Centre for Separation Science and Technology (CSST), Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala
Lumpur, Malaysia
b
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur, Malaysia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 December 2015
Received in revised form
4 April 2016
Accepted 15 May 2016
Available online 17 May 2016
A rst-ever theoretical model describing the cell rupture mechanism for microwave-assisted extraction
(MAE) of bioactive compounds from plant samples is presented. This model incorporates the microwave
heating of intracellular moisture within the plant cells using Lamberts law. It then calculates the heating
time and the intrinsic energy required to pressurize and stretch the plant cells until rupture using
thermodynamic relations. The attainment of cell rupture is determined from elasticity theory for solids.
The simulation requires the inputs of the effective shear modulus of the plant cell wall and the incident
microwave irradiation ux entering the extraction mixture. The predicted cell rupture time by the
intrinsic energy validated excellently against the optimum extraction time found in experiments. This
model is generally applicable over a wide extraction parameters and microwave systems.
2016 Elsevier Ltd. All rights reserved.
Keywords:
Theoretical model
Microwave heating
Cell rupture
Extraction time
Bioactive compounds
1. Introduction
Microwave-assisted extraction (MAE) is among the efcient
techniques to extract bioactive compounds from plants. It employs
microwave to enhance the heating of the extraction solvent containing the plant materials. Generally, it requires shorter extraction
time and lower volume of solvent compared to those use conventional heating such as Soxhlet extraction (Chan et al., 2011; Wang
and Weller, 2006). Despite its superior performance, MAE is
widely adopted only in the laboratory scale because the technique
is difcult to scale up and its optimum operating condition is hard
to gauge using different congurations. As such, the optimum
operating conditions for MAE reported in the literature are applicable only for specic systems and on a restricted scale. These issues, which arise from a lack of fundamental understanding of the
underlying physico-chemical processes, should be resolved before
MAE can be fruitfully commercialized.
To this end, various optimization and modeling methods had
been developed for optimization and scaling up of MAE. The
modeling of MAE has been conventionally based on twoparametric empirical models such as lm theory (Stankovic et al.,
1994) and chemical kinetic equation (Rakotondramasy-Rabesiaka
* Corresponding author.
E-mail address: ch_chan@um.edu.my (C.-H. Chan).
http://dx.doi.org/10.1016/j.jfoodeng.2016.05.017
0260-8774/ 2016 Elsevier Ltd. All rights reserved.
microwave system and heating modes (e.g. constant-power, intermittent-power and constant temperature). Despite the apparent
success of the later developments, all parameters from the abovementioned models have no physical meanings thus they are not
suitable to be used for equipment design, process optimization and
scale up. Hence, to complete the picture, theoretical modeling of
MAE should consider the mechanism of rupturing plant cell as had
been suggested by various works (Gujar et al., 2010; Yan et al., 2010;
Zhang et al., 2013). To the best of our knowledge, there was no
literature available on this topic.
For the rst time the cell rupture mechanism of MAE is
described using fundamental principles in this work. The ultimate
goal is to investigate the intrinsic energy to rupture plant cells and
to predict the optimum extraction time from the temporalevolutions of the intracellular thermodynamics during MAE. This
work presents the theoretical framework of the model in Section 2.
Following that, a case study is elucidated in Section 3, followed by
the results validated over a broad range of MAE conditions. Finally,
conclusions to this study are given in Section 5.
Pint Patm g0
Vc
Vc0
1=3
2tc0 G
rc0
Vc
Vc0
7=3 #
(1)
(2)
where tc0 and rc0 are the average thickness and radius of the cell
wall in original condition, and G is the shear modulus. The
parameter g0 which has the same units of but often a smaller
magnitude than shear modulus, is known as the mechanical
property constant of the plant cell wall. It can be interpreted as an
effective shear modulus modied by the geometry.
The pressure-volume relationship is approximately linear at the
beginning of the extension, by virtue of p
the
form of the equation.
