Journal of Colloid and Interface Science 428 (2014) 267–275

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Self-assembly of new surface active ionic liquids based on Aerosol-OT in

aqueous media
K. Srinivasa Rao a, Praveen Singh Gehlot a, Tushar J. Trivedi a, Arvind Kumar a,b,⇑
a
Academy of Scientific and Innovative Research (AcSIR), Central Salt and Marine Chemicals Research Institute, Council of Scientific & Industrial Research (CSIR), G.B. Marg,
Bhavnagar 364002, Gujarat, India
b
Salt & Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute, Council of Scientific & Industrial Research (CSIR), G.B. Marg, Bhavnagar 364002,
Gujarat, India

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

Article history: New anionic ionic liquid surfactants have been synthesized by replacing the sodium cation of Aerosol-OT
Received 25 March 2014 (sodium dioctylsulfosuccinate, [Na]AOT) with various biocompatible moieties, such as 1-butyl-3-methyl
Accepted 26 April 2014 imidazolium ([C4mim]), proliniumisopropylester ([ProC3]), cholinium ([Cho]), and guanidinium ([Gua]).
Available online 4 May 2014
The Aerosol-OT derived ionic liquids (AOT-ILs) were found fairly soluble in water and formed vesicles
above a critical vesicle concentration (CVC) which depended upon the nature of cation, and followed
Keywords: the order: [ProC3] < [C4mim] < [Gua] < [Cho] < Na+. The self-assembly process was characterized using
Surface active ionic liquid
surface tension (ST), isothermal titration calorimetry (ITC), conductivity, dynamic light scattering (DLS),
SAIL
Aerosol-OT
nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM). Unlike other AOT-ILs,
Counterion a structural transformation has been observed for [C4mim]AOT above CVC, because of certain amphiphilic
Vesicle character in the cation [C4mim]. Thermodynamic parameters calculated from ITC and conductivity tech-
Surfactant solubility niques revealed that the vesicle formation process is entropy driven for [C4mim]AOT, whereas the process
Hydrophobic ionic liquid is both enthalpy and entropy driven for other AOT-ILs. In order to check the versatility of synthesized AOT-
Isothermal titration calorimtry ILs we have tested their dissolution behavior in a different class of ionic liquids. All the AOT-ILs were found
fairly soluble in the hydrophilic IL, ethanolammonium formate (EOAF), whereas only [C4mim]AOT and
[ProC3]AOT were found soluble in hydrophobic IL, [C4mim]Tf2N. Such combinations can have potential
for construction of stable colloidal formulations or microemulsions in ionic liquid media.
Ó 2014 Elsevier Inc. All rights reserved.

1. Introduction
Ionic liquids (ILs) are compounds comprised entirely of ions
with melting points below 100 °C [1]. The physicochemical proper-
ties of ILs depend on cation, anion and their alkyl chain substitu-
tions [2,3] and can be tuned by changing the nature of
constituent components thus making them designer solvents [4].
Amphiphilicity can be imparted to ILs by attaching medium to
longer alkyl chain either to cation or anion or both and can be uti-
lized as surfactants. Similar to the conventional surfactants various
types of surface active ionic liquids (SAILs) such as cationic [5–19],
anionic [20–26], zwitterionic [27–29] and biamphiphilic or catan-
ionic SAILs [30–33] have been developed and investigated for their
self-assembling behavior in aqueous or IL media by several
research groups in the last few years. The SAILs, depending upon
the molecular structure, offer several advantages over the conven-
⇑ Corresponding author. Fax: +91 278 2567562.
E-mail addresses: mailme_arvind@yahoo.com, arvind@csmcri.org (A. Kumar).
tional surfactants of similar alkyl chain length. For example, the
imidazolium based cationic and zwitterionic SAILs can stabilize
the metal nanoparticles by surface charge covering [29–34]. The
imidazolium head group can act as both reducing and stabilizing
agent in chemical or photochemical synthesis of gold nanoparticles
by oxidizing itself into a ketone [35,36]. The imidazolium, and
pyridinium based SAILs with eight or more carbon chain substitu-
tion have shown antimicrobial activity in aqueous solution, which
increased with the increase in hydrophobicity [37,38]. On the other
hand, the advantage of anionic surfactant type SAILs is accessibility
of counterion with desired properties. For example, the bio based
counterions, such as amino acid derived, have shown many fold
advantages like in the synthesis of shape controlled nanomaterials
or in the mitigation of harmful algal blooms [39]. Such SAILs have
also shown improved emulsifying efficiency especially in the
preparation of IL based microemulsions, where the conventional
anionic surfactants are insoluble [40]. Thus SAILs are emerged as
potential new molecules in colloids and interface science.
As far as surface activity of SAILs is concerned, the ILs with med-
ium to long alkyl chain substituent either on cation or anion have

