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Food Research International 137 (2020) 109376

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Food Research International


journal homepage: www.elsevier.com/locate/foodres

Review

Recent advances in improving stability of food emulsion by plant T


polysaccharides
⁎ ⁎
Ping Shaoa, , Jieru Fenga, Peilong Suna, , Ning Xianga, Baiyi Lub, Dan Qiuc
a
Department of Food Science and Technology, Zhejiang University of Technology, Zhejiang, Hangzhou 310014, PR China
b
Department of Food Science and Nutrition, College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou 310058, PR China
c
School of Materials and Chemical Engineering, Ningbo University of Technology, Zhejiang, Ningbo 315211, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Emulsion is considered to be an excellent system for delivering nutraceuticals, but instability limits the appli-
Plant polysaccharides cation of the emulsion. Adding stabilizers is an effective method to improve the stability of the emulsion. Due to
Emulsion safety concerns, stabilizers from natural resources are attracting more and more attentions in food industry.
Interface Plant polysaccharides are natural biopolymers which are widely distributed in the cells of plants. Many plant
Stability
polysaccharides have been shown good emulsifying and thickening effects, therefore, they are widely used as
Steric interactions
stabilizers in emulsions. The application of plant polysaccharides in improving emulsion stability was reviewed
Electrostatic interactions
Polysaccharide characteristics in this paper. Firstly, the factors affecting the stability of the emulsion were elaborated in detail. On this basis,
the methods of improving the stability of the emulsion were discussed. Furthermore, the effects of the plant
polysaccharide structures on emulsion stability were explained, such as the molecular weight of the poly-
saccharide, the hydrophobic group of the polysaccharide, and the protein content of the polysaccharide.
Additionally, the application of several common plant polysaccharides and their derivatives in emulsions were
introduced. It is hoped that this review can provide sufficient theoretical basis for application of plant poly-
saccharides in emulsions in the future.

1. Introduction and effective approach for improving emulsion stability. Stabilizers are
mainly classified into three types: texture modifiers, ripening inhibitors,
Many bioactive components are considered to be nutraceuticals and weighting agents (Mcclements, 2011). Although most of these
which are beneficial to human health. However, low oral bioavail- stabilizers have no or only weak emulsifying properties, their interac-
ability limits their applications. Generally, bioactive components are tions with emulsifiers induce the formation of stable film at the oil and
incorporated into appropriate delivery systems for improvement of water interface to improve the stability. The stabilizers can also prevent
bioavailability. A wide range of colloidal delivery systems have been flocculation by forming a gel network structure in the emulsion system
developed to encapsulate bioactive components, such as molecular (Anal, Shrestha, & Sadiq, 2019). However, many stabilizers are derived
complexes, emulsions, liposomes, microemulsions, microgels, and bio- from toxic and synthetic materials, making them unsuitable for human
polymer particles. Emulsion-based delivery systems are particularly consumption. In order to develop edible emulsions for expanding their
suitable for protection of nutraceuticals because of mature application applications in food systems, applications of natural biopolymers as
in the food industry. However, many applications of emulsions are food-grade stabilizers with no or minimal toxicity concern have been
limited because of their undesirable physical and chemical stabilities explored extensively since last decade (Wei & Huang, 2019; Wei,
(Ghosh & Rousseau, 2011; Lam & Nickerson, 2013; Narukulla, Ojha, & Zheng, & Song, 2018; Xu, Sun, & Mcclements, 2019).
Sharma, 2019). At present, the common methods that are used to im- Polysaccharides are natural biopolymers with low toxicity, high
prove the stability of emulsions fall into the three major approaches: biocompatibility and biodegradability (Yang, Han, Zheng, Dong, & Liu,
chemical modification of emulsifiers, use of stabilizers, and optimiza- 2015). Natural polysaccharides can be extracted from the sources of
tion of fabrication techniques (Burgos-Díaz, Wandersleben, Marqués, & animals, plants and microorganisms, among which plants are the most
Rubilar, 2016; Gharibzahedi et al., 2019; Mcclements & Jafari, 2017). abundant sources for food-grade polysaccharides (Bai, Huan, Gu, &
Among the above methods, the use of stabilizers is the most convenient McClements, 2016; Koen, Martens, Kevin, Jo, & Smedt, 2013). Plant


Corresponding authors.
E-mail addresses: pingshao325@zjut.edu.cn (P. Shao), sunpl1964@163.com (P. Sun).

https://doi.org/10.1016/j.foodres.2020.109376
Received 31 January 2020; Received in revised form 11 May 2020; Accepted 2 June 2020
Available online 04 June 2020
0963-9969/ © 2020 Elsevier Ltd. All rights reserved.
P. Shao, et al. Food Research International 137 (2020) 109376

