foods
Article
Preparation and Characterization of a Novel Natural Quercetin
Self-Stabilizing Pickering Emulsion
Shenglan Lu 1 , Xueying Li 1 , Xunran Wei 1 , Caihuan Huang 1 , Jie Zheng 1 , Shiyi Ou 1 , Tao Yang 2 and Fu Liu 1, *
Citation: Lu, S.; Li, X.; Wei, X.;
Huang, C.; Zheng, J.; Ou, S.; Yang, T.;
Liu, F. Preparation and
Characterization of a Novel Natural
Quercetin Self-Stabilizing Pickering
Emulsion. Foods 2023, 12, 1415.
https://doi.org/10.3390/
foods12071415
Academic Editors: Arshad
Mehmood Abbasi, Xinbo Guo,
Yongsheng Chen and Laura
Salvia Trujillo
Received: 18 January 2023
Revised: 12 March 2023
Accepted: 20 March 2023
Published: 27 March 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Foods 2023, 12, 1415. https://doi.org/10.3390/foods12071415
1 Department of Food Science and Engineering, Jinan University, Guangzhou 510632, China
2 School of Pharmacy, Hainan Medical University, Haikou 571199, China
* Correspondence: liu_fu@jnu.edu.cn; Tel.: +86-020-85226630
Abstract: In contrast to their well-known physiological properties, phytochemicals, such as flavonoids,
have been less frequently examined for their physiochemical properties (e.g., surface activity). A
natural quercetin self-stabilizing Pickering emulsion was fabricated and characterized in the present
study. The antisolvent precipitation method was used to modify quercetin (in dihydrate form), and
the obtained particles were characterized by light microscope, atom force microscope, XRD, and
contact angle. The antisolvent treatment was found to reduce the particle size, crystallinity, and
surface hydrophobicity of quercetin. We then examined the effects of the antisolvent ratio, particle
concentration, and oil fraction on the properties of the quercetin particle-stabilized emulsions. In ad-
dition, increasing the antisolvent ratio (1:1~1:10) effectively improved the emulsification performance
of the quercetin particles. The emulsion showed good storage stability, and the particle size of the
emulsion decreased with the rising particle concentration and increased with the rising oil phase
ratio. The findings indicate that natural quercetin treated with antisolvent method has a good ability
to stabilize Pickering emulsion, and this emulsion may have good prospective application potential
for the development of novel and functional emulsion foods.
Keywords: quercetin; Pickering; antisolvent precipitation; crystalline
1. Introduction
Due to their surfactant-free nature, high stability, and good delivery capacity, Pickering
emulsions, or particle-stabilized emulsions, have good prospects for application in food
and pharmaceutical fields [1–12]. Traditional Pickering emulsions are mostly stabilized
by inorganic particles, such as silica, which are limited in applications in food and other
industries. Therefore, the search for more natural and safe particle stabilizers with good
compatibility is one of the hot research topics in recent years in the field of food colloids,
etc. [3,6,8,13]. Through their material source, the particles that have been reported to
stabilize food-grade Pickering emulsions are mainly protein-based particles, polysaccharide-
based particles, and other particles. These particles, however, are highly variable in nature,
usually need to be modified or compounded, and mainly serve a single purpose. As a result,
the search for food grade particle stabilizers with more sustainability and functionality are
still ongoing.
In addition to their well-known physiological properties, natural phytochemicals,
such as flavonoid, have also been found to stabilize Pickering emulsions [14,15]. Murray
et al. previously discovered that different types of natural flavonoids could stabilize
oil-in-water Pickering emulsions and further investigated the effect of pH on emulsions
properties [16,17]. They then found that water-insoluble natural polyphenols (quercetin
and curcumin) dispersed in the oil phase could stabilize water-in-oil Pickering emulsions,
and that the addition of protein emulsifiers in the aqueous phase could have a synergistic
stabilizing effect [18,19]. Nanosized natural substances can also be used for Pickering
emulsion stabilization. Typically, there are two kinds of methods used to reduce materials
https://www.mdpi.com/journal/foods
Foods 2023, 12, 1415 2 of 13

into nanosized particles: top-down and bottom-up [20]. The top-down method often
involves a high energy input, such as high-pressure homogenization and wet milling
technology [21–23]. Zhang et al. found that puerarin nanocrystals obtained using high
pressure homogenization can stabilize oil-in-water Pickering emulsions [24]. Wang et al.
reported that quercetin nanocrystals obtained by high pressure homogenization could be
used for the stabilization of oil-in-water Pickering emulsions [25]. Silybin nanocrystals
with 340 nm were also fabricated using high-pressure homogenization methods under
>80 MPa [26]. This method often requires a high energy input and only reduce the particles
size, without significantly changing the surface properties. In contrast to high-pressure
homogenization, antisolvent precipitation or solvent volatilization is a low energy method
(bottom-up) that can not only reduce the particle size, but also potentially change the
surface properties of the particles [27–29]. Aditya et al. obtained amorphous curcumin
nanoparticles using an antisolvent precipitation process and successfully used them for the
stabilization of Pickering emulsion [30]. Liu et al. also used the antisolvent precipitation
method to treat phytosterols, which was successfully used for the stabilization of water-in-
oil Pickering emulsions [31,32]. Compared with the particles obtained by high-pressure
homogenization, the antisolvent precipitation method has the advantages of being energy
saving and easy to change the surface properties of the particles. At present, this technology
is mainly used for the preparation of bioactive substances for nano-sizing and delivery. This
technique has not been fully investigated for the preparation of food-grade nanoparticles
(especially phytochemical-based) for the stabilization of Pickering emulsions.
Quercetin is a flavonoid compound widely found in vegetables and fruits, which
has antioxidant, anti-inflammatory, antiviral, and cardiovascular protective effects [33–35].
However, the low solubility, chemical instability, and low bioavailability of quercetin in
water limit their many applications [36–41]. Many scholars have designed delivery systems
(e.g., emulsions, liposomes, nanoparticles, etc.) to solve this problem, but they often suffer
from a low drug loading capacity and extensive use of surfactants [36,42–50]. In the studies
of bioactives such as quercetin, the main focus has been on their physiological functions
and how they potentiate, with less attention paid to their physicochemical properties
(amphiphilicity). The inherent crystalline nature of flavonoids makes them excellent
candidates for stabilizing Pickering emulsions (particle-stabilized emulsions) if they have
proper surface wettability. Although some recent studies have successively found that
flavonoids can stabilize Pickering emulsions, most of these flavonoids are used in their
native state or are high-pressure processed [17,18,25]. The effect of antisolvent precipitation
on the performance of flavonoids (e.g., quercetin) in Pickering emulsion stabilization have
been less frequently studied.
In this paper, quercetin was treated by an antisolvent precipitation method with low
energy consumption and the properties of its emulsion were investigated. Firstly, the
quercetin particles obtained by antisolvent precipitation were characterized in terms of
their morphology, size, crystallinity, and contact angle. Secondly, the basic properties of the
above quercetin particle-stabilized emulsions, including the type of emulsion, particle size,
and microstructure, were investigated.

