Colloids and Surfaces A 529 (2017) 64–72

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Effect of biological buffers on the colloidal behavior of sodium dodecyl MARK

sulfate (SDS)
⁎
Bhupender S. Gupta, Chi-Ren Shen, Ming-Jer Lee
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106-07, Taiwan

H I G H L I G H T S G RA P H I C A L AB S T R A C T

• tions
MCs of SDS in aqueous buffer solu-
were measured.
• The studied buffers include TRIS, TES,
and TAPS.
• TRIS increased the CMC, while TES
and TAPS decreased the CMC.
• Results were explained on partitioning
of buffers to water or micelle.

A R T I C L E I N F O A B S T R A C T

Keywords: This study investigates the influence of three commonly used buffers (TRIS, TES and TAPS) on the conductivities
Surfactant and the colloidal behavior of the aqueous solutions containing a surfactant, sodium dodecyl sulfate (SDS). To
Aggregation find the effect of these buffers on the aggregation behavior of the aqueous SDS solutions, we experimentally
Biological buffers determined the conductivities of the solutions containing different concentrations of SDS (0.002 M–0.025 M) in
Conductivity
water and in 0.2 M, 0.5 M, and 1.0 M TRIS, TES, and TAPS buffers, respectively, at 298.2 K under atmospheric
Pyrene
pressure. To get insight into the effect of the buffers on the aggregation behavior of the aqueous SDS solutions,
the critical micelle concentration (CMC) values of the aqueous solutions are estimated from the experimental
results of conductivity measurements. Interestingly, in comparison with the CMC of SDS in water, the presence of
TRIS is found to increase the CMC, whereas the addition of TES or TAPS is found to decrease the CMC, especially
at higher concentration (1.0 M). The influence of the buffers on the CMC or aggregation of the SDS is further
characterized by calculating various aggregation parameters such as the degree of ionization of the micelle (αm),
the degree of counter ion binding in micelle (fm), and the standard Gibbs free energy of micellization (ΔG°m) for
all the studied systems. Moreover, the outcomes from the conductivities measurement are reconfirmed by using
the fluorescence probe analysis.

⁎
Corresponding author.
E-mail addresses: mjlee@mail.ntust.edu.tw, mjl6626@gmail.com (M.-J. Lee).

http://dx.doi.org/10.1016/j.colsurfa.2017.05.066
Received 13 March 2017; Received in revised form 16 May 2017; Accepted 22 May 2017
Available online 29 May 2017
0927-7757/ © 2017 Elsevier B.V. All rights reserved.
B.S. Gupta et al.
1. Introduction
The studies on the aggregation or colloidal behavior and the inter-
molecular interactions in the aqueous mixtures containing surfactants
are one of attractive research topics [1]. The main challenge arises from
the co-existence of the hydrophobic and hydrophilic segments on the
same surfactant molecule, which makes the molecule susceptible to
exhibit a variety of interactions [2]. Moreover, surfactants have also
been known to possess the tendency to form aggregated structures such
as micelle or liposomes at particular concentration of surfactant, known
as the critical micelle concentration (CMC) [3]. Since those aggregated
structures may dramatically change the thermophysical properties of
the aqueous solutions, the determination of the CMC is fundamentally
important for the practical applications [4–6].
It is also a well-established fact that by modifying the surfactants
properties such as their interfacial activity, the size of aggregate, and
the morphology of the aggregate, the performance of the surfactants
may be improved to a great extent [7]. Therefore, modulating the
thermophysical properties of surfactant mixtures is highly desirable and
is an attractive task from the industrial point of view. Particularly, in
pharmaceutical industries, where surfactant aggregate structures (mi-
celle or liposomes) are utilized as a drug delivery vesicle, improvement
and understanding of the aggregation behavior could make the design
of the related applications more effective [8]. A number of methodol-
ogies to induce expected alteration in the properties of surfactant sys-
tems have been proposed by the researchers, for example, by modifying
the chemical structure of surfactants [9,10], and by mixing with other
surfactants [11–13]. Apart from these suggested methods, the addition
of an external additive, which can markedly change the physiochemical
properties of surfactant mixtures, is identified as a convenient method
[14]. For this purpose, various potential additives such as salts and
other organic compounds have been already suggested by the re-
searchers [15–20]. Recently, ionic liquids, a new class of green and user
tailored materials, have also been recognized as a suitable candidate to
modify the physiochemical properties of the surfactant systems
[21–26].
