Synthesis and Physicochemical Properties of Alanine-Based Surfactants

Article abstract of DOI:10.1007/s11743-016-1878-8

The synthesis of a homologous series of alanine-based surfactants, namely sodium salts of n-alkanesulfonamido-2-propanoic acids in which n-alkane is n-dodecane, n-tetradecane, n–hexadecane, and n-octadecane having the formula RSO₂NHCH (CH₃)COO^?Na⁺, is described. The starting materials used were a mixture of secondary positional isomers of n-alkanesulfonyl chlorides obtained by photosulfochlorination reaction using sulfuryl chloride and a catalyst. Surface properties of the aqueous solutions of the synthesized surfactants, including the critical micelle concentration and minimal surface tension δ_min, were determined using surface tension measurements at 25?°C. The surface excess Γ and minimum area per molecule (A_min) where calculated using the Gibbs equation. The foaming power was also determined by the Bartsh method, and the R₅ parameter was calculated to estimate the stability of the foam formed. The results obtained were compared to those of a commercial surfactant, sodium dodecylsulfate, and a series of synthesized glycine-based surfactants. The results obtained clearly show that the alanine-based surfactants possess good surface properties. The investigations highlight the influence on the surface properties of the addition of a methyl group in the hydrophilic part.

Full text of DOI:10.1007/s11743-016-1878-8

J Surfact Deterg
DOI 10.1007/s11743-016-1878-8
ORIGINAL ARTICLE
Synthesis and Physicochemical Properties of Alanine-Based
Surfactants
1
1
1
M. Bougueroua
•
R. Mousli
•
A. Tazerouti
Received: 15 March 2016 / Accepted: 2 September 2016
Ó AOCS 2016
Abstract The synthesis of a homologous series of alanine-
based surfactants, namely sodium salts of n-alkanesulfon-
amido-2-propanoic acids in which n-alkane is n-dodecane,
n-tetradecane, n–hexadecane, and n-octadecane having the
Keywords Anionic surfactants Á Sulfonamide derivatives Á
Alanine-based surfactants Á Photosulfochlorination Á
Physicochemical properties Á Foam power
-
?
formula RSO NHCH (CH )COO Na , is described. The
2
3
starting materials used were a mixture of secondary posi-
tional isomers of n-alkanesulfonyl chlorides obtained by
photosulfochlorination reaction using sulfuryl chloride and
a catalyst. Surface properties of the aqueous solutions of
the synthesized surfactants, including the critical micelle
concentration and minimal surface tension dmin, were
determined using surface tension measurements at 25 °C.
The surface excess C and minimum area per molecule
Introduction
Amino acid-based surfactants are of a great interest in the
field of novel surfactants research because of their envi-
ronmentally friendly character. They are characterized by
low toxicity and quick biodegradation [1]. They can be
produced either by biotechnological or chemical methods
using renewable raw materials such as amino acids and
vegetable oils [2–5]. They are defined as surfactants having
an amino acid or its residue as hydrophilic head [1]. These
surfactants with a carboxylate group are recommended as
detergents, emulsifiers, and wetting and antistatic agents.
They are also used as lubricants and finishing agents for
glass and rock fibers [6, 7]. Another important property of
these surfactants is their ability to cause solubilization
[8, 9]. These surfactants are also found to be active against
various diseases [10–12]. They are somewhat stronger than
soaps and have good surfactant and detergent properties
[6, 7]. The most frequent amino acids used in the synthesis
of amino acid-based surfactants are alanine, serine, and
leucine owing to the properties of the condensates with
various fatty acids [6, 7]. As a result of the various appli-
cations of sulfonamide surfactants as detergent agents,
different methods for their synthesis have been reported.
The sulfonylation of amines in the presence of a base is the
most typical method for preparing sulfonamides. Different
reactions of synthesized alkanesulfonamides using ammo-
nia as starting materiel were described [13]. As an exam-
ple, the reaction of methyl or benzylsulfonyl chloride
dissolved in toluene or benzene and gaseous ammonia was
(
Amin) where calculated using the Gibbs equation. The
foaming power was also determined by the Bartsh method,
and the R parameter was calculated to estimate the sta-
5
bility of the foam formed. The results obtained were
compared to those of a commercial surfactant, sodium
dodecylsulfate, and a series of synthesized glycine-based
surfactants. The results obtained clearly show that the
alanine-based surfactants possess good surface properties.
