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Ultrasonics Sonochemistry 36 (2017) 286–300

Contents lists available at ScienceDirect

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

Effect of ultrasound-assisted osmotic dehydration pretreatment on the


convective drying of strawberry
Ezzeddine Amami a,⇑, Wissal Khezami a, Salma Mezrigui a, Laxmikant S. Badwaik b, Asma Kammoun Bejar c,
Carmen Tellez Perez d, Nabil Kechaou c
a
Université de Tunis El Manar, Unité de recherche «Chimie des matériaux et de l’Environnement», Institut Supérieur des Sciences Biologiques Appliquées de Tunis (ISSBAT), 9,
rue Zouhair Essafi, Tunis 1006, Tunisia
b
Department of Food Engineering and Technology, School of Engineering, Tezpur University, Napaam, Assam, India
c
Université de Sfax, Groupe de recherche en Génie des Procédés Agroalimentaires, Laboratoire de recherche en Mécanique des Fluides Appliquée – Génie des
Procédés–Environnement, Ecole Nationale d’Ingénieurs de Sfax (ENIS), Tunisia
d
University of La Rochelle-Faculty of Science and Technology, Laboratory of Engineering Science for Environment (LaSIE UMR 7356 CNRS), Avenue Michel Crépeau, 17042 La
Rochelle, France

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

Article history: The work was planned to produce dietetic dehydrated strawberries with application of ultrasound osmo-
Received 29 September 2016 tic dehydration (UOD) as pretreatment. A Box-Behnken design (BBD) were employed to characterize the
Received in revised form 4 December 2016 UOD strawberry process, optimize and investigate the effect of independent variables like ultrasound
Accepted 5 December 2016
time (10, 20 and 30 min), concentration of osmotic solution (distilled water, 32.5 and 65 °Brix) and tem-
Available online 7 December 2016
perature (20, 30 and 40 °C) on the water loss (WL), solid gain (SG) and weight reduction (WR). The same
BBD were used to estimate the main effects of OD without ultrasound treatment. A multi-criteria opti-
Keywords:
mization based on maximal possible values of WL and WR and minimal value of SG was achieved.
Ultrasound assisted osmotic dehydration
Convective air drying
This was 20.5 min of ultrasound time, 47.5 °Brix osmotic solution concentration and 31 °C medium tem-
Dietetic dehydrated strawberry perature. The effects of UOD carried out under the optimized operating conditions on kinetics of convec-
Moisture diffusivity with shrinkage tive air drying of strawberry at 40, 50 and 60 °C, and velocity of 1 m/s, using the phenomenological model
Color and phytochemical analysis of Coupled Washing/Diffusion (CWD). Starting accessibility, moisture effective diffusivity Deff value and
X-ray diffraction activation energy (Ea) were calculated from similar-Fick’s law and analogous Arrhenius equation, respec-
tively with and without shrinkage correction. Color difference, Chroma and hue angle of fresh and UOD-
air dried strawberries were evaluated. Quality attributes were estimated through the assessment of the
phenolic content, antioxidant activity, rehydration capacity, and X-ray powder diffraction characteristics.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction Drying is a complex operation, which usually includes simulta-


neous phenomena of heat and mass transfers. Models of drying
Due to its outstanding wealth of nutrient, delicious flavor and kinetics have been studied through different fundamental, phe-
health benefits strawberry (cv. camarosa) is consumed to maintain nomenological, kinematical, and empirical ways [5]. Recently, a
good health by minimizing the risk of chronic illnesses such as the Coupled Washing/Diffusion CWD model was adequately phe-
cardiovascular disease, hypertension, obesity and type 2-diabetes nomenologically defined [5]. When one can assume that external
[1]. According to FAOSTAT (Food and Agriculture Organization transfers are not the limiting phenomena, the main part of the dry-
2013), the international production of strawberry was over 4.3 mil- ing kinetics is revealed by the diffusion of liquid water within the
lion tons in 2011 [2]. Dehydration could preserve nutritional com- matrix. Thus, air flow velocity is assumed to be higher than the
ponents and provide extension of shelf-life of strawberry [3]. Critical Airflow Velocity CAV. Another key-point of CWD model is
Consumption of healthy dehydrated strawberry as a part of food- to consider the specific initial short time stage of interaction
stuffs (e.g., ice creams, cookies, breakfast cereals, cakes, energy between hot air and the superficial zone of the product, which
bars and dairy products), has gained a noticeable increase [4]. should be a diffusion-free washing stage; this brings together the
concept of starting accessibility dXs. This Coupled Washing/
Diffusion CWD model allows determining the effective moisture
⇑ Corresponding author. diffusivity Deff based on similar second Fick’s law with or without
E-mail address: ezzeddineamami@yahoo.fr (E. Amami). shrinkage consideration [6], by using the only information

http://dx.doi.org/10.1016/j.ultsonch.2016.12.007
1350-4177/Ó 2016 Elsevier B.V. All rights reserved.
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 287

gathered from experimental drying data excluding the part able to of strawberries. The rehydration is a complex process aims at the
be attributed to the starting accessibility stage. restoration of raw material properties and is widely used as a qual-
Shrinkage is generally closely related to the amount of water ity indicator. Rehydration indicates the chemical and physical
released during drying before the material crosses glass transition changes caused by drying and pretreatments [25].
level. It normally leads to a modification in functional behavior X-ray powder diffraction analysis is a common technique of
such as the diffusivity value [5]. The shrinkage in biological tissues fundamental importance used to confirm the crystalline–amor-
is predicted with preferably simple empirical models considering phous state of sugars of dried products in a powder form. The
the volume in the product with respect to their initial values. Ideal amorphous materials (diffuse and large peaks due to the disorderly
shrinkage model is normally based on assuming that the volume displayed molecules producing disperse bands) [26] show no X-ray
loss of the product during drying should correspond to the volume patterns that are typical of crystalline materials (yield a series of
of the evaporated water [7]. A linear relationship between shrink- sharp and defined peaks since they are presented in a highly
age and moisture content during drying is reported in several ordered state) [27]. Analysis of Crystalline state is of great impor-
works using different drying procedures of numerous fruits and tance for the stability of powder usually used for juice preparation.
vegetables [7–10]. Obtaining powders containing crystalline state sugars is of funda-
Since the drying is highly energy consuming operation, nowa- mental importance for their stability [26]. The high sugar content
days it is very important to act in reducing the energy consump- of dried powders, mostly present in amorphous state, are very
tion, increasing the energy efficiency and reducing the processing hygroscopic, having a stickiness tendency and forming high
time [11]. Besides, normally drying can promote total phenolic agglomerates. This tendency to agglomeration may become accen-
degradation, antioxidant activity reduction and undesirable tuated as the amorphous state sugar transforms into crystalline
changes of color [12]. sugar through adsorption of small amounts of water [26]. The
Osmotic dehydration (OD) with or without ultrasound has glassy or amorphous powders are considered as melted liquids,
received considerable attention in recent years as one of the sim- characterized by the absence of a lucid fusion temperature.
plest and inexpensive pre-drying treatment of strawberries in Thereby, the induction of sugar crystallization during drying
order to reduce energy consumption, improve food quality, and through physical methods such ultrasound may make the dehy-
speed up the drying time [13]. Fruits osmotic dehydration (OD) drated powders steady vis-à-vis their functional properties.
occurs naturally, following their placement in hypertonic solutions The physicochemical quality of strawberry such as color, total
presenting a high osmotic pressure and low water activity. Conse- phenolic, antioxidant activity and rehydration capacity can be
quently a simultaneous diffusion phenomenon takes place where affected during drying. The antioxidant activity and total phenolics
water outflows from the food to the solution and the solute from fruit contents were investigated by Alonzo-Macıas [28] in swell
the solution to the food. These mechanisms lead to a water loss and convective drying strawberry fruits, in power ultrasound
(WL) and solids gain (SG) from and into the food respectively. It assisted convection drying of strawberries by Gamboa-Santos
is often desired in this case to maximize the WL and minimize et al. [29], in acoustically assisted drying treatments kinetics of
the SG [14]. The efficiency of the OD process depends upon many pineapple by Rodríguez et al. [12], in osmotic concentration
parameters, such as the concentration and temperature of the assisted continuous high frequency ultrasound and dehydration
osmotic solution, the immersion time, agitation (mechanical, cen- of rabbiteye blueberries by Stojanovic and Silvain [30] and recently
trifugal or ultrasonic waves), the structure of the fruit and its in immersion and contact ultrasound treatment of the apple tissue
geometry, as well as the liquid/solid ratio [15]. by Artur Wiktor et al. [31]. Although, ultrasound assisted osmotic
New technologies such as ultrasonic (US) waves are recently dehydration has been applied to strawberry [13] and freeze dried
used to enhance food osmotic dehydration with tendency to opti- strawberry [32], however, According to our knowledge, there are
mize nutrients intake in human diets [16,17]. Ultrasonic waves in a few scientific work has as yet been reported worldwide concerning
frequency range of 20–100 kHz can generate quick series of alter- the effect of UOD-convective air drying processing on the overall
native compressions and expansions in solid media in an analogue quality of strawberries.
to a sponge when it is squeezed and relaxed repeatedly. Thus lead- This study has investigated the use of ultrasound for strawberry
ing to the deformation of internal microscopic channels porous osmotic dehydration. Precisely, a Box-Behnken design (BBD) con-
fruits that facilitate the convective water removal [18]. Wave fre- jugated with Derringer’s desired function methodology was
quency, power and treatment time of the US greatly affect the employed to optimize and study the induction of the key process
osmotic dehydration rate and the final product’s structure. Fernan- variables such as ultrasound time, and concentration and temper-
des and Rodrigues [17] reported soluble solid losses (mostly sugar) ature of osmotic solution (independent variables) on WL, WR and
for several fruits in ultrasound-assisted osmotic dehydration SG (dependent variables). Thus, The specific objectives taken were
experiments. Due to the discrepancy in the results obtained for dif- (1) to determine the drying, rehydration characteristics and X-ray
ferent fruit, more studies on the effect of ultrasound on osmotic diffraction of UOD-convective dried strawberry and to compare
dehydration are still needed. and contrast the quality of these dehydrated strawberries in terms
Response Surface Methodology (RSM) is widely used as a statis- of their polyphenol compounds, the antioxidant activity, and color
tical technic in process optimization and product quality ameliora- to that convective dried strawberries., (2) to study the effective
tion in a short time period and minimum experiences [19]. RSM moisture diffusivity with and without shrinkage consideration
based on the principles of design of experiments (DOE) and opti- during the convective drying of strawberry tissue pretreated by
mization techniques is characteristically used for mapping of the UOD using the phenomenological model of Coupled Washing/Dif-
response over the experimental domain to select the optimum fusion and to investigate the effect of air drying temperature on
conditions for desirable responses [20–22]. The most frequently drying time.
utilized Box–Behnken quadratic design (BBD) was specifically
selected since it requires fewer design points than a Central Com- 2. Materials and methods
posite Design in cases of the same number of factors and operates
at a high efficiency [19]. Several studies have been carried out in 2.1. Fresh materials
the area of osmotic dehydration of strawberry [13,23,24].
However, to the best of our knowledge RSM is still lacking as a Fresh strawberries of the same size, color and ripeness were
modeling and optimization tool for ultrasound osmotic dehydration purchased from a local market in Tunis (Tunisia) and stored in a
288 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

