Trends in Food Science & Technology 50 (2016) 159e174

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Trends in Food Science & Technology

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Review

Food-grade particles for emulsion stabilization

Iris Tavernier a, *, 1, Wahyu Wijaya b, 1, Paul Van der Meeren b, Koen Dewettinck a,
Ashok R. Patel a, **
a
Laboratory of Food Technology and Engineering, Ghent University, Coupure Links 653, 9000, Gent, Belgium
b
Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University,
Coupure Links 653, B-9000, Gent, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: The use of solid, food-grade particles as emulsion stabilizers is highly promising in the field of food
Received 23 June 2015 science and technology. Food-grade particles (e.g. fat and wax crystals, protein particles, and protein-
Received in revised form polysaccharide complexes) can form alternatives to inorganic particles (e.g. silica, alumina or clays),
11 January 2016
which are incompatible and mostly unserviceable when considering food and nutraceutical applications.
Accepted 28 January 2016
This review provides a concise insight into the concept of Pickering stabilization with the emphasis on
Available online 4 February 2016
the available food-grade particles that have been researched in this field. The innovative food applica-
tions of particle-stabilized emulsions are also discussed.
Keywords:
Pickering
© 2016 Elsevier Ltd. All rights reserved.
Emulsions
Food-grade

1. Introduction stability with steric hindrance and/or electrostatic repulsion be-

In the last few years, micro- and nano-particles of biological
origins have been extensively explored as colloid stabilizers (i.e.
stabilization of liquideliquid and/or liquidevapor interfaces) for
application in bio-related fields, such as foods and nutraceuticals.
Interestingly, this concept has been applied for centuries in food
products, without being scientifically researched. For instance, in
mayonnaise (a concentrated oil-in-water emulsion which has been
used for ages), the fine mustard particles contribute to physical and
colloidal stability of the emulsion by preventing the coalescence of
oil droplets (Binks, 2007).
As its name implies, particle stabilized emulsions use solid
particles to obtain stable emulsions. This concept was first intro-
duced as Pickering stabilization in the early 1900s (Pickering, 1907;
Ramsden, 1903). The mechanism of stabilization is quite different
from conventional emulsion stabilization, in which the oil-water
interface is generally stabilized using low molecular weight com-
ponents with amphiphilic characteristics. These low molecular
weight emulsifiers decrease the interfacial tension and introduce
* Corresponding author.
** Corresponding author.
E-mail addresses: Iris.Tavernier@Ugent.be (I. Tavernier), Patel.Ashok@Ugent.be
(A.R. Patel).
1
Both authors contributed equally to this work.
tween the droplets (Rayner et al., 2014). Solid particles can also
adsorb on the oil-water interface and create a mechanical barrier
that protects the emulsion droplets against destabilization
(Dickinson, 2012). However, unlike low molecular weight emulsi-
fiers, the adsorption of particles is considered to be irreversible.
Therefore, Pickering emulsions show an outstanding stabilization
against coalescence and Ostwald ripening in comparison to emul-
sions stabilized with low molecular weight emulsifiers (Kargar,
Fayazmanesh, Alavi, Spyropoulos, & Norton, 2012; Timgren,
Rayner, Sjo€o€, & Dejmek, 2011).
Pickering emulsion droplets are stabilized by particles which
feature a partial dual wettability by both the oil and water phase.
This property leads to the accumulation of the particles at the oil-
water interface. Aforementioned particles can stabilize both oil-
in-water (O/W) and water-in-oil (W/O) emulsions. The type of
emulsion that is preferably stabilized by a particle can be deduced
from the contact angle at the oileparticleewater interface (Fig. 1).
The liquid phase that wets the solid more than the other liquid, will
likely be the continuous phase. Particles with a contact angle
smaller than 90
will form an O/W emulsion, while particles with a
contact angle greater than 90
usually form W/O emulsions (Finkle,
Draper, & Hildebrand, 1923).
Particle wettability and surface activity of insoluble particles
may be further altered by adsorption of suitable surfactants or by
chemical modification (Binks, Rodrigues, & Frith, 2007). However,