The investigations highlight the influence on the surface
properties of the addition of a methyl group in the hydro-
philic part.
&
A. Tazerouti
ameltazerouti@gmail.com; atazerouti@usthb.dz
1
Laboratory of Applied Organic Chemistry, Faculty of
Chemistry, University of Sciences and Technology Houari
Boumediene (USTHB), BP 32, El Alia,
Bab Ezzouar 16111, Algiers, Algeria
1
23

J Surfact Deterg
described, but this method is limited by the use of a gas and
by a drop in the yield caused by crystallization in toluene
until colorless, was added drop by drop to 0.345 mol of n-
alkane (n-dodecane, n-tetradecane, n-hexadecane, or n-
octadecane) (Fluka, 99 % pure) in the presence of pyridine
[
13]. Another method consists of the direct oxidative
conversion of thiols into sulfonamides with H O /SOCl
2
-
2
(Fluka, 99.8 % pure) as catalyst (10 M) under visible
light irradiation (150 W). The reaction temperature was
maintained between 25 and 35 °C. The reaction mixture
was bubbled with nitrogen before the addition of SO Cl
2
2
and amines [14]. A modification of the reaction of sulfur
dioxide with various organometallic reagents to give sul-
finic acid salts has been reported. It is proposed to treat
organometallic reagents directly with sulfuryl chloride and
amine to furnish sulfonamides in good yields. But in this
reaction, a bench-stable colorless solid charge transfer
complex is needed. It is obtained from the combination of
DABCO (1,4-diazabicyclo[2.2.2]octane) and sulfur diox-
ide, and so can replace gaseous sulfur dioxide in organic
synthesis [14]. Most of these reported syntheses need
various products and steps. In previous works, amino acid-
based surfactants and n-alkanesulfonamides with chain
length C –C were prepared using glycine and N,N-di-
2
2
and at the end of the reaction. The obtained n-alkanesul-
fonyl chlorides, a mixture of primary and secondary iso-
mers, were separated from the reaction mixture by solvent
extraction using acetonitrile (Fluka, 97 % pure), which was
then evaporated leading to a yellow liquid. They were then
purified on a silica gel column. The resulting n-alkane-
sulfonyl chlorides (n-dodecane, n-tetradecane, n-hexade-
cane, and n-octadecane) were analyzed by FTIR and GC/
MS/IE after their derivatization into the more thermally
stable N,N-diethyl n-alkanesulfonamides.
1
2
18
ethylamine, respectively [15–20]. In the current work, a
simple method was used. It consists in the conversion of n-
alkanesulfonyl chlorides synthesized into sodium salts of n-
alkanesulfonamido-2-propanoic acids in only one step. The
compounds obtained are new amino acid (alanine)-based
surfactants. They contain in their hydrophilic head an
additional methyl group when compared to glycine-based
surfactants. The alanine-based surfactants are obtained by
Synthesis of N,N-Diethyl n-Alkanesulfonamides
The n-alkanesulfonyl chlorides produced were then
derivatized into the corresponding N,N-diethyl n-alkane-
sulfonamides by addition of diethylamine (Aldrich, 99.5 %
pure) using Berthold’s method [16]. The primary isomers
were identified in GC analysis by cross injection with pure
samples obtained by Grignard reaction using commercial
1-chloroalkanes (Fluka, [99 % pure).The secondary sul-
fonamide derivatives were identify by GC/MS/EI.
the reaction of n-alkanesulfonyl chlorides RSO Cl (R =
2
C –C ), a mixture of secondary positional isomers for
1
2
18
each length chain, with alanine to give a series of anionic
-
-
surfactants of general formula RSO NHCH(CH )COO
2
3
?
