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Industrial Crops and Products 85 (2016) 213–220

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Industrial Crops and Products


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

Avocado seed: Modeling extraction of bioactive compounds


Francisco J. Segovia, Juan J. Corral-Pérez, María P. Almajano ∗
Chemical Engineering Department, Technical University of Catalonia, Av. Diagonal 647, 08028 Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Avocado seed is a by-product that contains a large amount of extractable polyphenols, which have
Received 30 November 2015 attracted the attention of food and cosmetic industries due to their high antioxidant capacity. This fact
Received in revised form 4 February 2016 makes it a promising candidate for the cheap and sustainable extraction of such compounds. This work
Accepted 2 March 2016
aims to evaluate the effect of ultrasound power (0–104 W) and temperature (20–60 ◦ C) on the extrac-
tion of total polyphenols from avocado seed using water as a green solvent. Increasing temperature and
Keywords:
ultrasound power resulted in extracts with higher polyphenol content and antioxidant capacity. Differ-
Avocado
ent mathematical models (Peleg’s, empirical, film theory and Fick’s law) were also used to find the one
Polyphenols
Extraction
that best fit the extraction kinetics. Models based on film theory and Fick’s law were able to predict
Modeling the ultrasound-assisted batch and continuous extractions, respectively, at 95% accuracy. Using a model
Diffusivity based on Fick’s law, diffusion coefficients of polyphenols in both fast and slow stages were calculated
Ultrasound for the extractions. In addition, a linear relationship between total polyphenolic content and antioxidant
capacity was proposed.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction tory diseases and preventing lipid oxidation (Moure et al., 2001).
Furthermore, the use of synthetic antioxidants, like BHA (buty-
The food industry is generating many organic by-products and it lated hydroxyanisole) and BHT (butylated hydroxytoluene), are
is well known that the food wastes such as seeds, hulls, wood, bark, restricted because concern is expressed about the possible negative
roots and leaves are potential sources of antioxidants compounds effects on human health (Jayaprakasha et al., 2003).
(Rubilar et al., 2006; Soong and Barlow, 2004; Velioglu et al., 1998). In addition, it is necessary to point out that processes, such as
In this work, avocado seed is proposed to be a potential candidate solid-liquid extraction, can be modeled and simulated thanks to
for polyphenol extraction. There are several studies about avocado the numerical methods and computational advances. A model for
and its high antioxidant capacity, as well as its large amount of the extraction of polyphenols and the estimation of their effective
extractable polyphenols, from quantifying its total polyphenolic diffusivity is required in order to analyze and design an extrac-
yield until how it prevents food matrices or emulsions oil-water tion process in industry (Guerrero et al., 2008; Pinelo et al., 2005;
from oxidation (Logaraj et al., 2008; Rodríguez-Carpena et al., 2011; Rodríguez-Fernández et al., 2007). Unfortunately, most of the stud-
Soong and Barlow, 2004; Wang et al., 2012, 2010). ies about these extraction processes are scarce and their point is not
In the other hand, the intake of polyphenols as natural sub- from engineering (Guerrero et al., 2008).
stances through the diet, such as food products enriched with them, The solid-liquid extraction of polyphenols is a multi-phase and
is a fact whose popularity has greatly increased in recent years. It unsteady-state transfer mass operation, where the concentration
is widely accepted that high intakes of fruit and vegetables pre- of the solute inside the solid varies continuously. Experimental
vent people from some diseases due to the presence of various studies about kinetics extraction are required to estimate effective
antioxidants (Johnson, 2004). diffusivity. The liquid phase concentration as a function of time is
Natural antioxidants, particularly polyphenols, have poten- used to fit the experimental data to theoretical models, which are
tial to be used in pharmaceutical and food industries because under some hypothesis and specific kinetics parameters (Mantell
of their numerous benefits like reducing the risk of inflamma- et al., 2002).
A large number of mathematical models can be applied to
extraction kinetics. These models are generally based on modi-
fications of Fick’s law such as the film theory, which has been
∗ Corresponding author. used to model the extraction of bioactive compounds from plants.
E-mail addresses: m.pilar.almajano@upc.edu, mariapilar09@gmail.com However, it is worth to mention that empirical equations like
(M.P. Almajano).

