Colloids and Surfaces A: Physicochem. Eng.

Aspects 424 (2013) 2632

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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
j our nal homepage: www. el sevi er . com/ l ocat e/ col sur f a
Improvement of Ca
2+
-tolerance by the introduction of EO groups for
the anionic surfactants: Molecular dynamics simulation
Yijian Chen, Guiying Xu

Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100, Peoples Republic of China
h i g h l i g h t s
Some Ca
2+
ions enter into the inter-
face only in the SDES and SDBES
systems.
The appearance of Ca
2+
ions
decreases the interactions between
O SO
3

groups and Na
+
ions.
The introduced EO groups can bind
Ca
2+
ions and restrict the mobility of
Ca
2+
ions.
Only a few free Ca
2+
ions interact
with the head groups for the exist-
ence of EO groups.
The presence of EO groups also
increases the hydration ability of
O SO
3

groups.
g r a p h i c a l a b s t r a c t
In the SDS and SDBS systems, the Ca
2+
ions are mostly around the head groups, and tend to precipitate
surfactants, while more Ca
2+
ions should close to the O
p
in the SDES and SDBES systems, andonly afew Ca
2+
ions appear to the head groups, then the surfactants would not precipitate easily, so the Ca
2+
-tolerances
of SDES and SDBES molecules are higher than that of SDS and SDBS molecules.
a r t i c l e i n f o
Article history:
Received 7 November 2012
Received in revised form2 February 2013
Accepted 8 February 2013
Available online 27 February 2013
Keywords:
Ca
2+
-tolerance
Anionic surfactant
Oxyethylene
Molecular dynamics simulation
a b s t r a c t
The inuence of Ca
2+
on the aggregation of sodium dodecyl sulfate (SDS), sodium dodecyl oxyethy-
lene sulfate (SDES), sodium dodecyl benzene sulfate (SDBS) and sodium dodecyl benzene oxyethylene
sulfate (SDBES) at airwater interface were compared to investigate the role of oxyethylene unit by
means of the molecular dynamics simulation. In the SDES and SDBES systems, the interaction between
O SO
3

groups and Na
+
ions decreases, the diffusion coefcient of Na
+
increases, while the interac-
tion between surfactants and Ca
2+
ions increases, and the diffusion coefcient of Ca
2+
ions decreases.
Unlike SDS and SDBS systems, the EO groups introduced may bind Ca
2+
ions and the interaction between
Ca
2+
ions O SO
3

groups is weakened, consequently, the precipitation of anionic surfactant by Ca

2+
ion is restrained, i.e., the Ca
2+
-tolerance of anionic surfactants via the introduction of EO groups may be
improved. The present results could help in choosing of anionic surfactants used in aqueous solution with
inorganic salts.
2013 Elsevier B.V. All rights reserved.
1. Introduction
The effects of counterions onthe aggregationbehavior of surfac-
tants have been widely investigated [18]. Many researches focus
on the inuence of inorganic salt on the aggregation of anionic sur-
factants [918], for example, the aggregate size and structure of the

Corresponding author. Fax: +86 531 88564750.

E-mail address: xuguiying@sdu.edu.cn (G. Xu).
sodium dodecyl sulfate (SDS) micelles were changed by the addi-
tion of sodiumchloride (NaCl) or calciumchloride (CaCl
2
) [9], and
inthe systemwithCa
2+
ions, more compact andstable SDS micelles
formed due to the presence of Ca
2+
ions salt-bridge. Our previous
results indicated that the potential of mean force (PMF) between
the interacting ion-pair reveal the binding ability of SDS or sodium
dodecyl sulfonate (SDSn) to Ca
2+
or Mg
2+
ions [10]. Both ions can
enter into the rst hydration shell of head groups to disrupt the
H-bond structure between head groups and water molecules, but
the energy barriers to ion-pairing betweenthe headgroupandCa
2+
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.02.026
Y. Chen, G. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 424 (2013) 2632 27
andMg
2+
inthe SDSnsystemwere higher thanthose inthe SDS sys-
tem, dodecyl sulfate ion (SD