http://dx.doi.org/10.1016/j.jcis.2014.04.062
0021-9797/Ó 2014 Elsevier Inc. All rights reserved.
268 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275
shown improved surface activity as compared to the analogous
conventional surfactants in aqueous media [8,41]. Some of the imi-
dazolium based ILs have also shown distinct transitions in the
aggregated structures in aqueous media [42,43], examples include
micelle to vesicle transitions shown by cationic surfactant type sin-
gle tail SAIL [Cnmim] Br (n = 10, 12, 14) [42] and micellar transi-
tions shown by anionic surfactant type SAIL, [C4mim][C8OSO3]
[43]. Manifold improved surface activity has been shown by the
surfactants with bigger organic counterions, e.g. amino acid
derived SAILs have been found greater than tenfold surface active
as compared to its conventional analogues without dropping the
solubility in aqueous media [39,44].
SAILs have been used for the construction of supramolecular
structures such as vesicles in aqueous solutions by mixing with
other oppositely charged surfactants or oppositely charged SAILs
in aqueous media [45–47]. Very recently we have demonstrated
that catanionic type of biamphiphilic SAILs with a sufficiently long
alkyl chain both in cation and anion formed vesicles in aqueous
solution [33]. Since the double chain anionic surfactants, such as
sodium dioctylsulfosuccinate (Aerosol-OT) forms vesicles in water
and have very high emulsifying efficiency [48], it is likely that by
converting Aerosol-OT into SAIL by replacing the metal counterion
with bigger and biocompatible counterions, one can have many
advantages in terms of higher surface activity, emulsifying capacity
and higher solvability in water or any other media. Also, as the
insolubility of anionic surfactants in hydrophobic ILs limits the
applicability of ILs as greener replacements for oil phases in emul-
sions, the problem can be solved by the development of new Aer-
osol-OT based SAILs that are soluble in hydrophobic ILs.
In this contribution we have synthesized four anionic surfactant
type SAILs with diotylsulfosuccinate (anion of Aerosol-OT) as anion
choice and biologically important molecules which have greener
credentials, such as proline, choline, guanidine or imidazole as
source of cation. For convenience and ease to follow, these surfac-
tants are named in this manuscript as ‘‘[counterion] AOT’’ i.e.,
[ProC3]AOT, [C4mim]AOT, [Gua]AOT, or [Cho]AOT since all these
were synthesized taking AOT as a precursor. AOT-ILs have been
investigated in detail for their self-assembling behavior in aqueous
media using various physical and imaging techniques, role of coun-
terion in self-assembly is defined and their dissolution behavior in
a hydrophobic and a hydrophilic ionic liquid is tested. Among the
four AOT-ILs only [C4mim] AOT is reported early in the literature
[25], however this work deals with the earlier unexplored impor-
tant properties such as vesicle formation, unusual dual transitions
in self-assembly, thermodynamics of self-assembly and solubility
in hydrophobic IL media.
2. Experimental section
2.1. Materials
Dioctyl sodium sulfosuccinate (Aerosol-OT) (>98%) was pur-
chased from Otto chemicals, 1-methyl imidazole, n-bromobutane
and proline were purchased from SRL, India. Isopropanol and thio-
nyl chloride were purchased from SD fine chemicals Ltd. India.
Cholinium chloride and guanidinium hydrochloride were pur-
chased from Sigma–Aldrich. All the chemicals were of AR grade
and were used as received. Millipore grade water of specific
conductivity 3 lS cm1 was used for the whole study.
2.2. Synthesis of IL-surfactants
2.2.1. Synthesis of 1-butyl-3methyl imidazolium bromide
1:1.2 M ratio of 1-methyl imidazole, bromobutane were dis-
solved in water and refluxed for 5 h, the reaction was monitored
by TLC. After completion of the reaction water was removed at
reduced pressures. The obtained reaction mixture was washed
with ethyl acetate to remove the excess bromobutane present, fol-
lowed by the removal of solvent. The obtained yellow viscous
liquid was characterized with LCMS and 1HNMR techniques and
dried for several hours using a rotary evaporator to remove mois-
ture present prior to further use.
2.2.2. Synthesis of prolineisopropylester hydrochloride (ProC3HCl)
The prolineisopropylester hydrochloride was synthesized by
following earlier reported procedure [39]. In brief, 0.13 mol of thio-
nyl chloride was added in drop wise to isopropanol at 0 °C followed
by the slow addition of 0.11 mol of proline at room temperature
after complete mixing the reaction mixture was refluxed for 4 h,
and the reaction was monitored by TLC. Thus obtained crude ProC3-
HCl was washed with hexane and dried under vacuum followed by
recrystallization with methanol. The obtained pure hygroscopic