refrigerator at 4 °C for maximum 4 days until use. The strawberries experimental points (Table 2). Experiments were carried out in
were removed from refrigeration and left for equilibrium at room random order. Obviously, the same Box–Behnken design and the
temperature before experimentations. Then, the fruits were same methodology were used to estimate the main effects of OD
washed and dried with absorbent tissue paper. Following this step, without ultrasound treatment (Table 2).
the strawberries were manually cut parallel to the main axis into Therefore, the general designs are given in terms of standard-
semi-spherical halves of average 3.7 ± 2 cm length, 3.6 ± 2 cm ized coded variables (Xi), which in any particular application are
width and 1.5 ± 0.1 cm thickness with a stainless steel knife and linearly related to actual factor (xi) by the following equations
weighted. The °Brix (11 ± 1) and moisture content of fresh straw- [19–21]:
berry (89 ± 1% w/w moisture content, wet basis) was observed in
x1  20 x2  32:5 x3  30
the fresh samples. X1 ¼ ; X2 ¼ ; X3 ¼
10 32:5 10

2.2. Osmotic treatment


2.5. Optimization
A solution of distilled water (0 °Brix) and two different osmotic
solutions were prepared using commercial sugar and distilled The RSM was applied to the experimental data using the soft-
water to give a concentration of 32.5 and 65 °Brix. The osmotic ware STATISTICA (Trial Version Statsoft. Inc, 2010). The method
dehydration was carried out in separate 100 ml Erlenmeyer flasks. of linear regression of the polynomial model with 10 coefficients,
including quadratic and linear effects of factors and linear effect
of interactions, was supposed to depict relationships between
2.3. Ultrasound assisted osmotic dehydration
response (Y) and the independent variables (X1, X2 and X3) as given
in Eq. (1).
The halves strawberries were loaded into the Erlenmeyer flask
sealed by plastic film to avoid loss of solvent solution/fruit ratio Y ¼ b0 þ b1 X 1 þ b2 X 2 þ b3 X 3 þ b12 X 1 X 2 þ b13 X 1 X 3 þ b23 X 2 X 3
was set at 4:1 w/w. The sample flask was immersed into the ultra-
þ b11 X 21 þ b22 X 22 þ b33 X 23 ð1Þ
sonic bath (Skymen JP-020S, volume: 3L, China) for irradiation dur-
ing a period of 10 to 30 min [13]. The frequency of the ultrasonic where, Y is the response variable of removal efficiency (WL, WR and
frequency was 40 kHz and the intensity was 0.2 W/cm2. The ultra- SG (%)), b0 is the estimated coefficient of fitted response regression
sound intensity was determined by calorimetric method described at the center point, b1, b2 and b3 are linear coefficients, b12, b13 and
by Löning et al. [33]. The experiments were carried out at 20, 30 b23 are cross product coefficients, b11, b22 and b33 are quadratic coef-
and 40 °C in the ultrasound bath. To evaluate the effect of ultra- ficients. The b coefficient is the amplitude of these values and gives
sound, the same procedure was repeated in the ultrasonic free ideas about the contribution of each factor in the prediction of the
environment (OD). The experiments were carried out in triplicates response. For a positive value of b, the impact of the correspondent
and the mean values were used to fit the parameters. parameter is higher if b is greater, while negative term indicates an
When the immersion time was reached (respectively 10, 20, antagonistic effect upon the response.
and 30 min), sample was withdrawn from the glass beakers and Numerical optimization using the Derringer’s desirability func-
quickly rinsed with fresh water to eliminate excess solution. Sub- tion (DF) method was carried out by defining constraint criteria at
sequently, it was slightly wiped with an absorbent paper and maximum and minimum ranges of responses to determine the
weighted using an analytical balance (FA 1004, China) with an optimum values of independent variables. DF distinguishes and
accuracy of ±0.0001 g. Moisture content of the samples was deter- creates a function for each individual response (di). The geometric
mined by a gravimetric method, according to AOAC 930.04 [34]. mean of individual desires was used to determine the overall desir-
Weighed Sample was placed in a drying oven at 105 °C until ability function (D) that should be maximum following selection of
weight stabilization. The samples were cooled down in desiccators optimum value of affective variables with considering their
and reweighed. Moisture content and solid content of the samples interaction. This algorithm varies on a scale of 0–1, where 0 repre-
were then calculated from the sample weights before and after sents a completely undesirable response, and 1 depicts the most
drying. The °Brix of osmotic solution was measured simultane- desirable one [21,22].
ously with a digital refractometer (Reichert Leica AR200). The
water loss and solid gain were calculated according to the method 2.6. Air drying
proposed by Amami et al. [25].
The amount of sample is two strawberries halves of 30 ± 1 g.
2.4. Experimental design and statistical analysis Fresh and UOD pretreated strawberry halves at optimized condi-
tions were placed in petri dishes (flat surface up) in a single-
BBD with three variables at three levels (Table 1) was used to layer arrangement and dried in a forced circulation air-drying oven
investigate responses and then to characterize the optimal combi- (Binder FD 53, Tuttlingen, Germany). Air temperature in the oven
nation of variables for UOD process. The three independent was set at 40, 50 and 60 °C and an air velocity of 1.0 m/s. Cross-
variables used in this study were ultrasound time, and concentra- flow air moved from side to side of the dryer at 1 m/s, flowing par-
tion and temperature of osmotic solution. The dependent variables allel to the width of the dryer shelves. The amount of water
were WL, WR and SG. The complete design generated 15 removed during the drying process was recorded at 5 min intervals

Table 1
The level of actual and coded values used for ultrasound osmotic dehydration process.

Actual Factor Coded Factor Independent Variables Coded levels of variables


1 0 +1
x1 X1 Ultrasound-Osmotic time (min) 10 20 30
x2 X2 °Brix (%) 0 32.5 65
x3 X3 Temperature (°C) 20 30 40
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 289

Table 2
Box-Behnken design matrix with experimental values of response variables for ultrasound and without ultrasound osmotic dehydration process.