2. Materials and Methods

2.1. Materials
The quercetin (dihydrate, >97%) was purchased from Shanghai Aladdin Reagent
Co., Ltd. (Shanghai, China). The soybean oil was purchased from a local supermarket in
Guangzhou (China). All of the other reagents were analytically pure.

2.2. Antisolvent Precipitation Treatment for Quercetin

Quercetin was dissolved in anhydrous ethanol (1%, w/v) and kept at 45 ◦ C for 5 min.
The organic phase containing quercetin was added to the aqueous phase (10 mM phosphate
buffer, pH = 7.0) within 1 min using a high-speed homogenizer (IKA T25 digital ultraturrox,
IKA, Staufen, Germany) under vigorous stirring at 8000 rpm, and homogenized for 2.5 min
Foods 2023, 12, 1415 3 of 13

after complete addition. The antisolvent ratios (defined as “the volume ratio of organic
phase to aqueous phase”) were 1:1, 1:2.5, 1:5, 1:10, respectively. After rotary evaporation
(N-1300, Tokyo Riken Instruments Co., Tokyo, Japan), the ethanol and part of the water
were removed until the solids content of the quercetin aqueous dispersion was 3% (w/v).
In order to obtain dried quercetin pellets with different antisolvent ratios, the aqueous
dispersion was freeze-dried for 72 h in a freeze-dryer (SCIENTZ-10N, Ningbo Xinzhi
Biotechnology Co., Ltd., Ningbo, China).

2.3. Characterization of Quercetin Particles

2.3.1. Visual Appearance
A certain amount of the aqueous dispersion of quercetin pellets at 1% (w/v) with
different antisolvent ratios was taken and left in a transparent serum bottle to observe its
appearance. The visual photos were taken by a cell phone (Apple 12, Apple Inc., Cupertino,
CA, USA). The quercetin without antisolvent treatment at the same concentration was used
as a control.

2.3.2. Microstructural Observation and Estimated Size of Quercetin Particles

The microstructure of quercetin in the aqueous dispersions was studied using light
microscopy (LM) with 40× objective (BMC-500, Phoenix Optics Co., Ltd., Jiangxi, China).
The microstructure of the quercetin particles was also studied using atomic force
microscopy (AFM). The aqueous dispersions of the native quercetin particles and the
quercetin particles obtained by the antisolvent precipitation method were diluted to 0.01%
(w/v), dropped onto freshly exfoliated mica sheets and dried naturally, and observed using
AFM (Nanoscope IIIa, Bruker AXS, Santa Barbara, CA, USA) with a tapping mode.
The estimated size of the quercetin particles was manually measured over 50 particles
from the AFM image using the microscopic image analysis software (Nano Measurer 1.2,
Fudan University, Shanghai, China) [51–53]. As the quercetin particles are rod-like, the
average of the measured diameters of over 50 particles was defined as the calculated
diameter.

2.3.3. XRD
The crystallinity of the quercetin pellets was analyzed using X-ray diffraction (XRD)
(Bruker AXS D8, Karlsruhe, Germany). The dried quercetin particles were placed on a
glass sample table, flattened, and then placed on the bench for measurement. The scanning
range was between 3◦ and 80◦ with a step size of 0.02◦ , and the subsequent analysis was
performed using X-ray diffraction analysis software.
For a better comparison of the difference in crystallinity between the different samples,
the relative crystallinity (%) was calculated as follows:

At
Relative crystallinity (%) = × 100%
A0

where At and A0 are the area of the typic peak in the XRD curve for the quercetin obtained
by antisolvent-treated and the native quercetin, respectively.

2.3.4. Contact Angle

In surfactant stabilized emulsions, the HLB is often used to characterize the hy-
drophilicity/hydrophobicity of the surfactant, whereas in the case of Pickering emulsions,
the contact angle is used to characterize the wettability of particles, which is important
for emulsion stabilization. In general, solid particles with contact angles less than 90◦ are
considered hydrophilic, while those with contact angles greater than 90◦ are considered
hydrophobic. The contact angle can be used to indicate changes in the surface properties
of quercetin particles after antisolvent precipitation treatment and to determine whether
the particles are stable as O/W emulsions or stable W/O emulsions [54]. The contact
angle of the quercetin was measured by a contact angle analyzer (OCA 20 AMP, Data 118
Foods 2023, 12, 1415 4 of 13

physics Instruments, Germany). Next, 200 mg native quercetin pellets and lyophilized
quercetin pellets treated by the antisolvent precipitation method were each pressed into
13 mm diameter and 2 mm thick slices using a tablet press; then, the slices were placed
in an optical glass dish containing soybean oil, and 5 µL of water droplets were precisely
released onto the sample surface using a syringe, and the droplet behavior images were
captured using a camera and analyzed using SCA20 software for analysis. The above
samples were measured twice in parallel, and each pressed tablet was titrated at least twice
to minimize experimental errors.

2.4. Preparation and Characterization of Quercetin Pickering Emulsion

2.4.1. Preparation of Quercetin Pickering Emulsion
The aqueous dispersions of the quercetin particles were diluted using 10 mM PBS (pH
7.0) to obtain aqueous dispersions with quercetin concentrations (c) of 0.5%, 1.0%, 1.5%,
2.0%, 2.5%, and 3% (w/v). Subsequently, the quercetin dispersions were mixed with soy
oil at different ratios. The mixture was homogenized for 2 min using a T25 high-speed
homogenizer (IKA, Staufen, Germany) at 10,000 rpm to obtain the emulsions. All of the
emulsions were then immediately sealed and stored at room temperature.

2.4.2. Visual Photos

The series samples were left to stand for 7 days, and their appearance was pho-
tographed at 0 and 7 days to observe the change condition of their appearance.

2.4.3. Microstructure and Particle Size Analysis

The microstructures of various quercetin emulsions were evaluated by light mi-
croscopy (LM) using a digital microscope (BMC-500, Phoenix Optics Co., Ltd., China)
at 0 and 7 days, respectively. For the LM observations, the emulsion was gently dropped
onto a slide and observed without a coverslip using a 10× objective. If necessary, dilute the
emulsion with deionized water for clearer observation.
The droplet size of emulsions at 0 and 7 days was measured using a laser diffraction
particle size analyzer (SALD-2300, Shimadzu Corporation, Kyoto, Japan).

2.5. Statistical Analysis

The data statistics are expressed as mean ± standard deviation and combined with
graphical analysis using SPSS and origin 2018 software.

