Ultrasonics - Sonochemistry 48 (2018) 311–320

Contents lists available at ScienceDirect

Ultrasonics - Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Ultrasound assisted adsorption and desorption of blueberry anthocyanins T

using macroporous resins
⁎ ⁎
Yue Wua, Yongbin Hana, , Yang Taoa, , Siqi Fana, Dinh-Toi Chub, Xiaosong Yec, Mingru Yec,
Guangjie Xiec
a
College of Food Science and Technology, Nanjing Agricultural University, Nanjing, Jiangsu 210095, China
b
Faculty of Biology, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Viet Nam
c
Zhihai Postgraduate Working Station, Zhenjiang, Jiangsu 212000, China

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

Keywords: In this study, the impact of ultrasound on the adsorption and desorption features of blueberry anthocyanins on
Ultrasound macroporous resins were studied. Sonication was performed at 106–279 W/L and 20–30 °C in a pulsed mode,
Adsorption respectively. Generally, ultrasound treatments within the selected experimental range enhanced the adsorption/
Desorption desorption process of anthocyanins on macroporous resins. The recovery of blueberry anthocyanins after ul-
Blueberry anthocyanins
trasound-assisted adsorption/desorption process at 279 W/L and 20 °C was 82.12%, which was 52.84% higher
Marcoporous resins
than that obtained after adsorption/desorption with shaking at 100 rpm. Meanwhile, higher acoustic energy
density (AED) levels and lower temperatures benefited the adsorption process through enhancing the adsorption
capacity and shortening the equilibrium time, whereas higher temperatures promoted the desorption process.
Furthermore, malvidin-3-galactoside had the highest adsorption and desorption capacities among all the studied
monomeric anthocyanins. No organic acids and sugars were detected after adsorption/desorption processes,
indicating the successful improvement of anthocyanin purification. Sonication mainly enhanced the adsorption
process by means of strengthening the formation of hydrogen bond on resins surface and increasing their surface
roughness. Overall, ultrasound can be an effective tool to improve the purification of anthocyanins using
macroporous resins.

1. Introduction from berries has been investigated by high-speed counter-current

Blueberry (Vaccinium L.) is a rich source of dietary bioactivities
compounds, such as organic acids and polyphenols, especially antho-
cyanins. According to the regulation of USDA [1], it has a series of
health-related benefits, such as anti-oxidant, anti-cancer, anti-athero-
sclerosis, and anti-cholesterol activities [2–4]. It has been listed as one
of the five healthy fruits by United Nations Food and Agriculture Or-
ganization [5]. However, many researches indicated that a harsh
stickiness problem appeared during blueberry dehydration processes
because of the high contents of sugars and acids in berries, resulting in
poor quality properties, low yield and high energy consumption [6,7].
Besides, it has been confirmed that phytochemicals extracted with low
sugar and acid contents from berries were more effective and healthier
than whole fruits for obese patients and diabetics [8]. Therefore, it is
necessary to produce anthocyanin concentrates with few or no sugars
and acids as a dietary supplement or health care product.
In previous studies, the concentration of sugar-free anthocyanins
chromatography [9], preparative high-performance liquid chromato-
graphy [10] and others. However, some insufficiencies still exist in
these methods, such as time-consuming, expensive and unable to meet
the need of industrial-scale production. Macroporous resins have at-
tracted a lot of attention in concentration of anthocyanins with no su-
gars and acids from berry-related fruits due to their outstanding ad-
sorption properties, such as high mechanical feature, low solvent
consumption, good selectivity and low cost [11,12]. Generally, mac-
roporous resins usually adsorb adsorbates through noncovalent
bonding in aqueous solution. Next, adsorbates can be desorbed from the
adsorbents using some organic solvents [13]. There are different types
of macroporous resins that can be used for the adsorption of phenolics,
including polar, non-polar and weak-polar ones. Among them, XAD-
7HP resins had a satisfactory performance on adsorption and desorption
of anthocyanins as a result of its low polarity and large surface area
[11,14]. On the other hand, it is time-consuming for both adsorption
and desorption processes to reach the equilibrium when it comes to use

⁎
Corresponding authors.
E-mail addresses: hanyongbin@njau.edu.cn (Y. Han), yang.tao@njau.edu.cn (Y. Tao).

