Microporous and Mesoporous Materials 85 (2005) 2531

www.elsevier.com/locate/micromeso

Spectroscopic study of the inclusion complexes

of 1-methyl-4-[4 0 -aminostyryl] quinolinium iodide
with a,b,c-cyclodextrins in the ground and excited states
El-Sayed A.M. Al-Sherbini

Department of Measurements and Environmental Applications, National Institute of Laser Enhanced Science (NILES),
Cairo University, Cairo 12613, Egypt
Received 25 April 2004; received in revised form 3 June 2005; accepted 14 June 2005
Available online 27 July 2005

Abstract
Inclusion complexes of 1-methyl-4-[4 0 -aminostyryl] quinolinium iodide, (Q = +NH2)I
with a,b,c-cyclodextrins have been investigated in the ground and excited states. The formation constant of the inclusion complexes has been determined from the spectral
changes in the ground state. The higher values of the formation constant (Kf = 25,01025,200) reect the stability of the inclusion
complexes. The increase in the formation constant in case of b-cyclodextrin (25,200) reveal that the dye was accommodated in the
cavity. In the excited state, the uorescence quantum yield (Qf) has been determined and it was 0.043 in water, 0.06 in c-CD, 0.08 in
a-CD, and 0.38 in b-CD. The increase in the uorescence quantum yield (Qf) indicates that the dye is highly accommodated in b-CD
compared to the other cavities. On the other side, at 0.01 mol dm
3, the results showed a red shifts by 1113 nm in the absorption
maximum in case of a,c-CDs respectively, while in the excited states the spectra show an additional band at longer wavelength in
case of c-CD. This may be attributed to an excimer of two adjacent (Q = +NH2)I
molecules.

2005 Elsevier Inc. All rights reserved.

1. Introduction
Cyclodextrins (CDs) are cyclic oligosaccharides produced from starch by enzymatic degradation. They are
comprised of six, seven or eight glucose units and carry
the name of a,b,c-cyclodextrins together with small
amount of higher analogous [1]. For instance, these
compounds have been used as enzyme model for proteases and have proved to be good catalysts for hydrolysis
of esters. Applications of cyclodextrins and their derivatives cover various areas of chemistry, including the
sensing of organic molecules, analytical chemistry, pharmaceutical, food, encapsulation of drugs and other

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doi:10.1016/j.micromeso.2005.06.016

industrial areas [16,18]. The structure of cyclodextrin

has been discussed and illustrated that the glucose
monomers are arranged in a torus-shaped and attached
by a-(1,4) linkages (Fig. 1).
The primary hydroxyl, O(6)H, groups project from
one edge of the torus and the secondary hydroxyl,
O(2)H, and O(3)H, groups constitute the other wider
rim [7]. Due to the more exibility in the size and
length of the guest binding sites, cyclodextrins have
been widely used to control the environment. The most
remarkable property of cyclodextrines is their ability to
form inclusion complexes with a variety of organic and
inorganic molecules in aqueous solutions [8]. The molecules t partially or wholly into the cavity [9], depending on the size of their hydrophobic and the size of the
guest molecules [3,1014]. Geometric rather than the
chemical factors are decisive in determining the kind

26

El-Sayed A.M. Al-Sherbini / Microporous and Mesoporous Materials 85 (2005) 2531

of guest molecules, which can penetrate into the cavity.

