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Colloids and Surfaces A: Physicochem. Eng. Aspects
352 (2009) 1–4
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ColloidsandSurfacesA:PhysicochemicalandEngineeringAspects
Study the effect of 
,
,
-cyclodextrins on the critical micelles concentration(c.m.c.) of sodium dodecyl sulphate (SDS) by using1-methyl-4-[4
-aminostyryl]pyridinium iodide
El-Sayed A.M. Al-Sherbini
Department of Measurements and Environmental Applications, National Institute of Laser Enhanced Science (NILES), Cairo University, P.O. Box 12613, Cairo 202, Egypt 
a r t i c l e i n f o
 Article history:
Received 19 July 2009Accepted 6 September 2009
Available online 11 September 2009
Keywords:
Critical micelles concentration (c.m.c.)Cyclodextrin (CD)
a b s t r a c t
The study of the effect of 
 
,
,
-cyclodextrins on the critical micelles concentration (c.m.c.) of sodiumdodecyl sulphate (SDS) has been carried out by UV–vis spectroscopic measurements. The results revealthat, the complex formation between
 
,
,
-cyclodextrins and SDS micelles shifts c.m.c. to highervalues depending on the cavity size. It was 1.24
×
10
2
, 1.4
×
10
2
, and 1.61
×
10
2
moldm
3
for
 
,
,
-cyclodextrins, respectively.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
Amphiphilic molecules such as surfactants can self-associateto a variety of structured assemblies in aqueous solutions. One of these assemblies is known as micelles [1–3], where the hydropho- bicpartoftheaggregatesformsthemicellercoreandthepolarheadgroups which are located at the micellar surface. In aqueous solu-tions the point at which the micelles start to aggregate is knownas critical micelle concentration (c.m.c.). The shape of the micellesdepends upon the surfactant concentration. At low concentra-tions the micelles were spherical with small diameters (15–30Å)[4,5] containing about 40–100 monomers whereas, they have rod-like shapes at higher concentrations. Most results of microscopicpolarities of micelles were obtained from the absorption and flu-orescence spectroscopy. Some suggestions indicated that lots of watermoleculespenetrateintothesphericalionicmoleculeslead-ing the interior of the micelles to be relatively polar [6].Several alternatives are available including changing the cellsize by using a microcell, changing of geometry and changingthe affinity of organic compounds. One of these alternatives is acyclic oligosaccharide produced from starch by enzymatic degra-dation and named cyclodextrins. These cyclic products consistingof six, seven or eight glucose units known as
 
,
,
-cyclodextrinstogether with small amount of higher analogous of cyclodextrins[7–9]. Numerous investigations were carried out illustrating thatcyclodextrins (CDs) form inclusion complexes with a variety of 
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hydrophobic and amphiphilic species. Physicochemical propertiesoforganicmoleculesincludedinthecavityofcyclodextrinprovidea hydrophobic environment for guest molecules while remainingin aqueous solution. Moreover, complicated behavior of formationof the inclusion complex has been observed [10] especially when the solubility of hydrophobic molecules in cyclodextrin solution ispoorcomparedwithothersystemssuchasaqueousmicelles.Thesefactors are considered to be serious disadvantage of cyclodextrinsystems. Another approach to improve this system is by addinga third component to the host–guest systems which gave morehydrophobic environment [8,11–13]. It is expected that the third molecule, which contains a hydrophobic moiety, can interact withcyclodextrin to increase the hydrophobicity of the cyclodextrin byexcluding water molecules from the cavity. This may lead to thedifferent organizations of the host–guest systems.Inthepresentstudy,theaggregationofthesurfactantmoleculeshave been investigated spectrophotometrically in a variety of aqueous solutions of 
,
,
-cyclodextrins by using 1-methyl-4-[4
-aminostyryl] pyridinium iodide (M
 +
NH
2
)I
2. Experimental methods
 2.1. Materials
SDS (Fluka) was used after purification according to the litera-ture procedure [14]. An aqueous stock solution of 10
2
dm
3
SDSwasfreshlyprepared.
,
,
-Cyclodextrins(Fluka,>99%)wereusedwithoutfurtherpurification.Doubledistilledwaterwasusedforallthe measurements.
0927-7757/$ – see front matter
© 2009 Elsevier B.V. All rights reserved.
 
