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Received: 29 September 2020 Revised: 23 March 2021 Accepted: 2 May 2021

DOI: 10.1111/1750-3841.15788

CONCISE REVIEWS & H YPOTH ESES IN FOOD SCIENCE

Oleogel-based emulsions: Concepts, structuring agents, and


applications in food

Thais J. Silva Daniel Barrera-Arellano Ana Paula B. Ribeiro

Laboratory of Oils and Fats, Department


of Food Technology, School of Food Abstract: This review discusses the application of oleogel technology in emulsi-
Engineering, University of Campinas, fied systems. In these systems of mimetic fats, water-in-oil or oil-in-water emul-
Campinas, São Paulo, Brazil
sions can be obtained, but, here, we cover emulsions with an oil continuous
Correspondence phase in detail. Depending on the percentage of water added to the oleogels, sys-
Thais J. Silva, Laboratory of Oils and Fats, tems with different textures and rheological properties can be developed. These
School of Food Engineering, Department
of Food Technology, University of Camp- properties are affected by the characteristics and concentration of the added com-
inas, Campinas, Brazil. ponents and emulsion preparation methods. In addition, some gelators exhibit
Email: thais.jordania12@gmail.com
interfacial properties, resulting in more stable emulsions than those of con-
ventional emulsions. Oleogel-based emulsion are differentiated by continuous
and dispersed phases and the structuring/emulsification components. Crucially,
these emulsions could be applied by the food industry for preparing, for example,
meat products and margarines, as well as by the cosmetics industry. We present
the different processes of emulsion elaboration, the main gelators used, the influ-
ence of the water content on the structuring of water-in-oleogel emulsions, and
the structuring mechanisms (Pickering, network, and combined Pickering and
network stabilization). Finally, we highlight the applications of these systems as
alternatives for reducing processed food lipid content and saturated fat levels.

KEYWORDS
emulsion, fatty acids, lipids, nutrition, oleogel, Pickering

1 INTRODUCTION the suitability of existing processing technologies (Chaves


et al., 2018).
The consumption of food with high trans- and saturated Thus, fat mimetics are being developed as healthier
fatty acid contents increases the risk of cardiovascular dis- alternatives to replace conventional fats. These fats can
eases (Briggs et al., 2017). The first regulatory measure to be obtained as polymers, polysaccharides, proteins, or
guarantee healthier fat-based products for consumers was lipids and all behave differently. The area of fat mimet-
the exclusion of partially hydrogenated fats. This guide- ics has recently undergone significant progress, triggered
line was initially launched by the World Health Organiza- by the need to develop replacements for trans and satu-
tion and has been deployed by regulatory bodies in various rated fats, especially because food-related regulation has
countries worldwide (Alburquerquea et al., 2017). How- become stricter. Many different food types have been stud-
ever, industrially produced foods still contain high levels ied for fat mimetic applications, such as cakes, choco-
of saturated fatty acids because these are used to replace late, cream cheese, margarine, meat products, and spreads
trans-fats because of their similar sensory impact and (Marangoni et al., 2020; Patel et al. 2020). Oleogels are

J. Food Sci. 2021;86:2785–2801. wileyonlinelibrary.com/journal/jfds © 2021 Institute of Food Technologists


R 2785
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2786 oleogel-based emulsions

examples of mimetic fats, defined as viscoelastic materials erties, potential applications, structuring agents, oxidative
comprising a nonpolar liquid phase (oil) and structuring stability, health effects, oleogelation process, and sensory
agents or gelators that immobilize the lipid phase through issues (Chaves et al., 2018, 2019; Dassanayake et al., 2011;
the formation of a three-dimensional network, resulting in Hwang, 2020; Marangoni et al., 2020; Martins et al., 2015;
systems of varying consistencies (Dassanayake et al., 2011; Mattice & Marangoni, 2019). Because of the importance of
Lupi et al., 2016; Meng et al., 2017). Chaves et al. (2018) oleogels as alternatives to trans-fats and highly saturated
describe the potential application of oleogels as fat substi- fats in foods, this review provides an overview of the use of
tute in the foods such as margarines, meat products, cakes, oleogels in W/O emulsions. The review is structured as fol-
spreads, ice cream, cookies, and cream cheese. Neverthe- lows: we give (i) an initial description of conventional crys-
less, there remain challenges in this field, mainly related to tallization and oleogelation; (ii) a description of the main
the application of these fats in water-containing systems. concepts involving oleogels and oleogel-based emulsions;
Most fat-based foods have high water contents, for exam- (iii) a description of structuring mechanisms involved in
ple, margarine and spreads, which can be formulated with obtaining oleogel-based emulsions, as well as their influ-
up to 80% water content (Patel & Dewettinck, 2016). The ence on the stability of the system; (iv) the applications of
fact that many food types have a water component high- oleogel-based emulsion in food; and (v) the main structur-
lights the importance of understanding the structuring ing agents applied in water-in-oleogel emulsions for food
agents in oleogels in low and high water-content regimes applications with a special focus on so-called “clean label”
(Munk et al., 2019). formulations. Therefore, this review considers prospects
The structuring in emulsions may involve the aqueous for using oleogel technology in W/O emulsified systems.
phase, oil phase, or interface emulsion (Mao & Miao, 2015).
However, most studies have investigated aqueous-phase
continuous emulsions, and few studies have considered 2 CONVENTIONAL
oil-phase continuous emulsions. Olegel-based emulsions CRYSTALLIZATION VERSUS
show large potential for trans-fat replacement and satu- OLEOGELATION
rated fat reduction in fat-based food products (Jimenez-
Colmenero et al., 2015; Patel, Rodriguez, et al., 2014). These 2.1 Conventional crystallization
emulsions are obtained using mechanical forces that pro-
mote the formation of small droplets, as well as the use In fats and oils, conventional crystallization involves the
of compounds that act at the interfaces, thus reducing formation of fat crystals that are characterized by partial
the interfacial tension. This homogenization force can be or total movement restriction caused by chemical or phys-
provided by high-speed blenders, colloidal mills, or high- ical bonds between the triacylglycerol molecules. Crystal
pressure homogenizers (Mao & Miao, 2015). formation involves four main steps: nucleation, growth,
Continuous phase structuring can occur through three crystallization, and polymorphism. During nucleation, the
mechanisms: stabilization with solid particles (“Pickering” molecules in the liquid state bind and begin to form sta-
crystals), the formation of a three-dimensional network ble nuclei. In the growth stage, the molecules of adjacent
that confines the water and oil molecules, or a combina- triacylglycerol molecules bind together, resulting in the
tion of Pickering particles and network formation (Ghosh growth of crystalline nuclei. Then, the crystals undergo
& Rousseau, 2011). Depending on the structuring mecha- structural changes (size, shape, and orientation). At that
nism, type, and gelator concentration, emulsions in solid moment, the fat crystals form different polymorphs, that
or semisolid states can be obtained. In particular, lipid crys- is, different arrangements of the crystal structure; for
tallization in biphasic systems prevents water droplet sed- example, α (hexagonal), β (triclinic), and β’(orthorhombic)
imentation or coalescence (McClements, 2015; Rousseau, (Chaves et al., 2019). Conventional crystallization occurs in
2000). When the emulsions form solid or semisolid struc- the majority of products containing vegetable fats in their
tures, there is a greater potential to achieve kinetic stabil- formulations, such as chocolate, ice cream, bakery prod-
ity because of the reduced particle mobility. Oil-in-water ucts, lipsticks, and margarine.
(O/W) emulsions are normally stabilized by electrostatic
and steric repulsions, whereas water-in-oil (W/O) emul-
sions are normally stabilized by steric repulsion because 2.2 Oleogelation
of the low electrical conductivity of the continuous phase
(Ushikubo & Cunha, 2014). Oleogel systems have emerged as alternatives to conven-
In the literature, it is possible to find several articles and tional fats with high levels of trans-fatty acids and sat-
book chapters that address various issues associated with urated fatty acids. In oleogel systems, lipids composed
oleogels, such as structuring mechanisms, physical prop- of unsaturated triacylglycerols, such as liquid vegetable
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oleogel-based emulsions 2787