Indeed, surfactants have been utilized in many industries and var-
ious applications of the surfactants such as an emulsifier, wetting agent,
dispersant, stabilizer and foam maker or detergent are well-recognized
in the whole world [27,28]. Due to their specific interactions with
various proteins, they have also been gained great attention in biolo-
gical research. Particularly, in the biotechnology and biochemical field,
surfactants provide great help in the solubilization, crystallization,
purification, characterization, extraction and structure determination of
proteins [29,30–33]. Among various available surfactants, the selected
sodium dodecyl sulfate (SDS) is widely used in the protein research to
perform specific tasks. The structure of SDS contains hydrophilic sulfate
group in the head and hydrophobic dodecyl group in the tail (as shown
Fig. 1. Schematic structures of the chemicals.
65
Colloids and Surfaces A 529 (2017) 64–72
Fig. 1). It is an anionic surfactant, well-known for its strong interaction
with various proteins. In general, it is believed that at low concentra-
tion (less than the CMC) of SDS, it electrostatically interacts with pro-
tein and forms SDS-protein complexes. While at the concentration
higher than the CMC value, SDS solubilizes the protein in the interior of
the aggregated structures. For example, Miksovska et al. [34] have
studied the interaction of SDS with horse heart myoglobin (Mb) protein
at surfactant concentration below its CMC. They reported that the SDS
binds to the Mb and makes the heme binding pocket of Mb relatively
exposed to the solvents compared with the native Mb. The results from
Lad et al. [35] have also revealed that about eight SDS anion molecules
may bind with different positively charged amino acid residue on the
surface of per lysozyme molecule, at low concentration. Further, Ghosh
and Banerjee [36] have found that the presence of SDS at the con-
centration above its CMC, the surfactant molecules form aggregates
with trypsin, and the aggregates decrease the binding of counter ion.
Certainly, tremendous efforts have been made worldwide to explore
the aggregation behavior of the surfactants in the presence of a suitable
additive [15–20,21–26]. Also, the mechanism of interactions between
the anionic surfactant SDS and proteins is well understood [37–41] and
various models have been proposed already [42–44]. However, little
attention has been paid to the influence of commonly used buffers on
the aggregation behavior of SDS in biological systems. Since the
structure of protein is mainly composed of a series of amino acids, the
proper functional activity of protein significantly relies on the physio-
logical pH of the medium. Even a minor change in the pH of medium
could be sufficient to induce a deprotonation or protonation in the
amino acid residues and thus may lead to a significant loss in the
functional activity of the protein. Therefore, to protect the native
structure of protein and to keep its functional active, a buffer compound
is always added in a biological medium. The buffer compounds suitably
release or absorb hydronium ion in the medium according to the re-
quirements and thus they keep the pH of medium constant.
For an appropriate biological buffer, in addition to maintaining the
required pH of the medium, it is also expected to provide other ad-
vantageous properties, such as high solubility in the water, highly inert
and stable nature, very low absorbance of UV–vis light, etc. The se-
lected buffers, TRIS, TES, and TAPS are known to meet most of the
requirements of biological buffers and provide a good coverage of pH in
the range of 6.5–9.5. They are structurally related compounds. For
example, TAPS differs from TES by only presence of an extra hydro-
phobic carbon in its chemical structure, while TRIS differs from TES or
TAPS by the absence of sulfonic group and a comparative lack of hy-
drophobic alkyl chain (Fig. 1). Indeed, they are widely employed in
various research areas, including biology, biochemistry, and environ-
mental studies [45]. However, their expected inert nature is constantly
doubted and their complexations with various metal ions have been
already reported in the literature [46–48]. Previously, we have also
B.S. Gupta et al.
highlighted the influence of the commonly used buffers on the protein
or enzyme structure and have reported that most of the buffers possess
the tendency to interact with protein and thus we should consider those
interactions and their adverse effects on our main system of research
[49–51].
With our continuing interest in the buffer molecules, in the present
study, we would like to bring into notice that despite the plenty of
research being performed on the systems involving SDS in buffer so-
lutions, relatively little information has been provided on the me-
chanism of SDS–buffer interactions and the influence of such interac-
tions on the aggregation behavior of SDS. Therefore, in this study we
aim to investigate the influence of the three commonly used buffers,
TRIS, TES and TAPS on the aggregation behavior of the surfactant so-
dium dodecyl sulfate (SDS) in aqueous solutions. For this purpose, we
measure the conductivities of a series of solutions containing different
concentrations of SDS in water and in 0.2 M, 0.5 M, and 1.0 M aqueous
solution of buffers, TRIS, TES, and TAPS, respectively, at 298.2 K under
atmospheric pressure. By using the measured conductometric profile
(conductivities versus SDS concentration), the critical micelle con-
centration (CMC) is determined for each investigated system.