2
 E.-S.A.M. Al-Sherbini / Colloids and Surfaces A: Physicochem. Eng. Aspects
 352 (2009) 1–4
Fig. 1.
 1-methyl-4-[4
-aminostyryl] pyridiniumiodide, (M
 +
NH
2
)I
.
 2.2. Synthesis of 1-methyl-4-[4
-aminostyryl] pyridinium iodide(M 
 +
NH 
 2
)I 
 p-
Amino benzaldehyde 1.21gm (10mmol) dissolved in a min-imum amount of absolute ethanol was added dropwise to 2.35g(10mmol)of1-methylpicoliniumiodidedissolvedin25mlofabso-lute ethanol. 1.5ml of piperidine was added and the mixture wasstirred for 20h at room temperature and then refluxed for half anhour.Theobtainedlightbrownprecipitatewasfilteredandrecrys-tallizedtwiceindistilledwater.Themeltingpointwas278–280
C.The elemental analyses are as follows:
C H N IFound (%): 49.49 4.32 8.04 37.24Calculated (%): 49.72 4.47 8.28 37.53
 2.3. Instrumentation
UV–vis absorption spectral measurements were carried out ona
 PerkinElmer Lambda-17 
 spectrophotometer with matched quartzcells with path length 1cm.
3. Results and discussions
 3.1. Micellar formation in aqueous micellar solution
At the critical micelle concentrations aggregation begins withthe formation of relatively small micelles. These small micellesgrow rapidly and remain approximately constant in size withfurther increasing in the concentrations. Fig. 2A indicates the absorption spectra of the dye in aqueous solution at differentconcentrations of SDS. Within the range between 4
×
10
2
and8
×
10
3
moldm
3
the absorption spectra exhibit a significant redshiftsfrom
max
=402nminH
2
Oto
max
=440nminmicellarsolu-tion and the optical density slightly decreases. The observed redshiftssuggestthatthedyeincorporatedintothemicellerinterface.With gradual decreasing in SDS concentrations between 7
×
10
3
and 5
×
10
3
moldm
3
, the absorption spectra decrease remark-ably with slightly blue shift in the absorption spectra. At the rangebetween 1
×
10
4
and 1
×
10
6
moldm
3
the absorption max-ima of the dye showed the same spectra as in aqueous medium,
Fig.2.
 (AandB)Absorptionandnormalizedspectraof3
×
10
5
moldm
3
1-methyl-4-[4
-aminostyryl] pyridinium iodide in different concentration of SDS.
max
=402nm. The figure showed that the dye has two absorptionbands; one of them is in aqueous phase and the other is in themicellar phase. These results reveal that above the c.m.c. the elec-trostatic and hydrophobic force interactions between the micellesandthedyeincrease.Inthiscasethedyemaybepresentintheinnerlayer of the micellar interface. With gradual dilution the electro-static and hydrophobic forces decrease, the micelles disaggregateand the dye behaves the same as spectral properties as in aqueousmedium.Thecriticalmicelleconcentrationwascalculatedfromthenormalized absorption spectra at
 
max
=440nm (Fig. 2B) and was 8.1
×
10
3
±
0.0002moldm
3
. The aggregation number is equal to
64 and was calculated according to the following [15]:
 =
R
(
c.m.c)(M
 +
NH
2
)I
 (1)where
 R
 is equal to unity at low concentration of thedye generally around 10
5
moldm
3
,
 