http://dx.doi.org/10.1016/j.tifs.2016.01.023
0924-2244/© 2016 Elsevier Ltd. All rights reserved.
160 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
Fig. 1. Bending behavior of oilewater interface for a contact angle less than 90
(left) and greater than 90
(right). The contact angle equal to 90
corresponds to the point of phase
inversion. Reproduced with permission from Elsevier (Aveyard et al., 2003).
the implementation of modified particles in the food and phar-
maceutical industry is quite limited because the required modifi-
cations to render them suitably surface-active are most often not
permitted in foods. Notable exceptions are the inert silica particles
with a hydrophobic coating of lecithin which are used as emulsi-
fiers of triglyceride O/W emulsions (Eskandar, Simovic, & Prestidge,
2007), starch granules chemically modified with octenyl succinic
anhydride (OSA) to increase their hydrophobicity (Matos, Timgren,
€o
Sjo €, Dejmek, & Rayner, 2013; Rayner, Timgren, Sjo €o
€ , & Dejmek,
2012) and other types of food-grade modified starches such as
distarch phosphate and acetylated distarch phosphate (Prochaska,
Ke˛ dziora, Le Thanh, & Lewandowicz, 2007). Also some hydro-
phobically modified cellulose fibers, such as hydroxypropyl meth-
ylcellulose phthalate (HP), can stabilize emulsions and produce
superstable Pickering foams and emulsions (Wege, Kim, Paunov,
Zhong, & Velev, 2008).
Particles used to stabilize food emulsions should be food-grade
and therefore, the options are limited to particles of biological
origin, such as fat crystals, cellulose derivatives, dairy and plant
proteins, protein-polysaccharide complexes and flavonoids (Rayner
et al., 2014). Pickering emulsions stabilized with food-grade parti-
cles have a wide application range. They can be used to encapsulate
active ingredients or to enhance the nutritional profile, texture or
structure of several processed foods (Berton-Carabin & Schroe €n,
2015).
This review aims to provide an insight in the Pickering stabili-
zation concept and the preparation and characterization of the
particles and the emulsions. Moreover, an overview of food-grade
particles is also given with particular emphasis on innovative
food applications.
2. Kinetic and energetic aspects of solid-particle adsorption
on the interface
The kinetic aspects of solid-particle adsorption on the oil-water
interface are different compared to those of low molecular weight
surfactant. This is caused by the large particle size of the solid
particles, compared to that of surfactant and protein molecules. The
adsorption of solid particles results in stronger capillary forces
between the particles trapped in the liquid films (Velikov, Durst, &
Velev, 1998). Therefore, adsorbed solid particles display a high
desorption energy barrier, but also show a high barrier to particle
adsorption (Tcholakova, Denkov, & Lips, 2008). Consequently, the
particle adsorption shows much slower kinetics than the adsorp-
tion of low molecular weight surfactants but, once adsorbed on the
interface, the adsorption of particles is considered to be irreversible
due to the high desorption energy barrier. Again, this is in contrast
to low molecular weight surfactants, which are in rapid and dy-
namic equilibrium between the oil-water interface and the bulk
phase.
The energy of attachment of a particle to a fluidefluid interface
is not only related to the contact angle, but also to the tension of the
oil-water interface gow. Since the Pickering particles are small,
gravity and buoyancy effects can be neglected. The energy (E)
required to remove a particle from the interface is given by Eq. (1).
E ¼ pr 2 gow ð1  jcosqjÞ2 (1)
where r is the radius of the Pickering particle, gow the surface
tension of the oil-water interface and q the contact angle. This
detachment energy is in the order of 103 kT for a 10 nm particle at
angles of around 90
, but falls quite rapidly as the particle contact
angle decreases or increases (Dickinson, 2010). When the particles
are either too hydrophilic (low W) or too hydrophobic (high W), they
remain in the aqueous or oil phase respectively, giving rise to very
unstable emulsions (Binks, 2002).
3. Stability of Pickering emulsions
In general, Pickering emulsions provide outstanding stability
against Ostwald ripening and coalescence (Kargar et al., 2012;
Timgren et al., 2011). However, multiple factors will influence the
overall emulsion stability. These stability-influencing properties are
related to the solid particles themselves (particle wettability which
is mentioned above, particle size, particle concentration and par-
ticle shape), to the oil phase (type of oil) and to the water phase (pH
and electrolyte concentration) (Aveyard, Binks, & Clint, 2003;
Binks, 2002).
As mentioned above, particle size is an important factor in
determining the emulsion stability. The size of particles that can be
used to stabilize emulsions ranges from nanometers to several
micrometers. For successful stabilization, the particles should be
several orders of size smaller than the emulsified droplets for the
particles to be properly located around the droplets. The size of
emulsion droplets is determined by the amount of particles relative
to the dispersed phase. Generally, droplet size decreases with
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
increasing particle concentration (at a fixed dispersed phase con-
tent) to a certain point after which the droplet size levels out (Binks
& Lumsdon, 2001). Small size is of interest since droplet size is
strongly correlated with high emulsion stability in conventional
emulsion systems. However, in Pickering emulsions, larger droplet
sizes are also stable to coalescence over extended periods of time
(Arditty, Schmitt, Giermanska-Kahn, & Leal-Calderon, 2004). The
particles of biological origin used in food applications are usually
polydisperse in size, which results in polydispersity of the discon-
tinuous phase and therefore less stable emulsions.
Regarding the morphology of the particles, there is some debate
upon the effect of surface roughness. Vignati, Piazza, and Lockhart
(2003) showed that particle surface roughness appreciably lowers
the emulsifying efficiency. However, according to the results of San-
Miguel and Behrens (2012) particle roughness can significantly
improve the emulsifying capacity of the particles. The maximum
capillary pressure2 initially increases with increasing particle
roughness to almost twice the value for smooth particles. Yet, the
roughest particles are no longer homogeneously wetted which
results in a decrease of the maximum capillary pressure and of the
stability of the resulting emulsions. This aspect is especially
important for particles of natural origin, since they often show
surface roughness (Lam, Velikov, & Velev, 2014).
Particle shape can be described using the aspect ratio, which is
the ratio of the smallest diameter to the largest diameter orthog-
onal to it. The aspect ratio of a circle is 1:1 for example. For both O/
W and W/O emulsions, Madivala, Vandebril, Fransaer, and Vermant
(2009) observed a strong dependence of emulsion stability on the
particle aspect ratio. Particles with a higher aspect ratio could
stabilize biphasic systems at a lower concentration, and in certain
cases were able to stabilize systems which particles of spherical
shape could not. Binks and Horozov (2006) confirmed this in a
geometrical analysis by considering the effect of the particle shape
on the free energy of detachment in the case of rod- and disk-like
particles which both have an aspect ratio of 2.5 to a sphere of
equivalent volume. The respective detachment energies at a con-
tact angle of 90
were 31.5% (rod-like particles) and 57.9% (disk-like
particles) higher than the sphere case. A well-accepted hypothesis
for this phenomenon is that anisotropic particles induce greater
capillary deformations at the interface, resulting in larger capillary
attractive forces between neighboring particles adsorbed at the
interface (Madivala et al., 2009). Higher aspect ratios generally lead
to higher desorption energies, due to the higher potential contact
area of the particles with the interface, and thus to more stable
emulsions (Binks & Horozov, 2006).
The type of oil used also significantly influences the emulsion
stability. Binks and Lumsdon (2000) found that on the one hand
particles are more hydrophobic at polar oil-water interfaces (esters
and alcohols), preferring water-in-oil (W/O) emulsions, and on the
other hand they are more hydrophilic at non-polar oil-water in-
terfaces (alkanes), which results in an oil-in-water (O/W) type of
emulsion.
The pH and electrolyte concentration in the water phase in-
fluences the electrostatic and steric interactions and therefore, the
emulsion stability. The particles adsorbed at the oil-water inter-
phase create a physical barrier preventing contact between drop-
lets. The thickness of this barrier changes at varying salt
concentration and pH (Rayner et al., 2014). The thinner this physical
barrier, the less repulsion there is between the droplets and the less
stable the emulsion is.
2
The maximum capillary pressure describes the maximum pressure that the
liquid film between two emulsion droplets in contact can withstand before
rupturing, after which coalescence occurs (San-Miguel & Behrens, 2012).
161
Colloidal particles also stabilize emulsions by modifying the
rheological properties of the interfacial region and of the contin-
uous phase. Colloid-laden interfaces exhibit viscoelastic behavior,
which improves the stability by increasing the magnitude of steric
hindrance and by retarding the rate of liquid drainage between
coalescing emulsion droplets (Tambe & Sharma, 1994). Moreover,
the presence of aggregated excess particles in the continuous phase
can enhance the viscosity and reduce the rate and extent of
creaming (Midmore, 1998).
4. Instability processes of Pickering emulsions and their
assessment
Pickering emulsions are considered to be stable against coales-
cence and Ostwald ripening. Instability processes that can occur are
creaming for O/W emulsions (or sedimentation for W/O emul-
sions), flocculation, and phase inversion. The most basic technique
to assess creaming involves the monitoring of the lower creaming
boundary using graduated cylinders at constant temperature. This
technique is useful in creaming of emulsions where the lower
boundary is sharp and visible. Yet often, emulsions consist out of
three phases: (a) a lower layer devoid of droplets; (b) a middle
layer, with approximately the same droplet concentration as the
original emulsion; and (c) an upper layer where the droplets are
closely packed (Robins, 2000). In the latter case, it is more conve-
nient to use alternative techniques such as turbidity measurements
as a function of height at various times. Centrifugation may be
applied to accelerate the rate of creaming (Tadros, 2004).
Coalescence and Ostwald ripening are monitored by measuring
the changes in droplet size distribution. The rate of flocculation can
be measured by determining the turbidity as a function of time in
dilute emulsions. Flocculation can also be assessed by direct droplet
counting using optical microscopy, Coulter counter, light diffraction
techniques and photo-sedimentation techniques (Tadros, 2004).
Evaluation of phase inversion can be done by measuring the
conductivity or the viscosity of the emulsion as a function of the
volume fraction (catastrophic phase inversion), increase of tem-
perature and/or addition of electrolyte (transitional phase inver-
sion). Tadros (2004) and Torres, Iturbe, Snowden, Chowdhry, and
Leharne (2007) have shown how steady state shear stress-shear
rate, constant stress and oscillatory rheological measurements
can be used to assess stability to creaming, flocculation, coalescence
and phase inversion.
In addition to emulsion instability, assessments related to
physiological processes and sensory properties are also considered
for food applications. Shimoni, Shani Levi, Levi Tal, and Lesmes
(2013) developed an analytical centrifugation technique that
investigated the behavior of Pickering emulsions in artificial saliva
and in-vitro gastric conditions. This work provides an under-
standing of the behavior of Pickering emulsions in the human body
and allows researchers and product developers to modify Pickering
emulsions in such a way that the emulsions positively impact
health aspects and sensorial properties.
5. Physicochemical characterization of the particles and the
pickering emulsions
Characterization of the particles themselves and of the
Pickering-based emulsion systems they form is imperative for un-
derstanding and predicting the physical and chemical stability of
both the particles themselves and of the emulsions, including the
behavior during processing, compatibility with the food matrix,
overall sensory quality of the product and functionality. The
physicochemical characterization can be categorized into micro-
structural, molecular (intra- and intermolecular), and macro-level
162 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174

techniques. These characterization techniques are summarized in et al., 2012).

Table 1.
Microstructure characterization techniques are mainly based on
light scattering and advanced microscopy, which allow us to un-
derstand the structure of the particles and of the emulsion systems.
Some techniques such as light microscopy (Destribats, Rouvet,
Gehin-Delval, Schmitt, & Binks, 2014; Rayner et al., 2012),
confocal laser scanning microscopy (Kalashnikova, Bizot, Cathala, &
Capron, 2011; Y. Tan et al., 2012), fluorescence microscopy (Paunov
et al., 2007), TEM (de Folter, van Ruijven, & Velikov, 2012), SEM
(Paunov et al., 2007; Rayner et al., 2012), and dynamic or static light
scattering (Destribats et al., 2014; Tzoumaki, Moschakis,
Kiosseoglou, & Biliaderis, 2011) have been commonly used to
study particle morphology, particle size and colloid instabilities
(e.g. flocculation, aggregation). The surface morphology and
lamellar thickness could be studied with small angle X-ray scat-
tering (SAXS) and Atomic Force Microscopy (AFM) (Lesmes, Cohen,
Shener, & Shimoni, 2009; Zabar, Lesmes, Katz, Shimoni, & Bianco-
Peled, 2010).
Molecular characterization techniques elucidate the intra- and
intermolecular physicochemical properties. Intramolecular prop-
erties, such as enthalpies, crystallization and glass transition events
have been successfully monitored through differential scanning
calorimetry (DSC) (Skelhon, Grossiord, Morgan, & Bon, 2012).
Intermolecular properties include the interaction between parti-
cleseparticles or particles-droplets and their chemical structure.
These can be investigated through advanced methods, such as
Fourier transform infrared spectroscopy (FTIR) (Crupi et al., 2007),
isothermal titration calorimetry (Patel, Seijen-ten-Hoorn, & Veli-
kov, 2011), mass spectrometry (MS) (Oliver, Kher, McNaughton, &
Augustin, 2009) and nuclear magnetic resonance (NMR) (Y. Tan
Other types of characterization techniques focus on the macro-
level or bulk system properties such as interface behavior and
product instability. The O/W interface can be characterized by
measuring the change in surface tension after particle adsorption
and by determining the contact angle. The surface tension de-
creases when surface active particles are adsorbed at the O/W
interface. The extent of the decrease is correlated to the stability of
the emulsion. From the contact angle measurements, it can be
deduced whether particles have a more hydrophilic character and
will preferentially stabilize O/W emulsions or have a more hydro-
phobic character and will stabilize W/O emulsions.
The contact angle and the surface tension are determined using
the same measuring methods (de Folter et al., 2012; Destribats
et al., 2014; Gao et al., 2014). Examples of traditional techniques
are the Wilhelmy plate method and du Noüy ring method, which
measure the force needed to traverse an object through an inter-
face, the drop volume method, based on the balance of gravity
forces against capillary forces, the spinning drop method, which
studies droplet distortion caused by centripetal acceleration, and
the pendant and sessile drop methods that involve analysis of
gravity-distorted drop shapes (Moran, Yeung, & Masliyah, 1999).
6. Food-grade particles
In Table 2, a summary of literature reports on the utilization of
particles which can be considered as food stabilizers is presented.
Fig. 2 illustrates the interface stabilization of emulsion droplets by
biopolymeric particles that can be considered for food applications
The following paragraphs will elucidate some of these examples.