ProC3HCl was dried and stored in desiccator.
2.2.3. Synthesis of AOT based IL-surfactants
An equimolar mixture of [C4mim] Br (or) ProC3HCl (or) Guanid-
inium hydrochloride and dioctyl sodium sulfosuccinate (Aerosol-
OT) were dissolved in dichloromethane (DCM) and stirred for
24 h at room temperature. The precipitated NaBr (or) NaCl was fil-
tered with Whatmann filter paper. The DCM layer was washed
with water for several times to completely remove Cl or Br ion
present. The washing was performed until the aqueous layer gives
clear solution even with the addition of excess 1 M AgNO3. The
DCM layer was then dried over Na2SO4 followed by removal of sol-
vent. Thus obtained IL-surfactants were dried for several hours
under vacuum and stored in desiccator prior to use. All the SAILs
were characterized by LCMS and 1HNMR techniques (Supporting
information). Detailed characterization of synthesized materials
is provided in Supporting information.
2.2.4. Synthesis of [Cho]AOT
Since choline chloride is insoluble in DCM, [Cho]AOT has been
synthesized in aqueous medium unlike other AOT-ILs. For this,
equimolar amounts of choline chloride and Aerosol-OT are taken
in water and kept for stirring for 24 h at room temperature. The
progress of the reaction is monitored by TLC. After completion of
the reaction the product is extracted into DCM layer, followed by
washing the DCM layer with water for several times to complete
remove the chloride ion present. The washing was performed until
the aqueous layer gives a clear solution even with the addition of
excess 1 M AgNO3. The DCM layer is then distilled to get pure
[Cho]AOT. Further, [Cho]AOT is dried under vacuum for several
hours to remove the moisture present and stored in desiccator.
Thus synthesized [Cho]AOT was characterized by using 1HNMR,
LC-MS. The 1HNMR spectrum and LCMS data are given in Support-
ing information.
2.3. Methods
2.3.1. Differential Scanning Calorimetry (DSC)
DSC experiments were performed on NETZSCH DSC 204 F1
PhoenixÒ using Al crucible at a heating rate of 5 °C/min.
2.3.2. Tensiometry
The surface tension of the aqueous solutions of AOT-ILs was
measured using Data Physics DCATII automated Tensiometer by
employing Wilhelmy plate method. The temperature of the instru-
ment was controlled by Julabo thermostat within the error limit of
±0.1 K. The surface tension was measured after each 100 ll aliquot
addition of AOT-IL stock solutions to 40 ml Millipore water, mea-
surements were taken after ensuring homogeneous mixing. The
 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275
data was collected in triplicate and was found to be accurate
within 0.1 mN m1. The concentration of stock solutions prepared
was in the range of 25–35 mM, varied according to the experiment.
2.3.3. Isothermal Titration Calorimetry (ITC)
Calorimetric titrations were performed with MicroCal iTC200
micro calorimeter. Prior to the measurements, sample and refer-
ence cells are cleaned with Millipore water for several times and
dried. Initially the sample and reference cells are filled with
200 ll millipore water. Both the cells are maintained at 298.15 K,
after attaining thermal equilibrium (DT = 0), stock solutions of IL-
surfactants prepared in Millipore water were added to sample cell
in 2 ll aliquots by the instrument controlled Hamiltonian syringe
with continuous stirring at 500 rpm. The parameters like time of
addition and duration between each addition were controlled by
software provided with the instrument. The enthalpy change at
each addition was measured and plotted against concentration
by using data analysis software ORIGIN 7.0 provided with the
instrument.
2.3.4. Conductometry
Specific conductivity was measured at 298.15 K at by using a
digital conductivity meter (Systronics 308) using a cell with a unit
cell constant. The temperature of the measurement cell was con-
trolled by a Julabo water thermostat within the error limit of
±0.1 K. The conductivity after each addition was measured by add-
ing aliquots of concentrated IL-surfactants aqueous solutions to a
conductivity cell containing water. Measurements were performed
with an uncertainty of less than 0.5%.
2.3.5. Dynamic light scattering
DLS measurements were performed at 298.15 K by using a
NaBiTec Spectro-Size300 light scattering apparatus (NaBiTec, Ger-
many) with a He–Ne laser (633 nm, 4 Mw). The temperature of the
measurements was controlled with an accuracy of ±0.1 K. The data
evaluation of the dynamic light scattering measurements was per-
formed with the inbuilt CONTIN algorithm. Prior to the measure-
ments all the colloidal solutions were filtered with 0.45 lm
nylon syringe filter.
2.3.6. Transmission Electron Microscopy (TEM)
Imaging of the colloidal solutions was done using JEOL JEM-
2100 electron microscope at a working voltage of 200 kV. For sam-
