Chitosan-Based Pickering Emulsions and Their Applications A Review
Chitosan-Based Pickering Emulsions and Their Applications A Review
Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol
Review
A R T I C L E I N F O A B S T R A C T
Keywords: Pickering emulsions, which are emulsions stabilized by solid particles, have gained increased research interest
Pickering emulsions owing to their eco-friendliness and high stability. Among a wide range of solid particles, chitosan particles and
Chitosan chitosan-based particles have become attractive candidates as Pickering stabilizers due to their biodegradable,
Nanoparticles
biocompatible and nontoxic properties. This review aims to provide an insight into the recent advances in the
Wettability
production and physicochemical properties of these systems. Moreover, this paper highlights the research
Food applications
Topical delivery progress in employing chitosan-based Pickering emulsions in different application areas, such as food and
Biodegradable cosmetic applications, and environmental research. Chitosan-based Pickering emulsions have opened new ave
Emulsion stability nues for the designing and production of innovative materials. The review also sheds light on the novel materials
that are synthesized from these Pickering emulsion systems. Future research directions and opportunities on
these promising Pickering systems are also addressed.
1. Introduction bind with fat, and therefore it is used to control obesity (Bakshi et al.,
2019). Additionally, chitosan, as a dietary fiber, has been reported to
Chitosan is a linear polysaccharide obtained by the deacetylation of have hypocholesterolemic activity as it is capable of reducing total
chitin, naturally occurring in the exoskeletons of crustaceans, insect cholesterol and low-density lipoprotein cholesterol (van der Gronde,
cuticles and cell walls of some fungi. Chitosan is constantly inspiring Hartog, van Hees, Pellikaan, & Pieters, 2016). Its film-forming proper
industrial and academic sectors to develop novel chitosan-based for ties and potent antimicrobial activity allowed its use in food packaging
mulations and materials (Bernkop-Schnürch & Dünnhaupt, 2012). It is a applications. Moreover, it is used in food coating and protection to
biopolymer with antibacterial, antifungal, mucoadhesive and gelling enhance the sensory properties of food (Mujtaba et al., 2019).
properties. It has been known as a promising candidate in the areas of Chitosan is of great interest for the cosmetic industry due to its anti-
tissue engineering and drug delivery due to its non-toxicity, biode oxidant and antibacterial properties (Aranaz et al., 2018). It has been
gradability, and biocompatibility. Its diverse properties and cationic reported to have superior skin hydration effects due to its high
nature make it unique in comparison with other polymers. The cationic “water-holding” capacity (Chen & Heh, 2000). Chitosan is also used as a
nature of chitosan has allowed its use in several applications, taking viscosity controlling agent in cosmetic formulations since product vis
advantage of the interaction with the negatively charged moieties in cosity can be modified by changing polymer concentration and molec
proteins, enzymes, cell membranes and various other polymers (Bern ular weight (Aranaz et al., 2018). It has also been employed to preserve
kop-Schnürch & Dünnhaupt, 2012; de Farias, Sant’Anna Cadaval Junior, the sensory properties of fragrances and prolong their release (Lopes
& de Almeida Pinto, 2019). Chitosan has been used in several materials et al., 2019).
such as aerogels, hydrogels, electrospun fibers, microcapsules and Emulsions, such as creams, gels, pastes, ointments, and lotions are
nanoparticles. widely used in cosmetic, food and pharmaceutical applications. Simple
With regard to the food industry, chitosan has been used in many conventional emulsions are colloidal dispersions that are formed of two
countries as a dietary food additive and as a food processing co-adjuvant phases, the oil phase and the aqueous phase. Emulsions are thermody
agent (Bakshi, Selvakumar, Kadirvelu, & Kumar, 2019; Costa, Gomes, & namically unstable systems as they are susceptible to phase separation,
Cunha, 2018). Chitosan has dietary health benefits owing to its ability to coalescence and Ostwald ripening (McClements & Jafari, 2018).
* Corresponding authors.
E-mail addresses: [email protected] (M.F. Barreiro), [email protected] (A.E. Rodrigues).
https://doi.org/10.1016/j.carbpol.2020.116885
Received 28 April 2020; Received in revised form 25 June 2020; Accepted 1 August 2020
Available online 11 August 2020
0144-8617/© 2020 Elsevier Ltd. All rights reserved.
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
2
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
chitosan has been reported to be 34–36.7 (Klinkesorn, 2013; Schulz, reported the utilization of chitosan nanoparticles prepared by self-
Rodríguez, Del Blanco, Pistonesi, & Agulló, 1998). This value indicates aggregation in the preparation and stabilization of Pickering emul
that chitosan has emulsifying capacity. Nevertheless, it is not as high as sions (Asfour, Elmotasem, Mostafa, & Salama, 2017; Liu, Wang, Zou,
the other conventional emulsifiers. It is postulated that the structural Wei, & Tong, 2012; Mwangi, Ho, Tey et al., 2016). The presence of
heterogeneity of chitosan is the reason for its emulsifying capacity. The amino groups within chitosan structure makes it a pH-responsive poly
D-glucosamine units which are the major component of chitosan repre mer. Chitosan nanoparticles are obtained at a pH slightly higher than
sent the hydrophilic moieties, whereas the N-acetyl groups represent the chitosan pKa (pKa ~6.5) (Ho et al., 2016). At low pH, chitosan has a
hydrophobic parts. So, it is expected that chitosan with a high degree of cationic character due to the protonation of its amino groups, which
deacetylation (i.e., with a low number of N-acetyl groups) would be results in high transmittance and a transparent solution. At pH close to
more hydrophilic. This heterogeneity allows chitosan to be adsorbed at 6.5 (near the pKa of chitosan), the amino groups of chitosan become
the oil/water interface providing mechanical and electrostatic hin deprotonated leading to the formation of interpolymer inter
drance and preventing droplets coalescence (Schulz et al., 1998). actions/associations which result in the formation of nanoparticles. The
However, the emulsifying capacity of chitosan is considered “a matter of formation of the nanoparticles turns the solution opalescent. At higher
debate” (Klinkesorn, 2013). It has been reported that chitosan has no pH (e.g., pH 9), aggregates/precipitates are formed, and hence the
surface activity at low concentrations but its emulsification capability transmittance significantly decreases. By decreasing the pH, the aggre
was enhanced at a concentration of 0.75 % (Li & Xia, 2011). It has been gates become dissolved, and the solution gets transparent again,
also reported that the emulsification properties of chitosan are influ reflecting the pH-tunable sol-gel transition character of chitosan.
enced by the DDA. Solutions of chitosan with DDA between 73 % and 95 The stability of Pickering emulsions produced by self-aggregated
% were investigated for their emulsification properties. It was found that chitosan particles depends on the initial pH of the aqueous phase. Liu
the optimal DDA values lay between 80 %–89 %, and the best ones were et al. observed that no emulsions were formed at low pH (4.1) (chitosan
namely 81 % and 88 % as they have resulted in complete emulsification solution); which indicates that “chitosan itself is not a surfactant” at this
without showing any residual oil in the preparation of o/w emulsions. It pH. This was confirmed by determining the interfacial tension of chi
was also observed that highly deacetylated chitosan has poor emulsifi tosan solution at this pH, which was found to be similar to that of water.
cation properties. However, the authors noted that the changes in the In contrast, the nanoparticles produced at a pH close to 6.5, and the
type/nature of oil can influence the obtained emulsion characteristics aggregates (precipitate) produced at pH > 9 were able to form Pickering
and may require chitosan with different DDA (Agulló, Rodríguez, emulsions. The formed Pickering emulsions stabilized by chitosan par
Ramos, & Albertengo, 2003; Del Blanco, Rodriguez, Schulz, & Agulló, ticles produced at pH > 6.5 maintained their stability for 2 months,
1999). whereas the Pickering emulsions stabilized by the particles produced at
pH < 6.5 were unstable as they rapidly demulsified after 2 days of
4. Chitosan-based particles as Pickering emulsion stabilizers preparation. The results reflected that chitosan nanoparticles produced
at pH 6–6.5 have a high hydrophilic surface due to the partial depro
Chitosan nanoparticles have long been used as effective carriers for tonation of the amino groups, making them weak emulsifiers for o/w
controlled drug delivery (Ali & Ahmed, 2018), and more recently, they Pickering emulsion stabilization. The chitosan aggregates formed at pH
have been successfully employed as Pickering stabilizers. > 9 have a relatively hydrophobic surface due to the complete depro
Chitosan-based particles used in Pickering emulsion stabilization can be tonation of the amino groups making them suitable emulsifiers for o/w
made of chitosan solely, by complexing with other polymers, or through Pickering emulsions (Liu et al., 2012).
the hydrophobic modification of its structure. The preparation methods
of chitosan-based Pickering particles can be classified into four main
4.2. Ionic gelation
methods (Fig. 2), and are discussed in the following subsections.
The production of chitosan nanoparticles by the ionic gelation
4.1. Self-aggregation method is attracting increasing attention as it is simple and economic.
This method is promoted by the ionic attraction between the positively
The most common methodology to prepare chitosan nanoparticles is charged amino groups of chitosan (at pH < pKa (6.5)) and the negatively
self-aggregation. It occurs through the deprotonation of the amino charged groups of a polyanion. In this context, the polyanion tripoly
groups at alkaline pH, which reduces the surface charge, leading to the phosphate (TPP) has been extensively used for the ionic gelation of
self-assembly of chitosan into colloidal particles. Several studies have chitosan and the production of chitosan-based particles. These particles
Fig. 2. Production methods of the chitosan-based particles used in the stabilization of Pickering emulsions.
3
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
have been used for the encapsulation of bioactive agents (Hosseini, interactions (Nan et al., 2014). Another example is the complexation
Zandi, Rezaei, & Farahmandghavi, 2013; Luo, Zhang, Cheng, & Wang, between chitosan and polystyrene (PS) particles, which has been re
2010), and recently as Pickering emulsion stabilizers (Shah, Li et al., ported to enhance the stability of Pickering emulsions in comparison
2016; Tian, Lu, Yu, Chen, & Hu, 2019). Pickering emulsions stabilized with systems produced by only PS particles or chitosan (Zhang, Zhou, &
by chitosan-based particles produced through the ionic-gelation method Yang, 2015). The emulsification mechanism of the complexes depended
have been employed to control the rate of lipid digestion, and as vehicles on the adsorption of chitosan onto the PS particles which subsequently
for the successful oral delivery of different bioactive agents (as will be induced their flocculation, enabling them to be anchored at the oil-water
discussed in Section 8.1). interface. When chitosan was added at low concentrations (0.05− 0.1 wt
%), the flocculation of the particles improved the emulsifying capacity.
4.3. Polyelectrolyte complexation However, complexes became more hydrophilic with the increase of
chitosan concentration above this range, which led to lower emulsifi
The formation of chitosan-based nanoparticles through poly cation ability (Zhang et al., 2015). In the same context,
electrolyte complexation between chitosan and an oppositely charged chitosan-modified silica nanoparticles were investigated to produce
polymer has been frequently reported for the encapsulation and delivery stable Pickering emulsions (Alison et al., 2018, 2016). The hydropho
of bioactive agents (Li, Chen et al., 2018; Mumuni, Kenechukwu, Ofo bicity of the negatively charged inorganic silica nanoparticles was
kansi, Attama, & Díaz, 2020). Complexation between chitosan and other increased by the adsorption of the positively charged chitosan through
polymers is mainly promoted by intermolecular electrostatic attraction electrostatic modification. The obtained food-grade emulsions were
between the positive charges of chitosan at acidic pH and the negatively found to be stable for more than 3 months. The microstructure of the
charged polymers at the same pH. Besides, it involves intermolecular produced emulsions was influenced by chitosan concentration. At a low
hydrogen bonding formation, Van der Waals forces and hydrophobic concentration of chitosan (1 wt %, silica-basis), a film of particles was
interactions (Wu et al., 2020). Sometimes polyelectrolyte complexation formed at the oil/water interface, while at a higher concentration (5 wt
is referred to as ionic gelation (Avadi et al., 2010); since the charged %, silica-basis) the droplets became surrounded by a percolating
polymers act as polyions. Chitosan-based complex nanoparticles have network of the particles responsible for the stabilization of the formed
opened new avenues for the development of various novel Pickering Pickering emulsions (Alison et al., 2016).
emulsion systems. Complexation of chitosan with other polymers ren Chitosan-based complex particles can be also obtained by the
ders it more surface-active (Murray, 2019), and thus facilitates the complexation of chitosan derivatives with other polymers. Glycidyl
tuning of its wettability. This subsequently leads to increasing the sta trimethylammonium chloride (GTMAC)-chitosan, which is a water-
bility of the produced Pickering emulsions. The polyelectrolyte soluble chitosan derivative, was prepared by the reaction between the
complexation method allows the formation of various chitosan-based amino groups of chitosan and the epoxy group GTMAC (a quaternary
Pickering particles through the electrostatic attraction of chitosan with ammonium compound containing a glycidyl group). The produced
negatively charged materials, such as organic and inorganic polymers, GTMAC-chitosan was complexed with phosphorylated cellulose nano
surfactants, polymeric particles and some bacteria. crystals to produce complex particles that were successfully used to
Chitosan-based complex particles can be obtained by the electro stabilize Pickering emulsions (Baek, Wahid-Pedro, Kim, Kim, & Tam,
static complexation of chitosan with either proteins or polysaccharides 2019).
