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Food Hydrocolloids
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Article history:
Received 16 March 2013
Accepted 19 November 2013
This study aimed at characterizing four formulations of cassava starch, glycerol, carnauba wax and
stearic acid-based edible coatings/lms, evaluating their water vapor resistance, the respiration rate of
coated apple slices, surface solid density, solubility, mechanical properties, thermal properties and
microstructure. Among the formulations evaluated, only the formulation with higher wax content did
not promote an effective barrier to oxygen and water vapor and resulted in more rigid lms. Formulations with higher glycerol content promoted lower respiration rate of apple slices, good water vapor
resistance and exible lms, but the microstructure analysis showed a non-homogenous surface of the
lms with higher wax content. The glycerol added in formulations increased the solubility and reduced
the melting temperature of the lms. Formulation with 0.2% carnauba wax showed intermediate values
of analyzed properties and promoted lms with a more regular surface. Formulation containing 3% (w/
w) cassava starch, 1.5% (w/w) glycerol, 0.2% (w/w) carnauba wax and 0.8% (w/w) stearic acid, presented
lms with a cohesive matrix, resulting in better mechanical properties, barrier to moisture and gas
exchange.
2013 Elsevier Ltd. All rights reserved.
Keywords:
Cassava starch
Respiration rate
Water vapor resistance
Microstructure
Fresh-cut apple
1. Introduction
The market for minimally processed fruits and vegetables has
increased in recent years. These products are ready to eat, convenient and maintain the freshness and nutritional quality of the
whole product. On the other hand, the peeling and cutting operations can accelerate the metabolic activities of plant tissue, making
the minimally processed product more perishable than intact fruits
and vegetables (Olivas & Barbosa-Cnovas, 2005). So, new strategies and technologies to maintain quality and extend shelf life are
required.
The use of edible coatings is a promising technology to preserve the quality of whole and minimally processed fruits (Han &
Gennadios, 2005; Talens & Krochta, 2005; Vargas, Pastor, Chiralt,
McClements, & Gonzlez-Martnez, 2008; Zahedi, Ghanbarzadeh,
& Sedaghat, 2010). The coatings act as barriers to water loss and
gas exchange, controlling the transfer of moisture, oxygen, carbon dioxide, lipids and avor components, with similar effect to
that promoted by storage under controlled or modied atmosphere (Vargas et al., 2008). A range of polymers can be used in
edible coatings formulation. However, their mechanical and
barrier properties are intrinsically linked to physical and chemical characteristics of their constituents. The polymers most
commonly used in the preparation of edible lms and coatings
are proteins (gelatin, casein, wheat gluten and zein), polysaccharides (starch, pectin, cellulose, alginate and carrageenan)
and lipids (stearic acid, waxes and fatty acid esters), which can
be used alone or in combinations (Sothornvit & Krochta, 2001;
Vargas et al., 2008).
Polysaccharides-based coatings have low oxygen permeability,
which can reduce the respiration rate of minimally processed
products. Starch is the most important polysaccharide used in the
formulation of biodegradable lms and edible coatings. Cassava
starch-based coatings are tasteless, odorless and transparent, not
changing the taste, aroma and appearance of the product
(Chiumarelli, Pereira, Ferrari, Sarantpoulos, & Hubinger, 2010;
Garcia, Pereira, Sarantpoulos, & Hubinger, 2010; Pareta &
Edirisinghe, 2006). Although the starch is a cheap and abundant
material, able to form a continuous polymer matrix, it exhibits a
strong hydrophilic character, constituting poor barriers to water
vapor (Averous & Boquillon, 2004; Ghanbarzadeh, Almasi, &
Entezami, 2011; Karbowiak, Debeaufort, & Voilley, 2007; Liu,
2005; Vargas et al., 2008). The addition of lipids can reduce water
vapor permeability, but it can affect coatings transparency and
mechanical properties, despite the lipid offers after taste, which
may impair the sensory characteristic of food (Bourlieu, Guillard,
Table 1
Cassava starch (CS), glycerol (GLY), carnauba wax (CW) and stearic acid (SA) concentrations on coatings/lms formulations.
