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Food Chemistry
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Department of Food Science and Technology, Tokyo University of Marine Science and Technology, 5-7 Konan 4, Minato-ku, Tokyo 108-8477, Japan
Department of Home Economics, Kokugakuin Tochigi Junior College, 608 Hirai, Tochigi 328-8588, Japan
a r t i c l e
i n f o
Article history:
Received 9 July 2009
Received in revised form 17 January 2010
Accepted 23 March 2010
Keywords:
Gelatin
Emulsion lm
Shark skin
Stearic acid
Oleic acid
a b s t r a c t
Incorporation of fatty acids (stearic and oleic) into edible lms based on blue shark (Prionace glauca) skin
gelatin was investigated to modify properties such as water vapour barrier and exibility due to their
hydrophobicity and plasticizing effect, respectively. Addition of stearic acid from 0% to 100% of protein
concentration in the lm-forming solution considerably decreased water vapour permeability of gelatinfatty acid emulsion lms compared to addition of oleic acid at the same fatty acid concentration.
Increasing concentrations of both fatty acids decreased tensile strength, but increased elongation at break
due to their plasticizing effect. At the same concentration, oleic acid gave a greater plasticizing effect than
did stearic acid. On the other hand, transparency of the gelatinstearic acid emulsion lm was lower than
that of the gelatinoleic acid emulsion lm. Faster stirring speed of homogenisation improved properties
of only the gelatinstearic acid emulsion lm.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Edible lm, a thin layer of biomaterial, has attracted the packaging industry, since it can provide a barrier to moisture, oxygen and
solute movement of foods (Guilbert, 1986). Amongst protein-based
edible lms, gelatin lm has received attention for edible and pharmaceutical products, such as capsules, meats and sausage casing
components, since gelatin is unique amongst hydrocolloids in
forming thermo-reversible gels with a melting point close to body
temperature (Achet & He, 1995). Gelatin lm properties depend on
several factors, including the gelatin source and the gelatin lmmaking process. Non-bovine gelatin sources, especially marine
species, have currently received attention in response to the bovine
spongiform encephalopathy (BSE) crisis. In our previous study, gelatin lm from blue shark (Prionance glauca) skin was characterized
in order to enhance the utilisation of by-products from shark processing (Limpisophon, Tanaka, Weng, Abe, & Osako, 2009). Gelatin
lm from shark skin has a lower water vapour permeability (WVP)
and higher opacity at 280 nm (UV wavelength) than have gelatin
lms from other sh. This gelatin lm can thus be applied to pharmaceutical products or foods rich in fat due to its excellent barrier
properties against water vapour and UV. However, WVP of shark
skin gelatin lm was higher than that of other edible lms.
Materials, such as fatty acids, lipids and waxes, are commonly
used as edible coatings to reduce WVP due to their nonpolar or
* Corresponding author. Tel./fax: +81 3 5463 0620.
E-mail address: osako@kaiyodai.ac.jp (K. Osako).
0308-8146/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2010.03.090
hydrophobic characteristics. Moreover, they bring about visual appeal (gloss) to products (Talens & Krochta, 2005). There are many
reports of lipid incorporation in protein-based lms to retard water
migration (Anker, Berntsen, Hermansson, & Stading, 2002; Bertan,
Tanada-Palmu, Siani, & Grosso, 2005; Perez-Gago & Krochta, 2001).
Proteinlipid lms can be prepared by two methods: lamination
and emulsication. During casting of lipid onto protein lm for
the lamination, temperatures of lm and lipid can be easily and
separately controlled. On the other hand, the temperature of the
emulsion must be above the melting point of the lipid but below
the melting temperature of gelation and solvent volatilisation temperature for the structural network of emulsion lms. The main
disadvantage of laminate lms is that the preparation technique
requires four stages; protein lm casting, protein lm drying, lipid
casting onto protein lm and nal lipid lamination. This is the reason why laminate lms are less popular in the food industry, despite their good barrier property against water vapour.
On the other hand, the preparation of emulsion lms requires
only one emulsion solution casting and one drying step. However,
the water vapour barrier property of nished lms is rather poor,
since water molecules still permeate through the non-lipid phase
(Anker et al., 2002). In the case of emulsion lms, the water barrier
efciency increases with a decrease in lipid globule size and with
distribution of homogeneous hydrophobic substances (Debeaufort
& Voilley, 1995; Perez-Gago & Krochta, 2001). Stirring speed during the emulsication process can thus be considered as an important factor for obtaining homogeneous lms and it has a great
inuence on their performance (Garcia, Martino, & Zaritzky,
1096
TSMPa Fmax=A
where F max = maximum load (N) needed to pull the sample apart;
A = cross-sectional area (m2) of the samples; EAB (%) was calculated
by following equation:
1097
Table 1
Effect of fatty acid concentration on thickness, water vapour permeability (WVP), tensile strength (TS), and elongation at break (EAB) of gelatinfatty acid emulsion lms.a,b
WVPc (1010 g m1 Pa1 s1)
TSd (MPa)
EABe (%)
1.30 0.12c
0.95 0.07b
0.96 0.04b
0.70 0.06a
23.26 2.03c
17.21 0.76b
16.74 0.34b
13.62 0.32a
80.78 4.54a
99.31 5.96b
110. 32 6.90c
108.41 9.77c
1.30 0.12c
1.17 0.14bc
1.01 0.03ab
0.91 0.06a
23.26 2.03c
13.23 1.58b
14.16 0.87b
9.46 0.36a
Thickness (lm)
80.78 4.54a
178.56 12.38b
222.12 11.04c
257.17 7.13c
1098
Table 2
Effect of fatty acid concentration on transparencya of gelatinfatty acid emulsion lms.
