Journal of Colloid and Interface Science 490 (2017) 762–773

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

Micelle-vesicle-micelle transition in aqueous solution of anionic

surfactant and cationic imidazolium surfactants: Alteration of the
location of different fluorophores
Rupam Dutta, Surajit Ghosh, Pavel Banerjee, Sangita Kundu, Nilmoni Sarkar ⇑
Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, WB, India

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o a b s t r a c t

Article history: The presence of different surfactants can alter the physicochemical behaviors of aqueous organized
Received 28 September 2016 assemblies. In this article, we have investigated the location of hydrophobic molecule (Coumarin 153,
Revised 5 December 2016 C153) and hydrophilic molecule (Rhodamine 6G perchlorate, R6G) during micelle-vesicle-micelle transi-
Accepted 5 December 2016
tion in aqueous medium in presence of anionic surfactant, sodium dodecylbenzenesulfonate (SDBS) and
Available online 8 December 2016
cationic imidazolium-based surfactant, 1-alkyl-3-methylimidazolium chloride (CnmimCl; n = 12, 16).
Initially, the physicochemical properties of anionic micellar solution of SDBS has been investigated in
Keywords:
presence of imidazolium-based surfactant, CnmimCl (n = 12, 16) in aqueous medium by visual observa-
Imidazolium-based surfactant
Zeta potential (f)
tion, turbidity measurement, zeta potential (f), dynamics light scattering (DLS), and transmission elec-
Rotational motion tron microscopy (TEM). Zeta potential (f) measurement clearly indicates that the incorporation
Translational diffusion efficiency of C16mimCl in SDBS micelle is better than the other one due to the involvement of strong
hydrophobic as well as electrostatic interaction between the two associated molecules. Turbidity and
DLS measurements clearly suggest the formation of vesicles over a wide range of concentration.
Finally, the rotational motion of C153 and R6G has also been monitored at different mole fractions of
CnmimCl in SDBS-CnmimCl (n = 12, 16) solution mixtures. The hydrophobic C153 molecules preferen-
tially located in the bilayer region of vesicle, whereas hydrophilic R6G can be solubilized at surface of
the bilayer, inner water pool or outer surface of vesicles. It is observed that rotational motion of R6G

⇑ Corresponding author.
E-mail address: nilmoni@chem.iitkgp.ernet.in (N. Sarkar).