Na . The surface properties of their aqueous solutions at
different concentrations were studied at 25 °C using sur-
face tension measurements. The critical micelle concen-
tration (CMC), minimum area per molecule (Amin) at the
air/water interface, and superficial concentrations (C) were
evaluated. The foaming power was also determined by the
Bartsch method. The results obtained were compared to
those of a commercial surfactant, sodium dodecylsulfate
Synthesis of Sodium Salts of n-Alkanesulfonamido-2-
Propanoic Acids
Alanine (4.6 mmol; Merck, 99 % pure) was treated with
15 mL of 10 % NaOH. Then, a solution of 1.86 mmol of n-
alkanesulfonyl chlorides (C –C ) in 40 mL of dichlor-
1
2
18
omethane (Merck, 99 % pure) was added drop by drop
under magnetic agitation at 0 °C. At the end of the addi-
tion, the mixture was heated to reflux for 90 min. The
mixture was cooled, and a white solid was collected by
filtration. The products were then purified by recrystal-
lization in petroleum ether and the obtained yields were
about 83, 78, 85, and 64 % for the following mixture of
(
SDS), and those of glycine-based surfactants prepared in
previous works [15]. The influence of the structure of the
hydrophilic part on the surfactant properties was also
examined.
positional
isomers
of
alanine-based
surfactants
Experimental Procedures
Synthesis
respectively:
C12-Ala: sodium salts of n-dodecanesulfonamido-2-
propanoic acids
Synthesis of n-Alkanesulfonyl Chlorides
C14-Ala: sodium salt of n-tetradecanesulfonamido-2-
propanoic acids
The n-alkanesulfonyl chlorides (RSO Cl) which are con-
2
C16-Ala: sodium salt of n-hexadecanesulfonamido-2-
propanoic acids
sidered as raw material, were obtained by photosul-
fochlorination. Thus, 0.172 mol of sulfuryl chloride (Fluka,
C18-Ala: sodium salt of n-octadecanesulfonamido-2-
propanoic acids
9
7 % pure), freshly distilled under a stream of nitrogen
1
23

J Surfact Deterg
These compounds were characterized by FTIR and LC-
HRMS.
with a platinum Wilhelmy plate. The pH value of the
aqueous surfactant solution is 8. All measurements were
repeated three times. In most cases, the accuracy of surface
tension measurements was ± 0.1 mN/m.
Instrumentation
Fourier Transform Infrared Spectroscopy (FTIR)
Foaming Power
The presence of the different functions in the synthesized
products was confirmed by FTIR using a Perkin Elmer
Paragon 500 spectrophotometer using KBr.
The study of foam power and foam stability of aqueous
solutions of the alanine-based surfactants for different
-
2
concentrations (from 10 M until the disappearance of the
foam) reported here has been carried at 25 °C using the
Bartsh method [15, 21]. Thus 10 mL aliquots of aqueous
surfactant solutions were prepared and introduced into a
Gas Chromatography (GC)
GC separations were performed with a Perkin Elmer Clarus
100-mL graduated cylinder. The cylinder containing the
5
9
00 gas chromatograph. An ULTRA 2, a poly (5 % phenyl/
solution was turned upside down a total of ten times at a
rate of one turn every 2 s [15]. The foaming stability is
5 % methylsiloxane) capillary column 25 m 9 0.20 mm
I.D., 0.33 lm film thickness (Hewlett-Packard) was used
with N carrier gas (0.6 mL/s). The analysis of the reaction
determined by calculating the R parameter. It represents
5
2
the quotient of the foam height after 5 min to the initial
mixture was carried out with the following temperature
program: initial temperature 180 °C and then increased at a
rate of 20 °C/min to 270 °C. Injector and flame ionization
detector (FID) temperatures were 300 °C.
foam [15, 21, 22]. So the initial foam height, H , after
5
5
min was measured for all surfactants. The residual foam
ratio R % was calculated as follows in Eq. 1:
5
ꢀ
ꢁ
H
R5 ¼
5=
 100
ð1Þ
H
0
GC/MS/EI
where H is the initial foam height and H the foam height
5
0
A gas chromatograph, Hewlett-Packard model 6890, was
coupled to an MSD 5973 mass spectrometer. An HP-5ms
capillary column 30 m 9 0.25 mm I.D. was used with N2
carrier gas (0.6 mL/s). The products were detected by EI
measured after 5 min.
Results and Discussion
(
70 eV).
