Micellization and Adsorption Properties of New Cationic Gemini Surfactants Having Hydroxyisopropyl Group

Article abstract of DOI:10.1021/acs.jced.8b00815

A series of cationic gemini surfactants, N,N′-bis(alkyl)-N,N′-bis(2-hydroxypropyl)ethylenediammonium dibromide, [C_nH_2n+1(CH₃CH(OH)CH₂)NH(CH₂)₂NH(CH₂CH(OH)CH₃)C_nH_2n+1]Br₂ (where n is the tail chain length, n = 9, 12, and 14), referred to as C_nC₂C_n[iso-Pr(OH)] was synthesized. Via conductometric and tensiometric methods, at different temperatures (283 to 313 K), specific electrical conductivities and surface tensions of the aqueous solutions of these cationic gemini surfactants were determined. According to the obtained values, micellization and adsorption parameters such as critical micellization concentration (CMC), maximum surface excess (Δ_max), minimal cross sectional surface area of surfactant polar group (A_min), adsorption efficiency (pC₂₀), surface pressure (π), and binding degree of counterion (β) were calculated. The values of standard Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also computed. Via the dynamic light scattering method, diameters of aggregates of the synthesized cationic gemini surfactants were determined in water. It was established that the diameters of these aggregates decrease with a temperature rise. Antibacterial properties of the synthesized cationic surfactants against sulfate-reducing bacteria (SRB) were studied.

Full text of DOI:10.1021/acs.jced.8b00815

Article
pubs.acs.org/jced
Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Micellization and Adsorption Properties of New Cationic Gemini
Surfactants Having Hydroxyisopropyl Group
Ziyafaddin H. Asadov,† Gulnara A. Ahmadova,† Ravan A. Rahimov,*,†,‡ Seyid-Zeynab F. Hashimzade,†
Etibar H. Ismailov,† Nahida Z. Asadova,§ Samira A. Suleymanova,† Fedor I. Zubkov,∥
Ayaz M. Mammadov,† and Durna B. Agamaliyeva†
†Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences, Hojaly ave. 30, AZ 1025, Baku, Azerbaijan
‡Department of Chemical Engineering, Baku Engineering University, Hasan Aliyev str. 120, Baku, Absheron AZ0101, Azerbaijan
§Faculty of Biology, Baku State University, Z. Xalilov str. 23, Az 1148 Baku, Azerbaijan
∥Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), 6
Miklukho-Maklaya St., Moscow, 117198, Russian Federation
S
* Supporting Information
ABSTRACT: A series of cationic gemini surfactants, N,N′-bis(alkyl)-N,N′-bis(2-
hydroxypropyl)ethylenediammonium dibromide, [CnH2n+1(CH3CH(OH)CH2)-
NH(CH2)2NH(CH2CH(OH)CH3)CnH2n+1]Br2 (where n is the tail chain length,
n = 9, 12, and 14), referred to as CnC2Cn[iso-Pr(OH)] was synthesized. Via
conductometric and tensiometric methods, at different temperatures (283 to 313
K), specific electrical conductivities and surface tensions of the aqueous solutions of
these cationic gemini surfactants were determined. According to the obtained
values, micellization and adsorption parameters such as critical micellization
concentration (CMC), maximum surface excess (Γmax), minimal cross sectional
surface area of surfactant polar group (Amin), adsorption efficiency (pC20), surface
pressure (π), and binding degree of counterion (β) were calculated. The values of
standard Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also
computed. Via the dynamic light scattering method, diameters of aggregates of the
synthesized cationic gemini surfactants were determined in water. It was established that the diameters of these aggregates
decrease with a temperature rise. Antibacterial properties of the synthesized cationic surfactants against sulfate-reducing bacteria
(SRB) were studied.
the nature and length of the alkyl group in the hydrophilic part,
it is possible to change properties of the surfactants.2,7 The
gemini surfactants containing a hydroxyl group may be divided
into two parts:8−11 (1) the gemini surfactants having an OH
fragment in the headgroup and (2) the gemini surfactants
having fragments with OH groups in the spacer. Using various
methods, Huang et al.12 have studied properties of the 12-s-
12(OH) type gemini surfactants where two −CH2CH2OH
groups are linked to a nitrogen atom in the headgroup, to form
aggregates. It was established that, in these surfactants, distinct
from the surfactants where the methyl group is connected to
the nitrogen atom, hydrogen bonding between head-groups is
observed and propensity to self-assembly is much stronger.
The formation of hydrogen bonds increases elasticity between
adsorption layers and, as a result, enables the obtainment of
stable emulsions and foams. Borse et al.13,14 have studied
surface tension and specific electric conductivity properties of
the 12-s-12(OH) type cationic surfactants having methyl and
1. INTRODUCTION
In recent years, the attention of researchers has been focused
on gemini surfactants, which are also termed surfactants with
dialkyl groups. In gemini surfactants, there are two hydro-
phobic and two hydrophilic groups. These hydrophilic groups
are bridged between each other. The groups linking them are
called spacers.1,2 Gemini surfactants are different from one
another by hydrophobic chain length, hydrophilic group
nature, and spacer group length and nature. Gemini surfactants
have some advantages over surfactants with monoalkyl groups
of similar structure. Thus, these surfactants possess a low
CMC, a small surface tension value, a good wetting capacity, a
low Krafft temperature, and effective rheological properties.3−5
From this point of view, obtaining and studying new kinds of
gemini surfactants is of scientific and practical interest.6
The gemini surfactants studied most of all are of the
following structure:
[CnH2n+1(Alk)2N(CH2)sN(Alk)2CnH2n+1]Br2, where s = 2−
10, n = 10−18, Alk = Me, Et, Pr, Bu.
The surfactants of this type are abbreviated as m-s-m(Alk).
As is seen from the formula, in such surfactants, when varying
the length of the alkyl chain, the length of the spacer chain, and
Received: September 13, 2018
Accepted: February 6, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.jced.8b00815
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Journal of Chemical & Engineering Data
Article
Table 1. Specification of Chemical Samples
initial mass
purification
final mole
fraction purity
analysis
method
chemical name
1-bromononane
source
fraction purity
CAS no.
693-58-3
method
Alfa Aesar GmbH
& Co KG
>99%
none
1-bromododecane
1-bromotetradecane
Propylene oxide
Alfa Aesar
Sigma-Aldrich
“Organic Synthesis”
factory
>98%
>97%
>99%
143-15-7
112-71-0
75-56-9
none
none
none
ethylenediamine
N,N′-Bis(2-hydroxypropyl)ethylenediamine
Alfa Aesar
synthesis
≥99%
107-15-3
none
recrystallization
a
>95%
>96%
>97%
>95%
NMR,
b
IR
N,N′-bis(nonyl)-N,N′-bis(2-hydroxypropyl)
synthesis
synthesis
synthesis
recrystallization
recrystallization
recrystallization
NMR, IR
NMR, IR
NMR, IR
ethylenediammonium bromide
N,N′-bis(dodecyl)-N,N′-bis(2-hydroxypropyl)
ethylenediammonium bromide
N,N′-bis(tetradecyl)-N,N′-bis(2-hydroxypropyl)
ethylenediammonium bromide
a
b
Nuclear magnetic resonance. Infrared spectroscopy.