X1 X2 X3 UOD OD
SG (%) WL (%) WR (%) SG (%) WL (%) WR (%)
10 65 30 0.56 5.714 6.275 0.38 5.230 5.608
30 65 30 0.31 13.106 12.797 0.39 13.12 12.73
20 65 20 0.31 6.539 6.848 0.136 5.768 5.632
20 65 40 0.17 8.102 7.933 0.262 9.319 9.057
10 0 30 0.60 5.167 5.770 0.40 4.642 5.044
30 0 30 0.80 2.600 3.404 0.51 4.470 4.979
20 0 20 0.39 1.318 1.707 0.16 4.054 4.214
20 0 40 1.09 4.408 5.504 0.78 6.394 7.173
20 32.5 30 0.55 8.341 8.897 0.38 10.45 10.83
20 32.5 30 0.57 7.775 8.348 0.36 10.31 10.67
20 32.5 30 0.53 8.246 8.782 0.36 8.888 9.250
10 32.5 20 0.01 3.107 3.119 0.089 4.110 4.021
30 32.5 20 0.14 4.016 4.158 0.500 4.404 3.905
10 32.5 40 1.13 2.323 3.460 0.70 4.941 5.640
30 32.5 40 0.29 8.542 8.253 0.474 9.613 9.139

for the first 30 min then at 30 min intervals to 3 h of drying and where: X, Xt1, and Xeq are the water content dry basis (g H2O/g d.m.)
then every hour by means of an analytical balance (FA 1004, in the solid matrix at time t, at the initial time range chosen for
China), with an accuracy of ±0.0001 g. Drying is stopped when studying diffusion stage t = t1, and at the equilibrium time
the sample weight shows to be fairly constant in time. (t ? 1), respectively.
Approximations to the analytical solution of diffusion model
2.6.1. Determination of bulk shrinkage Fick’s second law can be arbitrarily classified into constant volume
Determination of bulk shrinkage of each strawberry halves was and variable volume models.
achieved by using a slide gauge of 102 mm accuracy. Volumetric 2.6.2.1.1. Approximate model 1: Constant radius (without shrinkage).
shrinkage (Sb) of semi-spherical strawberry was calculated accord- The diffusion model Fick’s second law in spherical coordinates (Eq.
ing to Eq. (2): (6)) with the assumptions of i/ constant internal water diffusivity,
ii/ constant internal temperature, and iii/ negligible shrinkage dur-
Sb ð%Þ ¼ ðV f =V 0 Þ  100 ð2Þ
ing long drying times has been applied to fit drying data within the
considered range (t > t1) [35,36].
where V0 and Vf are the volume of the semispherical strawberry
!
before and after drying, respectively. 6 X1
1 n2 p2 Deff1=2 ðt  t 1 Þ
The shrinkage during thin layer convective air drying of straw- X rt1 ¼ exp  ð6Þ
p n¼1 n2
2 r21=2
berry half is described as a linear relationship between volume (V/
V0) and moisture ratios (X/X0) and calculated using Eq. (3) [7,10]: where Deff1/2 is the effective diffusion coefficient for the semispher-
V=Vo ¼ AðX=X0 Þ þ B ð3Þ ical fruit (m2/s); r1/2 is the radius of the semispherical fresh fruit
(m).
From the afore-mentioned relationship, Eq. (4) was obtained to For long drying times Eq. (6) can be simplified by limiting this
determine the change of the characteristic diffusion dimension expression to its first term. Logarithmic transformation allows
(r1/2) during drying and, afterwards, included in the modeling of implementing a straight-line equation. The effective diffusivity
the drying kinetics to provide a more realistic estimation of the value is typically determined by plotting experimental drying data
effective moisture diffusivity. in terms of ln (Xrt1) versus time [36]. A plot of ln (Xrt1) versus time
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
   should give a straight line slope of:
3 X
r 1=2 ¼ A þ B  r 30 ð4Þ p2 Deff1=2
X0 Slope ¼ ð7Þ
r 21=2
where subscript 0 refers to the initial time.
2.6.2.1.2. Approximate model 2: Radius variable with moisture content
(with shrinkage). This model integrates the radius change during
2.6.2. Mass transfers: Coupled Washing/Diffusion CWD model
drying as a function of moisture content. To take the shrinkage
2.6.2.1. Effective moisture diffusivity Deff. The effective moisture dif-
observed during strawberry drying into consideration in Eq. (6),
fusivity Deff should reveal various mass transfer phenomena of liq-
the strawberry half equivalent radius must be account as a
uid water within the solid matrix, which has gradient of water
function of time in Eq. (6), the sample equivalent radius must be
concentration dry basis X as driving force. Deff should be calculated
considered as a function of time (r1/2 = r1/2(t)) and is obtained from
on the base of similar-second Fick’s law from the data gathered
Eq. (4).
from experimental drying results excluding those able to be
Eq. (6) becomes [35]:
inserted in the specific range of initial airflow/superficial interac- !
tion (washing stage t < t1). Crank method used to determine effec- 6 X
1
1 n2 p2 Deff1=2 ðt  t 1 Þ
tive diffusivity implies defining the reduced dimensionless water X rt1 ¼ 2 exp  ð8Þ
p n¼1 n2 r 1=2 ðtÞ2
content Xrt1 ratio relative to the time t1 as a dependent variable
of time [6]. It was calculated for the range of t > t1 as established For long drying times Eq. (8) can be simplified to a straight-line
by Allaf et al. [5]: equation and become:
!
X  X eq 6 p2 Deff1=2 ðt  t1 Þ
X rt1 ¼ ð5Þ X rt1 ¼ exp  ð9Þ
X t1  X eq p2 r 1=2 ðtÞ2
290 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

The moisture diffusivity is thus estimated using method of (or ‘‘saturation”). It ranges from 0, which is completely unsaturated
slopes. Its values are generally determined from the slopes of ln (neutral grey, black or white) to 100 for very high Chroma (satura-
(Xrt1) vs. t/[r1/2(t)]2 straight-line. These values identified for differ- tion) or ‘‘color purity”. The hue (h) is the angle that represents the
ent temperatures: 40, 50 and 60 °C for strawberry sample of 14.40– saturated color in the color space. It is represented in degrees,
17.65 mm initial equivalent spherical radius. which ranges from 0° (red), through 90° (yellow), 180° (green),
The drying data from the drying tests were then expressed as 270° (blue) to 360° (red). The results were presented as DL, DC
the dimensionless moisture ratio (Xr) versus drying time or drying and Dh, because each samples had slight differences in color.
rate versus moisture ratio at different air temperatures.The tem-
perature effect can be assessed by a fitting of calculated Deff1/2 2.6.3.3. Determination of rehydration ratio. Rehydration ratio (RR)
Ea
values to the Arrhenius law (Deff ¼ D1 e RT ) as mentioned by Amami was evaluated by soaking one quart of the dried strawberry (about
et al. [11]. The activation energy Ea can be determined from the 0.2–0.5 g) [28] in a sufficient volume of distilled water (approxi-
plot of ln(Deff) versus 1/T. The slope of the line is (Ea/R) and the mately 200 times the weight of dried strawberry) in a Stainless
intercept equals ln(D1),where Ea is the activation energy (J/mol), Steel Mesh Infuser in 100 ml flask beaker at 20 °C for 4 h [28].
D1 is the diffusion coefficient corresponding to infinite tempera- The samples were then removed after each specific time intervals
ture (m2/s.), T is the air flow temperature (K) and R is the universal (0, 5, 10, 15, 20, 25, 30, 60, 90, 120, 180 and 240 min), drained
gas constant (R = 8.3145 J mol1 K1). for 30 s, and weighed. All measures were done in triplicate. The
In order to analyze the influence of shrinkage on the values of water content was expressed as grams of water absorbed per hun-
water diffusivity and activation energy for a non-shrinking and dred gram dry matter.
for a shrinking models were evaluated and compared.
2.6.3.4. Phytochemical analysis.
2.6.2.2. Starting accessibility dXs. Since the diffusion model concerns 2.6.3.4.1. Sample extraction preparation. After dehydration, each
are only for t > t1, the extrapolated value computed at t = 0 has a sample (air dried or UOD-air dried) was ground with a grinder
water content Xo with a distinct value from the real initial water (AR110510, Moulinex, France) into powders. These powders were
content Xi. The difference is defined as the starting accessibility also used for Analysis of X-ray powder diffraction in the following
dXs expressed as % db or g H2O/g db [6]: dXs = Xi-Xo. sections. Subsequently, 1 g of sample aliquots was weighed and
dXs reflects the amount of water available on the surface and placed in a 100 ml Erlenmeyer flasks then extracted with 20 ml
extracted from it in a very short time independently from the dif- 50% ethanol at 31 °C for 21 min in the ultrasonic cleaning bath
fusion process. (Skymen JP-020S, China, 40 kHz, power 120 W and volume: 3L).
Afterward, the extract was centrifuged for 10 min (15000 rpm)
for further extraction. Subsequently, the supernatant was filtered
2.6.3. Quality analyses
using a medium-speed filter under a vacuum at room temperature,
2.6.3.1. Water activity. The water activity (Aw) was measured
and stored at 4 °C to be used within 24 h.
before and after drying experiments. The determination of Aw
value was directly measured using a ‘‘NOVASINA” apparatus (Aw
2.6.3.4.2. Determination of total phenolic content (TPC). The total
Sprint TH-500) at 25 °C with the accuracy of 0.001. The fresh/dried
phenols content was determined according to the Folin-Ciocalteu
samples were placed in a converter chamber and kept there until
method [37] with slight modifications. Briefly, 100 lL of filtered
equilibrium was reached. Aw measurements were carried out in
ethanolic extract added with 100 lL of EtOH (50%) and 100 ll of
triplicate and the arithmetic mean was calculated.
Folin’s solution (2 N, Sigma) were incubated for 2 min then 2 ml
of Na2CO3 (75 g/l) is added. The mixtures were vortexed briefly
2.6.3.2. Color analysis. Another important quality parameter was
and left in the dark for 30 min at room temperature. The absor-
the color measurement. The color of the fresh and treated (dried
bance of the solutions was measured using UV–Visible spectropho-
and UOD/dried) strawberry were measured from external and
tometer at a wavelength of 720 nm against sample without extract.
internal side using a handheld tristimulus colorimeter (Minolta
The total phenolic content was calculated based on the calibration
Chroma Meter CR-300, CIE, 1976) and the color was recorded using
curve build using increasing concentrations (10–500 lg/ml) of Gal-
CIE L⁄a⁄b⁄ color spaces. L⁄ indicates lightness, and its value ranges
lic acid described by the equation y = 0.0033x + 0.0368 (R2 = 0.99).
from 0 (black) to 100 (white), a⁄ is a measure of greenness (a⁄)/
The results were expressed as milligrams of Gallic Acid Equivalent
redness (+a⁄) and b⁄ is the grade of blueness (b⁄)/yellowness
(mg GAE/mg of dry matter (dm)). All measurements were done in
(+b⁄). The colorimeter was calibrated against a Minolta standard-
triplicate for each extract.
white reflector plate before each actual color measurement. In
addition, for derived color parameters the total color difference
2.6.3.4.3. Determination of antioxidant activity (DPPH Assay). The
(DE), Chroma or color saturation value (C), hue angle (h°), and
antioxidant activity of the ethanol extracts was evaluated spec-
the (DL) were calculated using the following equations [32]:
trophotometrically by the modified DPPH method [38] which is
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  2 based on the quantification of free radical-scavenging. An ethanolic
ðL0  L Þ þ ða0  a Þ2 þ ðb0  b Þ
2
Total colordifference ðDEÞ ¼
solution (7.3 mg DPPH in 180 mL ethanol) was prepared. After
ð10Þ adjusting the blank with ethanol, an aliquot of 15 ll of dried straw-
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi berry extract was added to 1500 ll of a (100 mM) DPPH solution. A
Chroma ðC  Þ ¼ ða Þ2 þ ðb Þ
 2
ð11Þ volume of the mixture was vigorously shaken and left to stand in
the dark at room temperature for 30 min. The antioxidant activity
 was then measured by the decrease in absorption at 517 nm using
 b
hue angleðh Þ ¼ arctan ð12Þ UV–Visible spectrophotometer against 50% ethanol in DPPH solu-
a tion. The percent inhibition of the DPPH radical was calculated
thus:
DL ¼ L  L0 ð13Þ