=concentration of sur-factant, c.m.c.=critical micelles concentration, (M
 +
NH
2
)I
=concentrationofthedyeand
=1
×
(0.01
8.1
×
10
3
±
0.0002/3
×
10
5
)=
64.
 3.2. Micellar formation in aqueous solution of cyclodextrins–amphiphilic complex system
Fig. 3 illustrates the absorption spectra of 3
×
10
5
moldm
3
of (M
 +
NH
2
)I
dye in water and 1
×
10
2
moldm
3
of 
 
,
,
-cyclodextrins. The red shift observed from
 
max
=402nm inaqueous solution to
 
max
=415nm in
 
-CD,
 
max
=412nm in
 
-CD, and
 
max
=404 in
 
-CDnm indicate that the dye was insertedor partially inserted into the cavities. In case of 
-cyclodextrin theabsorption spectra of the dye is nearly the same as that in aqueoussolution.Theslightdifferenceintheopticaldensityandtheredshift(2nm) means that the dye is rattle in the cavity with a very slighteffect.For
-cyclodextrintheredshift(
10nm)illustratesthatthedye was more included into the cavity. In case of 
-CD the signifi-cant red shift observed (13nm) suggests that the dye fits snugly inthecavity.Theformationanddissociationconstantoftheinclusioncomplexes of 
 
,
,
-cyclodextrins is determined by the spectralchanges between the free and complex molecules (Table 1). Fig. 4 illustrates the absorption spectra of (M
 +
NH
2
)I
dye in aqueoussolution, and at different concentrations of 
-CD. At concentration1
×
10
1
moldm
3
-CD a significant changes in both optical den-sity and absorption band observed compared to that in aqueoussolution. A well defined isosbestic point at
 
=419nm indicatedthat the dye forms an inclusion complex with
 
-CD. With grad-ual dilution the spectral bands shows blue shifts toward the sameposition as in aqueous medium.
Fig. 3.
 Absorption spectra of 3
×
10
5
moledm
3
of 1-methyl-4-[4
-aminostyryl]pyridinium iodide in 1-H
2
O, and 1
×
10
2
moldm
3
3-
,4-
, 2-
-cyclodextrins.
 
E.-S.A.M. Al-Sherbini / Colloids and Surfaces A: Physicochem. Eng. Aspects
 352 (2009) 1–4
3
 Table 1
Illustrate the critical micelles concentration, formation constants, and aggregationnumber of 1-methyl-4-[4
-aminostyryl] pyrimidinium iodide in different medium.Medium
 
max
 c.m.c.
×
10
2
moldm
3a
b
dc
H
2
O 402 1-SDS 440 0.81
±
0.0002 3.35
×
10
4
64
±
22-
-CD 419 3.33
×
10
5
3-B-CD 412 0.33
×
10
5
4-
-CD 404 0.34
×
10
5
5-
-CD+SDS 435 1.24
±
0.0002
 
126 94
±
26-B-CD+SDS 435 1.4
±
0.0002 106
±
27-
-CD+SDS 435 1.61
±
0.0002 122
±
2
a
Critical micelles concentration.
b
Formation constant.
c
Aggregation number.
It is well known that the inclusion process in the cyclodextrincavity, which is similar to that in micellar solution, is a dynamicequilibrium process and can be illustrated by the following equa-tion:CD
+
(M
 +
NH
2
)I
 
d
CD
(M
 +
NH
2
)I
(2)where CD is cyclodextrin concentration (M
 +
NH
2
)I
=Is guestmolecule CD–(M
 +
NH
2
)I
=Is the inclusion complex.Thestabilityoftheinclusioncomplexcanbedescribedintermsof the formation constant (
) or dissociation constant (
d
) asdefined in the above Eq. (1):
 =
[CD
(M
 +
NH
2
)I
][CD][(M
 +
NH
2
)I
] (3)and
 K 
d
=1/
.Table 1 shows the formation constants of the inclusion com-plexes. The results reflect the stability of the inclusion complexfor all cavities but in case of 
 
