Food Hydrocolloids 30 (2013) 358e367

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Food Hydrocolloids
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Interfacial and emulsifying properties of sucrose ester in coconut milk emulsions

in comparison with Tween
Suwimon Ariyaprakai a, *, Tanachote Limpachoti a, Pasawadee Pradipasena b
a
b

Department of Food Biotechnology, Faculty of Biotechnology, Assumption University, Ram Khamhaeng Rd. Soi 24, Hua Mak Campus, Bangkok 10240, Thailand
Department of Food Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 2 January 2012
Accepted 6 June 2012

In this study, sucrose esters were presented as a promising alternative to petrochemically synthesized
Tweens for application in coconut milk emulsions. The interfacial and emulsier properties of sucrose
ester (SE), mainly sucrose monostearate, had been investigated in comparison with Tween 60 (TW), an
ethoxylate surfactant. The interfacial tension measurement showed that SE had a slightly better ability to
lower the interfacial tension at coconut oilewater interface. These surfactants (0.25 wt%) were applied in
coconut milk emulsions with 5 wt% fat content. The effects of changes in pH, salt concentration, and
temperature on emulsion stability were analyzed from visual appearance, optical micrograph, droplet
charges, particle size distributions, and creaming index. Oil droplets in both SE and TW coconut milk
emulsions extensively occulated at pH 4, or around the pI of the coconut proteins. Salt addition induced
occulation in both emulsions. The pH and salt dependence indicated polyelectrolyte nature of proteins,
suggesting that the proteins on the surface of oil droplets were not completely displaced by either added
nonionic SE or TW. TW coconut milk emulsions appeared to be thermally unstable with some coalesced
oil drops after heating and some oil layers separated on top after freeze thawing. The change in
temperature had much lesser inuence on stability of SE coconut milk emulsions and, especially, it was
found that SE emulsions were remarkably stable after the freeze thawing.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Sucrose esters, or sugar-based surfactants, are in current interest
because they are produced from natural resources such as sucrose
and vegetable oil. They are biodegradable and more biocompatible
when compared to other petrochemically synthesized surfactants.
Sucrose esters are non-toxic and safe for food and are approved as
a food additive under food regulations and laws in several countries
i.e. Japan, USA, and EC. It had been reported that sucrose esters have
excellent emulsifying properties and be able to apply in various food
products (Garti, 2001). Their wide range of hydrophilicelipophilic
balance (HLB), depending on degree of esterication of fatty acids
and sucrose, provides ultimate application of sucrose esters to each
product type.
Coconut milk is one of food emulsions that require additional
surfactants or emulsiers to improve emulsion stability. Several recent
works have been carried out on physicochemical characterization of

* Corresponding author. Tel.: 66 2 300 4553x3796; fax: 66 2 300 4553x3792.

E-mail address: suwimona@yahoo.com (S. Ariyaprakai).
0268-005X/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodhyd.2012.06.003

coconut milk employing other small molecule surfactants such as

Tweens and sodium dodecyl sulfate (Tangsuphoom & Coupland,
2009a,b), however, data on sucrose esters remain fewer. In those
studies, coconut milk emulsions after addition of surfactants were
reported to smaller in average droplet size, decrease in total surface
protein concentration, and change in droplet surface charges
(Tangsuphoom & Coupland, 2008b, 2009a).
This study aims to gain more understanding on the relationship
between interfacial properties and stability of coconut milk emulsions with addition of sucrose ester. We described the comparative
interfacial and emulsier properties between sucrose ester (SE),
mainly sucrose monostearate, and Tween 60, or polyoxyethylene
sorbitan monostearate (TW). Their structures were displayed in
Fig. 1. The difference between the carbohydrate and ethoxylate
headgroups provided an interesting comparison. Their adsorption
behaviors at the coconut oil and aqueous interface were investigated by the interfacial tension measurement. The coconut milk
emulsions prepared with SE and with TW were processed at
different temperatures (121
C, 100
C and 20
C) and their
stability was investigated at different pH (2e8) and salt concentrations (0 and 20 mM CaCl2).

S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

359

CH OH
O

O
HO

HO

OH

HO HC

OH
HO

O
OH

HO
O

O
OH

O
O

O
O

Fig. 1. Chemical structures of (a) sucrose monosterate (SE) and (b) Tween 60 or ethoxylated sorbitan monostearate (TW).