Variables
CS (% w/w)
GLY (% w/w)
CW (% w/w)
SA (% w/w)
WF
dP
1
$
dt
A
"
2
2.50
2.82
0.10
0.90
2.50
2.61
0.38
0.62
3.50
1.00
0.40
0.60
3.00
1.50
0.20
0.80
(1)
Formulation
1
21
WVR
!
#
RH
aw 100
1
$Pwv $
WF
R$T
(2)
22
SSD
Xs $Mcoating
As
(3)
RR (mL CO2
kg1 h1)
WVR (s cm1)
SSD (103
g cm2)
Sol (%)
1
2
3
4
5.75 0.22B
4.99 0.27C
9.13 0.66A
6.13 0.12B
36.91 2.26B
50.75 5.29A
25.95 2.04C
44.51 2.15A
2.25 0.16A
2.39 0.33A
3.42 0.21B
3.45 0.48B
43.14 0.70A
42.96 2.07A
27.50 2.67C
37.87 1.74B
Values with the same letter within the column are not signicantly different
p 0.05.
a
Formulation 1 2.50% CS; 2.82% GLY; 0.10% CW; 0.90% SA; formulation
2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY;
0.40% CW; 0.60% SA; formulation 4 3.00% CS; 1.50% GLY; 0.20% CW; 0.80% SA.
23
Table 3
Tensile strength (TS), elongation at break (Elo), elastic modulus (EM) and coating
strength (TS/EM) of lms with cassava starch, glycerol, carnauba wax and stearic
acid.
Formulationa TS (MPa)
1
2
3
4
0.220 0.015A
0.211 0.011A
1.067 0.099B
0.729 0.015C
Elo (%)
EM (MPa)
Coating
strength
(TS/EM)
17.673 0.342A
18.618 1.012A
24.217 1.704B
31.074 2.278C
0.197 0.019A
0.077 0.007B
0.504 0.023C
0.221 0.029A
1.182 0.058A
1.446 0.207A
2.009 0.120B
4.047 0.221C
Values with the same letter within the column are not signicantly different
p 0.05.
a
Formulation 1 2.50% CS; 2.82% GLY; 0.10% CW; 0.90% SA; formulation
2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY;
0.40% CW; 0.60% SA; formulation 4 3.00% CS; 1.50% GLY; 0.20% CW; 0.80% SA.
24
Table 4
Transition temperature (Tm) and enthalpy of transition (DH) of carnauba wax, stearic
acid and lms with cassava starch, glycerol, carnauba wax and stearic acid.
Samplea
1st Peak
Tm1 [ C]
2nd Peak
58.13 0.20
0.58 0.11
60.48 0.82 134.02 10.42
A
56.18 0.39
19.83 0.92A
54.59 0.63B
10.30 0.81B
55.64 0.80AB 11.49 0.48B
56.05 0.42A 20.19 0.54A
83.38 1.10
e
71.46 0.25A
74.73 0.39B
75.80 0.50C
73.87 0.14B
DH2 [J g1]d.b.
171.83 4.74
e
0.36 0.05A
2.91 0.54B
4.29 0.20C
1.84 0.05D
Values with the same letter within the column are not signicantly different
p 0.05.
a
Formulation 1 2.50% CS; 2.82% GLY; 0.10% CW; 0.90% SA; formulation
2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY;
0.40% CW; 0.60% SA; formulation 4 3.00% CS; 1.50% GLY; 0.20% CW; 0.80% SA.
b
Dry basis.
second peak represents the melting of long carbon chain components of carnauba wax. In formulations containing higher carnauba
wax content (Formulations 2 and 3), the rst endothermic peak was
smaller and the second peak had become more prominent when
compared with other formulations.
The glass transition temperature could not be observed in these
thermograms. According to Ghanbarzadeh, Almasi, and Entezami
(2010) and Ghanbarzadeh and Almasi (2011), the glass transition
of carbohydrate lms with plasticizer is difcult to be determined
by DSC analysis, because the change of heat capacity is very low in
the glass transition.
The transition temperature (Tm) and the enthalpy of transition
(DH) of carnauba wax, stearic acid and lms samples are shown in
Table 4.
