Journal of Oleo Science

Copyright ©2012 by Japan Oil Chemists’ Society

J. Oleo Sci. 61, (1) 29-34 (2012)

α-Gel Prepared in Sodium Methyl Stearoyl Taurate/

Behenyl Alcohol/Water System-Characterization of
Structural Changes with Water Concentration
Kei Watanabe, Haruhiko Inoue, Takashi Teshigawara and Tomoko Kimura
Research Center (Shin-yokohama), Shiseido Co. Ltd. (2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama, Kanagawa 224-8558, JAPAN)

Abstract: In this study, the changes in the structural and physicochemical properties of an α-crystalline
phase (often called an “α-gel”) were assessed in a sodium methyl stearoyl taurate (SMT)/behenyl alcohol/
water system. The α-gels were characterized focusing on the effects of the alcohol/surfactant ratio and water
concentration. Water molecules solubilized in the interlayer of the α-crystalline phase resulting in expanded
interlayer spacing. Beyond the solubilization limit of 85 %, water molecules were trapped in the matrix of
the α-crystalline phase in non-equilibrium (i.e., two phases). Accordingly, different self-diffusion coefficients
for the solubilized and trapped water molecules were measured using a Fourier transform pulsed gradient
spin echo technique to monitor the 1H NMR spectra. It was concluded that the two self-diffusion coefficients
correspond to the water solubilized in the interlayer, i.e., “slow water,” and trapped in the matrix of the
α-crystalline phase, i.e., “fast water.”

Key words: α-crystalline phase, structural and physicochemical properties, sodium methyl stearoyl taurate (SMT)/behenyl
alcohol/water system,

1 INTRODUCTION A unique characteristic of the α-crystalline phase in sur-

The α-crystalline phase（often called an“α-gel”）is clas- factant systems is the considerable amount of water that is
sified as a hydrated crystalline state of surfactants and solubilized between the interlayers. Additionally, the
lipids that appears as a highly viscous gel1, 2）. The long-dis- α-crystalline phase forms a network structure（matrix）that
tance structure of the α-crystalline phase comprises re- permits the gelation of solvent that is unable to dissolve
peated bi-layers（i.e., a layered structure）with lipophilic the components of the α-crystalline phase7, 8）. For example,
groups forming a hexagonal sub-lattice. a system that traps excess water beyond the limit of solu-
The α-crystalline phase is often confused with a lamellar bilization of the interlayer of an α-crystalline phase, i.e., a
liquid crystalline phase since they both have repeated bi- two-phase system with the α-crystalline phase coexisting
layer structures. However, they can clearly be distin- with the water phase in equilibrium, often appears as a
guished via wide-angle X-ray scattering measurements completely homogeneous gel9, 10）. Such gels that comprise
since the lipophilic groups of the lamellar liquid crystalline α-crystalline and excess-water phases are important
phase are in the liquid state and have no specific sub-lattice because they permit the stabilization of additional oil drop-
structure. In the wide-angle X-ray scattering pattern of the lets as emulsions with a small amount of surfactant. This
α-crystalline phase, a sharp peak is observed at 15 nm−1 kind of system is widely used in industrial applications
（Bragg angle of 21° ）, which corresponds to the diffraction such as cosmetic creams, shampoos, hair conditioners, ex-
of the sub-lattice. In contrast, no peak is evident for the ternal medicine, etc.11）
sub-lattice structure in lamellar liquid crystalline phases. The α-crystalline phases of surfactant systems are nor-
Although many studies on lipid systems （e.g., triacylglyc- mally prepared below the Krafft point of the surfactant
erol3）, fatty acid4−6）, and others）have been reported, most aqueous solution although they can also be prepared above
focus on the sub-lattice structure of the alkyl groups. the Krafft point by combining a higher alcohol with a sur-
There remain many additional interesting features that factant/water system.
should be addressed in surfactant systems. Using a surfactant/higher alcohol/water system, the