Synthesis and Characterizations of n-Alkanesulfonyl
Chlorides and N,N-Diethyl n-Alkanesulfonamides
LC/HRMS
A liquid chromatograph coupled to a high resolution mass
spectrometer was used (LC/HRMS). The LC method was
realized on an ACQUITY UPLC WATERS-SN 475 M,
and the separation was performed using an ACQUITY
UPLC BEH C18: 1.7 lm 2.1 9 50 mm column. Then,
The starting materials, i.e., n-alkanesulfonyl chlorides
(RSO Cl where R = C12–C18) obtained by photosul-
2
fochlorination of n-alkanes using sulfuryl chloride, were
first analyzed by FTIR. The results show the characteristic
absorption bands of the SO stretching vibrations between
2
-
1
5
-lL aliquots of each sample which were filtered using
1368 and 1160 cm , which is in good agreement with
literature data [18]. As long-chain n-alkanesulfonyl chlo-
rides can hardly be analyzed directly by GC because of
their instability and their low volatility, they were deriva-
tized into N,N-diethylsulfonamides for their analysis by GC
and GC–MS in electron impact (EI) mode. The isomeric
compositions were well determined by GC analysis; the
ratios of primary/secondary isomers are 20:80, 23:77,
regenerated glucose (0.2 lm), diluted 100 times, and stored
at room temperature were then injected using mobile phase
which consists of HCOONH /10 mM, pH 8/CH CN,
4
3
delivered at a flow of 0.45 mL/min. The mass spectro-
metric detection was performed with a Xevo Q-Tof
WATERS-SN: YAA122 and fitted with an electrospray
interface (ESI).
2
2:78, and 18:82 corresponding respectively to the com-
pounds C12 N(C N(C
H SO N(C H ) , and C H SO N(C H ) . The results
Surface Tension Measurements
H
25SO
2
2
H
5
)
2
, C14
H
29SO
2
H ) , C16-
2 5 2
3
3
2
2
5 2
18 37
2
2 5 2
The measurements were performed at 25 °C for freshly
prepared solutions of alanine-based surfactants in the
showed the presence of the positional isomers for each
length chain. Indeed, it was possible to separate the six
-
1
-4
concentration ranges of 10 –10 mol/L using a ten-
siometer (Prolabo Tensimat-Densimat TD 2000) equipped
isomers for n-C12
H
25SO
2
N(C
2
H
5
)
2
. We were also able to
N(C H ) ,
2 5 2
separate six of the seven isomers for C14
H
29SO
2
1
23

J Surfact Deterg
seven of the eight isomers for C H SO N(C H ) , and
1
minima near the CMC in the surface tension plots. The
chemical structure of these compounds was checked by
FTIR and LC/HRMS. For the four synthesized surfactants,
the FTIR spectra showed the expected absorption bands of
the N–H stretching vibrations at 3453, 3436, 3453, and
6
33
2
2 5 2
eight of the nine isomers for C H SO N(C H ) as a
1
8
37
2
2 5 2
result of the co-elution of the internal position isomers. The
GC/MS/EI analysis with EI mode was useful for analyzing
the position isomers of these N,N-diethylsulfonamide
derivatives. The most important peaks of mass spectra in
EI mode characterizing the presence of N,N-diethylsul-
-
1
3495 cm . The O=C–O asymmetric stretch appeared at
-
1590–1630 cm , the O=C–O symmetric stretch at
1
-
1450–1460 cm , and the stretching of the sulfonate group
1
fonamide group in the molecules for all isomers of each
?
-1
at 1175–1180 cm . The band at 2925–2850 cm
-1
alkyl chain length were m/z = 73 for [HN(CH CH ) ]
3 2
,
is
2
?
m/z = 58 for [CH CH HN = CH ] , m/z = 107 for [HN
assigned to symmetric and asymmetric stretches of CH of
2
3
2
2
?
CH )(C H )] , m/z = 122 for [HSO NH(CH )(C H )] ,
?
(
linear hydrocarbon chain. These results are in agreement
with the data given in the literature [15].
2
2
5
2
2
2 5
?
and m/z = 137 for [HSO N(CH CH ) ] . The peak m/z 73
2
2
3 2
was present with a relative intensity of 100 % for all
isomers.
The liquid chromatograms of LC/HRMS presented in
Fig. 1 show many well-separated and resolved peaks
related to different positional isomers for each chain
length (Fig. 1a–d). The main observation, for all the
chromatograms, is that one isomer is not well separated
for each chain length. This behavior has already been
observed in the case of GC and GC/MS analysis of
N,N-diethyl n-alkanesulfonamides where the obtained
results led to the conclusion that the internal positional
isomers are often co-eluted [18–20]. As seen in Fig. 1a,
it was possible to separate five of six isomers for C12-
Ala as a result of the co-elution of isomers 5 and 6.