3. Results and Discussion

3.1. Physicochemical Properties of Quercetin Dihydrate Particles
The quercetin pellet dispersions were obtained using the antisolvent treatment method,
followed by rotary evaporation to remove solvents and part of the antisolvent (see Figure 1).
As water and ethanol are highly acceptable in food, water was chosen here as the antisolvent
and ethanol as the solvent [30]. As seen in Figure 1, both the native quercetin and the
antisolvent-treated quercetin could be dispersed in water to form an opaque, slightly yellow
suspension, indicating that quercetin may exist in a larger particulate form. Similar results
have been reported in many other particles using the same method, including zein particles,
phytosterol particles, and curcumin particles [30,32,55].
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Figure
Figure 1.
Figure1. Water
1.Water dispersions
Water dispersions of native
dispersions of
of nativequercetin
native quercetinand
quercetin andquercetin
and quercetinparticles
quercetin particles
particles (c
(c (c == 1%)
= 1%)1%) formed
formed
formed by
byby antisol-
antisol-
antisolvent
vent precipitation
vent precipitation under
under various
various solvent/antisolvent
solvent/antisolvent ratios.
ratios.
precipitation under various solvent/antisolvent ratios.

The
The antisolvent
Theantisolvent treatment
antisolventtreatment significantly
treatmentsignificantly
significantlychangedchanged
changedthe the particle
theparticle morphology
particlemorphology
morphologyand and size
andsize of
sizeofof
the
the quercetin.
quercetin. The
The optical
optical microscopy
microscopy results
results of
of the
the particle
particle dispersions
dispersions
the quercetin. The optical microscopy results of the particle dispersions (Figure 2) showed (Figure
(Figure 2)
2) showed
showed
that
that the
thatthe native
thenative quercetin
nativequercetin
quercetinwas was present
waspresent
presentas as aggregated
asaggregated
aggregatedcoarse coarse rod-like
coarserod-like crystals
rod-likecrystals
crystalsup up
uptoto several
toseveral
several
tens
tens
tensofof microns
ofmicrons
micronsin in size
insize (see
size(see Figure
(seeFigure
Figure2A).2A). This
2A).This
Thisis isissimilar
similar
similarto to the
tothe results
theresults (e.g.,
results(e.g., 50.1
(e.g.,50.1
50.1µm)µm) reported
µm)reported
reported
in
in the
inthe literature
theliterature [56].
literature [56]. After
[56]. After
After thethe antisolvent
the antisolvent treatment(Figure
antisolvent treatment
treatment (Figure2B–E),
(Figure 2B–E),the
2B–E), thesize
the sizeofof
size ofthe
thequercetin
the querce-
querce-
tin
tin
was was
was significantly
significantly
significantly reduced
reduced
reduced andmore
and
and moreuniformly
more uniformlydispersed.
uniformly dispersed. Specifically,
dispersed. Specifically, it it appears
appears
appears thatthat
that
the
the 1:1 quercetin shows a needle-like morphology with
the 1:1 quercetin shows a needle-like morphology with length of about 10 µm, andthe
1:1 quercetin shows a needle-like morphology with length
length of
of about
about 10
10 µm,
µm, and
and the
the
1:2.5,
1:2.5, 1:5,
1:2.5,1:5, and
1:5,and 1:10
and1:10
1:10 quercetin
quercetin
quercetin are
arearesmaller
smaller
smaller in size,
in size,
in size, but have
but but
havehave some
somesome degree
degree of aggregation.
of aggregation.
degree of aggregation. The
The
size
size
Theof of
size theofparticles
the particles was closely
was
the particles closely
was related
related
closely to the
to
related the process
toprocess
the process of antisolvent
of antisolvent
of antisolvent treatment
treatment
treatment which
which in-
in-
which
cludes
cludes
includes nucleation
nucleation
nucleation andand
and crystal
crystal
crystalgrowth.
growth.
growth. TheThe
The greater
greater the formation
the
greater formation
the formationof nucleation
of nucleation
of nucleation and and
and the
the
slower
the slower
slower the crystal
the crystal growth,
the crystal growth,
growth, the smaller
the smaller
the smallerthe particle
the particle
the particlesize.size.
size. As aa As
As result, the final
a result,
result, the final size of
the final
size of the
the
size of
particles
the particles
particles remains
remains unchanged
remains unchanged
unchanged due to
due to the
due the crystal
tocrystal
the crystal stop stop
stop growth
growth growthat certain
at certain stages,
at certain
stages, which
stages,
which de-
which
de-
pends
depends
pends on on
on particle-particle
particle-particle
particle-particle interactions.
interactions.
interactions. Therefore,
Therefore,
Therefore, the
the the size ofofthe
sizeof
size the particles
theparticles obtained
particlesobtained
obtainedfrom from
from
theantisolvent
the
the antisolventtreatment
antisolvent treatmentare
treatment arealways
are alwayssmaller
always smallerthan
smaller thanthe
than thenative
the nativeparticles
native particleswhen
particles whendispersed
when dispersedin
dispersed in
in
water.Increasing
water.
water. Increasingthe
Increasing theantisolvent
the antisolventratio
antisolvent ratiofurther
ratio furtherdecreases
further decreasesthe
decreases thesize,
the size,which
size, whichis
which isismainly
mainlydue
mainly dueto
due to
to
retardedcrystal-growth
retarded
retarded crystal-growthand
crystal-growth andaggregation.
and aggregation.
aggregation.

Figure
Figure
Figure2.2. Light
2.Light microscopic
Lightmicroscopic images of
microscopic images
images of native
nativequercetin
native quercetinparticles
quercetin particlesdispersion
particles dispersion(A)
dispersion (A)and
(A) and
and quercetin
quercetin
quercetin parti-
parti-
particles
cles
cles dispersion
dispersion
dispersion formed
formed
formed by antisolvent
by antisolvent
by antisolvent precipitation
precipitation
precipitation with
withwith various
various
various antisolvent
antisolvent
antisolvent ratios
ratios
ratios ((B),
((B),((B), 1:1;
1:1; 1:1; (C),
(C),(C), 1:2.5;
1:2.5;
1:2.5; (D),
(D),
(D), 1:5;
1:5; (E),
(E), 1:10).
1:10). The
The scale
scale bar
bar is
is
1:5; (E), 1:10). The scale bar is 50 µm. 50
50 µm.
µm.