＊
Correspondence to: Kei Watanabe, Research Center (Shin-yokohama), Shiseido Co. Ltd., 2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama,
Kanagawa 224-8558, JAPAN
E-mail: kei.watanabe@to.shiseido.co.jp
Accepted August 24, 2011 (received for review May 25, 2011)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/  http://mc.manusriptcentral.com/jjocs

29
 K. Watanabe, H. Inoue, T. Teshigawara and T. Kimura

α-crystalline phase is generally prepared via the following 2

［−Dsel
A＝A0 exp （Gγδ）
（Δ−δ/3）］, （1）
procedure. First, the higher alcohol is heated above its
melting point and then mixed with the surfactant aqueous where A0 is the echo amplitude in the absence of a magnet-
solution. Consequently, the molten higher alcohol is dis- ic field, γ is the proton gyromagnetic ratio, and Δ is the in-
persed in the surfactant aqueous solution in the form of oil terval between field gradient pulses of magnitude G and
droplets. In the next step, the mixture is cooled and mole- variable duration, δ. The time over which diffusion was fol-
cules of the higher alcohol are incorporated between the lowed, Δ, was varied from 1 to 1000 ms, which corresponds
surfactant molecules to form the α-crystalline phase. to diffusion over distances of 0.1-10 μs for typical values of
It is known that the characteristics of the α-crystalline Dsel. During a measurement, Δ and G were kept constant.
phase change dramatically depending on the ratio of the Linear least-squares analysis was used according to equa-
higher alcohol to the surfactant. The phase transition tem- tion（1）to extract the diffusion coefficient when the peak
perature of the α-crystalline phase in a hexadecanol/octa- from the protons of the measured species did not overlap
decyl trimethyl ammonium chloride（OTAC）/water system with that from protons of other species. Accordingly, if two
was studied in detail using differential scanning calorimeter peaks overlapped, a biexponential nonlinear least-squares
（DSC）. The results revealed that the melting point of the analysis was used.
α-crystalline phase increases with increasing hexadecanol/ 2.2.3 Small-angle X-ray Scattering （SAXS） measurements
OTAC mole ratio and reaches a maximum at a ratio of 3/13）. Interlayer spacing measurements of an α-crystalline and
In the present study, we focus on the micro- and macro- lamellar liquid crystalline phase were performed using a
scopic structural changes in a gel system comprising an SAXSess small-angle X-ray scattering instrument（Anton
α-crystalline phase prepared in an SMT/behenyl alcohol/ Paar, Graz, Austria）.
water system in order to discuss its practical long-term 2.2.4 Differential Scanning Calorimeter（ DSC）measure-
stability. The α-gels are characterized from the perspective ments
of the effects of the concentration of water in the system The melting and transition points of the gel were mea-
and the behenyl alcohol/SMT ratio. Further, a Fourier sured using a DSC120 with SSC/5200（Seiko Instruments,
transform pulsed gradient spin echo technique to monitor Tokyo）.
the 1H NMR spectra is used to simultaneously characterize
the self-diffusion coefficients of the solubilized and trapped
water molecules12）.
3 RESULTS AND DISCUSSION
3.1 An α-crystalline phase region in a sodium methyl
stearoyl taurate/behenyl alcohol/water system
2 EXPERIMENTAL PROCEDURES In the ternary phase diagram, the α-crystalline phase
2.1 Materials region is evident as a large ellipsoid on a straight center
Sodium methyl stearoyl taurate（purity＜85％）was pur- line that indicates a behenyl alcohol/SMT mole ratio of 3/1
chased from Nikko Chemicals（ Tokyo, Japan）. Behenyl （Fig. 1）. The minimum concentration of water that pro-
alcohol（purity＜65％）was purchased from Kokyu Alcohol vides a one-phase α-crystalline region is 20％; this phase is
Kogyo（Narita, Japan）. maintained until the concentration of water reaches 85％.
Beyond the phase boundary that occurs at 85％ water, a
2.2 Methods two-phase region exists comprising the α-crystalline phase
2.2.1 Preparation of a gel containing an α-crystalline phase and an excess-water phase. In the SMT-rich side of the
Various ratios of constituents were poured into a 200 mL regions, a multi-phase region with an α-crystalline phase
glass vessel and mixed using a homogenizer（Tokusyukika, and hydrated crystals of SMT is present. Accordingly, in
Tokyo）at 90℃. The samples were then cooled to 30℃ in the behenyl alcohol-rich side of the regions, a multi-phase
an ice/water bath. region with an α-crystalline phase and hydrated crystals of
2.2.2 NMR measurements behenyl alcohol exists. The regions with the hydrated crys-
（Dsel）of the samples in this
The self-diffusion coefficients tals are indicated as“multi-phase”since no clear phase
system were measured using a Fourier transform pulsed boundaries were determined.
gradient spin echo technique to monitor the 1H NMR The α-crystalline phase region exists on the center line
spectra8）. The samples were sealed in 5 mm tubes and then that indicates a behenyl alcohol/SMT mole ratio of 3/1,
analyzed using a JNM ECA-400 NMR spectrometer（JEOL, which is the preferable behenyl alcohol/SMT mole ratio in
Tokyo, Japan）operating at 399.0 MHz with a 90-δ-180-δ this system; this is in good agreement with that of a previ-
pulse sequence. The self-diffusion coefficient of a proton ously reported α-crystalline phase comprising hexadeca-
was determined from the decay of its echo amplitude, A, nol/OTAC/water.
according to the following equation: The effect of the behenyl alcohol/SMT mole ratio on the
30
J. Oleo Sci. 61, (1) 29-34 (2012)
 α -Gel Prepared in Sodium Methyl Stearoyl Taurate/Behenyl Alcohol/Water System