as long as the two polymers become oppositely charged at the same pH In a slightly different approach, bacteria/chitosan self-assembled
range. The majority of the studies on Pickering emulsions stabilized by networks were produced by complexation between negatively charged
chitosan-based complex nanoparticles involved the complexation of bacterial cells and positively charged chitosan. The produced particles
chitosan with proteins, such as chitosan/gelatin (Wang & Heuzey, gave rise to highly stable o/w Pickering emulsions, which can be
2016b), chitosan/gliadin (Li, He et al., 2019) and zein/chitosan (Wang considered as sustainable microreactors. They depend on the bacterial
et al., 2016) complex particles. However, very few studies reported the cells and the biodegradability of chitosan and can find use in various
production of Pickering emulsions stabilized by complex nanoparticles organic synthesis assisted by microorganisms (Wongkongkatep et al.,
formed by chitosan and other polysaccharides, e.g. chitosan/gum Arabic 2012). In that study, chitosan significantly modified the wettability of
(Sharkawy, Barreiro, & Rodrigues, 2019), and chitosan/octenyl succinic the bacterial cells (E. coli) as the value of the contact angle was found to
anhydride (OSA) starch (Yan et al., 2019) complex particles. change from 15.8 ± 1.0◦ to 54.5 ± 2.0◦ . Thus, chitosan had an important
Most of the chitosan-based complex particles are used solely to sta role in the stability of the obtained Pickering emulsions.
bilize Pickering emulsions. However, in some cases, an emulsifier is also
incorporated in the system to offer a synergistic stabilization effect. For 4.4. Hydrophobic modification
example, zein/chitosan complex particles were used along with RH40 (a
non-ionic emulsifier) to enhance the stability of the developed Pickering The fourth method to obtain chitosan-based particles for Pickering
emulsions (Zhang et al., 2017). stabilization involves the hydrophobic modification of chitosan. The
Chitosan-based complex Pickering particles can be also formed by modification usually takes place through the reaction of chitosan amino
the complexation of chitosan with a surfactant. Complex particles of groups with the carboxyl groups of compounds possessing alkyl groups,
chitosan/sodium dodecyl sulfate (SDS) (an anionic surfactant) were which leads to the addition of a hydrophobic segment to chitosan, and
formed by non-covalent electrostatic attraction. The complexation of thus results in improving its emulsifying properties. In this context,
chitosan with SDS, even at trace amounts of SDS, was found to enhance Atarian and co-workers prepared chitosan/stearic acid nanogel particles
the hydrophobicity and surface activity of chitosan (Ren & Zhang, through amide bond formation between the amino groups of chitosan
2020). The produced Pickering emulsions presented switch-ability and the carboxylic groups of stearic acid. This covalent cross-linking
behavior; as they were reversibly destabilized by the introduction of reaction is mediated through EDC (1-ethyl-3-(3-dimethylaminopropyl)
hexadecyltrimethylammonium bromide (CTAB), which promotes the carbodiimide) that activates the carboxyl groups. The resulting chito
desorption of SDS from chitosan and initiates its combination with san/stearic acid nanogel particles were used to develop sunflower o/w
CTAB. Pickering emulsions (Atarian et al., 2019). The authors reported that
Chitosan-based Pickering stabilizers can be synthesized by the more stable emulsions were obtained at higher stearic acid to chitosan
coating of polymeric particles with chitosan through complexation. For ratios, and alkaline pH. Similarly, chitosan/myristic acid nanogel par
example, the coating of alginate particles with chitosan reduced the high ticles were prepared through the formation of amide bonds between
hydrophilicity of alginate giving rise to stable Pickering emulsions. chitosan and myristic acid by an EDC-mediated reaction (Hosseini,
Chitosan was adsorbed onto alginate particles by electrostatic Rajaei, Tabatabaei, Mohsenifar, & Jahanbin, 2019). The most stable
4
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
Pickering emulsions were obtained at a myristic acid to chitosan ratio of be designed and modulated to have different morphologies and sizes,
0.75:1 and pH 8. depending on their composition and preparation method.
It is noteworthy that chitosan-based Pickering particles can be
formed by the combination of the hydrophobic modification method 5. Factors influencing the formation of Pickering emulsions by
and another method. For instance, particles formed of dihydrocaffeic chitosan-based particles
acid modified chitosan and tripolyphosphate were prepared through
amidation reaction and ionic gelation (Zhang et al., 2019). The dihy 5.1. Wettability
drocaffeic acid/chitosan copolymer amidation synthesis reaction was
also mediated by EDC, followed by the formation of particles through The wettability of the particles is an important criterion to prepare
ionic gelation with sodium tripolyphosphate. These particles produced Pickering emulsions as it controls the type of the formed Pickering
Pickering emulsions that were stable over a wide pH range (2–10) emulsion, as well as its stability. The wettability of the particles is
(Zhang et al., 2019). determined by the value of the contact angle (θ) (Fig. 4). Particles with
The formation of amide bonds can also take place between chitosan contact angle (θ) of less than 90◦ are hydrophilic and tend to form o/w
derivatives and carboxylic acids through the same EDC-mediated reac emulsions, whereas particles with contact angle higher than 90◦ are
tion. An example of this reaction is the amide bond formation between hydrophobic and form w/o emulsions. The most stable Pickering
the water-soluble chitosan hydrochloride and carboxymethyl starch (Li, emulsions are formed when the contact angle is close to 90◦ (Binks,
He et al., 2019). The developed nanogel particles were employed to 2002). Consequently, developing particles of an amphiphilic nature or
produce Pickering emulsions, where they formed a densely packed layer with an appropriate wettability is one of the most important steps in
around the emulsion droplets which significantly contributed to main formulating Pickering emulsions (Yang et al., 2017). The suitable
taining emulsion stability. It is worth mentioning that in this study, and wettability enhances particles adsorption at the water/oil interface and
in contrast to the previous ones on amide linkage formation, carbox subsequently provides a steric hindrance that guards against emulsion
ymethyl starch was used to decrease the hydrophobic character of chi droplets coalescence.
tosan hydrochloride and tune the contact angle to near-neutral The amount of energy required to remove (desorb) a solid particle
wettability (as further discussed in Section 5.1). from the oil/water interface is given by Eq. (1):
Fig. 3 shows examples of chitosan-based particles that are used in the
stabilization of Pickering emulsions. It can be observed that they could ΔE = πr2 γ o/w (1 ± cosθ)2 (1)
5
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
Fig. 4. Schematic representation of the wettability of solid particles at the oil/water interface as determined by the value of the contact angle (θow) (Binks, 2002);
(left) hydrophilic particle, (right) lipophilic particle and (center) equally hydrophilic and lipophilic particle (i.e. particle with an intermediate wettability).
where r is the particle radius, γ o/w is the oil/water interfacial tension particles with pH increase. The increased lipophilicity is attributed to
(Binks, 2002; Binks & Yin, 2016). The plus sign refers to the particle the increased interaction between gliadin and chitosan by the electro
desorption into the oil phase, whereas the minus sign refers to that in static attraction and hydrogen bonding (Li, He et al., 2019). It was also
case of the water phase (Binks & Yin, 2016). The value of ΔE for observed that the wettability of octenyl succinic anhydride (OSA) starch
sub-micron particles is always greater than the thermal energy of the was enhanced by the addition of chitosan (Yan et al., 2019). The contact
particle. Therefore, when solid particles are adsorbed at the interface, angle of OSA starch was reported to be 36.83◦ indicating that it is
they can be considered as being irreversibly anchored (Binks & Yin, extremely hydrophilic and has a weak adsorption capacity at the oil/
2016; Tang, Quinlan, & Tam, 2015). water interface. In the same study, the contact angle of the chitosan
Chitosan nanoparticles used as Pickering stabilizers have been re solution was 136.50◦ . Perhaps this hydrophobicity is related to a low
ported to be hydrophilic. Asfour et al. reported that chitosan nano degree of DDA, although the DDA was not mentioned in that study. The
particles produced by self-aggregation with NaOH had a contact angle of contact angle of the hybrid particles increased by increasing the con
42.47 ± 1.19◦ (Asfour et al., 2017). To enhance the wettability of centration of chitosan, indicating the modification of the wettability of
chitosan-based nanoparticles, Pickering stabilizers formed of chitosan OSA starch by the presence of chitosan. It was also observed that the
and other polymers have been developed. Moreover, the modification of contact angle of the particles increased from 56.67◦ to 95.70◦ when the
the wettability of chitosan-based particles (hybrid particles) to obtain a pH value increased from 3 to 7 due to the stronger interaction between
near-neutral wettability has been achieved by some strategies that were OSA starch and chitosan through electrostatic interactions (Yan et al.,
reported in several studies. Fig. 5 summarizes these strategies. The first 2019). In another study, chitosan hydrochloride was reported to be
strategy involves adjusting the pH. For example, the contact angle of predominantly hydrophobic; as it showed a contact angle of 116.20◦
gliadin/chitosan complex nanoparticles was reported to increase as the (with a DDA% of 85.47 %), whereas carboxymethyl starch had a contact
pH increases. At a pH of 3, the contact angle of the particles was 37.88◦ angle of 37.45◦ , which reflects its high hydrophilicity. Chitosan hydro
which indicates their weak adsorption capacity at the oil/water inter chloride/carboxymethyl starch nanogel particles that were produced
face. The contact angle increased to 82.74◦ and 96.32◦ by increasing the through amide bond formation between the two polymers had a contact
pH to 5 and 7, respectively, suggesting enhanced lipophilicity of the angle close to 90◦ , indicating wettability tuning to a near-neutral value,
Fig. 5. Wettability tuning strategies for chitosan-based particles used as Pickering stabilizers.
6
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
which helped in acquiring stable Pickering emulsions (Li, He et al., be influenced by pH. It was observed that gliadin/chitosan nanoparticles
2019). exhibited a bigger size by increasing the pH which is attributed to the
Aside from the pH, the wettability of chitosan-based complex parti increase in the electrostatic interactions between gliadin and chitosan
cles can be also tailored through using different mass ratios of chitosan (Li, He et al., 2019. The same particles resulted in emulsions of high
to the other polymer. Sharkawy et al. developed chitosan/gum Arabic stability since the wettability was also enhanced by increasing the pH.
nanoparticles with different mass ratios (4:1, 2:1, 1:1, 1:2 and 1:4) and Similarly, the particle size of OSA starch/chitosan particles was reported
observed that the contact angle of the particles increased by increasing to increase by increasing the pH. This is also attributed to the increased
the amount of gum Arabic (Sharkawy et al., 2019). The increase in the electrostatic interactions between chitosan and OSA starch as pH in
contact angle value is attributed to the amphiphilic structural moieties creases (Yan et al., 2019).
of gum Arabic. It was concluded that nanoparticles formed using a Ultrasonication treatment affects the size and the polydispersity of
chitosan/gum Arabic mass ratio of 1:1 had a contact angle of 89.2◦ , chitosan particles used as Pickering stabilizers. The untreated particles
which was the closest to 90◦ among the tested mass ratios, suggesting have shown a unimodal size distribution and a large size (~ 1000 nm),
that they are more suitable Pickering stabilizers than the ones formed while when ultrasonic treatment was applied, smaller and bimodal size
using other chitosan/gum Arabic mass ratios. In another study, Wang distributions were obtained. The study suggested that smaller particles
et al. reported that the contact angle of zein/chitosan complex particles are more easily adsorbed producing a more homogenous layer around
could be tuned through using different mass ratios of chitosan and zein the emulsion droplet, which enhances emulsion stability (Costa et al.,
(Wang et al., 2016). It was shown that the interaction between zein 2018).
(which is highly hydrophobic) and chitosan introduces hydrophilic The value of the surface charge of chitosan-based complex particles
moieties (the amino and hydroxyl groups of chitosan) to the nano can be modulated by changing the pH and ionic strength, and by using
particles, and thus the hydrophobicity of the particles decreases to a different mass ratios of chitosan to the other complexing polymer. The
suitable value. In this study, it was found that the contact angle closest to impact of the particle charge on the emulsion stability is a matter of
90◦ was obtained at a chitosan-to-zein ratio of 1:10 and 1:20. Although debate/dispute. Theoretically, it has been suggested that highly charged
the ratios of chitosan-to-zein protein in these complex particles are low, particles cannot produce Pickering emulsions as they will experience
the role of chitosan was important in tuning the wettability of the par strong repulsion between the charges on the particle surface and similar
ticles, which is a key prerequisite in the formation of Pickering emul charges at the oil/water interface, inhibiting their adsorption (Low,
sions. This was proved by the enhanced interfacial adsorption of the Siva, Ho, Chan, & Tey, 2020; Wang, Singh, & Behrens, 2012). This was
complex particles that promoted the formation of stable emulsions. reported in several studies related to chitosan-based Pickering emul
Similarly, chitosan in gliadin/chitosan complex Pickering particles, sions. For example, in the case of gliadin/chitosan nanoparticles, it was
despite its low amount, had an important role in modulating the surface observed that the lower the particles’ surface charge, the higher the
properties of gliadin to produce complex particles with enhanced obtained interfacial absorption (Li, He et al., 2019). In the same study,
wettability (Zeng et al., 2017). zeta-potential of the particles was measured at different pH values (3, 5
The third method for tuning the wettability of chitosan-based par and 7), and it was observed that the surface charge of gliadin/chitosan
ticles involves ultrasonication pre-treatment. The ultrasonication of particles decreases as pH increases, leading to greater accumulation of
chitosan, before particle production, decreases the contact angle of the the particles at the oil/water interface due to the weakening of the
produced particles in comparison with particles formed from a chitosan electrostatic repulsion force between the particles, and also due to the
solution not subjected to ultrasonication (Ho et al., 2016). This increase improved wettability (as discussed previously in Section 5.1) (Li, He
in the hydrophilicity (reduced hydrophobicity) of chitosan nano et al., 2019). However, this is not always the case since chitosan-based
particles by ultrasonication of the initial chitosan solution can be Pickering emulsions stabilized with highly charged particles have also
attributed to the fact that ultrasonication reduces chitosan polymer been reported. Zein/chitosan micro-sized complex particles with a high
chains length, leading to the production of a higher number of shorter surface charge (+65 mV) were able to produce Pickering emulsions of
chains with a lower number of N-acetyl-D-glucosamine units. These units high stability (Wang et al., 2016).
are considered the hydrophobic moieties of chitosan, and when they
decrease in number, chitosan hydrophilicity increases. The ultra 5.3. Particle concentration
sonicated chitosan solution (i.e., the solution with a higher number of
shorter chains, but with fewer hydrophobic units) results in the pro The stability of chitosan-based Pickering emulsions improves with
duction of a higher number of particles, smaller in size, but with higher increasing the concentration of the particles, regardless of their type.
hydrophilicity levels. Therefore, ultrasonication pretreatment of chito The increase of particle concentration is linked to the increase of the
san can be considered as a solution to produce chitosan nanocomplexes available number of particles to cover a larger interfacial area and hence
with polymers of high hydrophobicity. increases emulsion stability. Furthermore, at high chitosan particle
concentration, particles were found to form networks in the continuous
5.2. Size and surface charge of particles phase which helped in reducing the droplet collisions and guarded
against eventual coalescence (Mwangi, Ho, Tey et al., 2016).