Atomic
Atomic force
Atomicforce microscopy
forcemicroscopy
microscopy(AFM)(AFM)
(AFM)was was used
wasused
usedto to observe
toobserve
observethethe detail
thedetail of
detailof the
ofthe morphological
themorphological
morphological
changes
changes
changesof of the
ofthe quercetin
thequercetin particles
quercetinparticles after
particlesafter the
afterthe antisolvent
theantisolvent treatment
antisolventtreatment
treatment(see(see Figure
(seeFigure 3A–E).
Figure3A–E).
3A–E).TheThe
The
size
size (diameter)
(diameter) of
of the
the quercetin
quercetin was
was estimated
estimated based
based on
on the
the AFM
AFM
size (diameter) the quercetin was estimated based on the AFM images using the software images
images using
using the
the soft-
soft-
ware
ware
(Nano (Nano
(Nano measurer
measurer
measurer 1.2),
1.2),
1.2), and and
and
the the results
the
results results
are shown are shown
are shown
in in3F.
in
Figure Figure
Figure 3F. As
3F.
As shown Asinshown
shown in
Figurein Figure
Figure
3, the native3,
3,
the
the native presents
native
quercetin quercetina presents
quercetin presents
very largeaarod
veryshape,
very largewith
large rod shape,
rod shape, with(the
with
a diameter aa diameter
diameter (the
smallest(the
unit)smallest
smallest unit)
of aboutunit) of
of
1.7 µm.
about
about 1.7 µm.
1.7
After the µm. After
After the
antisolvent the antisolvent
antisolvent
treatment, treatment,
treatment,
the diameter the
ofthe diameter
thediameter
quercetinof of the quercetin
the quercetin
decreases decreases
decreases
significantly, sig-
e.g.,sig-
the
nificantly,
nificantly,
diameter of e.g.,
e.g., the diameter
the
quercetindiameter of quercetin
of quercetin
(antisolvent (antisolvent
(antisolvent
ratio, 1:1) is about 0.6ratio,
ratio, 1:1)
µm.1:1) is about
is aboutthe
Increasing 0.6antisolvent
0.6 µm. Increasing
µm. Increasing
ratio
the antisolvent
the antisolvent ratio
ratio to
to 1:10,
1:10, there
there isis aa further
further decrease
decrease inin the
the quercetin
quercetin particle
particle diameter
diameter
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(0.13 µm),
to 1:10, butisthe
there degreedecrease
a further of aggregation increases.particle
in the quercetin The AFM results(0.13
diameter are µm),
well inbutagreement
the degree
with
of aggregation increases. The AFM results are well in agreement with the opticalincrease
the optical microscopy results. The decrease in the particle size due to the microscopy in
the antisolvent
results. ratio is common
The decrease in the literature,
in the particle size due to which is mainlyindue
the increase thetoantisolvent
the self-assembly
ratio is
process
common (nucleation-crystallization
in the literature, which isgrowth)
mainly ofdue thetosubstance [56,57]. The
the self-assembly increase
process in the
(nucleation-
degree of aggregation
crystallization growth)isofmainly due to [56,57].
the substance an increase in the interparticle
The increase in the degree interactions,
of aggregationsug-is
gesting
mainlythat
duethe antisolvent
to an treatment
increase in may haveinteractions,
the interparticle altered the surface
suggestingproperties
that theofantisolvent
the quer-
cetin particles.
treatment may Ashave
a result, the the
altered antisolvent treatment plays
surface properties of thetwo roles inparticles.
quercetin regard to As quercetin:
a result,
itthe
decreases the size
antisolvent (the diameter
treatment plays twoof minimum unit)toofquercetin:
roles in regard quercetin itand it changes
decreases the the
sizesur-
(the
face properties
diameter of quercetin,
of minimum which
unit) of enhances
quercetin the
and it interactions
changes between
the surface neighboring
properties quer-
of quercetin,
cetin
whichparticles.
enhances the interactions between neighboring quercetin particles.

F 2.0

Calculated diameter (μm)

1.5

1.0

0.5

0.0
native 1:1 1:2.5 1:5 1:10
Quercetin particles

Figure
Figure3.3.Atomic
Atomicforce
forcemicroscopic
microscopicimages
images(A−E)
(A–E)and
andcalculated
calculateddiameter
diameter(F)
(F)ofofnative
nativequercetin
quercetin(A)
(A)
and quercetin particles formed by antisolvent precipitation with various antisolvent ratios ((B), 1:1;
and quercetin particles formed by antisolvent precipitation with various antisolvent ratios ((B), 1:1;
(C), 1:2.5; (D), 1:5; (E), 1:10).
(C), 1:2.5; (D), 1:5; (E), 1:10).

3.2.
3.2.Crystallinity
Crystallinityand andContact
ContactAngleAngleofofQuercetin
QuercetinParticles
Particles
The effect of the antisolvent treatment on
The effect of the antisolvent treatment on the crystalline the crystalline nature
nature of quercetin
of quercetin waswas eval-
evaluated
uated
usingusing
the XRD the technique.
XRD technique. As shown As shown in Figure
in Figure 4A, the4A, XRDthespectra
XRD spectraat 10–30 ◦
at 10–30°
showedshowed
a series
aofseries
sharpofpeaks,
sharp indicating
peaks, indicating the crystalline
the crystalline nature ofnature of quercetin.
quercetin. The typicThe peakstypic peaks
of the of
native
the native quercetin
quercetin are mainly are
at mainly at 2𝜃 ◦of
2θ of 6.3–7.3 ◦ , 12.510.8°,
6.3–7.3°,
, 10.8 ◦ , 13.6–14.3
12.5°,◦13.6–14.3°,
, 15.7–18.0◦15.7–18.0°,
, 24.4◦ , and24.4°,
27.3◦ ,
and
which27.3°, which represented
represented the crystalline thepart
crystalline part[25].
of quercetin of quercetin
Compared [25].
with Compared
the native with the
quercetin,
native quercetin,
the quercetin the quercetin
particles obtained by particles obtained
antisolvent by antisolvent
precipitation have theprecipitation
same diffraction havepeaks
the
same
of 12.5 ◦ , 13.6–14.3
diffraction ◦ , 24.4
peaks of◦ ,12.5°,
and 27.3 ◦ , but have
13.6–14.3°, 24.4°, and 27.3°,
almost but havepeaks
no diffraction almost ofno ◦ , 10.9◦ ,
diffraction
6.3–7.3
peaks of 6.3–7.3°,
and 15.7–18.0 ◦ . Moreover,
10.9°, and 15.7–18.0°.
compared to Moreover,
the native compared
quercetin,to the native
intensity quercetin,
of the samethe
diffraction
intensity of peak
the sameof quercetin
diffraction is also
peak reduced significantly
of quercetin is alsoafter antisolvent
reduced precipitation
significantly after anti-and
furtherprecipitation
solvent reduced upon increasing
and the antisolvent
further reduced ratio fromthe
upon increasing 1:1antisolvent
to 1:10. Theratiodecline
from in1:1
the
peak intensity indicated a decrease in crystallinity. The decrease
to 1:10. The decline in the peak intensity indicated a decrease in crystallinity. The decrease in the crystallinity could
inbethe
further quantitatively
crystallinity could be evaluated by the relativeevaluated
further quantitatively crystallinity
by calculated
the relativefrom the XRD
crystallinity
spectra. As
calculated shown
from the inXRDFigure 4B, the
spectra. As order
shownofinthe relative
Figure 4B,crystallinity
the order ofbetweenthe relativethe different
crystal-
quercetin
linity betweenwerethe as follows:
differentnative (100%)
quercetin were> 1:1
as (48.1%)
follows:>native
1:2.5 (41.18%)
(100%) >>1:1 1:5(48.1%)
(27.62%)> >1:2.5
1:10
(19.52%).> The
(41.18%) decrease in
1:5 (27.62%) the crystallinity
> 1:10 (19.52%). The indicates
decrease an increase in the degree
in the crystallinity of the particles’
indicates an in-
amorphousness.
crease in the degree Much of particles
of the the literature has also reported
amorphousness. Muchthat the literature
of the crystallinity hasdecreases
also re-
ported that the crystallinity decreases after antisolvent treatment, such as in curcuminin
after antisolvent treatment, such as in curcumin and phytosterol [30,32]. The change andthe
crystallinity and morphology of quercetin may be accompanied
phytosterol [30,32]. The change in the crystallinity and morphology of quercetin may be by a change in its surface
properties (e.g.,
accompanied by awettability)
change in its [32].
surface properties (e.g., wettability) [32].
Foods 2023, 12, x FOR PEER REVIEW 7 of 13
Foods 2023, 12, 1415 7 of 13