Fig. 1 Phase diagram of a sodium stearoyl methyl

taurate (SMT) /behenyl alcohol/water system.
Compositions A to F will be discussed in other
figures. The α-crystalline phase is represented
by “α-gel.

phase transition temperature of the system was assessed

Fig. 2 Differential scanning calorimetry measurements
via DSC measurements（ Fig. 2）. The concentration of
water is fixed at 90％. The melting temperature is 65℃ at of an α-crystalline phase of the SMT/behenyl
a behenyl alcohol/SMT mole ratio of 0.5/1 and increased to alcohol/water system with varying behenyl al-
77℃ at a ratio of 3/1 beyond which the melting tempera- cohol/SMT mole ratios. The open circle, closed
ture remained constant. At ratios lower than 1/1, the Krafft circle, open square, and closed square represent
point of the hydrated SMT crystals was observed at ∼ the melting point the of α-crystalline phase, the
50℃. At ratios above 5/1, the melting and α-β crystal tran- Krafft point of SMT, the melting point of behe-
sition points of behenyl alcohol were observed at 62℃ and nyl alcohol, and the α-form/β-form transition
48℃, respectively. For ratios in the range of 1.5/1 to 4.5/1, point of behenyl alcohol, respectively. Composi-
a two-phase region that features the coexistence of an tion E and F correspond to those in the phase
α-crystalline phase with an excess water phase is present, diagram (Fig. 1) . The α-crystalline phase is rep-
as indicated by the sole presence of a melting point for the resented by “α-gel.
α-crystalline phase.
The melting point of 77℃ is superior to that of the previ- packing of the alkyl chains. In contrast, above the melting
ously reported“stable α-crystalline phase”of the hexadec- point（80℃） , the peaks at 0.39 and 0.78 nm−1 are relatively
anol/OTAC/water system, which has a melting point of 72 broad and the peaks at 1.18 nm−1 and 15 nm−1 were not
℃. This is the reflection of the melting point of hexadeca- evident. These results indicate a lamellar liquid crystalline
nol（52℃）being lower than that of behenyl alcohol. Addi- phase with interlayer spacing identical to that of the
tionally, there is a considerable difference between the α-crystalline phase above the melting temperature. The
SMT/behenyl alcohol/water system and the hexadecanol/ identical interlayer distance suggests that there are no sig-
OTAC/water system. In the hexadecanol/OTAC/water nificant differences in the bilayer thickness between the la-
system, the two-phase region is present at mole ratios of mellar liquid crystalline phase and α-crystalline phase.
1.5/1 to 3/1 whereas the two-phase region exists in a wider
mole ratio range of 1.5/1 to 4.5/1 in the present system. To 3.2 Effect of the concentration of water on the interlayer
discuss the reasons for the extended range in this system, spacing of the α-crystalline phase
some additional data on the phase equilibrium are re- Figure 4 shows the variation of the interlayer spacing
quired. with water concentration of gels comprising either the
In Fig. 3, small- and wide-angle X-ray scattering patterns α-crystalline phase or the α-crystalline phase coexisting
for the α-crystalline phase with 70％ water at 60℃ are with excess water. The plots represent the values mea-
shown in addition to a pattern measured above the melting sured using SAXS. At the lowest concentration of water
point. Below the melting point （60℃） , sharp peaks at scat- （20％）, the interlayer spacing was approximately 8 nm; it
tering vectors（q）of 0.39 and 0.78 nm−1 and a shoulder at expands to approximately 28 nm at 85％ water, which is
1.18 nm −1 were observed. At around 15 nm −1, another close to the phase boundary of the one-phase and two-
sharp peak was observed that indicates the hexagonal phase regions.
31
J. Oleo Sci. 61, (1) 29-34 (2012)
 K. Watanabe, H. Inoue, T. Teshigawara and T. Kimura