ple preparation a drop of colloidal solution was put on parafilm, a
carbon coated copper grid (300 mesh) with the help of tweezers
was touched on one side, tilted and kept for drying. The samples
were taken for analysis after 24 h of drying in a desiccator.
2.3.7. 1HNMR measurements
The 1H NMR spectra of the IL mixtures in various concentration
regimes were recorded using a Brüker 200 MHz spectrometer. The
proton chemical shifts were referenced with respect to a TMS
external standard (d = 0.000 ppm) in C6D6 (deuterated benzene).
The chemical shifts of the peaks of interest were determined using
the peak pick feature.
3. Results and discussion
3.1. Melting points
The anionic surfactants with melting point less than 100 °C are
called as anionic surface active ionic liquids (ASAILs). Among the
four newly synthesized AOT-ILs (Scheme 1), [Gua]AOT appears as
solid, [Cho]AOT appears as gel like material, whereas, [C4mim]AOT
and [ProC3]AOT are liquids at room temperature. The melting (Tm)
269
temperature measured for these AOT–ILs are found to be 112 °C,
49.3 °C, 31.3 °C and 57.5 °C respectively for [Gua]AOT,
[Cho]AOT, [C4mim]AOT and [ProC3]AOT. The melting point data
suggest that among synthesized surfactants except [Gua]AOT
(which has slightly higher melting point as compared to the gener-
ally accepted definition of ionic liquids) all other compounds can
be considered as SAILs. DSC thermograms are provided in Support-
ing information, Fig. S1. It is observed that with the increase in size
of the counter ion, the melting point of the corresponding IL
decreased, suggesting the larger or unsymmetrical (in molecular
structure) counterions decreases the melting points of correspond-
ing ionic compound.
3.2. Surface tension
The surface activity of AOT derived SAILs in aqueous media have
been estimated by performing the surface tension measurements
at 298.15 K (Fig. 1). The surface tension of water decreased with
increasing the concentration of AOT-ILs before reaching a plateau.
The intersection of linear fitted lines before and after the plateau
values provided the vesicle forming concentration CVC. In general,
CMC/CVC values of surfactants depend on the chain length, head
group and counterion. The increase in the ionic size and hydropho-
bicity of counterion enhances the micellization and eventually
decreases the CMC of the corresponding surfactant [49]. The CVC
values obtained for all the four AOT-ILs (Table 1) are less than
the CVC value of their analogues with sodium (Na+) or quaternary
ammonium counterions (ammonium (NH+4), tetramethylammo-
nium (TMA), tetraethylammonium (TEA)) and higher than tetra-
propylammonium (TPA) and tetrabutylammonium (TBA)
counterions [49]. Hydrophobic interactions of counterions in
[TEA]AOT, [TPA]AOT or [TBA]AOT with hydrocarbon core of anion
decrease the CMC values and is always lower than [Na]AOT. Such
interactions are absent in cases of Aerosol-OT based surfactants
containing TMA, NH+4 as counterions leading to higher CMC values.
The intermediate values of CVC for AOT-ILs as compared to those of
AOT surfactants comprising of counterions, TMA, NH+4, Na+, TEA,
TPA and TBA suggests the importance of hydrophobic interactions.
The CVC values of AOT-ILs are found to be decreased with the
increase in size and hydrophobicity of the counter cation and fol-
lowed the order: [ProC3] < [C4mim] < [Gua] < [Cho]. Here it is note-
worthy that even though the size of the [Cho] is bigger than [Gua],
but [Cho]AOT experiences higher CVC than [Gua]AOT, because of
less hydrophobicity of cholinium ion due to the presence of the
polar hydroxyl group. The CVC results suggest that the hydropho-
bicity of AOT-ILs investigated falls between those surfactants hav-
ing quaternary ammonium as counterions i.e. less than those
having TPA or TBA and greater than those having TMA or TEA as
counterions.
Adsorption efficiency of AOT-ILs is evaluated by calculating pC20
using the relation (1) [50]
pC 20 ¼  log C 20 ð1Þ
where C20 is the concentration needed to reduce the surface tension
of the solvent (water in the present case) by 20 mN m1. The higher
pC20 value indicates high adsorption efficiency of the surfactant
[50]. The values obtained for all AOT-ILs except [Gua]AOT are higher
than [Na]AOT (Table 1). Effectiveness of surface tension reduction is
the other parameter that measures the adsorption efficiency of a
surfactant, denoted by Pcvc and calculated using the relation (2)
Pcv c ¼ c0  ccv c ð2Þ
where c0 stands for the surface tension of the pure solvent and ccvc
stands for the surface tension of the solvent medium at CVC. The
pC20, Pcvcvalues are higher than conventional surfactant
Aerosol-OT, indicating AOT-ILs are more efficient surfactants than
270 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275