To provide a deep understanding about the effect of these buffers on
the aggregation behavior of SDS, we estimate various aggregation
parameters, including the degree of ionization of micelle (αm), the de-
gree of counter ion binding in micelle (fm), and the standard Gibbs free
energy of micellization (ΔG°m) at 298.2 K for all the studied systems. To
re-confirm the influence of these buffers on the CMC or aggregation
behavior of SDS, we also measure the fluorescence spectra for a series of
solutions with different concentrations of SDS in water and in 0.2 M,
0.5 M, and 1.0 M TRIS, TES, and TAPS aqueous buffer solutions, re-
spectively, by using pyrene as a fluorescence probe at ambient condi-
tion. The results from the fluorescence analysis are found good agree-
ment with the findings from the conductivities data.
2. Experimental section
2.1. Materials
The buffer compounds, TRIS (mass fraction purity > 0.99), TES
(mass fraction purity > 0.99), and TAPS (mass fraction purity > 0.99)
were purchased from Sigma Chemical Co. (USA). The surfactant SDS
(mass fraction purity > 0.99) was also obtained from the Sigma
Chemical Co. (USA). The fluorescence probe pyrene (mass fraction
purity > 0.98) was supplied by Acros Organics (USA). Since all the
chemicals are of analytical grade and purchased from the commercial
sources, they were used directly as received, without any further pur-
ification treatment. The descriptions of chemicals, including the mass
fraction purity level and the suppliers are provided in Table 1. The
double distilled de-ionized water used in the preparation of aqueous
solutions of SDS was obtained from the water purifying system (NANO
pure- Ultra pure) at operating resistivity of 19 MΩ cm. The stock so-
lution of SDS is prepared in water and this solution was used to prepare
the analysis samples containing different concentrations of SDS (in the
range of 0–0.25 M) in water or in 0.2 M, 0.5 M, and 1.0 M TRIS, TES,
and TAPS buffer solutions, respectively.
Table 1
Description of the materials.
Materials Source
TRIS Sigma Chemical Co (USA)
TES Sigma Chemical Co (USA)
TAPS Sigma Chemical Co (USA)
SDS Sigma Chemical Co (USA)
Pyrene Across organics Co. (USA)
Water Our lab water purifying system
66
Colloids and Surfaces A 529 (2017) 64–72
2.2. Conductivity measurement
The electrical conductivity of the prepared samples with different
concentrations of SDS in water and in 0.2 M, 0.5 M, and 1.0 M aqueous
buffer solutions were measured by using a conductometer, (WTW 3210,
Germany) at 298.2 ± 0.2 K. The measurement was performed in a
closed and jacketed measuring cell with an internal volume of 30 cm3,
equipped with a magnetic stirrer for promotion of mixing. The tem-
perature in the cell was controlled by circulating thermostatic water
(FIRSTEK, B402L, Taiwan). The temperature of the prepared solution
inside the cell was measured with a precise digital thermometer
(Model-1560, Hart Scientific Co., USA) with an uncertainty of 0.1 K.
The uncertainty of the conductivity measurement was estimated
as ± 0.01 μS cm−1.
2.3. Fluorescence measurement
Using pyrene as a fluorescence probe and a 1.0 cm quartz-glass cell,
the fluorescence spectra of the samples of SDS in water and in the
aqueous buffer solutions, were measured with a spectro-fluor-
ophotometer (FP-8300, JASCO, Japan) under ambient conditions. The
spectra were obtained at an excited wavelength of 335 nm for the
emission range of 350 nm to 450 nm, with excitation and emission slit
width of 2.5 nm. A series of samples containing different concentrations
of SDS in water and in 0.2 M, 0.5 M, and 1.0 M aqueous buffer (TRIS,
TES and TAPS) solutions, respectively, were prepared. A stock solution
of pyrene (0.5 mg per ml) in methanol was also prepared, and this so-
lution was diluted to 20 times. About 50 microliters of this diluted
solution of pyrene were added to each sample vial.
3. Results and discussions
Conductometry is identified as one of highly efficient methods for
estimating the CMC of SDS in aqueous solutions, especially in the
presence of external additives [52–56]. Therefore, to first understand
the conductometric behavior and then calculate the CMC of the aqu-
eous solutions of SDS in the presence of the commonly used biological
buffers, TRIS, TES, and TAPS, we measured the conductivities of the
series of aqueous solutions containing different concentrations of SDS in
water and in 0.2 M, 0.5 M, and 1.0 M aqueous buffer (TRIS, TES, and
TAPS) solutions at 298.2 K under atmospheric pressure. The purity of
SDS is considered as a major issue in determining the CMC of SDS.
Previous researchers [57–59] highlighted that the surface active prop-
erties of surfactant could be greatly affected by the impurities may
induce such as dodecyl alcohol, polyvalent inorganic and large organic
cations. However, in the present case the stock solution of the SDS is
prepared in large amount and used throughout the study to demon-
strate the relative effect of the buffer on the aggregation behavior of the
SDS. So we believe that, even with contamination due to any newly
formed impurities, the overall relative trend in the aggregation beha-
vior of SDS in the presence of different buffers will remain unaltered.