Scheme 1. Reaction Scheme of the Synthesis of N,N′-Bis(2-hydroxypropyl)ethylenediamine
Scheme 2. Synthesis of Cationic Gemini Surfactants by Interaction of N,N′-Bis(2-hydroxypropyl)ethylenediamine with 1-
Bromoalkanes
hydroxyethyl groups at the nitrogen atom of the headgroup.
They have established that the values of CMC and micelle
dissociation degree decrease with a rise of polarity of the
headgroup, but with an elongation of the spacer chain, the
mentioned values increase. As is seen, with a rise in polarity of
the headgroup in the surfactant molecules, their properties are
improved still more. There is an option to change properties of
the surfactant under the action of not only ethylol but also the
isopropylol group.15 However, in the literature, the gemini
surfactants containing a headgroup having an isopropylol
fragment at the nitrogen atom are actually not described. At
the same time, synthesis of the surfactants containing an
isopropylol group is easier and simpler.16 Moreover, in the case
of the surfactants having an isopropylol fragment in the
headgroup, effective petroleum-collecting, antibacterial, and
other properties are observed.15,17−19 From this standpoint,
the submitted article is dedicated to obtaining new-class
gemini surfactants containing an isopropylol fragment, study-
ing of their colloidal-chemical properties, as well as calculation
of thermodynamic parameters of micellization and adsorption
processes. Bactericide properties of the obtained gemini
surfactants against SRB are also investigated.
(Alfa Aesar GmbH & Co. KG, Germany), 1-bromododecane
(Alfa Aesar, England), and 1-bromotetradecane (Sigma-
Aldrich, Japan) of analytical grade were used. Information on
the chemicals, their purities, and suppliers is given in Table 1.
2.2. Method of N,N′-Bis(2-hydroxypropyl)-
ethylenediamine Synthesis. N,N′-bis(2-hydroxypropyl)-
ethylenediamine was synthesized through interaction of
ethylenediamine with PO at a 1:2 molar ratio according to
the following scheme (Scheme 1).
To synthesize N,N′-bis(2-hydroxypropyl)ethylenediamine,
0.1 mol of ethylenediamine was entered into a flat-bottom
flask, and 0.2 mol of PO was added to it. The reaction was
conducted at room temperature, in a nitrogen atmosphere over
24 h stirring with a magnetic mixer. As the reaction is
exothermal, the flask was placed into a water bath, and in this
way, a high temperature was prevented. Thus, generation of
byproducts did not take place. The yield of the reaction
product was 95%. It is a white paste-like substance. It dissolves
well in water, ethanol, acetone, ethyl acetate, and CCl4 and
partially in hexane. The structure of the synthesized N,N′-
bis(2-hydroxypropyl)ethylenediamine was confirmed by meth-
ods of NMR and IR spectroscopy. The spectra are given in
Figures S1 and S2 (Supporting Information).
2. EXPERIMENTAL PROCEDURES
2.3. Synthesis of Cationic Gemini Surfactants Based
on N,N′-Bis(2-hydroxypropyl)ethylenediamine. A total
of 0.025 mol of N,N′-bis(2-hydroxypropyl)ethylenediamine
and 25 mL of hexane were poured into a flat-bottom two-neck
flask. After formation of a homogeneous mixture, 0.055 mol of
1-bromononane (1-bromododecane or 1-bromotertadecane)
was added to it. The reaction was carried out in a flask
equipped with a magnetic stirrer, a reflux condenser, and a
heater over 18−20 h at the temperature of the boiling mixture.
2.1. Reagents and Instrumentation. Spectra of 1H
NMR and 13C NMR were recorded using a Bruker TOP SPIN
spectrometer (300.13 and 75.46 MHz) with chemical shifts (δ
in ppm) downfield from TMS using such a solvent as DMSO-
d6. IR spectra were registered by ALPHA FT-IR spectrometer
(Bruker) using KBr disks. Propylene oxide (PO) was a product
of the “Organic Synthesis” factory (Sumgayit, Azerbaijan).
Ethylenediamine (Alfa Aesar, Great Britain), 1-bromononane
B
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A scheme of the obtainment of the surfactants may be
presented as in Scheme 2.
doses of 15, 75, and 150 mg/kg. Incubation of the system was
made at a contact time of 3.0 h; all of the systems were
cultured in specific media for SRB over 21 days at a
temperature of 303 K.
To isolate the synthesized gemini surfactant from the
reaction mixture, vacuum distillation was performed. In this
way, the gemini surfactant was separated from the solvent and
unreacted 1-bromalkane. To purify the synthesized gemini
surfactants, they were recrystallized from acetone three times.
The yield of the obtained gemini surfactants equaled 93−95%.
They dissolve well in ethanol, acetone, and ethyl acetate and
partially in water. The purity degree of the cationic gemini
surfactants was determined by methods of NMR and IR
spectroscopy. The NMR and IR spectra of the surfactants and
their identification are given in Figures S4−S12 (Supporting
Information).
3. RESULTS AND DISCUSSION
3.1. Surface Properties of Synthesized Gemini
Surfactants. 3.1.1. Critical Micelle Concentration (CMC).
Surface tension values of the aqueous solutions of the
synthesized cationic gemini surfactants at the border with air
were determined at different temperatures (283, 293, 303, and
313 K), and γ−f(C) plots were built (Figures 1−3 or
2.4. Surface-Tension Measurements. The values of
surface tension at the border of aqueous solutions of the
synthesized cationic gemini surfactants with air were
determined using a KSV Sigma 702 tensiometer (Finland),
functioning according to the ring detachment method with an
accuracy of 0.1 mN/m. For preparing these solutions,
deionized water was used. The surface tension of this water at
the border with air at 298 K equals 72.1 mN/m. The
measurements were conducted at 283, 293, 303, and 313 K
with a temperature deviation 0.01 K. For maintaining the
needed temperature, water was circulated via the jacket of the
container.17
2.5. Electrical Conductometric Measurements. Specific
electrical conductivity (κ) of the aqueous solutions of the
purified cationic gemini surfactants was measured using an
“ANION 4120” (Russian Federation) conductometer.17 The
range of these measurements was 10−4 S/m to 10 S/m with a
relative error of no more than 2%. Temperature variation was
in the range from 273 up to 373 K.
Figure 1. Surface tension vs concentration plot of C9C2C9[iso-
Pr(OH)] at different temperatures. Temperature, K: (1) 283, (2)
293, (3) 303, (4) 313.