where L⁄0, a⁄0, b⁄0 are the values for fresh strawberry. Three replicates ðAc  AsÞ
Ið%Þ ¼  100 ð14Þ
were measured and results averaged. The C axis represents Chroma Ac
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 291

where I%: Percentage of the anti-radical activity; Ac and As are the only about 2.86 and 1.03% of sample variation for SG and WL,
absorbance values of the control and test sample, respectively. For respectively. The value of the adjusted determination coefficient
each sample, three replications were done. (adjusted R2 = 0. 9201 for SG, adjusted R2 = 0. 969 for WL and
2.6.3.4.4. Analysis of X-ray powder diffraction. The X-ray diffraction adjusted R2 = 0. 9713 for WR) was also high to indicate a high sig-
patterns of air-dried, powdered strawberry were used to monitor nificance of the model.
the crystallization process with an X-ray diffractometer equipped Fig. 1 shows the closeness of the observed SG of ultrasound-
with a Cu-Ka source at 1.540 Å (XRD, Bruker-AXS D8 Advanced assisted OD of strawberry versus those from the empirical model
Bragg-Brentano X-ray Powder Diffractometer, GMBH (Germany)) Eq. (15). Point above or below the diagonal line represented areas
with an input energy of 40 kV and 30 mA. The powder was placed of over or under prediction. It is apparent from these figures that
and slightly pressed on an aluminum sample tray using a glass the predicted data closely banding around the straight line, which
slide and scanned at a diffraction angle (2h) between 0° and 60°, proves that no significant violations of the model were found in the
with a stepped increase of 0.02° 2h and 0.5 s/step at room temper- analysis in the range of the operating variables.
ature. The XRD patterns of all the samples were plotted using Win- All linear terms have significant effect at 5% level of significance
PLOTR 2015 software for comparison [39]. except for the process temperature no significantly affect SG. The
main effects of UOD time and °Brix on all independent variables
were highly significant as was evident from their respective P-
3. Results and discussion
values (0.00005 < p < 0.00285). When the concentration of sugar
in the osmotic solution is increased, WL rate (p = 0.00005) is more
3.1. Effect of ultrasound assisted osmotic dehydration on WL and SG of
affected than SG (p = 0.0009), promote an important apparent
strawberry
selectivity of transfer [40]. The relative magnitude of b values
(Eq. (16)) indicates the maximum positive effect of osmotic solu-
The non-parametric Wilcoxon Matched Pairs Test at a 95% level
tion concentration (b = 2.496) followed by process duration
of confidence was carried out to compare the results of the osmotic
(b = 1.49) and temperature (b = 1.049) on water loss.
dehydration experiments with and without the application of
The Response surface and contour plots were generated as a
ultrasound. The results showed a considerable difference signified
function of two independent variables at a time with the third
by a positive significant Marked tests (2215 < Z < 3407) was
being maintained at the central level are more helpful in. The
observed between these two treatments considering SG
three-dimensional surface curves were plotted to understand both
(p = 0.00065), WL (p = 0.0076) and WR (p = 0.0267).
the main and the interactive effects of these two factors and pro-
vide useful information about the behavior of the system within
3.2. Statistical analysis the experimental design. The response surface plots for water loss
(WL) are shown in Fig. 2, for significant factor interaction resulted
The multiple regressions testing was carried out on trial data. from the ANOVA.
The quadratic model in coded unit shows the role of every variable Fig. 2(A) shows the increased water loss with increase in osmo-
and their interactions in independent variables. The mathematical tic solution concentration and UOD time. This is mainly because of
equation in terms of coded factors for ultrasound assisted osmotic the increase in the osmotic pressure gradient. A similar variation in
dehydration of strawberry on SG, WL and WR model are shown in water loss with UOD time and temperature has also been observed
Eqs. (15)–(17). in Fig. 2(B). This might be because of the decreases of the viscosity
SG ¼ 0:555 þ 0:245X 1 þ 0:312X 2  0:115X 3 þ 0:267X 1 X 2 of the osmotic solution and thus reduces the external resistance to
mass transfer at product surface and yield better water transfer
þ 0:389X 1 X 3 þ 0:296X 2 X 3 þ 0:148X 21  0:007X 22 characteristics [41].
þ 0:156X 23 ð15Þ Only the quadratic term of UOD time and temperature has sig-
nificant effect on WL and WR at 5% level. The temperature has sig-
WL ¼ 8:12 þ 1:49X 1 þ 2:496X 2 þ 1:049X 3 þ 2:489X 1 X 2 nificant negative effect on WL and WR in quadratic term. The result
also indicated that temperature could act as limiting factors, and
þ 1:327X 1 X 3  0:381X 2 X 3  1:034X 21  0:439X 22 increase in their values cause changes in the structure of cell mem-
 2:589X 23 ð16Þ branes, resulting in loss of selectivity with an increase of the

WR ¼ 8:675 þ 1:248X 1 þ 2:183X 2 þ 1:164X 3 þ 2:222X 1 X 2 0,6


þ 0:938X 1 X 3 þ 0:296X 2 X 3  0:678X 21 þ 0:431X 22
0,3
 2:745X 23 ð17Þ
Predicted Values

0,0
The sufficiency of the model was evaluated through analysis of
variance (ANOVA). Moreover, the variation of the data around the -0,3
fitted model designed by the Lack of Fit was also checked. In the
present study, with regards to WL and WR, the Lack of Fit is not sig- -0,6
nificant relative to the pure error, indicating good response to the
model. Only the fitted SG model exhibits lack of fit (p = 0.012 for -0,9
both UOD and OD) at the confidence level indicates that there is
still some statistically significant variability left that cannot be -1,2
accounted by the factors and their interactions. ANOVA for SG,
WL and WR, respectively indicated that the second-order polyno- -1,2 -0,9 -0,6 -0,3 0,0 0,3 0,6
mial model (Eq. (1)) was adequate to represent the actual relation-
Observed Values
ship between the response and the variables, with a high value of
coefficient of determination (R2 = 0. 9714 for SG, R2 = 0. 989 for WL Fig. 1. The predicted vs. observed values of SG of ultrasound-assisted OD of
and R2 = 0.9897 for WR). This means that the model did not explain strawberry using RSM.
292 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

Fig. 2. Influence of process variables on water loss (A) UOD time and °Brix for 30 °C of temperature process (B) UOD time and temperature at 32.5°Brix of osmotic solution
concentration.