http://dx.doi.org/10.1016/j.indcrop.2016.03.005
0926-6690/© 2016 Elsevier B.V. All rights reserved.
214 F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220

Peleg’s model can also provide a proper fitting to extraction pro- et al., 2014c). Samples were taken from the prepared extracts. The
cesses. sample was placed in a plate by triplicate, adding 4% (v/v) of the
Several experimental studies about estimating effective diffu- Folin-Ciocalteu’s reagent, 12% (v/v) sodium carbonate anhydrous
sivities and mass transfer coefficients of polyphenols (or specific solution (20%) and finally 80 ␮L of milli-Q water. Allowed to react
phenolic compounds) from a food by-product have been carried out for 1 h in the dark room, the absorbance was measured at 765 nm
for these years. Diffusivities and models are estimated by expres- using a Fluorimetrics Fluostar Omega (Perkin–Elmer, Paris, France).
sions from Fick’s second law of diffusion (Amendola et al., 2010; The total phenolic content was expressed as mg Gallic Acid Equiv-
Cacace and Mazza, 2003; Espinoza-Pérez et al., 2007; Guerrero alents (GAE)/l or mg GAE/fresh matter in final extract.
et al., 2008; Pinelo et al., 2006). In these works, many variables such
as temperature, ultrasound power and extraction time in batch 2.5. Determination of total antioxidant capacity (ORAC assay)
extractions were studied (Bucić-Kojić et al., 2013; Capparucci et al.,
2011; Dibert et al., 1989; Gironi and Piemonte, 2011; Guerrero et al., Antioxidant activities of avocado extracts were determined by
2008; Pinelo et al., 2006). the ORAC assay, as reported by Segovia et al., 2014b. The assay was
The aim of this work is to model the solid-liquid ultrasound- carried out using a Fluorimetrics Fluostar Omega (Perkin–Elmer,
assisted extraction in batch and continuous of total polyphenols Paris, France) equipped with a temperature-controlled incubation
from avocado seed, as well as estimate the effective diffusivity of chamber. The incubator temperature was set at 37 ◦ C. The extract
polyphenols and its influence with temperature and ultrasound samples were diluted 1:20 with milli-Q water. The assay was per-
power. Antioxidant activity was also studied to find its relationship formed as follows: 20% of sample was mixed with Fluorescein
with total polyphenol yield. (0.01 mM) and an initial reading was taken with excitation wave-
length, 485 nm, and emission wavelength, 520 nm. Then, AAPH
2. Materials and methods (0.3 M) was added and measurements were made for 2 h. This
method includes the time and decrease of fluorescence. The area
2.1. Sample preparation under the curve (AUC) was calculated. A calibration curve was
made each time with the standard Trolox (500, 400, 250, 200, 100,
Avocado (Persea gratissima) seeds from domestic consumption 50 mM). The blank was 0.01 M phosphate buffered saline (pH 7.4).
were used. The seeds were manually separated from avocado. ORAC values were expressed as mmol Trolox Equivalents (TE)/mg
The fresh seeds were ground by using a Moulinex mill (A5052HF, of fresh matter in final extract.
Moulinex, Lyon, France). Afterwards, the ground seeds were sieved
to particle size of 2.00–2.36 mm. The average particle diameter of
2.6. Calculation of the diffusion coefficients
the samples was estimated to be 2.19 mm. Finally, the ground seeds
were stored in a dark bottle under refrigeration at 4 ◦ C until use.
A model based on Fick’s law was used in order to find the diffu-
sion coefficients for each stage of the extraction:
2.2. Ultrasound-assisted batch extraction (UABE)     
C∞ − C 6 2 D1 t 2 D2 t
Batch extraction was carried out following the procedure = 2 f1 exp − + f2 exp − (1)
C∞  r2 r2
described by Segovia et al. (2014b) with some slight modifica-
tions. About 8 ± 0.1 g (measured precisely) of avocado seeds were where f1 and f2 are the fractions of the solute, which are extracted
extracted in batch with 500 mL of water. The extractions were car- with diffusion coefficients D1 and D2 , respectively. C∞ is concen-
ried out in sealed flasks. These experiments were performed in tration in equilibrium, C is concentration in time t and r the particle
triplicate at different temperatures (20, 40 and 60 ◦ C). At specific radius.
intervals of time, 1000 ␮L of extraction were sampled and put in The next conditions were established to apply the above equa-
the fridge (away from light) at 4 ◦ C. After two hours, the samples tion (Chan et al., 2013):
were analyzed to determinate total phenolic content and antioxi- (1) Symmetrical and porous sample particles. The geometry of
dant capacity. solid particles is assumed to be spherical with radius of r.
Ultrasound assisted extraction was performed in an ultrasonic (2) The solid particle is assumed to be of a pseudo- homogeneous
bath (Type T 710 DH, 580VA, 40 KhZ, PROLABO, Germany) using the medium. The concentration of the active compounds in the solid
procedure mentioned above. The ultrasonic output ranged from 0 particle depends on time and radius, r.
to 80% (100% equals 130 W). (3) Uniform distribution of active compounds in the sample
matrix.
2.3. Ultrasound-assisted continuous extraction (UACE) (4) Homogeneous mixing between solvent and plant sample
particles. The concentration of the solute in the solvent only
The experimental extraction setup was similar to what Pinelo depends on time.
et al. (2006) reported. The column extractor was 0.75 cm of radius (5) The mass transfer of active compounds from the solid is a
and 10 cm of height. The extractor was placed in the aforemen- diffusion phenomenon in which the diffusion coefficient is inde-
tioned ultrasonic bath under the same experimental conditions. pendent of time.
Extraction was accomplished by continuous pumping of fresh (6) Diffusion of the solute and other compounds are in parallel
water (4.17 mL/min) through the column. The solvent was pumped and no interaction between them.
upward from the bottom. The outlet extract was sampled at (7) External mass transfer resistance is negligible. The concen-
specific intervals of time to record the polyphenol concentration tration of the solute in the solvent at the interior of the solid particle
and antioxidant capacity. At the end of the process, all these extracts is equal to the concentration of the solute in the bulk solvent.
were collected and stored as the final one. According to the method followed by Hojnik et al. (2008), in later
stages of the extraction, only the second term on the right-hand side
2.4. Determination of total polyphenolics content (TPC) of Eq. (1) remains significant. The parameter D2 is obtained from the
slope and the parameter f2, from the intercept of the curve where
Total phenol content of the extract was determined using the ln[C∞/(C∞-C)] is plotted as function of time t. In earlier stages of
Folin–Ciocalteu reagent method with a slight modification (Segovia the extraction, the second exponential term is close to unity and
F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220 215