Scheme 1. Molecular structure of various cations and anions of synthesized AOT-ILs.

GuaAOT ChoAOT
50 50

40 40

30
30
γ (mN.m-1)

20
0.01 0.1 1 0.01 0.1 1

BmimAOT PC3AOT
50
50

40
40

30 30

0.01 0.1 1 0.01 0.1 1

C (mM)

Fig. 1. c-log C plots for AOT based IL-surfactants in aqueous medium at 298.15 K.

Aerosol-OT. Molecular structure of the surfactant (volume of the
hydrophilic head group and hydrophobic tail group) generally indi-
cate the thermodynamic feasibility of adsorption of surfactant at
interface, the efficiency of which is influenced by exterior factors
such as the temperature, concentration and counterion etc. [51].
Bigger counterions, because of their higher hydrophobicity
experiences less hydration and adsorb in more number at interface,
thus facilitating more adsorption of surfactant at the interface by
minimizing like charge repulsion between the head groups. The
same is true in the present case of AOT-ILs, where the bigger coun-
terions, [Gua], [Cho], [C4mim] and [ProC3] employed improved the
surface efficiency as compared to [Na]AOT. The lower ccvc values
 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275
Table 1
Critical vesicle concentration (CVC), surface tension at CAC (ccvc), adsorption efficiency (pC20), effective surface tension reduction (pcvc), maximum surface excess concentration
(Cmax), and area occupied by a single molecule at the air–water interface (Amin) of IL-surfactants in aqueous medium at 298.15 K.
Surfactant CVC (mM) ccvc (mN m1)
[Na]AOT 2.59 29.04
[Gua]AOT 1.69 26.66
[Cho]AOT 1.87 26.22
[C4mim]AOT 1.65 26.41
[ProC3]AOT 1.45 26.26
obtained for all AOT-ILs than [Na]AOT further supports the
improved population of AOT-ILs at the interface.
The amount of AOT-ILs adsorbed at the interface is estimated by
deriving surface excess concentration (Cmax) using Gibbs adsorp-
tion Eq. (3) that allowed the estimation of minimum area occupied
by AOT-ILs at the interface (Amin) using (4).
1 @c
Cmax ¼ 
nRT @ ln C
1 3.4. Thermodynamics of vesicle formation
Amin ¼
Cmax N A
where ‘‘o c/o ln C’’ is the slope of c-ln C plot in the pre CVC region,
obtained by fitting the data to a second degree polynomial equation,
NA is Avogadro number and n is the pre-factor, taken as 2 for all
AOT-ILs by considering 1:1 dissociation in aqueous medium [53].
The concentration just below CVC is considered to obtain Cmax from
which it is possible to obtain Amin value at nearly saturation of the
interface. In the case of Aerosol-OT, small amount of divalent metal
ion impurities are known to influence Cmax value. Thomas et al. and
Eastoe et al. have reported from the surface tension experiments
that the addition of small amounts of tetrasodium ethylenedi-
aminetetraacetate (EDTA) binds with the trace metal ion impurities
and minimizes their influence on the adsorption of surfactant which
consequently gives the Cmax values of good accuracy comparable to
the values obtained from neutron reflection (NR) experiments
[52,53]. Thus, the discrepancy in the parameter values calculated
in this work and reported values may be due to the presence of
trace amount of hydrophobic and divalent metal ion impurities in
AOT-ILs [52,53]. All calculated parameter values for four investi-
gated AOT-ILs is given in Table 1.
3.3. Counterion binding (b)
The ionic surfactants do not completely dissociate in aqueous
medium. Some of the counterions remain bounded with the head
groups in the stern layer and the fraction of counterions which
remain bound in the stern layer is known as counterion binding
(b) that significantly influence the CVC and surface charge of the
aggregates. Also, b is a critical parameter in the accurate estimation
of free energy of micelle/vesicle formation which is estimated by
measuring the ratio of slopes of lines drawn before and after a
sharp transition, i.e., CVC from conductivity-concentration plot
(the plots of j-C is given in Supporting information, Fig. S2). b
for [Gua]AOT, [C4mim]AOT, and [ProC3] AOT are estimated from
conductivity experiments, however, could not estimate for
[Na]AOT or [Cho]AOT because of lack of transitions in the conduc-
