Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

Article abstract of DOI:10.1007/s11743-015-1759-6

A series of cetyl alcohol based anionic bis-sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ _CMC), surface pressure at the CMC (π _CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ _CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.

Full text of DOI:10.1007/s11743-015-1759-6

J Surfact Deterg
DOI 10.1007/s11743-015-1759-6
ORIGINAL ARTICLE
Surface and Aggregation Properties of Synthesized Cetyl Alcohol
Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution
Vinayika Singh1 Rashmi Tyagi1
•
Received: 4 March 2015 / Accepted: 5 November 2015
Ó AOCS 2015
Abstract A series of cetyl alcohol based anionic bis-sul-
fosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6
and BSGSCA1,8) with different spacer lengths was pre-
pared using dibromoalkanes. The surfactant structure was
elucidated using elemental analysis, Fourier transform
infrared spectroscopy (FT-IR) and nuclear magnetic reso-
nance spectroscopy (NMR). Surface tension measurements
were used to determine the critical micelle concentration
(CMC), the surface tension at the CMC (cCMC), surface
pressure at the CMC (pCMC) and efficiency of adsorption
(pC20). On the basis of surface studies, the CMC and cCMC
decreases with increasing length of the spacer group. The
micelle aggregation number, determined by fluorescence
quenching studies, increases with increasing surfactant
concentration above the CMC. The micropolarity in the
micelle increases with increasing length of the spacer and
decreases with increasing surfactant concentration.
detergents and cleaning products, cosmetics and toiletries
etc. due to good water solubility, low CMC, better wetting
ability, foaming, aggregation and rheological properties as
well as excellent surface activity in aqueous solution as
compared to single chain conventional surfactants [1–6].
In recent years, researchers have investigated the prop-
erties of anionic dimeric surfactants [7–9]. Numerous
reports have been published on the synthesis and surface
properties of anionic gemini surfactants such as carboxy-
late [10–13], sulfate [14, 15], sulfonate [16], and phosphate
[17–20]. The properties of anionic gemini surfactant with
sulfosuccinate head groups have been comparatively less
reported [21]. Anionic sulfosuccinate surfactants are
amongst the mildest of all the anionic surfactants [22].
Sulfosuccinate surfactants have good performance proper-
ties as well as surface active properties viz. low critical
micelle concentration, high effectiveness in reducing sur-
face tension, strong wetting etc. and can used in numerous
fields such as cosmetics, textile and polymers [23].
Keywords Bis-sulfosuccinate gemini surfactants Á
Surface active properties Á Critical micelle concentration Á
Aggregation number Á Micropolarity
The purpose of this research work is to synthesize cetyl
alcohol based gemini sulfosuccinate surfactants
(BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8). Three dif-
ferent a,x-dibromo alkanes, i.e., 1,4-dibromo butane; 1,6-
dibromo hexane and 1,8-dibromo octane were used as a
flexible spacers. The surface and aggregation properties
were investigated in aqueous solutions.
Introduction
Gemini surfactants are dimeric surfactants with two
amphiphilic moieties connected with a spacer group.
Gemini surfactants are used in numerous fields, such as
Experimental Section
Materials
& Vinayika Singh
vinayika28singh@gmail.com
Rashmi Tyagi
rashmi.tyagi@juet.ac.in
Cetyl alcohol (99.0 %), maleic anhydride (99.0 %), ethylene
glycol (99.0 %), sodium bisulfite (58.0 %), p-toluene sul-
fonic acid (98.0 %), benzophenone (99.0 %), chloroform
1
Department of Chemical Engineering, Jaypee University of
Engineering and Technology, Guna, MP 473226, India
123

J Surfact Deterg
(99.0–99.4 %), petroleum ether (60–800 C) and sodium
chloride (99.5 %) were procured from Loba Chemie Pvt.