polysaccharides are natural polymers and account for the largest pro- 2.1.1. Steric interactions
portion of all biomass. Plant polysaccharides are widely found in the Steric interactions are the dominant factor affecting emulsion sta-
cell walls of plants. They are composed of a variety of monosaccharides, bility which is closely related to the interfacial properties of an emul-
and their structures are quite different. Compared with other biopoly- sion system. During the formation of emulsion, the emulsifier adsorbs
mers, their large number of reactive functional groups have excellent on the oil–water interface of the droplets to form a stable emulsion
modifiability. The common feature of plant polysaccharides is their (Oss, 2007). The different types of emulsifiers result in different inter-
stable structures due to their strong intermolecular interactions, making facial layer thicknesses, which have a strong influence on the strength
them difficult to be deformed with the changes of pH and temperature. of the steric interaction between the droplets. When the interfacial layer
In addition, they have strong hydrophilicity and viscosity which can formed by the emulsifier which has sufficient thickness, the emulsion is
change rheological properties of the fluid system. In fact, they are stabilized by strong spatial repulsive force (Tadros, 2015). However,
biodegradable polymers with a variety of physical, chemical and bio- when the interface layer of the droplet is not thick enough, it tends to
logical properties. From a resource perspective, plants can be con- cause the emulsion destabilization and lose its original physicochemical
sidered as one of the most important sources of polysaccharides. properties (Fig. 2) (Cai et al., 2018). One example of such destabiliza-
Moreover, low processing cost and superior biological properties make tion is the occurrence of creaming phenomenon and Ostwald ripening.
them suitable for use as food emulsion stabilizers. Because of these Creaming occurs when the density of the droplet (dispersed phase) is
reasons, plant polysaccharides, such as pectin, cellulose and starch are lower than that of the continuous phase. The density of the droplet can
considered as excellent emulsion stabilizers, and are widely used in the be explained by the following equation:
preparation of emulsions for food applications (Bai, Greca, et al., 2019;
rρcore + 3δρshell
Bai, Lv, et al., 2019; Hu et al., 2016; Jain & Anal, 2018; Salminen & ρ=
r + 3δ (1)
Weiss, 2014).
In industrial production, most emulsions are stabilized by com- where ρ is the total density of the droplets, ρcore is the density of pure oil
bining emulsifiers with plant polysaccharides (Dickinson, 2011). Pre- droplets, ρshell is the density of droplets containing emulsifiers, and δ is
vious studies showed that different mechanisms led to different abilities the thickness of the interfacial layer. According to the above equation,
of polysaccharides for improving emulsion stability. Recent papers only the ρ value would increase when the density of the interfacial layer
outlined mechanisms on improvement of emulsion stability by poly- increased. Therefore, the sparse interfacial layer would lead to a re-
saccharides, but the characteristics of different polysaccharides were duction in the droplet density of the emulsion, thus triggering the
not discussed. Plant polysaccharides are widely used in food emulsions, creaming phenomenon. Ostwald ripening is the key factor leading to
so it is important to analyze the mechanism of different polysaccharides destabilization of emulsions (Benjamin, Monika, Lutz, & Jochen, 2012;
for improving emulsion stability. It helps to provide a theoretical basis Suriyarak & Weiss, 2014). In the process of Ostwald ripening, smaller
for selection and application of suitable polysaccharides in different droplets in the emulsion system increase the size of larger droplets at
emulsion systems. In order to deepen the understanding of plant the expense of themselves. The driving force for this process is the
polysaccharides as emulsion stabilizers, this review focuses on the effect higher solubility of the oil molecules in the vicinity of the smaller
of different polysaccharide characteristics on improving emulsion sta- droplets compared to the larger droplets due to curvature effects
bility. The characteristics of gum arabic, pectin, alginate and starch and (Kabalnov & Shchukin, 1992). The rate of this process can be described
other plant polysaccharides in emulsions were summarized separately by Eq. (2).
as well. There are many researchers conducted in-depth and completely d < r >3 8γVm S∞ D
new research on these polysaccharides in recent years. These studies =
dt 9RT (2)
have helped to improve their application efficiency in emulsions, so
they were also discussed. It is hoped that this review will provide suf- Here S∞ is the equilibrium solubility of oil phase in water phase, γ is
ficient theoretical basis for application of plant polysaccharides in the interfacial tension, r is the radius of droplets, Vm is the volume of
emulsions in the future. oil phase, T is the absolute temperature, R is the gas constant, and D is
the translation diffusion coefficient of oil through water phase.
Therefore, there are a number of factors may impact the rate of Ostwald
2. Emulsion stability ripening.

2.1. Factors affecting emulsion stability 2.1.2. Electrostatic interactions


When the interfacial strength of the droplets is insufficient, the
Emulsion can be easily destabilized under various conditions during electrostatic interactions will play a key role in the stability of the
preparation and storage. Therefore, it is necessary to understand the emulsion. It is a short-to-long range interaction when droplets carry
factors that influence the stability of the emulsion, which is essential for electrical charges. The intensity of the electrostatic repulsion relates to
subsequent studies of emulsion stability. The factors affecting the sta- the charge density and ionic strength of the droplets. Once the elec-
bility of emulsions generally fall into two categories: steric interactions trostatic interaction weakens, the emulsion may become unstable. In
and electrostatic interactions (Fig. 1). this case, coalescence and flocculation are the main mechanisms of
emulsion destabilization. Their mechanisms are similar, with the

Fig. 1. The different interactions between droplets that affect the stability of the emulsion.