) can bind the ions more easily than

the dodecyl sulfonate ion. As for alkyl benzene sulfonate interfacial
monolayer, the addition of counterions (Na
+
, Mg
2+
and Ca
2+
) would
screen electrostatic repulsions between head group, and enter into
their hydration shell [11]. The salt-tolerance of alkyl benzene sul-
fonate with branched chain were superior to that with linear chain
[11]. Penfold and co-workers also showed that the addition of Ca
2+
ions wouldinuencetheaggregates of alkyl benzenesulfonatewith
linear chain more than that with branched chain [12].
The addition of other surfactants or polymers can also change
the aggregates of anionic surfactants [1927]. The mixed micelles
of SDS and pentaethylene glycol mono-n-dodecyl ether (C
12
EO
5
)
show a higher cloud point and a lower Krafft point relative to SDS
micelles [19]. The aggregation behavior of the mixtures of sodium
6-dodecyl benzene-4 sulfonate with the nonionic surfactants mon-
ododecyl octaethylene glycol and monododecyl triiscosaethylene
glycol in the presence of Ca
2+
and Na
+
ions were compared by Pen-
fold et al. [1]. The phase transition of mixtures were correlative to
the number of EO groups. The addition of C
12
EO
6
(hexaethylene
glycol mono-n-dodecyl ether) can remove the bound SDS fromthe
poly(vinylpyrrolidone) chain, and the mixed SDS/C
12
EO
6
micelles
were formed simultaneously [22]. The C
12
EO
6
would change the
electrostatic interactions between the O SO
3

groups of SDS
molecules. The aggregation number of micelle increases with the
addition of tetraoxyethylene dodecyl ether into the SDS micel-
lar solutions for decrease of the electrical surface potential [23].
In the mixtures of SDS and tetraethylene glycolmonooctyl ether
(C
8
EO
4
), Na
+
ions act as a connector between the SD

ions and the

ether oxygen atomof C
8
EO
4
molecules by the electrical attraction
[27].
The oxyethylated sodium alkyl sulfates (C
n
E
m
SO
4
Na) may be
considered as oxyethylene units introduced into C
n
SO
4
Na. Com-
pare toC
n
E
m
andC
n
SO
4
Na, the C
n
E
m
SO
4
Na have higher cloudpoint,
high salt-tolerance and lower Kraff point. The sodium dodecyl
oxyethylene sulfate (SDE
n
S) was widely investigated for the excel-
lent properties [2832]. The critical micelle concentrations and
average aggregation numbers are independent of the EO numbers,
which may be induced by the intermolecular interaction of the
O SO
3