To carry out measurements of specific electrical con-
ductivity, aqueous solutions of the gemini surfactants were
prepared at various concentrations in the interval 0.001−2%.
The solutions of these surfactants were thermostated at a
necessary temperature in a water bath (deviations were no
more than 0.1 K). After each dilution, measurements were
made 3 min later. An average value of three to five
measurements was taken. In these measurements, bidistillate
water was used. Specific electrical conductivity of this water
had a value in the range 1.2−1.5 μS/cm at 298 K.
2.6. Dynamic Light Scattering (DLS) Measurements.
Dynamic light scattering (DLS) measurements were per-
formed via particle size analyzer (HORIBA LB-550, Japan).
The interval of size measurements was from 1 nm up to 6 μm.
The light source was a 650 nm laser diode of power 5 mW.
The measurements were conducted three times in the
temperature range 293−323 K. To estimate hydrodynamic
diameter (dh), the Stokes−Einstein equation (dh = kBT/
(3πηD) was applied, D being the diffusion coefficient; kB, the
Boltzmann constant; and η, solvent viscosity at absolute
temperature T.20 To carry out DLS measurements, three
concentrations were taken: 0.1, 0.2, and 0.3%.
2.7. Bactericidal Effectiveness Activity against Sul-
fate-Reducing Bacteria. The bactericide effectiveness of the
synthesized gemini surfactants against SRB growth was studied
in accordance with the serial dilution method. The used water
was put to a microbial inhibition test. This test was performed
according to ASTM D4412-84.21 A growth of about 1 000 000
bacteria cells in 1 g of water was reached. The synthesized
gemini surfactants were tested as a bactericide against SRB at
Figure 2. Surface tension vs concentration plot of C12C2C12[iso-
Pr(OH)] at different temperatures. Temperature, K: (1) 283, (2)
293, (3) 303, (4) 313.
Supporting Information Tables S1−S4). As is seen from
these plots, the surface tension values for these surfactants
become stabilized after a certain concentration. This indicates
full micellization at these concentrations. This concentration
corresponds to CMC. The CMC values for all three gemini
surfactants were determined at four different temperatures, and
these values are listed in Table 2. As is evident from the table,
with a temperature increase, the CMC value of the synthesized
cationic gemini surfactants decreases. This decrease of CMC
with a temperature increase is related to dehydration at the
C
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ethylol and propylol groups, the CMC values are lowered
when temperature rises. The CMC value of the similar
monomer-type surfactants containing an isopropylol group is
smaller than the value for surfactants having an ethylol group.
When the number of ethylol groups bonded to a nitrogen atom
rises, the CMC value decreases still more.13,14 As is seen from
Table 2, when the length of the alkyl chain in the synthesized
gemini surfactants is increased, the values of the CMC are
lowered, owing to more intensive hydrophobic interactions
between the surfactant molecules and micellar core. This
situation is observed in the case of similar surfactants with the
respective monoalkyl chain.22,23
3.1.2. Efficiency (pC20). The negative logarithmic value of
the surfactants concentration (C20) required lowering of the
surface tension at the water−air border by 20 mN/m, which is
called adsorption efficiency. It is expressed as pC20. The
adsorption efficiencies of the synthesized cationic gemini
surfactants are shown in Table 2. As is apparent from the table,
the values of pC20 for the obtained gemini surfactants vary in
the range 4.19−4.97. The pC20 value decreases as temperature
rises. If the pC20 value of the C12C2C12[iso-Pr(OH)] gemini
surfactant is compared with that of dodecylisopropylol
ammonium bromide,22 it will be clear that the pC20 value of
the gemini surfactant is higher. In comparison with
dodecylethylolisopropylol ammonium bromide, the values of
pC20 at the same temperature are very close to each other.22
When the alkyl chain of the obtained cationic gemini
surfactants becomes elongated, the pC20 value augments.
Therefore, elongation of the alkyl chain brings about a greater
tendency of the surfactant to be adsorbed at the water−air
interface. A similar regularity is observed in the case of other
gemini surfactants.24,25
Figure 3. Surface tension vs concentration plot of C14C2C14[iso-
Pr(OH)] at different temperatures. Temperature, K: (1) 283, (2)
293, (3) 303, (4) 313.
hydrophilic groups of the surfactants molecules. If, with a
temperature increase, the CMC value were increased, it would
be related to the destruction of water aggregates near the
hydrophobic fragments. Thus, of these two possible and
opposite processes, a prevalent one will determine the
character of the CMC variation in the given temperature
interval. Therefore, in the case of the synthesized surfactants,
the first phenomenondehydration near the hydrophilic
groupsis dominant, and this process continues in the
studied temperature interval.7 In the headgroup of butane-
diyl-1,4-bis(dodecyldialkyl)ammonium bromide-type surfac-
tants, an increase of alkyl group volume in the series methyl-,
ethyl-, propyl-, and butyl- causes a decrease in CMC.7 In the
case of the surfactants having methyl- and ethyl fragments in
the headgroup, with a temperature increase from 287.15 to
318.15 K, the CMC decreases at the beginning of this
temperature range, then rises.7 But, in the case of the
surfactants with propyl and butyl fragments, the CMC
decreases in most of that temperature range and only then
increases.7 In the case of the surfactants containing both
3.1.3. Effectiveness or Surface Pressure (πCMC). The surface
pressure values were computed using the following formula:
πCMC = γ0 − γCMC, where γ0 is the surface tension at the border
of water with air in the absence of surfactants and γCMC is the
surface tension value at the CMC. In Table 2, the values of the
surface pressure of the synthesized cationic gemini surfactants
are given at different temperatures. As is evident from the table,
Table 2. Surface Activity Parameters (Temperature, T; Critical Micelle Concentration, CMC; Equilibrium Surface Tension at
the CMC, γCMC; Effectiveness, πCMC; Efficiency, pC20; Maximum Surface Excess, Γmax; Minimum Surface Area, Amin; Degree of
Counterion Binding to Micelles, β; Free Energy of Micellization, ΔG°mic; Free Energy of Adsorption, ΔGa°d) of the Synthesized
a
Gemini Surfactants at 283, 293, 303, and 313 K
CMC × 103,
π,
γCMC
,
ΔGm°ic, kJ/
ΔGa°d, kJ/
surfactants
T, K
β
mol/kg
Γ
max × 1010, mol/cm2
A
min, Å2 mN/m
pC20
mN/m
mol
mol
b
c
C9C2C9[iso-Pr(OH)]
283
293
303
313
283
293
303
313
283
293
303
313
0.55
0.53
0.51
0.48
0.52
0.50
0.46
0.43
0.49
0.44
0.40
0.36
1.68
1.45
1.27
1.07
0.93
0.73
0.62
0.56
0.84
0.66
0.53
0.47
1.69
1.44
1.26
1.05
0.91
0.74
0.62
0.55
0.82
0.65
0.53
0.45
0.94
0.82
0.73
0.66
1.16
1.08
1.02
0.93
1.01
0.92
0.85
0.79
177.4
43.4
42.7
41.2
40.1
46.3
45.8
45.0
43.7
43.3
42.1
41.5
40.7
4.19
4.40
4.62
4.88
4.35
4.47
4.64
4.82
4.34
4.54
4.74
4.97
30.9
30.1
30.0
29.4
28.0
27.0
26.2
25.8
31.0
30.7
29.7
28.8
−51.38
−52.98
−54.40
−55.27
−52.88
−54.68
−55.14
−55.76
−51.81
−51.99
−52.41
−52.46
−56.01
−58.17
−60.03
−61.32
−56.86
−58.92
−59.55
−60.44
−56.12
−56.57
−57.27
−57.62
201.7
226.7
250.5
142.9
153.5
162.5
177.8
165.2
180.6
194.8
210.6
C12C2C12[iso-Pr(OH)]
C14C2C14[iso-Pr(OH)]
a
The standard uncertaintiesu are u(T) = 0.01 K and u(p) = 10 kPa. The combined expanded uncertainties Uc are Uc(β) = 0.005, Uc(CMC) = 2
× 10−5 mol/kg, Uc(Γmax × 1010) = 0.01 mol/cm2, Uc(Amin) = 0.5 Å2, Uc(π) = 0.1 mN/m, Uc(pC20) = 0.02, Uc(γ) = 0.1 mN/m, and Uc(ΔG°) =
0.03 kJ/mol (0.95 level of confidence). The CMC value is determined by surface tension measurements. The CMC value is determined by
specific electroconductivity measurements.