https://doi.org/10.1016/j.ultsonch.2018.06.016
Received 2 February 2018; Received in revised form 11 June 2018; Accepted 18 June 2018
Available online 21 June 2018
1350-4177/ © 2018 Elsevier B.V. All rights reserved.
Y. Wu et al.
Fig. 1. Diagram of the experimental set-up for ultrasound-assisted adsorption/desorption of blueberry anthocyanins using macroporous resins. 1: Generator; 2:
Electro-thermostatic Water Cabinet; 3: Ultrasonic probe; 4: Conical flask wrapped up in tinfoil containing blueberry extracts and resins; 5: Propeller; 6: Water.
marcoporous resins for anthocyanin purification [11,13]. Thus, it is of
significance to develop novel technologies to enhance the anthocyanins
adsorption/desorption processes. In the last decade, a series of studies
have reported that ultrasound is an effective tool to assist the adsorp-
tion and desorption of target compounds using various materials as
adsorbents [15–17].
The principles of ultrasound for the enhancement of adsorption/
desorption process are its physical and cavitational properties.
Ultrasound can enhance the mass transfer process from solutions to
adsorbents and break the affinity between adsorbents and adsorbates by
ultrasonic cavitation [18]. Hamdaoui et al. [19] reported that ultra-
sound improved the adsorption rate in the adsorption of p-chlorophenol
with granular activated carbon. Jing et al. [17] found that ultrasound
could both raise adsorption rate and shorten equilibrium time of
chromium using polymeric resins, but it had no influence on deso-
rption. Korkut et al. [20] reported that ultrasound promoted the des-
orption of Cu (II), but had an adverse impact on Pb (II) desorption.
Karimi et al. [21] demonstrated that the impact of ultrasound on nitrate
desorption was positive at low temperature. However, most studies of
ultrasound-assisted adsorption/desorption were focused on the ad-
sorption/desorption of metal ions and organic pollutants, which have
not yet included adsorption/desorption of anthocyanins. Therefore, it is
meaningful to study how ultrasound affects adsorption and desorption
of anthocyanins using macroporous resins for the pigment purification.
This study aimed at studying the effects of different acoustic energy
densities (AED, 106, 199 and 279 W/L) and temperatures (20 and
30 °C) on adsorption and desorption of anthocyanins using macro-
porous resins. The kinetic analysis of adsorption/desorption processes,
component changes and resins characterization were investgated. This
work can provide guidance to food industry for the separation and
purification of anthocyanins pigments more efficiently.
312
Ultrasonics - Sonochemistry 48 (2018) 311–320
2. Materials and methods
2.1. Materials
Fresh blueberries (Vacciniumashei) were provided by a local plan-
tation in Lishui, Nanjing, China. After reaching the laboratory, blue-
berry samples were immediately stored at −18 °C, prior to use. XAD-
7HP resins and standards of anthocyanins were purchased from
Solarbio Technology Co., Ltd. (Shanghai, China). All other chemicals
used were of analytical or chromatographic grade.
2.2. Preparation of macroporous resins
Before application, the XAD-7HP resins were pretreated following
the method of Buran et al. [13]. Specifically, resins were filled in a glass
column (I.D. × L: 30 × 150 mm) and then washed with 200 mL of 95%
ethanol, followed by deionized water until eluate was clear. Next,
200 mL of 4% HCl was used for resin rinsing. After that, deionized
water was utilized again to resins until neutral. 200 mL of 5% NaOH
was further used for resins rinsing. Lastly, resins were rinsed by deio-
nized water until the pH value of eluate reached 7.0.
The aforementioned resins were vacuum-dried at 60 °C and 0.1 MPa
until constant weight was achieved.
2.3. Extraction of blueberry anthocyanins
Crude anthocyanin extracts were recovered from blueberries fol-
lowing the method of Buran et al. [13] with slight modifications. To be
exacted, frozen blueberries were thawed at room temperature for 12 h.
Next, thawed blueberries were crushed by a beater and mixed with
distilled water containing 0.02% HCl at a ratio of 1:10 (g:mL). After
that, the mixture was sonicated in an ultrasonic cell grinder (XO-
Y. Wu et al.
1200D, ATPIO Co., Ltd, Nanjing, China) at 25 °C and 500 W/L for
30 min. The resulting suspension was filtered through 8-layer gauze and
the supernatant was collected. The obtained supernatant was further
centrifuged at 5000 rpm for 15 min. The crude blueberry anthocyanin
extracts were stored at −18 °C until use.
2.4. Ultrasound-assisted adsorption/desorption procedures
Ultrasound-assisted adsorption/desorption processes were carried
out in a thermostatic water bath system (DC-0506, Fandilang Tech,
Nanjing, China) coupled with a 20 kHz ultrasound probe system
(VCX130, Sonics and Materials Inc., Newtown, USA) with a tip dia-
meter of 10 mm. The detailed experimental setup is illustrated in Fig. 1.
For adsorption test, activated resins (500 mg dry weight) were
added to 50 mL of crude blueberry anthocyanin extract in a 100-mL
conical flask. This flask was then placed in the aforementioned water
bath at target temperatures. Ultrasound probe was inserted in the flask
to a depth of 20 mm in the dispersion, so as to promote the adsorption
of phenolics to macroporous resins. The anthocyanin content in the
solvent was determined after sonication for 0, 10, 20, 30, 45, 60, 90,
120, 150, 180, 210, 240, 270 and 300 min, respectively. For each
sampling time, 1 mL sample was taken away from the dispersion and
then centrifuged. Besides, the actual acoustic energy density dissipated
in the adsorption system was determined using the calorimetric method
[22].
The adsorption capacity and ratio were quantified as follows:
Qe = (C0−Ce ) × Vi / W (1)
Qre = (C0−Ce )/ C0 × 100% (2)
where C0 and Ce are the initial and equilibrium concentrations of an-
thocyanins in the blueberry anthocyanin extract solution (mg/L). Vi
represents the volume of blueberry anthocyanin extract solution used
(mL). W is the dry weight of the resins used (g). Qe is the adsorption
capacity (mg/g dry resins) and Qre is the adsorption ratio (%) at equi-
librium.
For desorption test, 500 mg dried resins was added to 50 mL of
crude blueberry anthocyanin extract in a 100-mL conical flask. The
flask was stirred (100 rpm) at 20 °C until the equilibrium was reached.
The dispersion was passed through a Whatman filter paper (Grade 4,
Whatman Co., Ltd, Maidstone, Britain) to collect macroporous resins.
Then, the resins (500 mg wet weight) loaded with anthocyanins were
washed with deionized water and added to a 100-mL conical flask
containing 50 mL 80% aqueous ethanol [11,13]. This flask was placed
again in the water bath and ultrasound probe was inserted in the same
position as described in adsorption test. The variation of anthocyanins
content in the solvent was monitored periodically (0, 10, 20, 30, 40, 50
and 60 min).
The desorption capacity and recovery were quantified as follows:
Qd = Cd × Vd/ W (3)
D = Cd × Vd/(C0−Ce )/ Vi × 100% (4)
R = Cd × Vd/ C0/ V0 × 100% (5)
where Cd is the concentration of anthocyanins in the desorption solu-
tion (mg/L). Vd represents the volume of desorption solution (mL). Qd is
the desorption capacity (mg/g), D is the desorption ratio (%) and R is
the recovery (%) at desorption equilibrium.
2.5. Experimental design
The effects of AED levels (106, 199, 279 W/L) and temperatures (20,
30 °C) on the adsorption/desorption kinetics under sonication were
studied. A full-factorial design was used to generate the experimental
runs. For the comparison purpose, both the static adsorption/deso-
rption tests and adsorption/desorption tests under stirring at 100 rpm
313
Ultrasonics - Sonochemistry 48 (2018) 311–320
on a vibratory shaker were performed at 20 °C. All the experiments
were conducted in triplicate.
2.6. Adsorption kinetic modeling
Adsorption kinetics was evaluated using both pseudo first and
second order models [23].
Pseudo first order model is written as:
Ln(Qe−Qt ) = lnQe−ka t (6)
Pseudo second order model is written as:
t / Qt = 1/(kb Qe2) + t / Qe (7)
where Qe and Qt are the content of anthocyanins adsorbed at equili-
brium and time t (mg/g). ka and kb are the rate constant of the pseudo
first-order model and pseudo second-order model, respectively.
2.7. Chemical analysis
2.7.1. Determination of total anthocyanin content
Total anthocyanin content was determined using the method de-
scribed by Ivanova et al. [24]. Samples were diluted with a solution
consisting of ethanol/water/HCl = 69/30/1 (v/v/v) properly and the
absorbance was measured at 540 nm (1 cm optical path in the cuvette).
The total anthocyanin content was calculated using the following
equation:
Total anthocyanin content = A540 nm × 16.7 × d (8)
where A540 nm is absorbance at 540 nm, d is dilution factor; total an-
thocyanin content was expressed in mg L−1 as malvidin-3-glucoside
equivalents.
2.7.2. Determination of titratable acid and total sugar content
Contents of titratable acid and total sugar in blueberry anthocyanins
extracts were assayed according to the methods of Mohideen et al. [25]
and Gong et al. [26], respectively. To be exacted, titratable acid content
was measured by pipetting 5 mL of blueberry anthocyanin extract,
mixed with 45 mL distilled water into a 100-mL beaker. The diluted