groups and intermolecular ion-dipole attraction of the

OCH
2
dipole of the oxyethylene (OE) group [29]. The growth of
sodiumdodecyl trioxyethylene sulfate (SDE
3
S) micelles was inves-
tigated with different salts, AlCl
3
, MgCl
2
, CaCl
2
, and NaCl [30].
The interactions between cations and SDE
3
S head groups would
change the packing parameter of SDE
3
S, and the micellar growth
was enhanced with the following order: Al
3+
>Mg
2+
>Ca
2+
>Na
+
.
Another result alsoshowedthat theadditionof monododecyl dode-
caethylene glycol (C
12
EO
12
) wouldinhibit the transitions of sodium
dodecyl dioxyethylene sulfate (SDE
2
S) frommonolayer to bilayer,
trilayer and multilayer induced by Al
3+
ions at the airwater inter-
face [2]. In solution, C
12
EO
12
suppressed the transition of SDES
micelles to lamellar structures and ultimately precipitation. These
inhibitions were all caused by the steric hindrance of EO groups.
However, it is still unclear about their salt-tolerant mechanisms,
especially the role of the oxyethylene units. Also in the systems
with poly (ethylene glycol) (PEG) and liposome [33], the Ca
2+
ions
combined tightly to the lipid head groups, but there was no inter-
action between Ca
2+
ions with PEG, the presence of EO groups in
the PEG would inhibit liposome fusion induced by Ca
2+
ions.
Molecular dynamics (MD) simulations are powerful methods to
investigate the relationship between the molecular structure and
their properties at the atomistic level [10,11,3440]. To examine
theinuenceof oxyethylenegroupfor theCa
2+
-tolerances of anionc
surfactants, we used MD simulations to study the aggregation of
sodiumdodecyl sulfate (SDS), sodiumdodecyl oxyethylene sulfate
(SDES), sodiumdodecyl benzenesulfate(SDBS) andsodiumdodecyl
benzene oxyethylene sulfate (SDBES) molecules (Scheme 1) at the
airwater interface in the presence of Ca
2+
ions.
2. Simulation details
The molecular structures of SDS, SDES, SDBS and SDBES are
shown in Scheme 1 and only the charges of oxygen atoms are
labeled. The different systems are processed after charges and
potentials were assigned into each atom. Water molecule is
described by simple point charge (SPC) model. Similar to our pre-
vious work [11], we set up a system with two monolayers on
opposite sides of a aqueous solution that is thick enough to isolate
two monolayers. The original systems contain 18 surfactants (each
monolayer 9) and 400 water molecules, the 18 Na
+
ions separating
fromthe surfactants and 9 CaCl
2
are place into the aqueous phase.
The thickness of aqueous box is about 32

A and the dimension of
the simulation box is 2121160

A
3
.
The MD simulations are performed with the standard periodical
boundary conditions using Materials Studio 4.4 molecular dynam-
ics program package. The potential functions and parameters are
taken from the PCFF force eld. All the initial congurations are
minimized with the Smart Minimizer method. After the minimi-
zation, all simulations are equilibrated 1ns with a time step of 1fs
in the NVT ensemble at 298K kept constant by the HooverNse
thermostat with a relaxation time of 0.2ps [41]. Another 1ns simu-
lation is calculated for equilibrium. For the long-range electrostatic
Scheme 1. Structure of SDS, SDES, SDBS and SDBES (only the charge of oxygen atoms are shown and hydrogen atoms are omitted for clarity).
28 Y. Chen, G. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 424 (2013) 2632
Fig. 1. Snapshots of the conguration at the end of simulation of different systems
(A, SDS; B, SDES; C, SDBS and D, SDBES). The carbon atoms (gray), hydrogen atoms
in the carbon chains (white), sulfur atoms (yellow), oxygen atoms in the sulfate
groups (red), sodium ions (purple) and calcium ions (green) are highlighted. (For
interpretation of the references to color in this gure legend, the reader is referred
to the web version of the article.)
potential, the Ewald method is used and the interactions are cut off
at 9.5

A.
3. Results and discussion
3.1. The structural properties of the aggregates
Monolayers are formed at the water surface (Fig. 1), the aggre-
gates of SDS and SDBS (Fig. 1A and C) are more roughness than
that of SDES and SDBES (Fig. 1B and D). Since the presence of EO
groupwouldreduce the charge of sulfate group, andthenthe repul-
sions between the O SO
3

groups decrease, the monolayers are

compact and the carbon chains are orderly in the SDES and SDBES
systems. While the monolayers are rough and the carbon chains
are disorderly in the SDS and SDBS systems. In the SDES and SDBES
systems, more Ca
2+
ions close to the interface compared to SDS
and SDBS systems. The more details of the aggregates of the surfac-
tants are analyzed by density proles in a direction normal to the
plane of the interface (Z direction) (Fig. 2). Some similar results are
obtained in all systems: the distributions of O SO
3