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P. Shao, et al. Food Research International 137 (2020) 109376

Fig. 2. Different mechanisms of emulsion instability (Creaming, Flocculation, Coalescence, Sedimentation and Ostwald ripening).

common feature that the electrostatic repulsion between droplets is not 2018). The structure of plant polysaccharides from different sources
strong enough to resist the attractive interaction (Van der Waals in- varies greatly. They are long-chain polymers which consist of different
teraction) (Delahaije, Hilgers, Wierenga, & Gruppen, 2017). In the monosaccharides by glycoside bonds. These polysaccharides are mate-
meantime, coalescence rupture the interfacial layer of the smaller rials that support the structure of plants. Because of their excellent
droplets and then they fuse together to form larger droplets. biocompatibility and biodegradability, they are often used in the pro-
duction of products closely related to human life. In addition, poly-
2.2. Methods for improving emulsion stability saccharides have high physicochemical characteristics of high hydro-
philicity and high viscosity, which can change the rheological
Based on the factors affecting emulsion stability, the researchers properties of many systems (Shao, Shao, Jiang, & Sun, 2016). According
have developed a number of methods to improve emulsion stability, to many research results, they also have relatively stable structures and
which have been proved to be effective. Optimization of producing do not denature due to slight changes in the temperature, pH and ion
process is the most commonly used method. Energy input must be ap- concentration of the system (Qian, Decker, Xiao, & McClements, 2011).
plied to obtain a stable emulsion system. Currently, emulsions are Consequently, plant polysaccharides have good safety and excellent
generally prepared by high pressure homogenization, ultrasonic tech- stability, they are suitable for addition to food emulsion systems.
nology, or microchannel emulsification (MCE) (Bai et al., 2016; Khalid,
Shu, Kobayashi, Nakajima, & Barrow, 2017). The coarse emulsion is 3.1. Mechanism of polysaccharides improving emulsion stability
impacted by strong mechanical force (rapid pressure drop and shock) in
the high pressure homogenizer, causing implosion of cavitation bub- There are many kinds of plants on the earth, polysaccharides come
bles, resulting in breaking larger droplets (Floury, Desrumaux, & from various sources and have different structures. The physicochem-
Lardières, 2000). In addition to improving the processing method, the ical properties of polysaccharides are different due to their diversified
most effective way to improve the stability of the emulsion is to add structures, so there is a great gap between the antioxidant effect,
stabilizers which can compensate the defects of the emulsifiers rheological properties and emulsifying effect of different poly-
(Mcclements, Bai, & Chung, 2017). For example, emulsifiers and sta- saccharides. Accordingly, the mechanisms about stabilizing emulsions
bilizers with the same negative charge at the oil–water interface in- by different polysaccharides are not the same (Bai, Huan, Li, &
crease the total negative charge on the droplets, thereby preventing the McClements, 2017). In addition to hydrophilic hydroxyl groups, some
droplets from coalescence to larger particles (Zhao et al., 2015). Many polysaccharides contain acetyl and methoxy groups, thus they are
researchers believe that polysaccharides are the preferred stabilizer. Xu amphiphilic (Dickinson, 2003). In this case, the polysaccharide adsorb
et al. used the soybean polysaccharide to assist sodium caseinate to at the oil–water interface, reducing the interfacial tension and forming
stabilize the emulsion, which formed a dense interfacial film through stable droplets. The morphology of the polysaccharide at the oil–water
electrostatic and hydrophobic interactions, thereby improving emulsion interface is related to its free energy of mixing with the solvent
stability (Xu, Wang, & Ping, 2017). Xanthan gum is a high viscous (Kontogiorgos, 2019). They can be analyzed by the following thermo-
polysaccharide that is often added to emulsions to improve stability. dynamic formulas (Eq. (3), Eq. (4), Eq. (5)).
They form a network of oil droplets by increasing the viscosity of the (3)
ΔG = ΔH − T ΔS
continuous phase and delaying the speed of creaming (Krstonošić,
Dokić, Nikolić, & Milanović, 2015). Similar polysaccharides have been Here, ΔG is free energy, ΔH is enthalpy, T is temperature, ΔS is
widely used in the production of food products such as ice cream, entropy.
beverages, and cakes (Cheng, Ying, Li, Yan, & Jie, 2015; Lin, Tay, Yang,
ΔS = −k (n1lnφ1 + n2lnφ2) (4)
Yang, & Li, 2017; Liu et al., 2017).
Here, k is Boltzmann constant, n1 or n2 is the amount of solvent or
3. Plant polysaccharides improve emulsion stability polysaccharide molecules, φ1 or φ2 is volume fraction of solvent or
polysaccharide molecules.
Plant polysaccharides are natural macromolecular polymers that are ΔH = n1 φ2 χkT (5)
widely found in the cell walls of plants and have molecular weights
ranging from tens of thousands to millions Da (Yu, Shen, Song, & Xie, Here, χ is the dimensionless Flory–Huggins interaction parameter.

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P. Shao, et al. Food Research International 137 (2020) 109376

Fig. 3. Polysaccharides adsorb at the oil–-


water interface in different states. The hy-
drophilic chain is represented by the green
line and the hydrophobic chain is re-
presented by the red line. (a) homopolymer;
(b) diblock copolymer; (c) triblock copo-
lymer; (d) random copolymer; (e) branched
copolymer. (For interpretation of the refer-
ences to colour in this figure legend, the
reader is referred to the web version of this
article.)