Table 1 between two samples, where every sample was taken by triplicate.
Mathematical models used in the kinetic study of UABE.
Matlab R2013a (The Mathworks Inc., Natick, MA, USA) was used to
Model Equation make the analysis.
Empirical C = Cw [1 − exp (−kw t)] + Cd [1 − exp (−kd t)]
t
Peleg’s C = Co + k +k t
Rate Law C= t
1 2
3. Results and discussion
1+ t
h C∞
C −kt
Film Theory = 1 − (1 − b) e
C∞
3.1. UABE modeling

In order to evaluate the use of ultrasound in the extraction, the


with the addition of f2 from the previous calculation, D1 and f1 can
change in amount of extracted polyphenols over time was deter-
be determined.
mined. Fig. 1 shows the effect of ultrasound on the extraction of
polyphenols from avocado seed at 60 ◦ C. At 20 and 40 ◦ C, a similar
2.7. Mathematical modeling of UABE
trend was followed (Fig. 2 and Fig. 3). Independent variables such
as temperature, power and time were chosen based upon our pre-
The equations of Table 1 have been applied in order to model the
vious studies (Segovia et al., 2014c). The highest temperature was
curves obtained experimentally. The choice of the best model was
set at 60 ◦ C according to the previous literature (Kosińska et al.,
based on the analysis of the highest correlation coefficient (R2 ),
2012; Segovia et al., 2014c), preventing polyphenols from degra-
lowest sum of squares due to error (SSE) and root mean squared
dation. The range of ultrasound power (0–100 W) was selected
error (RMSE) of experimental data to the equations.
according to reported works that studied the extraction of active
compounds from black chokeberry (Galvan d’Alessandro et al.,
2.8. Mathematical modeling of UACE 2012), Epimedium (Zhang et al., 2009) and sweet tea tree (Xie et al.,
2012), among others.
For the continuous extraction, Eq. (1) from Fick’s law was As seen in Fig. 1, the extraction of polyphenols was enhanced
applied to find and compare the diffusion coefficients as Petrović when ultrasound power was raised, as expected. Similar results
et al. (2012) reported. were reported on other organic samples (Da Porto et al., 2013a;
Golmohamadi et al., 2013). While the equilibrium was reached
2.9. Statistical methods in less than one hour thanks to the ultrasound extraction,
classical extraction methods using solvents at moderated temper-
The analysis of variance (ANOVA) was performed. A significance atures needed longer time (Bucic-Kojic et al., 2013; Gironi and
level of 5% was considered to determine significant differences Piemonte, 2011). This happens because ultrasounds break the cells

50 0%
40%
80%
TPC (mg GAE/l)

40

30

20

10

0
0 20 40 60 80 100 120
Time (min)
Fig. 1. The influence of ultrasound power on UABE kinetics of total polyphenols from avocado seed at 60 ◦ C.

Fig. 2. The influence of ultrasound power on UACE kinetics of total polyphenols from avocado seed at 60 ◦ C.
216 F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220

improving the diffusion of solvents into the tissue and conse- Table 2
Error analysis for fitting experimental data to different models in UABE of polyphe-
quently, the extraction. Furthermore, ultrasounds enhances the
nols from avocado seed.
solubility of the compounds in the extracting solvent (Lou et al.,
2010). In some extractions, like those at 40 ◦ C and 0–40% power, the Conditions
equilibrium was reached later than one hour. As shown in Fig. 3, at Model Temperature, ◦ C Power, % R2 SSE RMSE
20 and 60 ◦ C, there were significant differences between the extrac-
0 0.90 1.50 0.40
tions with and without ultrasounds. However, at 40 ◦ C, extractions 20 40 0.87 2.51 0.53
at 0 and 40% ultrasound power did not show any significant differ- 80 0.85 8.99 0.99
ence between them. 0 0.81 2.31 0.51
The following equation was used to measure the ultrasound Peleg’s 40 40 0.88 1.82 0.45
80 0.93 10.7 1.09
effect on the extraction (Galvan d’Alessandro et al., 2012): 0 0.84 20.96 1.53
60 40 0.92 85.36 3.08
A−B
Ultrasoundeffect (%) = × 100 (2) 80 0.88 211.8 4.85
B 0 0.93 1.20 0.41
20 40 0.90 1.96 0.53
80 0.88 7.51 1.04
where A is the extracted amount of polyphenols using ultrasounds
0 0.95 0.68 0.31
and B is the extracted amount without using them. Empirical 40 40 0.96 0.65 0.3
At 60 ◦ C, extractions at 40 and 80% ultrasound power showed 80 0.96 6.42 0.96
a 125% and 208% ultrasound effect, respectively. Therefore, ultra- 0 0.91 4.59 1.29
sound power played an important role in enhancing the extraction 60 40 0.95 51.1 2.70