oils or semisolids, are structured as gels (Chaves et al., and mechanical resistance of the gels (Park & Maleky,
2018; Pernetti et al., 2007). Thus, oleogels comprise a liq- 2020). Oxidative stability is a challenge due to the high con-
uid organic phase that is structured via gelling agents tent of unsaturated fatty acids that are more conducive to
that form a three-dimensional network for oil entrapment. oxidative reactions; however, there is evidence that the net-
These oleogels are thermoreversible and behave in a sim- work formed by the oleogel can protect liquid oil from oxi-
ilar way to solid fats, even when they have high unsat- dation, delaying its degradation (Silva et al., 2021; Hwang,
urated fatty acid content (Blake et al., 2014). Crucially, 2020).
the formation of an oleogel does not require chemical or The advantages of oleogels are the simplification of pre-
structural changes in the triacylglycerol molecules, thus established technological processes, zero-trans and low
maintaining the nutritional characteristics of the oil used, saturated products, low-fat products, products enriched
content of unsaturated fatty acids, and natural regiospe- with polyunsaturated fatty acids, and cost reduction
cific distribution (Pernetti et al., 2007; Sundram et al., with facilities. However, as limitations have a modifi-
2007). cation of pre-established technological processes requir-
Oleogels are usually produced by dissolving gelators ing new facilities, maintenance of sensory character-
(waxes, fatty acids, fatty alcohols, monoacylglycerols, phy- istics, effective structuring with low concentrations of
tosterols, among others), in low concentration, in veg- structuring agents, regulatory issues (use of structur-
etable oil, by heating (above the melting point), followed ing agents generally recognized as safe), thermal and
by cooling for gelation (Hwang & Winkler-Moser, 2020). mechanical resistance, oxidation, and seasonality of some
The replacement of solid fat in W/O emulsion for oleogel structuring agents (Martins et al., 2020; Park & Maleky,
is a new approach to these structuring systems (Contreras- 2020).
Ramírez et al., 2020). Oleogels may be developed from var-
ious vegetable oils, and their physical and structural char-
acteristics are directly related to the characteristics of the 3 EMULSION STRUCTURING:
lipid phase. Vegetable oil with potential for the production CONCEPTS AND MECHANISMS
of oleogels are soybean oil, high oleic sunflower oil, olive
oil, and palm oil, due to their composition, availability, and 3.1 Conventional emulsion
cost (Chaves et al., 2018). The higher the saturation level of
the oil, the smaller the quantity of gelator required for gela- By definition, an emulsion consists of a colloidal system
tion (Patel, 2015). The ideal gelators are defined as those formed of two immiscible or partially miscible liquids in
capable of structuring liquid oils at low concentrations, which one is dispersed in the other as droplets (Dickin-
that are recognized as safe, and that have thermoreversible son & Stainsby, 1982). Being thermodynamically unsta-
properties. The study of these gelator properties at different ble, conventional or nonconventional emulsions must be
concentrations and vegetable oils is crucial to enable the stabilized by agents that form a phase-separation barrier.
development of a plethora of oleogels with various tech- Depending on the dispersant phase polarity, these systems
nological application characteristics (Pehlivanoğlu et al., can be W/O (oil continuous phase) or O/W (water contin-
2016). uous phase). The emulsifiers in emulsions act by adsorb-
The structuring of oleogels has been studied for many ing at the droplet (oil or water) surface, thus reducing the
years, and it is known that their structuring is driven interfacial tension and allowing this system to be stabilized
by low-molecular-weight crystalline particles or polymer against phenomena such as flocculation, coalescence, and
self-assembly. The differences in the structuring mech- sedimentation (Bouyer et al., 2012; Rousseau & Hodge,
anisms are due to the gelator type, size, shape, and 2005).
chemical and physical properties (Dassanayake et al.,
2011). The size and shape of the crystals formed can
be controlled through refrigeration and shear, determin- 3.2 Structured emulsions
ing the mechanical properties of the network (Pernetti
et al., 2007). Usefully, oleogel structuring can occur with Structured emulsions are more sophisticated than con-
only one component or with multicomponent struc- ventional emulsions and can be either W/O or O/W, for
turing systems, acting in synergy (Patel & Dewettinck, example, gelled emulsions, multilayer emulsions, multiple
2016). emulsions, hydrogelled emulsions, Pickering emulsions,
In oleogels, the stability is associated with the ability to and oleogels (Jimenez-Colmenero et al., 2015; Mao & Miao,
bind oil, oxidative and thermal stability. The oil binding 2015; McClements, 2010). The focus of this review was on
capacity can be associated with organizing the network water-in-oleogel emulsions.
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2788 oleogel-based emulsions