b
c
D
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the values of the surfactants surface pressures are reduced as
temperature is raised. When the alkyl chain length in the
obtained gemini surfactants is elongated from C9 to C14, at
first, the value of surface pressure rises then decreases. For the
gemini surfactants with a C12 alkyl chain, the πCMC value is
higher.
3.1.4. Maximum Surface Excess (Γmax). Maximum surface
excess (Γmax) characterizes the surface area occupied by
surfactant molecules at the unit area of the interface. This
quantity varies depending on the length of the hydrophobic
chain, nature and structure of the hydrophilic group as well as
temperature. The Γmax values were computed according to the
surface tension isotherm using the Gibbs equation:26
dγ
1
nRT
Γmax = −
lim
CMC
C→C
(1)
d ln C
Figure 4. Dependence of specific electrical conductivity on
concentration of C9C2C9[iso-Pr(OH)] at different temperatures.
Temperature, K: (1) 283, (2) 293, (3) 303, (4) 313.
where dγ/(d ln C) denotes surface activity at a certain absolute
temperature T and R is the universal gas constant. From Table
2, it may be seen that the Γmax value decreases with a
temperature increase. In the case of gemini surfactants with an
alkyl chain length of C12, the Γmax value is higher as compared
with the other surfactants. As temperature increases, thermal
motion of the surfactant molecules is intensified, and packing
capacity becomes deteriorated. As a result, the number of the
surfactant molecules adsorbed on a unit area, i.e., the Γmax
value, becomes lowered.
3.1.5. Minimum Surface Area (Amin). When an area of
minimal surface of a polar group is spoken about, a minimum
surface area occupied by one molecule during adsorption at the
interface is meant. This parameter is calculated by the formula
shown below:
Amin = 1016/N Γmax
(2)
A
Figure 5. Dependence of specific electrical conductivity on
concentration of C12C2C12[iso-Pr(OH)] at different temperatures.
Temperature, K: (1) 283, (2) 293, (3) 303, (4) 313.
In Table 2, the Amin values of the synthesized gemini
surfactants are given at various temperatures. As is seen from
the table, with a temperature increase, the Γmax value is
lowered. So, the Amin value increases. It is known that, in the
case of gemini surfactants, with an elongation of the alkyl
chain, the Amin value augments. However, for the synthesized
gemini surfactants, as the alkyl chain length increases from C9
to C12, the Amin value decreases, but at the transition from C12
to C14, the value of Amin starts to increase. A similar regularity
is observed in the case of surfactants of other classes, too.27,28
Small values of Amin indicate that the molecules of that
surfactant are placed at the interface more tightly and
compactly. Among main factors impacting the Amin value,
nature and structure of the polar group of surfactant should be
named. In gemini surfactants, with an elongation of the spacer
chain and with an increase of the number of hydroxy groups,
the Amin value rises.13 In the case of cationic-type gemini
surfactants, when methyl groups linked to the nitrogen atom in
the polar group are replaced by ethylol groups, an increase of
the Amin value is observed.14 Similarly, in conventional cationic
surfactants, when the ethylol group in the polar fragment is
substituted by a isopropylol group, an increase in the Amin
value takes place.23
Figure 6. Dependence of specific electrical conductivity on
concentration of C14C2C14[iso-Pr(OH)] at different temperatures.
Temperature, K: (1) 283, (2) 293, (3) 303, (4) 313.
3.2. Specific Electrical Conductivity. The values of
specific electrical conductivity values of aqueous solutions of
the synthesized gemini surfactants have been determined at
different (273, 283, 303, and 313 K) temperatures. According
to these values, plots of specific electrical conductivity from
surfactant concentration were built (Figures 4−6). As is
evident from the figures, there is a linear dependence of the κ
values on the concentration. This dependence is expressed in
the form of two straight lines. Their intersection point
corresponds to CMC. To find more correct results, the
derivative plots were also used (Figure S13, Supporting
Information). The values of CMC determined by conducto-
E
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metric method are presented in Table 2. It is noticed from the
table that CMC values determined via the tensiometric
method are close to those found via the conductometric
method. The ratio of the slopes at the concentrations higher
(S2) and lower (S1) than CMC equals a dissociation degree
(α) of a counterion: α = S2/S1. A binding degree of the
counterion (β) is found via the following formula:
of dodecylisopropylolammonium bromide, which is a conven-
tional cationic surfactant with a similar headgroup, is 0.28 at
298 K.22 In the case of C9C2C9[iso-Pr(OH)], at 293−313 K, β
varies in the interval 0.43−0.52.
3.3. Dependence of Aggregates Dimensions on
Surfactant Concentration and Temperature. The diam-
eters of the aggregates formed by the synthesized gemini
surfactants in aqueous solutions have been determined via
dynamic light scattering (DLS) method. With this purpose,
solutions at three different concentrations higher than CMC
have been prepared, and the diameters of the surfactant
aggregates formed in them have been determined (Figures
8−10). As is seen in Figure 8, when the concentration of
β = 1 − α
(3)
In Table 2, the values of β for the obtained gemini surfactants
are given at various temperatures. As is seen from the table, the
β values diminish as temperature rises. One of the reasons for
such correlation is intensification of thermal motion of the
surfactant aggregates with temperature increasing and the
resulting transition of the counterions from the inner parts of
the aggregates to the aqueous phase. The other reason is
discussed in the next section. The plot β vs temperature is
depicted in Figure 7. As is clear from the figure, this
Figure 8. DLS measurements of the size distributions for C9C2C9[iso-
Pr(OH)] at different concentrations. Concentration, wt %: (1) 0.1,
(2) 0.2, (3) 0.3.