If the guest molecules are too small, it will easily pass
in and out the cavity with little or no bonding at all.
Complex formation with guest molecules signicantly
larger than the cavity may be possible, but the complex
is formed in such a way that only certain groups or side
chains penetrate into the cyclodextrin cavity [1519].
Generally a-cyclodextrin has been found to be selective
toward aliphatic hydrocarbon chains and single-ring
aromatic compounds, while the larger b-cyclodextrin
is more selective towards molecules containing two
aromatic rings, and c-cyclodextrin is selective toward
the molecules containing condensed aromatic rings
[2023].
The eect of cyclodextrin on UVvisible spectra of
various guest molecules has been studied [2]. The results
generally showed that a bathochromic shifts as well as
optical density changes can be observed in the presence
of cyclodextrins. Therefore, the inuence of the size of
guest and host molecules on the excited state have been
studied [28]. Cyclodextrins have been found to enhance
uorescent and phosphorescent emissions from molecules present in the CD cavity. This enhancement of
the uorescence resulted from the fact that, the use of
cyclodextrins protects the uorescing singlet state or
phosphorescing triplet state of the substrate from the
external quenchers. In addition as a consequence of
inclusion complex formation, the rotation of the guest
molecules decreases [2432]. Both of these eects can
result in decrease in the vibration relaxation. A good
correlation between the probe sizes was observed. This
observation showed that there is a potential possibility
of two probe molecules to be included in the same cavity at the same time. For condensed aromatic hydrocarbons included in the cavity in c-cyclodextrins an
additional emission band is observed illustrating the
enhancement of cyclodextrin cavity to yield excimers
by inclusion of two molecules into the cyclodextrin
cavity [3336].
In the present study, we have investigated the eect of
(Q = +NH2)I
dye on the inclusion complexes with
a,b,c-cyclodextrins, in the ground and excited states.

2. Experimental
2.1. Materials
a,b,c-cyclodextrins (Fluka, >99%) were used without
further purication. Double distilled water was used for
all the measurements.
2.1.1. Synthesis of the dye used in this study
1-Methyl-4-[4 0 -aminostyryl] quinolinium iodide,
(Q = +NH2)I was prepared according to Ref. [38] as follows: p-amino benzaldhyde (10 mmol) dissolved in a
minimum amount of absolute ethanol, was added drop
wise to (10 mmol) of 1-methyl-4-methyl quinolinium
iodide in 25 ml of absolute ethanol. 1.5 ml pipredine
was added and the mixture stirred for 20 h at room
temperature and then reuxed for half an hour. The
light brown precipitate was ltered and recrystalized
twice from distilled water. The melting point was determined and found to be 257259 C, of 1-methyl-4-[4 0 aminostyryl] quinolinium iodide, (Q = +NH2)I
(Fig. 2).
2.2. Instrumentation
UVvisible absorption spectra measurements were
carried out using Perkin Elmer lambda-17 spectrophotometer, with matched quartz cells with pathlength of
1 cm. The uorescence spectra measurements were
made on a Shimadzu RF-5000 luminescence spectrometer, using quartz cells and a 1-cm cuvette holder.
Fluorescence intensities were measured at right angles
to the exciting light. The slit width was at narrow entrance in order to minimize the intensity of the exciting
light. All the measurements were carried out at room
temperature. The uorescence quantum yields measurements (Qf) were measured relative to merocyanine
dye [37].
The samples were prepared according to the following procedure: 0.4 ml of the stock solution of
1 10
3 mol dm
3 of (Q = +NH2)I
dye and an accurate weight of the desired concentration of a,b,c-cyclodextrins was mixed in 10 ml volumetric ask. The
mixture was dissolved and completed to 10 ml with double distilled water. The nal concentration of
(Q = +NH2)I
dye was 4 10
5 mol dm
3 and was constant at all dierent concentrations of the cyclodextrins.

CH3 N
I

Fig. 1. b-Cyclodextrin.

+
NH2

Fig. 2. 1-Methyl-4-[4 0 -aminostyryl] quinolinium iodide, (Q = +NH2)I
.