Table 1
Common characterization methods of food-grade particles and Pickering based formulation.

Characterization Common available Examples Types (P ¼ particles; E ¼ emulsion)

methods

Microstructure Light microscopy Whey protein isolate P (Destribats et al., 2014)

O/W emulsion stabilized by quinoa; chitin E (Rayner et al., 2012)
Confocal laser scanning Starch nanospheres P (Tan et al., 2012)
microscopy O/W emulsion stabilized by bacterial cellulose nanocrystal E (Kalashnikova et al., 2011)
Fluorescence microscopy Starch nanospheres P (Tan et al., 2012)
O/W emulsion stabilized by fat crystals, calcium carbonate-stearic E (Paunov et al., 2007)
acid, soy protein particles
TEM Zein; whey protein P (de Folter et al., 2012)
SEM Quinoa particles; fat crystals, calcium carbonate-stearic acid, soy P (Paunov et al., 2007; Rayner et al., 2012)
protein particles
O/W emulsion stabilized by microcrystalline cellulose and modified E (Kargar et al., 2012; Tan et al., 2012)
starch; starch nanospheres
SAXS Amylose particles P (Zabar et al., 2010)
AFM b-lactoglobulin-pectin; pea protein P (Jones, Decker, & McClements, 2010; Liang
& Tang, 2014)
X-ray diffraction O/W emulsion stabilized by fat crystals E (Ghosh et al., 2011)
Light scattering (DLS and Whey protein isolate P (Destribats et al., 2014)
SLS) O/W emulsion stabilized by chitin, whey protein isolate E (Destribats et al., 2014; Tzoumaki et al.,
2011)
Molecular (intra- and DSC W/O chocolate candy emulsion E (Skelhon et al., 2012)
intermolecular) Charge potential Zein, b-lactoglobulin-pectin P (Patel, Bouwens, & Velikov, 2010)
O/W emulsion stabilized by lactoferrin-pectin, alginate or E (Shimoni et al., 2013)
carrageenan
FTIR Genistein-b-cyclodextrin P (Crupi et al., 2007)
MS Glycated caseins P (Oliver et al., 2009)
1
H NMR Starch nanosphere P (Tan et al., 2012)
Isothermal titration Methylcellulose-polyphenol P (Patel, Seijen-ten-Hoorn et al., 2011)
calorimetry
Macro-level Surface tension and O/W emulsion stabilized by flavonoid or chitin; zein; zein-stearate; E (de Folter et al., 2012; Destribats et al., 2014;
contact angle sodium alginate-chitosan Gao et al., 2014)
Analytical centrifugation O/W emulsion stabilized by lactoferrin-pectin, alginate or E (Shimoni et al., 2013)
carrageenan
Rheology measurement O/W emulsion stabilized chitin E (Tzoumaki et al., 2011)
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174 163

Table 2
Summary of literature reports on the utilization of particles that can be considered as food stabilizers.

Materials Particles synthesis method Particle shape Particle size range Emulsion Reference(s)
(r ¼ radius, d ¼ diameter, type
l ¼ length, h ¼ height)

Fat crystals
Glycerol Spontaneous via homogenization >70
C, cooling Irregular crystal r ¼ 1 mm W/O (Ghosh et al., 2011)
monooleate at room temperature
(GMO)
Glyceryl stearyl Spontaneous quench-cooling hot O/W Elliptical d ¼ 152 nm O/W (Gupta & Rousseau, 2012)
citrate (GSC) nanoemulsions
Polysaccharides
Corn-starch Steam-jet cooking Partial spheres and d ¼ 5e10 mm O/W (Fanta, Felker, Eskins, &
fragments Baker, 1999)
Starch Acid hydrolysis of wax maize starch (Li, Sun, & Polygonal (C. Li et al., 40 nm < d < 3 mm (C. Li O/W (Li et al., 2012; Rayner et al.,
nanocrystals Yang, 2012); modification with octenyl succinic 2012); polyhedral et al., 2012); d ¼ 0.5e3 mm 2012)
anhydride (Rayner et al., 2012) (Rayner et al., 2012) (Rayner et al., 2012)
Cellulose Acid hydrolysis Rod-like l ¼ 855 nm O/W (Kalashnikova et al., 2011)
nanocrystals
(CNC)
Microcrystalline Heating the dispersion 300 nm < d < 10 mm O/W (Kargar et al., 2012)
cellulose
Nano- or microfibrillated cellulose (NFC/MFC) Homogenization of the Fibrils O/W
dispersion
(Winuprasith &
Suphantharika,
2013)
Methyl cellulose Acid hydrolysis (Capron & Cathala, 2013); pH Rod-like l ¼ 200 nm (Capron & O/W (Capron & Cathala, 2013;
(MCE) adjustment of MCE-TA dispersion (Patel et al., Cathala, 2013); (foamulsion) Patel et al., 2012)
2012) 55e110 nm (Patel et al.,
2012)
Chitin Acid hydrolysis Rod-like 240 nm  18 nm O/W (Tzoumaki et al., 2011;
Tzoumaki, Moschakis,
Scholten, & Biliaderis, 2013)
Chitosan Hydrolysis by glacial acetic acid Irregularly shaped 50 nm < d < 307.8 nm O/W (Liu et al., 2012; Wei et al.,
2012)
Proteins
b-lactoglobulin Sonication Spherical gel 80e360 nm O/W (Destribats et al., 2014)
Lactoferrin, Wet heating of dispersion Irregular 200 nm < d < 575 nm O/W (Shimoni et al., 2013)
Lactoferrin-
polysaccharide
Bovine serum Desolvation 14 nm  4 nm  14 nm O/W (HIPE) (Li, Xiao, Wang, & Ngai, 2013)
albumin (BSA)
Gelatin Two-step desolvation Sphere d ¼ 200 nm O/W (HIPE) (Tan et al., 2014)
Soy protein Wet heating of dispersion Aggregate d ¼ 100 nm O/W (Liu & Tang, 2013)
isolate (SPI)
Pea protein Dispersion of solid form Irregular 134e165 nm O/W (Liang & Tang, 2014)
Zein Antisolvent precipitation 70 nm < d < 82 nm O/W (de Folter et al., 2012)
Other
Flavonoid Dispersion of solid form Asymmetric 2r ¼ 0.1 mm O/W (Luo et al., 2011)
(tiliroside)
Wax Preparation of dispersion by hand shaking, Irregular 7 mm < d < 500 mm W/O (Binks & Rocher, 2009)
magnetic stirrer and sonication
Shellac-xanthan Dispersion of solid form O/W (Patel, Drost, Seijen-ten-
gum (concen- Hoorn, & Velikov, 2013)
trated)