sample was titrated to pH 8.2 using 0.1 M NaOH and the volume of
NaOH solution consumed was recorded. Then the total acid content was
calculated as:
Total acid content = 0.1 × M × VNaOH/Va (9)
where M is the molality of citric acid, the VNaOH is the volume of NaOH
used (L), and Va is the volume of blueberry extract solution (L).
The results were expressed as grams of citric acid equivalents per
liter of blueberry anthocyanins extracts. Total sugar content was mea-
sured by sulfuric acid-anthrone colorimetry method and the results
were expressed as grams of glucose equivalents per liter of blueberry
anthocyanins extracts.
2.7.3. Profile of anthocyanins, organic acids and sugars
Samples were centrifuged at 13,000 rpm for 5 min and the super-
natants were collected for further analysis. The changes of monomeric
anthocyanins (MA) contents during adsorption and desorption were
analyzed by a Shimadzu HPLC system (LC-2010A, Shimadzu
Corporation, Japan) following the method of Cui et al. [27]. An Agilent
TC-C18 column (250 × 4.6 mm, 5 μm) was used for separating antho-
cyanins. The binary mobile phase was composed of (A) trifluoroacetic
acid (0.5%) and (B) methanol at flow rate of 0.8 mL/min. The gradient
elution program was described as follows: 0–5 min, 10%–12% B;
5–14 min, 12%–13% B; 14–16 min, 13%–14% B; 16–18 min, 14%–16%
B; 18–19 min, 16%–18% B; 19–22 min, 18%–22% B; 22–35 min, 22%-
30% B; 35–45 min, 10% B. The column temperature and detection
wavelength were 30 °C and 520 nm, respectively. The injection volume
was 20 μL.
Y. Wu et al.
The variations of contents of specific organic acids were also de-
termined using the Shimadzu HPLC system coupled with the Agilent
TC-C18 column. The chromatographic conditions were shown as fol-
lows [28]: The mobile phase was 0.08 M mono potassium phosphate
solution (pH 2.9), and its flowing rate was 0.7 mL/min. The column
temperature was maintained at 30 °C and samples were detected at
210 nm using UV–Vis diode-array absorbance detection. The injection
volume was 20 μL.
Moreover, the sugar profile was assayed according to the method of
Araujodíaz, et al. [29] with slight modifications. 10 μL of supernatant
was injected into a HPLC system equipped with RID (Agilent 1200;
GMI, Ramsey, MN, USA). The column used was an Agilent Hi-Plex Ca
column (300 × 6.5 mm, 8 μm) and mobile phase was ultrapure water.
The column temperature was 80 °C and the detector temperature of RID
was 40 °C.
2.7.4. Characterization of macroporous resins
2.7.4.1. Fourier transform infrared spectroscopy (FTIR). For the
characterization of macroporous resins, all the samples were first
freeze-dried for 48 h to remove the residual water inside.
The FTIR analysis was performed in a Nicolet IR 200 FTIR spec-
troscopy (Thermo Electron Corporation, USA). 1 mg of macroporous
resins was mixed with 100 mg KBr, grounded and then tableted.
Samples were scanned from 4000 to 400 cm−1 under the infrared re-
gion.
2.7.4.2. Particle size distribution. Particle size distribution of
macroporous resins in blueberry anthocyanin extract solution was
determined by a laser particle size analyzer (LS-C(III), OMEC, Zhuhai,
China).
2.7.4.3. Scanning electron microscopy (SEM). The microstructures of
macroporous resins were observed by a scanning electron microscope
(JSM-5610LV, JEOL, Japan). Specifically, moderate resins were pasted
on dedicated nickel copper alloy of SEM, then a layer of conductive
gold film (about 15 nm) was gilded. The appearance of resins was
observed under SEM with the magnification of 100 and 500 times.
2.8. Statistical analyses
All of the treatments and analyses were conducted in triplicate. Data
were expressed as mean ± SD values. Statistical analysis was per-
formed by SAS 9.2 (SAS Institute, Cary, NC, USA). Significance of the
differences between variables was tested by one-way ANOVA. P values
less than 0.05 were considered statistically significant and the post hoc
test (Dunnett's test) was used to separate the mean differences.
3. Results and discussion
3.1. Comparison of adsorption and desorption processes with and without
sonication
Adsorption and desorption capacities are the most important in-
dicators to evaluate the purification performance when it comes to
recover target compounds through adsorption/desorption processes
[30]. The adsorption and desorption kinetic curves of anthocyanins
with the assistance of ultrasound at 20 °C and 106, 199, 279 W/L were
first compared with that in the absence of sonication (Supplementary
Fig. 1). Meanwhile, the adsorption and desorption capacities of an-
thocyanins on marcoporous resins under aforementioned conditions are
listed in Table 1.
As can be seen, ultrasound treatment significantly enhanced the
adsorption and desorption capacities of anthocyanins on marcoporous
resins, thus improving the recovery of anthocyanins from blueberry
extracts. For adsorption test, the highest adsorption capacity of antho-
cyanins (5.39 mg/g) was obtained when sonication was performed at
314
Ultrasonics - Sonochemistry 48 (2018) 311–320
279 W/L, followed by sonication at 199 W/L (4.85 mg/g), 106 W/L
(3.53 mg/g), shaking (2.48 mg/g) and standing (1.78 mg/g). Similar
results were reported by Jing et al. [17], who found that the sorption
rate of Cr (VI) on polymeric resin was enhanced by 2–3 times when
ultrasonic irradiation was performed during adsorption. Regarding
desorption test, the desorption capacity of anthocyanins after sonica-
tion at 279 W/L was 5.07 mg/g, which was 3.09 and 3.73 mg/g higher
than the desorption capacities obtained after shaking and standing. The
adsorption and desorption of anthocyanins on macroporous resins are
not only associated with the state of solution system and environmental
temperature, the adsorbent characteristics also play an important role
throughout the whole process [31,32]. Thus, the ultrasonic enhance-
ment of adsorption and desorption capacities of anthocyanins may be
attributed to the ultrasonic modification of solution state, adsorbent
properties, or both.
Additionally, the purity of anthocyanins in original blueberry ex-
tracts was 0.71%, while the corresponding purity increased to ap-
proximately 30% after marcoporous resins adsorption and desorption.
However, there was no significant difference (p > 0.05) in anthocya-
nins purity among treatments with and without sonication. For huck-
leberry extracts, they could be used as a food additive once the an-
thocyanins purity inside exceeds 25% [33]. Following this standard,
blueberry extracts purified by adsorption and desorption tests on
macroporous resins in this study could also be potentially used as food
colorants or additives directly.
3.2. Effects of AED and temperature levels on anthocyanins adsorption
behavior on macroporous resins
3.2.1. Effects on anthocyanins adsorption kinetics
Adsorption is a physio-chemical process that mainly involves the
mass transfer of a solute (adsorbate) from the fluid phase to the ad-
sorbent surface [32]. The adsorption kinetic curves of anthocyanins at
different AED and temperature levels are plotted in Fig. 2. It can be seen
that the anthocyanins adsorption capacity increased rapidly at the first
90 min and then increased slowly until equilibrium. The adsorption
capacity increased along with the increase of AED level. For example,
after adsorption for 1 h, the adsorption capacities of anthocyanins so-
nicated at 279, 199 and 106 W/L and 20 °C were 4.25, 3.58 and
2.07 mg/g, respectively. Moreover, the adsorption process reached
equilibrium faster when sonication was performed at higher AED levels.
There are three main factors influencing adsorption kinetics, including
characteristics of adsorbate and adsorbent, physio-chemical properties
of solution and environmental factors [34,35]. The positive effect of
AED levels on anthocyanins adsorption kinetics was probably due to the
formation of more violent ultrasound cavitation bubbles, which could
change the adsorbent features and enhance the anthocyanins transport.
On the other hand, temperature rising in the studied range hindered
the adsorption of anthocyanins on macroporous resins. Specifically, the
adsorption capacity at equilibrium during sonication at 106 W/L and
20 °C was 9.66% higher (p < 0.05) than that during sonication at
30 °C. Similar results were obtained from ultrasound-assisted adsorp-
tion at 199 and 279 W/L. Analogous discoveries have also been re-
ported by Buran et al. [13] that anthocyanins adsorption capacity on
FPX 66 resins decreased as temperature rose. There were three possible
reasons for this phenomenon. First, anthocyanins adsorption on mac-
roporous resins was a non-spontaneous and exothermic process [36].
Thus, a relatively low temperature could benefit the adsorption process.
Second, the solubility of anthocyanins in solution decreased with the
temperature decreasing. Moreover, an increase in temperature corre-
sponded to faster motion of anthocyanins molecules, leading to the
reduction of retention time of anthocyanins on resins surface [37]. It
was worth noting that the increase of ultrasonic density could attenuate
the influence of temperature on the adsorption capacity of macroporous
resin. Adsorption is an exothermic procedure and the increase of tem-
perature is not favorable for adsorption [36]. Thus, there was a higher
Y. Wu et al. Ultrasonics - Sonochemistry 48 (2018) 311–320