groups and
carbonchains are concentratedat the interface; most Na
+
ions close
tothe interface, a fewappear inother domains. While the proles of
Ca
2+
ions are different, there is anobvious peak inFig. 2Banda huge
peak in Fig. 2D corresponding to Fig. 2A or Fig. 2C, which reveals
more Ca
2+
ions enter into the interface in the SDES and SDBES sys-
tems. The entrance of more Ca
2+
ions would replace some Na
+
ions
fromthe interface by the electrostatic repulsion, and then there are
more Na
+
ions appear in aqueous solution in the SDES and SDBES
systems.
3.2. Interaction between surfactants and ions or water
The radial direction functions (RDFs) between different parts of
the systems are analyzed to compare the Ca
2+
-tolerance of the four
surfactants and to investigate the role of EO groups in detailed.
The correlations of O SO
3

groups with counterions are calcu-

lated in Fig. 3. As shown in Fig. 3A, the huge rst peaks of the RDFs
between O
24
atoms (oxygen atoms in O SO
3

group shown in
Scheme 1) and Na
+
ions are around 3.2

A, which means that around
the O
24
atoms, almost all the Na
+
locate at 3.2

A. While the rst
peak values of SDES and SDBES systems are lower than those of SDS
and SDBS systems. Also the same results are obtained for the RDFs
between O
1
atoms and Na
+
ions (Fig. 3B), which indicate that the
introduction of EO groups would decrease the interaction between
O SO
3

groups andNa
+
ions. FromFig. 3C, thepresenceof therst
small peak around 3

A means that only a fewCa
2+
ions can close to
O
24
atoms, more Ca
2+
ions locate about 5.4

A and 7.6

A around the
O
24
atoms. In the SDES and SDBES systems, the second and third
peak values are higher than those in SDS and SDBS systems. Differ-
ent results of the RDFs of O
1
atoms to Ca
2+
ions are shown in the
Fig. 3D, the intensities of rst peak of SDES and SDBES systems are
higher than those of SDS and SDBS systems, which reveal that the
interaction between Ca
2+
ions and O
1
atoms increase.
The RDFs of O
24
O
w
(O atom in the water molecule) and
O
1
O
w
are shown in Fig. 4, the rst peak around 3

A and second
peak around 5.2

A corresponds to the rst and second water shells
Fig. 2. Density prole of SDS (A), SDES (B), SDBS (C) and SDBES (D) systems in a direction normal to the plane of the interface.
Y. Chen, G. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 424 (2013) 2632 29
0 2 4 6 8 10
0
5
10
15
20
25
30
g
(
r
)
r /
SDS
SDES
SDBS
SDBES
A
0 2 4 6 8 10
0
5
10
15
20
25
30
r /
SDS
SDES
SDBS
SDBES
B
0 2 4 6 8 10
0
1
2
3
4
5
g
(
r
)
r /
SDS
SDES
SDBS
SDBES
C
0 2 4 6 8 10
0
1
2
3
4
5
g
(
r
)
r /
SDS
SDES
SDBS
SDBES
D
Fig. 3. RDF of O atoms in the O SO
3

groups to counterions, A, g(r

O
24
-Na
+ ), B, g(r
O
1
-Na
+ ), C, g(r
O
24
-Ca
2+ ) and D, g(r
O
1
-Ca
2+ ).
of the O
24
andO
1
atoms, respectively. FromFig. 3AandB, we know
that almost all Na
+
ions locate about 3.2

A around the O
24
and O
1
atoms, whichindicates that theNa
+
ions arealmost intherst water
shell of the O
24
and O
1
atoms. However, Fig. 3C shows that more
Ca
2+
ions locate about 5.4

A and 7.6

A around the O
24
atoms, so the
Ca
2+
ions are almost in the second water shells of O
24
atoms, only
a few Ca
2+
ions enter into the rst water shells. Different results
are received fromFig. 3D, in the SDES and SDBES systems, the Ca
2+
ions locate the rst and the second water shells of O
1
atoms, which
indicates that the existence of EO groups make the Ca
2+
ions close
to O
1
atoms and enhances the interaction between them.
To nd out why the introduced EO group can affect the inter-
action between O SO
3

groups and Ca
2+
ions, the RDFs of O
p
(oxygen atom in the EO group) to Ca
2+
ions and O
w
are analyzed
to investigate the interactions between EO groups and Ca
2+
ions
and water molecules (Fig. 5). As shown in Fig. 5A, the location of
rst peak is around 2.75