In general, for successful Pickering emulsion formation, the particles
should be smaller than the targeted emulsion droplets so that the par 6. Preparation methods of chitosan-based Pickering emulsions
ticles can be properly adsorbed on the surface of the droplets (Tavernier,
Wijaya, Van der Meeren, Dewettinck, & Patel, 2016). It should be taken Most of the chitosan-based Pickering emulsion formulations reported
into consideration while designing particles for Pickering emulsions that in the literature are prepared using rotor-stator homogenization. This is
very small sizes (<0.5 nm) result in poor emulsion stabilization. This due to the availability, simplicity and low energy requirement of the
fact can be explained in light of the previous Eq. (1) (Section 5.1). rotor-stator homogenizers (Albert et al., 2019). Recently,
Particles of very small size act similarly to surfactant molecules as they ultrasound-assisted emulsification has been applied to form different
easily become detached from the oil/water interface, and thus cannot be emulsions. However, it has been reported that chitosan can be depoly
considered as effective stabilizers, whereas larger particles require merized by ultrasonication since the high mechanical forces can break
greater desorption energy (Binks, 2002). the low energy glycosidic linkages. Moreover, it has been reported that
Chitosan-based particles that are used as Pickering stabilizers have the hydrophobicity of chitosan nanoparticles decreases when ultra
different sizes; most of them are in the nanoscale, but some are of micro- sonication pre-treatments are used prior to their utilization in Pickering
size. The size of chitosan-based complex particles has been reported to emulsions formation by rotor-stator homogenization. This
7
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
ultrasonication pretreatment of the chitosan nanoparticles eventually methods. The work studied the effect of the ultrasonication power and
resulted in Pickering emulsions with a high creaming index and low time on the stability of the formed Pickering emulsions. It was shown
stability (Ho et al., 2016). that the droplet size decreased as the ultrasonication power increased. It
The pH of the medium used during the preparation by the ultra was also observed that at high ultrasonication power, the emulsion
sonication process affects the type of the resulting chitosan-based droplets demonstrated bridging (particle sharing), which led to an in
emulsion; whether a Pickering emulsion or a conventional emulsion. crease in the viscosity and hence to the stability of the formed Pickering
High-intensity ultrasonication has a dual effect in the production of emulsions (Costa et al., 2018).
chitosan-based emulsions, including Pickering emulsions, as it aids in Table 1 shows examples of Pickering emulsions stabilized by
the homogenization and also depolymerization. The emulsions pro chitosan-based particles. The table summarizes the composition of the
duced by ultrasonication at different pH values, without the use of any particles, their size and wettability, and the composition of the dispersed
emulsifiers, were found to be stable up to 5 months. The ultrasonication phase. It can be noticed that most of the developed emulsions are of the
treatment led to the breaking and dispersing of chitosan agglomerates, o/w type. This is because most of the natural biopolymers, including
especially at pH ≥ 4.5, resulting in a decrease of its molecular weight. chitosan, are more compatible with water than with oil (Murray, 2019).
The emulsion stability and type (whether conventional or Pickering
emulsion) are controlled by the pH of the chitosan solution. It was 7. Physicochemical properties of chitosan-based Pickering
observed that by increasing the pH from 3.5 to 5.5, conventional emulsions
emulsions with stability from a few days to 2 months were formed. This
could be explained by the change of the conformation of chitosan 7.1. Morphology and interfacial structure
molecules from an extended structure to a more flexible one. At a pH of
6.5, ultrasonication causes chitosan molecules to self-assemble and form Almost all the reported chitosan-based Pickering emulsion droplets
nanoparticles leading to the formation of Pickering emulsions with up to have spherical morphology. This is a common case with other Pickering
5 months of stability. These results suggest that chitosan emulsification emulsions, as the spherical morphology results in the minimizing of the
ability is highly influenced by the pH value and ultrasonication treat surface energy (Yang et al., 2017). Confocal laser scanning microscopy
ment (Wang & Heuzey, 2016a). (CLSM) aids in the visualization of the interfacial structure of the Pick
A one-step ultrasound process has been recently used to produce ering emulsions and confirms the type of the formed emulsion. It in
Pickering emulsions stabilized with chitosan nanoparticles. The method volves the use of two different fluorescent stains to distinguish between
involved only an ultrasonication step that was not preceded by rotor- the oil phase and the adsorbed nanoparticles positioned at the oil/water
stator homogenization as in the conventional ultrasound-assisted interface. Nile Red is commonly used to stain the oil phase, while
Table 1
Examples of Pickering emulsions stabilized by chitosan-based nanoparticles available in the literature.
Composition of particles as Average size and wettability* of Oil phase Type of Emulsion droplet size Reference
Pickering stabilizers the particles emulsion
Chitosan nanoparticles obtained via 287.3 nm, 42.47◦ Rutin loaded in propylene o/w 5.8–18.7 μm (Asfour et al.,
self-aggregation glycol/oleic acid 2017)
Chitosan nanoparticles obtained via ~350 nm at pH 6.7, NA Medium-chain triglycerides o/w ~40–80 μm (Mwangi, Ho,
self-aggregation (MCT) Tey, et al., 2016)
Chitosan nanoparticles obtained via 474.6 nm, NA Roasted coffee oil o/w 8.7 μm (oil phase 50% w/ (Ribeiro et al.,
self-aggregation w of emulsion) 2019)
Zein/chitosan complex particles <1–2 μm, 80.98 (chitosan/zein
◦
n-tetradecane o/w 42.61-76.75 μm (φ= (L.-J. Wang
ratio= 1:20) 0.2–0.6) et al., 2016)
Chitosan/gum Arabic complex 108.6 nm, 89.2◦ (chitosan/gum Olive oil o/w 7–32 μm (Sharkawy et al.,
particles Arabic ratio= 1:1) 2019)
Chitosan/ lactic acid bacteria/ NA, ~90º Soybean oil o/w 0.04–0.12 mm (Rattanaburi
hydroxypropyl methylcellulose et al., 2019)
Gliadin/chitosan particles 190.3 ± 16.5 nm–588.8 ± 18.5 nm Corn oil (φ= 0.1-0.8) o/w 20–90 μm (D. B. Yuan
et al., 2017)
Gliadin/chitosan particles ~ 600 nm (pH 5), 82.74◦ (pH 5), and Corn oil loaded and unloaded o/w ~10–90 μm, ~50 μm (pH (M.-F. Li et al.,
96.32◦ (pH 7) with curcumin 5), ~90 μm (pH 7) 2019)
Gliadin/chitosan particles, and 588.8 ± 13.1 nm (pH 5), 84.0 ± 6.0◦ Corn oil o/w 93.5 ± 0.5 μm–25.5 ± 0.4 (Zeng et al.,
curcumin-loaded gliadin/chitosan μm 2017)
particles
Octenyl succinic anhydride (OSA) 912.9 nm, 88.83◦ (pH 6) DHA-rich algae oil (DHA: o/w 16.70 ± 0.24 μm (pH 6) (Yan et al.,
starch/ chitosan complex particles Docosahexaenoic acid), Oil 2019)
phase 75% w/w of emulsion
Hyaluronic acid/chitosan complex 420.9 nm at a hyaluronic acid/ White oil o/w 42.92–56.16 μm and (Zhao et al.,
colloidal particles, chitosan ratio of 2:1 (non-loaded 101.15–125.05 μm 2015)
particles)
Chitosan/ tripolyphosphate (TPP) 1.54 μm, NA Citral-loaded in medium chain o/w 14.4 μm (for fresh (Tian et al.,
particles triglycerides (MCT) emulsions) 2019)
Chitosan/ caseinophosphopeptides 20 nm at pH 5, NA Corn oil, Linseed oil (φ= 0.8) o/w 31.42–52.48 μm (Huang et al.,
nanocomplexes 2019)
Chitosan/myristic acid nanogels <200 nm, NA Flaxseed oil o/w ~10–75 μm (for fresh (E. Hosseini
emulsions at pH 8) et al., 2019)
Chitosan/ stearic acid nanogels <200 nm, NA Sunflower oil o/w Mean~10–60 μm (for fresh (Atarian et al.,
emulsions at pH 8) 2019)
Chitosan hydrochloride/ 378.2 nm, 89.30 for complex
◦
Corn oil o/w 8 μm (for oil phase ϕ= 0.5, (X.-M. Li et al.,
carboxymethyl starch (CHC-CMS) nanogels at CHC: CMS ratio of 2:1, mean size was constant for 2019)
complex nanogels and 116.20◦ for chitosan 3 months)
hydrochloride alone
*
Value of the contact angle if available.
8
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
chitosan insoluble complexes and nanoparticles have been reported to applications of the obtained Pickering emulsion (Low et al., 2020).
be stained by either fluorescein 5(6)-isothiocyanate (FITC) (Huang et al., Chitosan-based Pickering emulsions have a wide range of droplet di
2019; Nan et al., 2014; Wang et al., 2016), Acridine Orange (Dammak & ameters (as can be seen in Table 1). It has been reported that the droplet
José do Amaral Sobral, 2018) or Nile Blue (Calero, Muñoz, Cox, Heuer, size is influenced by the emulsion preparation method and used pa
& Guerrero, 2013; Sharkawy et al., 2019). Fig. 6 gives an insight into the rameters (Costa et al., 2018), namely particle concentration, oil volume
morphology and fluorescent staining of chitosan-stabilized Pickering fraction, pH, ionic strength (Mwangi, Ho, Tey et al., 2016) and oil type
emulsion droplets. The morphology and the particle adsorption of (Shah, Zhang, Li, & Li, 2016).
chitosan-based Pickering emulsions have been also investigated and Increasing the concentration of chitosan particles (Mwangi, Ho, Tey
visualized using scanning electron (SEM) microscopy (Zhang et al., et al., 2016), and chitosan-based complex particles (Sharkawy et al.,
2015) and cryo-SEM (Sharkawy et al., 2020). 2019), was found to decrease the droplet size of the formed Pickering
emulsion. This phenomenon is ascribed to the increase in the number of
the available particles as the particle concentration increases, which
7.2. Pickering emulsion droplet size
eventually leads to larger interfacial area coverage and the formation of
small droplet sizes (Mwangi, Ho, Tey et al., 2016).
The droplet size of Pickering emulsions is an important parameter to
The droplet size of chitosan-based Pickering emulsions is also
be determined since it strongly influences the properties, stability and
9
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
influenced by the pH. It has been reported that increasing the pH (in the 2019), it was observed that Pickering emulsions stabilized by gliadin/
range of 3–8) results in the reduction of the chitosan Pickering emulsion chitosan nanoparticles have shown higher values of (G′ ) and (G′′ ) as the
droplet size (obtained at low chitosan concentration 0.1 % w/v). This is pH increased from 3 to 5 and 7, which indicates that the pH value has a
attributed to the deprotonation of the amino groups with the pH in significant impact on the elasticity of the developed Pickering emul
crease, leading to a weak electrostatic repulsion between the polymer sions. To summarize, it can be concluded that the rheology of the
chains of chitosan, a higher adsorption at the interface, and eventually, chitosan-based Pickering emulsions can be readily tuned by changing
to a larger interfacial coverage (Mwangi, Ho, Tey et al., 2016). On the their composition and pH.
contrary, in another study, it has been reported that the increase in pH,
namely in the range 6.4–7, resulted in the increase of the emulsion 7.4. Emulsion stability
droplet size (Fig. 6E and F) (Wang, Wang, Rousseau, & Tang, 2020). This
finding is perhaps related to the higher chitosan concentration (1% w/v) Generally, Pickering emulsions show high stability against coales
used in the latter study, comparatively to the former one (0.1 % w/v) cence and Ostwald ripening (Chevalier & Bolzinger, 2013; Tavernier
(Mwangi, Ho, Tey et al., 2016). Higher chitosan concentration leads to et al., 2016). The stability of Pickering systems is influenced by the
the formation of a greater number of particles that saturate the interface. particle wettability, particle concentration, particle size, type and
Eventually, after the interface gets saturated with particles, and as the amount of the dispersed phase oil and environmental conditions (such as
pH increases, the unadsorbed chitosan particles from the continuous the pH and ionic strength) (Linke & Drusch, 2018; Tavernier et al.,
phase start to get deprotonated, which leads to a decrease in the 2016).
repulsion force and increase in the intra- and inter-particle interactions. Increasing the oil volume fraction, with the use of a fixed concen
This subsequently leads to their clustering and accumulation at the tration of chitosan complex particles, reduces phase separation and
oil/water interface, and thus results in an apparent increase of the enhances emulsion stability. This observation was reported when the oil
emulsion droplet size, which can be observed in the CLSM images pre fraction was increased from 0.2 to 0.7 in Pickering emulsions stabilized
sented in Fig. 6F (Wang et al., 2020). Similarly, the droplet size of by chitosan/gum Arabic particles (Sharkawy et al., 2019), and chito
Pickering emulsions stabilized by gliadin/chitosan complex particles san/zein particles (Wang et al., 2016), above which deformation of
significantly increased as the pH increased from 3 to 7 due to the emulsion droplets occurred due to the presence of an insufficient
decrease in the electrostatic repulsion between the particles, and their amount of particles to stabilize the oil/water interface.
subsequent increased adsorption and accumulation at the oil/water The influence of pH on the stability of Pickering emulsions stabilized
interface (Li, He et al., 2019). by chitosan nanoparticles was studied in the pH range of 2–8 (Mwangi,
The type and amount of oil also affect the emulsion droplet size. Ho, Tey et al., 2016). The emulsions have shown high stability against
Chitosan Pickering emulsions prepared with corn oil (it contains long- coalescence and creaming as the pH increased due to the decrease in the
chain fatty acids) had smaller emulsion droplet sizes, in comparison electrostatic repulsion which enhanced the non-adsorbed particles to
with those prepared with MCT (medium-chain triglyceride) (Shah, Li aggregate at the oil/water interface and thicken the interfacial film. The
et al., 2016). Additionally, at a fixed particle concentration, it was enhancement of emulsion stability by increasing the pH was also re
observed that the droplet size of chitosan-based emulsion increases by ported for Pickering emulsions stabilized with chitosan complex parti
increasing the oil volume fraction (Atarian et al., 2019; Sharkawy et al., cles, e.g. chitosan/gliadin complex particles (Li, He et al., 2019).