6.1. Fat crystals
Emulsions stabilized by fat crystals are typically found in W/O
emulsion systems. Fat crystals provide emulsion stabilization
through network formation in the bulk phase, Pickering stabiliza-
tion and a combination of these two mechanisms (Ghosh &
Rousseau, 2011). Emulsion stabilization by the Pickering mecha-
nism is different from the network stabilization mechanism. The
concept of network stabilization involves the immobilization of
dispersed phase in the continuous crystalline matrix, whereas
Pickering stabilization deals with the adsorption of fat crystals onto
the oil-water interface.
The properties of the fat crystals (and the lipid component
forming the crystals) determine the mode of stabilization in the W/
O emulsion. In general, triglycerides are considered to provide
stabilization via crystalline networks (Hodge & Rousseau, 2005).
Other types of fat derived from saturated monoglycerides have a
more amphiphilic and surface-active character. Thus, they can
adsorb onto the interface and do not form crystalline networks but
crystalline monolayers on the interface (Lucassen-Reynders & Van
Den Tempel, 1963).
Food-grade fat crystals which can be used as Pickering stabi-
lizers are mostly derived from monoglycerides which are less hy-
drophobic than di- or triglycerides (due to higher number of fatty
acid molecules in their structures). Ghosh, Tran, and Rousseau
(2011) have used glycerol monostearate (GMS) as Pickering stabi-
lizer in a W/O emulsion with 80 wt% canola oil. The effectiveness of
stabilization was compared to network stabilized emulsions made
by incorporating fully hydrogenated canola oil (HCO) (composed
mainly of tristearin) into the oil phase together with glycerol
164 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174

monooleate (as primary emulsifier). They found that Pickering
stabilization with particles of glycerol monostearate appeared to be
a more effective mechanism than network stabilization.
The microstructure properties of fat crystals including mean
size, shape and polymorphism are crucial factors that influence the
effectiveness of Pickering stabilization, the overall rheology and
appearance of the emulsion. The presence of sub-micron fat crys-
tals influences the adsorption and surface coverage density in the
interface (Fig. 3): smaller particles tend to provide better surface
coverage than larger particles (Rousseau, 2000). The shape of the
crystals determines their effectiveness to prevent destabilization.
Needle-like crystals, for example, will lead to rapid destabilization
(Garti, Binyamin, & Aserin, 1998).
The size and shape of fat crystals can be controlled by control-
ling their polymorphic transitions. The transition of unstable a form
to a more stable b0 and/or b can lead to needle-shaped crystals that
protrude through the interface, resulting in eventual bridging
among droplets and consequent emulsion destabilization

Fig. 2. Micrographs illustrating interface stabilization of emulsion droplets by biopolymeric particles that can be considered for food applications. (a) Polarized light micrographs of
a Pickering emulsion stabilized with GMS-HCO particles, scale bar ¼ 25 mm (Ghosh et al., 2011)4; (b) Optical micrograph of a quinoa starch granule stabilized O/W emulsion, scale
bar ¼ 100 mm (Rayner et al., 2012); (c) Scanning electron micrograph of a-tocopherol coated by cornstarch particles prepared by steam-jet cooking (Fanta, Felker, Eskins, & Baker,
1999); (d) Optical micrograph of a chitosan-based liquid paraffin-in-water emulsion (Liu et al., 2012)5; (e) Scanning electron micrograph of bacterial cellulose nanocrystals at the
interface of a polymerized styrene-water emulsion droplet (Kalashnikova, Bizot, Bertoncini, Cathala, & Capron, 2013); (f) Optical micrograph of the emulsion stabilized by SPI
nanoparticle aggregates, scale bar ¼ 100 mm (Liu & Tang, 2013)6; (g) Confocal micrograph of an O/W emulsions stabilized by zein/fluorescein isothiocyanate (FITC)-labeled chitosan
particles, scale bar ¼ 25 mm (Wang et al., 2015)7; (h) Optical microscopy images of W/O emulsion stabilized by Microklear 418 (Carnauba wax) at 700C, scale bar ¼ 400 mm (Binks &
Rocher, 2009); (i) Confocal micrograph of flavonoid particles (tiriloside), stabilizing the n-tetradecane/water interface (Luo, Murray, & Yusoff, 2011).8