2. Material and methods

2.1. Materials
Ryoto sucrose esters (S1670) were supplied by MitsubishiKagaku Foods Corporation (Tokyo, Japan). Ryoto S1670 contained
mainly of 50e53% sucrose monostearate with sucrose monopalmitate 18e20%, sucrose disterate 12e14 %, sucrose dipalmitate
5e6%, sucrose alkylate 5e10% and other ash and moisture. Tween
60 (Polyoxyethylene sorbitan monostearate), hydrochloric acid,
sodium hydroxide, sodium azide (NaN3), calcium chloride (CaCl2),
and Oil Red O were purchased from Sigma Chemical Company (St.
Louis, MO, USA). Coconut oil and soybean oil were supplied by
Tropicana Oil (Nakhonpathom, Thailand) and Thai Vegetable Oil
Public Company Limited (Nakhonpathom, Thailand), respectively.
Ground coconut meat was purchased locally. Distilled water was
used for emulsion preparation throughout experiment.
2.2. Interfacial tension measurement
Coconut oilewater interfacial tensions were measured according to Du Nouy ring method at 25
C using a digital tensiometer
(K10, Kruss Scientic, Hamburg, Germany). A series of SE and TW
aqueous solutions at different concentrations were prepared and
kept in plastic bottles prior measurements. The SE solutions had to
be preheated to 70
C due to its difculty to dissolve in water.
Before each measurement, the solution was poured into
a measurement vessel and coconut oil was overlaid on top of the
aqueous layer. The ring was cleaned with ethanol and distilled
water and amed with a Bunsen burner before each measurement.
Each measured point was an average from at least two replicates.
2.3. Coconut milk emulsion preparation
Coconut milk was produced by adding distilled water to ground
coconut meat at a weight ratio of 2:1. The mixture was manually
pressed and ltered through lter cloth to remove solid residues.
The fat contents of the obtained coconut milk were determined by
using Rose-Gottlieb method (AOAC, 2000). The extracted coconut
milk was further diluted with either distilled water or surfactant
aqueous solutions to a nal fat content of 5 wt% and a nal
surfactant concentration of 0 or 0.25 wt%. The surfactant
concentration of 0.25 wt% was chosen because this concentration
had been proven to provide sufcient stability to coconut milk
emulsions (Tangsuphoom & Coupland, 2009a). Sodium azide
0.02 wt% was added to prevent microbial growth. Each emulsion

was further homogenized by using a high speed homogenizer

(Ultra-turrax, IKA Labortechnik, Germany) for 3 min at the speed of
11,200 rpm.
2.4. Measurement of emulsion properties
2.4.1. Droplet size measurement
The particle size distributions of emulsions were measured by
using a laser diffraction particle size analyzer (Mastersizer 2000;
Malvern Instruments Ltd., Worcestershire, UK), with a dualwavelength detection system. Emulsion samples were dropped
and diluted in the test chamber that lled with distilled water in
order to prevent multiple light scattering effects. The size distributions of emulsions were obtained via a best t using Mie theory.
The refractive indices of 1.33 for water and 1.15 for coconut oil were
employed as optical properties of emulsions. The particle sizes
were
reported
as
surface-volume
average
diameters,
P
P
ni d3i = ni d2i , and volume-weighted average diameters,
d32
P
P
ni d4i = ni d3i , where di is the midpoint of the size interval i
d43
and ni is the number of particles in that interval.
2.4.2. z-potential measurement
The electrical charges on emulsion droplets were determined by
using a particle electrophoresis instrument (Zeta-Meter System
3.0, Zeta-Meter, Inc., Staunton, VA, USA). The emulsion sample
after 1/100 dilution was put into an electrophoresis cell that had
electrodes at both ends. The direction and velocity of emulsion
droplets that move in the applied electrical eld were observed
under a microscope and the charge or z-potential on emulsion
droplets was calculated. Each reported z-potential was an average
from ve replicates.
2.4.3. Optical microscopy
The emulsion microstructure was examined by using a standard
optical microscope (Alphaphot-2, YS2-H, Nikon Corporation, Japan)
equipped with a microscope eyepiece camera (AM423 Dino-Eye
USB, AnMo Electronics Corporation, Taipei, Taiwan) with a software (DinoCapture Software) installed on a computer. A few drops
of emulsion were put on a glass slide and fully covered with a cover
slid. The microscope magnication of 100 was employed.
2.4.4. Visual appearance and creaming index measurement
The emulsion sample (10 g) was transferred into a standard test
tube and tightly sealed with a cap. The appearance of the emulsion
sample was closely captured by a digital camera. After gently mixed
by inversion, the tube was left on a tube stand for 10 min. The height