weight amphiphilic structures may be able to stabilize


and structure W/O emulsions simultaneously. In this case,
the aqueous phase remains immobilized in the continu-
ous gelled oil phase (Hughes et al., 2009). Its preparation
involves the elaboration of the oleogel (more structuring
oil) and its homogenization with the aqueous phase, thus
resulting in stabilization (Patel, Cludts, Sintang, Lesaffer,
et al., 2014).
For many years, oleogels have evaluated the structuring
mechanisms, structuring agent types, structuring agent
concentration, and vegetable oil type (Park & Maleky,
2020). However, studies involving the application of
oleogels in emulsion systems have recently been devel-
oped as a more versatile and less costly alternative. César
and Campos (2020) investigated the influence of olive, sun-
F I G U R E 1 Conventional W/O emulsion, oleogels and flower, and macadamia oil on the texture profile, rheologi-
structured W/O emulsions for use as substitutes of fats in foods. The cal behavior, and sensory properties of oleogel-based emul-
black circles represent the emulsifier on the surface of the water sions for application in cosmetics. Sunflower oil was the
drop; the ‘‘traces’’ in the dispersed phase refers to their structuring one with the best texture properties and sensory analysis.
Contreras-Ramirez et al. (2020) evaluated the influence of
vegetable oil, monoacylglycerols, and polyglycerol polyri-
3.2.1 Oleogel-based emulsions cinoleate on the physical stability the oleogel-based emul-
sion and observed the formation of a structure that enabled
Hydrogelled, oleogelled, and Pickering emulsions are reduced mobility and delayed phase separation. Silva et al.
examples of structured emulsions that can have a contin- (2021) developed low- and high-lipid margarines with
uous oil phase (Figure 1) (Jimenez-Colmenero et al., 2015; oleogel-based emulsion. The margarines developed were
Mao & Miao, 2015; McClements, 2010). intended to eliminate the use of partially hydrogenated fat
Hydrogellation is controlled by embedding the emul- and saturated fats, resulting in a healthier product with
sified droplets within a continuous hydrogel matrix in ideal properties during the shelf life. This demonstrates
which two structures (emulsion and gel) co-exist (Jimenez- the effectiveness of oleogel-based emulsion systems for the
Colmenero et al., 2015). Emulsified droplets (W/O or O/W) application.
can be incorporated into a continuous hydrogel matrix,
resulting in the formation of hydrogel emulsions. Stabi-
lization and structuring are the results of the emulsifier 3.3 Structuring mechanisms
and aqueous and oily phases of W/O/W emulsions. In
these cases, the structuring of the aqueous phase is more Emulsifiers act through accumulation at the interface,
promising for promoting the production of systems with which results in a surface free energy reduction. Some
greater viscosity and stability (Dickinson, 2012 ; Jimenez- agents, such as monoacylglycerols, have favorable inter-
Colmenero et al., 2015). actions with interfaces and the oil continuous phase,
Pickering emulsions can be W/O or O/W and are stabi- thus allowing the modification of the emulsifying capac-
lized by solid particles that do not need to be amphiphilic. ity depending on the presence of another structuring
In addition, the partial wetting of the particles through the component (Ghosh & Rousseau, 2011). In addition,
water and oil phase allows strong anchoring of the particles monoacylglycerols can promote nucleation by changing
at the oil–water interface (Mao & Miao, 2015; Chevalier & the behavior of fat crystals, for example, delaying or accel-
Bollzinger, 2013). erating polymorphic transitions (Douaire et al., 2014). The
Oleogelled emulsions consist of an oleogel matrix in oleogel-based emulsions are stabilized by the presence of
an emulsified system. The continuous phase is structured amphiphilic compounds or by fat crystals that collect at
with solid fat crystals, and the aqueous phase is trapped the droplet interface (Rousseau, 2000). This stabilization
in the gelled network. The emulsions can be structured in can occur through three mechanisms (Figure 2): (i)
the aqueous phase with the aid of biopolymers or in the Pickering stabilization, (ii) network formation, and (iii)
oil phase by lipid structuring agents (Jimenez-Colmenero combined Pickering and network stabilization (Ghosh
et al., 2015; Patel & Dewettinck, 2016). Low-molecular- et al., 2011; Rousseau, 2000; Visintin et al., 2008).
17503841, 2021, 7, Downloaded from https://ift.onlinelibrary.wiley.com/doi/10.1111/1750-3841.15788 by CochraneItalia, Wiley Online Library on [28/03/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
oleogel-based emulsions 2789

effectively as Pickering stabilizers. If the particles tend to


be dispersed in both phases, there is no Pickering stabiliza-
tion. The characteristics of these particles are typically very
hydrophilic (low θ) or very hydrophobic (high θ) (Binks &
Clint, 2002; Yang et al., 2017).
Compared to conventional emulsions, Pickering emul-
sions have the advantage of being more stable because
there is a reduction in the coalescence probability. How-
ever, the stability of Pickering emulsions refers only to
coalescence, and they are not necessarily stable against
creaming or sedimentation (G. J. Lee et al., 2014; Linke &
Drusch, 2018; Yang et al., 2017). Particle wettability, con-
centration, size, packaging density, shape, aqueous phase
pH, and the presence of additives might affect the Picker-
ing emulsion stability (Linke & Drusch, 2018; Rousseau,
2000).
F I G U R E 2 Structuring mechanisms of water-in-oleogel
Linke and Drusch (2018) reviewed Pickering emulsions
emulsions. ( ): Represents the drops of water dispersed in the oil;
( ): Different fat crystals crystallized in the oil and/or
and discussed the possibilities and limitations of the par-
ticle stabilization approach in foods. For example, fat
interface or solid particles; ( )Three-dimensional network formed
by the structuring
crystals can stabilize (by adsorbing at the interface) or
destabilize (crystals in the dispersed phase can protrude
through the interface leading to droplet aggregation) an
3.3.1 Pickering stabilization emulsion depending on their preferred location (Ghosh &
Rousseau, 2011; Rousseau 2013). Foods such as whipped
In 1907, British chemist Percival Pickering discovered the cream, pasta, margarine, butter, and ice cream are stabi-
phenomenon that emulsions could be stabilized by small lized by Pickering particles, and they are also used for
particles instead of emulsifiers, and these systems are foods that require encapsulation or the sustained release of
known as “Pickering emulsions” (Pickering, 1970). From active ingredients (Ghosh & Rousseau, 2011; Mao & Miao,
this discovery, the term “Pickering system” is applied 2015).
to crystalline-particle-containing colloidal systems (Yang
et al., 2017). The dispersed particles accumulate at the
oil–water interface and form a mechanical (steric) barrier 3.3.2 Network stabilization
that protects the emulsion droplets from coalescence. The
extension of this protection depends on the packing den- During crystallization, triacylglycerols are thermodynam-
sity of the particles in the interfacial layer and the diffi- ically driven to associate, forming crystalline networks. In
culty in removing the adsorbed particles from the interface emulsions, fat nucleation and crystal growth stages occur
(Dickinson, 2012). heterogeneously (Arirna et al., 2009). In contrast, emulsion
The stabilization of Pickering emulsions can occur in stabilization by a network system is commonly observed
three ways: (i) the lipids can be crystallized at the interface in oleogels; however, this structuring/stabilization is a
encompassing the dispersed droplets; (ii) the solid particles highly complex process (Rousseau, 2000). It is character-
(nano or microspheres) can be adsorbed at the interface, ized by systems in which the crystals have no surface
creating a steric barrier between adjacent water droplets, activity (e.g., saturated triacylglycerols). Therefore, the sta-
and (iii) shear-crystallized droplet encapsulation matrices bilization of the system occurs through a physical bar-
can be formed by shearing and cooling, resulting in encap- rier because the formed crystals have little or no interfa-
sulated droplet-containing fat crystal clusters (Rousseau, cial activity. The stability is provided by the formation of
2013). a strong crystalline network via van der Waals forces in
As mentioned, Pickering emulsions can be both W/O the continuous phase, which slows the spread of droplets
and O/W, and the hydration capacity of solid particles at and, consequently, the coalescence with adjacent droplets
the interface, defined by the contact angle (θ), with the dis- (Rousseau, 2000).
persed or continuous phases determines the type of emul- Usually, highly saturated fats, such as fully hydro-
sion formation. In O/W emulsions, the contact angle is genated oils and vegetable waxes, are used for net-
less than 90◦ and in W/O emulsions it is greater than 90◦ . work stabilization. This demonstrates that these com-
When the contact angle is close to 90◦ , the particles act pounds have little or no interfacial activity but, instead,
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2790 oleogel-based emulsions