2019). This increase in the droplet size is attributed to the decrease in The coalescence and creaming stability of chitosan Pickering emul
the number of chitosan particles (relative to the oil amount) available to sions are enhanced by the addition of salts. NaCl reduces the electro
become adsorbed at the oil/water interface (Mwangi, Ho, Tey et al., static repulsion between the adsorbed and non-adsorbed particles,
2016). which allows more particles to be adsorbed at the interface. The parti
cles also tend to form a network in the continuous phase that retards the
7.3. Rheological properties movement of emulsion droplets and prevented their coalescence
(Mwangi, Ho, Tey et al., 2016). This phenomenon of stability
The rheological properties of the emulsions are important criteria to enhancement was observed at a salt concentration up to 200 mM, above
be studied as they control the stability of the emulsions (Yuan et al., which the emulsion stability was affected due to non-adsorbed particle
2017). They are also critical attributes for the successful application of precipitation.
the developed emulsions in food and cosmetics. Pickering emulsions The effect of increasing the temperature on the stability of chitosan
stabilized by chitosan nanoparticles exhibited shear-thinning behavior; Pickering emulsions was studied by Mwangi et al. Chitosan Pickering
which means that they have high viscosity at low shear rates that emulsions stabilized by self-aggregated chitosan particles were reported
decreased as the shear rate increased (Asfour et al., 2017). Besides, the to be stable with increasing temperature up to 50 ℃, above which the
viscosity of Pickering emulsions stabilized with self-aggregated chitosan mean droplet size started to significantly increase, and the emulsions
nanoparticles increases with increasing chitosan concentration. The started to become unstable. High temperature increases the Brownian
same phenomenon was observed in Pickering emulsions stabilized by motion of the particles and may result in the desorption of the particles
chitosan complex particles, such as chitosan/gum Arabic Pickering from the oil/water interface. Subsequently, the emulsion droplet’s sur
emulsions (Sharkawy et al., 2019) and zein/chitosan Pickering emul face becomes uncovered with particles and the droplets start to coalesce
sions (Wang et al., 2016). In these formulations, it was observed that the (Mwangi, Ho, Tey et al., 2016).
storage modulus (G′ ) and the loss modulus (G′′ ) increase as the con In general, chitosan-based emulsions have been reported to exhibit
centration of nanoparticles increases. It was also observed that the high storage stability while maintaining the physicochemical properties
storage modulus (G′ ) values of these formulations were higher than the of the fresh emulsions. Pickering emulsions stabilized by zein/chitosan
loss modulus (G′′ ) values (at oil volume fraction (φ) >0.5), which sug complex particles have shown remarkable stability over prolonged
gests the presence of elastic gel networks between the nanoparticles and storage. The creaming and phase separation after 9 months of storage
emulsion droplets. It is worth mentioning that the storage modulus (G′ ) decreased with the increase of the zein/chitosan particles concentration
reflects the elastic solid-like character of the material, whereas the loss and was found to be reversible with gentle shaking (Wang et al., 2016).
modulus (G′′ ) indicates the viscous behavior of the material. This in In contrast, Pickering emulsions stabilized by zein nanoparticles
dicates that the formed chitosan-based Pickering emulsions have pre (without complexation with chitosan) exhibited a significant instability
dominant elastic properties and that, rheologically, they are similar to and volume reduction after 2 weeks of preparation (De Folter, Van
gels. The values of (G′ ) and (G′′ ) were also reported to depend on the pH Ruijven, & Velikov, 2012). Moreover, Pickering emulsions stabilized by
of the produced Pickering emulsions. In a recent study (Li, He et al., zein/chitosan particles have shown high stability against any microbial
10
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
growth over 9 months without the addition of any antimicrobial addi lipid absorption. This property is attributed to the irreversible adsorp
tive. The authors attributed this microbiological stability to the presence tion of particles at the oil/water interface of the emulsion droplets,
of the chitosan at the oil/water interface, and also in the continuous which subsequently restricts the access of lipase enzymes and bile salts
phase (Wang et al., 2016). These results reflect the important role of to the dispersed phase, and hence delays its digestibility. The in vitro
chitosan (present in the produced zein/chitosan complex particles) in lipid digestion rate of Pickering emulsions stabilized by three different
enhancing the storage and microbiological stability of the developed food-grade polysaccharide particles (chitosan, cellulose crystals and
Pickering emulsions. cellulose nanofibers) was compared in a recent study (Costa et al.,
2020). It was found that Pickering emulsions stabilized with cellulose
8. Applications crystals and cellulose nanofibers were capable of inhibiting lipid
digestion due to the strong adsorption of the particles at the oil/water
8.1. Chitosan-based Pickering emulsions for food applications interface that prevented the action of lipase enzymes on the dispersed
phase. On the other hand, Pickering emulsions stabilized by chitosan
8.1.1. Encapsulation and delivery of bioactive compounds particles delayed the lipid hydrolysis because of the interactions be
The encapsulation of nutraceuticals is one of the most important tween chitosan chains at the near-neutral pH of the intestine and the
applications of chitosan-based Pickering emulsions in the food area. intestinal digestive fluids at the emulsion droplet surface (Costa et al.,
They have been reported to protect and enhance the bio-accessibility of 2020). Therefore, it could be concluded that Pickering emulsions with
the encapsulated active agents. In this context, Shah et al. have suc cellulose particles have the potential to be used as lipid digestion in
cessfully encapsulated curcumin in Pickering emulsions stabilized by hibitor systems, whereas chitosan-based Pickering emulsions can be
chitosan/tripolyphosphate nanoparticles. The developed Pickering used as oral delivery systems of nutraceuticals with delayed lipid
emulsions enhanced the stability of the encapsulated curcumin (Shah, Li hydrolysis
et al., 2016). Their findings indicate that chitosan/tripolyphosphate In another report, the digestion rate and bioaccessibility of
Pickering emulsions can be used as an effective oral delivery system for curcumin-loaded Pickering emulsions stabilized by chitosan/tripoly
highly lipophilic bioactive agents. In another study, hesperidin was phosphate particles were studied (Shah, Li et al., 2016). The emulsions
encapsulated in Pickering emulsions stabilized with chitosan and leci were prepared with either corn oil, as a long-chain triglyceride (LCT), or
thin (a food-grade emulsifier) (Dammak & José do Amaral Sobral, medium-chain triglyceride (MCT). Pickering emulsions have shown a
2018). The emulsions have shown high stability and were reported to slower rate of digestion in comparison with nanoemulsions, and subse
have the potential to be utilized for the encapsulation of other active quently, the amount of the released free fatty acids was lower from
agents. In a recent study, β-carotene was encapsulated in Pickering Pickering emulsions. Also, Pickering emulsions have shown lower bio
emulsions stabilized by chitosan hydrochloride/carboxymethyl starch accessibility values of curcumin which is dependent on the slower
nanogel particles (X.-M. Li et al., 2020). The encapsulation of β-carotene digestion rate. The slow bioaccessibility is due to the deprotonation of
in the developed Pickering emulsions protected β-carotene from pho chitosan at high pH value. At pH 7, the pancreatic lipase had little access
todegradation by UV (365 nm) and enhanced its thermal stability and to the lipids entrapped in the chitosan aggregates. These results show
bio-accessibility. that chitosan Pickering emulsions reduce lipids digestibility.
Rattanaburi et al. produced Pickering emulsions stabilized by chi In a different approach, some studies have shown that the incorpo
tosan/lactic acid bacteria/hydroxypropyl cellulose, which combines the ration of chitosan in Pickering emulsions stabilized by non-chitosan
health benefits of chitosan and the antimicrobial activity of bacteriocin particles influences their lipid digestion pattern. For example,
produced by the lactic acid bacteria. Stabilization of the emulsion was chitosan-coating of emulsions stabilized by octenyl succinic anhydride
aided by the hydroxypropyl cellulose, which was able to fill the gaps (OSA)-modified maize starch nanocrystals was found to decrease the
between chitosan/lactic acid bacteria network existing at the oil inter lipolysis of the emulsions and enhance their storage stability under
face, and thus was considered as a co-emulsifying agent. These Pickering acidic conditions (Jo, Ban, Goh, & Choi, 2019). The lipolysis rate of the
emulsions acted as producing and delivery vehicles for bacteriocin emulsions decreased with the increase of the thickness of the chitosan
(Rattanaburi, Charoenrat, Pongtharangkul, Suphantharika, & Wong layer, which suggests that the incorporated chitosan in the emulsions
kongkatep, 2019). has the potential to control lipid digestion.
Pickering high internal phase emulsions (Pickering HIPEs) stabilized
with gliadin/chitosan hybrid particles and encapsulating curcumin have 8.1.3. Retardation of lipid oxidation in food formulations
been reported to be a promising substitute for margarine to reduce the Lipid oxidation is a problematic issue for food product manufacturers
use of partially hydrogenated oils that increase the risk of cardiovascular since it negatively affects the sensorial properties of food formulations,
diseases (Zeng et al., 2017). In this study, the formed Pickering HIPEs produces harmful substances, and thus decreases the shelf-life of the
have shown viscoelastic properties contributing to the formation of stiff products.
solid-like materials (similar to margarine) owing to the percolating Atarian et al. reported that the rate of lipid oxidation was remarkably
network structure of the emulsion droplets. The encapsulation of cur reduced in sunflower oil-in-water Pickering emulsions stabilized by
cumin in the produced Pickering emulsions was found to protect it chitosan/stearic acid in comparison to sunflower oil-in-water emulsion
against the UV-induced degradation compared to the curcumin present stabilized with Tween 80. The enhanced lipid oxidative stability is
in bulk oil. attributed to the positively charged surface of the emulsion droplets
owing to the presence of free amino groups of chitosan in the chitosan/
8.1.2. Controlling lipid digestibility stearic acid nanogels. Subsequently, the positively charged transition
Controlling lipid digestibility is considered a unique feature for some metals (pro-oxidants present in the aqueous phase) were repelled away
colloidal food systems/products; as it renders them suitable for reducing from the surface of the oil droplets in the emulsion, retarding the lipid
obesity, boosting satiety and reducing caloric intake (Costa et al., 2020; oxidation (Atarian et al., 2019).
Yao et al., 2013). Furthermore, it assists in improving the bioavailability Food-grade Pickering emulsions stabilized by chitosan grafted with
of the lipophilic bioactive agents and their delivery (Tzoumaki, caffeic acid have been reported to have enhanced free radical scav
Moschakis, Scholten, & Biliaderis, 2013). Chitosan conventional emul enging properties (İlyasoğlu, Nadzieja, & Guo, 2019). The synthesis of
sions, when administered orally, have been reported to help in reducing caffeic acid grafted chitosan was promoted by ascorbic acid. The pro
body weight in rats, and thus, could be used as a low-calorie functional duced particulate emulsifier based on chitosan modification has
food to enhance satiety (Wani et al., 2016). improved the solubility of chitosan and was also reported to retard lipid
Some Pickering emulsions have been reported to be able to delay oxidation as it provided excellent antioxidant properties.
11
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
8.1.4. Enhancing the properties of edible films Pickering emulsions stabilized with chitosan/stearic acid nanogels
Biopolymeric films have recently attracted increasing attention containing clove essential oil in mayonnaise (Hosseini & Rajaei, 2020).
owing to their biodegradable, biocompatible and non-toxic properties, It was observed that the introduction of fish oil in an emulsified form
which make them an environmentally friendly alternative for plastic resulted in enhancing the oxidative stability and the rheological prop
films/packaging. The edible films and coatings have been used to extend erties of mayonnaise in comparison to non-emulsified (free) fish oil. The
the shelf life of food products and improve their quality (Agulló et al., study also showed that the presence of clove essential oil in the nanogels
2003). Interestingly, Pickering emulsions have been used in the forma significantly improved the elasticity and, subsequently, the textural
tion of edible films that have excellent oxygen barrier properties. Shi properties of mayonnaise. This study presents a new fortification strat
et al. produced Pickering emulsions stabilized by zein/chitosan colloidal egy of food systems with bioactive compounds based on the incorpo
particles and subsequently incorporated the produced Pickering emul ration of Pickering emulsions.
sions into a chitosan-based matrix under ultrasonication to form
self-supported emulsion films as shown in Fig. 7 (Shi et al., 2016). In 8.2. Chitosan-based Pickering emulsions for skin applications
another recent study, chitosan Pickering emulsions encapsulating hes
peridin were incorporated in gelatin-based films (Dammak, Lourenço, & The use of Pickering emulsions in dermal formulations has only
do Sobral, 2019). The films were produced by incorporating the chitosan emerged recently due to the increasing consumers’ demands for safer
Pickering emulsions at different concentrations (5, 10, 20, 30 and 50 g and green products, as well as the need to adopt green chemistry prin
oil/100 g gelatin). The films have shown high flexibility but less resis ciples and environmentally friendly processes by the industrial sector
tance to tension. Furthermore, the water vapor barrier activity of the (Marto, Ascenso, Simoes, Almeida, & Ribeiro, 2016). Most of the
films was enhanced by increasing the Pickering emulsion incorporation research on Pickering emulsions for dermal applications focused on the
levels. The films possessed good antioxidant activity owing to the use of inorganic particles, such as silica, titanium dioxide. Recently, the
encapsulated hesperidin. use of biodegradable synthetic particles (e.g., polylactide-based parti
cles) (Laredj-Bourezg, Bolzinger, Pelletier, & Chevalier, 2017), and
8.1.5. Incorporation in complex food systems particles of natural origin (e.g., starch and cyclodextrins) as Pickering
The incorporation of Pickering emulsions in complex food matrices is stabilizers for dermal formulations have been reported (Marku,
an innovative research area that has been explored just recently. Hos Wahlgren, Rayner, Sjöö, & Timgren, 2012; Marto et al., 2016).
seini and Rajaei investigated the incorporation of fish oil-in-water The delivery of active agents to or across the skin is a challenging
Fig. 7. 3D CLSM images of chitosan films loaded with Pickering emulsions stabilized with zein/chitosan colloidal particles as a function of oil-to-chitosan ratios: A)
5%; B) 10 %; C) 20 %; D) 30 % and E) 50 %. The green fluorescence from Nile Red indicates the spherical emulsion droplets. Reprinted from (Shi et al., 2016),
Copyright (2016), with permission from Elsevier.