El-Sayed A.M. Al-Sherbini / Microporous and Mesoporous Materials 85 (2005) 2531

3. Results and discussion

In our previous work [38], the electronic absorption
and uorescence spectra of (Q = +NH2)I
were measured in both aqueous and micellar solutions to obtain
a better understanding of its chemical and physical
behavior in dierent environments of dierent pHs.
The optical absorption spectra of 4 10
5 mol dm
3
of the dye, in aqueous buer solutions at dierent pHs
showed that there are two forms, the quinonoide structure with mono cation on the amino group Q = +NH2
which is considered the basic form, and the benzenoid
structure Q-+ NH3 with double cations in which the lone
pair of electrons are localized with the positive charge
present on the heterocyclic nitrogen atom, which is considered the acidic form (Fig. 3a and b). The study of the

27

eect of dierent pHs buer solution showed that there

is an acidbase equilibrium in homogeneous and heterogeneous systems in the ground and excited states.
The ground and excited states protonation constants
in case of aqueous solution were calculated and found
to be 3.24 and 0.19, respectively, while the equilibrium
constants in case of micellar solution of sodium dodecyl
sulphate (SDS) in the ground and excited states were
3.72 and
1.95, respectively.
3.1. Spectroscopic characterization in the ground state
Depending on the size of the cavities with considering
that, the dye has one aromatic ring in one side and two
aromatic rings in the other side, the most general behavior of the dye inclusion must change. Fig. 4 illustrate the

Fig. 3. (a) The basic and acidic forms of 4 10
5 mol dm
3 1-methyl-4-[4 0 -aminostyryl] quinolinium iodide in the ground and excited states in
aqueous and sodium dodecyl sulphate (SDS) micellar solutions. (b) Absorption spectra of 4 10
5 mol dm
3 of 1-methyl-4-[4 0 -aminostyryl]
quinolinium iodide at dierent pHs aqueous buer solutions (handled in dark).

28

El-Sayed A.M. Al-Sherbini / Microporous and Mesoporous Materials 85 (2005) 2531

OPTICAL DENSITY (O.D)

1.0

dynamic equilibrium process illustrated by the following

equation.

1
2
3

0.8

CD Q NH2 I
$ CD
Q NH2 I

where CD is the cyclodextrin; (Q = NH2)I is the guest

molecule and CD-(Q = +NH2)I
is the inclusion
complex.
The stability of the inclusion complex can be described in terms of the formation constant (Kf) or dissociation constant (Kd) as dened in the above equation
(1).

0.6

0.4

0.2

0.0
300

350

400
450
500
WAVELENGTH (nm)

550

600

Fig. 4. Absorption spectra of 4 10
5 mol dm
3 1-methyl-4-[4 0 aminostyryl] quinolinium iodide in 10
2 mol dm
3 of (1) a-cyclodextrin, (2) H2O, (3) c-cyclodextrin, (4) b-cyclodextrin.

absorption spectra of (Q = +NH2)I
dye in distilled

water and in 1 10
2 mol dm
3 of a,b,c-cyclodextrin
cavities. A slightly dierences in wavelength were obtained in the presence and absence of cyclodextrins
when we go from H2O, kmax = 447 nm to a-CD,
kmax = 449 nm and c-CD, kmax = 452 nm. The red shifts
showed that the dye was partially included into a-CD
and c-CD cavity was spacious for the dye. Fig. 4 also
illustrate, that the optical density of the inclusion complex increased in case of a-CD and decreased in case
c-CD. These eects are probably due to that the insertion of the dye in a,c-cyclodextrins took place in two different directions. Judging from the molecular structure
and molecular size of the dye and from the results mentioned earlier for the inclusion of single and double aromatic rings with cyclodextrin cavities, which indicated
that the single aromatic ring of the dye is included into
a-CD cavity and penetrate in and out in case of c-cyclodextrin cavities with expecting that these aromatic rings
inserted in such a form that the long axis is nearly parallel to the axis of the cavity by hydrophobic interaction
[36]. One can expect that dye was inserted into a-CD in a
single aromatic direction while it was inserted into ccyclodextrins from one aromatic ring or even from the
other two aromatic rings side. In case of b-cyclodextrin,
a signicant change in both absorption maxima and
optical density were observed upon addition the dye.
The results obtained illustrated that a dramatic shifts
in both, red shift and the decrease in the optical density
ranges, when we go from H2O kmax = 447 nm to bcyclodextrin kmax = 458 nm. This may be attributed to
that the dye is embedded in the b-cyclodextrin [21,23].
The formation and dissociation constants for the inclusion complexes of guest species have been determined
from the spectral changes between the free and complex
molecules at dierent concentrations considering that
the inclusion process in the cyclodextrin cavity is similar
to the process in micellar solution, which could be a