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of aqueous layer left after the emulsion droplets creamed to the top
and the height of initial total sample in the tube were measured. The
creaming index was determined from the percentage of the height
of the aqueous layer over the height of the total sample.
2.5. Coconut milk emulsion stability
2.5.1. Emulsion stability against pH and salt concentration
The emulsion sample (10 g) was transferred into a standard test
tube and adjusted to the specied pH values (2, 4, 6, and 8) by using
0.1 and 1 M HCl or 0.1 and 1 M NaOH. Noted that the normal pH of
extracted coconut milk was w6 before the adjustment. For the salt
experiment, CaCl2 salt was also added to a concentration of 20 mM.
The charges on the emulsion droplets were determined from
z-potential measurement and the stability of emulsion was
analyzed by z-potential measurement, creaming index measurement, and optical micrograph.

Fig. 2. Coconut oilewater interfacial tensions vs. logarithm of concentration (log C)

isotherms for (D) sucrose ester (SE) and (B) Tween 60 (TW).

2.5.2. Emulsion thermal stability

The emulsion samples (10 g each) were transferred into standard test tubes and kept in an autoclave at 121
C for 10 min, or in
a boiling water bath at 100
C for 20 min, or in a freezer at 20
C

Fig. 3. Visual appearance of phase separation of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition
of 0.25 wt% sucrose ester (SE) after thermal treatments at different temperatures. (a) White creamy emulsion. (b) Coagulated solid particles. (c) Destabilized oil layer (free oil).

S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

for 14 h. After removal from each storage conditions, the emulsions

were stored to reach room temperature prior further analysis. The
stability of emulsion was analyzed from droplet size measurement,
visual appearance, and optical micrograph.
In addition, freeze thaw stability of emulsions was assessed by
measuring amount of free oil (destabilized oil) after three freezethaw cycles (each cycle: 20
C for 22 h and 30
C for 2 h) using
the principle of dye dilution method (Palanuwech, Potineni,
Roberts, & Coupland, 2003; Thanasukarn, Pongsawatmanit, &
McClements, 2004b). The employed Oil-Red O is colored oil that
only dissolves in free oil but does not dissolve in emulsied oil
droplets. A stock solution of 0.0015 wt% Oil-Red O in soybean oil
was initially prepared. A series of coconut oil solutions were obtained by adding different amounts of coconut oil to the stock OilRed O solution. The absorbance of the solution series was measured
by using an ultravioletevisible spectrophotometer (Spectronic
Genesys 5, Milton Roy company, Rochester, NY, USA) at a wavelength of at 520 nm. The plot between the measured absorbance
and the coconut oil concentrations was used as a calibration curve.
To determine amount of free oil in emulsions, the emulsion sample
(35 g) was added with 3 g of the stock Oil-Red O solution, vortexed
for 30 s, and centrifuged at the speed of 5500 rpm for 5 min
(Universal centrifuge, Model PLC-012, Gemmy Industrial Corporation, Taipei, Taiwan). The colored oil on the upper layer was
transferred by a micro-pipette into a plastic cuvette and measured
its absorbance. The measured absorbance was converted to weight
percent of free oil by using the prepared calibration curve.

361

3. Results and discussion

3.1. Coconut oilewater interfacial behavior
The basic information about the interfacial properties of SE and
TW at coconut oilewater interface was obtained from the interfacial tension measurement. Fig. 2 is the plot between the measured
interfacial tensions of SE and TW aqueous solutions at various
concentrations. The gradually decrease in the measured interfacial
tension was observed as surfactant concentrations increased. After
the interfacial tensions reduced to a minimum value, it approached
a constant as surfactants started forming micellar aggregates. The
minimum interfacial tensions for SE and TW were <2 mN/m and
8 mN/m, respectively. Unfortunately, the minimum interfacial
tension for SE was too small to be measured precisely from our
existing instrument. It had reported that the lowest interfacial
tension of SE at the rapeseed oilewater interface was 1.5 mN/m
(Soultani, Ognier, Engasser, & Ghoul, 2003). SE tended to have
a slightly better ability than TW in reducing the oilewater interfacial tension. The critical aggregation concentrations (CAC) at
those minimum interfacial tensions in Fig. 2 were approaching to
0.05 wt% for SE and around 0.11 wt % for TW. The lower value of CAC
indicated more hydrophobicity of SE, most likely due to this
commercial SE also contained some proportion of diesters. Our
results agreed with the reported CAC value of 0.05 wt% SE at the
liquid parafnewater interface (Yanke, Shufen, Jinzong, & Qinghui,
2004).