12
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
issue since the skin functions as a natural barrier. The active agent needs 2019).
to overcome the stratum corneum (the outermost layer of the skin) in Magnetic imprinted polymers (MIPs) are in general produced by the
order to reach its delivery site, either to the inner skin layers (viable polymerization of suitable functional monomers in the presence of the
epidermis and dermis) or to the systemic circulation. The use of chitosan targeted template molecules. Upon removal of the template molecules,
in topical and transdermal delivery systems has gained much interest specific binding sites are formed within the polymer matrix. These sites
due to its ability to enhance skin penetration and permeation. Chitosan, have a high binding affinity to the template molecules. MIPs were pro
due to its positive charge, has been reported to depolarize the negative duced by Pickering emulsion polymerization and were used to adsorb
charges of the stratum corneum cell membrane, and subsequently leads erythromycin (an antibiotic that has hazardous effects when it accu
to the driving of the drug, or active agent, within and/or through the mulates in the ecosystem). The o/w Pickering emulsion was stabilized
skin (Ammala, 2013). Moreover, it was found that chitosan increases the by chitosan nanoparticles and contained Fe3O4 nanoparticles as the
water content of the stratum corneum, modifies the structure of its hydrophobic magnetic carrier. The MIP system was produced by poly
keratin content and decreases the HaCaT cells membrane potential, merization with the functional monomer in the oil phase. The produced
which results in a transdermal penetration enhancement (He, Guo, Xiao, MIP adsorbent system has shown high adsorption capacity and ability to
& Feng, 2009). recognize erythromycin (Ou et al., 2015). This system, which is based on
Despite the importance of chitosan in dermal and transdermal de a chitosan Pickering emulsion, provides an effective way to remove
livery systems, very few studies focused on the formulation of Pickering erythromycin from aqueous media and guards against its accumulation
emulsions stabilized by chitosan and chitosan-based particles for skin in the ecosystem.
applications. For example, it has been recently reported that rutin-
loaded Pickering emulsions stabilized by chitosan nanoparticles, and
8.4. Production of different structural materials from chitosan-based
containing 20 % (v/v) of oleic acid, enhanced wound healing in rat skin
Pickering emulsions
(Asfour et al., 2017). The findings of this study suggest that the suc
cessful dermal delivery of rutin from Pickering emulsions, as well as the
8.4.1. Microcapsules produced from chitosan-based Pickering emulsions
presence of chitosan and oleic acid, had a synergetic healing effect for
Microcapsules prepared from Pickering emulsions are advantageous
the cutaneous wounds present in rats.
in terms of their eco-friendliness owing to the absence of surfactants in
In another recent study, it has been reported that trans-resveratrol
their composition. The formation of microcapsules from Pickering
delivery to the viable epidermis and dermis was remarkably enhanced
emulsions stabilized by inorganic particles has been frequently reported
when it was incorporated in Pickering emulsions stabilized by chitosan/
in the literature, whereas studies on microcapsules derived from Pick
gum Arabic nanoparticles (Sharkawy et al., 2020). It was observed that
ering emulsions stabilized by biopolymeric nanoparticles (including
chitosan presented in the developed particles played an important role
chitosan derived particles) are scarce. Table 2 summarizes some
in the improvement of the dermal delivery of resveratrol. The dermal
microcapsule systems developed from chitosan-based Pickering emul
delivery enhancement is attributed to the cationic nature of chitosan
sions available in the literature. The production of microcapsules from
which allows it to open the tight junctions of the stratum corneum cells
Pickering emulsions involves the adoption of shell formation techniques
that are negatively charged, permitting resveratrol to cross the stratum
to anchor (lock) the particles at the oil-water interface (Bago Rodriguez
corneum and accumulate in the viable epidermis and dermis where it
& Binks, 2019). The formation of microcapsules from Pickering emul
would perform its cosmetic and skin repair effect (Sharkawy et al.,
sions has been reported to significantly increase the mechanical stability
2020).
of the emulsion oil droplets, which led to retaining the microcapsules’
round shape after drying (Zou, Sipponen, & Österberg, 2019).
8.3. Chitosan-based Pickering emulsions for environmental applications
Degradable microspheres have been produced from chitosan-based
Pickering emulsions by photopolymerization (Liu, Wei et al., 2014).
Chitosan and chitosan-based materials (such as nanoparticles,
The photopolymerization of the monomer trithiol (trimethylolpropane
hydrogels, electrospun fibers and membranes) have long been used in
tris(3-mercaptopropionate)), and multifunctional acrylates, in Pickering
different environmental applications because of their ability to remove
emulsions (containing chloroform-in-water and chitosan as a green
pollutants owing to the adsorption capacity of chitosan (Chauhan,
stabilizer), was initiated by UV irradiation. The microspheres were
Dwivedi, & Sankararamakrishnan, 2014; Mohammadzadeh Pakdel &
loaded with ibuprofen whose release rate was increased by pH and
Peighambardoust, 2018; Riegger, Bäurer, Mirzayeva, Tovar, & Bach,
temperature increase. Additionally, the produced microcapsules have
2018; Salehi, Daraei, & Arabi Shamsabadi, 2016).
shown high degradability in weak alkaline media. The results of this
Some studies have investigated the production of novel materials,
study demonstrated the potential of chitosan-based Pickering emulsions
based on Pickering emulsions stabilized by chitosan particles, to remove
in the production of green degradable microspheres.
the environmental pollutants. In a recent study (Li, Mao et al., 2019),
w/o chitosan-based Pickering emulsions were produced and used to
Table 2
prepare a chitosan/hydrophobic-modified montmorillonite composite
Examples of microcapsules synthesized from chitosan-based Pickering emul
via Pickering emulsion polymerization with glutaraldehyde. The resul
sions that are available in the literature.
tant microcomposite has shown a high capability of adsorbing iodide
Particles Organic phase in Microcapsule’s shell Reference
ion. It is worth mentioning that the radioactive isotopes of iodine (I131
composition Pickering emulsion composition
and I129) represent high environmental hazards due to their high vola
tility and solubility. It was observed that the developed composite could Chitosan Tocotrienol in Chitosan/sodium (Mwangi,
refined palm oil tripolyphosphate Ho, Ooi, Tey,
adsorb iodide ions efficiently because of the simultaneous adsorption & Chan,
from both chitosan and the hydrophobically modified montmorillonite. 2016)
Nevertheless, it was found that increasing the chitosan content in the Chitosan Dichloromethane Chitosan/poly-lactic- (Wei, Wang,
nanocomposite led to a better adsorption performance. The experiments (CH2Cl2)/poly- co-glycolic acid Zou, Liu, &
lactic-co-glycolic (PLGA) Tong, 2012)
were conducted with I127 instead of the radioactive iodine for safety
acid (PLGA)
concerns, yet this ion has similar properties. The eco-friendliness of this Chitosan-coated Ciprofloxacin and Chitosan-coated CLPs (Zou et al.,
composite which is produced from the polymerization of chitosan-based colloidal Tall oil fatty acid in crosslinked with 2019)
Pickering emulsion distinguishes it as a novel alternative for the lignin olive oil sodium
metal-based composites that have been previously employed for the particles tripolyphosphate
(CLPs)
removal and separation of radioactive iodine isotopes (Li, Mao et al.,
13
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
The effect of high-intensity ultrasonication (HIU) on the production the oil droplets, as well as the excess non-adsorbed nanoparticles,
of composite nanospheres from chitosan-based Pickering emulsions was enhanced the stability and strength of the produced hydrogels through
recently studied (Wang, Chen, Law, & Tang, 2017). In this study, Pick electrostatic attraction. Moreover, these systems have shown higher
ering emulsions were stabilized with chitosan particles (produced from stability in comparison to similar alginate hydrogels stabilized by Tween
HIU pretreated chitosan solutions) and contained poly 80.
(lactic-co-glycolic) acid (PLGA) in CH2Cl2 as the dispersed phase. It
was observed that the HIU assisted Pickering emulsions resulted in the 8.4.3. Highly porous materials from chitosan-based Pickering emulsions
formation of monodisperse composite nanospheres. In contrast, the The development of highly porous water-insoluble materials with
non-HIU assisted Pickering emulsions gave rise to the production of large surface area and interconnected porous structures finds increasing
microcapsules (not nanospheres) with wide distribution. The authors interest in various applications such as biomedical devices, packaging,
concluded that the Pickering emulsions HIU treatment generated a sorption and separation science, electronic materials and sensors (Stein,
strong shear force that successfully reduced the emulsion droplet size 2003; Zhou et al., 2019).
and thus improved the mono-dispersity. The produced monodisperse Biocompatible and biodegradable highly interconnected porous
composite nanospheres based on biodegradable polymers, such as chi structures obtained from high internal phase emulsions (HIPEs) have
tosan, have outstanding applications as drug delivery systems (Wang, received high research interest in particular due to their surfactant-free
Law, Chen, Chen, & Tang, 2017). properties and high microporosity. The production of such porous
The studies mentioned in Table 2 involve microcapsules developed structures for biomedical applications (e.g., scaffolds) based on HIPEs
from Pickering emulsions originally stabilized with chitosan particles, in involves the polymerization, or the cross-linking, of the continuous
which the microcapsules were obtained by crosslinking the particles to phase of the HIPEs followed by extraction/removal of the dispersed
form the microcapsule’s shell. In a different approach, the synthesis of phase (Tan et al., 2017).
microcapsules from Pickering emulsions stabilized by poly(ethyl In a recent study, Zhou et al. developed, for the first time, a simple
eneimine) surface modified Laponite particles was documented. The and non-toxic highly porous material by the freeze-drying of Pickering
shells of the microcapsules were then developed by the deposition of high internal phase emulsions (HIPEs) that are stabilized by gliadin-
chitosan and alginate on the Pickering emulsion droplets. The produced chitosan complex particles. The porous materials developed from the
nanocomposite microcapsules contain natural polymers, and hence have HIPEs (PM-HIPEs) (Fig. 8) were used as oil absorbents and have shown
great potential for applications in the food and medical areas (Liu, Gu, high oil absorption capacity (Zhou et al., 2019). These materials are of
Hu, Hu, & Wang, 2014). high importance in the mitigation of oil spills owing to their high
In another recent study (Palamarchuk, Artemov, & Bukreeva, 2018), porosity which provides them with high absorption capacity.
Pickering emulsions stabilized by hydrophobically modified silica
nanoparticles were used as templates for the formation of microcapsules 9. Conclusions and future directions
through the deposition of chitosan and alginate polyelectrolyte layers.
The use of chitosan and alginate in the microcapsule shell formation There has been considerable increasing interest in Pickering emul
enhanced the biocompatibility of the produced microcapsules, which sions stabilized with biopolymeric particles. Chitosan-based particles
enables their use in biomedical applications (Palamarchuk et al., 2018). are promising candidates as Pickering stabilizers, owing to their
Similarly, composite microcapsules loaded with citronella oil were biodegradable and biocompatible character, which allows them to
developed by citronella oil/water Pickering emulsions stabilized by replace the low molecular weight surfactants that have negative effects
hydroxyapatite nanoparticles. The shells of the composite microcapsules on the environment and health. Novel Pickering emulsions based on
consisted of hydroxyapatite/quaternary ammonium salt of chitosan/ chitosan are often obtained using hydrophobically modified chitosan or
sodium alginate. They were formed by the electrostatic adsorption of the chitosan complex particles rather than using chitosan itself. The role of
quaternary ammonium salt of chitosan and sodium alginate, followed by chitosan in the particles used as Pickering stabilizers can be related to
the chelation of alginate with the calcium ions released from the hy tuning the wettability and surface charge, aiming at improving the
droxyapatite nanoparticles (Wang et al., 2018). The produced micro stability of the resulting Pickering emulsions. Furthermore, in some
capsules have shown sustained release and effective antibacterial cases, it can be directly associated with the improvement of the func
properties and are suitable for food and agricultural applications. tionality of Pickering emulsions targeting specific applications, such as
retardation of lipid oxidation in food formulations, control of lipid
8.4.2. Chitosan-based pickering emulsion hydrogels digestion rate, or enhancement of the skin uptake of cosmeceuticals.
Hydrogels are three-dimensional networks of polymeric chains that Certainly, there is a significant research advancement in utilizing
swell when they come in contact with water but maintain their structure chitosan-based Pickering emulsions in different areas, such as food and
and resist dissolution (Qu & Luo, 2020). They have been widely used in skin applications, environmental research and novel materials devel
drug delivery and tissue engineering. In the swollen state, the mass of opment (e.g., microcapsules, hydrogels, films and porous materials).
water in the hydrogel is much higher than the mass of the polymer. The However, there are still some challenges and research opportunities to
ability of hydrogels to absorb water is due to the presence of hydrophilic be addressed.
functional in the polymer chains, at the same time they resist dissolution Despite the advanced ongoing studies in Pickering emulsions, in
because of the cross-linking between the network chains (Ahmed, 2015). general, it should be noted that the molecular-based emulsifiers are still
An innovative research trend has been applied recently to immobi the most commonly used in industry (McClements & Jafari, 2018).
lize Pickering emulsions in hydrogels, especially Pickering emulsions Therefore, the main challenge is to find the most studied Pickering
stabilized by protein-based particles (Xiao, Shi, Li, Pan, & Huang, 2017). emulsions utilized in real products in areas, such as food and beverages,
This immobilization permits higher stability of the produced Pickering pharmaceuticals and cosmetics (Murray, 2019). This can be successfully
emulsions at severe processing conditions, such as high temperature and achieved by scaling up studies, namely for the production of the parti
high alkaline media. In contrast, this trend of Pickering emulsions cles and the emulsions, together with conducting a cost-benefit analysis
immobilization in hydrogels has been recently applied to chitosan-based for the particles and the Pickering emulsions production method.