permeability of the cell wall, leading to greater solute uptake. Thus rates of water loss and, depending on the final product application;
explain the significant positive effect of temperature at 7% level of it would be also desirable to minimize the uptake of solutes. The
significance on the SG. Also the interaction between °Brix and aimed of our study was the use of strawberry for production of diet
Temperature had significant effects (PX2X3 = 0.00563). foods for diabetic, for thus it is essential to have a low incorpora-
The result also could be explained by the frequency histogram tion of sugar, for the maintenance of nutritional and sensory char-
Pareto chart of effects (Fig. 3). Pareto analysis is a technique that acteristics of fresh fruit.
helps to prioritize and focus resources visually. It shows the influ- The Derringer’s desirability function method was employed to
ence of each factor on the response in decreasing order. As it can be optimize the process variables, which would maximize WL, WR
seen (Fig. 3 (A)), the most important linear effect for SG were the and minimize SG. According to the software optimization step,
°Brix followed by the UOD time. The efficiency of SG was also the desired goal for each operational condition (UOD time, solution
affected significantly by all factor interactions such as UOD concentration and temperature) was chosen ‘‘within the range’’,
time  Temperature and UOD time  °Brix. Nevertheless, an excess while the responses WL and WR was defined as ‘‘maximum’’ and
of °Brix producing negative influence on the SG but is it statically the response SG was defined as ‘‘minimum’’. The second-order
non-significant. polynomial models obtained in this study were utilized for each
A Pareto chart of the main effects for SG of experiments carried response in order to obtain specified optimum conditions. As
out without application of ultrasound is shown in Fig. 3(B). It was shown in Fig. 4 the optimum conditions were found to be UOD
observed the same tendency as obviously and the most important time of 20.5 min, osmotic solution concentration of 47.5 °Brix,
linear effect for SG were the °Brix followed by the OD time, mean- and osmotic temperature of 31 °C, respectively with overall desir-
while with slightly inferior coefficients. This difference may be ability value of 0.62. At this optimum conditions, WL, WR, and SG
explained by the effect of ultrasound treatment. The use of ultra- were found to be 9.38%, 9.77%, and 0.387%. The optimized water
sound also decreases the amount of soluble solids, especially sugar, loss observed for strawberry in this study was very higher than the
of the fruit and produces a dried low-sugar fruit. Same tendency water loss observed for other strawberry study [13], which have
have been shown in the ultrasound-assisted osmotic dehydration lost only 2.3% weight basis under approximatively the same condi-
of pineapple and papaya [42]. All the results mentioned above tions; 40 kHz ultrasonic waves immersed in an osmotic solution of
are in agreement with many study which state that by using highly 50° Brix, also at 30 °C during 20 min.
concentrated solutions (60–70% by weight), a considerable product In order to verify the predictive capacity of the response surface
weight loss can be achieved along with a low solute gain [40]. models, three experiments were run under the recommended opti-
mum conditions. The observed experimental values for the WL,
3.3. Optimization and validation of the models WR, and SG were found to be 9.80%, 10.16%, and 0.36%, respec-
tively. The difference between experimental and predicted was less
The choice of the optimum process conditions for osmotic dehy- than 7% of deviation, thus indicating the adequacy of models fitted
dration depends on the application that would be given to the by RSM and confirm the predictability of SG and WL in the exper-
product. During osmotic dehydration, it is essential to achieve high imental condition used.

(A) (B)
MS Residual=,0282162
MS Residual=,0162974
X2 4,75
X2 6,921
X1*X3 6,095 X1 4,72
X1 5,440 X3^2 3,13
X2*X3 4,639 X3 -2,74
X1*X2 4,191 X1*X2 2,60
X3 -2,554 X1*X3 2,27
X3^3 2,356 X2*X3 2,21
X1^2 2,232 X1^2 2,11
X2^2 -,118
X2^2 -,47
p=,05
p=,05
Standardized Effect Estimate (Absolute Value) Standardized Effect Estimate (Absolute Value)

Fig. 3. The Pareto chart of standardized effect of the main effects for SG: (A) of UOD strawberry and (B) of OD strawberry.
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 293

UOD time (min) ∞Brix (%) Temperature (∞C) Desirability


,80000

,30883
0,

SG (%)
-,3871 ,5

-1,137
1,

-1,600
16,000

13,106
1,

WL (%)
9,3834 ,5

1,3176
0,
-2,000
16,000

12,797
1,

WR (%)
9,7705 ,5

1,7068
0,

-2,000

Desirability
,62097

10, 20,5 30, 0, 47,5 65, 20, 31 40,

Fig. 4. Desirability charts of variables for maximum WL and WR and minimal SG response for UOD strawberry.

For the osmotic dehydration experiments without ultrasound 45 and 75 °C (0.652–0.785) and recently reported by Dehghannya
the Derringer’s desirability function method was used at optimum et al. [7] for ultrasound-assisted osmotic dehydration pretreatment
conditions to determine the WL, WR and SG parameters. This of the drying Mirabelle plum at 80 °C and 1.4 m/s (0.640–0.764).
parameters reach the respective value of 10.69% (WL), 10.92 The increase of air temperature increases the amount of shrink-
(WR) and 0.23% (SG). The high obtained WL for OD can be age. The shrinkage of food materials increases with the volume of
explained as reported that the effect of the ultrasound-assisted water removed, since the more the water removed the more con-
osmotic dehydration on the water diffusivity depended on the traction stresses are originated in the material. Table 3 indicates
degree of breakdown of cells in the fruit tissue [17]. an increase in shrinkage with UOD pretreatment. This increase
Osmotic dehydration can’t obtain totally dried products and is may be explained by the low osmotic solution concentration
usually applied as pretreatment for other drying process. Further (47.5%) used and essentially the less immersion time in osmotic
study, was done to investigate the effect of ultrasound assisted solution (20.5 min). This result agree with thus of Dehghannya
osmotic dehydration carried out under the optimized operating et al. [7] who advanced that shrinkage of pretreated plum samples
conditions followed by hot-air drying process as a pretreatment at constant ultrasonication time and osmotic solution concentra-
for drying on the mass transfer properties (moisture content, water tion, increasing immersion time from 60 to 240 min decreased
activity, drying rate, water accessibility, diffusivity and activate the shrinkage. With respect to the solution concentration, a smaller
energy with and without shrinkage consideration) and on quality moisture content, and a consequently higher shrinkage were
properties (rehydration ratio, color, total phenolic content, antiox- observed for samples with lower osmotic solution concentrations.
idant activity and X-ray diffraction powder). The Mirabelle plums treated with ultrasound for 30 min and dehy-
drated at osmotic solution concentration of 70% for 240 min, prior
3.4. Drying operation to drying, were found to have the lowest shrinkage (64.1%) com-
pared to control (76.4%) [7].
3.4.1. Shrinkage
Table 3 shows the constants A and B of linear function (Eq. (3)) 3.4.2. CWD model and activation energy
of the volume change at different temperatures and pretreatment 3.4.2.1. The results of effective diffusivity. Moisture diffusivities were
with a coefficient of determination (R2) which presented higher evaluated from the slopes of ln[(X-Xeq)/(Xt1-Xeq)] vs. ratio time/[r
values (>0.99) for all the conditions. This equation is used to esti- (t)]2 fitted straight-line (as shown in Fig. 5 for UOD-air dried straw-
mate the particle radius of the strawberry in the numerical solu- berry) and for both constant sample equivalent radius. This linear
tion described previously. According to the literature, similar data fitting have a good linear fitting with a determination coeffi-
values have been reported describing the shrinkage in strawberry cient R2 > 0.995.
and other fruit. Thus, the slope values (0.628–0.676) of this rela- Identified diffusivities of fresh and UOD-air dried samples were
tionship for strawberry air dried at temperatures of 40–60 °C was summarized in Table 4. Equally shrinkage, temperature and pre-
in the range previously reported by Piotrowski et al. [43] for straw- treatment influences on their values were illustrated.
berry convectively dried at temperatures of 45–65 °C (0.62–0.68), The effective diffusivities of UOD-air dried samples were higher
by Gamboa-Santos et al. [10] for strawberry convectively dried at than fresh-air dried samples. In addition, the higher the tempera-
temperatures of 70 °C and 2 m/s (0.692), by Ramallo and Mascher- ture, the higher the Deff values. Indeed, increasing temperature
oni [44] for pineapple samples dried at temperatures of between normally greatly activates water molecules, speeding up the water
294 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

Table 3
Constants of Equation AX + B (Eq.3), which describes the Volume Change during Drying of strawberry at Different Temperatures and pretreatment.