Table 1
Comparison of anthocyanin adsorption processes on macroporous with and without sonication.
Conditions Adsorption capacity (Qe, mg/g) Adsorption ratio (Qre,%) Desorption capacity (Qd, mg/g) Desorption ratio (D,%) Recovery (R,%) Purity (%)

e e e e e
Standing 1.78 ± 0.06 26.64 ± 0.79 1.34 ± 0.06 75.28 ± 1.36 20.05 ± 0.83 29.28 ± 0.66
d d d d d
Shaking (100 rpm) 2.48 ± 0.04 36.53 ± 0.95 1.98 ± 0.03 80.16 ± 1.03 29.28 ± 0.23 29.44 ± 0.45
c c c c c
AED (106 W/L) 3.53 ± 0.09 59.33 ± 1.91 3.12 ± 0.06 88.40 ± 0.56 52.44 ± 0.46 29.97 ± 0.82
b b b b b
AED (199 W/L) 4.85 ± 0.12 75.59 ± 1.45 4.65 ± 0.04 95.96 ± 0.88 72.53 ± 0.99 30.02 ± 0.77
a a a a a
AED (279 W/L) 5.39 ± 0.17 83.55 ± 2.07 5.07 ± 0.04 98.20 ± 1.49 82.12 ± 1.13 30.13 ± 0.71

Note: Lowercase letters represent significant difference among different treatments (p < 0.05).

(a) 8
106 W/L
The adsorption linear regression and rate constants values derived
from Peuso first-order and Peuso second-order kinetic equations are
7 199 W/L summarized in Table 2. The correlation coefficients (R2) of Peuso first-
order model were in the range of 0.931 to 0.970, and the R2 values of
Adsorption capacity (mg/g)

6 279 W/L
Peuso second-order model ranged from 0.985 to 0.998. Thus, Peuso
5 second-order model had a better capacity than Peuso first-order model
to predict adsorption capacity of anthocyanins. Similar results have also
4
been reported in previous studies using macroporous resins for the
3 adsorption of anthocyanins from different resources [11,31,39].
The rate constant refers to reaction rate of a particular set of cir-
2
cumstances including temperature, catalysts, solid surface properties
1 and so on, whereas it is free from influence of reactant concentrations
[40]. Table 2 revealed that the equilibrium constant was improved with
0 the increase of AED level, as well as the decrease of temperature. In the
0 50 100 150 200 250 300
Time (min) selected experimental range, the highest k value (5.28) was obtained
when adsorption was carried out at 279 W/L and 20 °C.

(b) 8 3.2.2. Effects on profiles of anthocyanins, acids and sugars

106 W/L
7 The variations of profiles of anthocyanins, acids and sugars during
199 W/L
Adsorption capacity (mg/g)

6 macroporous resins adsorption at 20 °C were further studied. The major

279 W/L
anthocyanins in blueberry extract were malvidin 3-galactoside (MGA),
5 malvidin 3-glucoside (MGL), malvidin 3-arabinoside (MAR), delphi-
nidin 3-glucoside (DGL), peonidin 3-glucoside (PGL) and cyaniding 3-
4
glucoside (CGL) according to HPLC-MS analysis (data not shown). The
3 changes of contents of specific anthocyanins during adsorption are
shown in Fig. 3. It can be seen that the most abundant anthocyanin in
2
blueberry extracts was MGA, which accounted for 29% of the total
1 anthocyanins content. Similar to the aforementioned results, the ad-
sorption capacities of monomeric anthocyanin also increased sig-
0
nificantly with AED level, especially for MGA, MGL, DGL and MAR.
0 50 100 150 200 250 300
Time (min) Moreover, MGA had the highest adsorption capacity when the ad-
sorption reached the equilibrium, being 1.23 mg/g at 106 W/L,
Fig. 2. Adsorption kinetic curves of total anthocyanins under different AED 1.61 mg/g at 199 W/L and 1.71 mg/g at 279 W/L. CGL had the lowest
levels at 20 °C (a) and 30 °C (b).
adsorption capacity. The study of Buran et al. [13] also reported that
MGA had the highest affinity on macroporous resins among all the
monomeric anthocyanins studied. Additionally, the adsorption of each
energy barrier that adsorbed molecules needed to overcome, so as to
monomeric anthocyanin reached equilibrium faster when the applied
leave the solution at higher temperatures [38]. In this case, higher ul-
AED level increased. At all the AED levels used, the adsorption of CGL
trasonic density could supply more energies to assist resin to adsorb
always reached the equilibrium first, followed by the adsorption of PGL.
anthocyanins at higher temperatures.
The different adsorption behaviors of monomeric anthocyanins on

Table 2
Pseudo first and second order kinetic parameters of ultrasound-assisted adsorption of anthocyanins on marcoporous resins.
Temperature (°C) AED (W/L) Pseudo first-order Pseudo second-order

Ka (min−1) qe (mg/g) R2 Kb (g/mg·min−1) qe (mg/g) R2

20 106 0.029 3.23 0.955 7.50 × 10−3 3.49 0.998

199 0.035 4.55 0.948 8.65 × 10−3 4.75 0.994
279 0.036 5.09 0.931 8.80 × 10−3 5.28 0.985

30 106 0.027 2.99 0.970 7.12 × 10−3 3.17 0.992

199 0.034 4.23 0.968 8.30 × 10−3 4.50 0.990
279 0.035 4.95 0.966 8.62 × 10−3 5.21 0.992

315
Y. Wu et al. Ultrasonics - Sonochemistry 48 (2018) 311–320

(a) 24 DGL CGL

The changes of acid and sugar profiles in blueberry extract during
adsorption are listed in Table 3. The richest organic acid in blueberry
PGL MGL
20
MAR MGA
extract was quininic acid (741.26 mg/L), followed by malic acid
(61.86 mg/L). Meanwhile, glucose had the highest content in blueberry
MA content (mg/L)