Pickering emulsions for increasing the stability of the developed Another major challenge for Pickering emulsion formulators is to
hydrogels. It has been reported that the stability of alginate hydrogels further improve the stability of emulsions (Gonzalez Ortiz,
was highly improved by the immobilization of chitosan Pickering Pochat-Bohatier, Cambedouzou, Bechelany, & Miele, 2020). For
emulsions in them (Lim et al., 2020). In this study, it was observed that instance, more research is required to investigate the stability of the
the chitosan nanoparticles that are adsorbed at the oil-water interface of food-grade Pickering emulsions in real food systems. The stability of
14
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
Fig. 8. SEM images of water-insoluble porous materials obtained from the freeze-drying of high internal phase Pickering emulsions stabilized by 2 % chitosan/
gliadin particles with φ = 0.8. Image G1 is a magnification of image G. Reprinted with permission from (Zhou et al., 2019), Copyright (2019) American Chemi
cal Society.
many chitosan-based Pickering emulsions has been investigated under MCTES to CIMO (UIDB/00690/2020). Asma Sharkawy acknowledges
different environmental conditions (e.g., temperature, pH and ionic the financial support from the FCT doctoral grant (PD/BD/135085/
strength changes). However, research that explores the possible in 2017).
teractions of chitosan Pickering emulsions with food systems scarcely
exists. References
Moreover, there is a lack of information on the contact angle values
of some chitosan-based particles that are being proposed as novel Agulló, E., Rodríguez, M. S., Ramos, V., & Albertengo, L. (2003). Present and future role
of chitin and chitosan in food. Macromolecular Bioscience, 3(10), 521–530. https://
Pickering stabilizers. A better understanding of the wettability of the doi.org/10.1002/mabi.200300010.
developed particles would, undoubtedly, enable improving the stability Ahmed, E. M. (2015). Hydrogel: Preparation, characterization, and applications: A
of the developed chitosan-based Pickering emulsion systems. Further review. Journal of Advanced Research, 6(2), 105–121. https://doi.org/10.1016/j.
jare.2013.07.006.
more, the identification and utilization of new natural biopolymers, that Albert, C., Beladjine, M., Tsapis, N., Fattal, E., Agnely, F., & Huang, N. (2019). Pickering
can complex with chitosan, to tune the wettability of chitosan particles emulsions: Preparation processes, key parameters governing their properties and
are of great importance for exploratory future studies. Also, most of the potential for pharmaceutical applications. Journal of Controlled Release, 309,
302–332. https://doi.org/10.1016/J.JCONREL.2019.07.003.
reported preparation methods of chitosan-based Pickering emulsions are Ali, A., & Ahmed, S. (2018). A review on chitosan and its nanocomposites in drug
limited to the rotor-stator homogenization and ultrasonication methods. delivery. International Journal of Biological Macromolecules, 109, 273–286. https://
Other preparation methodologies, such as microfluidic emulsification doi.org/10.1016/J.IJBIOMAC.2017.12.078.
Alison, L., Demirörs, A. F., Tervoort, E., Teleki, A., Vermant, J., & Studart, A. R. (2018).
and membrane emulsification should be explored in future studies, and
Emulsions stabilized by chitosan-modified silica nanoparticles: PH control of
investigated for improving the emulsion stability. structure-property relations. Langmuir, 34(21), 6147–6160. https://doi.org/
The studies on using chitosan-based Pickering emulsions, and ma 10.1021/acs.langmuir.8b00622.
terials thereof, in skin applications are very few, which represents a Alison, L., Rühs, P. A., Tervoort, E., Teleki, A., Zanini, M., Isa, L., … Studart, A. R. (2016).
Pickering and network stabilization of biocompatible emulsions using chitosan-
valuable research opportunity in this area in order to leverage chitosan modified silica nanoparticles. Langmuir, 32(50), 13446–13457. https://doi.org/
non-toxic and biodegradable properties, as well as its skin benefits. The 10.1021/acs.langmuir.6b03439.
sensorial perception of cosmetic Pickering emulsions stabilized with Ammala, A. (2013). Biodegradable polymers as encapsulation materials for cosmetics
and personal care markets. International Journal of Cosmetic Science, 35(2), 113–124.
chitosan particles has never been studied. The type of particles https://doi.org/10.1111/ics.12017.
remarkably influences the sensory properties of the developed cosmetic Aranaz, I., Acosta, N., Civera, C., Elorza, B., Mingo, J., Castro, C., … Caballero, A. H.
Pickering emulsions as they determine the level of greasiness, whitening (2018). Cosmetics and cosmeceutical applications of chitin, chitosan and their
derivatives. Polymers, 10(2). https://doi.org/10.3390/polym10020213.
residues, ease of spreading and glossiness (Terescenco, Hucher, Picard, Asfour, M. H., Elmotasem, H., Mostafa, D. M., & Salama, A. A. A. (2017). Chitosan based
& Savary, 2020). Although these aspects are crucial for the commer Pickering emulsion as a promising approach for topical application of rutin in a
cialization of Pickering emulsions intended for cosmetic use, such solubilized form intended for wound healing: In vitro and in vivo study. International
Journal of Pharmaceutics, 534(1–2), 325–338. https://doi.org/10.1016/J.
studies were only performed for Pickering emulsions stabilized by IJPHARM.2017.10.044.
inorganic particles. Therefore, future efforts should be also directed Atarian, M., Rajaei, A., Tabatabaei, M., Mohsenifar, A., & Bodaghi, H. (2019).
towards the study of the sensory properties of Pickering emulsions sta Formulation of Pickering sunflower oil-in-water emulsion stabilized by chitosan-
stearic acid nanogel and studying its oxidative stability. Carbohydrate Polymers, 210,
bilized by different chitosan particles.
47–55. https://doi.org/10.1016/J.CARBPOL.2019.01.008.
Finally, it must be highlighted in this review that almost all the Avadi, M. R., Sadeghi, A. M. M., Mohammadpour, N., Abedin, S., Atyabi, F.,
chitosan-based Pickering emulsions that are developed for food and Dinarvand, R., … Rafiee-Tehrani, M. (2010). Preparation and characterization of
cosmetic applications were tested only by in vitro studies. However, it is insulin nanoparticles using chitosan and Arabic gum with ionic gelation method.
Nanomedicine: Nanotechnology, Biology and Medicine, 6(1), 58–63. https://doi.org/
recommended that the in vitro examination should be complemented by 10.1016/J.NANO.2009.04.007.
in vivo studies. The combination of both types of tests provides a Baek, J., Wahid-Pedro, F., Kim, K., Kim, K., & Tam, K. C. (2019). Phosphorylated-CNC/
comprehensive and thorough evaluation of the developed emulsion for modified-chitosan nanocomplexes for the stabilization of Pickering emulsions.
Carbohydrate Polymers, 206, 520–527. https://doi.org/10.1016/j.
the validation of the potential application. carbpol.2018.11.006.
Bago Rodriguez, A. M., & Binks, B. P. (2019). Capsules from Pickering emulsion
templates. Current Opinion in Colloid & Interface Science, 44, 107–129. https://doi.
Acknowledgments
org/10.1016/J.COCIS.2019.09.006.
Bakshi, P. S., Selvakumar, D., Kadirvelu, K., & Kumar, N. S. (2019). Chitosan as an
This work was financially supported by the Base Funding - UIDB/ environment friendly biomaterial – A review on recent modifications and
applications. International Journal of Biological Macromolecules. https://doi.org/
50020/2020 of the Associate Laboratory LSRE-LCM- funded by national
10.1016/J.IJBIOMAC.2019.10.113.
funds through FCT/MCTES (PIDDAC). To theFoundation for Science and
Technology (FCT, Portugal) for financial support by national funds FCT/
15
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
Bernkop-Schnürch, A., & Dünnhaupt, S. (2012). Chitosan-based drug delivery systems. microemulsion. Solid State Sciences, 14(5), 622–625. https://doi.org/10.1016/j.
European Journal of Pharmaceutics and Biopharmaceutics, 81(3), 463–469. https://doi. solidstatesciences.2012.01.016.
org/10.1016/J.EJPB.2012.04.007. Huang, X.-N., Zhou, F.-Z., Yang, T., Yin, S.-W., Tang, C.-H., & Yang, X.-Q. (2019).
Binks, B. P. (2002). Particles as surfactants—Similarities and differences. Current Opinion Fabrication and characterization of Pickering High Internal Phase Emulsions (HIPEs)
in Colloid & Interface Science, 7(1–2), 21–41. https://doi.org/10.1016/S1359-0294 stabilized by chitosan-caseinophosphopeptides nanocomplexes as oral delivery
(02)00008-0. vehicles. Food Hydrocolloids, 93, 34–45. https://doi.org/10.1016/J.
Binks, B. P., & Yin, D. (2016). Pickering emulsions stabilized by hydrophilic FOODHYD.2019.02.005.
nanoparticles:: In situ surface modification by oil. Soft Matter, 12(32), 6858–6867. İlyasoğlu, H., Nadzieja, M., & Guo, Z. (2019). Caffeic acid grafted chitosan as a novel
https://doi.org/10.1039/c6sm01214k. dual-functional stabilizer for food-grade emulsions and additive antioxidant
Calero, N., Muñoz, J., Cox, P. W., Heuer, A., & Guerrero, A. (2013). Influence of chitosan property. Food Hydrocolloids, 95, 168–176. https://doi.org/10.1016/J.
concentration on the stability, microstructure and rheological properties of O/W FOODHYD.2019.04.043.
emulsions formulated with high-oleic sunflower oil and potato protein. Food Jo, M., Ban, C., Goh, K. K. T., & Choi, Y. J. (2019). Influence of chitosan-coating on the
Hydrocolloids, 30(1), 152–162. https://doi.org/10.1016/j.foodhyd.2012.05.004. stability and digestion of emulsions stabilized by waxy maize starch crystals. Food
Chauhan, D., Dwivedi, J., & Sankararamakrishnan, N. (2014). Novel chitosan/PVA/ Hydrocolloids, 94, 603–612. https://doi.org/10.1016/j.foodhyd.2019.04.010.
zerovalent iron biopolymeric nanofibers with enhanced arsenic removal Klinkesorn, U. (2013). The role of chitosan in emulsion formation and stabilization. Food
applications. Environmental Science and Pollution Research, 21(15), 9430–9442. Reviews International, 29(4), 371–393. https://doi.org/10.1080/
https://doi.org/10.1007/s11356-014-2864-1. 87559129.2013.818013.
Chen, R. H., & Heh, R. S. (2000). Skin hydration effects, physico-chemical properties and Laredj-Bourezg, F., Bolzinger, M. A., Pelletier, J., & Chevalier, Y. (2017). Pickering
vitamin E release ratio of vital moisture creams containing water-soluble chitosans. emulsions stabilized by biodegradable block copolymer micelles for controlled
International Journal of Cosmetic Science, 22(5), 349–360. https://doi.org/10.1111/ topical drug delivery. International Journal of Pharmaceutics, 531(1), 134–142.
j.1467-2494.2000.00036.x. https://doi.org/10.1016/j.ijpharm.2017.08.065.
Chevalier, Y., & Bolzinger, M. A. (2013). Emulsions stabilized with solid nanoparticles: Li, X., & Xia, W. (2011). Effects of concentration, degree of deacetylation and molecular
Pickering emulsions. Colloids and Surfaces A: Physicochemical and Engineering Aspects, weight on emulsifying properties of chitosan. International Journal of Biological
439, 23–34. https://doi.org/10.1016/j.colsurfa.2013.02.054. Macromolecules, 48(5), 768–772. https://doi.org/10.1016/J.