The measured results are given in Table S1 of the supplementary in-
formation. The conductometric profiles demonstrating changes in the
conductivities of the investigated solutions against the increasing con-
centration of SDS are presented in Fig. 2(a–d).
Mass fraction purity Purification method
> 0.999 no further purification
> 0.990 no further purification
> 0.995 no further purification
> 0.990 no further purification
> 0.990 no further purification
> 0.998 Nanopure-Ultrapure purifying system
B.S. Gupta et al.
Fig. 2. (a–d). The variation of conductivities of aqueous solution of SDS containing different concentrations of buffer (0–1.0 M) at 298.2 K. (a) SDS in TRIS, (b) SDS in TES, (c) SDS in
TAPS, and (d) comparison of the conductivities of SDS in 1.0 M of TRIS, TES, and TAPS aqueous solutions at 298.2 K under atmospheric pressure.
SDS in aqueous solution, at low concentration, behaves as a strong
electrolyte and dissociates completely into ionic species, which con-
tribute to the conductivity of the solution. Therefore, the conductivity
of the monomeric region increases sharply with an increase of SDS
concentration. As the concentration of SDS approaches to its CMC
value, micellization of SDS occurs in the solution. In the micellization
process, a fraction of the counter ions condenses in the Stern layer of
the micelle microstructure due to the columbic attractions [2]. This
condensation of the counter ions decreases the net charge carriers in the
solution and consequently, also decreases the rate of increment of
conductivity with an increase of SDS concentration in the post-micelle
region. Thus, the conductometric profile of SDS involving pre-micelle
region (monomeric) and post-micelle region (aggregates) shows a sharp
break point at the intersection of these two linear regions. This inter-
section point of the pre- and post-micelle regions is taken as the CMC of
the surfactant [60,61]. From Fig. 2(a–c), it can be seen that the con-
ductivities of SDS in 0.2 M, 0.5 M, and 1.0 M TRIS, TES, and TAPS
buffer solutions are significantly higher than those of SDS in water.
Since these buffers (TRIS, TES, and TAPS) are zwitterionic compounds
in nature and in aqueous solutions, they behave like normal kosmo-
tropic salts [62]. The observed higher values of the conductivities of
SDS in the presence of these investigated buffers are expected from the
contribution of buffers in the total charge carriers.
The conductivity profiles of SDS in 0.2 M TRIS, TES, and TAPS
67
Colloids and Surfaces A 529 (2017) 64–72
aqueous solutions are found to be similar in shape to that of SDS in
water. However, the conductivity profiles are non-identical to each
other at higher concentrations (0.5 M and 1.0 M). Especially in case of
the TES and TAPS buffers, a relative decrease in the slope of the pre-
micelle region is noticed with increasing the buffer concentration. This
trend in the slope of the pre-micelle region with respect to the increase
in the respective buffer concentration is expected due to the large size
and high molecular weight of the TES and TAPS buffer. Moreover, the
break point between the pre- and post-micelle regions of the con-
ductivity profile disappears for SDS in 1.0 M TES, and in 0.5 M and
1.0 M TAPS aqueous solutions. The dis-appearance of the break point or
the pre-micelle region indicates that in the aqueous solution containing
higher concentration of these buffers (TES or TAPS), the aggregation or
micelle formation of SDS take place below the investigated range of the
SDS concentration. The conductivities of SDS in aqueous solutions of
TRIS, TES, and TAPS at higher concentration (1.0 M) are compared in
Fig. 2(d). From this figure, it can be seen that the overall influence of
these buffers on the conductivities of SDS follows the order of T-
APS > TRIS > TES.
Various methods have been employed to estimate the CMC value of
a surfactant in aqueous solution from conductivity profile. The con-
ventional method involves the identification of the break point between
pre- and post-micelle regions of the conductivity profile [63–65]. This
marking of the break point or CMC value is generally carried out by
B.S. Gupta et al. Colloids and Surfaces A 529 (2017) 64–72

either selecting a suitable point in the breaking region of the con-

ductivity profile by our visual inspection or by taking the intersection
point of two linear fits in the pre- and post-micelle regions [66,67].