The maximum of Pint occurs at Vc =Vco 7 regardless of the value
of go. The maximum point is also known as yield point whereby
extension beyond this point can be interpreted as the plastic-ow
state of cell wall (Li et al., 2010). While the elasticity principle
could not predict a priori whether the cell wall would rupture at,
below or above this maximum pressure, for this pressure-volume
model, the maximum pressure is assumed to be the cell rupture
pressure. Upon rounding up, the cell rupture pressure is:
2. Theoretical framework
"
g0
99
(3)
pn2 m Vs rt
(4)
n
R
m Z
(5)
rt
1
1
SF Vp rp
(6)
100
Ls
R nDp
n1
(7)
Lw
1=3
Vw
(8)
Lp Dp Lw
Ix I0 e2bx
P v x
(10)
dIx
2bI0 e2bx
dx
(11)
v
u s
2
u
u
uk
1
1 k=k
2pf t
b
c
2
(12)
where c is the speed of light, f is the frequency of microwave radiation, k0 is the relative dielectric constant of the medium and k is
the relative dielectric loss of the medium. For microwave heating in
a multi-layered medium, the corresponding expression for the
transmitted power ux, Ii and power absorbed per unit volume, PVi
at the ith medium are given as follows (Ayappa et al., 1991):
0
Ii x I0 exp@
i1
X
V
xdV
Pw
Pw:av
rw
(15)
dV
PVw(x)
where
is the localized heating power of moisture medium
(i w) per unit volume, V indicates the cylindrical volume of the
extraction mixture and rw is the density of moisture.
It is vital to re-emphasize that the formulation above hinges on
relatively stationary particles throughout the extraction mixture. At
high solvent loading, the plant particles tend to move around
within the extraction mixture, carried along by convection currents. Hence, the average heating power experienced by the
moisture within the particles cannot be approximated by simple
volume-average. A more sophisticated approach accounting for the
hydrodynamics will be required. The approach proposed here is the
simplest rst attempt, which nevertheless is in line with the economic need to operate at low solvent loading.
(16)
1
2bj Lj Aexp 2bi x xi1 ;
j1
100
Z 0C
(13)
2bi Ii x; xi1 x xi
t12
Cp
dT
Pw:av
(17)
250 C
xi1 x xi
PiV x
(9)
101
(14)
where, Q1-2 is the heat absorbed per unit mass of moisture, Cp is the
specic heat capacity of water, T is the intracellular temperature.
The second heating stage vaporizes the intracellular moisture at
constant pressure to stretch the vacuole to its maximum volume,
completely ll up the cavity within the cell wall (state 3, vaporliquid equilibrium, 1 atm). As vapor volume at low pressure is
much larger than the liquid volume, it is unlikely that all liquid
water has been vaporized at this juncture, hence a vapor-liquid
equilibrium should exist. Thermodynamic relations in Eqs. (18)
and (19) can be used to describe this boiling stage:
102
3. Case study
t23
(18)
u3 u2 Pint v3 v2
Pw:av
(19)
where u and v are the specic internal energy and specic volume
of moisture in the cell. The specic volume v3 can be estimated
from the specic volume of moisture in a plant particle:
v3
a Vp
(20)
mw
Zv4
dQ34 Pw:av dt34 du
Pint dv
(21)
v3
ninc
Vc
v
Vc0 v3
(22)
we have
Pabs
p
Z7
Pw:av dt34 du v3
Pint dvinc
(23)
t34
p
u4 u3 v3 Patm
7 1 32g0 71=3 1 34g0 72=3 1
Pw:av
(24)
(25)
ms Cp:s DTs
tH
ZZ Z2p ZR
0
(26)
I0
tH pZ 1 2BRe2bR e2bR
(27)
The performance of the model to predict the optimum extraction time was validated with the experimental values in the MAE of
bioactive compounds from cocoa (Theobroma cacao L.) leaves reported in Chan et al., 2013. The MAE was conducted at constant
heating power mode using a conventional microwave oven
(2.45 GHz). The input parameters for this validation study are
tabulated in Table 1.