Fresh-AD 40 °C Fresh-AD 50 °C Fresh-AD 60 °C UOD-AD 40 °C UOD-AD 50 °C UOD-AD 60 °C


r1/2i (cm) 1.633 1.439 1.483 1.764 1.498 1.62
r1/2eq (cm) 1.174 1.004 1.018 1.151 0.962 0.980
V0 (cm3) 9.127 6.248 6.840 11.500 7.041 8.924
Veq (cm3) 3.394 2.114 2.214 3.193 1.864 1.965
A 0.628 0.661 0.676 0.722 0.735 0.780
B 0.372 0.338 0.323 0.277 0.265 0.220

transfer from the core to the surface of the matrix. The effective values with their predicted values. The experimental and predicted
diffusivities varied from 8.42  1010 to 23.27  1010 m2/s for Xr values for UOD-air dried strawberry at 40, 50 and 60 °C lay
fresh-air dried samples and from 12.41  1010 to around the straight line (Fig. 6). The coefficient of correlation (R2)
25.96  1010 m2/s for UOD-air dried samples over the tempera- between the experimental and predicted value of the model is usu-
ture range 40–60 °C for non-corrected drying for shrinkage. These ally >99.4%. There is a better accordance between experimental
diffusivities values were in the same range as those obtained by and predicted Xr values obtained by the model 2 with shrinkage
García-Noguera et al. [13] during the drying (60 °C, 0.5 m/s) of consideration. This favorable effect is more important for high
UOD strawberry halves (50 °Brix and 20 min immersion) when temperature of drying.
the shrinkage was not considered. They obtained Moisture diffu-
sivity values of 33.16  1010 m2/s. 3.4.2.3. Activation energy. Activation energy estimated from the
Values of Deff were somewhat smaller when taking shrinkage Arrhenius type equation is the amount of energy required for
into consideration. This difference increased with drying tempera- removing moisture from the materials. The graphic representation
ture, from 38% lower at 40 °C until 49% at 60 °C. These diffusivities for the different assays carried out is presented in Fig. 7 with Linear
varied from 5.05  1010 to 12.20  1010 m2/s for fresh-air dried correlation coefficients higher than 0.979. The activation energy
samples and from 7.66  1010 to 13.20  1010 m2/s for pre- values without shrinkage correction were found to be 44.4 ± 1
treated samples over the temperature range 40–60 °C. Effective and 32.02 ± 2 kJ/mol for fresh-air dried and UOD-air dried straw-
diffusivity coefficients considering shrinkage but not varying with berry halves, respectively. The values obtained was within the
moisture content were reported by Simal et al. [45], who obtained range with reported values by other researches [11,13,36,46]. The
diffusivities of around 4.7  10–10 to 1  10–9 m2s–1 for grapes [46]. identified Ea values with shrinkage correction decreased to
These diffusivities values were in the same range as those 38.5 ± 1.1 and 23.47 ± 0.8 kJ/mol for fresh-air dried and UOD-air
obtained by Gamboa-Santos et al. [10] during the drying of straw- dried strawberry halves, respectively.
berry cubes of 8.5 mm when considering the phenomenon of
shrinkage, moreover the external resistance (ER) to mass transfer
3.4.2.4. Starting accessibility dxs. Fig. 8 represents a typical kinetics
and diffusion equation of nonlinear character. They obtained Mois-
of airflow drying at 60 °C from fresh-air dried (open circles) and
ture diffusivity values of 0.763–1.305  1010 m2/s over the same
UOD-air dried (full symbols) strawberry. As seen the extrapolation
temperature range of 40–60 °C.
of the diffusion model can be performed to determine Xo as the
theoretical value of X at t = 0. The experimental value of initial
3.4.2.2. Comparison between prediction models. Evaluation of diffu- water content Xi and the extrapolated calculated water content
sional model (Eq. (9) with shrinkage) for moisture prediction can Xo at t = 0 from the diffusion model corresponds to the starting
be wrought comparing the experimental dimensionless moisture accessibility dry basis dXs = Xi  Xo. It represents that the water
quickly removed from the surface independently from the diffu-
sion process.
The starting accessibility for the control sample (Fresh-air dried
strawberry) in our study was in the range of the value 0.0030 g wa-
ter/g d.b found by Alonzo-Macías [28] for the control Hot Air Dried
strawberry at 65 °C and 1.2 m/s.
As presented in Table 4, after UOD pretreatment, the starting
accessibility was systematically greater to 1.65 times more than
fresh-air dried sample at 60 °C (CWD model with shrinkage). These
increases indicate that the acoustic energy contributes to decrease
the internal mass transfer resistance and it could be linked to the
alternative compressions and decompressions produced by the
ultrasound waves at matrix surface, which could make easier the
removal of superficial water [47].
As expected and mentioned by Allaf et al. [5] the higher the
temperature, the higher the starting accessibility. The starting
accessibility was 1.85 and 2.85 higher at 60 °C then 40 °C for the
fresh-air dried and UOD-air dried strawberry, respectively.
Our objectives were to identify the strict conditions of adopting
hot air drying HAD as diffusion-controlled operation. The values
obtained with these experiments have been very interesting. The
fact that the initial accessibility is very low shows that we are
Fig. 5. The natural logarithm of the dimensionless moisture versus time to square
not at all far from a complete diffusion process over the operation.
equivalent radius ratio of UOD pretreated half strawberry dried at 40 (square), 50 In this study the Airflow Velocity of 1 m/s can be assumed very
(triangle) and 60 °C (circle). near of the value of Critical Airflow Velocity CAV defined by Allaf
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 295

Table 4
Modeling of drying kinetics of air dried and UOD-air dried strawberry. Identified Parameters: effective diffusivity and starting accessibility with shrinkage and drying
temperature.

CWD model without shrinkage CWD model with shrinkage


Starting accessibility dXs (% db) Deff0 (1010 m2/s) Starting accessibility dXs (% db) DeffS (1010 m2 s1) Relative error E (%) (Deff0  DeffS)/Deff0
Fresh-AD 40 °C 0.163 8.42 0.565 5.05 40.04
Fresh-AD 50 °C 0.231 14.82 0.803 8.58 42.09
Fresh-AD 60 °C 0.361 23.27 0.998 12.20 47.37
UOD-AD 40 °C 0.201 12.41 0.541 7.66 38.30
UOD-AD 50 °C 0.258 18.26 0.978 9.75 46.62
UOD-AD 60 °C 0.957 25.96 1.614 13.20 49.29

Fig. 6. Experimental (Xrexp) vs. calculated with CWD model with shrinkage (Xrcalc) dimensionless moisture ratio of UOD pretreated half strawberry dried at 40 (square), 50
(triangle) and 60 °C (circle).

1/T (k-1)
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
-19.6
-19.8
-20
y = -5341.3x - 3.8014
Ln (Deff)

-20.2 R² = 0.9791
y = -3851.3x - 8.207
R² = 0.9999
-20.4
-20.6
-20.8
-21 y = -2823.6x - 11.986
R² = 0.9936
-21.2
-21.4 y = -4630.7x - 6.5955
-21.6 R² = 0.9908

Fig. 7. Identification of the Arrhenius’ equation parameters for air dried (circles) and UOD-air dried strawberry (triangles); Discontinuous lines (– – –) Deff from the CWD
model without shrinkage; Continuous line (—) Deff from the CWD model with shrinkage.

et al. [5]. As long as hot air velocity is lower than CAV, drying kinet- 3.4.3. Effect of temperature and UOD on the drying kinetics
ics depends on airflow velocity and drying operation cannot be a Fig. 9 presents the kinetic curves Xr(t), obtained for the fresh
diffusion controlled process. In their study for untreated carrot, and UOD pretreated strawberry tissue, dried at temperatures 40,
CAV was 1 m/s. 50 and 60 °C. The experimental results showed that the drying
296 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

Dimensionless moisture rao,Xr


0,8

0,6

0,4

0,2

0
0 500 1000 1500 2000
Time (min)

Fig. 8. Typical kinetics of Airflow drying at 60 °C from untreated (open circles) and 1
UOD pre-treated (full symbols) strawberry: experimental data and diffusion model

Dimensionless moisture rao,Xr


used to calculate effective diffusivity Deff and starting accessibility dWs = Wi  Wo.
(—) represents the diffusion model and discontinuous lines (– – –) represent the 0,8
extrapolation of diffusion model.