Fig. 3 Small- and wide-angle X-ray scattering patterns of an α-crystalline phase comprising SMT/behenyl alcohol/wa-
ter (i.e., composition B in the phase diagram, Fig. 1) at (a) 60° and (b) 80°.

In Fig. 4, the solid line represents the theoretical value

calculated using the following equation:

d＝2ℓ（φwρw＋φsρs）/φsρs, （2）
where d represents the interlayer spacing, ρw represents
the density of water （1 g/cm3）, ρs represents the density of
the lipophilic group（0.84 g/cm3 according to a reported
, φw and
value for stearyl alcohol in the supercooled state13））
φs represent the total weight fraction of water and the sur-
factant and higher alcohol in the system, respectively, and
ℓ represents the monolayer thickness of the lipophilic
group（assumed to be ∼2 nm） .
The theoretical and measured values correspond very
well in the range of 20-80％ water. Above 85％, a deviation
of the experimental values from the theoretical values was
observed due to incorporation of the excess water beyond
the solubilization limit in the matrix of the α-crystalline
phase instead of in the interlayer.
Fig. 4 Interlayer spacing, d, of an α-crystalline phase Figure 5 shows the volume fraction of excess water
as a function of water concentration. The open phase separated from the gel comprising the α-crystalline
circle represents the value measured using phase and the water phase by centrifugation at 40,000 G
SAXS. The full line represents the value calcu- for 3 h. At water concentrations below 80％, no water
lated using the following equation: phase separates from the gel. Gels with water concentra-
d =2ℓ (φwρw + φsρs)/φsρs, tions of 90 and 95％ separated water layer at a bottom.
where d represents the interlayer spacing, ρw The volume fraction of water layers were 5 vol％ and 40
vol％ of total volume of the systems, respectively. The
represents the density of water (1 g/cm 3), ρ s
weight ratios of water included in the gels at upper layers
represents the density of the lipophilic groups
were calculated to be 0.89 and 0.91 for the 90 and 95％
(0.84 g/cm3 according to a reported value for
water systems, respectively. These values are close to 0.85,
stearyl alcohol in a supercooled state), φw and φs which is the maximum weight ratio of water that can be
represent the total weight fraction of water and solubilized in the interlayer in equilibrium. These results
the surfactant and higher alcohol in the system, strongly suggest that the water that separates is the excess
and ℓ represents the monolayer thickness of the water that was incorporated into the matrix of the
lipophilic group (assumed to be ~2 nm). Com- α-crystalline phase in non-equilibrium.
positions A, B, C, and D correspond to those in These results also suggest the importance of considering
the phase diagram (Fig. 1). that water molecules in different locations have different
32
J. Oleo Sci. 61, (1) 29-34 (2012)
 α -Gel Prepared in Sodium Methyl Stearoyl Taurate/Behenyl Alcohol/Water System