Fig. 4. The diffusion, penetration and rearrangement of proteins at the oil–water interface are promoted by gum arabic.

Fig. 5. Micrographs of complex coacervates,


coacervated microcapsules using upright
microscope. (A) Gelatin and high methyl
pectin coacervate; (B) Cinnamaldehyde
multinuclear microcapsules based on gelatin
and high methyl pectin; (C) Gelatin and low
methyl pectin coacervate; (D)
Cinnamaldehyde multinuclear micro-
capsules based on gelatin and low methyl
pectin (Bertrand et al., 2019).

Therefore, χ plays a decisive role in the state of the polysaccharide polysaccharide chain at the interface can be roughly classified into five
in the solvent. When χ < 0.5, the polymer can be well dissolved in the types (Fig. 3). In one case, the molecular chains of the polysaccharide
solvent. Since the polysaccharide is adsorbed on the surface of the are all closely adsorbed on the surface of the droplets (Fig. 3a). Once the
droplet, it is dissolved in a solvent of χ < 0.5 while having the hy- concentration of the polysaccharide reaches a certain level, they in-
drophobic portion of χ > 0.5. At this time, the conformation of the evitably stick to the surface of multiple droplets, resulting in bridge

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P. Shao, et al. Food Research International 137 (2020) 109376

flocculation (Adachi & Xiao, 2013). In another case, part of the mole-

Yang, Liu, & Han, 2017


Fioramonti et al., 2019
cular chains of polysaccharides are adsorbed on the oil–water interface.

Yesiltas et al., 2018


Iqbal et al., 2019
Zhao et al., 2018 A random copolymer like that illustrated schematically in Fig. 3d has

Sato et al., 2014

Dai et al., 2018


several separate regions available for anchoring to the surface. Fig. 3b
Reference

and c show the structures of the diblock copolymer and the triblock
copolymer which are adsorbed at the interface, and the repulsive force
between the polymers makes the system spatially stable. Some poly-
saccharides have multiple branches, and the system is stabilized by one
Stronger electrostatic complexes were formed by whey protein isolate and sodium alginate, forming a rigid emulsion

The presence of alginate increased the viscosity of the emulsion, delayed the diffusion of oxygen within the system,
When the pH of the emulsion reduces to 4–5, sodium alginate will adsorb on the protein layer to form the double

of the hydrophobic branched chains adsorbed at the interface (Fig. 3e).

The zein-propylene glycol alginate particle forms a densely packed layer around the surface of the oil droplets to
The modified alginate increased the stability of the emulsion and the emulsion had a lower creaming index. In addition to the polysaccharides mentioned above, some poly-
saccharides have poor lipophilic properties and cannot be adsorbed at
the oil–water interface, but they still function to stabilize the emulsions.
Although these polysaccharides are difficult to adsorb on the oil–water
interface, they can wrap on the droplet surface. Therefore, poly-
saccharides and emulsifiers stabilize the emulsion through electrostatic
interaction and steric interaction (Xu, Luo, Liu, & Mcclements, 2017).
The remaining polysaccharides are dispersed in the continuous phase,
they have the ability to thicken or form a three-dimensional gel-like
The particle size of emulsion droplets under microscope is small and uniform.

droplet network, thereby hindering the movement of the droplets to


Alginate improved emulsion freeze–thaw stability by inhibiting coalescence.

interfacial layer and increase the absolute value of the emulsion potential.

prevent aggregation.

3.2. Effect of polysaccharide characteristics on improving emulsion stability

3.2.1. Molecular weight of polysaccharides


Molecular weight is the most significant characteristic of poly-
saccharides. Therefore, molecular weight is crucial for the stabilization
effect of polysaccharides on the emulsion. Generally, for polysaccharide
with emulsifying properties, the lower the molecular weight it has, the
faster it adsorbs to the oil–water interface. Li et al. used the xylanase to
thus prevented oxidation of the grease.

hydrolyze Artemisia sphaerocephala Krasch polysaccharide. They found


ensure the stability of the emulsion.

that the interfacial tension was significantly reduced by the low mole-
cular weight polysaccharide, which helped to reduce the free energy on
the interface (Li et al., 2016). Degradation of polysaccharides by Fe,
H2O2 and vitamin C showed that polysaccharides with low molecular
weight were easier to migrate to the interface. According to the de-
scription in Section 3.1, the polysaccharide that does not adsorb on the
interface may also play a role in preventing the emulsion from desta-
Stability

bilization. In this case, the higher molecular weight allows the poly-
saccharide to have a stronger ability to stabilize the emulsion. For ex-
gel.

ample, β-glucan contains only hydrophilic groups, whereas the higher


molecular weight oat β-glucan has a better thickening effect than barley
double-layered O/W

β-glucan (Karp, Wyrwisz, & Kurek, 2019). Therefore, the emulsion


Emulsion type

which had oat β-glucan added has a higher viscosity and a better sta-
bility.
O/W

W/O

O/W

O/W

O/W
O/W

3.2.2. Lipophilic groups of polysaccharide


Some plant polysaccharides in nature not only have hydrophilic
Octyl-grafted alginate-amide gel particle
Zein - propylene glycol alginate particle
Sugar ester and alginate, Tween 20 and
The application of different alginates in emulsion preparation.