Ltd., Mumbai (India). Toluene (99 %) was purchased from
Merck specialities, Pvt. Ltd., Mumbai. 1,4-dibromo butane
(98.0 %), 1,6-dibromo hexane (98.0 %) and 1,8-dibromo
octane (98.0 %) were obtained from Spectrochem Pvt. Ltd.,
Mumbai (India). Pyrene (98 %) was purchased from Sigma–
Aldrich Chemie GmbH, Riedstr. Steinheim. Absolute etha-
nol (99.9 %) was purchased from Changshu Yangyuan,
Chemical, China. All the reagents and chemicals were used
without any further purification. Surfactant solutions were
prepared with deionized and doubled distilled water.
BSGSCA1,6; BSGSCA1,8 were synthesized by refluxing a
mixture of monoalkyl sulfosuccinate ester (0.1 mol) and
a,x-dibromo alkanes (0.05 mol) in an ethanolic solution of
sodium hydroxide (0.1 %) for 8 h at 70 °C. The three
different end products, i.e., bis-sulfosuccinate gemini sur-
factants with different spacer lengths were obtained after
the separation and crystallization of the product with pet-
roleum ether (60–80 °C) [21].
Characterization of Synthesized Gemini Surfactants
The molecular structures of synthesized gemini surfactants
(BSGSCA1,4; BSGSCA1,6; BSGSCA1,8) were confirmed
by Fourier transform infrared spectroscopy (FT-IR) and
Preparation of the Monoester of Maleic Acid
(STEP-1)
1
nuclear magnetic resonance spectroscopy (NMR), i.e., H
NMR and 13C NMR. The structural confirmation spectral
techniques were performed at the Sophisticated Analytical
Instrumental Facility (SAIF), Cochin, Kerala, India.
Equal molar ratio of maleic anhydride (0.4 mol) and cetyl
alcohol (0.4 mol) were reacted to synthesize the monoe-
ster. Cetyl alcohol was heated to 40 °C for about 15 min
and then reacted with maleic anhydride. The monoester
was obtained after stirring for 2 h at a constant temperature
50–60 °C. Acid values were determined at different inter-
vals to confirm the formation of ester bonds [22].
Surface Tension Measurements
The surface tension measurements were performed using a
du Nou¨y tensiometer (Jencon, India) by the platinum ring
detachment technique [24]. The tensiometer was calibrated
or standardized against double distilled water. The platinum
ring was completely cleaned and dried before every
observation. The surfactants solutions for the surface ten-
sion measurements were prepared in the concentration
range 10-2–10-8 mol l-1 using double distilled water. The
maximum force required to detach the ring from the inter-
face was used to calculate the surface tension. The critical
micelle concentration (CMC) and the surface tension at the
CMC (cCMC) were determined from the sharp breakpoint of
the surface tension versus concentration profile. All mea-
surements were carried out at 25 °C. The results were
accurate within ?0.1 mN/m. Other important surface active
properties like pC20 and pCMC were also calculated. Effi-
ciency of adsorption of the surfactant (pC20) was calculated
by using the curve of surface tension versus the logarithm of
the molar concentration [25–28]. The surface pressure at the
CMC was calculated using Eq. 1:
Preparation of the Mono Alkyl Sulfosuccinate Ester
(STEP-2)
Mono alkyl sulfosuccinate ester was synthesized by react-
ing equal molar amounts of the maleic acid monoester
(0.2 mol) and ethylene glycol (0.2 mol) for a 6-h duration.
Toluene (100 ml) and p-toluene sulfonic acid (0.1 %) were
used as a solvent and catalyst in the reaction, respectively.
Water was completely removed azeotropically using a Dean
and Stark assembly. After complete removal of solvent and
water from the reaction mixture, it was washed with a
chloroform/H2O (50v/20v) and sodium chloride (30 % w/
v) mixture using vigorous stirring. The reaction mixture was
allowed to separate into two phases. The aqueous layer
contained excessive amount of ethylene glycol was washed
two or three additional times with chloroform. The chlo-
roform layers were combined and distilled to isolate the
mono alkyl maleate esters of ethylene glycol. The mono
alkyl sulfosuccinate ester was obtained by refluxing equal
molar amounts of alkyl maleate ester (0.26 mol) and
aqueous sodium bisulfite solution (0.26 mol) for 2 h [21].
pCMC ¼ coÀ cCMC
ð1Þ
where co and cCMC are the surface tension of pure water
and the surface tension at the CMC respectively [26].