16
extract, followed by fructose. The contents of both acids and sugars did
12 not change significantly (p > 0.05) during adsorption, demonstrating
that anthocyanins could be well separated from the raw blueberry ex-
8
tract and ultrasound could accelerate the separation process.
4
3.2.3. Effects on resin characteristics
0
0 50 100 150 200 250 300
The FTIR spectra of blueberry extracts, original macroporous resins
Time (min) and resins after ultrasound-assisted adsorption are plotted in Fig. 4a.
The characteristic wavelengths of original macroporous resins at
1735 cm−1 corresponded to the stretching vibration of C]O. At the
(b) 24
DGL CGL
same time, the adsorption peaks at 1473 and 1394 cm−1 represented
20 PGL MGL
the bending vibration of CeH [45]. Moreover, the weak peaks at 3560
MAR MGA
and 2975 cm−1 were correlated with the stretching vibration of OeH
MA content (mg/L)

16
and CeH bonds [4]. Regarding the spectrum of anthocyanins extracts
12 alone, some specific wavenumbers at 3390, 2939, 1637 and 1050 cm−1
were observed. Similarly, the bands at 3390 and 2939 cm−1 were as-
8
sociated with stretching of OeH and CeH bonds [4]. The band at
4 1637 cm−1 referred to the stretching vibration of aromatic C]C bond
of anthocyanins [46]. And the region around 1050 cm−1 mainly de-
0
0 50 100 150 200 250 300 noted the CeO stretching vibration of sugars and acids in blueberry
Time (min) extracts [47].
There were some new changes in the FTIR spectrum of marcoporous
resins after ultrasound-assisted adsorption. To be exact, the appearance
of wavenumber at 1637 cm−1 indicated that anthocyanins were ad-
(c) 24
DGL CGL
sorbed by resins successfully. Meanwhile, the adsorption peak at
3560 cm−1 in the original marcoporous resins disappeared, whereas a
PGL MGL
20 new peak at 3440 cm−1 was formed. This result implied that phenol
MAR MGA
hydroxyls of resin surface might interact with the hydroxyls of antho-
MA content (mg/L)

16
12
8 tions between macroporous resins and blueberry anthocyanins. Besides,
4
0 acids and sugars from anthocyanins.
0 50 100 150 200
Time (min)
Fig. 3. Changes of contents of monomeric anthocyanins during ultrasound-as-
sisted adsorption process at 106 (a), 199 (b) and 279 (c) W/L.
macroporous resins were probably related to their concentrations and
structures [41].
Generally, monomeric anthocyanin had a stronger driving force to
penetrate deep inside the resin framework at high concentration gra-
dient [42]. Meanwhile, methoxy and hydroxyl groups in B-ring of an-
thocyanins could enhance their binding capacity with resins [43], while
the methoxy group had a higher effect than hydroxyl substituent
[41,43]. Malvidin had more methoxy groups in B-ring than the other
investigated anthocyanins, which gave a higher capacity to be adsorbed
by resins. Moreover, the type of glucoside can influence the reactions
between anthocyanins and resins. Since arabinose had one hydroxyl
less than glucose and galactose, which meant that MAR had less op-
portunities to be adsorbed by the resins via the formation of hydrogen
bond [44]. Furthermore, the hydroxyl of galactose lied on the a-bond,
while the hydroxyl of glucose was located on the e-bond. The higher
activity of hydroxyl on the a-bond gave anthocyanins with galactose a
stronger capacity to interact with macroporous resins [44].
cyanins, resulting in the formation of hydrogen bonds [48]. The peak
intensity of this hydrogen bond on FTIR spectrum increased with ul-
trasound energy, demonstrating that ultrasound promoted the interac-
the band at 1050 cm−1 that was related to acids and sugars got weak
significantly after adsorption, verifying the successful separation of
250 300 The particle distributions of resins at different AED levels are shown
in Fig. 5. The average particle size of resins (D50) before ultrasound was
167.25 μm. After ultrasound-assisted adsorption, the D50 value of resins
firstly increased and then decreased with AED levels, being 209.06 μm
at 106 W/L, 247.19 μm at 199 W/L and 158.73 μm at 279 W/L. Ultra-
sound at moderate intensity may enhance the swelling degree of resins
in solutions and increase the resin size [44]. Resins with larger particle
sizes tended to have higher mass exchange rates and allow more ma-
terial to be transferred to and from the resins, hence increasing the
adsorption capacity [13].
The SEM morphologies of marcoporous resins after adsorption are
plotted in Fig. 6. Meanwhile, the SEM images of resins with lower
magnification are shown in Supplementary Fig. 2. It can be observed
that macroporous resins before adsorption had an integrated spherical
geometry with a quantity of micropores on the surface. There were
some apparent structural changes after ultrasound-assisted adsorption.
Specifically, the surface roughness of macroporous resins was ag-
gravated with the increasing of AED level, which was probably due to
the effect of ultrasound cavitation [15]. After adsorption at 279 W/L for
5 h, the macroporous resins were even disrupted into some pieces. This
phenomenon could explain the results why the mean particle size of
macroporous resins sonicated at 279 W/L was smaller than that of

316
Y. Wu et al. Ultrasonics - Sonochemistry 48 (2018) 311–320

Table 3
Contents of acids and sugars before and after ultrasound-assisted adsorption of anthocyanins on macroporous resin at 20 °C.
Compounds Before adsorption After adsorption

106 W/L 199 W/L 279 W/L

Organic acids
Quininic acid (mg/L) 741.26 ± 11.95 750.26 ± 13.34 748.21 ± 12.34 740.17 ± 12.12
Malic acid (mg/L) 61.86 ± 0.95 61.15 ± 0.68 61.35 ± 0.70 61.28 ± 0.82
Tartaric acid (mg/L) 12.69 ± 0.67 12.70 ± 0.41 12.43 ± 0.63 12.17 ± 0.96
Citric acid (mg/L) 9.36 ± 0.25 9.23 ± 0.20 9.70 ± 0.26 9.56 ± 0.31
Shikimic acid (mg/L) 5.40 ± 0.17 5.61 ± 0.39 5.39 ± 0.20 5.42 ± 0.22
Oxalic acid (mg/L) 4.16 ± 0.18 4.22 ± 0.29 4.30 ± 0.20 4.28 ± 0.39
Total acids (mg/L) 1040.11 ± 20.02 1002.02 ± 18.11 1001.01 ± 18.73 1002.56 ± 13.88

Sugars
Glucose (mg/mL) 2.89 ± 0.05 2.91 ± 0.02 2.94 ± 0.02 2.92 ± 0.04
Fructose (mg/mL) 1.77 ± 0.02 1.81 ± 0.02 1.82 ± 0.02 1.82 ± 0.03
Sucrose (mg/mL) 0.09 ± 0.01 0.11 ± 0.01 0.12 ± 0.02 0.10 ± 0.01
Total sugars (mg/mL) 5.03 ± 0.23 5.00 ± 0.20 5.02 ± 0.19 5.02 ± 0.23

Note: There were no significant differences for contents of acids and sugars among different treatments (p > 0.05).

(a) 30 Before adsorption

25 AED (106 W/L)

279 W/L
1637 AED (199 W/L)
3440 2967 1733 20 AED (279 W/L)

Volume (%)
1470
1390
Transmittance (%)

199 W/L 15
981
1265 1050
1150 10
106 W/L

Anthocyanin extracts 5
1637
1050
3390 2939 Before adsorption 0
1394
0 200 400 600 800 1000
3560 2975 1735 1473 1154 Particle size (µm)
4000 3500 3000 2500 2000 1500 1000 500
Fig. 5. Particle size distribution of macroporous resins before and after ultra-
-1
Wavenumber (cm ) sound-assisted adsorption.