4
Reprinted (adapted) with permission from Ghosh, S., Tran, T., & Rousseau, D. (2011). Comparison of Pickering and network stabilization in water-in-oil emulsions.
Langmuir, 27(11), 6589e6597. http://dx.doi.org/10.1021/la200065y.
5
Reprinted (adapted) with permission from Liu, H., Wang, C., Zou, S., Wei, Z., and Tong, Z. (2012). Simple, reversible emulsion system switched by pH on the basis of
chitosan without any hydrophobic modification. Langmuir, 28, 11017e11024. http://dx.doi.org/10.1021/la3021113. Copyright (2012) American Chemical Society.
6
Reprinted (adapted) with permission from Liu, F., and Tang, C.-H. (2013). Soy protein nanoparticle aggregates as Pickering stabilizers for oil-in-water emulsions. Journal of
Agricultural and Food Chemistry, 61(37), 8888e98. http://dx.doi.org/10.1021/jf401859y. Copyright (2013) American Chemical Society.
7
Reprinted (adapted) with permission from Wang, L.-J., Hu, Y.-Q., Yin, S.-W., Yang, X.-Q., Lai, F.-R., and Wang, S.-Q. (2015). Fabrication and characterization of antioxidant
Pickering emulsions stabilized by zein/chitosan complex particles (ZCPs). Journal of Agricultural and Food Chemistry, 63(9), 2514e2524. http://dx.doi.org/10.1021/jf505227a.
Copyright (2015) American Chemical Society.
8
Reprinted (adapted) with permission from Luo, Z., Murray, B. S., and Yusoff, A. (2011). Particle-stabilizing effects of flavonoids at the oil water interface. Journal of
Agricultural and Food Chemistry, 59, 2636e2645. http://dx.doi.org/10.1021/jf1041855. Copyright (2011) American Chemical Society.
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
Fig. 3. Effect of fat crystals on droplet coverage: (A) ~1 mm crystals; (B) ~5 mm crystals;
(C) sub-micron crystals. Reproduced with permission from Elsevier (Rousseau, 2000).
(Rousseau, 2000). Furthermore, as a crystals are considered to be
slightly more hydrophilic than b and b0 (Johansson, Bergenståhl, &
Lundgren, 1995), different polymorphs might have different affinity
to the interface due to the difference in their wetting behavior.
6.2. Polysaccharides
6.2.1. Starch and modified starch particles
Starch is an abundant biopolymer commonly found in tubers
and cereals. It occurs as semi crystalline granules and it consists out
of two glucose polymers: amylose and amylopectin. Native starch
granules have potential as food-grade Pickering stabilizers due to
their morphology (size, shape) and composition. Starch granules
range in size from 0.5 to 100 mm (Jane, Leas, Zobel, & Robyt, 1994)
and vary in shape from being spherical, ellipsoidal, flat, polygonal
to rod-like with smooth or edgy surfaces. Different types of starch
contain different ratios of amylose and amylopectin.
Starch is hydrophilic and yet unmodified starch granules have
been shown to stabilize oil in water emulsion (C. Li, Li, Sun, & Yang,
2013). However, many studies use octenyl succinic anhydride (OSA)
to render the particles more hydrophobic and achieve improved
Pickering emulsion stability (Timgren et al., 2011; Yusoff & Murray,
2011). The hydrophobic octenyl group and the carboxyl or sodium
carboxylate group will increase the affinity of starches for the oil.
Rayner et al. (2012) showed that quinoa-OSA modified starch
granules with a diameter of 0.5e3 mm stabilized O/W emulsions.
The emulsions produced by high shear homogenization had droplet
sizes of 9e70 mm depending on the starch-to-oil ratio. The droplet
size decreased with an increase in the starch-to-oil ratio with a
volume of oil in the range of 5e33% oil (v/v). Although the droplets
were large and subject to creaming, their size remained unchanged
over a period of 7 days. OSA-modified starch (E1450) is approved
for food applications with a degree of modification up to 3% based
on the dry weight of starch (FDA., 1981). The hydrophobicity of
starch granules can also be improved by dry heat treatment
(Asghari, Norton, Mills, Sadd, & Spyropoulos, 2015; Timgren,
165
Rayner, Dejmek, Marku, & Sjo€o
€, 2013). The advantage of a heat
treatment over OSA modification is the unnecessity of labeling a
heat treatment with an E-number.
6.2.2. Chitin and chitosan
Chitin is a structural biopolymer found in the hard shell of
crustaceans. Natural chitin is semi-crystalline in structure, since the
polymer contains both crystalline and amorphous domains. The
amorphous domain can be cleaved by acid hydrolysis, resulting in
chitin with higher crystallinity, also known as chitin nanocrystals
(Belamie, Davidson, & Giraud-Guille, 2004). The size of chitin
nanocrystals by TEM was found to be on average 240 nm in length
and 18 nm in diameter (Tzoumaki, Moschakis, & Biliaderis, 2010).
The crystal surfaces were positively charged due to the protonation
of amino groups (Li, Revol, Naranjo, & Marchessault, 1996). The O/
W emulsions stabilized with these chitin nanocrystals were stable
during one month against coalescence (Tzoumaki et al., 2011).
Increasing the concentration of chitin nanocrystals influenced the
rheological properties and the stability of emulsions. The contri-
bution to the overall rheology of emulsions came from both the
built-up of an inter-droplet network due to the adsorbed particles
and the structuring of the continuous phase by a network of chitin
nanocrystals in the bulk phase.
Chitosan, unlike chitin, has a pH-dependent solubility in water.
At low pH, chitosan is positively charged but at higher pH, the
amino groups along the chitosan polymer become deprotonated
and the uncharged polymers associate and form particles (Liu,
Wang, Zou, Wei, & Tong, 2012). Liu et al. (2012) showed that un-
modified chitosan particles could adsorb at the oil/water interface
and stabilize O/W emulsions. In addition, Wei, Wang, Zou, Liu, and
Tong (2012) also investigated the ability of chitosan nanoparticles
to stabilize emulsions and used these Pickering emulsions for
synthesis of micron-sized poly(lactic-co-glycolic acid) (PLGA) par-
ticles. Since chitosan has pH dependent-solubility in water, the O/
W emulsions formed were reversible i.e. the lowering and
increasing of the pH resulted in de- and re-emulsification,
respectively.
6.2.3. Cellulose microparticles or nanocrystals
Cellulose consists of a linear chain of b(1 / 4) linked D-glucose
units and is an important structural component in the primary cell
wall of green plants and in biofilms produced by certain bacteria.
Cellulose is abundantly available, biodegradable and non-toxic.
Native cellulose exists as macroscopic fibers or as microfibrillated
cellulose (MFC) (Tingaut, Zimmermann, & Sebe, 2012). The amor-
phous domains can be removed by acid hydrolysis to yield micro-
crystalline cellulose (MCC). Sulfuric acid is commonly used to
remove the amorphous regions within cellulose microfibrils lead-
ing to high crystallinity. This step generally results in substantially
charged surfaces which enhances the hydrophilicity of the MCC
(Azizi Samir, Alloin, & Dufresne, 2005). If MCC is hydrolyzed for a
longer period of time, then nanocrystalline cellulose (NCC) is pro-
duced. Multiple researchers have demonstrated emulsions stabi-
lized with MFC, cellulose nanocrystals (CNCs) and nanocrystalline
cellulose (NCCs) (Kalashnikova et al., 2011; Winuprasith &
Suphantharika, 2013). Recently, Winuprasith and Suphantharika
(2013) showed that MFC originating from mangosteen rind could
stabilize O/W emulsions without any surfactant addition.
Kalashnikova et al. (2011) produced cellulose nanoparticles from a
chewy coconut-gel called nata de coco, via hydrochloric acid hy-
drolysis of bacterial cellulose. The resulting solid particles, called
bacterial CNCs, presented an elongated shape, low surface charge
density and formed a colloidal suspension in water. They stabilized
the hexadecane/water interface and promoted monodispersed O/
W droplets (±4 mm diameter) which were stable for several
166 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
months. Due to the low environmental impact of cellulose, the
emulsions stabilized with bacterial CNCs open-up opportunities for
the development of environmentally friendly new food products. In
addition, unmodified CNCs were able to adsorb at the oil-water
interface, suggesting surface active properties. These properties
have been attributed to a surface heterogeneity induced by the
crystalline organization. Unmodified CNCs have a more hydrophilic
character since they can be dispersed in water but not in organic
solvent. Thus, they may lead to ultra-stable and monodispersed
Pickering oil-in-water emulsions.
The use of CNCs for stabilization of water continuous high in-
ternal phase emulsions (HIPE) has also been reported. The crystals
had a rod-like shape with a length of 200 nm and thickness of
6e10 nm. These crystals could be used for the production of gel-
like, HIPEs in which more than 90% of the hydrophobic phase was
stabilized by less than 0.1% wt of unmodified CNCs (Capron &
Cathala, 2013).
Another approach to produce colloidal particles of cellulose-
based polymers is through non-covalent complexation with reac-
tive natural polyphenols. Colloidal complexes formed by sponta-
neous interaction of methylcellulose, MCE (a food-grade cellulose
derivative) and tannic acid showed excellent surface activity and
were further utilized for stabilization of foams, emulsions and
foamulsions (Patel, Drost, Blijdenstein, & Velikov, 2012). Interest-
ingly, high oil fraction ‘foamulsions’ stabilized by MCE/tannic acid
colloidal complexes exhibit a temperature dependent transition in
stability (Patel et al., 2012). MCE also exhibits strong interactions
with epigallocatechin gallate which is found in green tea. These
interactions can also be exploited to produce colloidal particles as
well as novel microcapsules with core shell morphology (Patel,
Nijsse, & Velikov, 2011; Patel, Seijen-ten-Hoorn et al., 2011).
6.3. Proteins
Proteins are amphiphilic biopolymers that have been exten-
sively studied as emulsion stabilizers. Many proteins are surface-
active molecules that can improve the stability and produce
desirable physicochemical properties in oil-in-water emulsions
(Norde, 2003). Proteins stabilize emulsions with a protective
membrane, creating a physical barrier between the droplets
(Walstra, 2003) and by generating repulsive interactions (e.g., steric
and electrostatic) between oil droplets (Wilde, Mackie, Husband,
Gunning, & Morris, 2004). In addition, emulsions can be stabi-
lized by the formation of protein aggregates in solution (Dickinson,
2010; Liu & Tang, 2013). This section focusses on the synthesis and
stabilization of protein-based particles from animal origin (whey
protein, bovine lactoglobulin, bovine serum albumin, a-lactal-
bumin, lactoferrin, gelatin) and plant origin (soy protein, pea pro-
tein and zein).
Micro- or nanoparticles of proteins can be produced by soni-
cation, desolvation, heating and pH adjustment, and anti-solvent
precipitation. Destribats et al. (2014) produced a microgel of
whey protein through sonication of the dispersion at pH 6.5,
resulting in microgel particles with an average hydrodynamic
diameter dh of 235 nm. These microparticles could stabilize tri-
glyceride oil-in-water emulsions over the whole range of pH and
salinity explored with exhibition of long term stability. Whey
protein aggregates have also been incorporated into ice cream
(Koxholt, McIntosh, & Eisenmann, 1999), soft cheese (Steffl, Krause,
Nussbaum, Freitsmiedl, & Kessler, 1997) or semi-hard cheese
(Schreiber, Post, & Kessler, 1998).
Bovine serum albumin, a-lactalbumin, and gelatin nanoparticles
can be formed through desolvation followed by chemical cross-
linking (Arroyo-Maya et al., 2012). Although they have already
been used as delivery device for functional compounds, only gelatin
has been reported to be capable of stabilizing emulsions (Tan, Sun,
Lin, Mu, & Ngai, 2014). Fairly monodispersed gelatin particles
(~200 nm) showed excellent Pickering stabilization in high internal
phase emulsions (HIPEs). The particles are irreversibly adsorbed at
the oil-water interface and prevent droplet coalescence. Pickering
HIPEs could be formed by a concentration as low as 0.5 wt % of
gelatin particles in the water phase at a pH far away from the iso-
electric point of the gelatin particles. The soft gelatin structure in-
sures that these biomolecules can deform and occupy large areas on
the interface, leading to the formation of viscoelastic adsorbed
layers, thus improving the emulsion stability.
Protein-based particles can, after a heat-treatment, complex
with polysaccharides via co-precipitation. Shimoni et al. (2013)
synthesized nanoparticles (NPs) by heating lactoferrin (LF) at the
pH close to the IEP of lactoferrin. Subsequently, these nanoparticles
formed complexes with alginate (Alg), and carrageenan (Car) by pH
adjustment. Emulsions stabilized by LF-Alg NPs showed poor sta-
bility. However, the use of LF-Alg NPs could also reduce the rate of
LF gastric proteolysis. The use of LF-Car NPs yielded emulsions with