Fluorescence Measurements
Preparation of Bis-Sulfosuccinate Gemini
Surfactants by Using a,x-Dibromo
Alkanes(STEP-3)
A very convenient and widely used technique to determine
the aggregation number is fluorescence spectroscopy.
In the current work, a Model RF-5301PC Spectrofluo-
rophotometer (Shimadzu) and steady-state fluorescence
quenching were used. Turro and Yekta [29] developed a
Three different bis-sulfosuccinate gemini surfactants were
prepared using three different a,x-dibromo alkanes. Three
different gemini surfactants symbolized as BSGSCA1,4;
123

J Surfact Deterg
technique for determining the aggregation number of
micelles based on the assumptions of the Tachiya [30]
model. The present studies were performed by using pyr-
ene and benzophenone as the probe and quencher,
respectively. To carry out the fluorescence studies suc-
cessfully, the perceptive approach of many researchers’
efforts [25, 29–36] were consulted. In current studies,
pyrene was excited at 335 nm and the emission spectra
were scanned from 340 to 600 nm [32]. All measurements
were carried out at 22 10 °C. The aggregation number
was calculated using Eqs. 2–4 [25, 33]:
prepared using the three steps in Scheme 1. The monoester
of maleic acid was prepared using an equal molar ratio of
cetyl alcohol and maleic anhydride. In this step, the acid
value of the product was determined at repeated intervals
after 1 h to confirm the complete conversion of alcohol into
the ester. The second step was carried out with slight
alteration, i.e., monoester of maleic acid (MMA) and
ethylene glycol were used in equal molar ratios as com-
pared to study carried out in [21]. The molar ratios were
selected on the basis of stoichiometry. Benzene was
replaced with toluene with a higher boiling point which is
favorable to completely remove the water azeotropically
with the help of a Dean and Stark assembly. The molecular
formula, molecular weight and yield of synthesized
BSGSCA’s are shown in Table 1.
Â
Ã
ln Io=Iq ¼ N½QŠ=C À CMC
Io=Iq ¼ expð½QŠ= micÞ
ð2Þ
ð3Þ
ð4Þ
N ¼ ðC À CMCÞ= mic
The chemical structures of the synthesized gemini sur-
factants were determined using elemental analysis, FT-IR
and NMR. Table 1 shows the results of elemental analysis
which is in good agreement with the theoretical calculated
values for all carbon, hydrogen and sulfur elements. The
result of FT-IR confirmed and satisfied the relevant fre-
quency ranges of the functional groups present in the
structures. The acceptable results of FT-IR were also cor-
roborated and supported with the literature [37].
The bands appeared in the FT-IR spectrum {m (cm-1)}
of BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8 displayed
at 2919.75; 2921.11 and 2921.29 {CH3 (terminal) asym-
metric bending}, 2851.25; 2851.99 and 2852.54 {CH3
(terminal) symmetric}, 1147.38; 1147.26 and 1146.58 {C–
O–C (Ether) asymmetric}, 1734.88; 1734.58 and 1734.18
{–C=O (Ester) stretching}, 1467.11; 1466.16 and 1465.05
{=CH2 (Scissoring)}, 1225.54; 1233.44 and 1228.03 {C–O
(Ester) stretching}, 721.36; 720.96 and 721.53{(CH2)8}
respectively [37].
where Iq and Io are the fluorescence intensities with and
without quencher, respectively, [Q] is the concentration of
quencher, N is the aggregation number, C is the surfactant
concentration, CMC is the critical micelle concentration of
the surfactant and 1/mic is the slope of the straight lines
obtained from the plot of ln (Io/Iq) versus quencher con-
centration. The Iq and Io values were obtained from the
fluorescence spectrum. Equations (2) and (3) can be solved
and rearranged as Eq. (4). Finally aggregation number can
be calculated by using the Eq. (4).