tivity profiles. The counterion binding for [Na]AOT has been esti-
mated by performing aggregation in electrolyte solutions
applying the Corrin–Harkins equation by Chatterjee et al. [54]
and Umlong et al. [55] and found that the data obtained by this
method is quite reliable and accurate. Therefore, we determined
the counterion binding for [Cho]AOT in a similar way by perform-
ing ITC experiments at different choline chloride concentrations.
The Corrin–Harkins equation [56] employed for obtaining b values
is
271
pcvc (mN m1) pC20 Cmax (lmol m2) Amin (Å2)
43.11 4.23 1.37 120.8
45.34 4.07 2.43 68.8
45.78 4.57 1.46 113.5
45.59 4.53 1.53 108.6
45.74 4.54 1.8 92.3
log CVC ¼ CONSTANT  b log½counterion ð5Þ
The plot drawn to estimate the b values is given in Supporting infor-
mation (Fig. S3). The b value obtained thus for [Cho]AOT is 0.56. The
counterion binding obtained for all the surfactants is given in
Table 2. The value of counterion binding is higher for AOT-ILs than
[Na]AOT which can be attributed to the lower solvation of bigger
counterions.
ð3Þ
ð4Þ
Isothermal titration calorimetry is a powerful tool to investigate
the thermodynamics of self-assembly of a surfactant [57,58]. Stock
solution approximately ten times higher than CVC is taken in syr-
inge for each ITC experiment. Thermograms obtained for all four
AOT-ILs is shown in Fig. 2 whereas the thermogram for Aerosol-
OT is given in Supporting information Fig. S4. Similar to the conven-
tional surfactants, three regions were detected in each of the
thermogram (except in case of [C4mim]AOT). A first constant region
where the collapse of vesicles takes place, followed by sharp transi-
tions (second region), where vesicle formation takes place, followed
by again constant region (third region, the concentration in the
third region is higher than CVC), where only vesicle dilution takes
place, since the number of vesicles in syringe are more than in sam-
ple cell [57]. Depending upon the nature of the surfactant ITC
results positive or negative peaks in the thermograms, positive
peaks are due to the heating of sample cell and a subsequent heat
flow from sample cell to solution, and are thus indicative of exo-
thermic reactions e.g., DH < 0. Similarly, negative peaks are due to
the heat flow to the sample cell indicative of endothermic reactions
e.g., DH > 0.DH at each addition is obtained by integrating the peak
of corresponding addition (released/gained in order to maintain a
thermal equilibrium with reference cell). The energy difference
between the third and the first region in enthalpogram gives the
standard enthalpy of vesicle formation ðDH0v es Þ as shown in Fig. 2
[59]. Thermograms for the investigated AOT-ILs are provided in
Supporting information (Fig. S5). The CVC values are obtained from
the first derivative graphs of thermograms and are given in Table 2.
All the CVC values obtained for AOT-ILs is less than the CVC values
obtained for Aerosol-OT and are in good agreement with the CVC
values obtained from surface tension measurements. In the ther-
mogram of [C4mim]AOT two transitions are observed, the first tran-
sition is exactly at the CVC concentration observed from surface
tension and NMR techniques and the second transition is at a con-
centration 2 times to that of CVC. Interestingly, the energy
changes of the first and second transitions are approximately same,
but with opposite sign, i.e., the heat energy gained during the
monomer to vesicle formation is released during the second transi-
tion. The second transition is further confirmed from NMR chemical
shift changes (discussed in later part of the manuscript).
DH0v es has been calculated from enthalpograms obtained from
the ITC as shown in the Fig. 2. The vesicle formation process is
endothermic in cases of Na+ and [C4mim] and [Cho] counterions,
whereas the process is exothermic in cases [Gua] and [ProC3] coun-
ter cations. The standard free energy of vesicle formation ðDG0v es Þ is
calculated using the relation (6), where b corresponds to the
272 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275