Figure 7. Variation of degree of counterion association (β) with
temperature (T) for the gemini surfactants: C9C2C9[iso-Pr(OH)]
(1), C12C2C12[iso-Pr(OH)] (2), and C14C2C14[iso-Pr(OH)]. The
solid lines are fitted curves (eq 4).
dependence is linear, and it may be expressed by the following
equation:
β = a + bT
(4)
where a and b are fitting parameters, their values being given in
Table 3. As is seen from Table 3, with an elongation of the
Table 3. Fitting Constants Obtained by Fitting the Plots of
β versus T (a, b) with eq 4
Gemini surfactants
a
b
Figure 9. DLS measurements of the size distributions for
C12C2C12[iso-Pr(OH)] at different concentrations. Concentration,
wt %: (1) 0.1, (2) 0.2, (3) 0.3.
C9C2C9[iso-Pr(OH)]
C12C2C12[iso-Pr(OH)]
C14C2C14[iso-Pr(OH)]
1.2029
1.4013
1.7039
0.0023
0.0031
0.0043
alkyl chain of the gemini surfactants, the value of a augments,
whereas the b value decreases. Moreover, when the alkyl chain
in the gemini surfactants is elongated, the β values diminish.
This effect is explained by a decrease in surface charge density
inside micelles. A longer hydrocarbon group promotes
micellization of surfactants with a lower surface/volume
ratio. This indicates a more compact packing of headgroups
and their binding a larger amount of counterions. The β value
C9C2C9[iso-Pr(OH)] rises from 0.1 to 0.2%, the diameter of
the aggregates increases from 11.4 to 450 nm. When the
concentration reaches 0.3%, the diameter of the aggregates
decreases down to 250 nm. Furthermore, with an increase of
the aggregates diameter, their polydispersity rises as well. In
the case of C12C2C12[iso-Pr(OH)] and C14C2C14[iso-Pr(OH)]
gemini surfactants, an increase in the concentration from 0.1 to
0.3% actually does not impact the dimensions of their
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Figure 10. DLS measurements of the size distributions for
C14C2C14[iso-Pr(OH)] at different concentrations. Concentration,
wt %: (1) 0.1, (2) 0.2, (3) 0.3.
Figure 12. DLS measurements of the size distributions for
C12C2C12[iso-Pr(OH)] at different temperatures.
aggregates in water. The diameters of aggregates of these two
gemini surfactants are very close to each other, equaling ∼150
nm. When temperature rises from 293 to 323 K, the character
of variation of the aggregates diameters has been determined
(Figures 11−13). The impact of temperature on the diameters
Figure 13. DLS measurements of the size distributions for
C14C2C14[iso-Pr(OH)] at different temperatures.
the aggregates increases. At 313 and 323 K, dispersity degrees
are approximately the same. Influence of temperature on the
dimensions of aggregates formed in a 0.2% aqueous solution of
C14C2C14[iso-Pr(OH)] gemini surfactant is the same as in the
case of C12C2C12[iso-Pr(OH)] (Figure 13). But, when
temperature rises from 293 to 323 K, the diameter of the
aggregates of C14C2C14[iso-Pr(OH)] diminishes; up to 313 K
the monodispersity degree increases and after 313 K decreases.
Many authors29,30 came to the conclusion that the binding
degree (β) of the surfactant counterion depends on
dimensions of the aggregates. When these dimensions increase,
more convenient conditions are created for the interaction of a
counterion with an aggregate. As dimensions of aggregates
decrease with a temperature increase, the value of β diminishes
as well. Though many researchers mentioned a decrease of
aggregate dimensions when the temperature is elevated, a
reason for this phenomenon was not explained.29−31
Figure 11. DLS measurements of the size distributions for
C9C2C9[iso-Pr(OH)] at different temperatures.
of the aggregates formed in 0.2% aqueous solution of the
C9C2C9[iso-Pr(OH)] gemini surfactant is depicted in Figure
11. As is seen from the figure, at 293 K the dimensions of the
aggregates vary in the range 100−1000 nm. When temperature
rises up to 303 K, the average diameter of the aggregates
decreases down to 8.7 nm, and monodispersity of the
aggregates increases 2.5 times. As temperature increases from
303 up to 323 K, the dimensions of the aggregates actually do
not alter. But monodispersity of the aggregates decreases, and
the tendency toward the formation of aggregates of small
diameters is enhanced. The influence of temperature on the
dimensions of the aggregates formed in an aqueous solution of
C12C2C12[iso-Pr(OH)] of 0.2% concentration is demonstrated
in Figure 12. As is noticeable from the figure, when the
temperature rises, the average diameter of the surfactant
aggregates decreases. So, at 293 K, the average diameter is
around 150 nm, whereas at 323 K, this diameter equals 87 nm.
In addition, with a temperature increase, the monodispersity of
3.4. Gibbs Energy of Micellization and Adsorption.
The change of Gibbs free energy in the micellization process
for gemini surfactants having two alkyl chains and two
monovalent counterions was computed according to the
following formula:32
°
ΔGmic = RT(1 + 2β) ln XCMC
(5)
G
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where R is the universal gas constant, T is the absolute
temperature, β is the binding degree of the counterion, and
X
CMC is the CMC in molar fraction. XCMC = CMC/55.4, where
CMC is expressed in mol/L; 55.4 shows the number of moles
in 1 L of water (298 K). Using eq 5, ΔG°mic values for the
synthesized gemini surfactants were calculated at different
temperatures and are presented in Table 2. As is clear from the
table, the values of ΔG°mic are negative, and they decrease as
temperature rises. Therefore, in the studied temperature
interval, the micellization process in an aqueous solution of
the obtained gemini surfactants occurs spontaneously. As the
length of the alkyl chain of the gemini surfactants increases
from C9 to C12, the ΔGm°ic value is lowered. But when the alkyl
chain is elongated from C12 to C14, the value of ΔG°mic rises. As
is seen from eq 5, under isothermal conditions, the ΔG°mic value
depends on CMC and β. As the alkyl chain length rises from
C9 to C14, the values of CMC and β decrease. According to eq
5, when XCMC decreases, ΔG°mic values are lowered, and when β
decreases, the ΔG°mic values are increased. When the alkyl chain
elongates from C12 to C14, an impact of the β value diminution
is predominant, and it influences the value of ΔG°mic more. As a
result, the value of ΔG°mic increases. A little larger decrease of
the β value is stipulated by hindrances created by isopropylol
fragments in the headgroup as well as the alkyl chain for
interaction of positively and negatively charged ions of the
surfactant. A similar regularity was observed in other classes of
surfactants as well.33
Figure 14. Variation of ΔG°mic (1), ΔH°mic (2), and − TΔS°mic (3) with
temperature for C9C2C9[iso-Pr(OH)] in aqueous solutions.