A smaller than that in Fig. 3C and D, and
the intensities are higher, also the Ca
2+
ions almost close to the
rst and second water shells, which means that the interaction of
O
p
Ca
2+
are stronger than O
24
Ca
2+
and O
1
Ca
2+
. From Fig. 5A
and B, the intensities of rst peak of SDES systems are higher than
those of SDBES system, which means that the interaction between
O
p
atoms and Ca
2+
ions is stronger and the hydration ability of O
p
is higher in the SDES systems, those may be attributed to the steric
hindrance of benzene ring in the SDBES molecules. It will be seen
fromthe above results that the interactions between the O
p
, O
1
and
O
24
atoms with Ca
2+
ions are different. The scheme of the inter-
action between O
p
, O
1
and O
24
atoms with Ca
2+
ions is shown
in Fig. 6. In the SDS and SDBS systems, the Ca
2+
ions are mostly
around the head groups, and tend to precipitate surfactants, while
more Ca
2+
ions should close to the O
p
in the SDES and SDBES sys-
tems, and only a fewCa
2+
ions appear to the head groups, then the
surfactants would not precipitate easily, so the Ca
2+
-tolerances of
SDES and SDBES molecules are higher than those of SDS and SDBS
molecules.
To further reveal the inuence of the introduced EO group, the
average coordination numbers are compared via the integral of the
RDFs (Figs. 3C, D, 4 and 5) fromzero to the rst minimum(the rst
peak). Since the cutoff distance of Ca
2+
ions is 3.0

A and a bond ion
is described if the distance between Ca
2+
ions and other oxygen
atoms less than 3.0

A [42], only the coordination numbers of the
rst peak for Ca
2+
ions are calculated. Also the same coordination
0 2 4 6 8 10
0
2
4
6
8
g
(
r
)
r /
SDS
SDES
SDBS
SDBES
A
0 2 4 6 8 10
0
2
4
6
g
(
r
)
r /
SDS
SDES
SDBS
SDBES
B
Fig. 4. RDF of O atoms in the O SO
3

groups to water molecules, A, g(r

O
24
-Ow
) B, g(r
O
1
-Ow
).
30 Y. Chen, G. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 424 (2013) 2632
0 2 4 6 8 10
0
2
4
6
8
10
g
(
r
)
r /
SDES
SDBES
A
0 2 4 6 8 10
0
2
4
6
8
B
g
(
r
)
r /
SDES
SDBES
Fig. 5. RDFs of Op (oxygen atomin the EO group) to Ca
2+
(A) and Ow (B).
Fig. 6. Scheme of the interaction between the Op, O
1
and O
24
atoms with Ca
2+
ions, carbon atoms (gray), sulfur atoms (yellow), oxygen atoms (red) and calcium
ions (green). (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of the article.)
Table 1
Coordination numbers of Ca
2+
ions and water molecules around the oxygen atoms
in the surfactants.
System Ca
2+
Ow
O
24
O
1
Op O
24
O
1
Op
SDS 0.22 0.14 6.89 2.41
SDES 0.13 1.59 2.55 7.22 2.59 2.74
SDBS 0.16 0.11 6.99 2.64
SDBES 0.16 1.58 2.18 7.59 2.73 2.46
numbers of rst peak for water molecules are compared to express
their hydration ability. The results are shown in Table 1. The
coordination numbers means the bond numbers of Ca
2+
ions or
water molecules for aimed atoms (O
24
, O
1
and O
p
), the higher
value means stronger interaction between them. For the SDS and
SDES systems, the number of bond Ca
2+
ions of the O
1
atoms is 1.59
in SDES systemand it is only 0.14 in SDS system. Also the numbers
of bond water molecules of the O
24
and O
1
atoms are a little
higher in the SDES systemthan those in the SDS system. However,
the number of bond Ca
2+
ions of the O
24
atoms are 0.13 in the
SDES system lower than that 0.22 in the SDS system. The similar
results are received from the SDBS and SDBES systems. These
results indicate that the introduced EO groups only enhance the
interaction between Ca
2+
ions and O
1
atoms remarkably; decrease
the interaction between Ca
2+
ions and O
24
atoms (SDES system)
or have little inuence (SDBES system); increase the hydration
ability of O
24
and O
1
atoms. Thus the Ca
2+
-tolerances of SDES and
SDBES systems are higher than those of SDS and SDBS systems.
3.3. Self-diffusion coefcients of counterions
As the interaction between surfactants and counterions were
affected by the introduced EO group, the dynamics properties of
counterions were analyzed by the self-diffusion coefcient, which
represent the mobility of transference for target ions in solution. To
receive the self-diffusion, the mean square displacements (MSD)
were shown in Fig. 7, which are calculated fromEq. (1).
MSD (t) =