http://dx.doi.org/10.1016/j.jcis.2016.12.009
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
is altered significantly in SDBS-CnmimCl solution mixtures in presence of different mole fractions of
CnmimCl. Additionally, the translational diffusion motion of R6G is monitored using fluorescence corre-
lation spectroscopy (FCS) techniques to get a complete scenario about the location and translational dif-
fusion of R6G.
1. Introduction
On account of widespread application of surfactant-based self-
assemblies, there is an increasing interest to investigate the struc-
tural aspects of their aggregates into the extensive variety of
nanostructures [1–4]. In aqueous medium, the physicochemical
behavior of surfactant assemblies mainly depend upon the temper-
ature, pH, external additives, ionic strength, nature of the surfac-
tants, counter ions, etc. [5–12,59]. Electrostatic, hydrophobic and
steric interactions between head groups and alkyl part of the sur-
factant molecules control the surfactant molecule containing self-
assembled nanoaggregates formation as well as the micelle-
vesicle-micelle transition [5,8,10]. The temperature or composition
induced transition between micelles and vesicles in surfactant
assemblies is an important phenomenon in colloid chemistry and
biological processes due to their application in drug delivery,
membrane protein reconstitution, and other useful purposes [13–
17]. The morphology of aggregates of two oppositely charged sur-
factant molecules depend upon the geometry of surfactant mole-
cules, pH of solution mixtures, ratio of mixing of surfactant
molecules, etc. [5,8,18–20]. As a consequence, a broad range of
aggregates like micelles, mixed micelles, (disks, ellipsoidal,
spheres, or wormlike), multilamellar or unilamellar vesicles are
found to be present in aqueous surfactant mixtures [5,8,19,21].
Recently, researchers are interested to investigate vesicle for-
mation in room temperature ionic liquid (RTILs) or using ionic liq-
uids [22–27]. The solvation capability of RTILs increase its
interaction with conventional surfactant molecules [24,25]. RTILs
are organic molten electrolytes that display unique physical char-
acteristics including thermal stability, broad liquidus range, low
vapor pressure, etc. Due to these special features, RTILs have exten-
sive use in catalysis, chemical synthesis as well as in separation
and extraction processes [28–31]. To establish IL-modified aqueous
surfactant systems, solvophobic interaction between ionic liquid
and amphiphilic (polymer, surfactant) molecules play the crucial
role [32–36]. Pandey et al. showed the modification in aggregation
behavior of aqueous solution surfactants in presence of ILs [36–
38]. Previously, we have also used ILs having chain length variation
of anion to modify the properties of zwitterionic micelles or catio-
nic micelles [33,34]. Generally, ILs, having short chain, behave like
ordinary inorganic salts. But, long hydrophobic alkyl chain contain-
ing ILs show amphiphilic nature, i.e., surface active properties [39–
41]. Basically, they are the members of an important series of ILs.
However, in this present experimental condition they are not ILs.
This study deals with the aggregation behavior of the oppositely
charged surfactants in aqueous solutions and not about the ILs.
These type of molecules, having hydrophobic long alkyl chain
and a charged hydrophilic head group in either of their cationic
or anionic moiety enhances the formation of various supramolecu-
lar nano-aggregates in aqueous medium [22,42,43]. The aggrega-
tion phenomenon of imidazolium-based surfactants in aqueous
as well as nonaqueous medium has been performed extensively
by applying various techniques [22,42–45]. Recently,
imidazolium-based surfactants are also used to form vesicle in
aqueous solution. Wang et al. demonstrated the concentration
dependent micelle-vesicle transition in aqueous 1-alkyl-3-
methylimidazolium bromides [Cnmim]Br (n = 10, 12, 14) solution
763
Ó 2016 Elsevier Inc. All rights reserved.
[23]. Besides, these surfactants can form vesicular assemblies in
presence of other additives or oppositely charged surfactant mole-
cules [19,46–48]. Oppositely charged surfactant molecules pene-
trate in the micellar assemblies which are formed from
surfactants along with firm interactions with concerned molecules
promote the facile approach to alter the nature of aggregation.
In this manuscript, we are interested to investigate the location
dependent behavior of hydrophobic molecule C153 and hydrophi-
lic molecule R6G during micelle-vesicle-micelle transition. We
have used sodium dodecylbenzenesulfonate (SDBS) as an anionic
surfactant which forms micelles in aqueous solution. Two different
imidazolium-based surfactants,1-dodecyl-3-methylimidazolium
chloride(C12mimCl) and 1-hexadecyl-3-methylimidazolium chlo-
ride (C16mimCl) having variation in their alkyl chain length are
used separately to observe the minute change in phase behavior
of aqueous surfactant solution. Turbidity, dynamic light scattering
(DLS), transmission electron microscopy (TEM) techniques and
finally zeta potential (f) measurements are applied to characterize
the micelle-vesicle-micelle transition in these oppositely charged
surfactant assemblies. Additionally, to obtain further information
regarding the interaction pattern of probe molecules with surfac-
tant aggregates during aggregate transition, we have monitored
the rotational motion of C153 and R6G in SDBS-C16mimCl and
SDBS-C12mimCl solution mixtures at different mole-fractions of
CnmimCl (vC n mimCl ). As the appearance of larger vesicle aggregates
containing solutions is dense white. Therefore, we have prepared
small vesicles of SDBS-C16mimCl and SDBS-C12mimCl mixtures at
different vC n mimCl values by probe sonication. The formations of
small vesicles are also structurally characterized by DLS and TEM
measurements.
Rotational motion of fluorophores in organized assemblies
mainly depends on its location inside organized assemblies along
with the nature of interaction with the surrounding environments
[49–51]. The solubilization site of probe molecules in surfactant
assemblies is controlled by the surface charge of vesicle and chem-
ical nature of probe molecules [51]. In micelles, the hydrophobic
molecules generally solubilized in hydrophobic core of micelles
and hydrophilic molecules preferentially located at hydrophilic
surfaces (interfaces) of micelle. Therefore, the microenvironments
experienced by hydrophobic and hydrophilic molecules are com-
pletely different in organized assemblies compared to the aqueous
solution. In vesicles, the inner hydrophilic water pool is enclosed
by hydrophobic bilayer formed by surfactant molecules. Therefore,
it would be important to study the rotational motion of C153 and
R6G during micelle-vesicle-micelle transition. Sodium dodecylben-
zenesulphonate (SDBS) forms tiny micelles in aqueous solution
(vC n mimCl ¼ 0:00). The interaction of imidazolium-based surfactants,
(1-alkyl-3-methyl imidazolium chloride, CnmimCl, n = 12, 16) with
aqueous SDBS solution results in formation of large vesicles which
subsequently converted into smaller ones by ultrasonic irradiation
using probe sonicator. Hydrophobic molecule, C153 is sparingly
water soluble and therefore, it is expected that it would be solubi-
lized in the hydrophobic bilayer region of vesicles, inner core of
micelles or mixed micelles at various vC n mimCl values. But due to
the hydrophilic nature of R6G, its location in SDBS-C16mimCl and
SDBS-C12mimCl aggregates depends upon the vC n mimCl values. This
can be ascribed due to different solubilization possibilities
764 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
(micellar or mixed micellar surfaces, hydrophobic bilayer of vesi-
cles or water pool of vesicles) of R6G in SDBS-CnmimCl aggregates
at different vC n mimCl values. To confirm this behavior of R6G, addi-
tionally, we have measured translational diffusion of R6G at differ-
ent vC n mimCl values of SDBS-CnmimCl aggregates using fluorescence
correlation spectroscopy(FCS) techniques.
2. Materials and methods
2.1. Materials
Sodium dodecylbenzenesulphonate (SDBS) was obtained from
Sigma-Aldrich and it might contain a mixture of various isomers
[61–63]. Still, the isomer of the SDBS, which we have used in this
study (shown in Scheme 1) is in higher amount compared to the
other isomers and it influences more in all the experiments than
the other isomers.1-alkyl-3-methyl imidazolium chloride (Cn-
mimCl, n = 12, 16) surfactants were purchased from Kanto Chemi-
cals (98% purity). Rhodamine 6G perchlorate (R6GClO4, laser
grade), and coumarin153 (C153, laser grade) were purchased from
Exciton. All these materials were used as received without further
purifications. Milli-Q water was used for the preparation of surfac-
tant solutions.
The structures of all these materials were shown in Scheme 1.
2.2. Instrumentation
2.2.1. Turbidity measurement
Transmittance of SDBS-C16mimCl, and SDBS-C12mimCl solution
mixtures at different mole fractions were measured using Shi-
madzu (model no: UV2405) spectrophotometer at 600 nm due to
absence of any absorption of the individual aqueous solution of
SDBS and CnmimCl (n = 12, 16). Thus obtained transmittance val-
ues were converted to turbidity.
2.2.2. Size distribution and zeta potential (f) measurements
To determine the size of the aggregates Malvern Nano ZS instru-
ment with 4 mW He-Ne laser (k = 632.8 nm) and thermostated
sample holder was used. The same instrument was used for zeta
potential (f) measurements. During DLS measurements, the
collected scattering intensities were analyzed to calculate the
hydrodynamic diameter (dh) of particles using following equation:
Sodium Dodecylbenzenesulfonate
N
N Cl
1-dodecyl-3-methylimidazolium chloride
(C12mimCl)
CF3
N O
Coumarin 153 (C-153)
Scheme 1. Structures of Sodium dodecylbenzenesulfonate (SDBS), 1-dodecyl-3-methylimidazolium chloride (C12mimCl), 1-hexadecyl-3-methylimidazolium chloride (C16-
mimCl), Coumarin 153 (C 153) and Rhodamine 6G perchlorate (R6G ClO4).
kB T
dh ¼ ð1Þ
3pgD
where kB, T, D and g denote Boltzmann constant, temperature, dif-
fusion coefficient and viscosity, respectively. The details of this
setup is already described in our earlier publication [51].
2.2.3. Transmission electron microscopy (TEM) measurement
The TEM measurements of surfactant aggregates were per-
formed using the JEOL model JEM 2010 transmission electron
microscope which operates at 120 kV voltage.
For TEM measurements, 10 lL aqueous solution of SDBS-
CnmimCl (n = 12, 16) mixtures of desired mole fraction was posi-
tioned on carbon coated copper grid. Freshly prepared 0.1 wt%
aqueous uranyl acetate solution was used to observe the morphol-
ogy of vesicles.
2.2.4. UV–Vis absorption and emission measurements
The absorption spectra of C153 and R6G in different micelle and
vesicle solutions were monitored using Shimadzu (model no. UV-
2450) spectrophotometer. Simultaneously, the emission spectra
were measured using Hitachi (model no. F-7000) spectrofluorime-
ter. To collect the emission spectra of C153 and R6G, the samples
were excited at 410 nm and 440 nm, respectively.
2.2.5. Time resolved anisotropy measurements
The time-resolved anisotropy decays were recorded using time
correlated single photon counting (TCSPC) instrument from IBH (U.
K.) In TCSPC set up, a picosecond diode laser (IBH, Nanoled) of
410 nm and 440 nm were used as excitation source. During aniso-
tropy measurement, a motorized polarizer was used on the emis-
sion side using a Hamamatsu microchannel plate photomultiplier
tube (3809U). The emission decays were collected at parallel Ik ðtÞ
and perpendicular I? ðtÞ polarizations at regular time intervals until
the desired peak difference between Ik ðtÞ and I? ðtÞ emission decays
was attained. Anisotropy decays were also analyzed using IBH DAS,
version 6, decay analysis software.
2.2.6. Fluorescence correlation spectroscopy (FCS) measurements