Costa, A. L. R., Gomes, A., & Cunha, R. L. (2018). One-step ultrasound producing O/W IJBIOMAC.2011.02.016.
emulsions stabilized by chitosan particles. Food Research International, 107, 717–725. Li, X.-M., Li, X., Wu, Z., Wang, Y., Cheng, J.-S., Wang, T., … Zhang, B. (2020). Chitosan
https://doi.org/10.1016/J.FOODRES.2018.02.057. hydrochloride/carboxymethyl starch complex nanogels stabilized Pickering
Costa, A. L. R., Gomes, A., Furtado, G., de, F., Tibolla, H., Menegalli, F. C., … Cunha, R. L. emulsions for oral delivery of β-carotene: Protection Effect and in Vitro Digestion
(2020). Modulating in vitro digestibility of Pickering emulsions stabilized by food- Study. Food Chemistry. , Article 126288. https://doi.org/10.1016/J.
grade polysaccharides particles. Carbohydrate Polymers, 227, Article 115344. https:// FOODCHEM.2020.126288.
doi.org/10.1016/J.CARBPOL.2019.115344. Li, M. F., Chen, L., Xu, M. Z., Zhang, J. L., Wang, Q., Zeng, Q. Z., … Yuan, Y. (2018). The
Croisier, F., & Jérôme, C. (2013). Chitosan-based biomaterials for tissue engineering. formation of zein-chitosan complex coacervated particles: Relationship to
European Polymer Journal, 49(4), 780–792. https://doi.org/10.1016/j. encapsulation and controlled release properties. International Journal of Biological
eurpolymj.2012.12.009. Macromolecules, 116, 1232–1239. https://doi.org/10.1016/j.ijbiomac.2018.05.107.
Dammak, I., & José do Amaral Sobral, P. (2018). Formulation optimization of lecithin- Li, M.-F., He, Z.-Y., Li, G.-Y., Zeng, Q.-Z., Su, D.-X., Zhang, J.-L., … He, S. (2019). The
enhanced pickering emulsions stabilized by chitosan nanoparticles for hesperidin formation and characterization of antioxidant pickering emulsions: Effect of the
encapsulation. Journal of Food Engineering, 229, 2–11. https://doi.org/10.1016/j. interactions between gliadin and chitosan. Food Hydrocolloids, 90, 482–489. https://
jfoodeng.2017.11.001. doi.org/10.1016/J.FOODHYD.2018.12.052.
Dammak, I., Lourenço, R. V., & do Sobral, P. J. A. (2019). Active gelatin films Li, Q., Mao, Q., Yang, C., Zhang, S., He, G., Zhang, X., … Zhang, W. (2019). Hydrophobic-
incorporated with Pickering emulsions encapsulating hesperidin: Preparation and modified montmorillonite coating onto crosslinked chitosan as the core-shell micro-
physicochemical characterization. Journal of Food Engineering, 240, 9–20. https:// sorbent for iodide adsorptive removal via Pickering emulsion polymerization.
doi.org/10.1016/J.JFOODENG.2018.07.002. International Journal of Biological Macromolecules, 141, 987–996. https://doi.org/
de Farias, B. S., Grundmann, D. D. R., Rizzi, F. Z., Martins, N. S. S., Sant’Anna Cadaval 10.1016/J.IJBIOMAC.2019.09.065.
Junior, T. R., & de Almeida Pinto, L. A. (2019). Production of low molecular weight Li, X.-M., Xie, Q.-T., Zhu, J., Pan, Y., Meng, R., Zhang, B., … Jin, Z.-Y. (2019). Chitosan
chitosan by acid and oxidative pathways: Effect on physicochemical properties. Food hydrochloride/carboxymethyl starch complex nanogels as novel Pickering
Research International, 123, 88–94. https://doi.org/10.1016/j.foodres.2019.04.051. stabilizers: Physical stability and rheological properties. Food Hydrocolloids, 93,
de Farias, B. S., Sant’Anna Cadaval Junior, T. R., & de Almeida Pinto, L. A. (2019). 215–225. https://doi.org/10.1016/J.FOODHYD.2019.02.021.
Chitosan-functionalized nanofibers: A comprehensive review on challenges and Lim, H.-P., Ho, K.-W., Surjit Singh, C. K., Ooi, C.-W., Tey, B.-T., & Chan, E.-S. (2020).
prospects for food applications. International Journal of Biological Macromolecules, Pickering emulsion hydrogel as a promising food delivery system: Synergistic effects
123, 210–220. https://doi.org/10.1016/J.IJBIOMAC.2018.11.042. of chitosan Pickering emulsifier and alginate matrix on hydrogel stability and
De Folter, J. W. J., Van Ruijven, M. W. M., & Velikov, K. P. (2012). Oil-in-water Pickering emulsion delivery. Food Hydrocolloids. , Article 105659. https://doi.org/10.1016/J.
emulsions stabilized by colloidal particles from the water-insoluble protein zein. Soft FOODHYD.2020.105659.
Matter, 8(25), 6807–6815. https://doi.org/10.1039/c2sm07417f. Linke, C., & Drusch, S. (2018). Pickering emulsions in foods - opportunities and
Del Blanco, L. F., Rodriguez, M. S., Schulz, P. C., & Agulló, E. (1999). Influence of the limitations. Critical Reviews in Food Science and Nutrition, 58(12), 1971–1985.
deacetylation degree on chitosan emulsification properties. Colloid and Polymer https://doi.org/10.1080/10408398.2017.1290578.
Science, 277(11), 1087–1092. https://doi.org/10.1007/s003960050495. Liu, H., Wang, C., Zou, S., Wei, Z., & Tong, Z. (2012). Simple, reversible emulsion system
Dickinson, E. (2009). Hydrocolloids as emulsifiers and emulsion stabilizers. Food switched by pH on the basis of chitosan without any hydrophobic modification.
Hydrocolloids, 23(6), 1473–1482. https://doi.org/10.1016/J. Langmuir, 28(30), 11017–11024. https://doi.org/10.1021/la3021113.
FOODHYD.2008.08.005. Liu, H., Gu, X., Hu, M., Hu, Y., & Wang, C. (2014). Facile fabrication of nanocomposite
Gonzalez Ortiz, D., Pochat-Bohatier, C., Cambedouzou, J., Bechelany, M., & Miele, P. microcapsules by combining layer-by-layer self-assembly and Pickering emulsion
(2020). Current trends in pickering emulsions: Particle morphology and templating. RSC Advances, 4(32), 16751–16758. https://doi.org/10.1039/
applications. Engineering. https://doi.org/10.1016/j.eng.2019.08.017. c4ra00089g.
He, W., Guo, X., Xiao, L., & Feng, M. (2009). Study on the mechanisms of chitosan and its Liu, H., Wei, Z., Hu, M., Deng, Y., Tong, Z., & Wang, C. (2014). Fabrication of degradable
derivatives used as transdermal penetration enhancers. International Journal of polymer microspheres via pH-responsive chitosan-based Pickering emulsion
Pharmaceutics, 382(1–2), 234–243. https://doi.org/10.1016/J. photopolymerization. RSC Advances, 4(55), 29344–29351. https://doi.org/10.1039/
IJPHARM.2009.07.038. c4ra01660b.
Ho, K. W., Ooi, C. W., Mwangi, W. W., Leong, W. F., Tey, B. T., & Chan, E.-S. (2016). Lopes, S., Afonso, C., Fernandes, I., Barreiro, M. F., Costa, P., & Rodrigues, A. E. (2019).
Comparison of self-aggregated chitosan particles prepared with and without Chitosan-cellulose particles as delivery vehicles for limonene fragrance. Industrial
ultrasonication pretreatment as Pickering emulsifier. Food Hydrocolloids, 52, Crops and Products, 139. https://doi.org/10.1016/j.indcrop.2019.05.057.
827–837. https://doi.org/10.1016/J.FOODHYD.2015.08.019. Low, L. E., Siva, S. P., Ho, Y. K., Chan, E. S., & Tey, B. T. (2020). Recent advances of
Hosseini, R. S., & Rajaei, A. (2020). Potential Pickering emulsion stabilized with characterization techniques for the formation, physical properties and stability of
chitosan-stearic acid nanogels incorporating clove essential oil to produce fish-oil- Pickering emulsion. Advances in Colloid and Interface Science, 277. https://doi.org/
enriched mayonnaise. Carbohydrate Polymers, 241, Article 116340. https://doi.org/ 10.1016/j.cis.2020.102117.
10.1016/j.carbpol.2020.116340. Luo, Y., Zhang, B., Cheng, W. H., & Wang, Q. (2010). Preparation, characterization and
Hosseini, E., Rajaei, A., Tabatabaei, M., Mohsenifar, A., & Jahanbin, K. (2019). evaluation of selenite-loaded chitosan/TPP nanoparticles with or without zein
Preparation of pickering flaxseed oil-in-water emulsion stabilized by chitosan- coating. Carbohydrate Polymers, 82(3), 942–951. https://doi.org/10.1016/j.
myristic acid nanogels and investigation of its oxidative stability in presence of clove carbpol.2010.06.029.
essential oil as antioxidant. Food Biophysics. https://doi.org/10.1007/s11483-019- Marku, D., Wahlgren, M., Rayner, M., Sjöö, M., & Timgren, A. (2012). Characterization of
09612-z. starch Pickering emulsions for potential applications in topical formulations.
Hosseini, S. F., Zandi, M., Rezaei, M., & Farahmandghavi, F. (2013). Two-step method for International Journal of Pharmaceutics, 428(1–2), 1–7. https://doi.org/10.1016/j.
encapsulation of oregano essential oil in chitosan nanoparticles: Preparation, ijpharm.2012.01.031.
characterization and in vitro release study. Carbohydrate Polymers, 95(1), 50–56. Martins, I. M., Rodrigues, S. N., Barreiro, M. F., & Rodrigues, A. E. (2011). Polylactide-
https://doi.org/10.1016/j.carbpol.2013.02.031. based thyme oil microcapsules production: Evaluation of surfactants. Industrial and
Housaindokht, M. R., & Nakhaei Pour, A. (2012). Study the effect of HLB of surfactant on Engineering Chemistry Research, 50(2), 898–904. https://doi.org/10.1021/ie101815f.
particle size distribution of hematite nanoparticles prepared via the reverse
16
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
Marto, J., Ascenso, A., Simoes, S., Almeida, A. J., & Ribeiro, H. M. (2016). Pickering Sharkawy, A., Fernandes, I. P., Barreiro, M. F., Rodrigues, A. E., & Shoeib, T. (2017).
emulsions: Challenges and opportunities in topical delivery. Expert Opinion on Drug Aroma-loaded microcapsules with antibacterial activity for eco-friendly textile
Delivery, 13(8), 1093–1107. https://doi.org/10.1080/17425247.2016.1182489. application: Synthesis, characterization, release, and green grafting. Industrial and
McClements, D. J., & Jafari, S. M. (2018). Improving emulsion formation, stability and Engineering Chemistry Research, 56(19), 5516–5526. https://doi.org/10.1021/acs.
performance using mixed emulsifiers: A review. Advances in Colloid and Interface iecr.7b00741.
Science, 251, 55–79. https://doi.org/10.1016/J.CIS.2017.12.001. Shi, W.-J., Tang, C.-H., Yin, S.-W., Yin, Y., Yang, X.-Q., Wu, L.-Y., … Zhao, Z.-G. (2016).
Mohammadzadeh Pakdel, P., & Peighambardoust, S. J. (2018). Review on recent Development and characterization of novel chitosan emulsion films via pickering
progress in chitosan-based hydrogels for wastewater treatment application. emulsions incorporation approach. Food Hydrocolloids, 52, 253–264. https://doi.
Carbohydrate Polymers, 201, 264–279. https://doi.org/10.1016/J. org/10.1016/J.FOODHYD.2015.07.008.
CARBPOL.2018.08.070. Stein, A. (2003). Advances in microporous and mesoporous solids – Highlights of recent
Mujtaba, M., Morsi, R. E., Kerch, G., Elsabee, M. Z., Kaya, M., Labidi, J., … Khawar, K. M. progress. Advanced Materials, 15(10), 763–775. https://doi.org/10.1002/
(2019). Current advancements in chitosan-based film production for food adma.200300007.
technology; A review. International Journal of Biological Macromolecules, 121, Tan, H., Wei, J., Sun, G., Mu, C., Lin, W., & Ngai, T. (2017). Interconnected macroporous
889–904. https://doi.org/10.1016/J.IJBIOMAC.2018.10.109. 3D scaffolds templated from gelatin nanoparticle-stabilized high internal phase
Mumuni, M. A., Kenechukwu, F. C., Ofokansi, K. C., Attama, A. A., & Díaz, D. D. (2020). emulsions for biomedical applications. Soft Matter, 13(21), 3871–3878. https://doi.
Insulin-loaded mucoadhesive nanoparticles based on mucin-chitosan complexes for org/10.1039/c7sm00706j.
oral delivery and diabetes treatment. Carbohydrate Polymers, 229. https://doi.org/ Tang, J., Quinlan, P. J., & Tam, K. C. (2015). Stimuli-responsive Pickering emulsions:
10.1016/j.carbpol.2019.115506. Recent advances and potential applications. Soft Matter, 11(18), 3512–3529. https://
Murray, B. S. (2019). Pickering emulsions for food and drinks. Current Opinion in Food doi.org/10.1039/c5sm00247h.
Science, 27, 57–63. https://doi.org/10.1016/j.cofs.2019.05.004. Tavernier, I., Wijaya, W., Van der Meeren, P., Dewettinck, K., & Patel, A. R. (2016). Food-
Mwangi, W. W., Ho, K.-W., Ooi, C.-W., Tey, B.-T., & Chan, E.-S. (2016). Facile method for grade particles for emulsion stabilization. Trends in Food Science and Technology, 50,
forming ionically cross-linked chitosan microcapsules from Pickering emulsion 159–174. https://doi.org/10.1016/j.tifs.2016.01.023.
templates. Food Hydrocolloids, 55, 26–33. https://doi.org/10.1016/J. Terescenco, D., Hucher, N., Picard, C., & Savary, G. (2020). Sensory perception of
FOODHYD.2015.10.022. textural properties of cosmetic Pickering emulsions. International Journal of Cosmetic
Mwangi, W. W., Ho, K.-W., Tey, B.-T., & Chan, E.-S. (2016). Effects of environmental Science.
factors on the physical stability of pickering-emulsions stabilized by chitosan Tian, H., Lu, Z., Yu, H., Chen, C., & Hu, J. (2019). Fabrication and characterization of
particles. Food Hydrocolloids, 60, 543–550. https://doi.org/10.1016/J. citral-loaded oil-in-water Pickering emulsions stabilized by chitosan-
FOODHYD.2016.04.023. tripolyphosphate particles. Food & Function, 10(5), 2595–2604. https://doi.org/
Nan, F., Wu, J., Qi, F., Liu, Y., Ngai, T., & Ma, G. (2014). Uniform chitosan-coated 10.1039/c8fo02002g.
alginate particles as emulsifiers for preparation of stable Pickering emulsions with Tzoumaki, M. V., Moschakis, T., Scholten, E., & Biliaderis, C. G. (2013). In vitro lipid
stimulus dependence. Colloids and Surfaces A: Physicochemical and Engineering digestion of chitin nanocrystal stabilized o/w emulsions. Food & Function, 4(1),
Aspects, 456(1), 246–252. https://doi.org/10.1016/j.colsurfa.2014.05.017. 121–129. https://doi.org/10.1039/c2fo30129f.