yield. The rising of extracted polyphenols thanks to ultrasound 80 0.93 116.5 4.08
application was also reported for rape seeds, with an 88% ultra- 0 0.90 1.50 0.41
sound effect (Szydłowska-Czerniak and Tułodziecka, 2014), as 20 40 0.87 2.51 0.53
80 0.85 8.99 0.99
well as for black chokeberries, from 25 to 85% effect (Galvan 0 0.81 2.31 0.50
d’Alessandro et al., 2012). Noteworthily, avocado seeds show the Rate Law 40 40 0.88 1.83 0.45
highest reported values of ultrasound effect so far. 80 0.94 10.7 1.09
For the purpose of describing the polyphenol extraction by 0 0.84 20.96 1.53
60 40 0.92 85.36 3.08
mathematical models, 4 different equations were applied: two
80 0.88 211.8 4.85
empirical (Peleg and empirical models), one from modified Fick’s
law (film theory) and the last one called Rate Law. In this kind of 0 0.96 0.05 0.07
20 40 0.98 0.01 0.04
extractions, two phases are included: (i) penetration of solvent into 80 0.94 0.06 0.08
the cells of the plant and solubilisation of the polyphenolic com- 0 0.96 0.03 0.06
pounds (fast); and (ii) diffusion of the solubilised compounds from Film Theory 40 40 0.99 0.01 0.03
the inner part of the plant into the solution (slow) (Chan et al., 80 0.93 0.05 0.07
0 0.98 0.02 0.04
2013).
60 40 0.99 0.01 0.04
The results of R2 , SSE and RMSE for the different models are 80 0.99 0.01 0.03
presented in Table 2. Peleg, Empirical and Rate Law models yielded
high R2 values, which ranged from 0.81 to 0.96, and high SSE and
RMSE, not indicating a good relation to the experimental data (Dong (slow, k). This trend was also observed in the extraction of oil from
et al., 2014). The film theory was the model that best fitted to the sunflower seeds (Perez et al., 2011).
experimental data as shown in Table 2. This model is based on Fick’s
law and assumes that extraction occurs due to the washing and 3.2. UACE modeling
diffusion processes (Chan et al., 2013). In literature, film theory has
been described to model the solid-liquid extraction of bioactive The evolution of polyphenol concentration as a function of
compounds from plants, having a R2 higher than 0.94 (Veličković extraction time is shown in Fig. 4. Extractions at 20 and 40 ◦ C
et al., 2006). present a similar trend (Fig. 5 and Fig. 6). It is possible to distin-
According to film theory model, Table 3 shows that the coeffi- guish two phases in the process: (i) the TPC of extracts decreases
cients in first stage (fast, b) are higher than those in second stage concomitantly with the increase in extraction time; (ii) a stabiliza-

Fig. 3. The effect of temperature and ultrasound power on total polyphenol content (a) and antioxidant capacity (b) of extracts in batch and continuous (BE: batch extractions;
CE: continuous extractions).
F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220 217

Fig. 4. The influence of ultrasound power on UACE kinetics of total polyphenols from avocado seed at 60 ◦ C.

Fig. 5. The influence of ultrasound power on UACE kinetics of total polyphenols from avocado seed at 20 ◦ C.

Fig. 6. The influence of ultrasound power on UACE kinetics of total polyphenols from avocado seed at 40 ◦ C.

Table 3 ences in polyphenolic yield content. Finally, at 60 ◦ C, the ultrasound


Parameter values entertained by the mathematical model labeled as film theory for
power did not have any significant influence on TPC extracted in
UABE of polyphenols from avocado seed.
continuous. Therefore, the rise of temperature decreased the influ-
Temperature, ◦ C Power, % ence of ultrasound power on continuous extractions.
0 40 80 Using Eq. (2), at 20 ◦ C, ultrasound effects of 280 and 260% were
−2 −2
found in extractions at 80 and 40% ultrasound power, respec-
b × 10 −k × 10 b × 10 −k × 10 b × 10 −k × 10−2
tively. At 40 ◦ C, a significant ultrasound effect of 270% was only
observed when 80% ultrasound power was applied. At 60 ◦ C, ultra-
b a
20 1.39 3.80 3.1 1.18 2.16 4.12a
40 2.20 2.05b 1.83 2.01b 2.62 5.39a
sound effects of 105 and 150% were found in extractions at 80
60 2.93 3.06b 1.68 5.00a 2.25 4.11a
and 40% ultrasound power, respectively. All these results clearly
b
constant is dimensionless and k is min−1 .
demonstrate that ultrasound is a competitive and effective extrac-
Different letters in superscript indicate significant differences in mean values.
tion technology. This is in good agreement with the results reported
in the extraction of polyphenols from grape marc (Tao et al., 2014)
tion of TPC was reached when the extraction time was prolonged and black seed (Abdullah and Koc, 2012), among others.
(beyond 50 min in this case). At 20 ◦ C, there were only significant In attempts to predict the evolution of UACE, a mathematical
differences between extractions at 0 and 80% ultrasound power. At model based on Fick’s law Eq. (1) was used. Thanks to this, diffusion
40 ◦ C, 0 and 40% ultrasound powers did not show significant differ- coefficients were determined (Table 5), as well as the fractions of
218 F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220

