monomer. After precipitation,
a powder sample of the inclusion complex was collected. To
confirm the existence of an inclusion complex, thermal analy-
sis was performed. The results of the DSC curves are sum-
marized in Figure 2. The monomer shows a melting point,
the b-cyclodextrin (b-CD) shows a peak corresponding to the
evaporation of bsorbed water, and the mixture of monomer/
b-CD shows two significant peaks during the heating cycle.
For the inclusion complex, no significant peak was observed,
thus indicating the formation of inclusion complex.31
Spectrophotometric Analysis
A sample of the powder of the prepared inclusion complex
was dissolved in pyridine. Figure 3(a) shows the UV-vis
absorption spectra of the monomer, a mixture of b-CD and
the monomer (CD/M ¼ 1.6:1), and the inclusion complex
(IC). The cyclodextrin alone does not produce any absorption
in the UV-vis region. As seen in Figure 3(a), no significant
difference between the monomer and the mixture of b-CD
It is noteworthy that the 310 nm photoinduced luminance of
the inclusion complex is located in the near UV region. Only
small parts of the luminance cover the visible region. Such
high energetic luminance can be used to excite another chro-
mophore for fluorescence. Furthermore, as seen in Figure
5(a), photo luminance induced from the inclusion complex is
much higher than that from either the monomer or the
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FIGURE 1 1H-NMR spectrum of the inclusion complex. [Color
figure can be viewed in the online issue, which is available at
www.interscience.wiley.com.]
monomer/b-cyclodextrin mixture. The results suggest that,
due to a relatively strong host-guest interaction in the inclu-
sion complex, formation of an excimer and emission of UV-
vis light shown in Figure 5(a) occurred effectively. In this
case, a smaller distance between the host and guest mole-
cules may favor excimer formation. Host-guest molecules in
the inclusion complex can be considered as intramolecular
to each other. As seen in Figure 3(a), the absorption peak
wavelength of the inclusion complex was observed at 310
nm. At 330 nm, the absorption of inclusion complex is much
lower than those of both the monomer and the monomer/b-
cyclodextrin mixture. However, as seen in Figure 5(b), photo
luminance induced from the inclusion complex is much
higher than that from either the monomer or the monomer/
b-cyclodextrin mixture. The results further evidence the
effect of host-guest interaction in the inclusion complex lead-
ing to the higher efficiency of near-UV luminance. The results
suggest that, for both monomer and monomer/b-cyclodex-
trin mixture, the absorbed UV light could not effectively pro-
mote species to excited state leading to the lower fluores-
cence. Sample cells in Figure 6 show the real induced
FIGURE 3 (a) UV-vis spectra of the monomer, the mixture of
monomer/b-CD, and the inclusion complex excited using 310
nm light, and (b) the thermal stability of UV-vis spectra of the
inclusion complex at various temperatures. [Color figure can
be viewed in the online issue, which is available at
www.interscience.wiley.com.]
FIGURE 2 DSC curves of the monomer, the b-CD, the mixture
of monomer/b-CD, and the inclusion complex (IC).
FIGURE 4 Absorption and fluorescence spectra of the inclusion
complex.
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FIGURE 7 SEM images of the self-assembled (a) nano fibers
and (b) nano balls from the inclusion complex and the mixture
of monomer/b-CD, respectively.
fluorescence from monomer/b-cyclodextrin mixture (left)
and inclusion complex (right), respectively.
Supramolecular Properties
To investigate the supramolecular physical properties of the
inclusion complex, the synthesized inclusion complex was
reprecipitated from pyridine/ethanol (1 mL/10 mL) and
compared with a mixture of monomer/b-CD in the solvent.
SEM images of the construction of the precipitated samples
are shown in Figure 7. A fibrous structure formed from the
inclusion complex and a ball structure formed from mixture
of monomer/b-CD. Figure 8 shows the TEM images of the
samples. The fibers from inclusion complex were further
fixed by epoxy resin and then frozen and cut into pieces
using microtone. Figure 8(a–c) show the TEM images of the
synthesized fibers, cross section of the fibers, and ball struc-
tures from mixture of monomer/b-CD in pyridine/ethanol,
respectively. The results in Figures 7 and 8 show that the
synthesized inclusion complex revealed significantly different
physical properties from mixture of monomers and b-CDs
due to the different solubility in pyridine/ethanol mixture.
FIGURE 5 Photoinduced fluorescence of the monomer, the
mixture of monomer/b-CD, and the inclusion complex using (a)
310 nm, and (b) 330 nm UV light.
In addition, as seen in Figure 9, a bright fibrous structure of
self-assembled inclusion complex under a polarized optical
microscope (POM) was observed.31,32 The result suggests
that the self-assembled inclusion complex is arranged in a
highly ordered fashion. The highly ordered aligned inclusion
complex revealed birefringence leading to the appearance of
bright texture under POM. Theoretically, linear polarized
light transmitted through an orderless isotropic material can
be absorbed completely by an analyzer.
FIGURE 8 TEM images of (a) the self-assembled inclusion com-
plex, (b) the cross section of the nano fiber in (a), and (c) the
self-assembled nano balls from a mixture of monomer/b-CD.
FIGURE 6 Real photo-induced fluorescence from monomer/b-
cyclodextrin mixture and inclusion complex, respectively.
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of monomers end-capped with a phenyl-[1,3,4]oxadiazolyl
group and threaded with b-cyclodextrin as well as the crea-
tion of near UV luminance through the inclusion complex.
The close distance between the host and guest in the inclu-
sion complex leads to a significant interaction between the
two components and leads to enhanced fluorescence.
The authors thank the National Science Council of the Republic
of China (Taiwan) for financially supporting this research under
contract No. NSC 97-2221-E-006-026.
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