K f CD-G=CDG

and Kd = 1/Kf where G is the guest molecule.

Table 1 illustrates the results of the formation and
dissociation constants obtained in this study, which reects the stability of the inclusion complex. The formation constant of a,c-cyclodextrins has the same values
(25,010). This indicate that the cavity size of a,c-cyclodextrins is less eective toward the (Q = +NH2)I
dye.
The spectral behavior dierences enhance these results.
In case of b-cyclodextrin the formation constant = 25,200. The higher value indicating that, the
cavity size of b-cyclodextrin is more eective than the
other two cavities. Fig. 5 Illustrates an imagination of
a,b,c-cyclodextrins inclusion complexes. It is expected
that the dye preferred to insert partially in a-cyclodextrin in a single aromatic direction, Fig. 5a, while the cavity space in case of c-cyclodextrin is large enough to
(Q = +NH2)I
to pass in and out with slightly hindering
(Fig. 5c). The red shift in the absorption spectra 11 nm
shows that, b-cyclodextrin is more favorable for inclusion complex with the dye (Fig. 5b). Fig. 6 shows the
absorption spectra of (Q = +NH2)I
dye in aqueous
solution and in 1 10
1 mol dm
3 of a,c-cyclodextrins.
The large bathochromic shifts are observed when the
dye transfers from water kmax = 447 nm to a-cyclodextrin kmax = 458 nm, and c-cyclodextrin kmax = 460 nm.
This indicates that there is more insertion of the dye into
the cyclodextrin cavities. As the a-cyclodextrin concentration increases the optical density increases as well.
This might be due to more tting of a single aromatic
ring with protruding the other two aromatic rings which
are large to t into a-cyclodextrin cavity. On the other
hand, a bathochromic shift is observed in c-cyclodextrin

Table 1
Formation and dissociation constants for the cyclodextrin complexes
with 1-methyl-4-[4 0 -aminostyryl] quinolinium iodide calculated from
the absorption spectra
Medium

Kf

Kd 10
5

Qf

1-H2O
1-a-CD
2-b-CD
3-k-CD

25,010
25,200
25,010

4
3.97
4

0.043
0.06
0.08
0.38

El-Sayed A.M. Al-Sherbini / Microporous and Mesoporous Materials 85 (2005) 2531

CH3

29

CH3

N -I

-I
CH3
N -I

NH2
+

NH2
+

-Cyclodextrin

-Cyclodextrin

NH2
+

-Cyclodextrin

+
NH2

CH3
N

-I

I-

NH2
+

N
CH3

-Cyclodextrin

Fig. 5. Schematic representation of the inclusion complexes of the dye with (a) a-, (b) b-, (c) c-cyclodextrins, and as diamar in (d) c-cyclodextrin.

3.2. Spectroscopic characterization in the excited state

OPTICAL DENSITY (O.D)

1.0
1
2
0.8

0.6

0.4

0.2

0.0
300

350

400

450

500

550

600

WAVELENGTH (nm)

Fig. 6. Absorption spectra of 4 10
5 mol dm
3 1-methyl-4-[4 0 aminostyryl] quinolinium iodide in 10
1 mol dm
3 of (1) a-, (2) ccyclodextrin, and in (3) H2O.

with (13 nm), may illustrate that a dimmer molecules

are formed in the ground state, since the cavity size is
large enough for one (Q = +NH2)I
molecule and we
expect that they are inserted in opposite directions to
each other as shown in Fig. 5d.