100
1:10
1:5

Relative crystallinity (%)

80

Intensity (A. U.)

1:2.5
60
1:1

40

20
native quercetin

10 20 30 40 50 0
2θ(°) native 1:1 1:2.5 1:5 1:10
Solvent/antisolvent ratio

(A) (B)
Figure 4. 4.XRD
Figure XRD(A)
(A)and
and relative crystallinity(%)
relative crystallinity (%)(B)
(B)
of of native
native quercetin
quercetin and and quercetin
quercetin particles
particles formed
formed by antisolvent precipitation with various antisolvent ratios (1:1, 1:2.5, 1:5,
by antisolvent precipitation with various antisolvent ratios (1:1, 1:2.5, 1:5, 1:10). 1:10).

TheThe hydrophilic/hydrophobic
hydrophilic/hydrophobic characteristics
characteristics (wettability)
(wettability) of of
particles can
particles canbebereflected
reflected
byby thethecontact angle (𝜃). To evaluate the effect of the antisolvent
contact angle (θ). To evaluate the effect of the antisolvent treatment on the treatment on the face
face
wettability
wettability ofofquercetin
quercetinparticles,
particles,thethe contact
contact angle of of the
thequercetin
quercetinparticles
particleswas wasmeasured,
meas-
ured,
and and the results
the results are summarized
are summarized in Table in1.Table
From1.Table
From Table
1, it 1, seen
can be it can bethe
that seen that the
contact angle
contact
of the angle
nativeof the native
quercetin is 102.65 ◦ , which
quercetin is 102.65°, which
is slightly is slightly This
hydrophobic. hydrophobic. This value
value is slightly higher
is than
slightlythathigher
of the than
quercetin
that of reported by Zembla
the quercetin et al.,by
reported which
Zemblais 89.9 at pH
et al., which3.0 is
and89.979.1
at at
pHpH
3.07.0
and[18]. This
79.1 discrepancy
at pH may discrepancy
7.0 [18]. This be due to themay use of
be different
due to the methods to obtain methods
use of different the contact
to angle.
obtainIn that
the work,angle.
contact the contact
In thatangles
work,ofthe thecontact
aqueous phase
angles ofand
the oil phase phase
aqueous were measured,
and oil
and were
phase the three-contact
measured, and angle
thewas calculatedangle
three-contact by Young’s equation,bywhereas
was calculated Young sinequation,
our work,
the three-contact
whereas in our work, angle
the is directly measured.
three-contact angle isAnother possible reason
directly measured. is that
Another the material
possible rea-
sonused is different
is that (quercetin
the material used isvs. quercetin
different dihydrate).
(quercetin After thedihydrate).
vs. quercetin antisolventAftertreatment,
the an-the
contact treatment,
angle of quercetin decreased significantly ◦ ), and further reduced upon
tisolvent the contact angle of quercetin (84.85–65.15
decreased significantly (84.85–65.15°),
increasing the antisolvent ratio from 1:1 to 1:10. The decrease
and further reduced upon increasing the antisolvent ratio from 1:1 to 1:10. The in the contact angle indicates
decrease
the enhanced hydrophilicity of the particles, which would also
in the contact angle indicates the enhanced hydrophilicity of the particles, which would help quercetin to partition
better between the oil and water phases.
also help quercetin to partition better between the oil and water phases.

Table
Table 1. 1. Contact
Contact angle
angle (𝜃)(θ)
ofof native
native quercetinand
quercetin andquercetin
quercetinparticles
particlesformed
formedby
byantisolvent
antisolventprecip-
precipita-
tion with various antisolvent ratios (1:1, 1:2.5, 1:5, 1:10).
itation 1:10)

Samples
Samples Native
Native 1:1
1:1 1:2.5
1:2.5 1:51:5 1:101:10
Contact
Contactangle
angle(°) 102.65 ± 0.64
102.65 ± 0.64 a
a 84.85 ± 0.21 b 75.63 ± 0.78 c 69.90 ± 2.62 d 65.15 ± 1.48 e
84.85 ± 0.21 b 75.63 ± 0.78 c 69.90 ± 2.62 d 65.15 ± 1.48 e
(◦ )
The contact angles were determined on quercetin tablets by sessile drop method. The letter a–e rep-
The contact
resented angles were statistical
the significant determineddifferences
on quercetin(ptablets
< 0.05)bybetween
sessile drop method.
different The letterparticles.
quercetin a–e represented the
significant statistical differences (p < 0.05) between different quercetin particles.