the most reduced creaming (<1 mm/s), even compared to emul-
sions stabilized by unheated LF.
Soy protein aggregates also exhibit good surface active proper-
ties, suggesting that this protein is a potential candidate to be used
for Pickering stabilization. Nanoparticle aggregates of soy protein
isolate (SPI) could be formed by heat treatments at 95
C for 15 min
(Liu & Tang, 2013). Paunov et al. (2007) reported that spray-dried
soy protein particles with calcium phosphate cores (Supro 651)
could effectively be adsorbed at the oil-water interface without
distinct changes in particle morphology, which implies that they
could potentially be used as Pickering stabilizers. In addition, Rawel
and Muschiolik (1994) found that milling of soy protein resulted in
an increase in the surface hydrophobicity of protein aggregates.
Such protein particles might therefore provide additional stabili-
zation of foams (and emulsions).
Pea protein isolate (PPI) exhibits Pickering stabilization for oil-
in-water emulsions (Liang & Tang, 2014). At pH 3.0, most of the
proteins in PPI were present in the nanoparticle form, with the
hydrodynamic diameter of 134e165 nm depending on the con-
centration (0.25e3.0 g/100 mL). At a specific oil fraction of 0.2 and
at a particle concentration higher than 2 g/100 mL, no creaming
occurred even after storage of 20 days. In general, the emulsifying
properties of legume proteins are dependent on their protein
composition of vicilin/legume ratio, pH, protein concentration and
oil fraction (Liang & Tang, 2014).
Zein, a class of proline-rich proteins or prolamins, is one of the
only known hydrophobic proteins and is characterized by a limited
solubility in water but a good solubility in some organic solvents
containing water (e.g. ethanol-water mixtures) (Lawton, 2002).
Based on solubility behavior and amino acid sequences, four classes
of zein can be distinguished: a-, b-, g- and d-zein (Esen, 1986). The
low solubility of zein in both water and oil allows controlled
fabrication of colloidal particles through anti-solvent precipitation
(Patel, Bouwens, et al., 2010; Patel, Hu, Tiwari, & Velikov, 2010). de
Folter et al. (2012) further demonstrated the ability of zein particles
(prepared through anti-solvent precipitation) to stabilize oil-in-
water Pickering emulsions. The stability of these emulsions was
affected by particle concentration, pH and ionic strength. It was
shown that the zein particles preferably adsorb on the O/W inter-
face and that they have three-phase contact angles qow close to 90
.
Under low pH condition (pH < pIZein), the resulting emulsions are
not stable against coalescence, whereas at high pH (pH > pIZein), the
oil droplets are stable against coalescence. The pH shifting could
affect the ratio between the hydrophilic and hydrophobic proper-
ties of the particles, resulting in variations in their ability to
aggregate.
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
6.4. Flavonoids
Flavonoids are a class of plant secondary metabolites. They are
polyphenols with a 15-carbon skeleton. Flavonoids exist as insol-
uble particles in the aqueous phase but they tend to adsorb at the
oil-water interface (Binks, 2007). The hydrophobicity of flavonoids
varies and is commonly expressed via the log10(P) parameter,
where P is the partition coefficient between n-octanol and water.
Most flavonoids with very high or very low P values are not good
emulsifiers, although also here there are exceptions, such as
tiliroside, which is very insoluble in water but also a reasonably
good emulsifier (Luo et al., 2012).
The flavonoids tiliroside, rutin and naringin have been investi-
gated as stabilizers of Pickering oil-in-water (O/W) emulsions (Luo
et al., 2012). The mean droplet size of the tetradecane emulsions
was considerably smaller at higher pH, especially for rutin. At a
higher pH (pH ¼ 8), the solubility of flavonoids (especially for
tiliroside and rutin) in the aqueous phase was 4e6 times higher
compared to pH 2, although all absolute solubilities remained low
(<1 mM). At pH 8, a significant increase in negative values of z-
potential of the flavonoid particles resulted in an enhanced emul-
sion stabilization (Luo et al., 2012).
6.5. Wax
Waxes can be both natural, e.g. beeswax, and synthetic, e.g.
polyethylene-based. A wax may contain a wide variety of long chain
alkanes, esters, polyesters and hydroxyl esters of long chain alco-
hols and fatty acids. Waxes are water-insoluble and are very hy-
drophobic, hence their use in waterproof fabrics (Binks & Rocher,
2009). Hodge and Rousseau (2003) showed that paraffin wax
crystals could stabilize W/O emulsions through Pickering stabili-
zation. The stabilization mechanism involves adsorption of wax
particles and the formation of a particle network in the continuous
oil phase which immobilizes coarse water droplets thereby pre-
venting sedimentation.
Florabeads and floraspheres are commercial wax particles. They
both consist of saturated esters of Jojoba oil (C38eC44). These wax
particles act as effective emulsifiers of water in oil (squalane)
emulsions. The stability of an emulsion produced by wax particles
is affected by the preliminary temperature treatment of the parti-
cles. If particles without prior temperature treatment are used for
emulsification at room temperature, then a subsequent increase of
temperature to the wax melting point leads to an increase in
sedimentation and coalescence because the particles melt and
desorb from interfaces. By contrast, if the particles are melted prior
to emulsification and not after, surface-active long chain ester or
acid molecules adsorb to the interface which gives rise to emulsions
with an excellent stability to coalescence at high temperatures.
Rapid cooling of the emulsion enhances its long-term stability as
solidification of the molten wax leads to a thickening of the
continuous oil phase (Binks & Rocher, 2009). Shellac wax (or ‘lac’) is
an edible natural wax used in foods for coating and glazing appli-
cations. Shellac particles can be prepared by anti-solvent precipi-
tation by first dissolving shellac in a polar solvent (e.g. ethanol)
followed by dilution with a water-glycerol mixture under high
shear conditions (Alargova, Bhatt, Paunov, & Velev, 2004). These
shellac particles have been reported to be surface active and used
for stabilization of aqueous foams (Campbell, Holt, Stoyanov, &
Paunov, 2008). Moreover, shellac particles can also form com-
plexes with xanthan gum which are stable at acidic pH but solu-
bilize at neutral-alkaline pH. These insoluble complexes could
therefore stabilize O/W emulsions with a pH responsive character
(Patel, Heussen, Hazekamp, & Velikov, 2011). In another example,
shellac wax crystals were also shown to stabilize oil continuous
167
emulsions when used in the oil continuous phase. As confirmed
from confocal microscopy and cryo-SEM images, the accumulation
of wax particles at the watereoil interface contributed to the sta-
bilization of the emulsion in addition to bulk network formation
(Patel & Dewettinck, 2015; Patel, Schatteman, De Vos, &
Dewettinck, 2013; Patel, Schatteman, De Vos, Lesaffer, &
Dewettinck, 2013). Emulsifier-free emulsions with water content
as high as 60%wt were prepared and they were stable for over 4
months of storage (Patel, Rajarethinem, Gre˛dowska, et al., 2014).
7. Future trends: case studies of Pickering emulsions
application in food
7.1. Colloidosomes: encapsulation of active ingredients
Pickering emulsions can be used to encapsulate ingredients
such as drugs, proteins, vitamins, or even living cells (probiotics).
The presence of these active compounds is masked by using cap-
sules smaller than 25 mm which are, depending on the food matrix,
under the sensorial perception limit of the consumer. The capsule
forms a barrier to protect sensitive components from hostile
environment, for example a moisture sensitive or hydrolysable
component in an aqueous environment or oxidation sensitive
substance in an oxidative environment. Encapsulation therefore
usually results in a longer shelf-life of food products. Encapsulation
can also insure controlled-release of bioactive components, for
example of probiotics in dairy products (Leal-Calderon, Schmitt, &
Bibette, 2007).
Colloidosomes are microcapsules whose shells consist of colloid
particles which do not show internal contact. The most common
way of colloidosome preparation is the self-assembly of colloidal
particles onto the interface of emulsions after which they are
locked together with heat or polyelectrolytes to form elastic shells
around the emulsion droplet (Dinsmore, Hsu, & Nikolaides, 2002).
The permeability and rupture stress of the capsules can be
controlled through the size of the particles and through post-
fabrication steps such as sintering, filling of the interstitial holes
with smaller particles or polymers or by chemical cross-linking
(Saraf, Rathi, Kaur, & Saraf, 2011). Besides control of the perme-
ability, also control of the packing density allows a variety of release
strategies. Control of the rupture stress can determine shear-
induced breakup. In some cases, it has been demonstrated that
the vesicular structures can also be formed by fused particles and
such encapsulated structures could be used to affect the digestion
rates of lipidic components (Rayner et al., 2014).
Following oral administration, several active ingredients, such
as living bacterial cells, need protection from the acidic stomach
environment and bile acids. Microencapsulation can provide this
functionality by controlling the mass transfer across the boundary
of the formed capsules (Keen, Slater, & Routh, 2012b). Keen, Slater,
and Routh (2012a) developed colloidosomes encapsulating pro-
biotics with poly(methyl methacrylate-co-butyl acrylate) latex
particles. The method involves emulsifying an aqueous phase
containing latex particles and bacterial cells within a continuous
sunflower oil phase. This type of latex particles were found to
aggregate when ethanol was added to their suspension. The par-
ticles were able to survive passage through an acidic environment,
similar to the stomach. Unfortunately, these latex particles are not
food-grade. So far, only few consumable colloidosomes have been
described. Gu, Decker, and McClements (2007) developed colloi-
dosomes from an oil-in-water emulsion consisting of large, anionic
oil droplets with small, cationic oil droplets adsorbed to their sur-
faces. For the stabilization and formation of these colloidosomes,
however, no particles but other oil droplets were used. So, these
emulsions cannot be described as true Pickering emulsions.
168 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
Another important potential application of colloidosomes is the
encapsulation of nutraceutical compounds, which are released
under specific stimuli (pH, temperature). However, unmodified
colloidosomes are not suitable for encapsulation of low molecular
weight drugs, aromas or flavors because of the large pores between
the colloidal particles adsorbed to the interface. Methodologies like
polymerization, to absorb and cross-link the colloidal particles, or
layer-by-layer deposition, including layers of smaller particles or
polymers to reduce the permeability of the colloidosomes, and
layers of bigger particles to contribute to the mechanical stability
are suitable modifications to avoid leakage of active components
from the colloidosomes (Rossier-Miranda, Schroe €n, & Boom, 2009).
7.2. Dairy based foods and drinks
Dairy based food products are milk products that may be low or
high viscosity fluids (e.g. milk and yoghurt, respectively), struc-
tured solids (e.g. butter, cheese, etc.) or aqueous foams (e.g.
whipped cream, ice cream). These products should be stable to
phase separation during storage, handling and utilization. There-
fore, a food-grade emulsifier or stabilizer is required to maintain
their stability.
Homogenized milk is a typical dairy-based beverage with a low
viscosity. It naturally contains colloidal particles of casein adsorbed
at the surface of milk fat globules which act as surfactants. Milk
products are usually subjected to high-temperature pretreatment
such as pasteurization or retorting. The particles therefore have to
be resistant to heat since heating can cause aggregation of milk
proteins. If the particle aggregation is more extensive, it can lead to
destabilization of the emulsion (e.g. creaming or coalescence)
(Euston, Finnigan, & Hirst, 2000). Some efforts are made to increase
the heat stability of the particles, such as ultrasound pretreatment
or mixed biopolymers conjugation. Ashokkumar et al. (2009) found
that ultrasonic treatment of whey proteins significantly increases
their stability to aggregation which can provide important benefits
for their application in dairy processing. Also, particles of b-lacto-
globulin-dextran produced by Maillard reaction show an increased