Table 4 Table 7
Error analysis for fitting experimental data to Fick’s law model in UACE of polyphe- Proposed correlations between TPC and ORAC in UABE and UACE (0–80% power) of
nols from avocado seed. polyphenols from avocado seed.

Conditions Condition Equations R2


◦ 2
Model Temperature, C Power, % R SSE RMSE UABE
0 0.99 0.01 0.03 20 ◦ C TPC = 0.072 × ORAC + 2.42 0.86
20 40 0.99 0.01 0.03 40 ◦ C TPC = 0.102 × ORAC + 1.02 0.99
80 0.97 0.05 0.07 60 ◦ C TPC = 0.323 × ORAC − 27.81 0.93

0 0.94 0.06 0.08 UACE


Fick’s law 40 40 0.86 0.22 0.15 20 ◦ C TPC = 0.203 × ORAC − 0.23 0.78
80 0.97 0.04 0.06 40 ◦ C TPC = 0.091 × ORAC + 0.51 0.99
60 ◦ C TPC = 0.346 × ORAC − 38.90 0.93
0 0.99 0.02 0.04
60 40 0.99 0.02 0.04
80 0.99 0.01 0.03
resulted in the increase of diffusion coefficient of polyphenols. At
40% power, the coefficients decreased at fast stages and rose at slow
Table 5 ones when increasing temperature. Firstly, the washing of external
Parameter values entertained by the mathematical model labeled as film theory for layers of cell is prevailing and then the diffusion starts inside the
UACE of polyphenols from avocado seed.
cell. The opposite happened at 80% power, when fast stages rose
Temperature, ◦ C Power, % decreasing the coefficients at slow stages. This fact was due to a
0 40 80
greater damage in cell walls (Hojnik et al., 2008).