However, a precise estimation of CMC by using these conventional
methods is considered problematic, especially in the presence of other
components in the medium. For example, in the presence of drugs or
surfactants with low aggregation number, the aggregation process be-
came complex and the conductivity profile shows a very limited var-
iation with an increase of SDS concentration [6]. This limited change in
the conductivities of SDS solution in the presence of other components
makes it difficult to pinout CMC value with high accuracy. Since ac-
curate identification of the exact aggregation point of surfactant is very
important in many biological systems and is also needed in industries
for effectively operating the surfactant related processes, a number of
methods and algorithms have been proposed by the researchers
[63,64,68,69] for calculation of CMC from the conductivity profile. In
this regard, Khan and Shah [6] have indicated the suitability of the non-
linear Gaussian fitting method over the conventional linear fitting
methods for accurate estimation of the CMC value. In this method, the
second differential values of conductivities to the concentration of
surfactant are plotted against the concentration of the surfactant and
fitted to the non-linear Gaussian equation, which leads to a bell-shaped
curve. The tip of this bell-shaped Gaussian curve is taken as the CMC
value. In the present study, we utilized this non-linear Gaussian curve
fitting method to determine the CMC of SDS in water or in aqueous
buffer solutions from their conductivity profiles. The scheme of de-
termining CMC from a conductivity profile is shown in Fig. S1. The
second derivatives curve of the conductivity data were calculated by
using an inbuilt function of the Origin (6.0) software and those curves
were fitted to the Gaussian equation by using a nonlinear fitting tool of
the software. The change in the second derivative of the conductivities
against concentration of SDS and the respective Gaussian fits for each
investigated system are shown in Fig. 3(a–c). The calculated values of
CMC from these second derivative curves are presented in Table 2. The
CMC value of SDS in water is in a good agreement with those reported
in literatures [66,70–72].
Fig. 3(a–c) and the tabulated values of CMC in Table 2 reveal that
the buffers (TRIS, TES, and TAPS) strongly affect the CMC of SDS in the
aqueous solutions. The tip of the Gaussian curve, which represents the
CMC, peak at 8.26 mM for the SDS in water. As seen from Fig. 3a, the
peak tips shift towards lower concentrations of SDS in the presence of
TRIS, 8.01 mM and 8.10 mM in 0.2 M and 0.5 M TRIS solutions, re-
spectively. At higher concentration of the TRIS (1.0 M), the peak tip
significantly shifts towards higher concentration end, 9.15 mM of SDS.
Nevertheless, in case of the TES or TAPS buffer, with the increase of the
buffer concentration, the tip of the Gaussian curve is observed to shift
towards lower concentration of SDS. For example, the peak tip appears
at 7.17 mM and 6.38 mM in 0.2 M and 0.5 M TES aqueous solutions,
respectively, (Fig. 3b), while the tip appears at 6.64 mM in 0.2 M TAPS
aqueous solution (Fig. 3c). Since only the shoulder of peak is observed
in 0.5 M TAPS aqueous solution and no peak tip is observed at higher
concentration of TES (1.0 M) and TAPS (1.0 M), it suggests that SDS in
aqueous solutions of TES or TAPS may exhibit aggregation even at very
Fig. 3. (a–c). The calculation of the CMC of SDS in water and in 0.2 M, 0.5 M, and 1.0 M
low concentration (< 1 mM) of the surfactant. These results reveal that TRIS, TES and TAPS aqueous solutions, respectively, at 298.2 K by using the second
the presence of TRIS with lower concentrations may promote the ag- derivative method. (a) SDS in TRIS, (b) SDS in TES, and (c) SDS in TAPS.
gregation of SDS, but as its concentration is higher than a certain of
level (for example 1.0 M), TRIS strongly suppresses the aggregation of the ammonium ion of these buffers electrostatically interacts with the
SDS. However, the presence of other investigated buffers (TES and T- anionic head group of SDS, and thus reduce the repulsion between the
APS) always enhance the aggregation of SDS. heads of SDS. With the increase of concentration of the buffer (TES or
The effect of buffers on the CMC of SDS is expected due to the hy- TAPS), both interactions (electrostatic and hydrophobic) also increase
drophobic and electrostatic interactions between buffer and SDS mo- and lead to the aggregation of the SDS, even at a relatively lower
lecules. It is well-known that the CMC of an ionic surfactant decreases concentration of the SDS. This finding explains the observed trend of
with increasing ionic strength of the solution [73]. It is also reported the decrease in the CMC of SDS with the increase in concentration of
that the hydrophobicity of the additives participates in the aggregation buffer (TES or TAPS). In addition, the effect of TAPS buffer on lowering
process and lower the CMC of the surfactant [60,74,75]. Probably, the the CMC is found greater than that of TES buffer because TAPS buffer
relatively hydrophobic buffers (TES and TAPS) enter the micelle region,

68
B.S. Gupta et al. Colloids and Surfaces A 529 (2017) 64–72

Table 2 of SDS concentration, the dodecyl chain of the surfactant may rupture
The CMC values of SDS in the aqueous buffer solutions at 298.2 K which are calculated the network and displace TRIS and water from the interior and lead to
from experimental conductivity data and fluorescence analysis.
the formation of micelle. This might be the reason for the observed shift
Buffer (M) CMC of SDS (mM) in micelle formation to a higher concentration of SDS in the presence of
TRIS.