Transition temperature of the rst peak (Tm1) was lower than
Tm1 of lipid components alone, due to glycerol. Formulations 1 and
4 did not differ statistically with respect to Tm1, since they had a
high concentration of fatty acid and low carnauba wax content.
Formulation 3 also did not signicantly differ from these two formulations, although containing lower stearic acid concentration
and a higher wax percentage. But formulation 3 contained low
glycerol content (1%), which contributed to non-signicant reduction in Tm1. Al-Hassan and Norziah (2012) reported that the increase
in glycerol concentration reduced the Tm and DH of starch and sh
Fig. 1. Thermograms of the lms prepared with cassava starch, glycerol, carnauba wax and stearic acid storage for 3 weeks at 58% RH. Formulation 1 2.50% CS; 2.82% GLY; 0.10%
CW; 0.90% SA; formulation 2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY; 0.40% CW; 0.60% SA; formulation 4 3.00% CS; 1.50% GLY; 0.20% CW;
0.80% SA.
gelatin lm, indicating that the plasticizer has reduced the intermolecular forces and increased polymer chain mobility. Formulation 2 showed the lowest Tm1 due to both a low stearic acid
percentage (0.62%) and a high glycerol concentration (2.61%).
For the second peak transition temperature (Tm2), only formulations 2 and 4 did not differ statistically. This peak may be representing the fusion of carnauba wax and stearic acid mixture, which
could explain the highest Tm2 obtained by formulation 3, since this
treatment has a higher wax percentage (0.40% w/w) which would
increase the melting point of lipid mixture. The presence of two
endothermic peaks can be related to a rich lipid fraction, because
there is a polymorphic transformation of fatty acids, from a form
(rst endothermic peak) to b form (second endothermic peak). The
melting temperature of stearic acid a form of is 55 C and of b form,
73 C (Lutton & Fehl, 1970), very close to the Tm1 and Tm2 values
found for all formulations (Table 4).
These transition temperatures (Tm1 and Tm2) may be related to
mechanical properties of lms, because they are dependent on
glycerol and lipids concentrations. Films with higher values of Tm1
and Tm2 showed high values of tensile strength and elastic
modulus, as shown by formulation 3; those with low tensile
strength and elastic modulus, such as formulation 2, showed the
lowest transition temperatures. Formulation 4, with high Tm1 and
intermediate value of Tm2 formed lms with high values of elongation and coating strength. The enthalpy of transition (DH) was
strongly inuenced by carnauba wax concentration on lms. Formulations 2 and 3, with higher wax content showed low enthalpy
for the rst peak and higher values of DH2 compared to formulations 1 and 4.
3.5. Scanning electron microscopy (SEM)
The microstructure of the lms was analyzed using the scanning
electron microscopy technique (SEM). Figs. 2 and 3 show the surface and the cross section microscopy of lms, respectively.
Microstructure was analyzed qualitatively in order to verify the
features promoted by different concentrations of cassava starch,
25
Fig. 2. SEM micrographs of the lms surface produced from formulations 1 (a), 2 (b), 3 (c) and 4 (d). Scale bar 10 mm. Arrows indicate lipid cluster. Formulation 1 2.50% CS; 2.82%
GLY; 0.10% CW; 0.90% SA; formulation 2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY; 0.40% CW; 0.60% SA; formulation 4 3.00% CS; 1.50% GLY;
0.20% CW; 0.80% SA.
26
Fig. 3. SEM micrographs of the lms cross section produced from formulations 1 (a), 2 (b), 3 (c) and 4 (d). Scale bar 10 mm. Arrows indicate lipid cluster. Formulation 1 2.50% CS;
2.82% GLY; 0.10% CW; 0.90% SA; formulation 2 2.50% CS; 2.61% GLY; 0.38% CW; 0.62% SA; formulation 3 3.50% CS; 1.00% GLY; 0.40% CW; 0.60% SA; formulation 4 3.00% CS;
1.50% GLY; 0.20% CW; 0.80% SA.
Acknowledgments
The authors are grateful to FAPESP (process number: 08/553431 and 09/51420-4) and CNPq for their nancial support.
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