Fig. 5 Volume fraction of an α-gel and separated water

as a function of the water concentration. Com-
positions A, B, C, and D correspond to those in
Fig. 6 Curve fitting of the decrease in the NMR signal
the phase diagram (Fig. 1) . The α-crystalline
intensity to calculate the self-diffusion coef-
phase is represented by “α-gel.”
ficient (Dsel) of water in an α-crystalline phase
stabilities. Since water in the interlayer cannot be separat- (one-phase, a) and an α-crystalline phase +
ed by centrifugation under the conditions used, it is water (two-phase, b) containing 70% and 90%
evident that the water solubilized in the interlayer and the water, respectively.
water incorporated into the matrix of the α-crystalline
phase are relatively stable and unstable against water sepa-
ration during long term storage, respectively.

3.3 Self-diffusion coefficients of solubilized and incorpo-

rated water molecules, as measured by NMR
Figure 6 shows the self-diffusion coefficients for water
molecules in an α-crystalline phase （water concentration of
70％）and in a gel comprising an α-crystalline phase coex-
isting with excess water（water concentration of 90％）. For
the α-crystalline phase（70％ water）, the decay curve of
the magnetic field shows good correlation with the Gauss-
（0.997）
ian function （Fig. 6 （a） ）. In contrast, the correlation
is quite low for the gel comprising the α-crystalline phase
coexisting with excess water （90％ water）; however, it was
improved by fitting the decay curve with two different
curves（0.928 and 0.985） . This implies that the water mole-
cules in the different locations in the gel were each repre-
sented by a different fitting.
The effect of the water concentration on the self-diffu-
Fig. 7 Self-diffusion coefficient for water molecules as
sion coefficient is shown in Fig. 7. Below a water concen-
a function of water concentration.
tration of 80％, only“slow water,”which has a self-diffu-
sion coefficient below 10−12 m2・s−1, was observed. The self-
diffusion coefficient for“slow water”tends to increase than 10−12 m2・s−1, and“slow water”were simultaneously
with increasing water concentration. On the other hand, observed above a water concentration of 85％. With in-
“fast water,”which has a self-diffusion coefficient greater creasing water concentration, the self-diffusion coefficient
33
J. Oleo Sci. 61, (1) 29-34 (2012)
 K. Watanabe, H. Inoue, T. Teshigawara and T. Kimura