A stock solution of pyrene (5 9 10-4 mol/l) was pre-
pared in ethanol. The surfactant solution was added and the
pyrene concentration was kept constant at (5 9 10-6 mol/
l) in the system [34]. The quencher concentration was used
in the range of 2–8 9 10-4 mol/l [34, 35]. The study was
carried out with the surfactant concentrations of 3*CMC,
5*CMC and 9*CMC for all the three synthesized gemini
surfactants to investigate the variation of the aggregation
number with surfactant concentration and to determine the
effect of the spacer groups on the aggregation number.
Pyrene intensity ratio (I1/I3) is a well-established
parameter which reflects the polarity experienced by the
pyrene probe and found to be sensitive to the polarity of
environment where the pyrene is located. In the present
study, the fluorescence peak intensities of first (I1) and third
(I3) vibronic bands were located at 376.0 and 387.0 nm
respectively in the fluorescence spectrums. Pyrene intensity
ratio was determined using a pyrene fluorescence probe to
investigate the micropolarity of the micelle [33].
Nuclear magnetic resonance spectroscopy was used to
confirm the structures of the Gemini surfactants. The
interpreted signals and peaks of 1H NMR and 13C NMR for
all three synthesized gemini surfactants is shown in
Table 2 [21, 38]. The ranges of 1H NMR peaks for
BSGSCA1,8 appeared in d (ppm) at 0.792–0.826 {t, 6H,
2CH3}, 1.251–1.279 {m, 60H, 2(CH2)15}, 1.384–1.511
{d,4H,(CH2–CHSO3)2}, 1.806–1.823 {t, 8H, (CH2 CH2
COO)2}, 2.099–2.244 {t, 2H, (CHCO)2}, 3.320–4.314 {t,
16H, O–(CH2)8–O}. The 13C NMR peaks for BSGSCA1,8
displayed in the ranges d (ppm) at 171.304 {ester –COO–},
67.985 {ether C–O–C}, 31.932 {C–SO2–R}, 22.690
{Terminal CH3}, 25.746–29.763 {CH2 chains of cetyl
alcohol}.
Results and Discussion
Synthesis of Gemini Surfactants
Surface Properties of BSGSCA
Cetyl alcohol based anionic bis-sulfosuccinate gemini
surfactants (BSGSCA1,4; BSGSCA1,6; BSGSCA1,8) were
The surface tension isotherms for the synthesized BSGSCA
at different concentrations are shown in Fig. 1. The surface
123

J Surfact Deterg
STEP 1
O
C
C16H33
50-600C
2 h
O
+
C16
H
33OH
O
O
O
COOH
Cetyl alcohol
Maleic anhydride
Monoester of maleic acid
(I)
STEP 2
C16H33OOCCH
CHCOOH
CH2OH
CHCOOCH2CH2OH
Mono alkyl maleate ester
HOH2C
C16H33OOCCH
+
-H20
Monoester of maleic acid
Ethylene glycol
(I)
NaHSO3
COOCH2CH2OH
C16H33OOCCH2CH
SO3Na
Monoalkyl sulfosuccinate ester
(II)
STEP 3
COOCH2CH2OH
C16H33OOCCH2CH
SO3Na
Monoalkyl sulfosuccinate ester
(II)
Where
n=4 for BSGSCA1,4
n=6 for BSGSCA1,6
n=8 for BSGSCA1,8
Br(CH2)nBr
C16H33OOC CH CH
O(CH2)nO CH2CH2OOC CHCH
2
COOC
H
COOCH2CH2
2
16 33
SO3Na
SO3Na
Bis-sulfosuccinate gemini surfactant
(III)
Scheme 1 Synthetic steps for the preparation of cetyl alcohol based bis-sulfosuccinate gemini surfactants
tension at the CMC (cCMC) decreases with elongation of
the spacer groups as shown in Table 3. This can be
explained on the basis of enhanced flexibility. As the
methylene chain length of the spacer group increases, the
flexibility of the spacer group increases and reduces the
cCMC [28].
