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Eect of Salts on Formation and Stability of Vitamin EEnriched Miniemulsions Produced by Spontaneous Emulsication
Amir Hossein Saberi, Yuan Fang, and David Julian McClements*,
Biopolymers and Colloids Laboratory, Department of Food Science, University of MassachusettsAmherst, Amherst,
Massachusetts 01003, United States
PepsiCo Global R&D, 100 Stevens Avenue, Valhalla, New York 10595, United States
ABSTRACT: Emulsion-based delivery systems are being utilized to incorporate lipophilic bioactive components into various
food, personal care, and pharmaceutical products. This study examined the inuence of inorganic salts (NaCl and CaCl2) on the
formation, stability, and properties of vitamin E-enriched emulsions prepared by spontaneous emulsication. These emulsions
were simply formed by titration of a mixture of vitamin E acetate (VE), carrier oil (MCT), and nonionic surfactant (Tween 80)
into an aqueous salt solution with continuous stirring. Salt type and concentration (01 N NaCl or 00.5 N CaCl2) did not have
a signicant inuence on the initial droplet size of the emulsions. On the other hand, the isothermal and thermal stabilities of the
emulsions depended strongly on salt levels. The cloud point of the emulsions decreased with increasing salt concentration, which
was attributed to accelerated droplet coalescence in the presence of salts. Dilution (26 times) of the emulsions with water
appreciably improved their thermal stability by increasing their cloud point, which was mainly attributed to the decrease in
aqueous phase salt levels. The isothermal storage stability of the emulsions also depended on salt concentration; however,
increasing the salt concentration decreased the rate of droplet growth, which was the opposite of its eect on thermal stability.
Potential physicochemical mechanisms for these eects are discussed in terms of the inuence of salt ions on van der Waals and
electrostatic interactions. This study provides important information about the eect of inorganic salts on the formation and
stability of vitamin E emulsions suitable for use in food, personal care, and pharmaceutical products.
KEYWORDS: emulsions, nanoemulsions, vitamin E, salts, stability, cloud point, spontaneous emulsication
INTRODUCTION
Emulsion-based delivery systems are nding increasing
utilization within food, personal care, and pharmaceutical
products to encapsulate, protect, and release lipophilic active
ingredients. This category of delivery system includes various
kinds of colloidal suspension that utilize lipid droplets as
building blocks, such as emulsions, solid lipid nanoparticles,
multilayer emulsions, multiple emulsions, and lled hydrogel
particles.1,2 Emulsions are the simplest type of emulsion-based
delivery system consisting of lipid droplets suspended in an
aqueous phase, with each lipid droplet being coated by a layer
of emulsier molecules. Nevertheless, the functional performance of emulsions can still be manipulated by altering oil phase
composition, emulsier type, and particle size distribution. For
example, reducing the particle size can lead to higher optical
clarity, greater stability to gravitational separation and droplet
aggregation, and higher oral bioavailability.35 Emulsions
containing very small droplets (d < 200 nm) are often referred
to as nanoemulsions, mini-emulsions, or ultrane emulsions. In
this paper, we will simply refer to them as emulsions for the
sake of convenience.
Emulsions can be prepared using several approaches, which
are usually categorized as either high-energy or low-energy
methods.6,7 High-energy methods use mechanical devices to
generate intense forces that intermingle and break up the oil
and water phases, such as high-pressure homogenizers,
microuidizers, and ultrasonic generators.3,8 Low-energy
methods rely on the spontaneous formation of ultrane
droplets within surfactantoilwater (SOW) mixtures when
2014 American Chemical Society
Article
water
NaCl
solution (1
N)
CaCl2
solution
(0.5 N)
relative
viscosity /
oa
refractive
index
relative
density
(kg/L)
excess interfacial
tensionb (mN/m)
1.000c
1.090c
1.333c
1.343c
1.000c
1.038c
0.0e
0.9e
1.070d
1.346c
1.044c
1.9e
a
Ratio of the absolute viscosity of solution at 20 C to the ratio of the
absolute viscosity of water at 20 C. bExcess interfacial tension is
dened as the dierence between interfacial tension of hydrocarbon/
salts solution and interfacial tension of hydrocarbon/water. cReference
50. dReference 51. eReference 52.