-cyclodextrin it is higher than
 
,
-cyclodextrins.It is expected that the third molecule contains a hydrophobicmoiety which can interact with
 
,
,
-cyclodextrins to increasethe hydrophobicity of the cavity by excluding internal watermolecules. The influence of SDS concentrations on the CD–SDScomplex was studied by varying SDS concentrations betweenpremicellization value 0.4
×
10
2
moldm
3
and postmicellizationvalue1.8
×
10
2
moldm
3
.Fig.5showsaredshiftintheabsorption spectra of the dye in aqueous medium,
 
max
=402nm and in caseof a mixture of 1.8
×
10
2
moldm
3
SDS and 1
×
10
2
moldm
3
of 
-cyclodextrin,
 
max
=435nm. The absorption maxima at 435nmcorresponding to the incorporation of the dye in the micellarinterface. With gradual decrease in the concentrations of SDS, at
Fig. 4.
 Absorption spectra of 3
×
10
5
moldm
3
of 1-methyl-4-[4
-aminostyryl]pyridinium iodide in different concentrations of 
-cyclodextrins.
Fig. 5.
 Absorption spectra of 3
×
10
5
moldm
3
1-methyl-4-[4
-aminostyryl] pyri-dinium iodide in 1
×
10
2
moldm
3
of 
-CD at different concentrations of SDS.
the same concentration of 
 
-cyclodextrin, a dramatic shift wasobserved in both of absorption spectra and optical density. Thesechanges can be divided into four domains. In the first one, at con-centration of 0.4
×
10
2
moldm
3
SDS, the absorption spectra isapproximatelythesameasinaqueoussolution,
max
=404nm.Inthis case, most of SDS monomers may complex with CD (SDS–CD)with displacement of (M
 +
NH
2
)I
dye to aqueous medium [15](Fig.5A).Intheseconddomain,withincreasingtheconcentrations of SDS between 0.6 and 1
×
10
2
moldm
3
, the ratio of CD–SDScomplex increases and some of small micelles or clusters beginto form due to the increasing in the SDS monomers and associ-ated with (M
 +
NH
2
)I
dye. The observed significant decrease inthe optical density with slight red shift in the absorption spec-tra,
 
max
=406nm, suggests the increasing in the interaction of 
-CD with favorable hydrocarbon tail with more SDS
mon
 associ-ated with the dye. It may assume that, some SDS
mon
 increaseswith increasing the surfactant concentrations before the micel-lization, while above the micellization point, SDS
mon
 remainsconstant due to the dynamic equilibrium between the micellesand SDS
mon
. Hence, with increasing the SDS concentrations thehydrophobicity increases and the micellization process beginsin small micelles, and the association between (M
 +
NH
2
)I
dyewith the small micelles starts. This can be understood from thedecreasing in the optical density at the concentrations between0.6
×
10
2
and 1
×
10
2
moldm
3
of SDS (Fig. 5B). With increas- ing the concentration above the micellization process most of CDsdepleted, and the small micelles grow due to the inhibition of the association of the micelles by CD. Hence the dye is incorpo-rated in to the micellar interface. So the red shift observed inthe absorption spectra to
 
max
=437nm at 1.2
×
10
2
moldm
3
of SDS may due to the growing in the micellar size. The exclud-ing water molecules originally from the micellar core leading toa more hydrophobic environment and gave the dye strong inter-action with the micelles (Fig. 5C). In the fourth domain, with further increasing the concentrations of SDS between 1.4
×
10
2
and 1.8
×
10
2
moldm
3
the optical density at
 
max
=437nmincreases and remain approximately constant. This may be due tothe growing of the micelles and may turn to wormlike micelles(Fig. 5D). The equilibrium between SDS surfactant and cyclodextrin (CD)is defined according to the following reaction:SDS
+
CD
 
d
CD
SDS (4)

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