physically convert the dispersed phase into a continu- 4 OLEOGEL-BASED EMULSION


ous crystalline matrix (Johansson & Bergenståhl, 1995). APPLICATIONS
Once formed, this network keeps the droplets separated
from one another because of the presence of intersti- The properties of oleogels often change when they are
tial crystals, thus reducing flocculation and coalescence. incorporated into foods, probably due to interactions with
However, in the absence of emulsifiers, this network pre- other ingredients, such as emulsifiers, preservatives, sugar,
vents crystals from migrating to the interface, which might water, salt, and processing (Hwang & Winkler-Moser,
result in the destabilization of the system (Ghosh et al., 2020). Although the rheological and microstructural prop-
2011). erties of oleogels are quite different from those of conven-
tional fats, they yield similar and, frequently, better results
when applied in foods (Patel et al., 2020). Studies involv-
3.3.3 Combined Pickering and network ing food-grade oleogels have already proven their applica-
stabilization bility in various food types, such as sausages (Zetzl et al.,
2012), cream cheese (Bemer et al., 2016), margarine (Silva
Stabilization and structuring mechanisms, such as fat crys- et al., 2018), cookies (Mert & Demirkesen, 2016), ice cream
tallization in the continuous oil phase and the interfacial (Zulim et al., 2013), and spreads (Patel, Rajarethinem, et al.,
Pickering effect, can occur at the same time (Jimenez- 2014).
Colmenero et al., 2015; Patel, Cludts, Sintang, Lewille, Fat replacement oleogels give foods a better lipid pro-
et al., 2014). For the simultaneous observation of these two file because of the lower levels of saturated fatty acids,
mechanisms, the emulsifier must be in a solid or liquid absence of trans-fats, and higher mono- and polyunsatu-
state, thus promoting heterogeneous interfacial nucleation rated fatty acid content (Chaves et al., 2018). Oleogels can
(Ghosh et al., 2011). have different functions during application in food systems
When fat crystals are simultaneously adsorbed at the as reduction in saturated fat, reduce oil migration, replace-
interface and present in the continuous oil phase as a net- ment of oil binder, partial replacement of palm oil, con-
work of fine particles, stabilization is considered to be pro- trolled volatile release, and decreased oil absorption (Mat-
vided by a combination of Pickering and network stabiliza- tice & Marangoni, 2019).
tion. This behavior can be observed in both W/O and O/W Table 1 presents some of the recent important stud-
emulsions. Margarine and butter are examples of indus- ies of water-in-oleogel emulsions, the stages of emulsion
trial food types stabilized by a combination of Pickering preparation, the structuring agents used, and their poten-
particles and network formation. In the processing of but- tial applications. It should be noted that although oleogels
ter, fat crystal formation results in the initial destabiliza- are well accepted, more studies on the role of structuring
tion of the cream (O/W). During the cooling stage, these agents in media containing different water activities are
intraglobular fat crystals grow and puncture the fat inter- needed. In most studies, the evaluated emulsions have had
face, resulting in the aggregation of globules and phase water contents of approximately 20%, and this is accepted
inversion. In margarine (W/O), the lipid crystals are inac- as the standard system.
tive at the interface but play a direct role in the emulsion Several studies have investigated the application of
stability (Ghosh et al., 2011). oleogels in foods (Chaves et al., 2018; Mattice & Marangoni,
Carnauba wax microspheres can also stabilize emul- 2019; Martins et al., 2020). In products with high water
sions. The microspheres are located on the surface of water contents, such as margarine and meat products, a sta-
droplets and in the continuous oil phase, leading to a com- ble oleogel is essential. In margarines, the difficulty in
bination of Pickering and network stabilization (Binks & applying oleogels is achieving a product of the correct
Rocher, 2009). Pickering crystals are more effective than consistency and having an adequate distribution of water
network crystals in terms of stabilization efficiency. How- droplets in the oil phase, which is essential for spreadabil-
ever, when the emulsion is heated, the thermal stability ity (Hwang et al., 2013). In meat products such as sausages,
results from the decreased diffusion as a result of the net- the oleogel must maintain the properties provided by ani-
work crystals. Thus, the combination of Pickering and net- mal fat, that is, remain stable during cooking and con-
work stabilization can yield greater system stability. When sumption (Panagiotopoulou et al., 2016).
the crystals are present at the interface and the contin- Currently, the fat mimetics available on the market are
uous oil phase simultaneously, both Pickering and net- those of the continuous aqueous phase type. Coasun™ is
work stabilization can synergistically slow coalescence and a commercial example of a fat produced with monoacyl-
sedimentation because of the high crystal concentration glycerols (3%–5%) (Marangoni & Idziak, 2010). It consists
(Ghosh & Rousseau, 2011). of a structured O/W emulsion containing 35%–40% water;
TA B L E 1 Water-in-oleogel emulsions with potential for application in food and cosmetics industry
Potential
Continuous/dispersed phase Structuring/emulsifiers Type Preparation conditions application Reference
Soybean oil (35% and 60%)water Candelilla wax, hard fat, W/O Rotor/stator at 11,000 rpm/1–2 Margarine Silva et al. (2021)
(65% and 40%) monoglycerides min
Canola oil (∼62%–65%)water Soybean oil hard fat, PGPR, GMO, W/O 200 rpm/10 min and rotor/stator Dye release Rafanan and Rousseau (2019b)
oleogel-based emulsions