Fig. 4. Optical micrographs of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition of 0.25 wt% sucrose
ester (SE) after thermal treatments at different temperatures. (a) Extensively coalesced oil drops. (b) Coalesced oil droplets. (c) Coagulated solid particles.

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S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

Fig. 5. Particle size distributions of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition of 0.25 wt%
sucrose ester (SE) after thermal treatments at different temperatures. (a) At room temperature. (b) At 121
C for 10 min. (c) At 100
C for 20 min. (d) At 20
C for 14 h. (e) All
thermal treatment results for coconut milk emulsions with addition of 0.25 wt% sucrose ester (SE). The arrows indicate extra peaks from coagulated solid particles.

S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

363

Table 1
The average particle sizes (d3,2 and d4,3) of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition of
0.25 wt% sucrose ester (SE) after thermal treatments at different temperatures.
Thermal treatments

Control coconut milk

TW coconut milk

Temperature

Holding time

d3,2 (mm)

d3,2 (mm)

28
C (Room temp.)
121
C
100
C
20
C

e
10 min
20 min
14 h

10.001
22.057
16.103
7.285






d4,3 (mm)
1.228
3.866
1.839
0.964

33.327
114.155
72.344
42.272






5.624
6.522
16.996
3.222

5.535
12.746
7.336
3.533






SE coconut milk
d4,3 (mm)

0.175
0.264
0.298
0.112

13.785
125.284
23.710
11.702






d3,2 (mm)
0.482
5.600
5.894
0.274

8.800
8.340
7.967
7.858






0.326
0.541
0.441
0.266

d4,3 (mm)
25.891
58.275
29.078
25.628






1.467
8.155
1.698
0.366

Means  standard deviation of at least two replicates.

3.2. Emulsion thermal stability

3.2.1. Coconut milk emulsions at room temperature
Coconut milk emulsions were prepared with and without
addition of SE or TW and kept at room temperature (w28
C) before
determining their characteristics from visual appearance (Fig. 3),
optical micrographs (Fig. 4), and particle size measurements
(Fig. 5a and Table 1). Fig. 3 shows that all three types of emulsions:
Control coconut milk (without addition of any surfactant), TW
coconut milk, and SE coconut milk, appeared as white creamy
emulsions. Their average sizes (d3,2) were 10.0 microns, 5.5
microns, and 8.8 microns, respectively (Table 1). The results from
the optical micrographs (Fig. 4) conrmed that the particle sizes of
coconut milk emulsions containing SE or TW were smaller than
Control coconut milk. More droplet occulation in SE emulsions
was suggested to be the reason of SE emulsions having larger
average size than TW emulsions. The bulky headgroup of TW
seemed to effectively provide steric barriers that prevented droplet
occulation in TW emulsions. Even though SE had a better ability
than TW in reducing the interfacial tension between coconut oil
and water interface, this was not enough to observe its effect on
emulsion droplet size.

three coconut milk emulsions (Fig. 3). The presence of such solid
aggregates had also been reported in other studies (Chiewchan,
Phungamngoen, & Siriwattanayothin, 2006; Tangsuphoom &
Coupland, 2009b). Those particles were denatured proteins which
were detected as solid substance in the optical micrographs (arrows
in Fig. 4) and as an extra population on the right to the size distribution of emulsion population (arrows in Fig. 5b). From the optical
micrographs, some large coalesced oil drops were observed in
Control coconut milk that were signicantly larger than oil droplets in

3.2.2. Stability of coconut milk emulsions after heating

Further investigation was assessing thermal stability of coconut
milk emulsions by heating the emulsions at 121
C for 10 min. After
the heating, the coagulated white solid particles were observed in all

Control coconut milk

TW coconut milk
SE coconut milk

b
% Destabilized oil (free oil)

100

80

60

40

20

0
1

2
3
Number of freeze-thaw cycles

Fig. 6. Percentage of destabilized oil (free oil) in coconut milk emulsions without
addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and
with addition of 0.25 wt% sucrose ester (SE) after 1, 2 and 3 freeze-thaw cycles.