Condutometry Fluorescence To further characterize the aggregation of SDS in the presence of
these buffers (TRIS, TES, and TAPS) we calculate the aggregation
SDS in water
0.0 8.26 ± 0.05(7.75a,8.00b, 8.26 ± 0.04 parameters, such as the degree of ionization of the micelle (αm), the
8.38c, 8.20d) degree of counter ion binding in micelle (fm), and the standard Gibbs
SDS in TRIS
free energy of micellization (ΔG°m) at 298.2 K. In the calculation of
0.2 8.01 ± 0.12 8.13 ± 0.06 these parameters, the mass balance model of SDS aggregation is used
0.5 8.10 ± 0.04 8.55 ± 0.05 with an assumption that the mobility of ionized SDS in micelle is
1.0 9.15 ± 0.09 9.26 ± 0.06 comparable with that of free surfactant [80]. The parameters, αm, fm,
SDS in TES and ΔG°m, were calculated from the following equations as suggested in
0.2 7.17 ± 0.07 6.44 ± 0.09 literature [2,66,81]:
0.5 6.38 ± 0.08 5.13 ± 0.09
1.0 – – M2
αm =
SDS in TAPS M1
0.2 6.64 ± 0.12 6.21 ± 0.07 fm = 1 − αm
0.5 – 4.35 ± 0.14
1.0 – – ΔG°m = (2 − αm) RTln (CMC )

a
Ref. [71].
where, M1 and M2 are the slopes of the conductivities profiles of SDS in
b
Ref. [70]. pre- and post-micelle linear regions, respectively. R and T represents the
c
Ref. [72]. gas constant in joule per kelvin per mole (JK−1 mol−1) and tempera-
d
Ref. [66]. ture in kelvin (K), respectively. The critical micelle concentration
(CMC) of SDS is expressed as the number of mole of SDS per liter of
solvent. To obtain the values of the slopes (M1 and M2) for each in-
has one more hydrophobic carbon backbone than TES buffer. It is
vestigated system, the experimental conductivity profiles in the pre-
suggested that the hydrophobic effect is dominant in the aggregation of
and the post-micelle regions were fitted to a linear equation, respec-
SDS. The similar conclusion was also remarked by Anand et al. [76] for
tively. The estimated values of these parameters are listed in Table 3.
the decrease in the CMC of SDS in aqueous solution of 1,4-dioxane.
It can be seen that the value αm increases and that of fm decreases
In comparison with the case of the SDS in water, the slightly low-
with increasing the hydrophobicity of buffer. However, in case of TRIS,
ering CMC value of the SDS in 0.2 M TRIS could also be explained on
the change in the value of parameters (αm and fm) with the increase of
the same basis of the electrostatic interaction between the ammonium
buffer concentration is not significant. It is suggested that the overall
ion of TRIS and the anionic head group of the SDS, which enhances the
structure of micelle remains unaltered in the aqueous TRIS solution and
aggregation of SDS. In addition, the observed increase in CMC of SDS
the presence of TRIS only suppresses the micellization process. Our
with increasing the concentration of TRIS further suggests that hydro-
expectations are in the accordance to the previous report [52], in which
phobicity is the dominating factor for inducing the spontaneous ag-
the authors observed that the calculated value of the degree of counter
gregation of the surfactant molecules. In comparison with TES or TAPS,
ion dissociation (α) for SDS in the presence of different concentration of
TRIS is the least hydrophobic. Our suggested mechanisms are also
ionic liquid [C5mim][PF6] did not change significantly and proposed
supported by the findings of Beyaz et al. [77] who investigated the CMC
that the presence of [C5mim][PF6] only delayed the aggregation
of SDS in various aqueous solutions containing of imidazolium-based
without change in the native structure of the micelle. In contrast, the
ionic liquids with increasing hydrophobicity. They found that the CMC
significant increase in the value of αm and decrease in the value of fm in
of SDS increases in the presence of hydrophilic ionic liquids and de-
the presence of TES or TAPS even at lower concentration (0.2 M and
creases by introducing hydrophobic ionic liquids. According to their
0.5 M TES or 0.2 M TAPS) indicate the alteration in the micelle struc-
observations, they concluded that the hydrophobic ionic liquid solubi-
ture. These results further support our proposed mechanism that
lizes in the micellar phase and derives the formation of aggregates to-
ward a lower concentration of SDS. Additionally, the hydrophilic ionic
Table 3
liquids may get involved in the interaction with SDS in the aqueous The estimated values of pre-micelle slope (M1), post-micelle slope (M2), degree of ioni-
phase and those interactions results in suppressing the aggregation zation of micelle (αm), degree of counter ion binding in micelle (fm), and standard free
process. energy of micellization (ΔG°m) at 298.2 K from the conductivity profiles.