groups, but also are connected with lipophilic groups. These poly-
Whey protein and Sodium alginate

Sodium caseinate and succinylated

saccharides have the possibility of adsorbing at the emulsion droplet


Whey protein isolate and Sodium

interface because of their lipophilic groups. Together with other


Gelatin and Sodium alginate

emulsifiers, they reduce the interfacial tension and stabilize the emul-
Emulsifiers and stabilizers

sion. The spruce galactoglucomannans obtained from the spruce saw-


dust is the good natural emulsifier because they are highly acetylated
(Bhattarai et al., 2018). In addition to natural amphiphilic poly-
saccharides, other polysaccharides can be further chemically modified
to covalently attach hydrophobic groups. It confers to the poly-
alginate

alginate

alginate

saccharide macromolecules the capacity to strongly adsorb at oil/water


interfaces. Amphiphilic alginates can be obtained by covalently cou-
pling dodecanol with sodium alginate via ester functional groups, ef-
Propylene glycol alginate

fectively reducing the interfacial tension (Yang, Jiang, He, & Xia, 2012).
Octyl-grafted alginate
Succinylated alginate

In addition, the nature, amount and substitution pattern of attached


Sodium alginate

Sodium alginate

Sodium alginate

hydrocarbon groups, may have a significant effect on the stabilizing


Alginate type

properties of these derivatives of polysaccharides. For example, it has


Alginate

been proved that amphiphilic dextran derivatives can be obtained by


Table 1

connecting various amounts of hydrocarbon aromatic groups to the


dextran chain. Dynamic interface tension measurements showed that

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P. Shao, et al. Food Research International 137 (2020) 109376

Fig. 6. Schematic illustration of the emulsifying and stability mechanism of OSA-starches with multi-scale structures (Zhao et al., 2018).

dextran derivatives with 20% degree of substitution could reduce the 4. Application of plant polysaccharide in improving emulsion
interfacial tension more effectively than other dextran derivatives stability
(Desbrières et al., 2017).
At present, natural plant polysaccharides have been widely used in
emulsion productions. Gum arabic, pectin, sodium alginate and starch
3.2.3. Protein content of polysaccharide are all abundant plant polysaccharides in nature, and their different
There are also some polysaccharides that contain proteins in their structural characteristics lead to different application effects. This re-
structure, which give them excellent emulsifying properties. These view will describe the structural characteristics of different poly-
polysaccharides have the following characteristics at the oil–water in- saccharides and summarize their recent application trends in emul-
terface. The protein-rich parts of the polysaccharide chain adsorb on sions, which provides evidence for future emulsion research.
the oil surface, while the hydrophilic parts protrude into the aqueous
solution. As the size is usually big, the polysaccharide chains adsorb
4.1. Gum arabic
slowly to the interface. Once at the interface, the protein portions are
unraveled to expose buried hydrophobic amino acids and then these
Gum arabic is a natural polysaccharide derived from acacia senegal
proteins realign themselves within the oil phase to develop a viscoe-
or acacia seyal. They are widely used in the food industry due to their
lastic film along with carbohydrate moieties within the aqueous phase
excellent emulsifying properties. The gum arabic is characterized by a
(Jin et al., 2017). The Ulva fasciata polysaccharide is derived from a
highly branched structure with a core of β1,3-linked galactose residue.
marine algae plant. The purified polysaccharide contains 0.81% pro-
Gum arabic contains a small amount of protein. Researchers have
tein, which gives it a certain emulsifying ability to prepare stable
confirmed that it is an arabinogalactan-protein complex, an extra-
emulsions (Shao, Qiu, Xiao, Zhu, & Sun, 2017). Sun et al. studied the
cellular proteoglycan involved in plant growth and development
amphiphilicity of flaxseed gum and found that it played a stabilizing
(Mahendran, Williams, Phillips, Al-Assaf, & Baldwin, 2008). In view of
role in emulsion, which was probably owing to its emulsifying proteins.
such characteristics, the emulsion was stabilized by gum arabic and
And the abundant hydrophobic amino acids in flaxseed gum contribute
emulsifiers which were adsorbed at the interface. With regard to the
to protein emulsification, the content of hydrophobic amino acids in
application of gum arabic in emulsions, the focus is now on improving
flaxseed gum is about 24% of total amino acids (Sun, Liu, Feng, Xu, &
the stability of protein-stabilized emulsions. This is due to the fact that
Zhou, 2019). Polysaccharides of this type have been widely used in the
emulsions prepared from proteins with excellent biological properties
food and pharmaceutical fields to deliver bioactive compounds.
are more suitable for human use. A solely protein system is generally

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P. Shao, et al. Food Research International 137 (2020) 109376

highly susceptible to environmental damage. In order to prevent or

Shrestha et al., 2018

Consoli et al., 2018

Chung et al., 2014

Zhong et al., 2018


delay this phenomenon, another biological macromolecule poly-

Li et al., 2019
saccharide is selected to add to compensate for protein defects. Dif-
ferent from other surfactants, protein adsorption at the oil–water in-
Reference

terface is divided into three stages (diffusion, penetration and


rearrangement). Gum arabic interacts with proteins to form the com-
plex through electrostatic interaction, thus promoting the adsorption of
Protein-polysaccharide conjugates have lower interfacial tension, and the conjugates formed by heating
The emulsion prepared from the conjugate has better creaming stability than the emulsion containing

proteins at the interface (Shao, Feng, Sun, & Ritzoulis, 2019). As shown
Starch plays a decisive role in the rheology of the emulsion, increasing the viscosity of the emulsion.

in Fig. 4, during the slow adsorption of proteins at the interface, gum


arabic acted as a promoter, allowing more protein to adsorb at the
oil–water interface. In addition, the preparation of protein-gum arabic
Starch increases the environmental stability of the emulsion at high ion concentrations.

conjugates by Maillard reaction is also an effective method. Zha et al.