In our present study to perform Fluorescence correlation spec-
troscopy (FCS) measurements we used DCS 120 Confocal Laser
O
S O Na
O
(SDBS)
N
N Cl
1-hexadecyl-3-methylimidazolium chloride
(C16mimCl)
C2H5HN O NHC2H5
ClO4
H3C CH3
O COOC2H5
Rhodamine 6G (R6G)
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
Scanning Microscope (CLSM) system (Becker & Hickl DCS-120)
with an inverted optical microscope of Zeiss (Carl Zeiss, Germany).
For the diffusion of a single component system, a three dimen-
sional (3D) fitting model can be defined as
    1
1 s 1 s 2
GðsÞ ¼ 1þ 1þ 2
N sD S sD
GðsÞ is called autocorrelation function for simple solution con-
taining one diffusing molecule (excluding the contribution of tri-
plet state). In this equation, the average number of fluorescent
molecules in the detection volume is N, and the average time of
fluorescent molecules diffusing in the detection volume is sD . S is
the structure parameter which is equal to the xxxyz where xz is the
longitudinal radius and xxy is the transversal or waist radius of
the confocal volume. The relation between sD and the translational
diffusion coefficient is as follows:
x2xy
sD ¼
4D
The structure parameter (S) of the excitation volume was deter-
mined using R6G in water as a reference sample of known diffusion
coefficient (Dt = 426 lm2 s1). The value of structure parameter is
found to be 5. This value has been fixed for the analysis of all data
obtained in our systems. Fitting of the FCS data of R6G in water
resulted in the diffusion time of 73.6 ls which has been used to
calculate the transverse radius and the confocal volume of our
set-up. The calculated transverse radius is 354 nm and the confo-
cal volume is 1.39 fL. The details of this setup is already described
in our earlier publication [51].
2.3. Solution preparation
We have used SDBS as an anionic surfactant. This type of linear
alkyl benzene sulfonate(ABS) surfactants generally consist of a
complex mixture of different chain lengths and positional isomers.
Ma et al., have investigated the solubility, self-assembly and phase
behavior of the six positional isomers of SDBS and the obtained
phase diagrams show different phase properties for different iso-
mers [61]. They also showed that, with increase in the concentra-
tion of surfactants, three of the six isomeric solutions of SDBS
undergo transition from a micellar, to a lamellar phase through a
hexagonal phase, whereas the hexagonal phase is absent for the
transition of other three isomers of SDBS. This difference is due
to the variation of local molecular and global aggregate packing
constraints of the isomers. Klein and co-workers have also
obtained similar kind of observations using molecular dynamics
study [62]. Thus, the mixture of isomers of SDBS may affect the
physicochemical properties in aqueous solution. However, there
will be greater proportion as well as higher contribution of the iso-
mer of SDBS (shown in Scheme 1) which we are actually willing to
use in this present study. At first, water was filtered using syringe
filter (0.2 lm) to remove dust particles. Afterwards, 150 mM aque-
ous solution of SDBS, C16mimCl, and C12mimCl were prepared sep-
arately in different volumetric flasks. These solution mixtures were
stirred and kept overnight for stabilization. Then the various sets of
solution mixtures containing SDBS-C16mimCl, and SDBS-C12mimCl
of desired mole fraction [vC n mimCl = mole fraction of CnmimCl
vC n mimCl
(n = 12, 16) = v v ] were prepared using appropriate volume
C n mimCl þ SDBS
of each stock solution. The solution mixtures were then stirred and
thermostated at 298 K for 2–3 days for stabilization.
Finally, these solution mixtures were used to characterize the
aggregate transition between micelle-vesicle-micelle by visual
observation, dynamic light scattering (DLS) measurement, zeta
potential study, TEM images, and eventually these solution mix-
765
tures were sonicated using probe sonicator and finally used for
spectroscopic measurements. During Spectroscopic measure-
ments, the corresponding fluorophore solution was allowed to
make solvent free through evaporation and then the desired mole
fractions of CnmimCl were added for the proper encapsulation of
the probe inside the micelle or vesicle aggregates.
ð2Þ
3. Results and discussion
3.1. Phase behavior study
In aqueous solution, surfactant molecules form tiny aggregates
called micelles of few nanometers in size. But, mixing of two oppo-
sitely charged amphiphilic molecules in certain mole fractions,
alter their aggregation behavior. These changes are reflected in
their phase behavior, which can be observed easily by naked eye.
Initially with the addition of imidazolium-based surfactants in
aqueous SDBS solution, the turbidity of the solution increases shar-
ð3Þ ply and it attains maxima around 0.45 mol fraction of
imidazolium-based surfactant. After vC n mimCl ¼ 0:45 the solution
becomes more turbid and sometimes precipitation appears which
indicates the formation of larger aggregates. At higher mole frac-
tion of imidazolium-based surfactant, i.e., vC n mimCl > 0.65, turbid-
ity again decreases. These visual changes in phase behavior of
surfactant and imidazolium-based surfactants mixtures are moni-
tored using UV–vis spectrophotometer by measuring the variation
of turbidity of the solution mixtures. The variation of turbidity at
different mole fractions of CnmimCl in SDBS-CnmimCl solutions is
shown in Fig. S1. Increase in mole fraction of CnmimCl from 0.20
to 0.45 (vC n mimCl ¼ 0:20 to vC n mimCl ¼ 0:45), the solutions become
turbid indicating the formation of large vesicle aggregates. Besides,
further increase in mole fraction of CnmimCl, i.e., vC n mimCl values,
the solution becomes more turbid and appearance of white precip-
itate confirms the spontaneous aggregation of normal vesicles to
larger ones. Actually, when the oppositely charged surfactants
are close to their equimolar ratio [24], there occurs charge neutral-
ization due to strong electrostatic attraction between the surfac-
tants [25] and as a result phase separation takes place and
precipitate settles out from aqueous solution. Precipitation indi-
cates the growth of the vesicles as the vesicles become larger in
size [60]. It is well-established that oppositely charged surfactants
can form different liquid crystalline phases due to the presence of
electrostatic and hydrophobic interactions [66,67]. There are vari-
ous crystalline states like cubic, micellar, hexagonal, lamellar, etc.
[66]. Bilayer (La) phase can be categorized into two phases, (a) pla-
nar lamellar phase (Lal) and (b) closed bilayer structure i.e., vesicle
phase (Lav). However in this present study, we haven’t found any
lamellar phase during TEM measurements. There are experimental
evidences, which tell that vesicle phase forms spontaneously due
to thermodynamic stability [67]. Due to this reason, we are obtain-
ing vesicle phase only and no lamellar phase. At higher molar ratio
(vC n mimCl > 0:65), the sharp decrement in turbidity of the solution
indicates the transition of larger vesicles to smaller vesicles, mixed
micelles or micelles. The vesicle region of these surfactant mix-
tures are quite broad and exists at low vC n mimCl values also. It is
interesting to note that at higher vC n mimCl , the decrease in turbidity
is more rapid for SDBS-C16mimCl solution compared to SDBS-
C12mimCl solution indicating the transition from vesicle to micelle
or mixed micelles. Due to the presence of strong hydrophobic
interaction between the surfactant and alkyl chain of C16mimCl,
the system reorganizes accordingly, so that surfactant molecules
can easily incorporate in imidazolium-based surfactant micelles
which induces the formation of mixed micelles with much smaller
sizes. In SDBS-C16mimCl aggregates, at higher vC 16 mimCl values, the
system contains cation rich mixed micelles composed of SDBS
766 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
and C16mimCl. Vesicle formation from oppositely charged surfac-
tants are well reported [14,15]. Several groups have also reported
vesicle formation involving of one conventional surfactant and
the another oppositely charged imidazolium-based surfactant
[19,24,25]. Moreover, two oppositely charged imidazolium-based
surfactants can also form vesicles [26]. The driving force of vesicle
formation is the electrostatic and hydrophobic interactions
between the two oppositely charged surfactants. The differences
between a conventional surfactant and an imidazolium surfactant
of same chain length appears due to the variation of charge density
and geometric packing of the head groups of the surfactants.
Therefore, the phase behaviors of conventional surfactant and
imidazolium-based surfactants are also very distinct [24]. Positive
charge delocalization is also higher for imidazolium cations com-
pared to alkyl substituted ammonium cations and thus the charge
density of the head groups of the surfactants cause the solubility
mismatch [64]. Kumar and co-workers have explained the advan-
tages of imidazolium cations that they can prevent precipitation
by maintaining the electrostatic interactions and thus increase
the concentration range of vesicular aggregates [65].
3.2. Dynamic light scattering (DLS) measurements
To observe the structural modification of SDBS micelles by
imidazolium-based surfactants, dynamic light scattering (DLS)
experiment has been performed at different vC n mimCl values. The
SDBS molecules form tiny micelles in aqueous solution as obtained
by DLS measurement. But variation in size of solution mixtures at
different vC n mimCl values show regular increase with increase in
vCn mimCl values and at higher vCn mimCl values the size of aggregates
again decreases. Therefore, the observed variations in DLS profiles
indicate micelle-vesicle-micelle transition in SDBS-CnmimCl solu-
tion mixtures. The intensity-size distribution profiles in SDBS-
C16mimCl and SDBS-C12mimCl aggregates at certain mole fraction
of imidazolium-based surfactants are shown in Figs. S2 and S3
(Supporting Information), respectively. The broad distribution of
DLS profiles indicate that the aggregate sizes are more than
300 nm, although small vesicles, and mixed micelles are also pre-
sent along with the larger aggregates. It is interesting that at higher
vC16 mimCl values, i.e., at vC16 mimCl = 0.80, the DLS profiles of SDBS-
C16mimCl indicate that the system mainly composed of mixed
micelles whereas in SDBS-C12mimCl solution mixtures, at
vC12 mimCl = 0.80, mainly vesicular aggregates are present in solution.
At vC n mimCl > 0.90, the systems contain mainly micellar phase. But,
at vC n mimCl = 1.00 an intense peak (minor population) is observed
in the larger diameter range, which indicates the presence of larger
aggregates. As the light scattering intensity (Iscatter) is directly pro-
portional to the sixth power of the diameter of particles (d6), in the
larger diameter range (i.e., at minor population) an intense peak is
also noticed. The DLS measurements along with turbidity study
clearly indicate the micelle-vesicle-micelle transition in aqueous
SDBS-C16mimCl and SDBS-C12mimCl aggregates with the variation
in vC n mimCl values.
(a) (b) (c)
Fig. 1. TEM images of SDBS-C16mimCl (a and b) and SDBS-C12mimCl (c–e) solution at
3.3. Transmission electron microscopy (TEM) studies
The formation of vesicles in mixtures of SDBS-CnmimCl (n = 12,
16) are further characterized by the analysis of TEM images. The
TEM micrographs of aqueous solutions of SDBS-C12mimCl, and
SDBS-C16mimCl at vC n mimCl = 0.50 are shown in Fig. 1 (a and b for
SDBS-C16mimCl and c–e for SDBS-C12mimCl, respectively). The
TEM images clearly indicate the formation of spherical vesicular
aggregates for each oppositely charged surfactant-mixtures. The
average diameters of these spherical aggregates are more than
300 nm. The TEM images of SDBS-C16mimCl and SDBS-
C12mimCl solution mixtures at these certain mole fractions also