0,6
air temperature enhances considerably the drying kinetics for both
fresh and UOD pretreated strawberry tissue. The UOD pre- 0,4
treatment enhances further the drying kinetics. In this study the
liquid water diffusivity was considered constant independently
on water content value. It would be possible that, for this reason 0,2
the CWD model without shrinkage describe more the experimental
results (smaller diffusivity normally linked to more compact struc- 0
ture should be compensated by smaller radius). 0 500 1000 1500 2000
Fig. 10 shows the drying curves presented in coordinates dXr/ Time (min)
dt versus Xr for the same experimental data. Drying rate decreases
continuously with decreasing moisture content. As expected from Fig. 9. Xr during the drying of untreated (open symbols) and UOD pre-treated (full
Fig. 10 increasing the air temperature and UOD pretreatment symbols) strawberry samples subjected to air temperature of 40 °C (diamonds);
50 °C (triangles); 60 °C (circles); Discontinuous lines (– – –) represent the CWD
increased the drying rate, and consequently decreased drying time.
model without shrinkage; Continuous line (—) represents the CWD model with
In the experimental and the CWD model without shrinkage curves, shrinkage.
the constant rate period was not visible or completely absent.
Thus, falling rate period drying occurred for strawberry samples
for both conventional air drying and UOD-air drying. Such behavior pretreatment generally reduced the total processing time. The
agrees with the observations of many studies [9,11,13,36]. In order difference in total time from the two works might be linked to
to distinguish correctly between the different drying periods, the the different product characteristics (initial moisture content and
drying rate has been calculated with the CWD model with shrink- °Brix), to the low drying speed used (only 0.5 m/s) and to the for-
age consideration. The plots obtained with the current radius plot mation of a small sucrose layer on the surface of the strawberries
exhibits a very short rising temperature period followed by a short due to positive SG in their cases.
constant-rate drying period and a long falling-rate drying period The percentage of time reduction compared to fresh-air dried
(diffusion phase) from which diffusivity was estimated. The most strawberries (total processing time) showed a decrease with tem-
accurate values of drying rate were obtained with moisture con- perature increase. Many previous works [10,13] have highlighted a
tent estimated by Fick’s– type diffusion with shrinkage (Model 2). similar tendency for ultrasound effect with temperature; it was
observed that ultrasound application increased the drying rate.
3.4.4. Optimal conditions However, as the drying temperature increases the influence of
For an osmotic dehydration process followed by hot air drying the ultrasound application on the drying rate decreases.
as suggested by Garcia-Noguera et al. [13] based in previously Ultrasound-assisted osmotic dehydration of strawberry halves
studies, the optimal processing time results when ultrasound at 40 kHz for 20.5 min in a 47.5% sucrose solution needed the
assisted osmotic dehydration allows increasing the drying rate of shortest total processing time of 401 min to achieve 90% reduction
fruit. in moisture content. When compared to fresh-air dried berries
Table 5 shows the values of total processing (pretreatment + air (450 min of processing time), these times resulted in a 49 min
drying) time to achieve 90% water content removal in strawberry reduction (10.88%) in total processing time.
halves. These values were compared to results of Garcia-Noguera
et al. [13]. In confirmation of their study it was observed that 3.4.5. Assessment quality
strawberry submitted to ultrasound-assisted osmotic dehydration 3.4.5.1. Water activity (Aw). The results of the water activity are
dries in less time during the air-drying stage than fresh fruit due to presented in Table 6. After both drying method applied, the final
changes in intercellular tissue as a consequence of the combined water activity of the dried fruits obtained ranged between 0.452
effects of osmotic pressure and fatigue induced by ultrasonic and 0.481. These values show that a microbiologically stable pro-
waves [13]. Ultrasound assisted osmotic dehydration during duct (Aw < 0.6) for each dried product was achieved independently
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 297

0,006 Table 6
Results of water activity and phytochemicals analysis of fresh and dried strawberry.

0,005 Water TPC Anti-radical activity


activity (mg GAE/g DM) (I %)
0,004 Fresh 0.915 27.77 95.00
-dXr/dt (min-1)

Fresh-AD 40 °C 0.474 13.41 67.95


0,003 Fresh-AD 50 °C 0.464 17.24 76.19
Fresh-AD 60 °C 0.466 14.80 53.29
UOD-AD 40 °C 0.452 17.31 65.66
0,002 UOD-AD 50 °C 0.479 14.99 75.27
UOD-AD 60 °C 0.481 13.34 67.03
0,001

0
The color comparisons of the dried strawberries produced by
0 0,2 0,4 0,6 0,8 1
UOD-air drying and by conventional air drying are shown in
Dimensionless moisture rao, Xr
Table 7. Drying had a major influence on color as all values (L⁄,
a⁄, b⁄) were affected. It is evident that Chroma of dehydrated mate-
0,006 rials is not strongly affected by air temperature. Chroma changes
are more intense during conventional than during UOD-drying at
0,005 the same temperature, indicating less saturation and a pale
appearance. In general evaluation, the color of fruits was found
to be better in UOD pretreatment in terms of brightness and red-
0,004
-dXr/dt (min-1)

ness. Only at 60 °C the UOD-air dried strawberries were harder


than the fresh air-dried strawberries. Similar tendency were
0,003 observed by Garcia-Noguera et al. [32], which showed that hue val-
ues decreased and the parameter L⁄ (lightness) have increased dur-
0,002 ing the osmosonication processes of strawberry. They explained
that by the increases of Anthocyanins color (responsible of red
color of strawberry upon the removal of water by displacement
0,001
of the hydration/dehydration equilibrium toward colored species
[32].
0 As seen in Table 7, the decrease of the hue (Dh) of internal side
0 0,2 0,4 0,6 0,8 1 was found significant and pre-treatments demonstrated effective-
Dimensionless moisture rao, Xr ness on saving the redness except at 60 °C. Therefore, it can be con-
cluded that the decrease of anthocyanin in fleshy part of fruit was
Fig. 10. Drying rates curves during drying of untreated (open symbols) and UOD significantly affected by the drying process. Similarly, the drying
pre-treated (full symbols) strawberry subjected to air temperature of 40 °C process affected the decrease of the external red color, but the
(diamonds); 50 °C (triangles); 60 °C (circles). Discontinuous lines (– – –) represent
effect of UOD pretreatments was found to be more significant.
the CWD model without shrinkage; Continuous line (—) represents the CWD model
with shrinkage. The brightness (DL) of the dried fruits increased both on external
and internal sides and they were differently affected by UOD pre-
treatments. It is shown that the increase in internal side brightness
from the drying conditions used. However, the lowest value was was higher than in external side brightness. In terms of pretreat-
achieved after convective drying at 40 °C with UOD pretreatment. ments, it can be seen that UOD-AD 50 °C saved the brightness of
both side color higher than UOD-AD 60 °C. UOD-air dried samples
3.4.5.2. Color assessment. The chromatic parameters L⁄, a⁄, and b⁄ of had the lowest difference chrome, indicating more saturation and
internal side of fresh strawberry were 70.2, 13.47 and 2.24, respec- an appearance that near to the vivid color of fresh strawberries.
tively, while they were 69.15, 9.12 and 2.2, respectively for exter- By reducing drying time, UOD minimized color losses during con-
nal side. The L, C and h mean values for fresh strawberry were vective air-drying.
70.44, 9.89 and 13.50, respectively. In comparison to the fresh fruit, Color change between raw material and dried samples was
the dried strawberry had higher L⁄ (lightness) and lower +a⁄ (red- mainly due to the differences in chrome, hue and lightness proper-
ness) and b⁄ (blueness) values. Moreno et al. [48] observed that ties. Color changes may be attributed to thermal degradation of
OD increased the illuminance of pretreated strawberry compared anthocyanins during strawberry dehydration [48]. The total color
with the fresh fruit. change (DE) of the dried samples varied from 8.75 to 11.66 units

Table 5
Total processing time (pretreatment + forced convective oven drying) to achieve 90% moisture content reduction at different conditions.

Treatment Pretreatment time Air drying time (min) Total processing time % time reduction compared to fresh, untreated
(min) (min) strawberries (total processing time)
AD 40 °C 0 1200 1200
AD 50 °C 0 540 540
AD 60 °C 0 450 450
AD 60 °C [13] 0 612 612
UOD (40 KHZ, 47.5 °Brix)+ AD 40 °C 21 840 861 (28.25%)
UOD (40 KHZ, 47.5 °Brix)+ AD 50 °C 21 420 441 (18.33%)
UOD (40 KHZ, 47.5 °Brix)+ AD 60 °C 21 380 401 (10.88%)
UOD (40 KHZ, 50 °Brix)+ AD 60 °C [13] 20 474 494 (19.28%)
298 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

Table 7
Color change (DL, DC, Dh and DE) of dried and UOD-dried strawberries as a function of air temperature processing.