The nanogel is adsorbed at the oil–water interface to form a dense interfacial layer.

incubated pea protein isolate and gum arabic to form Maillard reaction
products (Zha, Dong, Rao, & Chen, 2019). The formation of conjugates
greatly improved the solubility of proteins. At the same time, the ne-
gative charges around the protein molecules and the conjugated layer
promoted the electrostatic and steric repulsion between droplets, in-
creasing thermal stability of the emulsion. It is worth noting that due to
the highly branched structure and lowe molecular weight, gum arabic
does not significantly increase the viscosity of the emulsion. According
to this characteristic of gum arabic, it can be applied to suitable sys-
tems.
improve their ability to stabilize emulsions.

4.2. Pectin

Pectin is widely distributed in the cell wall of plants and the middle
layer of higher plants, which forms compact plant tissues by combining
with cellulose (Luo et al., 2017). Pectins sold in the market are mainly
extracted from by-products of citrus, sugar beet and apple. Due to the
wide range of the sources, the structures of pectins have large differ-
ences. D-galacturonic acid (D-GalA), an isomer of d-glucuronic acid (D-
only protein.

GlcA) is found to be a major constituent of all pectins (Marić et al.,


Stability

2018). According to the degree of methylation (DM) of C-6 carbox-


ymethyl group of GalA, pectin is classified into high DM pectin (HMP)
or low DM pectin (LMP). The methoxy group attached to the pectin
Emulsion type

chain is a hydrophobic group resulting in the certain emulsifying


property. When the hydrophobic group and the hydrophilic group
reach to a suitable ratio, it will provide good emulsifying property. The
O/W

O/W

O/W
O/W

O/W

pectins of three DE values (DE = 55, 70 and 84%) were analyzed for
interfacial and emulsifying properties. With the increase of DE, the
Tween 80, modified corn starch and locust bean gum
Sodium caseinate-corn starch hydrolysates conjugate

characteristic droplet size D90,3 of the emulsion decreased significantly


Culled banana resistant starch-soy protein isolate

(Schmidt, Schütz, & Schuchmann, 2017). The results indicated that


Phosphatidylcholine and OSA-modified starch
Chitosan hydrochloride/carboxymethyl starch

pectin with high esterification had stronger adsorption capacity at the


interface. Pectin has been used to prepare composite coagulants with
gelatin to encapsulate cinnamaldehyde. The particle size of the micro-
capsules encapsulated by HMP was smaller than LMP (Bertrand et al.,
The application of different starches in emulsion preparation.

2019) (Fig. 5). This was attributed to the fact that HMP adsorption
Emulsifiers and stabilizers

increased the emulsification effect of the emulsifier at the interface. The


findings have also shown that HMP inhibited flocculation of droplets
because of its high viscosity. LMP has the higher charge density and
stabilizes the emulsion by electrostatic interaction between the dro-
plets, which is not as effective as HMP. The W1/O/W2 nano-emulsions
conjugate

complex

prepared from whey protein-pectin complex and Tween 80 were com-


pared (Gharehbeglou, Jafari, Hamishekar, Homayouni, & Mirzaei,
2019). The change in the creaming index over time showed that the
Waxy maize modified corn starch

pectin added to the continuous phase increased the viscosity of the


Culled banana resistant starch

emulsion and reduced the creaming rate. Therefore, both HPM and LPM
have the ability to improve emulsion stability. HPM improves the
Corn starch hydrolysates

emulsion stability by reducing interfacial tension and increasing system


Carboxymethyl starch

OSA-modified starch

viscosity. LPM carries a lot of electric charge, and it inhibits the ag-
gregation of droplets through electrostatic interaction. However, LMP
Starch type

can easily cause the emulsion to form the gel structure, and the system
environment should be paid attention to when it is used.
Table 2

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P. Shao, et al. Food Research International 137 (2020) 109376