suggest a broad range of distribution in size of the vesicles. The
synergistic interaction between the cationic imidazolium moieties
with sulfate group of surfactant and also hydrophobic interaction
between alkyl parts of the concerned pairs are responsible for
the formation of these stable vesicles.
3.4. Zeta potential (f) measurements
Zeta potential (f) signifies the surface charge of the colloidal
particles in aqueous solution. It is the electrical potential difference
between stationary layer of fluid related to micellar aggregates and
dispersion medium which stretches out from the particle surface
due to thermal motion of solvent molecules. Better information
about potential stability of the aggregates can also be obtained
from f values.
In general, the surface of SDBS micelles is negatively charged
and as a result it shows the f value about 36.5 ± 2.0 mV. Initially,
on the addition of imidazolium-based surfactant, f value decreases
and in SDBS rich region the overall surface charge of vesicles is
negative. Now, on further addition of imidazolium-based surfac-
tants, surface charge increases and becomes positive in CnmimCl
rich aggregates. The variation of zeta potential values (Fig. S4) of
SDBS-C16mimCl, and SDBS-C12mimCl solution mixtures also pro-
vide an indication about the incorporation efficiency of different
imidazolium-based surfactants into micellar aggregates. The
increase in f value is more rapid in SDBS-C16mimCl solution com-
pared to SDBS-C12mimCl solutions. The strong interaction of long
alkyl chain containing imidazolium cation with the sulfate anion
of SDBS is responsible for the incorporation of C16mimCl into SDBS
micellar assemblies effectively. The observed trend in variation of
zeta potential values clearly suggests micelle-vesicle-micelle tran-
sition in aqueous SDBS-CnmimCl solution.
3.5. Transformation of large vesicles to small ones: Preparation and
characterizations
3.5.1. Preparation of small vesicles by ultrasonication
The mixing of two oppositely charged SDBS and CnmimCl solu-
tions lead to the large aggregates formation and the solution
becomes turbid. Therefore, to prepare the small aggregates, these
mixtures are sonicated using ultrasonicator (Processor SONOPROS
PR-250 MP, Oscar Ultrasonics Pvt. Ltd. India) having titanium
(d) (e)
vCn mimCl = 0.50.
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
probe (frequency 20 ± 3 kHz). The solution is then diluted with
Milli-Q water (1:1 ratio) and centrifuged to remove the titanium
particles (if present). These solutions are suitable for spectroscopic
measurement. We have chosen seven different mole fractions
(vC n mimCl = 0.00, 0.20, 0.35, 0.55, 0.65, 0.80 and 1.00) of SDBS-
C12mimCl and SDBS-C16mimCl mixtures for spectroscopic mea-
surements. We have chosen these vC n mimCl values where initial
two vC n mimCl values (vC n mimCl = 0.20 and 0.35), the surface charge of
SDBS-CnmimCl aggregates are negative. But at higher vC n mimCl val-
ues (vC n mimCl = 0.55, 0.65 and 0.80), the surface charge of SDBS-
CnmimCl aggregates becomes positive. The photographs of SDBS-
C16mimCl and SDBS-C12mimCl solution mixtures are shown in
Fig. S5 (Supporting Information).
3.5.2. Characterizations of small vesicles by dynamic light scattering
(DLS) and transmission electron microscopy (TEM)
Finally, DLS experiment is carried out to get the idea about the
size of SDBS-C16mimCl and SDBS-C12mimCl aggregates. The
intensity-size distribution profiles of SDBS-C16mimCl and SDBS-
C12mimCl aggregates are shown in Figs. S6 and S7, respectively.
DLS profiles indicate that the sizes of SDBS-C12mimCl aggregates
are around 80–100 nm range at all compositions (i.e.,
vC12 mimCl = 0.20, 0.35, 0.65, 0.80). At vC 12 mimCl = 0.55, the solution
mixture of SDBS-C12mimCl mixture is hazy (phase separation
occurs on standing), therefore, DLS measurement cannot be per-
formed at this particular mole fraction. But in SDBS-C16mimCl mix-
ture, diameter of aggregates at vC 16 mimCl = 0.20, 0.35, 0.55, 0.65 is
around 80–100 nm whereas at higher mole fraction
(vC 16 mimCl = 0.80) the diameter of the aggregate is less, around
10 nm. The DLS measurement along with visual observation sug-
gest that SDBS-C16mimCl mixture at higher mole fraction of
imidazolium-based surfactant forms cation rich mixed micelles.
To confirm the vesicle formation, TEM measurements were per-
formed for both the solution mixtures. TEM micrographs are
depicted in Figs. 2 and 3 for SDBS-C16mimCl and SDBS-C12mimCl
solution, respectively at vC n mimCl = 0.20, and vC n mimCl = 0.65. The for-
mation of spherical vesicles with distinct bilayer can be clearly
visualized from TEM images and which also nicely correlates with
DLS study.
(a) (b)
(d) (e)
Fig. 2. TEM images of SDBS-C16mimCl solution mixture at
767
In the next section, the location and dynamics of a hydrophobic
molecule (coumarin 153, C153) and a hydrophilic molecule (rho-
damine 6G perchlorate, R6GClO4) have been investigated in
SDBS-C16mimCl and SDBS-C12mimCl solution mixtures at different
vC n mimCl values to observe how the location of dye molecule alter
during micelle-vesicle-micelle transition.
3.6. Binding or location of hydrophobic and hydrophilic probe
molecules (C153 and R6G) in SDBS-C16mimCl and SDBS-C12mimCl
aggregates
3.6.1. Steady-state absorption and emission studies
The steady state absorption and emission spectra of C153 and
R6G were monitored in SDBS-C16mimCl and SDBS-C12mimCl
aggregates at all the above mentioned mole fractions of CnmimCl
to study the microenvironmental change around the probe mole-
cules upon micelle-vesicle-micelle transition. The variation of
absorption and emission spectra of R6G and C153 in SDBS, C16-
mimCl and C12mimCl micellar solutions are shown in Figs. S8
and S9, respectively. In water, C153 shows an emission maximum
at 549 nm. In neat SDBS solution, C153 exhibits intense emission
maxima around 540 nm whereas neat C16mimCl and C12mimCl
solution, it shows emission maxima around 536 nm and
537 nm respectively. Therefore, the large blue-shifted emission
maxima of C153 in micellar solution compared to water indicate
that the probe molecules are solubilized in micellar media of sur-
factants. But, the variation of emission spectra of C153) in SDBS-
C16mimCl and SDBS-C12mimCl solution shown in Figs. S10 and
S11 (Supporting Information) respectively, at different vC n mimCl val-
ues suggest that probe molecules are preferentially located in the
bilayers instead of water pool of the vesicles. The close inspection
of above mentioned spectral profiles clearly suggest that variations
of emission intensity are more prominent at the blue end of the
emission spectra of oppositely charged surfactant mixtures at dif-
ferent vC n mimCl values. These observations provide a clear idea that
the micropolarity experienced by the fluorophores is also depends
on the variation of SDBS and CnmimCl concentration.
Interestingly, the red shifts in absorption and emission maxima
(Fig. S8) of R6G in micellar assemblies compared to water indicate
(c)
(f)
vC16 mimCl = 0.20 (a–c) and vC16 mimCl = 0.65 (d–f).
768 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
(a) (b)
(d) (e)
Fig. 3. TEM images of SDBS-C12mimCl solution mixture at
the binding of it to surface of the micelles. At lower mole fraction of
imidazolium-based surfactant (i.e., vC n mimCl = 0.20, 0.35), slight red
shift in absorption and emission spectra of R6G is observed in
SDBS-C16mimCl and SDBS-C12mimCl aggregates shown in
Figs. S12 and S13 (Supporting Information), respectively. This
observation suggests that R6G molecules bind to the surface of
the SDBS-CnmimCl aggregates. Zeta potential measurements indi-
cate that surface charge of the aggregates at the above mentioned
mole fraction is negative, so, electrostatic interaction with R6G
allows it to bind to the surface efficiently. Again, at
vCn mimCl ¼ 0:55 or 0:65, the surface charge of the aggregates
becomes positive and also increased hydrophobicity allows R6G
molecules to migrate into the aqueous pool of the vesicles. As a
result, blue shift is observed in absorption and emission spectral
profiles of R6G. But at higher mole fraction of imidazolium-based
surfactant, although the surface charge of aggregates is high, again
red shift in absorption and emission spectra suggests binding of
R6G in the mixed micelles or vesicle surface. This observation also
suggests that in cation rich mixed micelles or vesicles, the
hydrophobicity of the vesicle bilayer is less than the anion rich
vesicles. Therefore, in conclusion, it can be considered that surface
charge and the hydrophobicity of the aggregates are the controlling
factors for the motion or binding of R6G molecule in SDBS-
CnmimCl aggregates.
3.6.2. Time-resolved anisotropy studies
The time-resolved anisotropy measurements provide better
information regarding the location of C153 and R6G during
micelle-vesicle-micelle transition in mixed surfactant aggregates.
To calculate the time-resolved anisotropy (r(t)) the following equa-
tion is used:
Ik ðtÞ  GI? ðtÞ
rðtÞ ¼ ð4Þ
Ik ðtÞ þ 2GI? ðtÞ
Ik ðtÞ and I? ðtÞ represent the emission decays which are polar-
ized in parallel and perpendicular direction with respect to the
direction of polarization of the excitation light, respectively. G is
the experimental correction factor and does not depend to the
property of the sample. G factor can be measured by exciting the
sample using the horizontally polarized light and then measuring
(c)
(f)
vC12 mimCl = 0.20 (a–c) and vC12 mimCl = 0.65 (d–f).
the horizontally and vertically polarized components of the emis-
sion intensity (HH and HV), each for the same period of time.
The ratio of IHV and IHH expresses the G value of the system; i.e.,
G = IHV/IHH and for our TCSPC set up, G value is 0.6.
The anisotropy decays of C153 and R6G in micellar solution
(SDBS, C16mimCl, and C12mimCl), are shown in Fig. 4. For all solu-
tions, the anisotropy decays of C153and R6G are biexponential in
nature and the corresponding decay parameters are shown in
Tables 1and 2, respectively. The average rotational time constant
(sr ) can be calculated utilizing the following equation:
sr ¼ a1 s1 þ a2 s2 ð5Þ
Anisotropy decays of C153 in water is single exponential in nat-
ure with a time constant of 100 ps [19]. Though, in micelles and
vesicles, the observed anisotropy decays are biexponential with
longer rotational time constants. In confined environment of
micelles or vesicles, the rotational motion of probe molecules
becomes hindered and as a result rotational relaxation time of
C153 increases. The average rotational relaxation time of C153 in
aqueous SDBS solution is 1.10 ns with components of 2.14 ns
(39%) and 0.43 ns (61%). Again the rotational time constants of
C153 in C16mimCl and C12mimCl solution are 0.72 ns (with com-
ponents of 1.76 ns (44%) and 0.28 ns (56%)) and 0.57 ns (with
components of 1.13 ns (31%) and 0.27 ns (69%)), respectively.
Therefore, the chain length of imidazolium-based surfactant also
influences the anisotropy of C153 molecules. Moreover, it is found
that, with the increment in chain length of imidazolium-based sur-
factant, the contribution of slow component increases significantly.
In SDBS-C16mimCl aggregates at vC 16 mimCl ¼ 0:20, the average rota-
tional time increases to 1.76 ns. But at higher vC n mimCl values, it
again decreases. Similar phenomenon is observed for SDBS-
C12mimCl aggregates. Interestingly, the decreases in rotational
time constant from vC n mimCl ¼ 0:65 to 0:80, is more prominent for
SDBS-C16mimCl solution compared to SDBS-C12mimCl aggregates.
The rotational time constant decreases 34% for SDBS-C16mimCl
aggregates; whereas for SDBS-C12mimCl aggregates only 24%
decrease is observed. This scenario is easily understandable by
considering the visual observation, DLS measurement of SDBS-
CnmimCl solution at vC n mimCl = 0.80. The observation suggests that
at this mole fraction SDBS-C16mimCl mixture remains as mixed
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773 769