heat stability at temperatures higher than 85 C at pH 5 (Jime nez-
Castan~ o, Lo
 pez-Fandin~ o, Olano, & Villamiel, 2005).
Yoghurt and cream cheese are milk fermented products, stored
and consumed in pH range 4.5e5.0. In this pH range, particle ag-
gregation and sedimentation may occur in the product
(McClements, 2014). Stabilization is introduced via particles, which
are formed through associative interaction between protein and
anionic polysaccharides (Ganzevles, Zinoviadou, van Vliet, Cohen
Stuart, & de Jongh, 2006). In addition, improving stabilization
properties of emulsions at low pH can also be achieved by protein-
pectin conjugates produced by Maillard reaction (Neirynck, Van der
Meeren, Bayarri Gorbe, Dierckx, & Dewettinck, 2004).
For structured solids such as butter, which is a W/O emulsion,
the stabilization is a result of both the fat crystals themselves as
well as of the network they form. During butter churning, the for-
mation of fat crystals at the interface and the development of the
fat crystal network play determining roles in the initial destabili-
zation of cream (an O/W emulsion). As the cream is cooled, intra-
globular fat crystals grow and puncture the interface between
two colliding globules leading to aggregation and eventually phase
inversion via partial coalescence. Darling and Birkett (1987) stated
that one of the main factors causing emulsion breakdown was
larger crystal size.
Foam-based dairy products are widely used as garnish in foods.
Therefore, they should be stable during storage and serving. The
factors influencing the stability of the foam are the ability of the
particles to attach at the airewater interface, the particleeparticle
DLVO repulsion through the aqueous phase, and the van der Waals
attraction through the aqueous and air phases (Abdel-Fattah & El-
Genk, 1998a, 1998b). In some instances, the presence of aggregated
protein particles (e.g., by whipping or heating) may improve foam
stability. Heating the milk protein b-lactoglobulin for instance,
forms insoluble aggregates which have a positive influence on foam
stability (Rullier, Novales, & Axelos, 2008).
7.3. Fat mimetic and substitute
Today, the most common way to structure liquid oil is with
crystalline triacylglycerol (TAG) hardstocks.3 However, these
hardstocks contain high amounts of saturated fatty acids (SAFA),
which are considered to be unhealthy as their consumption in-
creases the risk of cardiovascular disease (Keys & Parlin, 1966).
Therefore, there is a considerable interest to replace TAG hardstocks
with alternative oil structuring methods. A possible approach is the
use of Pickering emulsions as templates to structure low-viscosity
liquid oil into soft solids and oleogels. Gao et al. (2014) developed
a zein protein-sodium stearate-complex based O/W Pickering
emulsion as a suitable template for freeze-drying processes to
produce oil gels. Emulsions containing 10 mM sodium stearate and
0.5 wt% zein resulted in a homogeneous and translucent gel
without oil leakage, meaning that the oil content entrapped in the
matrix was more than 92 wt%. Adelmann, Binks, and Mezzenga
(2012) report on the use of silica stabilized O/W Pickering emul-
sions as a template for gels obtained by freeze-drying. A homoge-
neous, transparent gel containing 98 wt % of the oil was formed at
0.5 wt % particles.
The replacement of TAG hardstock with Pickering emulsion
templated oleogelation offers health benefits to the consumers by
reducing the dietary fat amount and controlling the fat digestibility.
However, any solid particles will need to be hidden during con-
sumption to prevent sandy/gritty sensations (Norton, Moore, &
Fryer, 2007). The minimum particle size that can be detected by
the palate is 25 mm (Engelen et al., 2005).
In addition to an alternative structuring method, the use of
particles in emulsions also has other advantages. The goal of
alternative structuring is to replace unhealthy saturated fats with
polyunsaturated lipids which are more beneficial for health.
However, polyunsaturated fatty acids (PUFA) are highly susceptible
to lipid oxidation and therefore the replacement of SAFA with PUFA
has been rather slow (Williams, 2000). Lipid oxidation has negative
effects on food qualities, such as taste, appearance and shelf-life
and also leads to the formation of off-flavors and toxicity. The
most common cause of oxidative instability in oil-in-water emul-
sions is the interaction between lipid hydroperoxides located at the
droplet surface and transition metals originating in the aqueous
phase (Mei, Decker, & McClements, 1998). This interaction leads to
the breakdown of lipid hydroperoxide into free highly reactive
radicals such as alkoxyl and peroxyl radicals (McClements &
Decker, 2000). A novel approach to reduce lipid oxidation in oil-
in-water emulsions involves the manipulation of the emulsions’
interfacial microstructure. Kargar, Spyropoulos, and Norton (2011)
investigated the oxidative stability of oil-in-water emulsions sta-
bilized by silica particles as only emulsifiers and showed that the
presence of these particles reduces lipid oxidation to a greater
extent than emulsions stabilized with surfactants alone. In further
research, Kargar et al. (2012) investigated the lipid oxidation in
emulsions stabilized with microcrystalline cellulose (MCC) and
modified starch (MS) particles which also both reduced the rate of
lipid oxidation to a much greater extent than low molecular weight
3
Hardstocks are fats (high melting triacylglycerols) that are crystalline at room
temperature.
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
emulsifiers. This effect appears to be due to the ability of particles to
physically separate the pro-oxidants in the continuous phase from
hydroperoxides located at the droplet interface.
7.4. Texture modification
The sensorial properties of water continuous emulsions are
determined by three parts of the system: (1) the fat or oil that is in
the interiors of the dispersed emulsion droplets; (2) the interfacial
material between the lipid material and the continuous phase and
(3) the external aqueous phase (Dalgleish, 2006).
The fat or oil affects texture mainly by its degree of crystallinity.
Oils which are liquid at the working temperatures, have little in-
fluence on the behavior of the emulsion unless they are incorpo-
rated at a very high volume fraction (Dalgleish, 2006). Crystalline
lipids, on the contrary, may significantly influence the texture of an
emulsion even at low volume fraction of dispersed droplets. The
best known example is the occurrence of partial coalescence in
which the fat crystals penetrate the interfacial layer between the fat
droplets. The mechanical strength of the internal fat crystal
network limits the rearrangement of the crystals thus hindering the
complete merging of the globules into the energetically preferred
spherical shape. Partial coalescence thus involves some features of
aggregation and of ‘true’ coalescence (Fredrick, Walstra, &
Dewettinck, 2010). This example clearly shows the importance of
the melting properties of the fat or oil on the functionality of an
emulsion in a food. Recently, a spread application of Pickering
stabilized oil continuous emulsions was demonstrated by Patel and
Dewettinck (2015) and Patel, Rajarethinem, Cludts, et al. (2014)
where in addition to achieving emulsifier-free stabilization, the
wax crystals also contributed to the overall consistency of the
emulsions resulting in spread-like consistency without the use of
any solid fats.
The interfacial layers of O/W Pickering emulsions consists of
particles, which have to be smaller than 25 mm to prevent detection
by the palate during oral consumption. The size of most particles
ranges between small nanometer to micrometer, so in most Pick-
ering emulsions, one should not be able to detect the individual
particles. However, the emulsified oil droplets could be bigger than
25 mm. Depending on the hardness of the interfacial layer, these oil
droplets can possibly be detected by the human palate during
consumption. An interesting application could be a sudden release
of aromas due to the collapse of the emulsion droplets during
mastication. Also in-mouth-melting or the degradation of the
interfacial layer due to temperature increase during the con-
sumption can be an interesting application of Pickering emulsions.
Finally, the aqueous phase may contain polysaccharides and can
thereby contribute to the structure of the emulsion since they can
exert a thickening or gelling effect.
7.5. Functional foods and nutraceuticals
The incorporation of lipophilic bioactive compounds such as u-3
fatty acids, conjugated linoleic acid, carotenoids, phytosterols, and
oil-soluble vitamins (A, D, E, and K) in food systems can provide
physiological benefits in combating heart diseases, weight gain,
hypertension, macular degeneration, cancer, and bone health
(McClements, Decker, & Weiss, 2007; Patel & Velikov, 2011). This
approach offers new possibilities for the development of novel
functional foods. When a functional food is intended to prevent or
treat a specific disease, it is called a nutraceutical (Kalra, 2003).
Lipophilic compounds typically have very low water solubility