abruptly aggregate to form micelles. The CMC values
shown in Table 3 indicate that the CMC decreases with
increasing spacer length. The reduction in the CMC with
increased spacer length may be result of the reduced
electrostatic repulsion between the two polar head groups
[28]. Similar results have been reported by Azira [27]. In
the present study, the flexible spacers can easily bend and
participate in the formation of the micelle hydrophobic
The critical micelle concentration (CMC) is related to
the concentration at which the surfactant monomers
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Table 1 Elemental analysis and yield of synthesized BSGSCA
Surfactant code
Molecular
formula/molecular
weight
Yield (%)
m p (°C)
Elemental analysis found/calculated (%)
C
H
S
BSGSCA1,4
BSGSCA1,6
BSGSCA1,8
C48H88O16S2Na2
(1031.32)
76.93
74.80
84.36
66–68
72–74
77–79
55.98
55.90
56.79
56.68
57.56
57.43
8.72
8.60
8.92
8.75
8.99
8.89
6.34
6.21
6.14
6.05
5.97
5.89
C50H92O16S2Na2
(1059.38)
C52H96O16S2Na2
(1087.43)
1
Table 2 Interpretation [21, 38] of synthesized BSGSCA’s by H NMR and 13C NMR
Surfactant code
BSGSCA1,4
1H NMR d (ppm)
13C NMR d (ppm)
0.792–0.826, {t, 6H, 2CH3}
171.233 {–C=O}
1.1–1.3, {m, 60H, 2(CH2)15
1.478–1.531,{d,4H,(CH2–CHSO3)2}
1.8, {t, 8H, (CH2 CH2 COO)2}
2.100, {t, 2H, (CHCO)2}
}
66.094 {ether C–O–C}
31.933 {C–SO2–R}
22.692 {Terminal CH3}
25.748–29.695{CH2 chains of cetyl alcohol}
3.087–4.314, {t, 8H, O–(CH2)4–O}
0.793–0.826, {t, 6H, 2CH3}
BSGSCA1,6
171.236 {–C=O}
1.1–1.3, {m, 60H, 2(CH2)15
}
63.109 {ether C–O–C} 31.936 {C–SO2–R}
22.690 {Terminal CH3}
1.497–1.513,{d,4H,(CH2–CHSO3)2}
1.803–1.827,{t, 8H, (CH2 CH2 COO)2}
2.100, {t, 2H, (CHCO)2}
25.859–29.763 {CH2 chains of cetyl alcohol}
3.328–4.237, {t, 12H, O–(CH2)6–O}
0.792–0.826, {t, 6H, 2CH3}
BSGSCA1,8
171.304 {–C=O}
1.251–1.279, {m, 60H, 2(CH2)15
}
67.985 {ether C–O–C}
1.384–1.511,{d,4H,(CH2–CHSO3)2}
1.806–1.823, {t, 8H,(CH2 CH2 COO)2}
2.099–2.244, {t, 2H, (CHCO)2}
31.932 {C–SO2–R}
22.690 {Terminal CH3}
25.746–29.763 {CH2 chains of cetyl alcohol}
3.320–4.314, {t, 16H, O–(CH2)8–O}
Table 3 Surface active properties of BSGSCA’s for different spacer
chain lengths at 25 1 °C
Surface active property BSGSCA1,4 BSGSCA1,6 BSGSCA1,8
ÇCMC (mN/m)
CMC (mol/L)
pC20 (mol/dm3)
pCMC (mN/m)
36.1
0.0010
35.3
0.00093
34.2
0.00087
6.7
7
7.2
35.5
36.3
37.4
core. Due to enhanced flexibility with increased spacer
length, more and more methylene groups contribute to
micelle formation and as a result, free energy and CMC
decreased for the gemini surfactants with longer spacer
group [25]. The results in Table 3 show that BGSCA1,8
had the greatest reduction in CMC value out of the three
Fig. 1 Plots of surface tension versus surfactant concentrations at
25 1 °C
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J Surfact Deterg
synthesized surfactants due to the presence of a more
flexible and elongated spacer group.
3*CMC
5*CMC
9*CMC
35
30
25
20
15
10
5
30
The efficiency or effectiveness of surfactant adsorption
is given by the pC20 value, the negative logarithm of
surfactant concentration required to reduce the surface
tension of water by 20 mN/m. The efficiency of gemini
surfactants to reduce the surface tension of water results in
larger pC20 values because of the higher surface activity
[25]. From Table 3, BSGSCA1,8 exhibited the highest
pC20 value, i.e., 7.2 mol/dm3, due to its elongated spacer
group.