0.4 0.4
R6G SDBS C 153 SDBS
C16mimCl
C16mimCl
0.3 C12mimCl 0.3
C12mimCl

r (t)

r (t)
0.2 0.2

0.1 0.1

0.0 0.0
0 3 6 9 12 15 0 3 6 9 12 15
Time (ns) Time (ns)

Fig. 4. Anisotropy decays of R6G and C 153 in SDBS, C16mimCl and C12mimCl.

Table 1
Anisotropy Decay Parameters of C-153 in SDBS, C16mimCl, C12mimCl, SDBS-C16mimCl and SDBS-C12mimCl surfactant mixture at different mole fractions.

System vCn mimCl aslow sslow afast sfast hsr ia

(n = 12, 16) (ns) (ns) (ns)

Neat SDBS 0.00 0.39 2.14 0.61 0.43 1.10

Neat C16mimCl 1.00 0.22 1.76 0.78 0.43 0.72
Neat C12mimCl 1.00 0.18 1.48 0.82 0.37 0.57
SDBS-C16mimCl 0.20 0.54 2.81 0.46 0.52 1.76
0.35 0.53 2.80 0.47 0.53 1.73
0.55 0.50 2.75 0.50 0.52 1.64
0.65 0.48 2.53 0.52 0.34 1.39
0.80 0.46 1.67 0.54 0.32 0.92
SDBS-C12mimCl 0.20 0.43 2.64 0.57 0.41 1.37
0.35 0.42 2.42 0.58 0.38 1.24
0.65 0.40 2.44 0.60 0.39 1.21
0.80 0.31 2.16 0.69 0.37 0.92
a
Experimental error 5%.

Table 2
Anisotropy Decay Parameters of R6G in SDBS, C16mimCl, C12mimCl, SDBS-C16mimCl and SDBS-C12mimCl surfactant mixture at different mole fractions.

System vCn mimCl aslow sslow afast sfast hsr ia

(n = 12, 16) (ns) (ns) (ns)

Neat SDBS 0.00 0.84 3.82 0.16 0.77 3.33

Neat C16mimCl 1.00 0.61 2.77 0.39 0.62 1.93
Neat C12mimCl 1.00 0.69 1.51 0.31 0.40 1.17
SDBS-C16mimCl 0.20 0.82 6.10 0.18 0.26 5.05
0.35 0.80 5.88 0.20 0.21 4.75
0.55 0.24 4.15 0.76 0.19 1.14
0.65 0.14 3.95 0.86 0.20 0.73
0.80 0.49 2.95 0.51 0.33 1.61
SDBS-C12mimCl 0.20 0.78 5.39 0.22 2.55 4.77
0.35 0.77 5.88 0.23 0.36 4.61
0.65 0.23 4.04 0.77 0.21 1.09
0.80 0.43 2.07 0.57 0.23 1.02
a
Experimental error 5%.

micelles, but, SDBS-C12mimCl solution exists as vesicles. As vesi-
cles provide more restriction on the rotational motion of
hydrophobic molecule, C153 than micelles or mixed micelles,
therefore, the anisotropy decays become faster in SDBS-C16mimCl
aggregates than SDBS-C12mimCl aggregates between
vCn mimCl ¼ 0:65 and vC n mimCl ¼ 0:80. The observed variation of aniso-
tropy values of C153 at different vC n mimCl value suggests micelle-
vesicle-micelle transition in SDBS-C16mimCl and SDBS-C12mimCl
solution.
The anisotropy decays of R6G in micellar solution of SDBS, C16-
mimCl and C12mimCl exhibit biexponential nature with average
time constant of 3.33 ns (with components of 3.82 ns (84%)
and 0.77 ns (14%)), 1.93 ns (with components of 2.77 ns
(61%) and 0.62 ns (39%)) and 1.17 ns (with components of
1.51 ns (69%) and 0.40 ns (31%)) respectively. The cationic
R6G molecules strongly bind to the surface of negatively charged
SDBS micellar aggregates, consequently, the rotational time con-
stant of R6G is higher in SDBS micelle compared to the cationic
micellar solution of C16mimCl and C12mimCl. Moreover, between
C16mimCl and C12mimCl micellar solution, the anisotropy decay
of R6G becomes slower in C16mimCl micelle as it offers better
restriction on rotational motion of R6G due to longer alkyl chain
length. The rotational time constant of R6G increases significantly
at vC n mimCl ¼ 0:20 and vC n mimCl ¼ 0:35 for both SDBS-C16mimCl and
770 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773

SDBS-C12mimCl aggregates. In aqueous medium the anisotropy
decay of R6G is single exponential, having a time constant around
0.26 ns [51]. In vesicular solution, the fast component of aniso-
tropy decay of R6G similar to time constant in aqueous phase
and the slow component corresponds to the rotation of R6G
entrapped in vesicle bilayer. As the surface charge of SDBS-
CnmimCl is negative (as indicated by zeta potential measurement),
R6G efficiently binds to the vesicle bilayer which results in
increased rotational time constant. At vC n mimCl ¼ 0:55 or 0:65, the
surface charge of the aggregates becomes positive and the
hydrophobicity of vesicle bilayer is also higher compared to
micelle. Therefore, R6G molecules may migrate towards the inner
water pool or outer aqueous phase from the vesicle bilayer. As
depicted in Table 2, the anisotropy decays of R6G at
vCn mimCl ¼ 0:55 or 0:65 in both aggregates of SDBS-C16mimCl and
SDBS-C12mimCl is also biexponential. But the relative contribution
of fast component of anisotropy decay increases significantly at
vCn mimCl ¼ 0:55 or 0:65 compared to vCn mimCl ¼ 0:20 or 0:35. There-
fore, the variation of anisotropy values and their relative contribu-
tion suggest that majority of the R6G molecules located in micelle-
water interface or outer aqueous phase of vesicles at
vCn mimCl ¼ 0:55 or 0:65. But at in SDBS-C16mimCl solution mixture,
at vC n mimCl ¼ 0:80, the solution mixtures mainly contains mixed
micelles, therefore, R6G molecules binds in hydrophobic surface
of mixed micelles, rotational time constant again increases. In
SDBS-C12mimCl solution mixtures, the systems mainly exist as
vesicles and it is expected that R6G mainly located in inner core
of vesicles or outer aqueous phase. As a result, the rotational time
constant of R6G decreases. Anisotropy decays of R6G and C 153 in
SDBS-C12mimCl and SDBS-C16mimCl mixtures at different mole
fractions are shown in Figs. 5 and 6 respectively. So, the average
rotational time constant values of R6G can provide the actual
picture about the location of probe molecules in SDBS-C16mimCl
and SDBS-C12mimCl aggregates during micelle-vesicle-micelle
transition.
3.6.3. Diffusion of R6G in SDBS-C16mimCl and SDBS-C12mimCl
aggregates
In order to get better insight about the micelle-vesicle-micelle
transition in SDBS-C16mimCl and SDBS-C12mimCl solution mix-
tures, the translational diffusion of R6G has been monitored using
fluorescence correlation spectroscopic (FCS) technique. In FCS
technique, the fluctuation of fluorescence intensity of dye molecule
is monitored in a small observation volume (1 fL) and eventually
these fluctuations in emission intensity are correlated to generate
the autocorrelation function. This correlation function can provide
information regarding different molecular processes e.g., reaction
kinetics, translational diffusion, conformation fluctuation, etc.
[52]. Therefore, this methodology has been applied extensively to
monitor bimolecular reaction, conformational dynamics of biomo-
lecules or translational diffusion in different organized assemblies
and ionic liquids [53–58].
FCS is an efficient technique to monitor the mobility of fluo-
rophore in various complex environments and the morphology,
structural heterogeneity of organized assemblies can influence
the diffusion coefficient (Dt) of dye molecule [51,58]. In SDBS-
CnmimCl aggregates, absorption-emission spectra and time
resolved anisotropy measurements clearly indicate that motion,
i.e., location of R6G can provide better visualization about
micelle-vesicle-micelle transition in surfactant assemblies than
C153. As R6G is a hydrophilic cationic dye molecule; therefore,
the motion of R6G strongly depends on hydrophobicity along with
the surface charge of bilayer. As being hydrophobic in nature, C153
preferentially resides in the bilayer of vesicles and experiences

0.4 0.4
SDBS-C16mimCl χ C16mimCl =0.20 SDBS-C12mimCl χ C mimCl =0.20
12
χ C16mimCl =0.35 χ C mimCl =0.35
R6G χ C16mimCl =0.55 R6G 12

0.3 0.3 χ C mimCl =0.65

χ C16mimCl =0.65 12

χ C16mimCl =0.80 χ C mimCl =0.80

12
r (t)

r (t)

0.2 0.2

0.1 0.1

0.0 0.0
0 3 6 9 12 15 0 3 6 9 12 15
Time (ns) Time (ns)

Fig. 5. Anisotropy decays of R6G in SDBS-C12mimCl and SDBS-C16mimCl mixtures at different mole fractions.