4.3. Alginate and its derivatives determinant of particle stability (Villamonte, Jury, & de Lamballerie,
2017). Some gelatinized starch can act as an emulsifier, such as waxy
Algae plants are widely distributed in waters, and alginates are rich rice starches, corn starches, wheat starches, and waxy corn starches
in their cells to form cell wall components or stored inside cells (Luría, Carter, Ramirez, & Sosa, 2019). During gelatinization, the starch
(Tavassoli-Kafrani, Shekarchizadeh, & Masoudpour-Behabadi, 2016). granules absorb water, which leads to both swelling and melting of the
Alginate is characterized by an unbranched block copolymer containing crystallites of starch granules (Ratnayake & Jackson, 2006). The per-
homopolymeric or heteromeric blocks of mannuronic acid and gu- formance of gelatinized starch acting as an emulsifier relies upon the
luronic acid units (Shanura, Daekyung, Jae-Woon, & You-Jin, 2019). degree of gelatinization. Emulsions prepared from starch with a high
Since alginates can be obtained from different algae varieties, they can degree of gelatinization had the smaller particle size and higher stabi-
have different physicochemical properties. Different composition and lity (Yulianingsih & Gohtani, 2019). Starch with a high degree of ge-
arrangement of uronic acid residues lead to their physicochemical latinization formed more the melted starch polymer in emulsions. The
properties. They are anionic polysaccharides with no emulsifying ac- polymer network, exhibiting steric repulsion, was thought to play an
tivity. They stabilized emulsion droplets primarily by electrostatic in- essential role in emulsion stabilization. Modification of octenyl succinic
teractions in the continuous phase. In order to expand the application of anhydride is the research trend of starch in recent years. As for the
alginate in emulsion, recent researches have focused on the preparation emulsification of the octenyl succinic anhydride (OSA) modified starch,
of amphiphilic alginate. The main chain of the alginate is attached with the hydrophobic OSA is grafted to the starch chain to enhance the
a number of hydroxyl groups and carboxyl groups, so that it is easy to hydrophobicity of the starch. It is noteworthy that the difference of
obtain various derivatives by chemical modification (Yang, Xie, & He, molecular weight and degree of substitution of starch result in different
2011). The hydroxyl group of the alginate can be oxidized to form the emulsifying stability of OSA modified starch (Zhao et al., 2018) (Fig. 6).
aldehyde group (Boontheekul, Kong, & Mooney, 2005). Then the al- These natural and modified starches all have the effect of promoting
dehyde group can be modified to produce an amphiphilic alginate de- emulsion stability. The effect of several starches on emulsion stability
rivative by reductive-amination (Kang, Shin, & Yang, 2002). The car- was shown in Table 2 (Chung, Degner, & McClements, 2014; Consoli
boxyl group of the alginate is always modified by chemical methods et al., 2018; Shrestha, Sadiq, & Anal, 2018; Zhong, Wang, & Qin, 2018).
such as esterification, georgy reaction and amidation so that the hy- Compared with other plant polysaccharides, starch is rarely used as a
drophobic group is added to the skeleton of the natural alginate. These stabilizer in emulsions, although it promotes the stability of the emul-
modifications change the solubility, hydrophobicity and other physi- sion.
cochemical properties of alginates. These modified alginates have been
used in the preparation of emulsions, and the applications of alginate 4.5. Other plant polysaccharides
and modified alginate in emulsions was summarized in Table 1
(Fioramonti, Stepanic, Tibaldo, Pavon, & Santiago, 2019; Iqbal, Xu, Besides the polysaccharides discussed above, many other plant
Huang, & Chen, 2019; Sato, Moraes, & Cunha, 2014; Yesiltas et al., polysaccharides are also considered as effective emulsion stabilizers.
2018; Zhao, Zhigang, & Tao, 2018). The results in Table 1 show that Inulin, the reserve polysaccharide in plants, has been shown to have
succinylated alginate, octyl-grafted alginate and propylene glycol al- biological activities such as anti-cancer and immune regulation. Inulin
ginate all contribute to the stability of emulsions. Compared with al- has been used in emulsions stabilized by β-lactoglobulin. Low con-
ginate, amphiphilic alginate derivatives effectively reduce the inter- centrations of inulin promote protein adsorption at the oil–water in-
facial tension of the emulsion and improve emulsion stability. terface, while high concentrations of inulin have thickening ability
Therefore, we can have a positive expectation for the future application (Luisa, Carlos, Sixto, & Cecilio, 2019). Guar gum is derived from guar, it
of alginate derivatives in emulsions. has a rod-like structure and is one of the most common sources of ga-
lactomannan. It has been added to the emulsion stabilized by soy so-
4.4. Starch and its derivatives luble polysaccharide (Chivero, Gohtani, Yoshii, & Nakamura, 2015).
Due to the high viscosity characteristics of guar gum, the viscosity of
Starch is one of the most common polysaccharides and the most the continuous phase increased and the movement of droplets was in-
abundant carbohydrate in human staple foods. They exist in various hibited. Hydroxypropyl methyl cellulose (HPMC) is an emulsifying
organs of higher plants in the form of granules as energy reserves of cellulose derivative with methoxy and hydroxypropyl groups. For ex-
plants. Starch is generally divided into two types: amylose and amy- ample, the emulsion stabilized by HPMC and sodium caseinate was
lopectin. The difference between the two is that amylose is a long-chain more stable than the emulsion stabilized by sodium caseinate alone
polysaccharide linked by the α-(1-4)-glycosidic bond of the D-glucose (Alizadeh, Abdolmaleki, Nayebzadeh, & Bahmaei, 2019). The HPMC
unit. On the other hand, amylopectin has the structure of highly and protein adsorbed at the droplet interface acted together to reduce
branched by α-(1-6)-glycosides. Starch is widely used to prepare the interfacial tension and delay the speed of phase separation.
Pickering emulsions because of its granular nature. However, natural
starch tends to be hydrophilic and insufficient in hydrophobicity, so it is 5. Conclusion and future outlook
not possible to stabilize the emulsion for a long period of time. In recent
years, researchers have focused on the modification of starch to give This review summarizes the recent application of plant poly-
them better performance. Both physical (non-solvent precipitation, saccharides on stabilizing food emulsion. Their physicochemical prop-
ultra-sonication, ionic gelation, milling, high-pressure treatment) and erties make them suitable for the stabilization of food emulsions.
chemical (otenyl succinic anhydride) modifications have been shown to Different polysaccharides have different mechanisms for inhibiting
be effective in increasing the stability of Pickering emulsions. emulsion instability. Some polysaccharides are directly added to the
Compared with natural starch, the granules of milled starch decreased aqueous phase to form a complex with the emulsifier, which prevents
from micron to nanometer (Lu, Xiao, & Huang, 2018). At the same time, the coalescence of the droplets through electrostatic interaction and
starch structure was destroyed and with the decreased molecular steric hindrance. The polysaccharides with emulsifying ability generally
weight. All these made the emulsifying ability of milled starch sig- decrease the tension at the oil–water interface together with the
nificantly enhanced. The granule stabilization mechanism of high- emulsifier, and maintain the stability of the droplets. Other poly-
pressure treated starch is different from that of milled starch. Results saccharides increase the viscosity of the emulsion by thickening,
from Villamonte et al. indicated that high-pressure treated starch was thereby preventing droplets from coalescing. Chemical modifications
gelatinized, double helix structures were formed by amylose and may be applied to plant polysaccharide to alter their structural prop-
amylopectin chains and the presence of starch-lipid complex were the erties for further improvement in their emulsion-stabilization