Fig. 7. Emulsion droplet charge (or z-potential) of () coconut milk emulsions without
addition of any surfactant (Control), (B) with addition of 0.25 wt% Tween 60 (TW),
and (D) with addition of 0.25 wt% sucrose ester (SE). (a) After only pH adjustment. (b)
After pH adjustment and addition of 20 mM CaCl2 salt.

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S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

either SE and TW emulsions (Fig. 4). Table 1 shows that the average
particle size (d3,2) of Control coconut milk increased from 10.0 to 22.1
microns (or by a factor of 2.2) and TW coconut milk increased from 5.5
to 12.7 microns (or by a factor of 2.3). However, the average particle
size of SE emulsion was still around 8e9 microns showing no
signicantly change (Table 1 and Fig. 5e). Noted that we chose the
surface-volume average diameter (d3,2) instead of d4,3 to analyze our
results of multi-modal distributions here. D3,2 was based on area
distribution and better representing the average size of smaller
particles (with more surface area) which supposed to be emulsion
droplets in this case. D4,3,or volume-weighted average diameter, was
calculated from volume distribution and more representing the
average size of larger particles (with more volume) which could be
the size of occulated droplets or solid aggregates.
Similarly, after coconut milk emulsions were kept at the
temperature of 100
C for 20 min, the average sizes of Control
coconut milk emulsions increased by a factor of 1.6 and the size of
TW emulsions slightly increased by a factor of 1.3, but SE emulsions
remained the same average size of 8e9 microns (Table 1 and Fig. 5c
and e). This was accompanied by the results from the optical
micrographs (Fig. 4) showing that SE and TW emulsions still
appeared as small oil droplets but Control coconut milks became

large coalesced oil drops. No coagulated solid particles oated in

TW or SE emulsions as observed in TW and SE coconut milk at
121
C (Fig. 3), suggesting that the degree of protein denaturation
was lesser at this lower temperature (100
C).
Coconut proteins, a natural coconut milk emulsier, when
denatured by heat lose their ability to stabilize emulsion droplets.
We observed large coalesced oil drops in Control coconut milk after
heated at 121
C or 100
C as oil droplets that come in close
proximity undergo extensively coalesce. Lesser degrees of droplet
coalescence in SE and TW emulsions when compared with Control
coconut milk indicated that heating stability of coconut milk
enhanced by addition of SE or TW. We found that SE stabilized
emulsions seemed to be more heat stable than TW emulsions as the
average sizes of SE emulsions (d3,2) did not signicantly alter after
the heating at both temperatures (Table 1 and Fig. 5e). The properties of SE had been reported to be lesser sensitive to temperature
variation when compared to other nonionic surfactants with oxyethylene groups (Stubenrauch, 2001).
3.2.3. Stability of coconut milk emulsions after freeze thawing
Coconut milk emulsions were kept at freezing temperature of
20
C for 14 h, and after being thawed at room temperature, their

Fig. 8. Optical micrographs of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition of 0.25 wt% sucrose
ester (SE) after pH adjustment (a) Extensive occulation. (b) Some occulation.