3.3. Effects of AED and temperature levels on anthocyanins desorption

behavior on macroporous resins
(b)
279 W/L
981
3.3.1. Effects on anthocyanins desorption kinetics
2975 1637 1394
3560
1734 1473 1154 Desorption is the reverse process of adsorption. The desorption ki-
1267
199 W/L netic curves of anthocyanins at different AED and temperature levels
are depicted in Fig. 7. It can be seen that the anthocyanins desorption
Transmittance (%)

capacity increased fast at the first 10 min and then increased slowly
106 W/L
until reaching the equilibrium. At the same time, the desorption capa-
city of anthocyanins increased with AED level. For instance, after des-
orption at 20 °C for 10 min, the desorption capacities of anthocyanins
Before desorption sonicated at 106, 199 and 279 W/L were 1.22, 1.85 and 2.36 mg/g,
1470 respectively. Besides, the desorption process reached equilibrium faster
2967
3440 when desorption was performed in ultrasonic fields. It took approxi-
1733
mately 10 min for the ultrasound-assisted desorption process at 279 W/
4000 3500 3000 2500 2000 1500 1000 500 L to reach the equilibrium, which was 10 min and 20 min shorter than
-1 the desorption processes sonicated at 199 and 106 W/L. The positive
Wavenumber (cm )
influence of ultrasound on anthocyanins desorption kinetics was
Fig. 4. FTIR spectrum of macroporous resins after ultrasound-assisted adsorp-
probably because of the ultrasonic enhanced mass transfer among re-
tion (a) and desorption (b).
sins/anthocyanins/ethanol phases, which can enhance the diffusion
coefficient of anthocyanins desorbed from resins [49].
macroporous resins sonicated at 199 W/L, which was previously men- On the other hand, temperature rising can benefit the detachment of
tioned in Fig. 5. Due to the ultrasonic damage to macroporous resins, anthocyanins from macroporous resins during desorption. Taking so-
the specific area of resins for adsorption was increased, thus strength- nication at 106 W/L for example, the equilibrium desorption capacity at
ening the affinity between marcoporous resins and anthocyanins 30 °C was 4.22% higher than the corresponding capacity at 20 °C.
[11,44]. Similar results were found for sonication at other AED levels. In the
literature, Chen et al. [11] and Yang et al. [50] also reported that the

317
Y. Wu et al.
Fig. 6. Scanning electron micrographs (500 × magnification) for resins before and after ultrasound-assisted adsorption. a: control resins. b: resins treated at 106 W/
L; c: resins treated at 199 W/L; d: resins treated at 279 W/L.
desorption capacity of phenolics from macroporous resins increased as
temperature rose. There were two possible reasons to explain this
phenomenon. On one hand, the desorption of anthocyanins on macro-
porous resins is a non-spontaneous and endothermic process [36]. Thus,
considerably high temperatures can benefit the desorption process. On
the other hand, the solubility of anthocyanins elevated with the tem-
perature increasing.
3.3.2. Effects on anthocyanins profile
The variation of anthocyanins profile during macroporous resin
desorption at 30 °C was further researched. The changes of contents of
some specific anthocyanins during desorption are shown in Fig. 8. Si-
milar to the aforementioned results, the desorption capacities of
monomeric anthocyanins also increased significantly with AED level,
particularly for MGA, MGL, DGL and MAR. Meanwhile, MGA had the
highest desorption capacity when desorption reached the equilibrium,
being 0.82 mg/g at 106 W/L, 1.01 mg/g at 199 W/L and 1.24 mg/g at
279 W/L. CGL was the monomeric anthocyanin that had the lowest
desorption capacity. Additionally, the desorption of all the monomeric
anthocyanins reached equilibrium faster when ultrasound was in-
troduced. At all the AED levels under investigation, CGL was always the
first monomeric anthocyanin to reach the desorption equilibrium, fol-
lowed by PGL. The concentrations of monomeric anthocyanins play an
important role on the desorption from macroporous resins [41,48]. It
has been reported by Natalia et al. [42] that adsorbates with higher
concentration gradient had a high driving force to penetrate deep inside
the resins framework, while the counterparts with lower concentration
gradients mainly accumulated on the resin surface. Therefore,
318
Ultrasonics - Sonochemistry 48 (2018) 311–320
adsorbates with low concentrations can be separated from the ad-
sorbents more easily. Since CGL had the lowest adsorption capacity on
marcoporous resins and most of them may locate on the resins surface,
CGL can be more easily washed from the resins during the desorption
process in comparison with other monomeric anthocyanins.
3.3.3. Effects on resin characteristics
The FTIR spectra of macroporous resins after ultrasound-assisted
desorption are plotted in Fig. 4b. Similar to the effect of ultrasound on
the FTIR spectra of marcoporous resins during adsorption, ultrasound
also produced some new changes in the FTIR spectrum of marcoporous
resins after desorption. The weakening of peak intensity at 1637 cm−1
indicated that anthocyanins were detached from macroporous resins
successfully and ultrasound promoted the desorption process. Mean-
while, the spectral region between 3600 and 3300 cm−1 made shift
towards higher wavelengths region and the absorption peak got weak
and narrow after sonication. This result implied that the hydrogen
bonds formed between phenol hydroxyls of resins surface and hydro-
xyls of anthocyanins may break during ultrasound-assisted desorption
[48]. It should be pointed out that the breakage of hydrogen bonds
needs energy from environment, and high-intensity ultrasound could
provide sufficient energy for this process [17].
4. Conclusions
This study has provided insights into the ultrasound-assisted pur-
ification of blueberry anthocyanins using macroporous resins. In com-
parison with shaking treatment (100 rpm), ultrasound significantly
Y. Wu et al. Ultrasonics - Sonochemistry 48 (2018) 311–320

(a) 3.5 106 W/L

(a) 10 DGL CGL
3 199 W/L PGL MGL
Desorption capacity (mg/g)

279 W/L 8
MAR MGA
2.5

MA content (mg/L)
6
2

1.5 4

1
2
0.5
0
0 0 10 20 30 40 50 60
0 10 20 30 40 50 60
Time (min)
Time (min)
(b) 12 DGL CGL

(b) 3.5
106 W/L
10 PGL MGL
MAR MGA
199 W/L

MA content (mg/L)
3 8
Desorption capacity (mg/g)