However, the restraining the aggregation process of SDS in 1.0 M
Buffer (M) M1 M2 αm fm ΔG°m (kJ mol−1)
TRIS could also be results from its strong affinity with water. This
strong affinity of TRIS towards water arises from its ability to form SDS in water
hydrogen bonds with water via its hydrogen bond donor or acceptor 0.0 63300 23800 0.376 0.623 −19.4
hydroxyl group [78]. In the pre-micelle region, water molecules are SDS in TRIS
known to form a well-oriented and hydrogen-bonded network of water 0.2 60300 25500 0.423 0.576 −18.9
molecules around the hydrophobic core of SDS. At CMC, the hydro- 0.5 55600 25300 0.455 0.545 −18.5
1.0 47100 23200 0.493 0.508 −17.5
phobic tails of SDS easily rupture this hydrogen-bonded network of
water molecules and thus due to increase in entropy of water micelli- SDS in TES
zation take place [79]. Therefore, it is more likely that in addition to the 0.2 57100 27900 0.489 0.512 −18.5
0.5 50500 32300 0.640 0.361 −17.1
electrostatic interaction between ammonium ion and anionic surfac- 1.0 – – – – –
tant, the strong interaction between the hydroxyl group of TRIS and
SDS in TAPS
water helps to maintain the well-oriented structure of water in the vi-
0.2 57200 29400 0.514 0.487 −18.5
cinity of SDS. Due to such combination of buffer-water network, the 0.5 – – – – –
overall entropy of system became less and SDS molecules are not al- 1.0 – – – – –
lowed to get closer and thus to form micelle. However, with an increase

69
B.S. Gupta et al.
hydrophobic buffers TES and TAPS enter the micelle interior and en-
hance the structure of the micelle. The interaction between sulfonic
group of buffer (TES or TAPS) in the micelle surface and water molecule
in the Stern layer may also contribute in the observed trend in the
values of parameters αm and fm. Moreover, the negative values of ΔG°m
in Table 3 reveal that the micellization process of SDS is feasible in the
presence of these investigated buffers.
This study further employs the fluorescence probe technique to
confirm the effect of these buffers (TRIS, TES, and TAPS) on the ag-
gregation or CMC behavior of SDS in the aqueous buffer solutions. This
technique is well-established and is commonly used in the studies re-
lated to the aggregation of surfactant systems [2,6,66,82,83]. We select
pyrene as a fluoresence probe due to its unique sensitivity towards any
change in the solvent polarity, especially in the vicinity of probe
[84,85]. Since the possibility of forming excimers in the analysis sample
can be avoided by using a low concentration of the probe [82], very low
concentration of the probe (2 mM) was used. The fluorescence spec-
trum of pyrene on excitation at 335 nm shows five distinct vibronic
bands at ∼373Ist, 378 IInd, 383IIIrd, 393IVth, and 415Vth nm [2,86]. The
emission spectra of pyrene at various concentrations of SDS in water
and in 1.0 M TRIS, TES, and TAPS aqueous solutions, respectively, are
shown in Fig. 4(a–d). The fluorescence spectra of pyrene in the aqueous
SDS solutions containing 0.2 M and 0.5 M of TRIS, TES, and TAPS are
provided in the supplementary Fig. S.2 (a–f). Fig. 4(a–d) and Fig. S.2
(a–d) display that each investigated system exhibits similar five distinct
peaks as reported in literature. These results suggest that the presence
of the buffers (TRIS, TES, and TAPS) do not affect the inherent nature of
Fig. 4. (a–d). The emission spectra of pyrene in aqueous solutions of SDS in the presence of higher concentration (1.0 M) of the investigated buffers at 298.2 K under atmospheric
pressure: (a) SDS in water, (b) SDS in 1.0 M TRIS, (c) SDS in 1.0 M TES, and (d) SDS in 1.0 M TAPS.
70
Colloids and Surfaces A 529 (2017) 64–72
the probe pyrene.
The intensities of vibronic bands in the spectra of pyrene depend on
the polarity of solvent. The first and third vibronic bands at 373 nm and
383 nm, respectively, are especially known for their great sensitivity
toward any polarity change in micro-environment around fluorophore
[85]. Therefore, monitoring the maximum intensity ratio (II/IIII) of
these two peaks in the presence of additives is used as a tool to deeply
understand the overall polarity behavior of the system [2,86,87]. The
variations in the intensity ratio (II/IIII) against the concentrations of SDS
in water and in 0.2 M, 0.5 M and 1.0 M TRIS, TES, and TAPS aqueous
solutions, respectively, are shown in supplementary Fig. S.3 (a–c). Prior
to the micellization, pyrene remains distributed in water and in SDS
region. But due to its hydrophobic nature, pyrene preferentially tends to
interact with the hydrophobic tail of SDS. Due to this preferred inter-
action, the surroundings of pyrene became slight hydrophobic, which
reflects as an initial small decrease in intensity ratio with increase of the
SDS concentration in the pre-micellar region (Fig. S.3 (a–c)). However,
as the concentration of SDS reaches and slightly exceeds the CMC value,
a larger fraction of pyrene is distributed in the micelle core, rather than
in the solvent region, leading to a sharp decrease in the intensity ratio.