For the other samples, it was possible to separate six of
the seven isomers for C14-Ala, seven of the eight
isomers for C16-Ala, and eight of the nine isomers for
C18-Ala (Fig. 1a–d). In the last case, the separation
was not as good as for the other surfactants in spite of
changing the concentration and the injected volume.
This could be due to the low solubility of C18-Ala in
the used mobile phase.
Synthesis and Characterization of Alanine-Based
Surfactants
Scheme 1 presents the synthesis of sodium salts of n-
alkanesulfonamido-2-propanoic acids. This homologous
series of surfactants corresponding to a mixture of primary
and secondary isomers for each length chain was obtained
in a one-step procedure (Scheme 1).
The alanine-based surfactants were obtained from a
convenient reaction of sodium hydroxide and alanine with
a yield of ca. 90 % and allowed to react with a mixture of
secondary alkanesulfonyl chlorides to give the final sodium
n-alkanesulfonamido-2-propanoate surfactants (C12-Ala,
C14-Ala, C16-Ala, and C18-Ala). All the synthesized
compounds were purified by crystallization in petroleum
ether, leading to a crystalline solid form with yields from
6
4 to 85 %. Their purity was confirmed by the absence of
Scheme 1 Synthesis of sodium salts of n-alkanesulfonamido-2-propanoic acids
1
23

J Surfact Deterg
Fig. 1 Liquid chromatogram of a C12-Ala, b C14-Ala, c C16-Ala, d C18-Ala
It is clear from the mass spectrometry analyses of LC/
HRMS that all the mass spectra exhibited the peak corre-
mation of the molecular weight of the synthesized surfac-
tants. The elemental composition report of the LC/HRMS
also confirmed that the proposed formula corresponds to
that of these alanine-based surfactants. The presence of the
sulfonamide function belonging to the alanine moiety in all
the isomer structures was also confirmed by the presence of
the characteristic fragments at m/z 249, 221, and 277 cor-
-
sponding to the molecular ion [M] with the general for-
-
mula RSO NHCH(CH )COO Na of each sample, at m/
?
2
3
z = 320, 348, 376, and 404 corresponding to C12-Ala,
C14-Ala, C16-Ala, and C18-Ala, respectively (Fig. 2).
These peaks with relatively high intensity allow a confir-
1
23

J Surfact Deterg
Fig. 1 continued
-
responding to [C H SO NHCH(CH )COO] , [C H SO
2
The value of n in the Gibbs equation is the number of
ionic species whose concentrations varied with the sur-
factant concentrations. In this study, n = 2. Cmax, Amin, and
dmin values are given in Table 1.
7
14
2
3
5
10
-
NHCH(CH )COO] , and [C H SO NC(HCH COO)] ,
-
3
9
17
2
3
respectively.
To estimate the performance of these novel alanine-
based surfactants, synthetic glycine-based surfactants and
sodium dodecylsulfate were used as reference surfactants.
It appears from Table 1 that the surface tension
increases when the chain length of the hydrophobic part of
these synthesized surfactants increases, which is in good
agreement with literature data [25–27]. Table 1 shows also
that CMC values decrease with increasing tail length. It
shows also that increasing the chain length leads to an
increase of Amin, and consequently, the Cmax values
decrease. The same tendency has been observed for gly-
cine-based surfactants as reported in Table 1. Concerning
the influence of the addition of a methyl group in the
hydrophilic part, the measured surface tensions are com-
pared well to those of glycine-based surfactants, but the
CMC values are more important. This can be explained by
the probable steric effect of the hydrophilic part which
results in the delay of the CMC. As expected, Amin values
of alanine-based surfactants increased approximately two-
fold, in comparison with those of glycine-based surfactants,
which explains the rapid saturation of the surface.
Surface Properties
CMC and Related Parameters
The curve of the variation of surface tension values versus
log concentration values for different aqueous solutions of
alanine-based surfactants show sharp breaks (Fig. 3),
which were used to determine CMC values of these sur-
factants (Table 1). The surface tension of the surfactant
solutions decreases as their concentrations increase as
shown in Fig. 3. Above the CMC, the surface tension of
surfactant solutions reaches a constant minimum value,
which indicates that the interface is saturated with the
surfactants. The saturation adsorption values Cmax (Gibbs
surface excess) at the air/water interface can be obtained by
using the Gibbs adsorption equation. On the basis of d-log
As expected, Fig. 4 shows that the CMC values decrease
linearly with the increase of the number of carbon atoms
for the two series of amino acid-based surfactants. As is
known, the CMC indeed depends on the hydrophobic part.