8
P. Shao, et al. Food Research International 137 (2020) 109376

functionality. Burgos-Díaz, C., Wandersleben, T., Marqués, A. M., & Rubilar, M. (2016). Multilayer
The safety of food emulsion has been paid special attention by re- emulsions stabilized by vegetable proteins and polysaccharides. Current Opinion in
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searchers. The excellent biocompatibility and low toxicity make some Cai, Y., Deng, X., Liu, T., Zhao, M., Zhao, Q., & Chen, S. (2018). Effect of xanthan gum on
plant polysaccharides become safe emulsion stabilizers. However, the walnut protein/xanthan gum mixtures, interfacial adsorption, and emulsion proper-
safety of some natural plant polysaccharides is not yet clear, there are ties. Food Hydrocolloids, 79, 391–398.
Cheng, J., Ying, M., Li, X., Yan, T., & Jie, C. (2015). Effects of milk protein-polysaccharide
certain risks in their application. In addition, since polysaccharide de- interactions on the stability ofice cream mix model systems. Food Hydrocolloids, 45,
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received widespread attention. The polysaccharide derivatives pre- Chivero, P., Gohtani, S., Yoshii, H., & Nakamura, A. (2015). Effect of xanthan and guar
gums on the formation and stability of soy soluble polysaccharide oil-in-water
pared by chemical modification, their toxicity to the human body also emulsions. Food Research International, 70, 7–14.
needs further research in the future. After being proved to have reliable Chung, C., Degner, B., & McClements, D. J. (2014). Understanding multicomponent
human safety, these plant polysaccharides have the application value in emulsion-based products: Influence of locust bean gum on fat droplet – Starch
granule mixtures. Food Hydrocolloids, 35(3), 315–323.
food emulsions.
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stability of emulsions by plant polysaccharides is not thorough enough. tained through the Maillard reaction as stabilizing agents in resveratrol-loaded
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zation ability of a polysaccharide. But the current research has not fo- contributions of charge and surface coverage on pH-induced flocculation of protein-
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structure of polysaccharides, their conformations in the solvent are 153–160.
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Acknowledgements
Spray dried flaxseed oil powdered microcapsules obtained using milk whey proteins-
alginate double layer emulsions. Food Research International, 119, 931–940.
This work was supported by Zhejiang province key research and Floury, J., Desrumaux, A., & Lardières, J. (2000). Effect of high-pressure homogenization
development program (No. 2019C02070, No. 2018C02012, No. on droplet size distributions and rheological properties of model oil-in-water emul-
sions. Innovative Food Science & Emerging Technologies, 1(2), 127–134.
2018C02005), National Natural Science Foundation of China (No. Gharehbeglou, P., Jafari, S. M., Hamishekar, H., Homayouni, A., & Mirzaei, H. (2019).
21706232, No. 31671813, No. 31901636), Public Applied Research Pectin-whey protein complexes vs. small molecule surfactants for stabilization of
Programs of Technology of Zhejiang Province (LGN18B060002). double nano-emulsions as novel bioactive delivery systems. Journal of Food
Engineering, 245, 139–148.
Science and Technology Project of Hangzhou (2019010A15). We con- Gharibzahedi, S. M. T., Hernández-Ortega, C., Welti-Chanes, J., Putnik, P., Barba, F. J.,
firm that there is no conflict of interest. Mallikarjunan, K., ... Roohinejad, S. (2019). High pressure processing of food-grade
emulsion systems: Antimicrobial activity, and effect on the physicochemical prop-
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