1
N
N

i=1

r
i
(t) r
i
(0)

(1)
where N is the number of target molecules and r
i
(t) is the position
of molecule i at time t. The mobility of different ions is compared by
self-diffusion coefcients (D

) from Eq. (2), the results are shown

in Table 2.
D

=
1
6N

lim
t
d
dt
N

i=1

[r
i
(t) r
i
(0)]
2

(2)
Fig. 7. Mean square displacements of Na
+
(A) and Ca
2+
(B).
Y. Chen, G. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 424 (2013) 2632 31
Table 2
Self-diffusion coefcients of the Na
+
ions and Ca
2+
ions.
System D(Na
+
)/ 10
5
cm
2
s
1
D(Ca
2+
)/ 10
5
cm
2
s
1
SDS 0.33 0.23
SDES 0.62 0.17
SDBS 0.47 0.20
SDBES 0.70 0.16
In SDS and SDBS systems, the mobility of Na
+
ions are low
by the restriction of Ca
2+
ions, and high electrostatic interaction
between O SO
3

groups and Na
+
ions also would decrease the
self-diffusion coefcients of Na
+
ions. While in the SDES and SDBES
systems, the EO groups combine more Ca
2+
ions and inhibit the
mobility of Ca
2+
ions, and then lower the self-diffusion coefcients
of Ca
2+
ions. The combined Ca
2+
ions would replace some Na
+
ions
from the head group, and then the mobility of Na
+
ions becomes
facile and the self-diffusion coefcients of Na
+
ions increase. The
results are coincident with those taken fromthe RDFs.
4. Conclusions
The inuence of introduced EO group on Ca
2+
-tolerance has
been investigated by molecular dynamics simulation in the SDS,
SDES, SDBS and SDBES systems. The results showthat concentrated
monolayers are formed at the interface for all systems. Na
+
ions are
almost near the rst water shell of the O
p
, O
1
and O
24
atoms in
all systems, while most Ca
2+
ions locate on second water shell of
the O
p
, O
1
and O
24
atoms in SDS and SDBS systems, some Ca
2+
ions enter into O
p
and O
1
atoms with the introduced EO groups in
the SDES andSDBES systems. The interactions betweenO
1
andO
24
withNa
+
ions are smaller inthe SDES andSDBES systems thanthose
in the SDS and SDBS systems as more Ca
2+
ions appearance. The
introduced EO groups can bind Ca
2+
ions and restrict the mobility
of Ca
2+
ions, only a fewfree Ca
2+
ions interact with the head groups,
and then the surfactants precipitate hardly, also the presence of EO
groups increases the hydrationability of O SO
3

groups, thus the

Ca
2+
-tolerances of SDES andSDBES molecules are muchhigher than
those of SDS and SDBS molecules.
Acknowledgments
This work is nancially supported by the National Nature Sci-
ence Foundation of China (Grant No. 20833010) and the Special
Program for Major Research of the Science and Technology, China
(Grant No. 2011ZX05024-004-08).
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