28
26
19
9
17
8
15
7
0
BSGSCA1,4
BSGSCA1,6
BSGSCA1,8
Concentration (mol/L)
Fluorescence Studies of BSGSCA
Fig. 3 Aggregation number for different BSGSCA’s at different
concentrations (3*CMC, 5*CMC, 9*CMC) at 22 1 °C
Micelle aggregation number was investigated using steady-
state fluorescence quenching. In the present study, pyrene-
benzophenone was used as a probe-quencher pair respec-
tively which has been found to be appropriate to investigate
the micelle aggregation number of anionic gemini surfac-
tants [25, 33]. The experimental curves shown in Fig. 2
give the relationship between [Q] and ln (Io/Iq) for the
prepared gemini surfactants. These plots give straight lines
for all the gemini surfactants and the slope of these straight
lines was used to calculate the aggregation number.
3*CMC
5*CMC
9*CMC
1.2
1.18
1.16
1.14
1.12
1.1
1.18
1.16
1.14
1.16
1.15
1.13
1.13
1.12
1.1
1.08
1.06
Aggregation number was determined at different sur-
factant concentration (3*CMC, 5*CMC and 9*CMC) at
22 ? 10 °C to investigate the effect of increased concen-
tration. Figure 3 shows the variation of aggregation num-
ber with different surfactant concentrations (3*CMC,
5*CMC and 9*CMC). The increased aggregation number
with increasing surfactant concentration indicates micelle
growth and tighter packing of the molecules in the aggre-
gate. Micellar growth with increased surfactant concen-
tration is typical for ionic surfactants [35].
BSGSCA1,4
BSGSCA1,6
BSGSCA1,8
Concentration (mol/L)
Fig. 4 Pyrene intensity ratio versus BSGSCA concentrations
intensity ratio (I1/I3) as a function of surfactant concen-
tration is shown in Fig. 4. Increasing the surfactant con-
centration from 3*CMC to 9*CMC decreases the pyrene
intensity ratio indicating a decrease in micropolarity. From
the fluorescence quenching experiments we know that
micelle aggregation number increases with increasing
surfactant concentration. Micellar growth increases pack-
ing density causing pyrene to be solubilized towards the
micelle core, consequently micropolarity decreases with
increasing surfactant concentration [33].
Micelle micropolarity can be determined from the
intensity ratio (I1/I3) of pyrene molecules solubilized in the
micelle. In general, reduced pyrene intensity ratio (I1/I3)
reflects a less polar microenvironment. The pyrene
BSGSCA1,4 ( 3* CMC)
BSGSCA1,6 ( 3* CMC)
Figure 4 also shows the increased micropolarity with
elongated spacer length. The increase in polarity upon
increasing the spacer chain length is likely due to pro-
gressive penetration of the spacer in the micelle
hydrophobic core which allows water to enter the palisade
layer of the micelle. The increased polarity is most noticed
for BSGSCA1,8 having the longest spacer [39].
BSGSCA1,8 (3* CMC)
2.5
R² = 0.998
R² = 0.995
2
1.5
1
R² = 0.998
0.5
0
Acknowledgments Authors gratefully acknowledge the Extra
Mular Research Division (II) Scheme No. 01/(2565)/12/ERM-II of
Council of Scientific and Industrial Research (CSIR), New Delhi,
Government of India for financial support to the research work.
Vinayika Singh is highly grateful to CSIR, New Delhi for the award
of a Senior Research fellowship.