279 W/L
2.5
6
2
4
1.5
2
1
0
0.5 0 10 20 30 40 50 60
Time (min)
0
0 10 20 30 40 50 60
Time (min) (c) 14 DGL CGL
PGL MGL
12
Fig. 7. Desorption kinetic curves of total anthocyanins under different AED MAR MGA
MA content (mg/L)

levels at 20 °C (a) and 30 °C (b). 10

8
enhanced the adsorption/desorption capacities of anthocaynins on
macroporous resins, as well as shortened the time reaching the equili- 6

brium. At the same time, anthocyanins purity after adsorption/deso- 4

rption on macroporous resins exceeded 25%, indicating that the re-
sulting anthocyanins could be directly used as food additives. The
ultrasound-enhanced adsorption process followed the pseudo second-
order model with R2 > 0.98. For adsorption process, the increase of
ultrasound input energy and the decrease of temperature could benefit
the adsorption of anthocyanins on the resins, while temperature rising
had a positive influence on desorption process. Malvidin-3-galactoside
had the highest adsorption/desorption capacities among all the
monomeric anthocyanins, while cyaniding-3-glucoside reached ad-
sorption/desorption equilibrium first. Through the analysis of resin
structure, it was found that ultrasound mainly promoted the formation
of hydrogen bond on the resin surface and increased the surface
roughness, so as to facilitate the adsorption process.
In summary, ultrasound can be an environmentally friendly, easily-
operating, and effective technology to improve the purification effi-
ciency of anthocyanins when macroporous resins are used.
Acknowledgements
The work was funded by the Provincial Natural Science Fund coded
BK 20170714, Jiangsu, China; National Natural Science Fund coded
31701616, China; the Fundamental Research funds for the Central
Universities, China; Yingcai Project, Zhenjiang, China; the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD).
2
0
0 10 20 30 40 50 60
Time (min)
Fig. 8. Change of contents of monomeric anthcoyanins during ultrasound-as-
sisted desorption process at 106 (a), 199 (b) and 279 (c) W/L.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.ultsonch.2018.06.016.
References
[1] U.S. Department of agriculture, agricultural research service, nutrient data la-
boratory. USDA National Nutrient Database for Standard Reference, release 26, U.S.
Department of Agriculture, Beltsville, MD, 2013.
[2] H.L. Jiang, J.L. Yang, Y.P. Shi, Optimization of ultrasonic cell grinder extraction of
anthocyanins from blueberry using response surface methodology, Ultrason.
Sonochem. 34 (2017) 325–331.
[3] H.L. Wang, X.B. Guo, X.D. Hu, T. Li, X. Fu, R.H. Liu, Comparison of phytochemical
profiles, antioxidant and cellular antioxidant activities of different varieties of
blueberry (Vaccinium spp.), Food Chem. 217 (2017) 773–781.
[4] Y. Tao, P. Wang, J.D. Wang, Y. Wu, Y.B. Han, J.Z. Zhou, Combining various wall
materials for encapsulation of blueberry anthocyanin extracts: optimization by ar-
tificial neural network and genetic algorithm and a comprehensive analysis of an-
thocyanin powder properties, Powder Technol. 311 (2017) 77–87.
[5] FAO. FAO, statistical yearbook 2013, World food and agriculture. Food and