0.4 0.4
χ C16mimCl =0.20 χ C12mimCl =0.20
C 153 C 153
SDBS-C16mimCl χ C16mimCl =0.35 SDBS-C12mimCl χ C12mimCl =0.35
0.3 χ C16mimCl =0.55 0.3 χ C12mimCl =0.65
χ C16mimCl =0.65
χ C12mimCl =0.80
χ C16mimCl =0.80
r (t)
r (t)

0.2 0.2

0.1 0.1

0.0 0.0
0 3 6 9 12 15 0 3 6 9 12 15
Time (ns) Time (ns)

Fig. 6. Anisotropy decays of C 153 in SDBS-C12mimCl and SDBS-C16mimCl mixtures at different mole fractions.
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
similar microenvironment in vesicle assemblies at all vC n mimCl val-
ues. Therefore, the diffusion of R6G molecule is monitored during
micelle-vesicle-micelle transition in aqueous SDBS-C16mimCl and
SDBS-C12mimCl solution mixtures at different vC n mimCl values. In
vesicle, the aqueous core is surrounded by surfactant bilayer dis-
persed in aqueous medium; whereas the hydrophobic tail part of
surfactant molecules is sequestered into the hydrophobic core in
surfactant micelle. Therefore, the basic interest of the present
study is to observe how R6G molecules oscillate between the sur-
face of micelle, vesicle or aqueous core during micelle-vesicle-
micelle transition.
The FCS traces of R6G in water, SDBS-C16mimCl and SDBS-
C12mimCl aggregates at different vC n mimCl values are presented in
Fig. 7. The FCS trace of R6G in water is fitted using one-
component fitting equation with diffusion coefficient (Dt) of
426 lm2 s1. But in SDBS-C16mimCl and SDBS-C12mimCl aggre-
gates, two component fitting equation is used to fit the experimen-
tally obtained FCS curves. During FCS curve fitting by two
component fitting equation, one component i.e., Dt value of R6G
in water is fixed and evaluated the other component. This other
component corresponds to diffusion of R6G entrapped in micelle
or vesicle aggregates. The calculated diffusion coefficients in these
systems are given in Table S1 (Supporting Information).
When cationic R6G molecules bind to anionic SDBS micelles,
the diffusion motion ascribed to the motion of that self-
assembly; therefore, the slow diffusion of R6G molecules are
observed in SDBS micelles compared to the diffusion of R6G in bulk
water. This clearly indicates efficient binding of the R6G within the
SDBS micelles. Similarly, in micellar solution of C12mimCl and C16-
mimCl, we have observed slow diffusion of R6G compared to
water. Moreover, between C16mimCl and C12mimCl micellar solu-
tion, the Dt value of R6G is lower in C16mimCl micellar solution.
The C16mimCl contains more number of alkyl chain, therefore,
the translational motion of R6G encapsulated in C16mimCl micelle
is slower than C12mimCl micelle. In vesicular solution at
vCn mimCl ¼ 0:20 and vCn mimCl ¼ 0:35, the diffusion time of R6G
increases significantly compared to the diffusion time of R6G in
SDBS micelle in both SDBS-C16mimCl and SDBS-C12mimCl
aggregates. Due to the negative surface charge, R6G
molecules strongly bind to the surface of vesicle bilayer
and therefore, their translational motion is very slow. But at
vCn mimCl ¼ 0:55 and vC n mimCl ¼ 0:65, the diffusion of R6G becomes
faster compared to SDBS micelle solution in SDBS-C16mimCl aggre-
gates. It is observed that the relative contribution of that compo-
nent decreases significantly at vC n mimCl ¼ 0:55 and vC n mimCl ¼ 0:65
compared to vC n mimCl ¼ 0:20 and vC n mimCl ¼ 0:35. This observation
suggests that at these mole fractions (vC n mimCl ¼ 0:55 and
vCn mimCl ¼ 0:65) small number of R6G molecules preferentially
solubilized into the vesicle aggregates. But in SDBS-C16mimCl
Water
1.0 (a) SDBS-C16mimCl
χ C16 mimCl=0.00
χ C16 mimCl=0.20
0.8
χ C16 mimCl=0.35
χ C16 mimCl=0.55
0.6
G (τ)
χ C16 mimCl=0.65
χ C16 mimCl=0.80
0.4
χ C16 mimCl=1.00
0.2
0.0
1
10 10 2
10 3
10 4
105
10
Time (μs)
Fig. 7. FCS traces of R6G in water, SDBS-C16mimCl and SDBS-C12mimCl solution mixtures at different mole fractions.
771
aggregates, at vC n mimCl ¼ 0:80, due to formation of mainly mixed
micelles containing SDBS and C16mimCl, the relative contribution
of diffusion coefficient increases significantly compared to
vC n mimCl ¼ 0:55 or vC n mimCl ¼ 0:65. Similarly, in SDBS-C12mimCl
aggregates, due to alteration in the location of R6G molecules at
different vC n mimCl values variation in diffusion time is also observed.
In SDBS-C16mimCl and SDBS-C12mimCl aggregates, at different
vC n mimCl values the translational diffusion motion of R6G clearly
depicts micelle-vesicle-micelle transition in surfactant assemblies.
The diffusion motion of R6G in SDBS-C12mimCl and SDBS-
C12mimCl aggregates clearly suggests that the location of R6G is
strongly influenced during micelle-vesicle-micelle transition. It is
found that the diffusion motion ofR6G is 18 times slower in anio-
nic SDBS micelles. But in cationic C16mimCl and C12mimCl
micelles, the diffusion times of R6G are 9 times and 7 times
slower than in water. As R6G is a cationic dye, the diffusion motion
becomes slower in anionic SDBS micelles than in cationic C16-
mimCl or C12mimCl micelles. However, in SDBS-CnmimCl (n = 12,
16) aggregates, variation in Dt values and their relative contribu-
tion signifies that with change in vC n mimCl values, location of R6G
molecules alter spontaneously, i.e., R6G molecules oscillate
between aqueous phase and surfactant containing aggregates.
4. Conclusions
There are several literature reports on the formation of
micelles/mixed micelles and vesicles from oppositely charged sur-
factants through fine regulation of the mixing ratio of surfactants
i.e., the anionic/cationic charge ratio [1–3,24,25]. In the previous
studies, our group has also reported micelle-vesicle-micelle transi-
tion from cationic/anionic surfactants and/or imidazolium-based
surfactants. Furthermore, they have monitored the rotational
motion of hydrophobic dye C153 during the aggregate transition
[19,26]. Cholesterol/surfactant mixture was also used to prepare
vesicles and subsequently the translational diffusion of hydrophilic
probe R6G was studied during this vesicular transition [51].
Recalling these observations, we further extend the work in
present study. In this article, the aggregate transition has been
investigated from micelles to vesicles and then again micelles in
mixed system containing anionic surfactant SDBS and cationic
imidazolium-based surfactants, C16mimCl and C12mimCl, respec-
tively. Moreover, we have also investigated how the location of a
hydrophilic dye R6G and a hydrophobic dye C153 alter during
micelle-vesicle-micelle transition using fluorescence spectroscopic
techniques. Steady state absorption-emission and time resolved
anisotropy measurements indicate that the location of C153
remains almost unaltered in vesicular aggregates at different
vC n mimCl values whereas the location of cationic R6G alters. As
C153 molecule is neutral and hydrophobic, the rotational motion
Water
1.0 (b) SDBS-C12mimCl
χ C12 mimCl=0.00
χ C12 mimCl=0.20
0.8
χ C12 mimCl=0.35
χ C12 mimCl=0.65
0.6
G (τ)
χ C12 mimCl=0.80
χ C12 mimCl=1.00
0.4
0.2
0.0
6
101 102 103 104 105 106
Time (μs)
772 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
indicates that it is located in the hydrophobic region of micelles or
vesicles. But due to the cationic nature of R6G, hydrophobicity and
surface charge of vesicle bilayer influence the location of R6G
molecules during micelle-vesicle-micelle transition. Finally, the
translational diffusion motion of R6G in SDBS-C16mimCl and
SDBS-C12mimCl aggregates at different vC n mimCl values has been
monitored using FCS study to confirm the alteration of location
during micelle-vesicle-micelle transition and it supports the previ-
ously obtained results.
Though there is a significant amount of work concerning the
micelle to vesicle transition and the study of translational diffusion
of hydrophilic as well as hydrophobic probe inside the aggregates
[54,58], here we have mainly focused on the effect of chain length
of imidazolium-based surfactants in the formation of micellar or
