Beruflich Dokumente
Kultur Dokumente
a r t i c l e
i n f o
Article history:
Received 28 February 2013
Received in revised form 17 July 2013
Accepted 19 July 2013
Available online 6 August 2013
Keywords:
Chemical potential
Extraction kinetics
Mass transfer
Mathematical modeling
Polyphenols
Ultrasonic irradiation
a b s t r a c t
The current study presents a mathematical formulation that describes the role of ultrasonic irradiation in
ultrasonic assisted extraction with thermodynamic terms. This model described the inuence of ultrasound irradiation on the chemical potential of extracted compounds and predicted the increase of the
yield of extraction using ultrasound irradiation. The term sono-chemical potential was described for
the rst time in an analogy to the piezo- or the electrochemical potential. Subsequently, the derived formula was applied on the extraction of polyphenols from spearmint, where the model showed the
increase factor in the extracted amounts during ultrasound assisted extraction; the predicted value for
a ve minute extraction was 2.89 and the experimental values were 2.99, 2.92 and 2.32 for the hydroxycinnamic acid derivatives content, the antioxidant activity and the total phenolics respectively. The
model could be further veried and used to explain the enhanced recovery of various compounds from
diverse matrixes.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Natural antioxidants have attracted attention due to their
health-promoting properties (Navarrete et al., 2011). The traditional extraction technique for polyphenols from plant materials
or food industry wastes is solidliquid extraction (maceration) (Azmir et al., 2013; Virot et al., 2010), but it has been linked with various disadvantages, such as (i) time-consuming extraction
procedures, (ii) the thermal degradation of phenolic compounds,
(iii) the use of less eco-friendly organic solvents, and (iv) low yield
of extraction (Grigonis et al., 2005). In the last two decades, innovative extraction techniques have been proposed that use added
energy such as ultrasound and microwave irradiation in order to
tackle the aforementioned drawbacks. The application of added energy usually achieves higher yield of polyphenols in shorter extraction time in comparison with solidliquid extraction.
Characteristically, the recovery of phenolic compounds from marjoram using ultrasound assisted extraction was 96% higher than
solidliquid extraction (Hossain et al., 2012). Ahmad-Qasem and
co-workers (2012) also reported that ultrasound irradiation reduced the extraction time from 24 h to 15 min without changes
in polyphenolic composition of olive leaf extracts.
Ultrasound-assisted extraction has been used successfully to recover polyphenols and other bioactive compounds from various
plants (Adj et al., 2010; Jerman Klen and Mozetic Vodopivec,
2011; Rodrguez-Rojo et al.2012). As a possible mechanism for
ultrasound assisted extraction was proposed the ultrasonic irradiation enhancement involves the shear force created by implosion
of cavitation bubbles upon the propagation of the acoustic waves
in the kHz range. Collapse of bubbles can produce physical, chemical and mechanical effects which result in the disruption of biological membranes to facilitate the release of extractable compounds
and enhance penetration of solvent into cellular materials and improve mass transfer (Dai and Mumper, 2010).
It is well-known that the extraction is affected by the diffusion
coefcient and the dissolution rate of compounds until they reach
the equilibrium concentration inside the solvent. The ability of
each polyphenol to be solubilized, transferred or diffused into a given solvent is governed by thermodynamics (Galanakis et al.,
2013). One of the primary thermodynamic factors describing the
extraction procedure is the chemical potential. The effect of ultrasound irradiation on chemical potential has not been described
mathematically yet. Previous attempts on mathematical modeling
of ultrasound assisted extraction have mainly focused on kinetic
parameters of the extraction (Pan et al., 2012; Yue et al., 2012),
the tting of kinetic models by linear regression (Cheung et al.,
2012) or second-order polynomial equations (Prakash Maran
et al., 2013) with terms that lack physical meaning. A phenomenological kinetic model also demonstrated that ultrasound-assisted
extraction is a two-step process with ultrasound irradiation inuencing only the rst step (Milic et al., 2013).
192
Nomenclature
E
G
Jj
ni
P
R
S
T
V
The main objective of the present work was to develop a mathematical model to describe the ultrasound assisted extraction of
compounds from matrix as food- to a solvent- phase in terms of
thermodynamics. In this attempt, the concept of sono-chemical potential is introduced for the rst time; an analogous term is the
electrochemical potential, which describes the enhancement of
the mass transfer due to the application of pulsed electric elds
(Toep et al., 2007). Furthermore, the developed phenomenological model was applied to study the ultrasound assisted extractionof phenolic compounds from an aromatic plant (Mentha viridis)
compared to the conventional solidliquid extraction.
Vi
ai
bi
ci
l
vi
coined by the authors, in an analogy to the piezo- or the electrochemical potential previously dened by Strathmann (2004).
2.2. Formulation
Following the Gibbs free energy ensemble approach, to the
thermodynamic parameters {T, P, ni} where T: temperature, P:
pressure and ni: the number of moles of a component i, the sound
energy density E is added in the presence of sound elds (Fig. 1b).