f1 f2 f1 f2 f1 f2
3.4. Antioxidant capacity
20 1.56 0.22b 1.48 0.08ab 1.52 0.25a
40 1.15 0.42b 1.47 0.48b 1.29 0.26a Antioxidant capacity of extracts was determined by using ORAC
60 1.47 0.14a 1.52 0.06a 1.65 0.04a
assay. This assay is widely used to found antioxidant capacity of
Different letters in superscript indicate significant differences in mean values. extracts from plants and food (Khan et al., 2010). While all col-
lected extracts were analyzed as only one in UACE, the last collected
Table 6 extract was analyzed in UABE. As shown in Fig. 7, the rising of ultra-
Diffusion coefficients of phenolic compounds for UABE and UACE from avocado seed. sound power can result in the increase of total antioxidant capacity,
Temperature, ◦ C Power, % since permeability of cell membranes is enhanced under sonica-
tion. Furthermore, the antioxidant capacity is related to extracted
0 40 80
polyphenol content (Khan et al., 2010; Segovia et al., 2014a). In this
D1 D2 D1 D2 D1 D2 work, a linear relation between ORAC and TPC was found, yielding
UABE R2 values that range from 0.78 to 0.99 as shown in Table 7. This cor-
20 0.58 0.63 0.31 1.86 1.62 0.2 relation was also reported in other works (Briones-Labarca et al.,
40 – – – – 0.36 1.76 2015; de Oliveira et al., 2009). Soong and Barlow (2004) found a
60 4.10 0.30 0.47 3.90 0.23 3.93
linear relation but R2 coefficient ranged from 0.828 to 0.966.
UACE While there was a progression in total polyphenol content and
20 0.88 0.009 1.45 0.028 1.17 0.058 antioxidant capacity at 20 and 60 ◦ C, there was none at 40 ◦ C and
40 1.12 0.036 1.27 0.029 1.43 0.062
60 1.78 0.058 1.15 0.045 1.43 0.042
40% ultrasound power. Under these conditions, the extraction yield
from avocado seed was not enhanced, indicating that ultrasound
D1 is Dfast × 10−8 ; and D2 is Dslow × 10−8 . Diffusion coefficients in m2 /s.
power and temperature did not have any effect on mass transfer
(Salmi et al., 2010).
solute that are extracted in each stage. Fitting experimental data
to this model corroborates that the extraction process can be also 3.5. Comparison between batch and continuous extractions
divided into both fast and slow stages. As shown in Table 4, values
of R2 were in the range from 0.86 to 0.99, suggesting a good fit to the As shown in Fig. 7, according to TPC and ORAC values, there is
model. Moreover, values of SSE and RMSE are close to 0, confirming no significant difference between UABE and UACE. However, differ-
a satisfactory quality of data prediction. ences can be seen in extraction time (Fig. 1–6). The UACE reaches
equilibrium up to 53% faster than UABE. This fact reduces energy
3.3. Diffusion coefficients in UABE and UACE consumption, making the process more efficient. In literature, a
reduction of 92% in extraction time was reported in the UABE of
Fick’s law has been commonly employed to determine diffu- polyphenols from grape seeds in oil (Da Porto et al., 2013b). The
sion coefficients by several authors who study the extraction of use of microwaves and electrical fields has also demonstrated such
bioactive compounds (Radha krishnan et al., 2013; Tao et al., 2014). enhancement (Chan et al., 2013).
Table 6 shows the calculated coefficients using Eq. (1). The values
of these coefficients change depending on the independent vari- 4. Conclusions
ables and damage of cell membranes caused by sonication. In some
cases, the temperature plays an important role in the extraction The experimental results showed that temperature and ultra-
stages (Hojnik et al., 2008). sound power had a significant influence on the extraction of
In batch extractions, diffusion coefficients do not present a linear polyphenols from avocado seed. Increasing temperature and ultra-
relationship with the temperature or ultrasound power. Further- sound power resulted in extracts with higher polyphenol content
more, it is commonly reported that a single stage is present in this and antioxidant capacity. A linear relationship between total
kind of extraction (Guerrero et al., 2008). polyphenol content and antioxidant capacity was found as well.
However, under no sonication, continuous extractions are simi- Noteworthily, water, which is considered as a green solvent, was
lar to classical ones: the rise of temperature and ultrasound power used for extracting the polyphenols.
F.J. Segovia et al. / Industrial Crops and Products 85 (2016) 213–220 219

Fig. 7. The effect of temperature and ultrasound power on total polyphenol content (a) and antioxidant capacity (b) of extracts in batch and continuous (BE: batch extractions;
CE: continuous extractions).

Thanks to the use of mathematical models, a better understand- Amendola, D., De Faveri, D.M., Spigno, G., 2010. Grape marc phenolics: extraction
ing of the extraction process divided into two stages (fast and kinetics, quality and stability of extracts. J. Food Eng. 97, 384–392, http://dx.
doi.org/10.1016/j.jfoodeng.2009.10.033.
slow ones) was provided. Models based on film theory and Fick’s Briones-Labarca, V., Plaza-Morales, M., Giovagnoli-Vicuña, C., Jamett, F., 2015. High
law were able to fit the ultrasound-assited batch and continuous hydrostatic pressure and ultrasound extractions of antioxidant compounds,
extractions, respectively, at 95% accuracy. Using Fick’s law model, sulforaphane and fatty acids from Chilean papaya (Vasconcellea pubescens)
seeds: effects of extraction conditions and methods. LWT—Food Sci. Technol.
diffusion coefficients of polyphenols cold be determined in both 60, 525–534, http://dx.doi.org/10.1016/j.lwt.2014.07.057.
stages. UACE reached the equilibrium faster than UABE, increasing Bucić-Kojić, A., Sovová, H., Planinić, M., Tomas, S., 2013. Temperature-dependent
the efficiency of the process. kinetics of grape seed phenolic compounds extraction: experiment and model.
Food Chem. 136, 1136–1140, http://dx.doi.org/10.1016/j.foodchem.2012.09.
Overall, ultrasound-assisted extractions proved to be more
087.
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