Beyond the CMC point, the pyrene mainly remain in the hydrophobic
core of the micelle [52] therefore, the intensity ratio II/IIII appears to be
a constant and independent of the surfactant concentration in the post-
micellar region. Further, these curves show that each investigated
buffer has a unique effect on the aggregation behavior of SDS. Fig. S.3a
shows that the curve shifts towards the high SDS concentration end as
increasing TRIS concentration. These results further confirm that the
B.S. Gupta et al.
presence of TRIS inhibits the aggregation process of SDS. The effects of
increasing concentration of TES and TAPS on the aggregation behavior
of SDS are shown in Fig. S.3b and S.3c, respectively. In the presence of
TES or TAPS, the observed shifting in the intensity ratio curve towards a
lower SDS concentration reconfirms the enhancing aggregation ability
of these two buffers (TES and TAPS). However, the overall tendency to
influence the aggregation behavior of SDS in the presence of the buffers
follows the order of TAPS > TES > TRIS. This trend is identical to
that from the conductivities measurement. Moreover, the dis-
appearance of the pre-micelle region in 1.0 M TES (Fig. S.3c) and in
1.0 M TAPS (Fig. S.3c) further supports our expectation that these two
buffers (TES and TAPS), due to the comparatively hydrophobic nature,
participate in the aggregation and promote the aggregation of SDS at a
very low concentration.
We used similar sigmoidal fitting method [86,87] to determine the
CMC value from the sigmoidal plot of intensity ratio (II/IIII) versus the
concentration of SDS. The experimental sigmoidal curves were fitted
with the following sigmoidal Boltzmann equation (SBE):
(Ai − Af )
Intensity Ratio (II / IIII ) = + Af
(1 + exp [(x − x°)/Δx ])
where Ai and Af represents the initial and final asymptotes of the sig-
moidal curve, respectively. The notations x and Δx denote the in-
dependent variable (concentration of SDS) and the interval of the in-
dependent variable, respectively. xo represents the concentration of SDS
at the center of the sigmoidal curve. The correlation between the ex-
perimental and the SBE equation is shown in Fig. S3 (a–c) in the sup-
plementary information. Aguiar et al. [87] suggested that the ratio of
the factor (xo/Δx) of the sigmoidal fitting curve can help in deciding the
value of CMC. They recommended that if the value of factor xo/Δx is
less than 10, then the value of x0 can be taken as the CMC. But if the
value of factor xo/Δx exceed 10, then the value of xo + Δx is the CMC.
Based on this proposed method, we determined the value of CMC for
SDS in water as well as in 0.2 M, 0.5 M, and 1.0 M TRIS, TES, and TAPS
aqueous solutions, respectively. The results of CMC calculations are
presented in Table 2. It can be seen that the determined values of CMC
are in good agreement with those obtained from conductivity analysis.
These results confirm that the investigated buffers possess the strong
tendency to influence the aggregation behavior and thus the CMC va-
lues of SDS in these aqueous solutions. This study is expected to provide
a comprehensive view of the influence of the investigated buffers (TRIS,
TES, and TAPS) on the conductometric and the aggregation behavior of
SDS as well as similar surfactants.
4. Conclusions
The CMC values of the surfactant SDS in water and in 0.2 M, 0.5 M,
and 1.0 M aqueous solution of commonly used buffers (TRIS, TES, and
TAPS) is estimated by using conductometry as well as fluorescence-
probe techniques. In general, the CMC of SDS increases with increasing
the concentration of TRIS, while the opposite trend was found for the
mixtures containing TES or TAPS. Based on the obtained CMC data, it is
concluding that the electrostatic and hydrophobic interactions of the
investigated buffers with SDS molecule bring the dramatic change in
the aggregation behavior or micelle formation of the SDS. The ammo-
nium head of these buffers decrease the electrostatic repulsion between
the anionic heads of the SDS and the hydrophobic chain of the buffer
(TES and TAPS) enhance the hydrophobic interaction. The results ob-
tained from this study could help in the deep understanding of the
process involving SDS and the buffers, and also may help in the de-
velopment of a new process using the investigated materials.
Acknowledgments
The authors are grateful for financing provided by the Ministry of
71
Colloids and Surfaces A 529 (2017) 64–72
Science and Technology (MOST), Taiwan, through granted No. MOST
105-2811-E-011-012 and MOST 105-2221-E-011-144-MY3.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.colsurfa.2017.05.066.
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