3.3. Microstructure and Particle Size of Quercetin Particle-Stabilized Emulsions

3.3. Microstructure and Particle Size of Quercetin Particle-Stabilized Emulsions
3.3.1.
3.3.1.Effect of of
Effect Solvent/Antisolvent
Solvent/Antisolvent Ratio
Ratio
WeWe first evaluated
first evaluated thethe
effect of of
effect thethe
antisolvent
antisolvent ratio onon
ratio thethe
properties
propertiesof of
thethe
quercetin
quercetin
emulsions. The appearance, types, and microstructures of the
emulsions. The appearance, types, and microstructures of the quercetin-stabilizedquercetin-stabilized emul-
emul-
sions with different antisolvent ratios are shown in Figure 5. As can
sions with different antisolvent ratios are shown in Figure 5. As can be seen in Figure be seen in Figure 5A,5A,
when
when soybean
soybean oiloil
waswasutilized
utilized as as
thethe
oiloil
phase,
phase,allall
of of
thethe
quercetin
quercetin particles
particlescreated
createdpale
pale
yellow emulsions. All of the emulsions were stable against creaming,
yellow emulsions. All of the emulsions were stable against creaming, with the exception with the exception
of of
thethenative
nativequercetin-stabilized
quercetin-stabilized emulsion.
emulsion. DueDueto to
thethesolid
solidparticulate
particulatenature
nature (crystals),
(crystals),
thetheemulsions
emulsionsstabilized
stabilized by quercetin particles
by quercetin particleswith
withoror without
without antisolvent
antisolvent treatment
treatment could
could be considered
be considered as forms
as forms of Pickering
of Pickering emulsions.
emulsions. The dropThe drop test (Figure
test (Figure 5B) showed
5B) showed that the
that the emulsions
emulsions formedformed
were allwere all oil-in-water
oil-in-water emulsions,
emulsions, which which is basically
is basically consistent
consistent with the
with the contact angle data of the quercetin particles. This is consistent
contact angle data of the quercetin particles. This is consistent with the previous with the previous
study by
study
Wang byetWang et al. (oil-in-water
al. (oil-in-water type), buttype), but different
different to that to bythat by Zembyla
Zembyla et al. (water-in-
et al. (water-in-oil type).
oilThe
type). The quercetin
quercetin used in theused in thestudy
current current
wasstudy
in thewas
forminofthe form ofand
dihydrate dihydrate and was
was pre-dispersed
pre-dispersed
in the waterin the water
phase beforephase before emulsification,
emulsification, which could which
explaincould
theexplain
differenttheresults.
different
This
Foods 2023, 12, x FOR PEER REVIEW 8 of 13
Foods 2023, 12, 1415 8 of 13

results. This would also provide an explanation for the native quercetin with a contact
angle
wouldofalso>90°provide
still forming an oil-in-water
an explanation for theemulsion. These results
native quercetin also show
with a contact that,
angle ◦ still
in addi-
of >90
tion to thean
forming contact angle, the
oil-in-water pre-location
emulsion. Thesebefore
resultsemulsification
also show that, could also greatly
in addition influence
to the contact
the emulsion
angle, properties. before
the pre-location The microstructure
emulsificationresults
could(Figure 5C) showed
also greatly influence thatthetheemulsion
particle
size of the native
properties. quercetin stabilized
The microstructure emulsion
results (Figure 5C)was very large
showed that the(~350 µm),size
particle whichof thealso ex-
native
quercetin
plained its stabilized emulsion Compared
easy delamination. was very large
with(~350 which alsothe
µm), quercetin,
the native explained
particle its sizeeasy de-
of the
lamination. Compared with the native quercetin, the particle size
antisolvent-treated quercetin-stabilized emulsion was significantly reduced (30–50 µm), of the antisolvent-treated
quercetin-stabilized
and the particle size ofemulsionthe emulsionwas significantly reduced
decreased slightly with(30–50 µm), and
the increase in the
the particle
proportion size
ofthe
of the antisolvent.
emulsion decreased slightly withofthe
The microstructures increase
the emulsions in the proportion
also of the antisolvent.
clearly confirm the above
The microstructures
results of the droplet of theSimilar
size. emulsions alsohave
results clearly
beenconfirm
foundthe in above results of the
other emulsions droplet
stabilized
size.
by Similar results
phytosterol haveand
particles been found inparticles
curcumin other emulsions
[30,32]. stabilized
The aboveby phytosterol
results indicated particles
that
and curcumin particles [30,32]. The above results indicated that
the antisolvent treatment significantly improved the emulsifying ability of the quercetin the antisolvent treatment
significantly
particles. improved
Combined with the emulsifying
the above resultsability of the
of the quercetin
particles particles. Combined
characteristics, the improve- with
the above results of the particles’ characteristics, the improvement
ment in the quercetin s emulsifying ability after the antisolvent treatment could be mainly in the quercetin’s emul-
sifying ability
attributed to itsafter the surface
better antisolvent treatment
wettability andcould be mainly
decreased attributed
particle to itsone
size. On better
hand,surface
the
wettability treatment
antisolvent and decreased reduced particle size. Onsize
the particle oneofhand, the antisolvent
the quercetin, whichtreatment
are favorable reduced
for
the particle size of the quercetin, which are favorable for emulsion
emulsion stabilization. On the other hand, the antisolvent treatment decreased the contact stabilization. On the
other hand, the antisolvent treatment decreased the contact angle apart from 90 ◦ , which is
angle apart from 90°, which is unfavorable for emulsion stabilization. Moreover, in addi-
unfavorable
tion for emulsion
to the improvement in stabilization.
the emulsion Moreover, in addition
s physical stability, thetoquercetin
the improvement
particles at inthe
the
emulsion’s physical stability, the quercetin particles at the interface
interface are also expected to improve the oxidation stability of the emulsions due to its are also expected to
improve the oxidation
antioxidative nature. stability of the emulsions due to its antioxidative nature.

(A) (B)