The change of Gibbs free energy for the adsorption process
of the surfactants at the water−air interface was calculated via
the formula given below:26
°
°
ΔGad = ΔGmic − 0.6023πCMCACMC
(6)
In Table 2, the values of ΔG°ad for the obtained gemini
surfactants at the water−air border are given. As becomes
evident from the table, with a temperature rise, the value of
ΔGa°d diminishes abruptly. In the case of C14C2C14[iso-
Pr(OH)], with a temperature increase, the ΔG°ad value is
lowered insignificantly. From a comparison of the values of
ΔGm°ic and ΔG°ad, it is evident that the adsorption process takes
place more readily than the micellization process.
Figure 15. Variation of ΔG°mic(1), ΔH°mic (2), and − TΔS°mic (3) with
temperature for C12C2C12[iso-Pr(OH)] in aqueous solutions.
3.5. Enthalpy−Entropy Compensation for Micelliza-
tion. The enthalpy change for the micellization process of the
synthesized gemini surfactants in aqueous solution was
calculated according to the Gibbs−Helmholtz equation:32
°
∂T
∂(ΔGmic/T)
ΔHmic = −T2
°
(7)
Using ΔG°mic and ΔHm°ic, the value of the entropy change for
the micellization process was computed via the following
formula:32
°
°
ΔHmic − ΔGmic
°
ΔSmic
=
(8)
T
The dependences of ΔG°mic, ΔH°mic, and ΔS°mic on temper-
ature are given in Figures 14−16. As is seen from the figures,
distinct from ΔGm°ic, the temperature dependences of ΔH°mic
and ΔSm°ic are more abrupt. When temperature rises, hydrogen
bonding in water becomes weaker. As a result, for hydrophobic
hydration, the entropic term becomes less important, whereas
dispersion interactions acquire prevalence.34 In this case, the
value of the −TΔS term increases, but the value of ΔH
decreases. As is seen from the figures, the ΔH value is negative
Figure 16. Variation of ΔG°mic (1), ΔH°mic (2), and − TΔS°mic (3) with
temperature for C14C2C14[iso-Pr(OH)] in aqueous solutions.
for C9C2C9[iso-Pr(OH)] in the 283−313 K interval and for
C12C2C12[iso-Pr(OH)] and C14C2C14[iso-Pr(OH)] in the
293−313 K range; i.e., at these temperature intervals,
micellization is an exothermal process. As is known, the
H
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enthalpy change of micelle formation in aqueous solution is
mainly a result of hydrophobic and electrostatic interac-
tions.34,35 When micellization takes place in water, the
hydrocarbon chains of gemini surfactant molecules have a
tendency to transition from the aqueous phase to the bulk of
micelles, and the hydrating H2O molecules are simultaneously
separated from the hydrocarbon fragment. This process is
exothermal.36 An overview of electrostatic interactions may be
taken from two standpoints. The first is repelling between
headgroups and counterions, this interaction being exothermal.
The second of them is attraction forces between headgroups
and counterions. This process is endothermal.37,38 In the given
case, repelling between gemini cations is stronger in
comparison with attraction. Hence, the overall character of
the electrostatic interactions is exothermal as well.
The values computed for ΔSm°ic are positive. This indicates
that the micelles are of a lesser order in comparison with the
free surfactant. Entropy is the main driving force for micelle
formation, where a very regular structure of the water near the
hydrophobic chains of surfactants is formed.39 With a rise in
temperature, the contribution of entropy to micellization
decreases, as at higher temperatures H2O molecules near the
hydrophobic chains of the surfactant molecule get certain
randomness; i.e., destruction of the iceberg structure takes
place.40 So, micelle formation is characterized by a prevalent
contribution of entropy at low temperatures, whereas
contributions of both the entropy and enthalpy are dominant
at high temperatures.38 At low temperatures, the micelle
formation process is driven by entropy (−TΔS < ΔH), but at
high temperatures, enthalpy becomes more decisive (−TΔS >
ΔH). Obviously, ΔGmic values are dependent on the relative
quantities of enthalpy and entropy in the two processes taking
place within the system.41
results, with an elongation of the alkyl chain of the synthesized
gemini surfactants, their antibacterial properties against SRB
are weakened. The highest antibacterial effect among the
obtained gemini surfactants is demonstrated by C9C2C9[iso-
Pr(OH)]. The biocidal impact of cationic surfactants is based
on electrostatic interaction. This interaction occurs between a
negatively charged cellular membrane and a positively charged
fragment of the surfactant. The main impact is related to the
positive charge, but a length of the alkyl chain is also
important. Thus, in conventional surfactants, with an
elongation of the alkyl chain, their adsorption ability rises.
One of the main reasons for a high antibacterial effect is a good
adsorption capacity.42 Some authors mentioned that the
cationic surfactants with the C12 chain possess a more effective
bactericidal property.43 But, in some cases, information is
reported that the cationic surfactants are more effective
bactericides when they contain a C10 chain.27 It may be
supposed that the surfactant C9C2C9[iso-Pr(OH)] has a higher
adsorption capacity due to a smaller value of ΔG°ad, and
therefore, it manifests a stronger antibacterial property.
4. CONCLUSION
A new class of gemini surfactants was synthesized on the basis
of N,N′-bis(2-hydroxypropyl)ethylenediamine and alkyl bro-
mides. The colloidal-chemical parameters of the synthesized
surfactants have been determined by tensiometric and
conductometric methods at various temperatures (283, 293,
303, and 313 K). It was established that, with a temperature
increase, CMC, πCMC, Γmax, and β decrease, but Amin and pC20
increase. At the same time, ΔG°mic, ΔHm°ic, and ΔSm°ic are
lowered with a temperature increase. Via the method of
dynamic light scattering, it was shown that the diameters of
aggregates of the cationic gemini surfactants C12C2C12[iso-
Pr(OH)] and C14C2C14[iso-Pr(OH)] in water do not actually
depend on the surfactant concentration, but with a temper-
ature increase, the diameters of the aggregates decrease. The
antibacterial properties of the synthesized cationic surfactants
against SRB depend on the length of the alkyl chain. With an
elongation of this chain, the antibacterial properties are
weakened.
3.6. SRB Bactericidal Properties of the Gemini
Surfactants. SRBs are one of the main sources of H2S,
which raises the acidity and corrosiveness of brine, causing
cracking and blistering in metals, especially in the field of
petroleum production. To fight SRBs, special reagents called
bactericides are used to inhibit the development of these very
dangerous bacteria. The obtained gemini cationics were tested
in accordance with the serial dilution method against SRB in
water. From Table 4, it is seen that the gemini surfactant
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.8b00815.