vesicular aggregates. It is interesting to note that at vC n mimCl = 0.80
SDBS-C16mimCl solution mixture forms mixed micelles, whereas
SDBS-C12mimCl solution mixture mainly exists as vesicles. As a
result, the location of R6G alters in these two aggregates which
are exhibited in the anisotropy and translational diffusion mea-
surements. Due to greater surface activity and directional polariz-
ability, imidazolium-based surfactants can form highly stable and
ordered supramolecular assemblies which can be used as reactor
for nanoparticle synthesis. This type of composition dependent
micelle to vesicle aggregate transition has potential application
in drug delivery [14] and the vesicles can be used as membrane
mimetic agent [13]. On the basis of the above experiment, as a
future plan we can use a long chain containing charged fluorophore
along with an oppositely charged surfactant to prepare different
dye-surfactant assemblies [60].
Acknowledgments
N.S. gratefully acknowledges SERB, Department of Science and
Technology (DST), Council of Scientific and Industrial Research
(CSIR), Government of India for providing generous research grant.
R.D., S.G., P.B and S.K. are thankful to CSIR for providing their
research fellowships.
Appendix A. Supplementary material
Diffusion co-efficient (Dt) of R6G in water and SDBS-CnmimCl
aggregates, variation of turbidity in aqueous SDBS-CnmimCl solu-
tions at different vC n mimCl , intensity size distribution of SDBS-
CnmimCl aggregates, variation of zeta potential (f) of SDBS solution
with addition of CnmimCl, visual observations of SDBS-CnmimCl
solution mixtures, intensity-size distribution profiles of SDBS-
CnmimCl aggregates ,normalized absorption and emission spectra
of R6G and C153 have been provided in the supporting informa-
tion. Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.jcis.2016.12.
009.
References
[1] E.W. Kaler, A.K. Murthy, B.E. Rodriguez, J.A.N. Zasadzinski, Spontaneous vesicle
formation in aqueous mixtures of single-tailed surfactants, Science 245 (1989)
1371–1374.
[2] L.M. Bergström, S. Skoglund, K. Edwards, J. Eriksson, I. Grillo, Spontaneous
transformations between surfactant bilayers of different topologies observed
in mixtures of sodium octyl sulfate and hexadecyltrimethylammonium
bromide, Langmuir 30 (2014) 3928–3938.
[3] E.W. Kaler, K.L. Herrington, A.K. Murthy, J.A.N. Zasadzinski, Phase behavior and
structures of mixtures of anionic and cationic surfactants, J. Phys. Chem. 96
(1992) 6698–6707.
[4] C. Tondre, C. Caillet, Properties of the amphiphilic films in mixed cationic/
anionic vesicles: a comprehensive view from a literature analysis, Adv. Colloid
Interface Sci. 93 (2001) 115–134.
[5] M. Tian, Y. Fan, G. Ji, Y. Wang, Spontaneous aggregate transition in mixtures of
a cationic gemini surfactant with a double-chain cationic surfactant, Langmuir
28 (2012) 12005–12014.
[6] T. Lu, Y. Lan, C. Liu, J. Huang, Y. Wang, Surface properties, aggregation behavior
and micellization thermodynamics of a class of gemini surfactants with ethyl
ammonium headgroups, J. Colloid Interface Sci. 377 (2012) 222–230.
[7] M. Benrraou, B.L. Bales, R. Zana, Effect of the nature of the counterion on the
properties of anionic surfactants. 1. Cmc, ionization degree at the cmc and
aggregation number of micelles of sodium, cesium, tetramethylammonium,
tetraethylammonium, tetrapropylammonium, and tetrabutylammonium
dodecyl sulfates, J. Phys. Chem. B 107 (2003) 13432–13440.
[8] M. Tian, L. Zhu, D. Yu, Y. Wang, S. Sun, Y. Wang, Aggregate transitions in
mixtures of anionic sulfonate gemini surfactant with cationic ammonium
single-chain surfactant, J. Phys. Chem. B 117 (2013) 433–440.
[9] H. Yin, S. Lei, S. Zhu, J. Huang, J. Ye, Micelle-to-vesicle transition induced by
organic additives in catanionic surfactant systems, Chem. Eur. J. 12 (2006)
2825–2835.
[10] L. Jiang, K. Wang, M. Deng, Y. Wang, J. Huang, Bile salt-induced vesicle-to-
micelle transition in catanionic surfactant systems: steric and electrostatic
interactions, Langmuir 24 (2008) 4600–4606.
[11] L. Ferrer-Tasies, E. Moreno-Calvo, M. Cano-Sarabia, M. Aguilella-Arzo, A.
Angelova, S. Lesieur, S. Ricart, J. Faraudo, N. Ventosa, J. Veciana, Quatsomes:
vesicles formed by self-assembly of sterols and quaternary ammonium
surfactants, Langmuir 29 (2013) 6519–6528.
[12] H. Yin, J. Huang, Y. Lin, Y. Zhang, S. Qiu, J. Ye, Heating-induced micelle to
vesicle transition in the cationic-anionic surfactant systems: comprehensive
study and understanding, J. Phys. Chem. B 109 (2005) 4104–4110.
[13] J.H. Fendler, Surfactant vesicles as membrane mimetic agents:
characterization and utilization, Acc. Chem. Res. 13 (1980) 7–13.
[14] I.I. Yaacob, A.C. Nunes, A. Bose, D.O. Shah, Synthesis and characterisation of
magnetic nanoparticles in spontaneously generated vesicles, J. Colloid
Interface Sci. 168 (1994) 289–301.
[15] E.J. Danoff, X. Wang, S.H. Tung, N.A. Sinkov, A.M. Kemme, S.R. Raghavan, D.S.
English, Surfactant vesicles for high-efficiency capture and separation of
charged organic solutes, Langmuir 23 (2007) 8965–8971.
[16] M. Dolder, A. Engel, M. Zulauff, The micelle to vesicle transition of lipids and
detergents in the presence of a membrane protein: towards a rationale for 2D
crystallization, FEBS Lett. 382 (1996) 203–208.
[17] G.P. Kumar, P. Rajeshwarrao, Nonionic surfactant vesicular systems for
effective drug delivery—an overview, Acta Pharm. Sin. B 1 (2011) 208–219.
[18] J.B. Engberts, J. Kevelam, Formation and stability of micelles and vesicles, Curr.
Opin. Colloid Interface Sci. 1 (1996) 779–789.
[19] S. Ghosh, C. Ghatak, C. Banerjee, S. Mandal, J. Kuchlyan, N. Sarkar, Spontaneous
transition of micelle – vesicle – micelle in a mixture of cationic surfactant and
anionic surfactant-like ionic liquid: a pure nonlipid small unilamellar vesicular
template used for solvent and rotational relaxation study, Langmuir 29 (2013)
10066–10076.
[20] Y.I. González, H. Nakanishi, M. Stjerndahl, E.W. Kaler, Influence of pH on the
micelle-to-vesicle transition in aqueous mixtures of sodium dodecyl
benzenesulfonate with histidine, J. Phys. Chem. B 109 (2005) 11675–11682.
[21] M. Kepczynski, J. Bednar, D. Kuzmicz, P. Wydro, M. Nowakowska, Spontaneous
formation of densely stacked multilamellar vesicles in dioctadecyldimethy-
lammonium bromide/oleosiloxane mixtures, Langmuir 26 (2010) 1551–1556.
[22] K.S. Rao, P.S. Gehlot, T.J. Trivedi, A. Kumar, Self-assembly of new surface active
ionic liquids based on Aerosol-OT in aqueous media, J. Colloid Interface Sci.
428 (2014) 267–275.
[23] H. Wang, L. Zhang, J. Wang, Z. Li, S. Zhang, The first evidence for unilamellar
vesicle formation of ionic liquids in aqueous solutions, Chem. Commun. 49
(2013) 5222–5224.
[24] J. Yuan, X. Bai, M. Zhao, L. Zheng, C12mimBr ionic liquid/SDS vesicle formation
and use as template for the synthesis of hollow silica spheres, Langmuir 26
(2010) 11726–11731.
[25] M. Zhao, J. Yuan, L. Zheng, Spontaneous formation of vesicles by N-dodecyl-N-
methylpyrrolidinium bromide (C12MPB) ionic liquid and sodium dodecyl
sulfate (SDS) in aqueous solution, Colloids Surf. A 407 (2012) 116–120.
[26] S. Mandal, J. Kuchlyan, D. Banik, S. Ghosh, C. Banerjee, V. Khorwal, N. Sarkar,
Ultrafast FRET to study spontaneous micelle-to-vesicle transitions in an
aqueous mixed surface-active ionic-liquid system, ChemPhysChem 15 (2014)
3544–3553.
[27] K.S. Rao, S. So, A. Kumar, Vesicles and reverse vesicles of an ionic liquid in ionic
liquids, Chem. Commun. 49 (2013) 8111–8113.
[28] T. Welton, Room-temperature ionic liquids. Solvents for synthesis and
catalysis, Chem. Rev. 99 (1999) 2071–2083.
[29] B. Tang, W. Bi, M. Tian, K.H. Row, Application of ionic liquid for extraction and
separation of bioactive compounds from plants, J. Chromatogr. B 904 (2012)
1–21.
[30] F.V. Rantwijk, R.A. Sheldon, Biocatalysis in ionic liquids, Chem. Rev. 107 (2007)
2757–2785.