S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

characteristics were examined. From their visual appearance

(Fig. 3), some oil layers were accumulated on top of Control and TW
coconut milk emulsions, but in a sharp contrast, no oil layer was
observed in SE coconut milk. The optical micrographs in Fig. 4 show
some coalesced oil droplets in the Control and TW samples. The
particles size distributions (Fig. 5d) and average sizes (d3,2) (Table 1)
of Control and TW emulsions were signicantly altered from their
original emulsions at room temperature. This deviation should be
reasoned that some oil droplets in emulsions were already coalesced and separated out as oil layers and those oil droplets were
not detected during the size measurement. Differently, SE emulsied droplets appeared the same as their originally prepared
emulsions (Fig. 4) and its particle size distribution remained the
same (Fig. 5e) with the average size w8 microns closed to its
original size (Table 1), revealing good emulsion stability.
To ensure our results, numbers of freeze-thaw cycles were
increased up to three and the amounts of destabilized oils were
determined after each cycle. Fig. 6 clearly demonstrated that the
amounts of destabilized oil coming out from SE emulsions after
each freezing cycle were much lesser than from Control and TW
emulsions. After the rst cycle, almost no destabilized oil was
detected in SE emulsions, while 93% and 68% of destabilized oils
were obtained from Control and TW emulsions, respectively. After
the third cycle, the percentage of destabilized oils in SE emulsions
was three times lesser than in Control or TW emulsions. Noted that
even though this dye-dilution method (Palanuwech et al., 2003)
might not be very precise to quantify amounts of oil, the results
should be accurate enough for comparing relative amounts of oil
coming out from each emulsion.
Many other studies have shown that their emulsions also
destabilized into oil layer after freeze thawing; for example, coconut
milks prepared from Tween 20 (Tangsuphoom & Coupland, 2009b),
palm oil emulsions prepared from Tween 20 (Thanasukarn et al.,
2004b; Thanasukarn, Pongsawatmanit, & McClements, 2006), and
n-alkanes emulsions prepared from SDS and Tween 20 (Cramp,
Docking, Ghosh, & Coupland, 2004). We noticed that those emulsions that prepared from Tweens were prone to be unstable similarly to our TW result. Several researchers aim to understand the
destabilization mechanism in order to improve freeze-thaw stability
of emulsions (Cramp et al., 2004; Ghosh & Coupland, 2008). Thus, it
is very interesting here to discover that emulsions prepared from SE
were more freeze-thaw stable than TW emulsions.
A number of studies have reported that the presence of sucrose
increased freeze-thaw stability of emulsions (Ghosh, Cramp, &
Coupland, 2006; Thanasukarn, Pongsawatmanit, & McClements,
2004a; Thanasukarn et al., 2006). Sucrose has been known to have
a cryo-protective property coming from sucrose ability to lower the
freezing point of water. Such unfrozen water protects other
compounds dissolving in the aqueous phase from the freeze damage.
The unfrozen water in emulsions protects oil droplets from penetration
of growing ice crystal that would disrupt the interfacial membrane and
cause droplet coalescence. We found that there was also a report about
the presence of unfrozen water in the aqueous solution of sugar-based
surfactant and its possible cryo-protective effect (Ogawa, Asakura, &
Osanai, 2009). We suspected that our SE coconut milk contained
some unfrozen water and this was the reason that SE coconut milk
emulsions were still stable after the freeze thawing.

365

net charge gradually reduced to zero when pH approached to the

value of 4, corresponding to the PI of coconut protein reported in
other literatures (Onsaard, Vittayanont, Srigam, & McClements,
2005; Tangsuphoom & Coupland, 2008a). When proteins lose
their net charge at this pH, the Control emulsion droplets became
extensively occulated (Fig. 8) and creamed rapidly with the
creaming index of 42% after ten-minute storage (Fig. 9). At other pH
values, the electrostatic repulsion provided by coconut proteins was
sufcient to prevent aggregation of droplets and no creaming was
observed.
The result of pH effect for SE and TW coconut milk was relatively
invariant to Control coconut milk. The z-potential of SE and TW
emulsions decreased from a positively charge at pH 2 to a negatively charge at pH 8 with a net zero charge at pH close to 4 (Fig. 7a).
SE and TW emulsions only creamed at pH 4 with the creaming
index after ten-minute storage of 8% for SE emulsions and of 50% for
TW emulsions (Fig. 9). The much lower in creaming index of SE
emulsions suggested that SE might also alter rheological property
of emulsions and benecial as a creaming stabilizer. The highest
creaming rate was accompanied by the highest occulation shown
in the micrographs at pH 4 in both emulsions (Fig. 8). It was a little
surprising that, after addition of nonionic surfactants such as SE
and TW, the charges on droplets were still dominant and sensitive
to the pH condition since nonionic surfactants would provide steric
stability and remove electrostatic effect of proteins. If the proteins
on emulsion droplets were completely displaced then the properties of the emulsion should be the same as the replacing surfactants
(McClements, 2004).
More investigation on the role of droplet charges was by addition
of 20 mM CaCl2 salt. The micrographs from Fig. 10 show that salt
addition induced droplet occulation at pH of 6 and 8, similarly in
Control, TW and SE emulsions. The occulation was obvious when
comparing the micrograph before (Fig. 8) and after salt addition
(Fig. 10). The presence of occulated droplets had been attributed to
ability of salt to screen charges of coconut proteins (Fig. 7b) and