319
Y. Wu et al.
Agriculture Organization of the United Nations, 2013.
[6] S.M. Jafari, M.G. Ghaienoei, D. Dehnad, Influence of spray drying on water solu-
bility index, apparent density, and anthocyanin content of pomegranate juice
powder, Powder Technol. 311 (2017) 59–65.
[7] I. Tontul, A. Topuz, Spray-drying of fruit and vegetable juices: effect of drying
conditions on the product yield and physical properties, Trends Food Sci. Technol.
63 (2017) 91–102.
[8] R.L. Prior, X. Wu, L. Gu, T.J. Hager, A. Hager, L.R. Howard, Whole berries versus
berry anthocyanins: interactions with dietary fat levels in the C57BL/6J mouse
model of obesity, J. Agric. Food. Chem. 56 (2008) 647–653.
[9] F. Sheng, Y. Wang, X. Zhao, N. Tian, H. Hu, P. Li, Separation and identification of
anthocyanin extracted from mulberry fruit and the pigment binding properties to-
ward human serum albumin, J. Agric. Food. Chem. 62 (2014) 6813–6819.
[10] E. Wang, Y. Yin, C. Xu, J. Liu, Isolation of high-purity anthocyanin mixtures and
monomers from blueberries using combined chromatographic techniques, J.
Chromatogr. A 1327 (2014) 39–48.
[11] Y. Chen, W. Zhang, T. Zhao, F. Li, M. Zhang, J. Li, Y. Zou, W. Wang, S.J. Cobbina,
X.Y. Wu, L.Q. Yang, Adsorption properties of macroporous adsorbent resins for
separation of anthocyanins from mulberry, Food Chem. 194 (2016) 712–722.
[12] Y. Zou, M.M. Zhao, K. Yang, L.Z. Lin, Y. Wang, Enrichment of antioxidants in black
garlic juice using macroporous resins and their protective effects on oxidation-da-
maged human erythrocytes, J. Chromatogr. B 1060 (2017) 443–450.
[13] T.J. Buran, A.K. Sandhu, Z. Li, C. Rock, W.H. Yang, L.W. Gu, Adsorption/desorption
characteristics and separation of anthocyanins and polyphenols from blueberries
using macroporous adsorbent resins, J. Food Eng. 128 (2014) 167–173.
[14] Z. Xu, Q. Zhang, J. Chen, G.K. Anderson, Adsorption of naphthalene derivatives on
hypercrosslinked polymeric adsorbents, Chemosphere 38 (1999) 2003–2011.
[15] Z. Li, X. Li, H. Xi, B. Hua, Effects of ultrasound on adsorption equilibrium of phenol
on polymeric adsorption resin, Chem. Eng. J. 86 (2002) 375–379.
[16] O. Hamdaoui, E. Naffrechoux, Adsorption kinetics of 4-chlorophenol onto granular
activated carbon in the presence of high frequency ultrasound, Ultrason. Sonochem.
16 (2009) 15–22.
[17] G.H. Jing, Z.M. Zhou, S. Lei, M.X. Dong, Ultrasound enhanced adsorption and
desorption of chromium (VI) on activated carbon and polymeric resin, Desalination
279 (2011) 423–427.
[18] M. Breitbach, D. Bathen, H. Schmidt-Traub, Desorption of a fixed-bed adsorber by
ultrasound, Ultrasonics 40 (2002) 679–682.
[19] O. Hamdaoui, E. Naffrechoux, L. Tifouti, C. Pétrierb, Effects of ultrasound on ad-
sorption-desorption of p-chlorophenol on granular activated carbon, Ultrason.
Sonochem. 10 (2003) 109–114.
[20] O. Korkut, E. Sayan, O. LaċN, B. Bayrak, Investigation of adsorption and ultrasound
assisted desorption of lead (II) and copper (II) on local bentonite: a modelling study,
Desalination 259 (2010) 243–248.
[21] M. Karimi, M.H. Entezari, M. Chamsaz, Sorption studies of nitrate ion by a modified
beet residue in the presence and absence of ultrasound, Ultrason. Sonochem. 17
(2010) 711–717.
[22] Y. Tao, P. Wang, Y.L. Wang, S.U. Kadam, Y.B. Han, J.D. Wang, J.Z. Zhou, Power
ultrasound as a pretreatment to convective drying of mulberry (Morus alba L.)
leaves: impact on drying kinetics and selected quality properties, Ultrason.
Sonochem. 31 (2016) 310–318.
[23] S.Q. Cao, S.Y. Pan, X.L. Yao, F.H. Fei, Isolation and purification of anthocyanins
from blood oranges by column chromatography, J. Integr. Agric. 9 (2010) 207–215.
[24] V. Ivanova, Á. Dörnyei, L. Márk, B. Vojnoski, T. Stafilov, M. Stefova, F. Kilár,
Polyphenolic content of Vranec wines produced by different vinification conditions,
Food Chem. 124 (2010) 316–325.
[25] F.W. Mohideen, K.M. Solval, J. Li, J. Li, A. Chouljenko, A. Chotiko, A.D. Predente,
J.D. Bankston, S. Sathivel, Effect of continuous ultra-sonication on microbial counts
and physico-chemical properties of blueberry (Vacciniumcorymbosum) juice, LWT –
Food Sci. Technol. 60 (2015) 563–570.
[26] Y.J. Gong, J. Zhang, F. Gao, J.W. Zhou, Z.N. Xiang, C.G. Zhou, L.S. Wan, J.C. Chen,
Structure features and in vitro hypoglycemic activities of polysaccharides from
different species of Maidong, Carbohydr. Polym. 173 (2017) 215–222.
[27] C. Cui, S.M. Zhang, L.J. You, J.Y. Ren, W. Luo, W.F. Chen, M.M. Zhao, Antioxidant
capacity of anthocyanins from Rhodomyrtus tomentosa (Ait.) and identification of
320
Ultrasonics - Sonochemistry 48 (2018) 311–320
the major anthocyanins, Food Chem. 139 (2013) 1–8.
[28] M.S. Lima, I.S. Silani, I.M. Toaldo, L.S. Correa, A.T. Biasoto, G.E. Pereira,
M. Bordignon-Luiz, J.L. Ninow, Phenolic compounds, organic acids and antioxidant
activity of grape juices produced from new Brazilian varieties planted in the
Northeast Region of Brazil, Food Chem. 161 (2014) 94–103.
[29] S.B. Araujo-Díaz, C. Leyva-Porras, P. Aguirre-Bañuelos, C. Alvarez-Salas,
Z. Saavedra-Leos, Evaluation of the physical properties and conservation of the
antioxidants content, employing inulin and maltodextrin in the spray drying of
blueberry juice, Carbohydr. Polym. 167 (2017) 317–325.
[30] L. Zhou, Q.Y. Yu, Y. Cui, F. Xie, W.J. Li, Y.W. Li, M.F. Chen, Adsorption properties of
activated carbon from reed with a high adsorption capacity, Ecol. Eng. 102 (2017)
443–450.
[31] X.L. Chang, D. Wang, B.Y. Chen, Y.M. Feng, S.H. Wen, P.Y. Zhan, Adsorption and
desorption properties of macroporous resins for anthocyanins from the calyx extract
of roselle (Hibiscus sabdariffa L.), J. Agric. Food. Chem. 60 (2012) 2368–2376.
[32] C. Jampani, A. Naik, K.S. Raghavarao, Purification of anthocyanins from jamun
(Syzygiumcumini, L.) employing adsorption, Sep. Purif. Technol. 125 (2014)
170–178.
[33] C. Artaria, R. Pace, G. Maramaldi, G. Appendino, Different brands of bilberry ex-
tract, a comparison of selected components, Nutra Foods 6 (2007) 13–18.
[34] M.H. Entezari, A.A. Shameli, Phase-transfer catalysis and ultrasonic waves I.
Cannizzaroreaction, Ultrason. Sonochem. 7 (2000) 169–172.
[35] M.H. Entezari, A. Keshavarzi, Phase-transfer catalysis and ultrasonic waves II, sa-
ponification of vegetable oil, Ultrason. Sonochem. 8 (2001) 213–216.
[36] J. Chandrasekhar, M.C. Madhusudhan, K.S.M.S. Raghavarao, Extraction of antho-
cyanins from red cabbage and purification using adsorption, Food Bioprod. Process.
90 (2012) 615–623.
[37] Z. Zhao, L. Dong, Y. Wu, F. Lin, Preliminary separation and purification of rutin and
quercetin from Euonymus alatus, (Thunb.) Siebold, extracts by macroporous resins,
Food Bioprod. Process. 89 (2011) 266–272.
[38] S. Saffarionpoura, S.Y. Tama, L.V. Wielen, E. Brouwer, M. Ottens, Influence of
ethanol and temperature on adsorption of flavor-active esters on hydrophobic re-
sins, Sep. Purif. Technol. (2018) In press.
[39] M.A. Abdullah, L. Chiang, M. Nadeem, Comparative evaluation of adsorption ki-
netics and isotherms of a natural product removal by Amberlite polymeric ad-
sorbents, Chem. Eng. J. 146 (2009) 370–376.
[40] H. Yamamoto, Nonuniform kinetic method applied to evolutionary process of a rate
constant in NaOH-gelatinization of rice starch, Food Hydrocolloids 73 (2017)
143–152.
[41] P. Mazzaracchio, M. Kindt, P.G. Pifferi, S. Tozzi, G. Barbiroli, Adsorption behaviour
of some anthocyanins by wheat gluten and its fractions in acidic conditions, Int. J.
Food Sci. Technol. 47 (2012) 390–398.
[42] N.A. Pinchukova, A.Y. Voloshko, M.A. Merko, Y.A. Bondarenko, V.A. Chebanov,
Intensification of ion exchange desorption of thiamine diphosphate by low-powered
ultrasound, Ultrason. Sonochem. 41 (2018) 261–266.
[43] J.E. Farr, G.T. Sigurdson, M.M. Giusti, Influence of cyanidin glycosylation patterns
on carboxypyranoanthocyanin formation, Food Chem. 259 (2018) 261–269.
[44] Y. Kohno, E. Haga, K. Yoda, M. Shibata, C. Fukuhara, Adsorption behavior of nat-
ural anthocyanin dye on mesoporous silica, J. Phys. Chem. Solids 75 (2014) 48–51.
[45] Z. Lin, J. Fischer, L. Wicker, Intermolecular binding of blueberry pectin-rich frac-
tions and anthocyanin, Food Chem. 194 (2016) 986–993.
[46] C.S. Pappas, G. Takidelli, E. Tsantili, P.A. Tarantilis, M.G. Polissiou, Quantitative
determination of anthocyanins in three sweet cherry varieties using diffuse re-
flectance infrared Fourier transform spectroscopy, J. Food Compos. Anal. 24 (2011)
17–21.
[47] Beullens, K. Kirsanov, D. Irudayaraj, J. Rudnitskaya, A. Legin, The electronic tongue
and ATR–FTIR for rapid detection of sugars and acids in tomatoes. Sensors &
Actuators B, Chemical 116 (2006) 107–115.
[48] E. Sritham, S. Gunasekaran, FTIR spectroscopic evaluation of sucrose-maltodextrin-
sodium citrate bioglass, Food Hydrocolloids 70 (2017) 371–382.
[49] Z. Li, K.F. Xu, X.B. Li, H.X. Xi, B. Hua, F.S. Li, Effect of ultrasound on desorption
kinetics of phenol from polymeric resin, Ultrason. Sonochem. 13 (2006) 225–231.
[50] Q. Yang, M. Zhao, L. Lin, Adsorption and desorption characteristics of adlay bran
free phenolics on macroporous resins, Food Chem. 194 (2016) 900–907.