Then the thermodynamic identity for G is the following:
Case Fig. 1a:
dli RTd ln ai
and
dli RTd ln ai V i dP
In this case the external eld is the sound energy supplied to the
solvent and neglecting hydrostatic pressure effects and assuming
isothermal conditions, the thermodynamic identity of the sonochemical potential, bi, of the component i is the following:
dbi RTd ln ai V i dE
and
lIIi l0i RT ln 1
(a)
193
(b)
Fig. 1. Simplied phases and components diagram of the extraction system (a) conventional and (b) ultrasound assisted extraction. Components: black spheres: the phenolic
compounds expressed (j), and white color in phase II, the solvent molecules (i).
and
I
i
0
i
l l RT2
And the difference in chemical potential between the two phases is:
10
11
3.3. Analytical methods
and
bIi
l0i RT ln aIi gV m E
12
13
4. Results-discussion
J ON
j
J OFF
j
2RT V m EII
V m EII
1
2RT
2RT
14
J j Dnj =A Dt
15
194
ultrasound assisted extraction to extracted polyphenols for solid liquid extraction was 3.87.
Then, the concentration of extracted hydroxycinnamic acid
derivatives was determined since previous work reported that
hydroxycinnamic acids such as rosmarinic acid, ferulic acid and
caffeic acid are the major polyphenols of spearmint (Papageorgiou
et al., 2008). A similar trend with phenolic compounds was also
Fig. 2. Experimental setup for solidliquid extraction with (On) and without (Off) ultrasound irradiation.
Fig. 3. Kinetics of extracted phenolic content using conventional (shown as h) and ultrasonic-assisted extraction (shown as ).
Fig. 4. Kinetics of extracted hydroxycinnamic acid derivatives using conventional (shown as h) and ultrasonic-assisted extraction (shown as ).
195
Fig. 5. Kinetics of presented antioxidant activity, expressed as FRAP value: using conventional (shown as h) and ultrasonic-assisted extraction (shown as ).
Table 1
Experimental and predicted values for the ratio of extracted phenols, hydroxycinnamic acid derivatives and antioxidant capacity (as FRAP value) using ultrasound assisted
extraction to solidliquid extraction. The symbols On and Off represented ultrasonic assisted extraction and solidliquid extraction, respectively.
Time/min
Predicted Jon/Joff
1
5
10
20
30
1.38
2.89
4.79
8.57
12.36
Experimental Con/Coff
Total phenols
FRAP
1.34
2.99
2.72
3.93
4.52
1.37
2.32
2.50
3.34
3.87
2.13
2.92
3.49
3.71
4.42
monitored. In particular, the ratio of conventional to ultrasonic-assisted extraction recovered hydroxycinnamic acid derivatives was
2.99 and 2.72 for the 5 and 10 min extraction respectively, the ratio
reached up to 4.52 at 30 min of extraction (Fig. 4). Moreover, a similar trend for the extracted amounts was observed during the
course of the extraction; the increase of extraction time resulted
in higher recovery of hydroxycinnamic acid derivatives for the
ultrasonic-assisted extraction, but not during conventional
extraction.
In addition, the antioxidant activity by FRAP assay of spearmint
extracts was determined, as a close correlation between polyphenols and antioxidant activity has been demonstrated for plant extracts (Dudonn et al., 2009). In agreement to the phenolic and
hydroxycinnamic acids content, the antioxidant value increased
throughout the ultrasonic assisted extraction but not during the
full-length of the conventional extraction, leading to an increase
of the former of a 2.92-fold and 3.49-fold for 5 and 10 min of
extraction respectively, and a highest ratio of 4.42 after 30 min of
extraction (Fig. 5).
In order to evaluate the proposed phenomenological model, the
ratio of the extracted polyphenols by ultrasound assisted extraction to the extracted polyphenols by solid liquid extraction was
calculated using equation (14). Characteristically, the predicted ratio for a 5 min (300 s) extraction is as follows:
J ON
j
J OFF
j
1
V m EII
51 cm3 mol 6Js1 300 s=10 cm3
1
2:89
1
2RT
2 8:314 J mol K1 298:15 K
which was the calculated ratio of uxes with and without the application of ultrasound energy. The experimental and predicted ratios
after 5, 10, 20 and 30 min of extraction are summarized in Table 1.
Results showed that the predicted ratio is closest to the experimental values for a 5 min extraction period, rather than a 10 min period.
The predicted ratio of the extracted amount of compounds from
ultrasonic-assisted extraction to the ones of the conventional
extraction after 5 min is 2.89 whereas the experimental values were
2.99 for the hydroxycinnamic acid derivatives, 2.92 for the FRAP
value (antioxidant potential) and 2.32 for the total phenolics. The
rather low ratio for phenolic content may be attributed to the limitations of spectrophotometric assay as it measures phenolic compounds at kmax = 280 nm, a non-selective wavelength. After
10 min of extraction the ratio calculated by the proposed model increases to 3.79, while the ratio of hydroxycinnamic acid derivatives
increased to 2.72, FRAP value to 3.49 and total phenolics to 2.50.
The comparison of experimental and predicted ratio showed that
the deviation of two ratios was increased as the extraction time increased. This fact was in line with the basics of phenomenological
models that they can be applied for rapid and linear changes in a
system, which could be the case in the present model as well. Figs
35 also illustrated a linear correlation between extracted polyphenols and extraction time up to 10 min.
5. Conclusions
In the present study, the effect of ultrasound irradiation on extracted amounts of spearmint polyphenols was determined and
described mathematically. A phenomenological model was developed to predict the enhancement of the yield of extraction using
ultrasound irradiation for short extraction times. We also try to
determine the effect of ultrasound irradiation on chemical potential, a thermodymanic term, and the concept of sono-chemical potential is described for rst time. The expansion of the present
model to longer extraction times, non-linear area, stands also a
challenging perspective.
Acknowledgments
Authors would like to thank Cyprus University of Technology
for funding the present study (EX-056/2010).
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