■
S
Table 4. Antibacterial Effect of the Synthesized Gemini
a
Surfactants against SRB
concentration of gemini surfactants,
mg/kg
1
IR, H NMR, and 13C NMR spectra of N,N′-bis(2-
hydroxypropyl)ethylenediamine and gemini surfactants
(Figures S1−S12); dependence of surface tension on
natural logarithm of molality for gemini surfactants at
different temperatures (Tables S1−S3); dependence of
specific electrical conductivity on concentration of
gemini surfactants at different temperatures (Tables
S4−S6) (PDF)
Gemini surfactants
15
75
150
C9C2C9[iso-Pr(OH)]
C12C2C12[iso-Pr(OH)]
C14C2C14[iso-Pr(OH)]
Nil
103
104
Nil
Nil
103
Nil
Nil
Nil
a
The figure in the table show the number of bacteria cells in 1 g of
water.
C9C2C9[iso-Pr(OH)] can completely stop the SRB growth at a
very low concentration (15 mg/kg). The gemini surfactant
C12C2C12[iso-Pr(OH)] does not fully inhibit development of
SRB at a concentration 15 mg/kg, but at a 75 mg/kg
concentration, it has an effective action. The gemini surfactant
C14C2C14[iso-Pr(OH)] exhibits a relatively weak effect at low
concentrations. At a concentration of 150 mg/kg, it is able to
fully stop the growth of SRB. As is evident from the obtained
AUTHOR INFORMATION
Corresponding Author
*Tel.: +99450 545 20 48. Fax: +99412 490 24 76. E-mail:
revan_chem@mail.ru.
■
ORCID
Ravan A. Rahimov: 0000-0001-5619-4041
Fedor I. Zubkov: 0000-0002-0289-0831
I
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hydroxyethyl and hydroxypropyl head group. J. Chem. Eng. Data
2017, 62, 3297−3305.
Funding
The publication was prepared with the support of the “RUDN
University Program 5-100.” The authors thank the Institute of
Petrochemical Processes of National Academy of Sciences of
Azerbaijan for supporting this research.
(18) Sun, Y.; Wang, Ch.; Wang, W.; Yang, X.; Di Serio, M.; Zhi, L.
Micellar Properties for Propoxylated Surfactants in Water/Alcohol
Solvent Mixtures and Their Antibacterial and Polyester Fabric
Antistatic Performances. J. Surfactants Deterg. 2016, 19, 543−552.
(19) Liu, W.; Liu, W.; Wei, D.; Li, M.; Zhao, Q.; Xu, Sh. nthesis of
N,N-Bis(2-hydroxypropyl)laurylamine and its flotation on quartz.
Chem. Eng. J. 2017, 309, 63−69.
Notes
The authors declare no competing financial interest.
(20) Taleb, K.; Mohamed-Benkada, M.; Benhamed, N.; Saidi-
Besbes, S.; Grohens, Y.; Derdour, A. Benzene ring containing cationic
gemini surfactants: Synthesis, surface properties and antibacterial
activity. J. Mol. Liq. 2017, 241, 81−90.
(21) ASTM D4412-84, Standard Test Methods for Sulfate-Reducing
Bacteria in Water and Water-Formed Deposits; ASTM International,
2009.
(22) Asadov, Z. H.; Rahimov, R. A.; Ahmadova, G. A.; Mammadova,
Kh.A.; Gurbanov, A. V. Synthesis and Characteristics of Dodecyl
Isopropylolamine and Derived Surfactants. J. Surfactants Deterg. 2016,
19, 145−153.
(23) Burczyk, B.; Wilk, K. A. Solution properties of selected
functionalized surfactants. Prog. Colloid Polym. Sci. 1990, 82, 249−
252.
REFERENCES
■
(1) Menger, F. M.; Keiper, J. S. Gemini Surfactants. Angew. Chem.,
Int. Ed. 2000, 39, 1906−1920.
(2) Zhang, Sh.; Yu, J.; Wu, J.; Tong, W.; Lei, Q.; Fang, W.
Micellization Parameters of Six Gemini Quaternary Ammonium
Surfactants from Measurements of Conductivity and Surface Tension.
J. Chem. Eng. Data 2014, 59, 2891−2900.
(3) Engin Ozdil, S.; Akbaş, H.; Boz, M. Synthesis and
Physicochemical Properties of Double-Chain Cationic Surfactants. J.
Chem. Eng. Data 2016, 61, 142−150.
(4) Mirgorodskaya, A. B.; Valeeva, F. G.; Lukashenko, S. S.;
Kushnazarova, R. A.; Prokop'eva, T. M.; Zubareva, T. M.; Mikhailov,
V. A.; Zakharova, L. Y. Dicationic hydroxylic surfactants: Aggregation
behavior, guesthost interaction and catalytic effect. J. Mol. Liq. 2018,
250, 229−235.
(5) El Achouri, M.; Infante, M. R.; Izquierdo, F.; Kertit, S.;
Gouttaya, H. M.; Nciri, B. Synthesis of some cationic gemini
surfactants and their inhibitive effect on iron corrosion in hydro-
chloric acid medium. Corros. Sci. 2001, 43, 19−35.
(6) Kumar, N.; Tyagi, R. Industrial Applications of Dimeric
Surfactants: A Review. J. Dispersion Sci. Technol. 2014, 35, 205−214.
(7) Zhang, Q.; Gao, Zh.; Xu, F.; Tai, Sh. Effect of hydrocarbon
structure of the headgroup on the thermodynamic properties of
micellization of cationic gemini surfactants: An electrical conductivity
study. J. Colloid Interface Sci. 2012, 371, 73−81.
(8) Li, Q.; Wang, X.; Yue, X.; Chen, X. Unique Phase Behaviors in
the Gemini Surfactant/EAN Binary System: The Role of the
Hydroxyl Group. Langmuir 2015, 31, 13511−13518.
(9) Zhou, T.; Liu, Sh.; You, Y.; Xu, R.; Zhao, J. Micellization and
Adsorption of Heterogemini Surfactants Containing a Hydroxyl
Headgroup in Aqueous Solution. J. Chem. Eng. Data 2016, 61, 2915−
2922.
̈
(24) Xu, D.; Ni, X.; Zhang, C.; Mao, J.; Song, Ch. Synthesis and
properties of biodegradable cationic gemini surfactants with diester
and flexible spacers. J. Mol. Liq. 2017, 240, 542−548.
(25) Ao, M.; Xu, G.; Zhu, Y.; Bai, Y. Synthesis and properties of
ionic liquid-type Gemini imidazolium surfactants. J. Colloid Interface
Sci. 2008, 326, 490−495.
(26) Rosen, M. J. Surfactants and Interfacial Phenomena, third ed.;
John Wiley: New Jersey, 2004.