0.0002
0.0004
0.0006
0.0008
Quencher Concentration (mol/L)
Fig. 2 Plot of ln (Io/Iq) vs quencher concentration for different
BSGSCAs at concentration 3*CMC at 22 1 °C
123

J Surfact Deterg
22. Deepika Tyagi VK (2006) Sulfosuccinates as mild surfactants.
J Oleo Sci 55:429–439
References
23. Schoenberg T (1997) Optimizing mild cleansers. SPC Soap
Perfum Cosmet 70:33–36
24. Du Nou¨y PL (1925) An interfacial tensiometer for universal use.
J Gen Physiol 7:625–633
25. Zhu S, Liu L, Cheng F (2011) Influence of spacer nature on the
aggregation properties of anionic gemini surfactants in aqueous
solutions. J Surf Deterg 14:221–225
1. Sohrabi B, Bazyari A, Hashemianzadeh M (2010) Effect of
ethylene glycol on micellization and surface properties of gemini
surfactant solutions. Coll Surf A 364:87–93
2. Abduallah A, Algeidi O (2014) Gemini-surfactant effect on the
inhibition of corrosion of brass in acid environment. Univ Zawia
Univ Bull 1:47–62
3. Kumar N, Tyagi R (2014) Industrial applications of dimeric
surfactants: a review. J Dispers Sci Technol 35:1–10
4. Kumar N, Tyagi R (2013) Dimeric surfactants: promising
ingredients of cosmetics and toiletries. Cosmetics 1:3–13
5. Liu JW, Xu JJ, Liu ZW, Liu XL, Che RC (2014) Hierarchical
magnetic core–shell nanostructures for microwave absorption:
synthesis, microstructure and property studies. Sci China Chem
57:3–12
6. Menger FM, Littau CA (1991) Gemini-surfactants: synthesis and
properties. J Am Chem Soc 113:1451–1452
7. Yoshimura T, Esumi K (2004) Synthesis and surface properties of
anionic Gemini surfactants with amide groups. J Coll Interface
Sci 276:231–238
8. Altenbach HJ, Ihizane R, Jakob B, Lange K, Schneider M, Yil-
maz Z, Nandi S (2010) Synthesis and characterization of novel
surfactants: combination products of fatty acids, hydroxycar-
boxylic acids and alcohols. J Surf Deterg 13:399–407
9. Shukla D, Tyagi VK (2006) Anionic Gemini surfactants: a dis-
tinct class of surfactants. J Oleo Sci 55:215–226
10. Zhu YP, Masuyama A, Kobata Y, Nakatsuji Y, Okahara M,
Rosen MJ (1993) Double-chain surfactants with two carboxylate
groups and their relation to similar double-chain compounds.
J Coll Interface Sci 158:40–45
11. Dix LR (2001) Sodium salts of bis(1-dodecenylsuccinamic
acids): a simple route to anionic gemini surfactants. J Coll
Interface Sci 238:447–448
12. Wattebled L, Laschewsky A (2007) New anionic gemini sur-
factant based on EDTA accessible by convenient synthesis. Coll
Polym Sci 285:1387–1393
26. El-Sadek BM (2011) Synthesis of selected gemini surfactants:
surface, biological activity, and corrosion efficiency against
hydrochloric medium. Der Chem Sin 2:125–137
27. Azira H, Tazerouti A (2007) Micellar behavior of anionic sur-
factants with sulfonate function in aqueous solutions. J Surf
Deterg 10:185–190
28. Tyagi P, Tyagi R (2011) Synthesis of bisphosphodiester surfac-
tants derived from tetradecanol and different methylene chains as
a spacer derived from a,x-alkyl dibromides. Tenside Surf Det
48:293–300
29. Turro NJ, Yekta A (1978) Luminescent probes for detergent
solutions: simple procedure for determination of the mean
aggregation number of micelles. J Am Chem Soc 100:5951–5952
30. Tachiya M (1975) Application of a generating function to reac-
tion kinetics in micelles. Kinetics of quenching of luminescent
probes in micelles. Chem Phys Lett 33:289–292
31. Hierrezuelo JM, Aguiar J, Ruiz CC (2004) Stability, interaction,
size and micro- environmental properties of mixed micelles of
docanoyl-N-methylglucamide and sodium dodecyl sulfate.