4. Results and discussion
4.1. Microwave heating characteristics in the extraction mixture
Generally, a medium with higher attenuation constant b such as
85% EtOH is capable of absorbing more microwave energy, as
simulated in Fig. 2(a). The plant material medium is inert to microwave thus its interaction with microwave is negligible. As a
result of power absorption, less microwave ux is transmitted
through the medium. Note that the local transmitted power ux is
continuous at the medium interfaces, whereas the local absorbed
103
Table 1
Input parameters of cell rupture model in validation study.
1.
2.
3.
4.
Specications
Values
k0
b (m1)
Water
85% EtOH
EtOH
Plant material
79.30
20.00
6.80
2.15
11.70
13.00
7.00
0.09
33.62
71.23
62.42
1.57
Extraction conditions
9.
10.
11.
12.
13.
14.
15.
16.
17.
a
b
c
d
100
200
300
600
200
250
300
100
100
W,
W,
W,
W,
W,
W,
W,
W,
W,
100
100
100
100
200
250
300
100
100
mL
mL
mL
mL
mL
mL
mL
mL
mL
of
of
of
of
of
of
of
of
of
85%
85%
85%
85%
85%
85%
85%
85%
85%
EtOH,
EtOH,
EtOH,
EtOH,
EtOH,
EtOH,
EtOH,
EtOH,
EtOH,
50
50
50
50
50
50
50
20
80
mL/g
mL/g
mL/g
mL/g
mL/g
mL/g
mL/g
mL/g
mL/g
33.3
11.6
5.4
2.2
20
13.5
11.9
30
27
Calculated
incoming ux, I0 (W/mm2)
0.0163
0.0467
0.1009
0.243
0.0271
0.0401
0.0456
0.0163
0.0163
Measured by pycnometer.
Properties taken from Navarrete et al. (2011) and Sato and Buchner (2004).
Values obtained from Chan et al. (2013).
Calculated using on Eq. (27).
Fig. 2. (a) Simulated transmitted power ux and absorbed power per unit volume in
solvent, plant material and moisture mediums. (b) Simulated local absorbed power in
the extraction mixture. MAE conditions: 85% EtOH, 300 W, 50 mL/g and 2 g of sample.
104
Fig. 3. Simulated average heating power of plant moisture per unit mass during MAE
at various incident power ux and extraction solvent. Error bars indicate the range of
variations at a solvent to solid ratio of 20e80 mL/g.
Fig. 4. Intracellular thermodynamics of a plant cell during MAE. MAE conditions: 85% v/v EtOH, 300 W, 50 mL/g and 2 g of sample. Normalized experimental yield was obtained
from work (Chan et al., 2013). Model input parameters: g0 0.7 MPa; I0 0.1 W/mm2. Tint is the intracellular temperature, Pint is the intracellular pressure and vinc is the volume
extension ratio of plant cell.
Fig. 5. Comparison between the simulated cell rupture time at g0 0.7 MPa and the
experimental optimum extraction time (Chan et al., 2013) of MAE of bioactive compounds from cocoa leaves. The solvent used was 85% (v/v) EtOH and the solvent to
solid ratio was 50 mL/g unless otherwise specied.
This suggests that the total energy absorbed could be related to the
change in a thermodynamic state, which is enthalpy, of the cellular
contents. The simulated total energy absorbed for cocoa leaves (5%
moisture, g0 0.7 MPa) in Fig. 6 was compared with the enthalpy
change of intracellular moisture at the start (liquid, 25 C, 1 atm)
and
at
the
end
(saturated
liquid-vapor,
pressure
Prup
p
z Patm 0.62g0 3z 0.535 MPa, specic volume v4
7aVp =mw 0.022 m /kg) of MAE. The simulated total energy
absorbed (666.7 J/g) is indeed close to the enthalpy change of the
moisture (671.6 J/g). The difference is attributable to the variable
pressure between stage 2 and stage 3, which makes the heating
path-dependent and not strictly equal to the enthalpy change.