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because they contained very small droplets that did not scatter
light strongly.36 At these low temperatures the surfactant is
relatively hydrophilic, and the corresponding optimum
curvature (p < 1) favors the formation of oil-in-water
emulsions. As temperature increases, the headgroup of the
nonionic surfactant (Tween 80) undergoes progressive
dehydration, causing the packing parameter to increase (Figure
1b). As a result, the rate of droplet coalescence increases
because of the reduced hydration repulsion between droplets
and the increase in interfacial exibility, and so there is a
corresponding increase in turbidity. However, when the
temperature reaches the PIT, the surfactant monolayer has
zero curvature, the packing parameter is close to unity (p = 1),
and the interfacial tension becomes ultralow (Figure 1b). These
changes favor the formation of a bicontinuous microemulsion
phase containing very small structures that do not scatter light
strongly, thereby leading to a reduction in turbidity. Increasing
the temperature above the PIT further dehydrates the
headgroups of the surfactant molecules, which increases their
lipophilicity, increases the packing parameter (p > 1), and
changes the optimum curvature so that it favors the formation
of water-in-oil emulsions (Figure 1b). The water droplets in the
water-in-oil emulsions formed above the PIT are relatively large
and therefore scatter light strongly, leading to increased
turbidity.3,29
The impact of salt on the turbiditytemperature proles of
the emulsions can be attributed to the fact that salt decreases
the PIT of the emulsions. In the absence of salt, the PIT is
relatively high, and therefore we observed only the initial
droplet coalescence regimen. In the presence of sucient salt,
the PIT moved into the experimental temperature range, and
we could observe droplet coalescence, microemulsion formation, and phase inversion. A similar behavior was observed in
the turbiditytemperature proles of vitamin E-enriched
emulsions in the absence and presence of glycerol; that is,
glycerol reduced the PIT.26
The turbidity versus temperature proles were used to
determine the cloud points of the emulsions so that we could
establish the inuence of salt type and concentration on their
thermal behavior. The cloud point of the emulsions decreased
from around 78 to 65 C when the NaCl concentration was
increased from 0 to 1 M and decreased from around 78 to 70
C when the CaCl2 concentration was increased from 0 to 0.5
N (Figure 1c). The ability of NaCl14,15,20,37 and CaCl214,15,37 to
decrease the cloud points of nonionic surfactant has been
reported previously. Our results are also in agreement with
previous studies that have reported that the cloud point and/or
PIT of nonionic surfactants is a linear function of their salt
concentration.15,38,39 The decrease in thermal stability (cloud
point) of emulsions in the presence of NaCl and CaCl2 can be
attributed to the eect of these salts on the solubility and
packing characteristics of nonionic surfactants.
Specic anionic19,40,41 and cationic12,16,19,40 salt ions may
either increase (salting in) or decrease (salting out) the
solubility of nonionic surfactants due to their eects on the
structural organization of water molecules. Ions can be
classied as either structure-makers (salting out) or
structure-breakers (salting in) according to their position in
the Hofmeister series.42,43 The presence of mineral ions in an
aqueous solution may alter the PIT of a nonionic surfactant by
altering the solubility and packing characteristics of the
surfactant molecules. In particular, salts may aect the optimum
curvature of the surfactants by altering the hydration of their
Figure 2. Inuence of dilution on the cloud point of vitamin Eenriched mini-emulsion produced using 10% oil phase (vitamin E/
MCT, 8:2), 10% surfactant phase (Tween 80), and 80% aqueous
phase (0.5 M salt). Oil phase concentrations were 10, 5, 3.33, 2.5, and
1.67, and salt concentrations were 0.4, 0.2, 0.13, 0.1, 0.08, and 0.067 N
for the emulsion diluted with dilution factors of 1, 2, 3, 4, 5, and 6,
respectively.
Article
suggest that the increase in cloud point observed when saltcontaining emulsions were diluted with buer solution was
primarily due to the reduced salt concentration in the aqueous
phase, rather than the reduced droplet concentration.
Inuence of Salts and Dilution on Isothermal
Stability. Physical stability of emulsion-based delivery systems
during storage, transport, and utilization is required for most
commercial applications. Emulsions may become unstable
through a number of dierent physicochemical processes,
including occulation, coalescence, Ostwald ripening, and
gravitational separation.10,33 The mechanism and rate of
breakdown depend on emulsion composition and microstructure, as well as the environmental conditions experienced
during its lifetime. We therefore examined the inuence of salt
addition and dilution on the storage stability of vitamin E
emulsions. A series of emulsions was fabricated with dierent
droplet concentrations (2.5 or 10 wt %) and salt concentrations
(0, 0.2, and 0.4 N NaCl or CaCl2) by diluting an initial
emulsion with dierent types and amounts of salt solution.
After preparation, the resulting emulsions were stored for 1
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AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
We thank William Mutilangi of PepsiCo for useful advice and
discussions on this research.
REFERENCES
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