(20%) GMS at 7000 rpm/3 min


Canola oilwater (10%–50%) PGPR, Rice bran wax W/O Rotor/stator at 12,000 rpm/4–6 Rheological Wijarnprecha et al. (2019)
min properties
Mineral oilWater (20%) Paraffin wax, Sorbitan monooleate, W/O Rotor/stator at 400rpm/30 min Model system Ma et al. (2017)
Span 80
Canola oilwater (20%) GMO, GMS, Soybean oil hard fat, W/O 150 rpm/10 min and Rotor/stator Rheological Rafanan and Rousseau (2019a)
PGPR at 8000 rpm/3 min properties
high-pressure homogenizer
(500, 700, and 7000 psi) and
impeller at 260 rpm
High oleic sunflower oilwater Candelilla wax, monoglycerides, W/O Rotor/stator at 10,000 rpm/3 min – Silva et al. (2019b)
(1%–30%) crambe oil hard fat
Sunflower oilwater (20%) Phytosterols, γ-oryzanol, Tween20 – Ultrassom at 20 kHz/2 min Yogurt Moschakis et al. (2017)
Rice oilwater (20%) Crude rice bran waxBleached rice W/O Ultrassom at 16,000 rpm/15 min Margarine Pandolsook and Kupongsak
bran wax (2017)
Virgin olive oilwater (24%) Beeswax, Tween 20 or 80, xanthan W/O Rotor/stator at 40,000 rpm/5 min Margarine Öğütcü et al. (2015)
gum
Canola oilwater (40%) Shellac W/O Rotor/stator at 110,00 rpm Margarine Patel, Rajarethinem, et al. (2014)
Safflower oil high in Candelilla wax, distilled W/O Homogenization at 200 bar Physical properties Toro-Vazquez et al. (2013)
trioleinwater (20%) monoglycerides, sunflower wax
Soybean oilwater (20%) Candelilla wax, distilled W/O 3000 rpm/7 min Margarine Hwang et al. (2013)
monoglycerides, sunflower wax
Canola oilwater (20%) Shellac W/O Rotor/stator at 11,000 rpm Rheological Patel, Schatteman, De Vos,
properties Lesaffer, et al. (2013)
Castor oilwater (40%) Carnauba wax, hard paraffin, W/O 10,000 g/5 min Lipstick Le Révérend et al. (2011)
microcrystalline wax, PGPR, span
80, Tween 80
Canola oilwater (20%) GMO, GMS, canola oil hard fat, W/O Rotor/stator at 27,000 rpm/1 min Salt release Ghosh et al. (2011); Ghosh and
PGPR and high-pressure Rousseau (2012)
homogenizer (69 MPa/6
cycles)
Abbreviations: GMO, glycerol monoleate; GMS, glycerol monostearate; PGPR, polyglycerol polyricinoleate.
*Hard fat: fully hydrogenated oil.
2791

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2792 oleogel-based emulsions

it is low in saturated fatty acids, has zero trans-fats, and is stearic acid (Gaudino et al., 2019), glycerol monooleate
highly stable on heating (Batte et al., 2007a, 2007b; Blake & (Rafanan & Rousseau, 2019b), sorbitan monooleate (Ma
Marangoni, 2015; Lin & Appleby, 2012). The replacement et al., 2017), propylene glycol monostearate (Kalnin et al.,
of conventional fat by Coasun in cookies and as a fat for 2004), polyglycerol polyricinoleate (PGPR) (Rafanan &
pastry lamination results in a reduction of 20% in satu- Rousseau, 2019b; Wijarnprecha et al., 2019), fully hydro-
rated fat and 43% in trans-fat (Blake & Marangoni, 2015; genated crambe oil, fully hydrogenated soybean oil, fully
Lin & Appleby, 2012). The performance of this fat can be hydrogenated palm oil (Silva et al., 2019b), hydrogenated
improved with the addition of waxes as components of the canola stearin, hydrogenated cottonseed stearin (Hodge &
oil phase (Blake & Marangoni, 2015). Rousseau, 2005), and ethylcellulose (Bemer et al., 2016;
Another commercial fat is Cubiq Foods’ “Smart Fat,” an Davidovich-Pinhas et al., 2015). These structuring agents
O/W emulsion containing 40%–50% water that is stabilized have been applied in continuous organic phase emulsions,
with vegan ingredients and has a melting point between 60 and the most common agents are oils: canola, coconut,
and 80◦ C. Smart Fat is mainly as a substitute for animal sunflower, high-oleic sunflower, castor, high-oleic saf-
fat and coconut oil, and also reduces the number of ingre- flower, virgin olive, soybean, and palm oils (Chaves et al.,
dients required for processed products, enabling so-called 2018). In the following sections, the use of these structuring
“clean labeling” (Cubiq Foods, cubiqfoods.com). agents in water-in-oleogel emulsions and their potential as
In contrast, olegel-based emulsions have not been used alternatives in food applications will be discussed in detail.
commercially yet, but they have potential for application
in several products. For example, structured emulsions
having a continuous oily phase could be used to pre- 5.1 Ethylcellulose
pare healthier meat products (Jimenez-Colmenero et al.,
2015). Another example is emulsions made with shellac Ethylcellulose is produced through cellulose polymer
oleogels, which have potential for application in spread- esterification. Ethylcellulose can form a gel in oil when
able products such as margarine and spreads without the the solution is heated above its glass transition tempera-
need for emulsifiers. In chocolate spreads, shellac oleogels ture (approximately 140◦ C), and this results in the partial
can replace the oil binders and can be used as alterna- solubilization of the polymer in the oil phase (Marangoni
tives for cake preparation (Patel, Cludts, Sintang, Lewille, et al., 2020). During cooling, a network is formed by hydro-
et al., 2014). Despite the already extensive knowledge of gen bonding between the polymer chains (Gravelle et al.,
the oleogels and the mechanisms involved, the addition 2012; Zetzl et al., 2012).
of water could result in even more versatile systems wide Several studies conducted with oleogels have already
for applications. The use of W/O emulsions in foods such demonstrated the potential of ethylcellulose structuring
as margarine and meat products represents an expanding in oils (Bemer et al., 2016; Davidovich-Pinhas et al., 2015;
trend with great potential in food technology. These food Gravelle et al., 2012; Zetzl et al., 2012, 2014). In emul-
products face questions related to the high content of satu- sions, ethylcellulose allows oil droplets to solidify and
rated and trans-fats, and oleogel-based emulsions are an can act as an emulsifier at high concentrations (Munk
alternative, healthier lipid source with tunable viscosity et al., 2019). However, processing is essential to achieve
properties. the desired properties for ethylcellulose-containing emul-
sions. On heating, ethylcellulose is directed to the oil
droplet interface. In contrast, at low temperatures, the oil
5 STRUCTURING AGENTS droplets are structured internally by ethylcellulose, result-
ing in a film at the oil droplet interface but without a vis-
A large number of lipid components is under study as cous structure (Munk et al., 2019).
structuring and, in some cases, emulsification agents Ethylcellulose can also stabilize Pickering W/O emul-
for water-in-oleogel emulsions. These include myverol sions without the use of synthetic emulsifiers and could
(Ojeda-Serna et al., 2019), 12-hydroxystearic acid (Tamura potentially replace fats in foods (Melzer et al., 2003), such
et al., 1997), β-sitosterol, γ-oryzanol, sterols (Sawalha et al., as ice cream (Munk et al., 2019). Oleogels developed with
2012), monoacylglycerols, candelilla wax (Silva et al., ethylcellulose and behenic acid (up to 6%) have been
2019a, 2019b; Toro-Vazquez et al., 2013), carnauba wax applied in emulsions having different water contents (5%,
(Öǧütcü & Yılmaz, 2014), rice bran wax (Hwang et al., 15%, 25%, 35%, and 45%). With increase in the water con-
2013; Wijarnprecha et al., 2019), paraffin wax (Hodge & tent, the volume of separated oil decreases moderately
Rousseau, 2003), beeswax (M. C. Lee et al., 2019), sun- (Ahmadi et al., 2020). This is associated with the adsorp-
flower wax (Hwang et al., 2013), shellac (Patel, Schat- tion (Melzer et al., 2003) or precipitation of ethylcellulose
teman, De Vos, Dewettinck, et al., 2013), soy lecithin, in the interface, thus forming a layer on the water droplets,
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oleogel-based emulsions 2793