-
2
(
concentration) plots, Cmax (mol m ) can be obtained
from the slope of the isotherms using the Gibbs adsorption
isotherm [23–25] as shown in Eqs. 2 and 3:
À1
dd
Cmax ¼
ð2Þ
ð3Þ
2
:303nRT dðlog CÞ
Foaming Power and Stability
1
6
1
0
Amin ¼
Different methods are generally used to determine foam
power and stability. Forster used sparge tube technique or
gas flow [28], Kocz o´ et al. foam beating and gas flow [29],
and Patel et al. a ‘‘whipping’’ method [30]. The most
widely used test for foaminess adopted by the ASTM as a
N C
A
max
NA is Avogadro’s number, R is the gas constant
-
8.31 J mol
1
-1
K ), T is the absolute temperature in kel-
(
vin, and C is the surfactant concentration.
1
23

J Surfact Deterg
Fig. 2 HRMS spectrum of a C12-Ala, b C14-Ala, c C16-Ala, d C18-Ala
1
23

J Surfact Deterg
Fig. 2 continued
standard method is the Ross–Miles method [30, 31] and
Bartsh method [15–17]. The results collected for the foam
ability of the synthesized surfactants are presented in
Fig. 5. As can be seen, the foam height decreases as the
time increase, and the foams become stable. The initial
volume and stability of foam of aqueous solutions depend
on the variation of surface tension: the lower surface
tension is, the greatest the foam volume is, which is in good
agreement with literature data [32].
The residual foam height ratio R , calculated using
5
Eq. 1, as a function of concentration is given in Table 2.
The reported values show that the foam of synthesized
surfactants is stable as R values are greater than 50 %;
5
R5 = 50 % indicates a metastable foam, whereas lower
1
23

J Surfact Deterg
Fig. 3 Variation of surface tension versus the concentration of
alanine based surfactants at 25 °C
Fig. 4 Critical micelle concentration as a function of the C chain
length of alanine and glycine based surfactants
values of R indicate foams of low stability [23]. Table 3
5
the low height and stability of their foam. Finally and as
shown in Table 3, the addition of one methyl group in the
hydrophilic part of these surfactants has an important
influence on their foam properties except for C12-Ala
which possesses better foam properties than the corre-
sponding C12-Gly.
shows the foam volume of the alanine- and glycine-based
surfactants at the same concentrations and foam conditions.
As shown, the volume of foam also seems to depend on the
nature of the hydrophilic group. Indeed, the addition of a
methyl group increases the initial foam volume, which is in
agreement with the low surface tension values obtained,
but decreases the foam stability after 30 min in comparison
with glycine-based surfactants. The high initial volume
foam value of C14-Ala could be explained by the inter-
chain cohesion. This latter imparts elastic and mechanical
strength to liquid lamellar enclosing the gas in the foam
while it increases with the increase of the length of the
hydrophobic part [28, 33]. The surfactants with longer
length chain C16-Ala and C18-Ala have low water solu-
bility at 25 °C which may probably explain the reason for
Conclusion
In this work a series of alanine-based surfactants, namely
sodium salts of n-alkanesulfonamido-2-propanoic acids,
was synthesized with good yields by a simple method using
synthesized secondary n-alkanesulfonyl chlorides and ala-
nine as starting materials. The structures of these surfac-
tants were determined using FTIR, GC/MS/EI, and LC/
Table 1 CMC values of
alanine-based surfactants at
5 °C
2
10
2
˚
Amin (A /molecule)
CMC mole/L
mN/m
Umax (erg/cm ) 10
2
-2
C12-Ala
1.77 9 10
3.54 9 10
1.65 9 10
6.04 9 10
1.08 9 10
2.2 9 10