Further, the minute difference indicates that the change in the internal energy dominates over the expansion work, which is expected for vapors with large temperature changes. As such, the
enthalpy change of the cellular contents can be related approximately as:
(28)
105
Symbols
c
Cp
Cp.s
Dp
Erup
Fig. 6. Time required for the moisture to rupture typical parenchyma cells under
various absorbed power of intracellular moisture.
f
G
106
I
I0
Ii
Li
Lp
Ls
Lw
m
ms
mw
n
Pabs
Pint
PVi
Prup
Patm
Pv
Pw.av
Q
r
R
rc
rc0
SF
T
Ts
t
tH
tc0
trup
u
V
v
Vc
Vc0
vinc
Vp
Vs
Vw
x
xi
z
Z
Greek letters
a
ratio of total intracellular volume to volume of a plant
particle (dimensionless)
b
attenuation constant of a medium (mm1)
bi
attenuation constant of the ith medium (mm1)
g0
mechanical property constant of plant cell (MPa)
q
angular direction (degree)
DH
enthalpy change of intracellular moisture (J/g)
k0
relative dielectric constant of a medium (dimensionless)
k00
relative dielectric loss of a medium (dimensionless)
rp
intrinsic density of the plant particle (g/cm3)
rt
rw
References
Ayappa, K.G., Davis, H.T., Crapiste, G., Davis, E.A., Gordon, J., 1991. Microwave
heating: an evaluation of power formulations. Chem. Eng. Sci. 46 (4),
1005e1016.
Biesaga, M., 2011. Inuence of extraction methods on stability of avonoids.
J. Chromatogr. A 1218 (18), 2505e2512.
Chan, C.-H., Lim, J.-J., Yusoff, R., Ngoh, G.-C., 2015a. A generalized energy-based
kinetic model for microwave-assisted extraction of bioactive compounds from
plants. Sep. Purif. Technol. 143 (0), 152e160.
Chan, C.-H., Yusoff, R., Ngoh, G.-C., 2013. Modeling and prediction of extraction
prole for microwave-assisted extraction based on absorbed microwave energy.
Food Chem. 140 (1e2), 147e153.
Chan, C.-H., Yusoff, R., Ngoh, G.-C., 2014. Modeling and kinetics study of conventional and assisted batch solvent extraction. Chem. Eng. Res. Des. 92 (6),
1169e1186.
Chan, C.-H., Yusoff, R., Ngoh, G.-C., 2015b. Assessment of scale-up parameters of
microwave-assisted extraction via the extraction of avonoids from cocoa
leaves. Chem. Eng. Technol. 38 (3), 489e496.
Chan, C.-H., Yusoff, R., Ngoh, G.-C., Kung, F.W.-L., 2011. Microwave-assisted extractions of active ingredients from plants. J. Chromatogr. A 1218 (37), 6213e6225.
Chumnanpaisont, N., Niamnuy, C., Devahastin, S., 2014. Mathematical model for
continuous and intermittent microwave-assisted extraction of bioactive compound from plant material: extraction of b-carotene from carrot peels. Chem.
Eng. Sci. 116 (0), 442e451.
Cutter, E.G., 1978. Plant Anatomy Part:I: Cells and Tissues. Edward Arnold, London.
Deng, X., Hu, Z.-A., Wang, H.-X., Wen, X.-G., Kuang, T.-Y., 2003. A comparison of
photosynthetic apparatus of the detached leaves of the resurrection plant Boea
hygrometrica with its non-tolerant relative Chirita heterotrichia in response to
dehydration and rehydration. Plant Sci. 165 (4), 851e861.