Table 2 imaging. The TEM image of a representative AOT-IL, [ProC3]AOT

Isothermal titration microcalorimetry derived critical vesicle concentration (CVC), at a concentration 5 times to that of CVC showing thick bilayer
standard Gibbs free energy (DG0ves), enthalpy (DH0ves), and entropy of vesicle
formation (DS0ves) for AOT based IL-surfactants in aqueous medium at 298.15 K.
ring is given in Fig. 3B.

Surfactant b CVC DH0v es DG0v es DS0v es

(mM)
3.6. Exceptional behavior of counterion [C4mim]
(kJ mol1) (kJ mol1) (J mol1)
[Na]AOT 0.4 3.09 3.78 34.00 126.71 Unlike other Aerosol-OT/AOT-ILs, two transitions are observed
[Gua]AOT 0.63 2.32 8.7 40.90 107.99
[Cho]AOT 0.56 2.38 3.34 38.89 119.25
for [C4mim]AOT in ITC thermogram with the first transition exactly
[C4mim]AOT 0.74 1.88 2.70 44.48 158.22 at CVC and the second transition at approximately double the CVC.
[ProC3]AOT 0.66 1.43 13.85 43.38 99.05 To confirm the second transition, NMR chemical shifts were plot-
ted against the concentration which clearly showed two break
points corresponding to the concentrations observed from ITC
degree of counterion binding and Xcvc is the CVC in mole fraction (Fig. 4A). The transitions were further rationalized from DLS mea-
units. surements performed in a concentration range 1–40 mM (covering
DG0v es ¼ ð1 þ bÞRT ln X cv c ð6Þ first and second transition). DLS showed no significant change in
the size of the vesicles (Fig. 4B). DLS size distributions of different
0
The negative DGv es indicate the vesicle formation by AOT-ILs in concentrations are given in Supporting information Fig. S6. TEM
aqueous media is spontaneous. The magnitude of DG0v es for image is taken for [C4mim]AOT (at 17 mM, well above the second
AOT-ILs is found to be higher than their conventional analogue transition concentration) revealed the formed aggregate are still
Aerosol-OT. the vesicles. A similar kind of transition was observed by our group
The standard entropy of vesicle formation ðDS0v es Þ is calculated previously in the case of [C4mim]C8OSO3. Investigation using 2D-
by applying the relation (7) using the obtained values of DG0v es NMR revealed that the additional transition is due to the penetra-
and DH0v es . tion of the counterion into the already formed aggregated structure
(micelle) causing rearrangement of ions at the interface of micelle
DH0v es  DG0v es
DS0v es ¼ ð7Þ formed [44]. DLS and cryo-TEM measurements done for [C4-
T mim]C8OSO3 at a concentration range covering both the transitions
The DS0v es obtained for investigated systems are positive and varied have shown no significant change in the size and type of the aggre-
with the nature of counterion. The derived thermodynamic param- gates formed [44]. The observations made for [C4mim]AOT are con-
eters suggest that the vesicle formation is entropy driven in cases of sistent with the observations made for [C4mim]C8OSO3. Also, no
[Na]AOT, [C4mim]AOT and [Cho]AOT, whereas the process is both such additional transition was observed for other three AOT-ILs
enthalpy and entropy driven in cases of [Gua]AOT and [ProC3]AOT prepared. Thus, the second transition observed in ITC (Fig. 2) mea-
at 298.15 K.The obtained thermodynamic parameters are given in surements can be accounted to the moderate amphiphilicity of
Table 2. counterion, [C4mim] due to the alkyl chain (4 carbon) attached to
the imidazolium ring. At second transition, a slight rearrangement
3.5. Dynamic Light Scattering (DLS) and TEM in vesicular structure happens wherein the counterion may enter
into the stern layer causing the rearrangement in the bilayer struc-
DLS measurements were carried out to estimate the size of the ture. This structural rearrangement however, does not alter the
vesicles formed by AOT-ILs at 298.15 K. The hydrodynamic radius basic vesicular structure as can be seen from TEM image
(Rh) was found in the range of 90–150 nm, typically matching the (Fig. 4C). These structural transitions limit to the moderate alkyl
size of vesicles (Fig. 3A), which is further confirmed by TEM chain counterions, since counterions with sufficiently higher

8
1

6
0

4 ΔΗves
Gua AOT -1 Cho AOT
2
-2
0
ΔΗ (kJ.mol )
-1

0 2 4 0 2 4
3
12 ProC3 AOT
Bmim AOT
2
8

1
4

0 0

0 2 4 6 8 0 1 2 3
C (mM)

Fig. 2. Enthalpograms of AOT-ILs in aqueous medium at 298.15 K.

 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275 273

0 200 400 600 800 1000

1.0
PC 3 AOT
0.5 A B
0.0
1.0 Bmim AOT
0.5
0.0
Intensity 1.0 Cho AOT
0.5
0.0
1.0 Gua AOT
0.5
0.0
1.0 Na AOT
0.5
0.0
0 200 400 600 800 1000
R h (nm)

Fig. 3. (A) Hydrodynamic radius (Rh) distributions of AOT-ILs in aqueous medium at 298.15 K. (B) The representative TEM image of vesicles of [ProC3]AOT.

70
8.80
A B C
Transition 2 60
R h (nm)
δ (ppm)

8.76 50
Transition 1
40
8.72
30

8.68 20
2 4 6 810 0 10 20 30
1/C (mM) C (mM)

Fig. 4. (A) Change in chemical shift of 2H proton of imidazolium ring with the concentration in [C4mim]AOT in aqueous medium. (B) Hydrodynamic radius of the
[C4mim]AOT vesicle at different concentrations. (C) TEM image of vesicles of [C4mim]AOT at 17 mM.