31
32
33
33
31
33
34
33
32.5
1.01
0.95
0.78
0.65
2.28
1.87
1.57
1.3
164.38
174.76
212.85
255.43
72.83
88.8
-
-
-
-
-
-
-
-
2
3
4
2
3
3
4
3
C14-Ala
C16-Ala
C18-Ala
C12-Gly [15]
C14- Gly [15]
C16-Gly [15]
C18-Gly [15]
SDS [24, 25]
1.2 9 10
105.76
127.73
53
3.01 9 10
7.94 9 10
3.6
C12-Gly, C14-Gly, C16-Gly, C18-Gly are glycine-based surfactants
1
23

J Surfact Deterg
Fig. 5 Variation of the foam height versus time for a C12-Ala, b C14-Ala, c C16-Ala, d C18-Ala
Table 2 Residual foam height ratio R
Concentration
5
Table 3 Foam volume of alanine- and glycine-based surfactants at
concentration of 6 mol/L
R
5
Initial foam
volume
Foam volume
after 30 min
(mm)
Foam
volume after
2 h (mm)
C12-Ala
C14-Ala
C16-Ala
C18-Ala
(
mm)
-
2
1
8
6
4
2
0
98.0
98.6
88
96.29
88.0
85.8
72.7
92.2
98.4
95.4
96.4
97.7
92.8
84.6
89.3
88.8
76.6
100
-3
-3
-3
-2
9 10
9 10
9 10
9 10
C12-Ala
90
88
55
59
14
75
50
30
37
73
5
C14-Ala
120
85
32
77
80
70
49
88.9
80.0
C16-Ala
4
C18-Ala
0
C12-Gly [15]
C14-Gly [15]
C16-Gly [15]
C18-Gly [15]
70
40
20
24
HRMS methods. The study of their physicochemical
properties shows that the surface tension values decrease
with the increase of surfactant hydrophobic lengths and
with the concentration of surfactants. The addition of one
methyl group to the hydrophilic part therefore has an
important influence on the surface parameters as the CMC,
Cmax, and Amin. From the foam study, it appears that the
sodium salts of n-alkanesulfonamido-2-propanoic acids
possess good foam properties, but that the addition of a
methyl group influences the foam stability over time.
1
23

J Surfact Deterg
1
1
1
7. Tazerouti A, Rahal S, Soumillion JPh (1994) The photochemical
chlorosulfonation of heptane by sulfuryl chloride: the role of
solvent and catalyst-a reinvestigation. J Chem Res 1:1101–1119
8. Azira H, Assassi N, Tazerouti A (2003) Synthesis of long-chain
alkanesulfonates by photosulfochlorination using sulfuryl chlo-
ride. J Surfact Deterg 6:55–59
9. Assassi N, Tazerouti A, Soumillion JP (2005) Analysis of chlo-
rinated, sulfochlorinated and sulfonamide derivatives of n-te-
tradecane by gas chromatography/mass spectrometry.
J Chromatogr A 1071:71–80
References
1
. Infante MR, P e´ rez L, Pinazo A, Clap e´ s P, Mor a´ n MC, Angelet M,
Garc ´ı a MT, Vinardell MP (2004) Amino acid-based surfactants.
CR Chimie 7:583–592
2
. Furutani T, Ooshima H, Kato J (1997) Preparation of N-O-diacyl
ethanolamine from N-acyl ethanolamine using lipase prepara-
tions. Enzyme Microbiol Technol 20:214–220
3
4
. Gallot B, Hassan HH (1989) Lyotropic lipo-amino-acids: syn-
thesis and structural study. Mol Cryst Liq Cryst 170:195–214
. Foley P, Kermanshahi-pour A, Beach SE, Zimmerman JB (2012)
Derivation and synthesis of renewable surfactants. Chem Soc Rev
2
2
0. Fekarcha L, Tazerouti A (2012) Surface activities, foam prop-
erties, HLB, and Krafft points of some n-alkanesulfonates (C14
18) with different isomeric distributions. J Surfact Deterg
5:419–431
-
C
1
4
1:1499–1518
5
6
. Walia NK, Cameotra SS (2015) Lipopeptides: biosynthesis and
applications. J Microb Biochem Technol 7:103–107
. Mohamed AS, Mohamed MZ, Ismail DA (2004) Alanine based
surfactants: synthesis and some surface properties. J Surfact
Deterg 7(4):415–419
1. Piispanen PS, Persson M, Claesson M, Norin T (2004) Surface
properties of surfactants derived from natural products. Part 2:
structure/property relationships—foaming, dispersion, and wet-
ting. J Surfact Deterg 7(2):161–167
2
2
2. Lunkenheimer K, Malysa K (2003) Simple and generally appli-
cable method of determining and evaluation of foam properties.