and is a result of changes in solubility (Ahmadi et al., 2020; 5.3 Shellac


Do et al., 2010).
Melzer et al. (2003) evaluated the emulsifying potential Shellac is a resin purified from the secretions of the insect
of ethylcellulose in W/O emulsions. Because ethylcellu- Laccifer lacca and is a complex mixture of polar and nonpo-
lose has interfacial activity, it can be used as a polymeric lar components consisting of polyhydroxy polycarboxylic
emulsifier, and the high stability of the resulting emulsions esters, acids, and alkanes. Shellac has a melting point of
is a result of the Pickering particles at the interface. The 80◦ C because of the presence of fatty esters and alcohols;
stability of W/O emulsions formed without emulsifiers it acts as a structuring agent through self-assembly into
is determined by the wettability of the adsorbed particles colloidal structures (Patel, Schatteman, De Vos, & Dewet-
(Binks & Lumsdon, 2000); therefore, the preparation tinck, 2013; Weinberger & Gardner, 1938).
temperature of the emulsion affects the stability. However, Shellac oleogels demonstrate thermoreversibility and
the solubility of ethylcellulose increases with increasing thixotropic behavior (Patel, Schatteman, De Vos, Lesaffer,
temperature and, consequently, the affinity of the col- et al., 2013). Shellac can structure oils at concentrations
loidal particles for oil also increases. Therefore, phase close to 2% and is a good example of a structuring agent
inversion can occur at low temperatures (Melzer et al., capable of stabilizing W/O emulsions for application in
2003). foods (pastes, cakes, and margarines) (Patel, Rajarethinem,
et al., 2014). In emulsions, shellac has the potential to pro-
mote stability in the absence of emulsifiers because of the
5.2 Proteins and polysaccharides high proportion of fatty alcohols having chain lengths of
C28 to C32, which increase the initial dispersion of water
Polysaccharides are hydrocolloids with high water reten- droplets and the interfacial and bulk crystallization of wax
tion and thickening capacity. These components display particles (Patel, Rajarethinem, et al., 2014; Patel, Schatte-
hydrophilic characteristics and have high molecular man, De Vos, Lesaffer, et al., 2013). Emulsions having 40%,
weights. Nonabsorbent polysaccharides (without inter- 50%, 60%, and 80% fat can be obtained using shellac wax
facial properties) can be used in emulsions. In these oleogel without the use of conventional emulsifiers. Usu-
cases, stabilization is achieved because of the increase in ally, the main problem in low-fat systems is that high-
viscosity and the difficulty in droplet diffusion. Polysac- performance emulsifiers are required to promote viscos-
charides widely used for application are xanthan gum, ity and stability (Patel, Rajarethinem, et al., 2014; Patel &
alginate, carrageenan, hyaluronic acid, chitosan, gum Dewettinck, 2016).
arabic, hydroxypropyl methylcellulose, galactomannans,
and pectin (Bouyer et al., 2012).
High-internal-phase emulsion oleogels have been devel- 5.4 Sterols
oped using carrageenan, locust bean gum, and xanthan
gum to gel the internal water droplet phase. These hydro- γ-Oryzanol and β-sitosterol are sterols that occur natu-
colloids must have low-temperature thermoreversible rally in many vegetable oils. Mixtures of these sterols
gelation characteristics, and the ideal choice is a combina- are known to structure edible oils and form oleogels and
tion of different hydrocolloids without surface activity to β-sitosterol, and γ-oryzanol can form crystals in oil, water,
prevent system inversion in continuous water gels (Patel, or emulsions, for example, forming tubules with the oil
Cludts, Sintang, Lewille, et al., 2014). Iqbal et al. (2019) phase inside and outside the tubules. However, an oleogel
developed W/O emulsions (40% water) with soybean oil is not formed immediately upon cooling, and mechanical
and PGPR containing high-methoxylated pectin, kappa- agitation such as shear is required to achieve an oleogel
carrageenan, and starch and assessed their rheological and (Dassanayake et al., 2011). In emulsions, these compo-
microstructural properties. nents can form structured systems (den Adel et al., 2010;
Proteins and polysaccharides are also used as thick- Bot et al., 2009). In emulsions containing β-sitosterol and
ening and gelling agents, and are ideal for low-fat γ-oryzanol, the water molecules bind to β-sitosterol, limit-
products. However, additional studies into the pro- ing self-assembly by reducing the consistency of the system
duction of W/O emulsions with polysaccharides and (Sawalha et al., 2012).
proteins are needed. This is especially true because W/O emulsions stabilized with β-sitosterol and γ-
these agents are highly influenced by the charac- oryzanol contain fibrillar crystals in the oil phase (Bot
teristics of the medium, such as pH, ionic strength, et al., 2011), and, in optical scattering experiments, their
concentration, and electrolytes, which affect emulsion W/O emulsions showed spherical water droplets with Mal-
stability. tese crosses, indicative of a radially oriented crystalline
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2794 oleogel-based emulsions

material within the dispersed aqueous phase. However, the


tubular microstructures characteristic of sterol oleogels are
not evident; instead, separate β-sitosterol and γ-oryzanol
crystals were observed (Co & Marangoni, 2012). The for-
mation of the tube structures is hampered by the binding
of β-sitosterol molecules with water, resulting in the forma-
tion of monohydrate crystals (weak gels). The promotion of
tube formation and greater firmness of the emulsion can be
achieved by the use of a lipid phase comprising less polar
oils (Sawalha et al., 2012).
Together, γ-oryzanol and phytosterols show good per-
formance for use in sausages. This kind of replacement
allows the reduction of saturated fats in meat products and
improves their lipid profile through the incorporation of
polyunsaturated fatty acids (Panagiotopoulou et al., 2016).
Crucially, emulsions based on phytosterols are rheologi-
cally dependent on the crystallization of these compounds.
The emulsification of phytosterols could be an effective
method to increase phytosterol solubility in the oil phase,
decrease crystallization, modulate the rheological proper- F I G U R E 3 Water-in-oleogel emulsions with a system of
ties, and increase the effectiveness of these bioactive com- synergism between wax and emulsifier
pounds (Moschakis et al., 2017).