Table 3 widely used anionic surfactant in the preparation of microemul-

Percentage solubility (wt%)/miscibility of Na+-AOT and AOT-ILs in aqueous and sions or reverse micelles in organic solvents [60]. However, in
IL-medium.
the preparation of microemulsions where the hydrophobic ILs
AOT-ILs Water EOAF [C4mim]Tf2N are used as dispersion medium, Aerosol-OT has shown poor emul-
[Na]AOT Soluble 80 Insoluble sifying efficiency due to solubility limitations. For example, 10% of
[Gua]AOT 8 9 Insoluble 1-hexanol was required to dissolve a very small amount of
[Cho]AOT Miscible 11 Insoluble Aerosol-OT in [C8mim]Tf2N [61]. Whereas, Aerosol-OT is difficult
[C4mim]AOT Miscible Miscible Miscible
to dissolve even with the addition of 1-hexanol in the small chain
[ProC3]AOT Miscible Miscible Miscible
hydrophobic ILs, such as, [C2mim]Tf2N and [C4mim]Tf2N [61]. Thus
the solubility of [Na]AOT in hydrophobic ILs is a serious limitation
amphiphilic character (n > 8) do not lead to such structural altera- and need to overcome in order to develop promising emulsifying
tions as these acts as catanionic type surfactant and counterion agents for formulating IL based microemulsions. Recently, we
directly involves in the aggregate formation [33]. observed that the solubility of an anionic surfactant sodium lauryl-
sulfate in hydrophobic IL, [C4mim]Tf2N could be improved by con-
4. Dissolution behavior of AOT-ILs in water and ILs verting it into an amino acid based ionic liquid surfactant,
proliniumisopropylester laurylsulfate [39,40]. We examined the
Among all the classes of surfactants, anionic surfactants show dissolution behavior of AOT-ILs in two different classes of ILs i.e.,
excellent emulsifying efficiency. Aerosol-OT is one of the most aprotic hydrophobic IL, [C4mim]Tf2N and protic hydrophilic IL

a b c d e
Fig. 5. Photographs showing the dissolution behavior of Na-AOT and AOT-ILs in hydrophobic IL [C4mim]Tf2N; (a) [Na]AOT, (b) [Gua]AOT, (c) [Cho]AOT, (d) [C4mim]AOT, and
(e) [ProC3]AOT.
274 K. Srinivasa Rao et al. / Journal of Colloid and Interface Science 428 (2014) 267–275
ethanolammonium formate (EOAF). The miscibility characteristics
of AOT-ILs along with conventional [Na]AOT in water and ILs at
room temperature is provided in Table 3 and representative photo-
graphs showing miscibility behavior of synthesized AOT-ILs in
[C4mim]Tf2N is shown in Fig. 5.
[C4mim]AOT and [ProC3]AOT were found miscible in both the
ILs and water over the whole composition range, whereas similar
to [Na]AOT, the [Cho]AOT and [Gua]AOT could not be solubilized
in [C4mim]Tf2N indicating that the improvement in the solubility
of anionic surfactants in hydrophobic ILs largely depends upon
not only the size but also on the nature of organic counter ions.
Detailed studies are needed to categorize the class of ions that
make IL-surfactants soluble in hydrophobic ILs. In the case of EOAF,
the [Gua]AOT showed a solubility of 9 wt% whereas, [Cho]AOT
could be dissolved up to 11 wt%. Unlike, Aerosol-OT derived IL-sur-
factant having the counterion TBA ([TBA]AOT), which is insoluble
in aqueous media [24], AOT-ILs synthesized herein are highly sol-
uble in water showing their versatility for utilization in a variety of
solvent media.
5. Conclusions
Novel Aerosol-OT derived anionic surfactant like ILs with bio-
compatible cations; 1-butyl-3-methyl imidazolium, proliniumiso-
propylester, cholinium, or guanidinium have been synthesized
and investigated for their self-assembling behavior in aqueous
media. The synthesized AOT-ILs were found to have higher surface
activities than the conventional analogue Aerosol-OT and formed
vesicles in water. The vesicle formation is entropy driven in cases
of [Na]AOT and [C4mim]AOT, whereas the process is both enthalpy
and entropy driven in cases of [Gua]AOT, [Cho]AOT, and [ProC3]-
AOT at 298.15 K. Unlike other AOT-ILs studied, [C4mim]AOT
showed a second transition above vesicle forming concentration
(CVC) due to the rearrangement of the vesicular structure induced
by the counterion amphiphilicty. Further, among the four AOT-ILs
studied, [C4mim]AOT and [ProC3]AOT are found to be miscible in
hydrophobic IL [C4mim]Tf2N throughout the composition range
thus overcoming the solubility limitations of conventional
Aerosol-OT [61,62]. [C4mim]AOT and [ProC3]AOT were also found
completely miscible in the hydrophilic IL EOAF whereas, the
[Gua]AOT and [Cho]AOT is solubilized to a reasonably good extent
i.e. 9 and 11 wt% respectively. The manuscript reports a significant
progress in the development of anionic type of IL-surfactants
which form vesicles in water. Two of the developed AOT-ILs are
IL-philic and can have potential for the preparation of IL based col-
loidal systems [61–64].
Acknowledgments
Authors are thankful to Department of Science and Technology
(DST), Government of India for financial support for this work (No.
SR/S1/PC-04/2010 and SB/S1/PC-104/2012). K.S. Rao is thankful to
CSIR for senior research fellowship. P.S. Gehlot is thankful to UGC
for JRF fellowship. Analytical division of CSMCRI is also acknowl-
edged for helping in sample characterization.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2014.04.062.
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