3.3. Emulsion stability against pH and salt concentrations

The charge characteristics of coconut protein on oil droplets
were investigated by exposing emulsions to different pH conditions.
Fig. 7a shows that the z-potential of Control coconut milk droplets
changed from a positively charge of 16 mV to a negatively charge
of 28 mV when increasing the pH from 2 to 8. From the graph, the

Fig. 9. Creaming index after ten-minute storage of () coconut milk emulsions
without addition of any surfactant (Control), (B) with addition of 0.25 wt% Tween 60
(TW), and (D) with addition of 0.25 wt% sucrose ester (SE) after adjustment to different
pH conditions.

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S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

Fig. 10. Optical micrographs of coconut milk emulsions without addition of any surfactant (Control), with addition of 0.25 wt% Tween 60 (TW), and with addition of 0.25 wt%
sucrose ester (SE) after pH adjustment and addition of 20 mM CaCl2 salt. (a) Extensive occulation.

reduced electrostatic repulsion between oil droplets. We noticed

that the oil droplets did not occulate after addition of salt at pH 2
where amino acids were mostly protonated and proteins had highly
net positively charge. It seemed that oil droplets were most repulsive at this low pH condition as also observed in emulsions stabilized
by other protein (Kim, Decker, & McClements, 2004).
The sensitivity to pH and salt conrmed the presence of proteins
at interfacial droplets in SE and TW emulsions. Thus, in the present
case, proteins on droplets of coconut milk emulsion were not
completely displaced by the SE or TW content of 0.25 wt%. We
postulated that SE or TW molecules stayed on oil droplet interface
together with coconut protein stabilizing emulsions by both steric
and electrostatic repulsion.
Further investigation on interfacial behaviors when coconut
proteins coexist with these surfactants is suggested. The interfacial
characteristics are governed by structure and thickness of
proteinesurfactant lms, the interfacial ratio of protein to surfactant, and the proteinesurfactant interactions (Rodriguez Patino,
Rodriguez Nino, & Carrera Sanchez, 2007). A previous study
showed that addition of sucrose ester decreased the interfacial
tension and the interfacial elasticity of milk protein membrane in

corresponding to the surfactant/protein ratio (Rouimi, Schorsch,

Valentini, & Vaslin, 2005). Some literature also evidenced that
Tween 60 only partially displaced sodium caseinate (Dalgleish,
Srinivasan, & Singh, 1995) and albumin (Seta, Baldino, Gabriele,
Lupi, & de Cindio, 2012) from the oilewater interface even at some
high surfactant/protein ratios.
4. Conclusions
This work clearly showed that sucrose ester (SE) exhibited
interesting interfacial and emulsifying properties when compared
with Tween 60 (TW). SE was slightly better in lowering the interfacial tension between coconut oil and water interface. The stability
and surface charge characteristics of coconut milk emulsions
emulsied with 0.25 wt% of nonionic SE or TW strongly depended
on pH and salt environments. Thus, it was likely that the addition of
SE or TW did not completely displace proteins on oil droplets to
remove their electrostatic interaction. The presence of either SE or
TW had a distinct effect on the thermal characteristics of coconut
milk emulsions: coconut milk emulsions emulsied with SE were
more thermally stable than TW emulsions. Especially, we found

S. Ariyaprakai et al. / Food Hydrocolloids 30 (2013) 358e367

that SE coconut milk emulsions were much more stable after freeze
thawing. The complex between coconut protein and SE seemed to
be an emulsifying membrane that could better protect coconut
milk emulsions from the heat and freeze damages.
Acknowledgment
This research was fully supported by the Research Grant for New
Scholar (MRG53) provided by the Thailand Research Fund and
Assumption University and the mentor of this project was Asst.
Prof. Pasawadee Pradipasena from Department of Food Technology,
Faculty of Science, Chulalongkorn University.
Special thanks to Ms.Treuktongjai Saenghiruna and Ms. Rungchat
Kladcharoen, undergraduate students from Assumption University
who dedicated in some experimental works and to Ms. Martha Intan
Budiati, a practical training student from Faculty of Agricultural
Technology, Soegijapranata Catholic University, Semarang, Indonesia,
who helped during sample preparation. Also thanks to Caltech Corp.,
Ltd. for kindly donating the sucrose ester used in this study.
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