(C)
Figure
Figure5.5.(A)Visual
(A) Visualappearances
appearancesofofemulsions
emulsionsstabilized
stabilizedbybynative
nativequercetin
quercetinand
andantisolvent-treated
antisolvent-treated
quercetin
quercetinatatantisolvent
antisolventratios
ratiosofof1:1,
1:1,1:2.5,
1:2.5,1:5,
1:5,1:10;
1:10;(B)
(B)Droplet
Droplettest
testresults
resultsof
ofemulsions
emulsionsstabilized
stabilized
by
by native quercetin and antisolvent-treated quercetin at antisolvent ratios of 1:1, 1:2.5, 1:10;
native quercetin and antisolvent-treated quercetin at antisolvent ratios of 1:1, 1:2.5, 1:5, (C)
1:5, 1:10;
Optical microscopy images of emulsions stabilized by native quercetin and antisolvent-treated quer-
(C) Optical microscopy images of emulsions stabilized by native quercetin and antisolvent-treated
cetin at antisolvent ratios of 1:1, 1:2.5, 1:5, 1:10. In Figure 5B, emulsion was dropped into pure water
quercetin at antisolvent ratios of 1:1, 1:2.5, 1:5, 1:10. In Figure 5B, emulsion was dropped into pure
(left tube) and pure oil (right tube), respectively. The emulsions were stabilized by 1% quercetin
particle(left
water andtube) and
the oil pure oilis(right
fraction tube),
0.5. The respectively.
scale The emulsions were stabilized by 1% quercetin
bar is 100 µm.
particle and the oil fraction is 0.5. The scale bar is 100 µm.
3.3.2.
3.3.2.Effect
Effectof ofParticle
ParticleConcentration
Concentration
The
Theeffect
effect of
of the
the particle concentrationon
particle concentration onthe
theproperties
propertiesofofthetheemulsions
emulsions stabilized
stabilized by
by the antisolvent-treated quercetin (antisolvent ratio is 1:1) is shown in Figure
the antisolvent-treated quercetin (antisolvent ratio is 1:1) is shown in Figure 6. As can be 6. As can
be seen
seen in Figure
in Figure 6A, 6A, the freshly
the freshly mademade quercetin
quercetin emulsions
emulsions all hadall had a light-yellow
a light-yellow color andcolor
had
and had begun to cream somewhat after seven days of storage. The extent
begun to cream somewhat after seven days of storage. The extent of the creaming graduallyof the creaming
gradually
reduced upon reduced upon increasing
increasing the
the particle particle concentration
concentration up to 2.0%,up andto remained
2.0%, andunchanged
remained
unchanged when further increasing the particle concentrations. Particle-stabilized
when further increasing the particle concentrations. Particle-stabilized emulsions frequently emul-
sions frequently
experience experiencephenomenon,
this creaming this creamingwhich
phenomenon, which
is primarily is primarily
caused caused
by the large sizeby
ofthe
the
large size of
emulsion the emulsion
droplet obtaineddroplet obtained
by low-energy by low-energy
emulsification emulsification
technology. technology.
As shown in FigureAs 6B,
shown in Figure 6B, with increasing the particle concentration from 0.5
with increasing the particle concentration from 0.5 to 1.5%, the droplet size of the emulsionto 1.5%, the
stabilized by quercetin obtained at a 1:1 antisolvent ratio decreased significantly from
Foods 2023, 12, x FOR PEER REVIEW 9 of 13

Foods 2023, 12, 1415 9 of 13

droplet size of the emulsion stabilized by quercetin obtained at a 1:1 antisolvent ratio de-
creased significantly from 130 µm to 95 µm, while further increases in the particle concen-
tration to 3% resulted in a decrease in size, to 80 µm. At a specific oil fraction (e.g., 0.5),
130 µm to 95 µm, while further increases in the particle concentration to 3% resulted
when the particle concentration is increased, more particles are available to stabilize the
in a decrease in size, to 80 µm. At a specific oil fraction (e.g., 0.5), when the particle
oil-water interface, thus facilitating the formation of smaller emulsion droplets. Moreover,
concentration is increased, more particles are available to stabilize the oil-water interface,
the microstructure of the emulsions (Figure 6C) shows that the particle size decreases as
thus facilitating the formation of smaller emulsion droplets. Moreover, the microstructure of
the particle concentration increases, confirming the particle size data above. With the ex-
the emulsions (Figure 6C) shows that the particle size decreases as the particle concentration
ception of the phenomenon of creaming, no oil was released on the top of the emulsion
increases, confirming the particle size data above. With the exception of the phenomenon
layer after seven days of storage. Additionally, a slight increase in the emulsion size oc-
of creaming, no oil was released on the top of the emulsion layer after seven days of storage.
curred at lowera slight
Additionally, concentrations,
increase inbut
the no furthersize
emulsion changes in the
occurred emulsion
at lower size occurred
concentrations, butat
no
higher
furtherconcentrations,
changes in theindicating thatoccurred
emulsion size the quercetin emulsions
at higher (especially
concentrations, at higher
indicating con-
that the
centrations) have high(especially
quercetin emulsions coalescence at stability during storage.have
higher concentrations) Pickering emulsions, stability
high coalescence which
have been widely reported in the literature, are known for their remarkable
during storage. Pickering emulsions, which have been widely reported in the literature, stability
against coalescence
are known for their[2,5,14,58].
remarkable stability against coalescence [2,5,14,58].

250
0 day
7 day

Mean diameter (μ m)
200

150

100

50
0.5 1.0 1.5 2.0 2.5 3.0
Concentrations of quercetin particles (%)

(A) (B)

(C)
Figure
Figure6.6.The
Theeffect
effect of
of particle concentrations
concentrationson onvisual
visualappearances
appearances (A),
(A), mean
mean diameter
diameter (B)(B)
andand
opti-
optical microscopy
cal microscopy images
images (C)(C)
of of emulsions
emulsions prepared
prepared byby antisolvent
antisolvent quercetin
quercetin particles
particles (the
(the antisol-
antisolvent
vent
ratioratio of quercetin
of quercetin particles
particles wasc 1:1,
was 1:1, c = 0–3%)
= 0–3%) after storage
after storage for dayfor dayday
0 and 0 and dayratio
7. The 7. The ratio of
of oil/water
oil/water of the emulsion is 1:1. The scale bar is 100 µm.
of the emulsion is 1:1. The scale bar is 100 µm.

3.3.3.
3.3.3.Effect
EffectofofOil
OilFraction
Fraction
The
Theeffect
effectof
ofthe
the oil
oil fraction onon the
theparticle
particlesizesizeand
andstability
stability ofof
thethe quercetin
quercetin emul-
emulsions
sions was evaluated,
was evaluated, and theandresults
the results are shown
are shown in Figurein Figure 7. As shown
7. As shown in Figurein Figure
7A, with 7A, with
soybean
oil as the
soybean oil oil phase,
as the 1% of 1%
oil phase, the of
quercetin particles
the quercetin (antisolvent
particles ratio ratio
(antisolvent is 1:1) is could form
1:1) could
emulsions
form emulsionswithwith
an oil
an fraction of 0.2–0.5,
oil fraction andand
of 0.2–0.5, above
above0.50.5
(oil(oil
fraction)
fraction)nono stable
stableemulsion
emul-
waswas
sion formed.
formed. TheTheformed
formedemulsions,
emulsions,after
afterbeing
being stored
stored for seven
seven days,
days,all allunderwent
underwent
different degrees of creaming, which is similar to those of the emulsions formed atatvarious
different degrees of creaming, which is similar to those of the emulsions formed various
concentrations of quercetin particles. As the oil fraction (ϕ) increased
concentrations of quercetin particles. As the oil fraction (φ) increased (from 0.2 to 0.5), (from 0.2 to the
0.5),
the emulsion
emulsion layerlayer
(upper(upper
layer)layer) gradually
gradually increased,
increased, while
while thethe height
height of ofthethelower
lowerlayer
layer
(aqueouslayer)
(aqueous layer) gradually
gradually decreased.
decreased.At Ata afixed particle
fixed concentration
particle concentration in thein aqueous phase,
the aqueous
the total
phase, the volume of theof
total volume emulsion droplets
the emulsion formed
droplets increases
formed as theasoilthe
increases fraction increases,
oil fraction in-
and thus the emulsion layer also increases. The changes in the droplets’
creases, and thus the emulsion layer also increases. The changes in the droplets size at size at various oil
fractions on days zero and seven are shown in Figure 7B. As shown in Figure 7B, when the
oil phase ratio is increased from 0.2 to 0.4, the emulsion particle size increases slowly from
62 µm to 78 µm. Further increasing the oil phase ratio to 0.5, the emulsion particle size
Foods 2023, 12, x FOR PEER REVIEW 10 of 13