tem structure and less thixotropic behavior (Wijarnprecha


5.5 Waxes et al., 2019).
In structural terms, waxes have no interfacial activ-
Waxes are defined as long-chain fatty acids that are ester- ity. However, emulsions containing amphiphilic emulsi-
ified with fatty alcohols having low polarities and high fiers can promote a synergistic effect, resulting in indi-
melting points, properties that contribute to their excellent rect wax crystal adsorption at the oil–water interface
crystallization in liquid oils. Chemically, waxes are com- (Figure 3). This adsorption mechanism occurs through
posed of wax esters, fatty acids, fatty alcohols, and linear the interaction of the hydrophilic part of the surfactant
hydrocarbons. Waxes are considered the most promising with water and that of the hydrophobic part with the wax.
structuring agents because of their high oil-binding capac- During emulsion formation, the emulsifier is incorporated
ity at low concentrations, low cost (ability to gel oils at into the newly formed crystalline network, thus chang-
weight concentrations below 0.5%), and approval for food ing the lamellar size and increasing the crystalline net-
use (Patel, 2015). The wax gelling mechanism is attributed work with wax aggregates with strong bonds in the dis-
to the distribution of n-alkanes or wax esters in small persed phase (Rousseau & Hodge, 2005). The long-chain
microcrystalline platelets, which form a complex three- esters in the interface and steric stability promote high coa-
dimensional network after aggregation that easily entraps lescence stability at high temperatures (Ma et al., 2017).
liquid oil (Blake et al., 2014; Martini et al., 2015; Patel, Therefore, the emulsifier may act by increasing the affinity
2015). between the wax crystal and the aqueous phase, changing
Understanding the use of waxes in emulsion systems the intercrystallite interactions, or by changing the crys-
could increase their use because these materials have talline structure itself (Binks & Rocher, 2009; Hodge &
proven efficient in oleogels. Some critical wax concentra- Rousseau, 2003).
tions for gel formation have been reported for canola oil In W/O emulsions, waxes can stabilize the system with-
using the following structuring agents: rice bran wax (1%), out the help of other emulsifiers. Structuring and emulsi-
sunflower wax (1%), candelilla wax (2%), and carnauba fication occur through van der Waals forces resulting in a
wax (4%) (Blake et al., 2014). The oleogels with different crystalline network that stabilizes the emulsion. Wax solid-
water contents developed with rice bran wax and PGPR in ification at the droplet interface or the migration of crystals
canola oil were assessed for their properties. System sta- to the interface promotes an increase in viscosity, which
bility was provided by the wax crystal network, which pre- reduces diffusion and increases stability (Visintin et al.,
vents coalescence and phase separation. In addition, it was 2008). Further, when crystals remain on the droplet sur-
noted that higher water contents resulted in a weaker sys- faces, they provide improved stability against coalescence
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oleogel-based emulsions 2795

by reducing collisions between droplets (Ghosh et al., 5.6 Monoacylglycerols


2015).
Rice bran wax can stabilize W/O emulsions without the Monoacylglycerols are fatty acid monoesters with glycerol
help of an emulsifying system. These emulsions have suit- and have hydrophilic and hydrophobic regions. They are
able characteristics for application in different types of considered excellent emulsifiers (Ferretti et al., 2010). In
margarine saturated fat substitutes (at 50 and 100 wt.%) addition to their emulsifying potential, these components
despite having lower hardness compared to oleogels hav- can act as structuring agents in oils, and emulsions can
ing the same composition (Pandolsook & Kupongsak, form a lyotropic crystalline phase that is assembled at the
2017). oil–water interface (da Silva et al., 2019). Monoacylglyc-
Oleogel-based emulsion with waxy crude oil and more erols have polymorphic and mesomorphic properties, so
than 30% water displays an increase in apparent viscosity, that systems structured with monoacylglycerols can occur
elasticity, and fluidity, in addition to increasing the stability in sub-α, α, β, liquid crystal lamellar and cubic phases
of the emulsion because the wax crystals cover the liquid– (Batte et al., 2007b; Wang & Marangoni, 2014). During
liquid surface (decreasing the tendency to coalesce) and the emulsification of oils by monoacylglycerols, the liquid
eliminating the free droplet movements within the emul- crystalline lamellar phase encapsulates the oil and creates
sion (Visintin et al., 2008). a material having the functionality and properties of a fat
The water content, wax content, and crystallization time (Marangoni et al., 2007).
have a direct influence on the rheological properties of The crystallization mechanism of monoacylglycerols
W/O emulsions. For example, the elasticity increases as occurs through the growth of a laminar crystal network.
the water content decreases, and the emulsion resistance During monoacylglycerol heating (above the Krafft tem-
increases with storage time because of the presence of perature) in water, the molecules are arranged in a lamel-
a dense wax crystal network and the greater number of lar phase. After homogenization, the oil phase is added
Pickering crystals. The reduction in deformation over time to the water, promoting the formation of a self-assembled
is dependent on wax crystal growth because this results system of monoacylglycerols in the crystalline phase. The
in solid bridges between existing crystals with higher structuring of oils by monoacylglycerols occurs mainly via
rigidity in the surrounding network (Haj-shafiei et al., hydrogen bonds. After cooling (below the Krafft tempera-
2013). ture), monoacylglycerols form a lamellar phase. This phase
Oleogels containing sunflower seed wax in rice bran oil is densely packed with hexagonal order in the middle of the
and interesterified fat were used to formulate W/O emul- bilayers, and the hydrocarbon chains lose their mobility,
sions with 20% water. The differences in the melting prop- beginning a transition to the α-gel phase. Below the crys-
erties and chemical composition of the wax esters and tallization point, the lamellar phases are transformed into
fat revealed a complex crystallization system (Doan et al., a sub-α crystalline phase with aliphatic chains packed in
2017), the interactions between the wax crystals resulted in an orthorhombic configuration. Monoacylglycerol crystal-
the increased stiffness of the network, and the crystalliza- lization involves the polymorphic transformation of lamel-
tion rate in the continuous phase rendered the emulsion lar monoacylglycerols (liquid-crystalline state) through
stable (Rousseau & Hodge, 2005). the α-gel to form the oleogel and β-gel laminar crystals in
Sausages developed with rice bran wax oleogel showed water (a coagel) (Bin Sintang et al., 2017; Chen & Terent-
similar characteristics to fat-containing sausages in firm- jev, 2009; Dassanayake et al., 2011; Lopez-Martínez et al.,
ness, chewiness, and springiness, without perceptible 2015; Wang et al., 2016; Wang & Marangoni, 2014). Gela-
changes in flavor and aroma (Wolfer et al., 2018). The tion occurs via the rapid crystallization in the lateral direc-
increase in the concentration of monoacylglycerols causes tion that occurs after monoacylglycerol crystal nucleus for-
a reduction in particle size because of their interfacial mation, thus forming the first space-filling network. This
activity and the lower degree of coalescence resulting from is followed by the formation of stacks of crystalline bilay-
droplet immobilization by the wax-based crystal network. ers (Bin Sintang et al., 2017; Chen & Terentjev, 2009; Das-
Although the crystallization of candelilla wax and monoa- sanayake et al., 2011; Lopez-Martínez et al., 2015; Wang
cylglycerols occurs independently (without mixed crystal et al., 2016).
formation), monoacylglycerols affect the intercrystal inter- The exploration of the properties of the long-chain sat-
actions in oleogels and emulsions (Toro-Vazquez et al., urated monoacylglycerol gel phases is essential for under-
2013). standing the structure of these compounds in edible oils
(Batte et al., 2007b; Heertje et al., 1991). During processing,
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2796 oleogel-based emulsions