Gibson, L.J., 2012. The hierarchical structure and mechanics of plant materials. J. R.
Soc. Interface 9, 2749e2766.
Gray, J.D., Kolesik, P., Hj, P.B., Coombe, B.G., 1999. Confocal measurement of the
three-dimensional size and shape of plant parenchyma cells in a developing
fruit tissue. Plant J. 19 (2), 229e236.
Gujar, J.G., Wagh, S.J., Gaikar, V.G., 2010. Experimental and modeling studies on
microwave-assisted extraction of thymol from seeds of Trachyspermum ammi
(TA). Sep. Purif. Technol. 70 (3), 257e264.
Hays, R., 1975. The thermal conductivity of leaves. Planta 125 (3), 281e287.
Holmgren, M., 2006. X Steam, Thermodynamic Properties of Water and Steam.
MATLAB Central File Exchange. Retrieved Mar 30, 2015. http://www.
mathworks.com/matlabcentral/leexchange/9817.
Juarez, J.A.G., Corral, G.R., Moraleda, J.C.G., Yang, T.S., 1999. New high intensity ultrasonic technology for food dehydration. Dry. Technol. 17 (3), 597e608.
Lewicki, P.P., 1998. Effect of pre-drying treatment, drying and rehydration on plant
tissue properties: a review. Int. J. Food Prop. 1, 1e22.
Li, X., Zhou, Y., Yan, Y., Cai, Z., Feng, F., 2010. A single cell model for pretreatment of
wood by microwave explosion. Holzforschung 64 (5), 633e637.
Lybeer, B., Koch, G., Acker, J.V., Goetghebeur, P., 2006. Lignication and cell wall
thickening in nodes of Phyllostachys viridiglaucescens and Phyllostachys nigra.
Ann. Bot. 97 (4), 529e539.
McMinn, W.A.M., Magee, T.R.A., 1997. Physical characteristics of dehydrated
potatoes-Part II. J. Food Eng. 33, 49e55.
ri, H., Pe
li, E.R., Georgieva, K., Tuba, Z., 2011. Changes in chloroplast
Nagy-De
morphology of different parenchyma cells in leaves of Haberlea rhodopensis
Friv. during desiccation and following rehydration. Photosynthetica 49 (1),
119e126.
Navarrete, A., Mato, R.B., Dimitrakis, G., Lester, E., Robinson, J.R., Cocero, M.J.,
Kingman, S., 2011. Measurement and estimation of aromatic plant dielectric
properties. Application to low moisture rosemary. Ind. Crops Prod. 33 (3),
697e703.
Rakotondramasy-Rabesiaka, L., Havet, J.-L., Porte, C., Fauduet, H., 2007. Solideliquid
extraction of protopine from Fumariaofcinalis L. e analysis determination,
kinetic reaction and model building. Sep. Purif. Technol. 54 (2), 253e261.
Sato, T., Buchner, R., 2004. Dielectric relaxation processes in ethanol/water mixtures. J. Phys. Chem. A 108 (23), 5007e5015.
Sinha, K., Chowdhury, S., Saha, P.D., Datta, S., 2013. Modeling of microwave-assisted
extraction of natural dye from seeds of Bixa orellana (Annatto) using response
surface methodology (RSM) and articial neural network (ANN). Ind. Crops
Prod. 41 (0), 165e171.
Sinha, K., Saha, P.D., Datta, S., 2012. Response surface optimization and articial
neural network modeling of microwave assisted natural dye extraction from
pomegranate rind. Ind. Crops Prod. 37 (1), 408e414.
Stankovic, M.Z., Cakic, M.D., Cvetkovic, D.M., Veljkovic, V.B., 1994. Kinetics of
extraction of resinoids from overground parts of sweet clover (Melilotus ofcinalis L.). J. Serb. Chem. Soc. 10 (39), 735e741.
Wang, L., Weller, C.L., 2006. Recent advances in extraction of nutraceuticals from
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