Inclusion complexes formation with cyclodextrins

usually results in higher uorescence quantum yield.
Fig. 7 showed the uorescence spectra of (Q = +NH2)I

dye in aqueous solution in absence and presence of
a,b,c-cyclodextrins excited at the corresponding kmax
of the absorption spectra. Only one uorescence bands
at kmax = 596 nm is observed attributing to the
(Q = +NH2)I
monomer. A weak uorescence intensity
of (Q = +NH2)I
dye has been observed in aqueous
solution, when the dye transfers from water to the nonpolar/semipolar interiors of cyclodextrin cavities, one
observes such enhanced intensities 1.6-fold in case of
c-cyclodextrin, 2.1-folds in case of a-cyclodextrin, and
7.7-folds in case b-cyclodextrin (Fig. 7). The uorescence quantum yields at kmax = 596 nm equal to
0.06, 0.08, 0.38 relative to the merocyanine dye [37] for
c,a,b-cyclodextrins, respectively. The enhancement of
the uorescence quantum yield with a blue shift
(2 nm) kmax = 598 nm is attributed to the inclusion
complex formation of the dye with b-cyclodextrin. The
decrease in the uorescence quantum yields in case of
a,c-cyclodextrins show that the dye is less favorable in

30

El-Sayed A.M. Al-Sherbini / Microporous and Mesoporous Materials 85 (2005) 2531

is attributed to (Q = +NH2)I
monomer molecule, while

the additional band at longer wavelength kem = 689 nm
may be attributed to the excimer uorescence of two
adjacent (Q = +NH2)I
molecules and incorporated
into the cavity in the opposite directions as shown in
Fig. 5d. The dramatic dierences in the spectroscopic
measurements in the ground and excited states illustrated that the dye is compatible in case of b-cyclodextrin rather than a,c-cyclodextrin cavities.

100
1 -CD (7.7 folds)
2 -CD (2.1 folds)
1

3 -CD (1.6 folds)

FLUORESCENCE INTENSITY
(ARBITRARY UNITS)

80

60

40

Acknowledgments
2
20

0
500

550

600

650

700

Fig. 7. Fluorescence spectra of 4 10
5 mol dm
3 1-methyl-4-[4 0 aminostyryl] quinolinium iodide in 10
2 mol dm
3 of (1) b, (2) a-, (3)
c-cyclodextrins, and in (4) H2O (excited at the corresponding
wavelengths).

case of a-cyclodextrin and specious in case c-cyclodextrin cavity. Fig. 8 has shown increasing in the uorescence intensity with increasing the concentration of
a,c-cyclodextrins to 1 10
1 mol dm
3. Only one uorescence band is observed for a-cyclodextrin at
kmax = 598 nm which attributed to inclusion of monomer molecule. The gure shows also an additional band
at kem = 689 nm in case of c-cyclodextrin which accompanied by a decrease in the intensity of the emission
band at 598 nm. The uorescence band at kem = 598 nm

FLUORESCENCE INTENSITY
(ARBITRARY UNITS)

100
1
80

1 -Cyclodextrin
2 -Cyclodextrin
3 H2O

60
2
40

20
3
0
500

550

600

650

700

750

800

WAVELENGTH (nm)

Fig. 8. Fluorescence spectra of 4 10
5 mol dm
3 1-methyl-4-[4 0 aminostyryl] quinolinium iodide in 10
1 mol dm
3 of (1) a-cyclodextrin, (2) c-cyclodextrin, and in (3) H2O (excited at the corresponding
wavelengths).

I am grateful to Prof. Dr. M.H. Abdel-Kader and

Prof. Dr. Jai P. Mittal for their interests and their revisions of this manuscript. I am also appreciating my colleague Prof. Dr. Tarek Yousef Abdel-Wahed for the
revisions of this manuscript.

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