(27) Li, H.; Yu, Ch.; Chen, R.; Li, J.; Li, J. Novel ionic liquid-type
Gemini surfactants: Synthesis, surface property and antimicrobial
activity. Colloids Surf., A 2012, 395, 116−124.
(28) Li, X.; Hu, Zh.; Zhu, H.; Zhao, S.; Cao, D. Synthesis and
Properties of Novel Alkyl Sulfonate Gemini Surfactants. J. Surfactants
Deterg. 2010, 13, 353−359.
(29) Frizzo, C. P.; Bender, C. R.; Salbego, P. R. S.; Black, G.; Villetti,
M. A.; Martins, M. A. P. Thermodynamic properties of the
aggregation behavior of a dicationicionic liquid determined by
different methods. Colloids Surf., A 2016, 494, 1−8.
(10) Pei, X.; You, Y.; Zhao, J.; Deng, Y.; Li, E.; Li, Zh. Adsorption
and aggregation of 2-hydroxyl-propanediyl-α,ω-bis(dimethyldodecyl
ammonium bromide) in aqueous solution: Effect of intermolecular
hydrogen-bonding. J. Colloid Interface Sci. 2010, 351, 457−465.
(11) Pei, X.; Zhang, Q.; Liu, Zh.; Song, B.; Li, R.; Zhao, J.; Cui, Zh.
Surface dilatational properties of Gemini surfactants containing
multiple hydroxyl groups. Colloid Polym. Sci. 2016, 294, 1405−1412.
(12) Huang, X.; Han, Y.; Wang, Y.; Cao, M.; Wang, Y. Aggregation
properties of cationic gemini surfactants with dihydroxyethylamino
headgroups in aqueous solution. Colloids Surf., A 2008, 325, 26−32.
(13) Borse, M. S.; Devi, S. Dependence of aggregation behavior and
physicochemical properties of bis-cationic surfactants on the polarity
of surfactant head group. Colloids Surf., A 2004, 245, 1−8.
(14) Borse, M.; Sharma, V.; Aswal, V. K.; Goyal, P. S.; Devi, S. Effect
of head group polarity and spacer chain length on the aggregation
properties of gemini surfactants in an aquatic environment. J. Colloid
Interface Sci. 2005, 284, 282−288.
(15) Asadov, Z. H.; Ahmadova, G. A.; Rahimov, R. A.; Abilova, A.
Z.; Zargarova, S. H.; Zubkov, F. I. Synthesis and properties of
quaternary ammonium surfactants based on alkylamine, propylene
oxide and 2-chloroethanol. J. Surfactants Deterg. 2018, 21, 247−254.
(16) Asadov, Z. H.; Rahimov, R. A.; Mammadova, Kh.A.;
Ahmadova, G. A.; Ahmadbayova, S. F. Synthesis and colloidal-
chemical properties of surfactants based on alkyl amines and
propylene oxide. Tenside, Surfactants, Deterg. 2015, 52, 287−293.
(17) Asadov, Z. H.; Ahmadova, G. A.; Rahimov, R. A.; Abilova, A.
Z.; Nazarov, I. G.; Zubkov, F. I. Surface activity, adsorption, and
micellization parameters of ammonium surfactants containing a
(30) Ao, M.; Huang, P.; Xu, G.; Yang, X.; Wang, Y. Aggregation and
thermodynamic properties of ionic liquid-type gemini imidazolium
surfactants with different spacer length. Colloid Polym. Sci. 2009, 287,
395−402.
(31) Wu, X.; Dai, C.; Fang, S.; Li, H.; Wu, Y.; Sun, X.; Zhao, M. The
effect of hydroxyl on the solution behavior of quaternary ammonium
gemini surfactant. Phys. Chem. Chem. Phys. 2017, 19, 16047−16056.
(32) Kabir-ud-Din; Koya, P. A. Micellar Properties and Related
Thermodynamic Parameters of the 14−6-14, 2Br- Gemini Surfactant
in Water + Organic Solvent Mixed Media. J. Chem. Eng. Data 2010,
55, 1921−1929.
(33) Xing, H.; Yan, P.; Zhao, K-Sh.; Xiao, J.-X. Effect of headgroup
size on the thermodynamic properties of micellization of dodecyl-
trialkylammonium bromides. J. Chem. Eng. Data 2011, 56, 865−873.
(34) Myers, D. Surfaces, Interfaces, and Colloids: Principles and
Applications, 2nd ed.; Wiley-VCH: New York, 1999.
(35) Muller, N. Temperature dependence of critical micelle
concentrations and heat capacities of micellization for ionic
surfactants. Langmuir 1993, 9, 96−100.
(36) Li, Y. J.; Reeve, J.; Wang, Y. L.; Thomas, R. K.; Wang, J. B.;
Yan, H. K. Microcalorimetric study on micellization of nonionic
surfactants with a benzene ring or adamantane in their hydrophobic
chains. J. Phys. Chem. B 2005, 109, 16070−16074.
(37) Shimizu, S.; Pires, P. A. R.; El Seoud, O. A. Thermodynamics of
micellization of benzyl (2-acylaminoethyl) dimethylammonium
chloride surfactants in aqueous solutions: A conductivity and titration
calorimetry study. Langmuir 2004, 20, 9551−9559.
J
DOI: 10.1021/acs.jced.8b00815
J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
(38) Shi, L. J.; Li, N.; Zheng, L. Q. Aggregation behavior of long
chain N-aryl imidazolium bromide in a room temperature ionic liquid.
J. Phys. Chem. C 2011, 115, 18295−18301.
(39) Hiemenz, P. C.; Rajagopalan, R. Principles of Colloid and Surface
Chemistry; Marcel Dekker Inc.: New York, 1997.
(40) Fan, Zh.; Tong, W.; Zheng, Q.; Lei, Q.; Fang, W. Surface
activity and micellization parameters of quaternary ammonium
surfactants containing a hydroxyethyl group. J. Chem. Eng. Data
2013, 58, 334−342.
(41) Wei, Y.; Wang, F.; Zhang, Zh.; Ren, Ch.; Lin, Y. Micellization
and thermodynamic study of 1-alkyl-3-methylimidazolium tetrafluor-
oborate ionic liquids in aqueous solution. J. Chem. Eng. Data 2014, 59,
1120−1129.
(42) Tawfik, S. M. Simple one step synthesis of gemini cationic
surfactant-based ionic liquids: Physicochemical, surface properties and
biological activity. J. Mol. Liq. 2015, 209, 320−326.
(43) Liu, W-Sh.; Wang, Ch-H.; Sun, J.-F.; Hou, G.-G.; Wang, Y.-P.;
Qu, R.-J. Synthesis, characterization and antibacterial properties of
dihydroxy quaternary ammonium salts with long chain alkyl bromides.
Chem. Biol. Drug Des. 2015, 85, 91−97.
K
DOI: 10.1021/acs.jced.8b00815
J. Chem. Eng. Data XXXX, XXX, XXX−XXX