Langmuir 20:10419–10426
32. Yoshimura T, Esumi K (2004) Synthesis and surface properties of
anionic gemini surfactants with amide groups. J Coll Interface Sci
276:231–238
33. Cao X, Li Z, Song X, Cui X, Wei Y, Cheng F, Wang J (2009)
Effects of spacers on surface activities and aggregation properties
of anionic gemini surfactants. J Surf Deterg 12:165–172
34. Pisarcik M, Devinsky F, Lacko I (2006) Steady-state fluorescence
quenching in micellar solutions of biodegradable gemini surfac-
tants. Acta Fac Pharm Univ Comen 53:184–192
35. Fang Y, Liu XF, Xia YM, Yang Y, Cai K, Xu YM, Zhao XY
(2001) Determination of critical micellar aggregation numbers by
steady-state fluorescence probe method. Acta Phys Chim Sin
17:828–831
13. Sakai K, Umemoto N, Matsuda W, Takamatsu Y, Matsumoto M,
Sakai H, Abe M (2011) Oleic acid-based gemini surfactants with
carboxylic acid headgroups. J Oleo Sci 60:411–417
14. Zhu YP, Masuyama A, Nagata T, Okahara M (1991) Preparation
and properties of double-chain surfactants bearing two sulfonate
groups. J Japan Oil Chem Soc (Yukagaku) 40:473–477
36. Singh V, Tyagi R (2014) Unique micellization and cmc aspects of
gemini surfactant: an overview.
35:1774–1792
J Dispers Sci Technol
15. Magdassi S, Moshe MB, Talmon Y, Danino
D (2003)
Microemulsions based on anionic gemini surfactant. Coll Surf A
212:1–7
16. Zhu YP, Masuyama A, Okahara M (1990) Preparation and sur-
face active properties of amphipathic compounds with two sulfate
groups and two lipophilic alkyl chains. J Am Oil Chem Soc
67:459–463
17. Menger FM, Littau CA (1993) Gemini surfactants: a new class of
self-assembling molecules. J Am Chem Soc 115:10083–10090
18. Menger FM, Littau CA (1991) Gemini-surfactants: synthesis and
properties. J Am Chem Soc 113:1451–1452
37. Tatchell AR, Furnis BS, Hannaford AJ, Smith PWG (1994)
Vogel’s textbook of practical organic chemistry, 5th edn. Long-
mann Group, UK 430
38. Silverstein RM (1981) Spectrometric identification of organic
compounds, 4th edn. John Wiley and Sons, New York,
pp 289–300
39. Zana R (2004) Gemini surfactants : synthesis, interfacial and
solution-phase behavior, and applications, vol 117. Marcel Dek-
ker, New York, pp 165–167
19. Duivenvoorde FL, Feiters MC, Gaast SJV, Engberts JBFN (1997)
Synthesis and properties of di-n-dodecyl-a,x-alkyl bisphosphate
surfactants. Langmuir 13:3737–3743
20. Tyagi P, Tyagi R (2010) Synthesis and properties of di-n-hex-
adecyl-a,x-alkyl bisphosphate surfactants. Tenside Surf Det
47:232–237
21. EI-Salam FHA (2009) Synthesis, antimicrobial activity, micel-
lization of gemini anionic surfactants in a pure state as well as
mixed with a conventional nonionic surfactant. J Surf Deterg
12:363–370
Vinayika Singh completed her B.Sc. degree from H. P. University
Shimla, Himachal Pradesh and her M.Sc. degree from Bundelkhand
University, Jhansi, Uttar Pradesh, India. She is currently working as a
Senior Research Fellow (SRF) for the project funded by Council of
Scientific and Industrial Research (CSIR), New Delhi, India as well as
pursuing her Ph.D. under the supervision of Dr. Rashmi Tyagi at the
Department of Chemical Engineering, Jaypee University of Engi-
neering and Technology, Guna, Madhya Pradesh, India.
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She is working as an associate professor in the Department of
Chemical Engineering, Jaypee University of Engineering and Tech-
nology, Guna, Madhya Pradesh, India.
Rashmi Tyagi completed her Ph.D. in Chemistry in 1995 and
obtained her second Masters and second Ph.D. in Chemical
Technology in 2000 and 2005 respectively from HBTI, Kanpur.
123