some steps may lead to the formation of emulsions with ble rheological properties. Some of the ingredients used
greater stability. For example, lower cooling rates increase in emulsions with oleogels come from natural sources
the stability of the α-gel phase, providing more time to form such as proteins, sterols, monoacylglycerols, and waxes.
fully hydrated lamellar structures. Shearing, in turn, accel- An example of a structuring agent derived from renew-
erates the polymorphic transition by disturbing the forma- able resources is ethylcellulose, and studies have shown its
tion of hydrated lamella. In contrast, storage at low tem- effectiveness in oleogels. The main applications of water-
peratures slows the polymorphic transition (Wang et al., in-oleogel emulsions are in different types of margarine
2016). When small amounts of water are added to oleogels because margarines are emulsions with different water
containing monoacylglycerols, the structure and function- contents. Furthermore, the use of emulsions as vehicles for
ality of these systems change depending on the behavior of functional components, dyes, or nutraceuticals is impor-
the mesomorphic phase (Vereecken et al., 2010). tant. There are no specific process conditions for obtaining
Goldstein et al. (2012) observed that structured monoa- water-in-oleogel emulsions, but the most commonly used
cylglyceride gels have greater stability and form two poly- method is high-intensity, high-energy homogenization.
morphs: α and β. The use of shear provides greater water The limitations of these fats are the requirement to
mobility within the gels, and the polymorphic transforma- modify pre-established technological processes, need to
tion from the α-gel phase to the coagel phase in emulsions maintain the sensory characteristics typical of the prod-
with monoacylglycerols results in the destabilization of the ucts, regulatory issues, achieving thermal and mechanical
emulsion and water syneresis (Wang & Marangoni, 2015b). resistance, and resistance to oil migration, oxidation, and
The α-gel phase has superior functionality for a variety of seasonality problems associated with some structuring
applications because it has a water-rich lamellar structure agents. Currently, a significant limitation is finding
(Wang & Marangoni, 2015a). Thus, the α-gel phase is the structures that promote viscosity and stabilize emulsions,
most favorable structure for structuring water in glycerol– thus avoiding problems such as water or oil syneresis,
water monostearate systems and is capable of forming a and provide these characteristics at low concentrations.
thermally reversible and metastable sub-α-gel phase when Studies of water in oleogels are usually focused on the
cooled below 13◦ C (Wang & Marangoni, 2014). 80:20 standard system (oleogel:water), but other ranges of
Saturated monoacylglycerols can form firm gels in water contents should be studied because increasing the
water because of the formation of a network. Unsaturated water content yields new structures.
monoacylglycerols, in contrast, are mainly used in phar- Consumers and regulatory agencies are increasingly
maceutical applications. In foods such as margarine, the concerned with the healthiness of food, especially issues
ideal combination of saturated and unsaturated monoa- such as the absence of trans-fats, reduced saturation, and
cylglycerols may result in appropriate melting profiles “clean label” products. In particular, the development
(Vereecken et al., 2010). of products without artificial additives, simple process-
Lupi et al. (2011) formulated water-in-oleogel emulsions ing, and the use of ingredients of sustainable origin is a
of myverol (mono- and diacylglycerol) with olive oil (high major trend. Oleogel-based emulsions can reduce the sat-
oleic-acid-containing oil) and cocoa butter. The obtained urated fat content in water-containing foods, provide func-
emulsions were compared with commercial margarine tional ingredients, and are a technological option for food
types and found to have suitable rheological properties for adaptation to the clean label concept. This is important
application as solid fats. because the clean label market has shown high growth
driven by consumer desire for more natural products.
However, understanding the structuring mechanisms of
6 FINAL CONSIDERATIONS oleogel-based emulsions with different structuring agents
is still a challenge. The addition of water to oleogels causes
Oleogels have been widely studied; however, they are changes in rheological and stability properties that still
widely consumed in foods as emulsions. Like oleogels, need to be better understood. Synergism between struc-
emulsions have excellent technological and nutraceutical turing agents is a current trend and aims to improve the
potential, and waxes and monoacylglycerols are examples properties of emulsions without high levels of structur-
of systems that act synergistically to produce structures ing agents. Finally, a significant challenge is the evalua-
with different rheologies. The main stabilization mecha- tion of these emulsions in foods such as meat products and
nisms for structured W/O emulsions are Pickering and net- margarine.
work stabilization. Pickering stabilization prevents droplet
coalescence by steric repulsion. In contrast, network sta- AC K N OW L E D G M E N T S
bilization reduces the droplet spread in the medium. This This work was financed in part by the Coordenação de
results in a kinetically stable system with easily modula- Aperfeiçoamento de Pessoal de Nível Superior - Brasil
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oleogel-based emulsions 2797

(CAPES - Brazil) - Finance Code 001. The authors also Binks, B. P., & Clint, J. H. (2002). Solid wettability from surface energy
thank the Conselho Nacional de Desenvolvimento Cien- components: Relevance to Pickering emulsions. Langmuir, 18(4),
tífico e Tecnológico-Processo: 303429/2018-6; Chamada 1270–1273. https://doi.org/10.1021/la011420k
Binks, B. P., & Rocher, A. (2009). Effects of temperature on water-
CNPq N◦ 09/2018 Modalidade: PQ. Categoria/Nível: 2, and
in-oil emulsions stabilised solely by wax microparticles. Journal
the Conselho Nacional de Desenvolvimento Científico e
of Colloid and Interface Science, 335(1), 94–104. https://doi.org/10.
Tecnológico-Projeto Universal Processo: 423082/2018-3. 1016/j.jcis.2009.03.089
Blake, A. I., Co, E. D., & Marangoni, A. G. (2014). Structure and phys-
AU T H O R CO N T R I B U T I O N S ical properties of plant wax crystal networks and their relationship
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