J Surfact Deterg 6:69–74
3. Tamura T, Kaneko Y, Ohyama M (1995) Dynamic surface ten-
sion and foaming properties of aqueous polyoxyethylene n-do-
decyl ether solutions. J Colloid Interf Sci 173:493–499
4. Myers D (2006) Surfactant science and technology, 3rd edn.
Wiley, New Jersey
5. Rosen MJ, Kunjappu JT (2012) Adsorption of surface-active
agents at interfaces the electrical double layer. In: Surfactants and
interfacial phenomena, 4th edn, Wiley, New Jersey
6. Holmberg K (2002) Handbook of colloid and surface chemistry,
Part 1. Wiley, London
7. Dahanayake M, Cohen AW, Rosen MJ (1986) Relationship of
structure to properties of surfactants. 13. Surface and thermody-
namic properties of some oxyethylenated sulfates and sulfonates.
J Phys Chem 90:2413–2418
7
8
9
. Al-Sabagh AM, Nasser NM, El-Azabawy OE, El-Tabey A (2016)
Corrosion inhibition behavior of new synthesized nonionic sur-
factants based on amino acid on carbon steel in acid media. J Mol
Liq 219:1078–1088
. Baier G, Baki A, Tomcin S, Mail a¨ nder V (2014) Stabilization of
nanoparticules synthesized by miniemulsion polymerization
using ‘‘green’’ amino-acid based surfactant. Macromol Symp
2
2
3
37:9–17
. Katz JS, Tan Y, Kuppannan K, Song Y, Brennan DJ, Young T,
Yao L, Jordan S (2016) Amino-acid-incorporating nonionic sur-
factants for stabilization of protein pharmaceuticals. ACS Bio-
mater Sci Eng 2(7):1093–1096. doi:10.1021/acsbiomaterials.
2
2
6
b00245
1
0. Yokota H, Sagawa K, Eguchi C, Takehara M, Ogino K, Shi-
bayama T (1985) New amphoteric surfactants derived from
e
lysine. I. Preparation and properties of N -acyllysine derivatives-
acyllysine derivatives. J Am Oil Chem Soc 62:1716–1719
2
8. Forster CF (1989) Foam and the activated sludge process. In:
Wilson AJ (ed) Foams: physics, chemistry and structure.
Springer, London, p 167
1
1
1. Braun
DB
(1989)
Developments
lipoamino acids and their salts. Cosmet Toilet 104:87–96
with -
2. Pinazo A, Manresa MA, Marques AM, Bustelo M, Espuny MJ,
Perez L (2015) Amino acid–based surfactants: new antimicrobial
agents. Adv Colloid Interface Sci 228:17–39. doi:10.1016/j.cis.
2
9. Kocz o´ K, R a´ cz G (1991) Foaming properties of surfactant solu-
tions. Colloid Surf 56:59–82
3
0. Patel PD, Stripp AM, Fry JC (1988) Whipping test for the
determination of foaming capacity of protein: a collaborative
study. Int J Food Sci Tech 23:57–63
2
015.11.007
1
1
3. Sandler SR, Schon SG, Gardner DM (1991) Process for the
preparation of alkane and arenesulfonamides. US Patent 5068427
4. Kołaczek A, Fusiarz I, Ławecka J, Branowska D (2014) Bio-
logical activity and synthesis of sulfonamide derivatives: a brief
review. Chemik 68(7):620–628
3
3
3
1. Ross J, Miles G (1941) An apparatus for comparison of foaming
properties of soaps and detergents. Oil Soap 18:99–102
2. Rosen M, Solash J (1969) Factors affecting initial foam height in
the Ross-Miles foam test. J Am Oil Chem Soc 46:399–402
3. Rosen M (2004) Foaming and antifoaming by aqueous solution of
surfactants. In: Surfactants and interfacial phenomena, 3rd edn.
Wiley, New York
1
1
5. Mousli R, Tazerouti A (2011) Synthesis and some surface
properties of glycine-based surfactants.
4:65–72
6. Tazerouti A, Rahal S, Soumillion JPh (1992) Simultaneous gas
chromatographic analysis of heptyl chloride-heptanesulfonyl
chloride isomeric mixtures. J Chromatogr A 596:132–137
J Surfact Deterg
1
1
23