Treatment Internal side External side


DL DC Dh DE DL DC Dh DE
Fresh-AD 40 °C 3.45 6.12 30.93 8.75 6.60 3.25 25.38 5.98
Fresh-AD 50 °C 7.59 6.28 31.44 11.66 7.69 3.26 24.95 7.58
Fresh-AD 60 °C 5.21 6.55 32.91 8.97 3.01 4.13 20.42 6.32
UOD-AD 40 °C 4.93 6.48 19.71 8.83 6.55 2.14 12.89 7.66
UOD-AD 50 °C 8.48 4.22 20.79 11.93 7.66 2.95 10.94 7.38
UOD-AD 60 °C 5.98 4.14 28.85 12.73 8.17 1.35 9.68 10.21

and from 5.98 to 7.58 in internal and external side, respectively atically to a decrease of the antioxidant activity. Indeed, with lower
depending on applied drying temperature. Except at 60 °C only phenolic content, one can also have a higher antioxidant activity.
minor color difference could be observed between fresh-air dried From these results, it can be concluded that total phenolic content
and UOD-air dried samples. For UOD-air dried samples at 60 °C might not be directly correlated with total antioxidant activity.
DE values among greater than fresh-air dried, which indicated that
samples were turning darker than the fresh. 3.4.5.4. Rehydration. Rehydration, often used to evaluate instant
products, is one of the most important quality parameters of dried
3.4.5.3. Total phenol content and antioxidant activity of ethanolic strawberries. For rehydration ratio, curves were plotted for g
extract of dried strawberry. The initial phenolic content was water/100 g dry matter versus time for each dried conditions
27.77 ± 0.16 mg Gallic acid g1 dry strawberry sample. Levels of (Fig. 11). For all experiments the amount of moisture uptake
phenols for unprocessed strawberry is in the range of those increased with rehydration time, but with decreasing rate up to
reported by other authors [49,50]. saturation level (Fig. 11). The same behavior was observed by
The present experiments showed that temperature and UOD Alonzo-Macıas [28] during rehydration of swell and convective
pretreatment had an important effect on the total phenolic content dried strawberry fruits and by Jambrak et al. [51] during rehydra-
compared to the fresh sample. During drying, TPC levels were gen- tion of mushrooms, brussels sprouts and cauliflower. The same
erally decreased. We observed losses of 51.70%, 37.91% and 46.68% range of RR data was reported by El-Beltagy et al. [52] (within
at 40, 50 and 60 °C, respectively, as compared to fresh sample. The the range 257–344) for strawberry samples of different geometries
longer processing time in 40 °C associated higher processing tem- subjected to solar drying for up to 24 h.
perature in 60 °C as compared to 50 °C contribute to diminish the Fig. 11 indicates increase in rehydration ratio with increased
protective effect against oxidative damage to cells. This is in line temperature. In cases when OD proceeded, the UOD-air dried sam-
with results reported by Alonzo-Macías [28] they reported a ples had higher water content than those of fresh-air dried sam-
decrease in phenolic content during air drying (16.8 mg Gal- ples. The lowest solid uptake might be the reason of maximized
lic acid g1 dry strawberries at 50 °C). For UOD- air dried straw- sample shrinkage during drying. This effect may be responsible
berry differences in phenolic stability occurred between air for the better water content of ultrasound osmotically treated sam-
temperatures, being higher at higher temperatures, they lost ples. Noshad et al. [53] reported that the lower rehydration ratios
37.65%, 46.01% and 51.94% of TPC over the same range of temper- of the osmotic-ultrasonic convective dried Quince osmo- blueberries
ature, respectively. The highest total phenolic content (TPC) was were attributed to the added the sugar on the dehydrated fruits,
recorded in plants dried by AD 50 °C and UOD-AD 40 °C and was which reduced the amount of water that could be absorbed during
38% low than those of fresh plants whereas the lowest content rehydration. Jambrak et al. [51] concluded that the rehydration
was found in the case of plants dried by UOD-AD 60 °C (51.94% properties for ultrasound treated button mushrooms were higher
low than fresh strawberry). The increase in total phenolic content than for untreated samples, so rehydration behavior of plant food
for UOD-AD 40 °C may be related to an increased extractability of could also be enhanced by the use of ultrasound.
some of the antioxidant components following ultrasound process-
ing who can give rise to pores in the vegetal tissue and, conse-
quently, improve the extraction of polyphenols during sample
preparation. However highest shrinkage related to negative quality
characterized by increased hardness, biochemical reactions and
brown appearance can explained values for UOD-AD 60 °C [50].
The DPPH scavenging activity of fresh fruit was determined to
be 95.03 ± 1.18% at 1000 lg/mL concentration. On the other hand,
the scavenging activity decreased significantly after the drying
process, and it was found to be 53.29% at 60 °C. As shown in Table 6,
there was no significant difference in (% I) of fresh-air dried and
UOD-air dried samples at 40 and 50 °C. Whereas, it is decreased
by 44% in air dried samples compared to 29.44% in UOD-air dried
samples. In this aspect, some authors reported same results. Woj-
dylo et al. [50] and Alonzo-Macías, [28] reported that convection
drying lowered antioxidant activity and total phenol content in
strawberry. Regardless of the processing method employed, the
temperature of 50 °C had greater antioxidant activity than the
others temperature. Too numerous factors are implied in antioxi-
dant activity and It is difficult to explain their evolution according Fig. 11. Rehydration kinetics of untreated (open symbols) and UOD pre-treated
to heat process conditions or phenolic content. Alonzo-Macías, [28] (full symbols) strawberry half subjected to air temperature of 40 °C (diamonds);
reported that a decrease in phenolic content does not lead system- 50 °C (triangles); 60 °C (squares).
E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300 299

3.4.5.5. X-ray powder diffraction. Fig. 12 shows XRD profile of the characteristics and exhibited no crystalline peak (Fig. 13). The
analysis of X-ray diffraction of the convective air dried fresh straw- absence of crystalline peaks confirmed that no substantive changes
berry at 40, 50 and 60 °C temperature. The air dried strawberry occurred on the hygroscopicity of air dried and UOD-air dried
powder showed amorphous characteristics at 40, 50 and 60 °C air strawberry powders obtained. The X-ray patterns and shapes for
drying temperature. This meant that the relatively low air temper- all the strawberry powders tested were similar to spray-dried
ature used in drying there no crystallization of sugars of the con- sucrose showing the predominance of sucrose sugars present in
vective air-dried strawberry powder. Mazza [54] attributed the strawberry [56,57].
lower rates of moisture transport observed in air drying of sucrose
treated carrots to the crystallization of sucrose during the subse-
quent air-drying process. 4. Conclusion
The diffractogram of air-dried strawberry powder obtained in
this study was comparable to the one reported by Haque et al. This work evaluated the production of osmotic-dehydrated
[55]. The rapid drying of low molecular weight sugars present in strawberry with low sugar content with applying ultrasound to
strawberry (sucrose, fructose and glucose) and organic acids that decrease the sugar uptake from the fruit. The influence of opera-
happened under air drying processes tend to produce amorphous tion parameters such as ultrasound and OD time, solution concen-
metastable state dried products due to the fact that during drying, tration and system temperature on water loss and solid gain are
the material did not reach the conditions necessary for occurrence discussed. The effect of ultrasonic osmosis on weight reduction is
of crystallization of sugars (above the glassy transition tempera- also studied. OD concentration, ultrasound treatment duration
ture) [26,56]. and temperature increase the amount of water removed during
Xray diffraction patterns of air-dried and UOD-air dried OD. However the ultrasound treatment decreases the intake of
strawberry powders at 60 °C clearly presented amorphous solids by the product. Then ultrasound OD is appropriated at
higher WL and limited solids (sugar) uptake (dietetic products).
BBD and RSM are demonstrated to be an effective technic for
modeling the effect of sonication on OD while minimizing the
number of experiments required. The second-order polynomial
models for all the response variables were found to be statistically
significant. The optimal conditions for maximum water loss and
weight reduction and minimum solid gain, were 20.5 min for
UOD time, 47.5 °Brix osmotic solution concentration and 31 °C
medium temperature in order to obtain water loss of
9.38 g/100 g fresh sample, weight reduction of 9.77 g/100 g fresh
sample and solid gain of 0.387 g/100 g fresh sample.
The result of this study indicate that increasing drying temper-
ature during the drying of strawberry increases the drying rate and
drying coefficient and consequently decreases drying time. UOD
before the air drying of strawberry tissue resulted in a spectacular
reduction of drying time and an increase in effective water diffu-
sivity because it is not influenced by slight sugar gain on the sur-
face of the fruit, which makes it easy for the water removal. The
Coupled Washing/Diffusion CWD model provides a simple mathe-
matical calculation tool for taking into account the shrinkage dur-
ing drying of fruits with high water content value. The differences
Fig. 12. X-ray diffraction patterns of convective air-dried fresh strawberry at 40 °C
(cross), 50 °C (squares) and 60 °C (circles). between the data corrected and non-corrected for shrinkage were
very significant, nearly one order of half magnitude. These results
showed that strawberry diffusivities were much overestimated
when shrinkage was not taken into account in drying data process-
ing. The drying time of strawberry halves was shortened by about
28% when the samples were previously treated with US (40 kHz) in
a 47.5% sucrose solution (31 °C for 21 min) prior to drying.
UOD for a short contact time minimized color losses during con-
vective air-drying. In terms of pretreatments, it can be seen that
UOD-AD 50 °C saved the brightness of both side color higher than
UOD-AD 60 °C. The highest total phenolic content (TPC) was
recorded in plants dried by AD 50 °C and UOD-AD 40 °C and was
38% low than those of fresh plants Regardless of the processing
method employed, the temperature of 50 °C had greater antioxi-
dant activity than the others temperature. The X-ray diffraction
patterns of air-dried and UOD-air dried strawberry powders clearly
presented amorphous characteristics and exhibited no crystalline
peak formation.
This method could make a significant contribution to the fruit
processing industry and confer a higher quality to the finished
products. Strawberries dehydrated by means of UOD can be an
Fig. 13. X-ray diffraction patterns of convective air-dried strawberry at 60 °C attractive component of popular breakfast cereals such as
(circles) and UOD + convective air dried strawberry at 60 °C (full circles). muesli.
300 E. Amami et al. / Ultrasonics Sonochemistry 36 (2017) 286–300

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