Foods 2023, 12, 1415 various oil fractions on days zero and seven are shown in Figure 7B. As shown in Figure 10 of 13
7B, when the oil phase ratio is increased from 0.2 to 0.4, the emulsion particle size increases
slowly from 62 µm to 78 µm. Further increasing the oil phase ratio to 0.5, the emulsion
particle
increasessize increases significantly
significantly to 100 µm. Theto 100 µm. The
increase increase
in the emulsionin the emulsion
size is mainlysize is mainly
a result of the
a increased
result of the increased interfacial area and droplet volume. Moreover, upon
interfacial area and droplet volume. Moreover, upon increasing the oil fraction, increasing
the
theoilamount
fraction,ofthe amountparticles
quercetin of quercetin
usedparticles usedthe
to stabilize to stabilize
oil-waterthe oil-water
interface areinterface
reduced,
are reduced,
resulting in aresulting in a lack particles
lack of sufficient of sufficient particles
to cover to cover
the newly the newly
formed formed
oil-water oil-water
interface. As a
interface. As a result,
result, a certain amount a certain amount
of droplet of droplet
coalescence and coalescence andincreased.
the droplet size the droplet sizeseven
After in-
creased.
days ofAfter seven
storage, thedays of storage,
droplet size ofthe
thedroplet
emulsionsizeremained
of the emulsion remained
unchanged at anunchanged
oil fraction
atofan0.2–0.4.
oil fraction of 0.2–0.4.
and slightly and slightly
increased at anincreased at an
oil fraction of oil
0.5.fraction of 0.5.suggested
The results The results sug-
that the
gested that the
emulsions emulsions
stabilized stabilized
by the by the 1%
1% quercetin quercetin
obtained obtained bytreatment
by antisolvent antisolvent treatment
(1:1) with an
(1:1) with anof
oil fraction oil0.2–0.4
fraction of 0.2–0.4
showed highshowed
stabilityhigh stability
against against coalescence.
coalescence.

140
0 day
7 day

Mean diameter ( μ m)
120

100

80

60

0.2 0.3 0.4 0.5

Oil fraction

(A) (B)
Figure
Figure7.7.Visual
Visualappearances
appearances(A)(A)and
anddroplet
dropletsize
size(B)
(B)of
of emulsions
emulsions prepared by antisolvent
prepared by antisolvent quercetin
querce-
tin particles
particles (theantisolvent
(the antisolventratio
ratioofofquercetin
quercetinparticles
particleswas
was 1:1,
1:1, cc == 1%)
1%) at
atvarious
variousoil
oilfractions
fractionsafter
after
storage for 0 day and 7 days.
storage for 0 day and 7 days.

4.4.Conclusions
Conclusions
The
Theantisolvent
antisolventtreatment
treatmentcancantransform
transformquercetin
quercetininto intoaagood
goodoil-in-water
oil-in-waterPickering
Pickering
emulsion
emulsionstabilizer.
stabilizer. The
The antisolvent
antisolvent treatment could
could significantly
significantlychange
changethethecharacteristics
characteris-
of quercetin
tics particles,
of quercetin including
particles, includinga reduced
a reduced size,
size,crystallinity,
crystallinity,andandcontact
contactangle,
angle,which
whichis
isstrongly
stronglyinfluenced
influencedby by the
the antisolvent ratio. Compared
Comparedwith withnative
nativequercetin,
quercetin,thetheability
ability
ofofantisolvent-treated
antisolvent-treatedquercetin
quercetintotostabilize
stabilizeemulsions
emulsionsand andits
itsemulsion
emulsionstability
stabilityagainst
against
coalescencewere
coalescence weresignificantly
significantlyimproved.
improved.The Theproperties
propertiesofofquercetin-stabilized
quercetin-stabilizedemulsions
emulsions
can be modulated by changing the antisolvent ratio, quercetin particle concentration,
can be modulated by changing the antisolvent ratio, quercetin particle concentration, and and
oilfraction.
oil fraction.The
Theresults
resultsofofthis
thispaper
paperareareinstructive
instructivefor forthe
thedevelopment
developmentofofhighly
highlystable
stable
emulsions,asaswell
emulsions, wellasasnovel
novelquercetin
quercetinfunctional
functionalfoods.
foods.

AuthorContributions:
Author Contributions: Conceptualization,
Conceptualization, F.L.;
F.L.; Data
Data curation,
curation, S.L., S.L.,
X.L., X.L., C.H.F.L.;
C.H. and andFormal
F.L.; Formal
anal-
analysis,
ysis, X.L.; Funding
X.L.; Funding acquisition,
acquisition, F.L.; Investigation,
F.L.; Investigation, X.W. andX.W.C.H.;
and C.H.; Methodology,
Methodology, S.L.X.L.;
S.L. and and Re-
X.L.;
Resources,
sources, X.W.;X.W.; Software,
Software, X.L.;
X.L.; Supervision,
Supervision, X.L.,
X.L., X.W.
X.W. andand F.L.;
F.L.; Validation,
Validation, S.L.
S.L. andand X.W.;
X.W.; Writing—
Writing—
originaldraft,
original draft,S.L.;
S.L.;Writing—review
Writing—reviewand andediting,
editing,C.H.,
C.H.,J.Z.,
J.Z.,S.O.,
S.O.,T.Y.
T.Y.and
andF.L.
F.L.All
Allauthors
authorshave
haveread
read
and agreed to the published version of the manuscript.
and agreed to the published version of the manuscript.
This work
Funding:This
Funding: work was
wassupported
supportedby the
by National Natural
the National ScienceScience
Natural Foundation of China of
Foundation (32172344),
China
Guangdong
(32172344), Basic and Applied
Guangdong Basic andBasic Research
Applied BasicFoundation (2021A1515010637).
Research Foundation (2021A1515010637).
Institutional
Informed Review
Consent Board Statement:
Statement: Not applicable.
Not applicable.
Informed Consent
Institutional ReviewStatement: Not applicable.
Board Statement: Not applicable
DataAvailability
Data AvailabilityStatement: Dataisiscontained
Statement:Data containedwithin
withinthe
thearticle.
article.
ConflictsofofInterest:
Conflicts Theauthors
Interest:The authorsdeclare
declareno
noconflict
conflictofofinterest.
interest.
Foods 2023, 12, 1415 11 of 13

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