and cannot simply be dispersed into an aqueous-based product.
Therefore, they must first be incorporated within an emulsion
based system. Emulsions stabilized by particles offer improved
169
physical-chemical stability related to the physiological and sensory
aspects.
The Pickering emulsion based delivery system will serve a
pharmacological purpose. Thus, the physiological impact on the
system should be assessed (Lesmes & McClements, 2009). Picker-
ing emulsions produced with Maillard-based b-lactoglobulin/
dextran conjugates showed good physicochemical stability and
control lipid digestibility (Dunlap & Co ^ te
, 2004). These results
suggest that the structure of lipid droplet coatings by the Maillard
reaction products, have an impact on the physical and chemical
stability of an emulsion. This will determine their potential
responsiveness to relevant digestive processes, e.g. emulsifier
displacement by bile and pancreatic lipase digestion of lipids
(McClements & Li, 2010). Other biopolymeric particles, such as
starch and protein derivatives, have also been investigated for their
potential application in food-grade delivery systems in terms of the
protection and controlled release of various bioactives. Hydro-
phobically modified starch can be used to increase water solubility
and to improve the in-vitro anti-carcinogenic activity of curcumin
(Lesmes & McClements, 2012). Some milk proteins have success-
fully self-assembled into nano-sized delivery vehicles loaded with
lipophilic bioactives. Examples are vitamin D and u-3 poly-
unsaturated fatty acids in casein micelles or epigallocatechingallate
(EGCG) and resveratrol in b-lactoglobulin nano-vehicles (Lesmes &
McClements, 2012).
Pickering emulsions can affect the sensory aspects of food. High
particle concentrations in the continuous phase may have a filler
effect or function as fat substitute. Skelhon et al. (2012) created a
healthier chocolate candy which was infused by fruit juice via w/o
Pickering emulsion (Fig. 4). The emulsion was stabilized with
fumed silica-chitosan particles under acidic conditions (pH
3.2e3.8). Up to 50 wt% of the fat content in chocolate was replaced
by fruit juice in the form of emulsion droplets. Fumed silica parti-
cles were also recently used to stabilize biphasic systems of oil and
water resulting in the formation of a relatively unexplored class of
soft matter systems called ‘bigels’ (Patel, Manko c, Bin Sintang,
Lesaffer, & Dewettinck, 2015). Although silica particles have been
used for oral drug delivery (Tan et al., 2010), the use of silica in food
becomes an important concern especially due to the stringent food
safety issues.
7.6. Responsive emulsions
Responsive emulsions or emulsions with on/off properties are
emulsions that can be de- and re-emulsified by application of the
appropriate triggers. The triggers or stimuli include pH, tempera-
ture (Ngai, Behrens, & Auweter, 2005), the addition of salts (Yang
et al., 2006) and magnetic fields (Brugger & Richtering, 2007).
Responsive emulsions have recently attracted a lot of interest due
to their wide application potential in both food (Liu et al., 2012) and
non-food areas (Hasan, Ghannam, & Esmail, 2010).
Fig. 4. Images of dark (left), milk (center) and white (right) chocolate emulsion for-
mulations via Pickering stabilization approach, in which 50 wt% of fat has been
replaced with cranberry juice. Images were taken after 14 days storage at 50
C.
Reproduced with permission from Royal Society of Chemistry (Skelhon et al., 2012).
170 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
Responsive emulsions can be used for delivery of bioactive
compounds, flavors or aromas at pre-defined rates or in response to
pre-determined conditions (Hughes, Marangoni, Wright, Rogers, &
Rush, 2009). For food applications, interesting triggers could be a
lowered pH (pH stomach z 1e3) or temperature (body tempera-
ture 37
C). The lowered pH in the stomach could for example
induce the release of bioactive components in the stomach.
Another way of exploiting pH triggered responsiveness is in the
formulation of actives which are required to be protected in the
acidic environment. In such cases, emulsions which limit the
release of oil soluble actives in the stomach due to flocculation but
release the actives in basic pH of the intestine due to re-
emulsification could be explored (Fig. 5).
Chitosan is a pH-responsive polymer due to the presence of
amino groups along its backbone. H. Liu et al. (2012) developed a
simple reversible Pickering emulsion with chitosan triggered by
pH. At pH > 6.0, chitosan was insoluble in water. Chitosan nano-
particles or micrometer-sized floccular precipitates were formed in
situ. These aggregates could adsorb at the interface of oil and water
to stabilize the O/W emulsions. At pH < 6.0, chitosan was soluble in
water and demulsification occurred. This pH responsive behavior
could be applied for the release of bioactive compounds in the
stomach (pH z 1e3).
Pickering emulsions stabilized with protein particles will also
destabilize at pH close to the iso-electric point of the protein due to
the aggregation of protein particles. Dispersions prepared with
whey protein microgel particles destabilize at the IEP (pH z 4.7).
The electrostatic repulsion between the particles is reduced, which
results in aggregation and the eventual sedimentation of the par-
ticles (Destribats et al., 2014). The same effect can be seen for
emulsions stabilized with zein particles. The average particle di-
ameters below pH 6 and above pH 8 are constant (~85 nm with a
polydispersity of around 15e20%), reflecting that the system is
stable and the particles within this pH range are well dispersed and
discrete. Close to the isoelectric point of zein (pH z 6.5), the
Fig. 5. Photographic and microstructure representation of responsive emulsions (stabilized by shellac-xanthan complexes) that show reversible flocculation and de-flocculation
under different pH conditions. Scale bars for confocal microscopy images (50 mm), scale bars for optical microscopy images (insets) from left to right ¼ 50, 100 and 50 mm.
Reproduced with permission from Royal Society of Chemistry (Patel, Drost, Seijen-ten-Hoorn, & Velikov, 2013).
dispersion becomes unstable. The particle diameters become
several micrometerfuls and the polydispersity increases drastically.
This apparent increase is due to aggregation of the particles (de
Folter et al., 2012). Particles obtained from protein-polysaccharide
complexes can also be used for the fabrication of pH responsive
emulsions, since the interactions between protein and poly-
saccharide are often electrostatic (Dickinson, 2008; McClements,
2006).
Emulsions stabilized with fat crystals could also be applied as
temperature responsive Pickering emulsions (Hodge & Rousseau,
2005). Fat crystals are stable during storage at ambient tempera-
tures but rapidly melt and then phase-invert at temperatures found
within the mouth (Norton, Fryer, & Moore, 2006).
Koo et al. (2006) used metal iron particles to achieve responsive
magnetic emulsions. This type of emulsions could be of interest for
iron fortification in food products, but apart from this, responsive
emulsions using magnetic fields as triggers know limited food
applications.
8. Conclusions and outlook
In the past few years, an enormous amount of research has been
conducted concerning food-grade Pickering emulsions. In Pickering
emulsions, solid particles accumulate and strongly adsorb at the
oil-water interface. As a result of this strong adsorption, which is
considered to be irreversible, Pickering emulsions exhibit
outstanding long-term coalescence stability. Therefore, there are
numerous application possibilities in the food industry, from
serving as a template for functional structures such as microcap-
sules to changing the texture of food products. For food applica-
tions, one is mostly limited to particles from a biological origin such
as fat crystals, polysaccharides, waxes, proteins and so on. The use
of these biomassebased particles conforms to the trend toward
replacing synthetic surface active agents with more biologically
and environmentally friendly alternatives. Pickering emulsions are
 I. Tavernier et al. / Trends in Food Science & Technology 50 (2016) 159e174
a valid alternative to emulsions stabilized with low molecular
weight surfactants.
However, there are some challenges that need to be addressed
to enable application of Pickering emulsions in food formulations.
The most prominent challenges such as identifying new food-grade
particles, exploratory research in stabilizing concentrated emul-
sions, investigative research on stability of Pickering emulsions in
real food systems (interactions with the food product matrix) and
understanding the de-structuring of emulsions in the gastro-
intestinal tract will need special considerations.
Acknowledgments
This literature review was made possible thanks to the BOF
(Special Research Fund) of Ghent University. The senior author
would like to acknowledge the financial support from Marie Curie
Career Integration Grant (call FP7-PEOPLE-2013-CIG, proposal no.
618157, acronym SAT-FAT-FREE) within the Seventh European
Community Framework Programme.
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