of the“fast water”increased toward the value for free emulsion system comprising α-crystalline, excess water,
water of 3.08×10−9 m2・s−1. Since the phase boundary at a and excess oil phases.
water concentration of 85％ divides the α-crystalline phase
from the two-phase region, it is reasonable to conclude
that the“slow water”and“fast water”correspond to
water molecules incorporated in the interlayers and matrix References
of the α-crystalline phase, respectively. The increase in the 1）Suzuki, T.; Takei, H. J. Chem. Soc. of Jpn. 5, 633-640
self-diffusion coefficient with increasing water concentra- （1986）.
tion for the“slow water”and the“fast water”are due to 2）Yamaguchi, M.; Noda, A. J. Chem. Soc. of Jpn. 5,
the increases of the interlayer spacing between the bilayers 1632-1638（1987）.
and the domain size of water in the matrix of the 3）Jensen, L. H.; Mabis, A. J. Crystal structure of
α-crystalline phase, respectively. β-tricaprin. Nature 197, 681-682 （1963）.
A larger water domain size corresponds to a smaller 4）Lomer, T. R. The crystal and molecular structure of
network structure and vice versa. This relationship is im- lauric acid（form A1）. Acta Crystallogr. 16, 984-988
portant considering that the viscosity of gel provides stabil- （1963）.
ity against phase separation（oil and/or water）. However, 5）Goto, M.; Asada, E. The crystal structure of the A-su-
no effective methods for characterization have been estab- per form of lauric acid. Bull. Chem. Soc. Jpn. 51,
lished to date. The present method, which exploits NMR 70-74（1978）.
measurements, enables the evaluation and comparison of 6）Sato, K.; Kobayashi, M.; Morishita, H. Stability, occur-
the domain sizes of a series of samples. Consequently, it is rence and step morphology of polymorphs and poly-
expected that this method can be applied to quantitatively types of stearic acid I. Stability and occurrence. J.
estimate the stability of gels including α-crystalline phases Cryst. Grouth 87, 236-242 （1988）.
for industrial applications such as cosmetic creams, sham- 7）Yamaguchi, M.; Noda, A. J. Chem. Soc. of Jpn. 1,
poos, hair conditioners, external medicine, etc. 26-32（1989）.
8）Yamagata, Y.; Senna, M. Change in viscoelastic behav-
iors due to phase transition of the assembly compris-
ing cetyltrimethylammonium chloride/cetyl alcohol/
4 CONCLUSION water. Langmuir 15, 4388-4391（1999） .
In this study, an α-crystalline phase prepared in an SMT/ 9）Suzuki, T.; Takei, H.; Yamazaki, S. Formation of fine
behenyl alcohol/water system was characterized with par- three-phase emulsions by the liquid crystal emulsifica-
ticular focus on the micro- and macroscopic structural tion method with arginine β-branched monoalkyl
changes due to varying water concentrations. It was deter- phosphate. J. Colloid Interface Sci. 129, 491-500
mined that water was solubilized in the interlayers of the （1989）.
α-crystalline phase in equilibrium resulting in the expan- 10）Junginger, H.; Akkermans, A. A. M. D.; Heering, W.
sion of the interlayer distance; additional water beyond the The ratio of interlamellarly fixed water to bulk water
solubilization limit of 85％ was trapped in the matrix of the in O/W creams. J. Soc. Cosmet. Chem. 35, 45-57
α-crystalline phase in non-equilibrium（i.e., a two-phase （1984）.
system）. By using a Fourier transform pulsed gradient spin 11）Konno, Y.; Sugaya, Y.; Naito, N. Stabilization and effi-
echo technique to monitor the 1H NMR spectra, a single cacy of o/w emulsions containing dermal-active elec-
self-diffusion coefficient for water molecules was measured trolytes. in 22nd IFSCC Congress, Edinburgh. Ab-
in the one-phase region whereas two self-diffusion coeffi- （2002）.
stract p. 152
cients for water molecules were measured in the two-phase 12）Lindman, B.; Stilbs, P.; Mosley, M. E. Fourier transform
region. It is concluded that the two self-diffusion coeffi- NMR self-diffusion and microemulsion strunture. J.
cients correspond to the water solubilized in the interlayer, Colloid Interface Sci. 83, 569-582（1981）.
i.e., the“slow water,”and the water trapped in the matrix 13）Watanabe, A. The synthesis and the physical proper-
of the α-crystalline phase, i.e., the“fast water,”respective- ties of normal higher primary alcohols. V. Thermal and
ly. X-ray studies of the polymorphism of alcohols of odd
The present method is valuable as it enables the evalua- carbon numbers from undecanol to heptatriacontanol
tion of the long-term practical stability of a widely used Bull. Chem. Soc. Jpn. 36, 336-340（1963）.

34
J. Oleo Sci. 61, (1) 29-34 (2012)