Ou, H., Chen, Q., Pan, J., Zhang, Y., Huang, Y., & Qi, X. (2015). Selective removal of van der Gronde, T., Hartog, A., van Hees, C., Pellikaan, H., & Pieters, T. (2016).
erythromycin by magnetic imprinted polymers synthesized from chitosan-stabilized Systematic review of the mechanisms and evidence behind the hypocholesterolaemic
Pickering emulsion. Journal of Hazardous Materials, 289, 28–37. https://doi.org/ effects of HPMC, pectin and chitosan in animal trials. Food Chemistry, 199, 746–759.
10.1016/J.JHAZMAT.2015.02.030. https://doi.org/10.1016/J.FOODCHEM.2015.12.050.
Palamarchuk, K. V., Artemov, V. V., & Bukreeva, T. V. (2018). Microcapsules based on Wang, X. Y., & Heuzey, M. C. (2016a). Chitosan-based conventional and pickering
pickering emulsion and polyelectrolyte layers: Biomedical applications. emulsions with long-term stability. Langmuir, 32(4), 929–936. https://doi.org/
Nanotechnologies in Russia, 13(3–4), 199–204. https://doi.org/10.1134/ 10.1021/acs.langmuir.5b03556.
S1995078018020076. Wang, X. Y., & Heuzey, M. C. (2016b). Pickering emulsion gels based on insoluble
Pickering, S. U. (1907). Emulsions. Journal of the Chemical Society, 91, 2001–2021. chitosan/gelatin electrostatic complexes. RSC Advances, 6(92), 89776–89784.
Pochanavanich, P., & Suntornsuk, W. (2002). Fungal chitosan production and its https://doi.org/10.1039/c6ra10378b.
characterization. Letters in Applied Microbiology, 35(1), 17–21. https://doi.org/ Wang, H., Singh, V., & Behrens, S. H. (2012). Image charge effects on the formation of
10.1046/j.1472-765X.2002.01118.x. pickering emulsions. Journal of Physical Chemistry Letters, 3(20), 2986–2990. https://
Qu, B., & Luo, Y. (2020). Chitosan-based hydrogel beads: Preparations, modifications and doi.org/10.1021/jz300909z.
applications in food and agriculture sectors – A review. International Journal of Wang, J., Li, X., Chen, M., Chen, Z., Wu, H., Zhang, P., … Hu, Y. (2018). Fabrication of
Biological Macromolecules, 152, 437–448. https://doi.org/10.1016/j. sustained-release and antibacterial citronella oil-loaded composite microcapsules
ijbiomac.2020.02.240. based on Pickering emulsion templates. Journal of Applied Polymer Science, 135(25).
Rattanaburi, P., Charoenrat, N., Pongtharangkul, T., Suphantharika, M., & https://doi.org/10.1002/app.46386.
Wongkongkatep, J. (2019). Hydroxypropyl methylcellulose enhances the stability of Wang, L.-J., Yin, S.-W., Wu, L.-Y., Qi, J.-R., Guo, J., & Yang, X.-Q. (2016). Fabrication
o/w Pickering emulsions stabilized with chitosan and the whole cells of Lactococcus and characterization of Pickering emulsions and oil gels stabilized by highly charged
lactis IO-1. Food Research International, 116, 559–565. https://doi.org/10.1016/J. zein/chitosan complex particles (ZCCPs). Food Chemistry, 213, 462–469. https://doi.
FOODRES.2018.08.074. org/10.1016/J.FOODCHEM.2016.06.119.
Ren, X., & Zhang, Y. (2020). Switching Pickering emulsion stabilized by Chitosan-SDS Wang, X. Y., Wang, J., Rousseau, D., & Tang, C. H. (2020). Chitosan-stabilized emulsion
complexes through ion competition. Colloids and Surfaces A: Physicochemical and gels via pH-induced droplet flocculation. Food Hydrocolloids, 105. https://doi.org/
Engineering Aspects, 587. https://doi.org/10.1016/j.colsurfa.2019.124316. 10.1016/j.foodhyd.2020.105811.
Ribeiro, E. F., Borreani, J., Moraga, G., Nicoletti, V. R., Quiles, A., & Hernando, I. (2019). Wang, J., Chen, D., Law, W. C., & Tang, C. Y. (2017). Influence of high intensity
Digestibility and bioaccessibility of pickering emulsions of roasted coffee oil ultrasonication on the fabrication of poly(lactic-co-glycolic acid)/ chitosan
stabilized by chitosan and chitosan-sodium tripolyphosphate nanoparticles. Food nanocomposites based on pickering emulsions. ICCM International Conferences on
Biophysics. https://doi.org/10.1007/s11483-019-09614-x. Composite Materials, 2017-Augus.
Riegger, B. R., Bäurer, B., Mirzayeva, A., Tovar, G. E. M., & Bach, M. (2018). A systematic Wang, J., Law, W. C., Chen, L., Chen, D., & Tang, C. Y. (2017). Fabrication of
approach of chitosan nanoparticle preparation via emulsion crosslinking as potential monodisperse drug-loaded poly(lactic-co-glycolic acid)–chitosan core-shell
adsorbent in wastewater treatment. Carbohydrate Polymers, 180, 46–54. https://doi. nanocomposites via pickering emulsion. Composites Part B: Engineering, 121, 99–107.
org/10.1016/J.CARBPOL.2017.10.002. https://doi.org/10.1016/j.compositesb.2017.03.032.
Salehi, E., Daraei, P., & Arabi Shamsabadi, A. (2016). A review on chitosan-based Wani, T. A., Shah, A. G., Wani, S. M., Wani, I. A., Masoodi, F. A., Nissar, N., …
adsorptive membranes. Carbohydrate Polymers, 152, 419–432. https://doi.org/ Shagoo, M. A. (2016). Suitability of different food grade materials for the
10.1016/J.CARBPOL.2016.07.033. encapsulation of some functional foods well reported for their advantages and
Schulz, P. C., Rodríguez, M. S., Del Blanco, L. F., Pistonesi, M., & Agulló, E. (1998). susceptibility. Critical Reviews in Food Science and Nutrition, 56(15), 2431–2454.
Emulsification properties of chitosan. Colloid and Polymer Science, 276(12), https://doi.org/10.1080/10408398.2013.845814.
1159–1165. https://doi.org/10.1007/s003960050359. Wei, Z., Wang, C., Zou, S., Liu, H., & Tong, Z. (2012). Chitosan nanoparticles as
Shah, B. R., Li, Y., Jin, W., An, Y., He, L., Li, Z., … Li, B. (2016). Preparation and particular emulsifier for preparation of novel pH-responsive Pickering emulsions and
optimization of Pickering emulsion stabilized by chitosan-tripolyphosphate PLGA microcapsules. Polymer, 53(6), 1229–1235. https://doi.org/10.1016/J.
nanoparticles for curcumin encapsulation. Food Hydrocolloids, 52, 369–377. https:// POLYMER.2012.02.015.
doi.org/10.1016/J.FOODHYD.2015.07.015. Wongkongkatep, P., Manopwisedjaroen, K., Tiposoth, P., Archakunakorn, S.,
Shah, B. R., Zhang, C., Li, Y., & Li, B. (2016). Bioaccessibility and antioxidant activity of Pongtharangkul, T., Suphantharika, M., … Wongkongkatep, J. (2012). Bacteria
curcumin after encapsulated by nano and Pickering emulsion based on chitosan- interface pickering emulsions stabilized by self-assembled bacteria-chitosan
tripolyphosphate nanoparticles. Food Research International, 89, 399–407. https:// network. Langmuir, 28(13), 5729–5736. https://doi.org/10.1021/la300660x.
doi.org/10.1016/j.foodres.2016.08.022. Wu, D., Zhu, L., Li, Y., Zhang, X., Xu, S., Yang, G., … Delair, T. (2020). Chitosan-based
Sharkawy, A., Barreiro, M. F., & Rodrigues, A. E. (2019). Preparation of chitosan/gum colloidal polyelectrolyte complexes for drug delivery: A review. Carbohydrate
Arabic nanoparticles and their use as novel stabilizers in oil/water Pickering Polymers, 238. https://doi.org/10.1016/j.carbpol.2020.116126.
emulsions. Carbohydrate Polymers, 224, Article 115190. https://doi.org/10.1016/J. Xiao, J., Shi, C., Li, Y., Pan, Y., & Huang, Q. (2017). Pickering emulsions immobilized
CARBPOL.2019.115190. within hydrogel matrix with enhanced resistance against harsh processing
Sharkawy, A., Casimiro, F. M., Barreiro, M. F., & Rodrigues, A. E. (2020). Enhancing conditions and sequential digestion. Food Hydrocolloids, 62, 35–42. https://doi.org/
trans-resveratrol topical delivery and photostability through entrapment in 10.1016/J.FOODHYD.2016.07.025.
chitosan/gum Arabic Pickering emulsions. International Journal of Biological Yan, C., McClements, D. J., Zhu, Y., Zou, L., Zhou, W., & Liu, W. (2019). Fabrication of
Macromolecules, 147, 150–159. https://doi.org/10.1016/J.IJBIOMAC.2020.01.057. OSA starch/chitosan polysaccharide-based high internal phase emulsion via altering
17
A. Sharkawy et al. Carbohydrate Polymers 250 (2020) 116885
interfacial behaviors. Journal of Agricultural and Food Chemistry, 67(39), Zhang, R., Hao, H., Zhang, C., Yang, R., Sun, M., Wong, C. P., … Xu, Y. (2019).
10937–10946. https://doi.org/10.1021/acs.jafc.9b04009. Bioadhesive hydrocaffeic acid modified chitosan colloidal particles using as
Yang, Y., Fang, Z., Chen, X., Zhang, W., Xie, Y., Chen, Y., … Yuan, W. (2017). An particulate emulsifiers. Journal of Dispersion Science and Technology, 40(11),
overview of pickering emulsions: Solid-particle materials, classification, 1559–1566. https://doi.org/10.1080/01932691.2018.1484755.
morphology, and applications. Frontiers in Pharmacology, 8(MAY). https://doi.org/ Zhang, S., Zhou, Y., & Yang, C. (2015). Pickering emulsions stabilized by the complex of
10.3389/fphar.2017.00287. polystyrene particles and chitosan. Colloids and Surfaces A: Physicochemical and
Yao, X., Wang, N., Fang, Y., Phillips, G. O., Jiang, F., Hu, J., … Tian, D. (2013). Impact of Engineering Aspects, 482, 338–344. https://doi.org/10.1016/J.
surfactants on the lipase digestibility of gum arabic-stabilized O/W emulsions. Food COLSURFA.2015.06.029.
Hydrocolloids, 33(2), 393–401. https://doi.org/10.1016/j.foodhyd.2013.04.013. Zhang, Y., Xu, X., Wang, Q., Zhang, H., Qian, A., Liu, T., … Xia, Q. (2017). Preparation
Yuan, D. B., Hu, Y. Q., Zeng, T., Yin, S. W., Tang, C. H., & Yang, X. Q. (2017). and characterization of colloidal particles synergistic with emulsifier stabilizing
Development of stable Pickering emulsions/oil powders and Pickering HIPEs Pickering emulsion. Integrated Ferroelectrics, 180(1), 24–36. https://doi.org/
stabilized by gliadin/chitosan complex particles. Food and Function, 8(6), 10.1080/10584587.2017.1336420.
2220–2230. https://doi.org/10.1039/c7fo00418d. Zhao, D., Wei, W., Zhu, Y., Sun, J., Hu, Q., & Liu, X. (2015). Stable emulsions prepared by
Zeng, T., Wu, Z., Zhu, J. Y., Yin, S. W., Tang, C. H., Wu, L. Y., … Yang, X. Q. (2017). self-assembly of hyaluronic acid and chitosan for papain loading. Macromolecular
Development of antioxidant Pickering high internal phase emulsions (HIPEs) Bioscience, 15(4), 558–567. https://doi.org/10.1002/mabi.201400486.
stabilized by protein/polysaccharide hybrid particles as potential alternative for Zhou, F. Z., Yu, X. H., Zeng, T., Yin, S. W., Tang, C. H., & Yang, X. Q. (2019). Fabrication
PHOs. Food Chemistry, 231, 122–130. https://doi.org/10.1016/j. and characterization of novel water-insoluble protein porous materials derived from
foodchem.2017.03.116. pickering high internal-phase emulsions stabilized by gliadin-chitosan-complex
Zhang, L., & Que, G. (2008). Influence of the HLB parameter of surfactants on the particles. Journal of Agricultural and Food Chemistry, 67(12), 3423–3431. https://doi.
dispersion properties of brine in residue. Colloids and Surfaces A: Physicochemical and org/10.1021/acs.jafc.9b00221.
Engineering Aspects, 320(1–3), 111–114. https://doi.org/10.1016/J. Zou, T., Sipponen, M. H., & Österberg, M. (2019). Natural shape-retaining microcapsules
COLSURFA.2008.01.035. with shells made of chitosan-coated colloidal lignin particles. Frontiers in Chemistry, 7
(MAY). https://doi.org/10.3389/fchem.2019.00370.
18