[31] J.P. Hallett, T. Welton, Room-temperature ionic liquids: solvents for synthesis
and catalysis. 2, Chem. Rev. 111 (2011) 3508–3576.
[32] S. Dey, A. Adhikari, D.K. Das, D.K. Sasmal, K. Bhattacharyya, Femtosecond
solvation dynamics in a micron-sized aggregate of an ionic liquid and P123
triblock copolymer, J. Phys. Chem. B 113 (2009) 959–965.
[33] V.G. Rao, C. Ghatak, S. Ghosh, S. Mandal, N. Sarkar, The chameleon-like nature
of zwitterionic micelles: the effect of ionic liquid addition on the properties of
aqueous sulfobetaine micelles, ChemPhysChem 13 (2012) 1893–1901.
 R. Dutta et al. / Journal of Colloid and Interface Science 490 (2017) 762–773
[34] V.G. Rao, C. Ghatak, S. Ghosh, R. Pramanik, S. Sarkar, S. Mandal, N. Sarkar, Ionic
liquid-induced changes in properties of aqueous cetyltrimethylammonium
bromide: a comparative study of two protic ionic liquids with different anions,
J. Phys. Chem. B 115 (2011) 3828–3837.
[35] L. Zheng, C. Guo, J. Wang, X. Liang, S. Chen, J. Ma, B. Yang, Y. Jiang, H. Liu, Effect
of ionic liquids on the aggregation behavior of PEO-PPO-PEO block copolymers
in aqueous solution, J. Phys. Chem. B 111 (2007) 1327–1333.
[36] R. Rai, G.A. Baker, K. Behera, P. Mohanty, N.D. Kurur, S. Pandey, Ionic liquid-
induced unprecedented size enhancement of aggregates within aqueous
sodium dodecylbenzene sulfonate, Langmuir 26 (2010) 17821–17826.
[37] K. Behera, H. Om, S. Pandey, Modifying properties of aqueous
cetyltrimethylammonium bromide with external additives: ionic liquid 1-
hexyl-3-methylimidazolium bromide versus cosurfactant n-
hexyltrimethylammonium bromide, J. Phys. Chem. B 113 (2009) 786–793.
[38] K. Behera, S. Pandey, Interaction between ionic liquid and zwitterionic
surfactant: a comparative study of two ionic liquids with different anions, J.
Colloid Interface Sci. 331 (2009) 196–205.
[39] O.A.E. Seoud, P.A.R. Pires, T. Abdel-Moghny, E.L. Bastos, Synthesis and micellar
properties of surface-active ionic liquids: 1-alkyl-3-methylimidazolium
chlorides, J. Colloid Interface Sci. 313 (2007) 296–304.
[40] P.D. Galgano, O.A.E. Seoud, Micellar properties of surface active ionic liquids: a
comparison of 1-hexadecyl-3-methylimidazolium chloride with structurally
related cationic surfactants, J. Colloid Interface Sci. 345 (2010) 1–11.
[41] M. Blesic, M.H. Marques, N.V. Plechkova, K.R. Seddon, L.P.N. Rebelo, A. Lopes,
Self-aggregation of ionic liquids: micelle formation in aqueous solution, Green
Chem. 9 (2007) 481–490.
[42] O. Nacham, A. Martín-Pérez, D.J. Steyer, M.J. Trujillo-Rodríguez, J.L. Anderson,
V. Pino, A.M. Afonso, Interfacial and aggregation behavior of dicationic and
tricationic ionic liquid-based surfactants in aqueous solution, Colloids Surf. A
469 (2015) 224–234.
[43] P. Brown, C.P. Butts, J. Eastoe, D. Fermin, I. Grillo, H.C. Lee, D. Parker, D. Plana, R.
M. Richardson, Anionic surfactant ionic liquids with 1-butyl-3-methyl-
imidazolium cations: characterization and application, Langmuir 28 (2012)
2502–2509.
[44] Q. Feng, H. Wang, S. Zhang, J. Wang, Aggregation behavior of 1-dodecyl-3-
methylimidazolium bromide ionic liquid in non-aqueous solvents, Colloids
Surf. A 367 (2010) 7–11.
[45] B. Dong, N. Li, L. Zheng, L. Yu, T. Inoue, Surface adsorption and micelle
formation of surface active ionic liquids in aqueous solution, Langmuir 23
(2007) 4178–4182.
[46] Y. Gu, L. Shi, X. Cheng, F. Lu, L. Zheng, Aggregation behavior of 1-dodecyl-3-
methylimidazolium bromide in aqueous solution: effect of ionic liquids with
aromatic anions, Langmuir 29 (2013) 6213–6220.
[47] S. Mandal, J. Kuchlyan, S. Ghosh, C. Banerjee, N. Kundu, D. Banik, N. Sarkar,
Vesicles formed in aqueous mixtures of cholesterol and imidazolium surface
active ionic liquid: a comparison with common cationic surfactant by water
dynamics, J. Phys. Chem. B 118 (2014) 5913–5923.
[48] S. Chabba, S. Kumar, V.K. Aswal, T.S. Kang, R.K. Mahajan, Interfacial and
aggregation behavior of aqueous mixtures of imidazolium based surface active
ionic liquids and anionic surfactant sodium dodecylbenzenesulfonate, Colloids
Surf. A 472 (2015) 9–20.
[49] G.B. Dutt, Do ionic and hydrophobic probes sense similar microenvironment in
Triton X-100 nonionic reverse micelles?, J Chem. Phys. 129 (2008) 014501(1)–
014501(6).
773
[50] K.S. Mali, G.B. Dutt, T. Mukherjee, Rotational diffusion of organic solutes in
surfactant-block copolymer micelles: role of electrostatic interactions and
micellar hydration, J. Phys. Chem. B 111 (2007) 5878–5884.
[51] S. Ghosh, A. Roy, D. Banik, N. Kundu, J. Kuchlyan, A. Dhir, N. Sarkar, How does
the surface charge of ionic surfactant and cholesterol forming vesicles control
rotational and translational motion of rhodamine 6G perchlorate (R6G ClO4)?,
Langmuir 31 (2015) 2310–2320
[52] W. Becker, The bh TCSPC Handbook, fourth ed., Becker & Hickl GmbH, 2010.
[53] N. Pal, S.D. Verma, M.K. Singh, S. Sen, Fluorescence correlation spectroscopy:
an efficient tool for measuring size, size-distribution and polydispersity of
microemulsion droplets in solution, Anal. Chem. 83 (2011) 7736–7744.
[54] S. Ghosh, A. Adhikari, S. Sen Mojumdar, K. Bhattacharyya, A fluorescence
correlation spectroscopy study of the diffusion of an organic dye in the gel
phase and fluid phase of a single lipid vesicle, J. Phys. Chem. B 114 (2010)
5736–5741.
[55] U. Haupts, S. Maiti, P. Schwille, W.W. Webb, Dynamics of fluorescence
fluctuations in green fluorescent protein observed by fluorescence correlation
spectroscopy, Proc. Natl. Acad. Sci. U.S.A. 95 (1998) 13573–13578.
[56] D.K. Sasmal, T. Mondal, S. Sen Mojumdar, A. Choudhury, R. Banerjee, K.
Bhattacharyya, An FCS study of unfolding and refolding of CPM-labeled human
serum albumin: role of ionic liquid, J. Phys. Chem. B 115 (2011) 13075–13083.
[57] T. Torres, M. Levitus, Conformational dynamics: a new FCS-FRET approach, J.
Phys. Chem. B 111 (2007) 7392–7400.
[58] S. Dey, U. Mandal, S. Sen Mojumdar, A.K. Mandal, K. Bhattacharyya, Diffusion
of organic dyes in immobilized and free catanionic vesicles, J. Phys. Chem. B
114 (2010) 15506–15511.
[59] X. Li, Y. Yang, J. Eastoe, J. Dong, Rich self-assembly behavior from a simple
amphiphile, ChemPhysChem 11 (2010) 3074–3077.
[60] J. Shen, X. Xin, T. Liu, S. Wang, Y. Yang, X. Luan, G. Xu, S. Yuan, Ionic self-
assembly of giant vesicle as smart microcarrier and microreactor, Langmuir 32
(2016) 9548–9556.
[61] J.G. Ma, B.J. Boyd, C.J. Drummond, Positional isomers of linear sodium dodecyl
benzene sulfonate: solubility, self-assembly, and air/water interfacial activity,
Langmuir 22 (2006) 8646–8654.
[62] X. He, W. Shinoda, R. DeVane, K.L. Anderson, M.L. Klein, Paramaterization of a
coarse-grained model for linear alkylbenzene sulfonate surfactants and
molecular dynamics studies of their self-assembly in aqueous solution,
Chem. Phys. Lett. 487 (2010) 71–76.
[63] L. He, A.S. Malcolm, M. Dimitrijev, S.A. Onaizi, H.H. Shen, S.A. Holt, A.F. Dexter,
R.K. Thomas, A.P.J. Middelberg, Cooperative tuneable interactions between a
designed peptide biosurfactant and positional isomers of SDOBS at the air-
water interface, Langmuir 25 (2009) 4021–4026.
[64] B.F.B. Silva, E.F. Marques, U. Olsson, R. Pons, Headgroup effects on the unusual
lamellar-lamellar coexistence and vesicle-to-micelle transition of salt-free
catanionic amphiphiles, Langmuir 26 (2010) 3058–3066.
[65] K.S. Rao, T. Singh, A. Kumar, Aqueous-mixed ionic liquid system: phase
transitions and synthesis of gold nanocrystals, Langmuir 27 (2011) 9261–
9269.
[66] K.J. Tangso, S. Lindberg, P.G. Hartley, R. Knott, P. Spicer, B.J. Boyd, Formation of
liquid-crystalline structures in the bile salt-chitosan system and triggered
release from lamellar phase bile salt-chitosan capsules, ACS Appl. Mater.
Interfaces 6 (2014) 12363–12371.
[67] Z. Yuan, S. Dong, W. Liu, J. Hao, Transition from vesicle phase to lamellar phase
in salt-free catanionic surfactant solution, Langmuir 25 (2009) 8974–8981.