Transparency (A/mm) at wavelength (nm)
200c
b
Control
Stearic acid concentration (%)
25
50
100
Oleic acid concentration (%)
25
50
100
a
b
c
280
350
400
500
600
800
28.69
10.09
6.83
5.69
5.24
4.65
18.85
14.80
10.23
7.09
5.49
3.84
5.67
4.32
2.91
4.75
3.47
2.31
4.24
2.95
1.99
3.70
2.40
1.72
25.07
25.11
24.92
9.22
9.50
8.57
7.12
7.06
5.96
5.56
5.30
4.09
4.68
4.42
3.15
3.62
3.53
2.26
Transparency (A/mm) = log T/x (A, absorbance at each wavelength; T, transmittance (%) at each wavelength; x, lm thickness (mm)).
Control is 2% gelatin lm with 50% glycerol.
Value could not be determined.
Control
Upper surface
Upper surfaces of all gelatin lms formulated with different levels of oleic acid showed even distributions of oil droplets (Fig. 1).
Lower surfaces of all lms did not have any oil droplets, indicating
that oleic acid was dispersed only on the top surface. This phenomenon would occur during FFS dehydration. Films with oleic acid did
not have crystalline particles like lms with stearic acid, since oleic
acid is in a liquid state at room temperature (m.p. = 1314 C).
This study revealed that gelatin emulsion lms with 100% fatty
acid (stearic acid or oleic acid) effectively gave the lowest WVP.
3.2. Effect of stirring speed on gelatinfatty acid emulsion lm
3.2.1. General
The gelatin emulsion lms with 100% stearic acid or 100% oleic
acid were used to study the effect of stirring speed on gelatinfatty
acid emulsion lm.
Lower surface
Fatty acid
concentration
(%)
Lower surface
Lower surface
25
50
100
Fig. 1. SEM micrographs of gelatin lm surfaces formulated with different fatty acid concentrations.
Fig. 2. Effect of stirring speed on distribution of fatty acid particles in FFS (A:
distribution of stearic acid particles in FFS, B: distribution of oleic acid particles in
FFS.).
1099
1100
Table 3
Effect of stirring speed on thickness, water vapour permeability (WVP), tensile strength (TS), and elongation at break (EAB) of gelatinfatty acid emulsion lms.a,b
Stirring speed (rpm)
Thickness (lm)
TSd (MPa)
EABe (%)
68.83 3.07a
68.65 2.26a
71.85 7.22a
1.04 0.09c
0.87 0.01b
0.70 0.06a
11.03 0.71a
11.83 0.48b
13.62 0.32c
74.35 7.06a
77.11 4.40a
108.41 9.77b
57.39 2.09a
56.10 3.33a
54.83 4.71a
1.02 0.06a
1.01 0.04a
0.91 0.06a
10.23 0.85a
9.73 0.66a
9.46 0.36a
259.80 27.75a
261.40 15.84a
257.17 7.13a
Stirring speed
(rpm)
Lower surface
Upper surface
Lower surface
8,000
13,500
24,000
Fig. 3. SEM micrographs of surfaces of gelatinfatty acid emulsion lms prepared by different stirring speeds.
these did not signicantly inuence WVP, TS or EAB (p > 0.05). This
may be because the particle size of oleic acid in the lm which was
prepared at a faster stirring speed was not considerably smaller
than that of stearic acid. Although faster homogenisation impacted
smaller particle size in FFS of oleic acid (Fig. 2), its particles became
aggregated after homogenisation, as shown in Figs. 2 and 3. The
melting point of oleic acid is around 1314 C, whereas melting
point of stearic acid is 69 C. Consequently, stearic acid is in the solid state whilst oleic acid is liquid in the emulsion lms during
casting and conditioning. It might be concluded that the fatty acid
state in the emulsion lm has a greater effect on the lm characteristics than has homogenisation speed.
From a practical point of view, gelatin lms with stearic acid or
oleic acid would be applied as wrapping of food to reduce moisture
Table 4
Effect of stirring speed on transparencya of gelatinfatty acid emulsion lms.
Stirring speed (rpm)
a
b
280
350
400
500
600
800
26.09
12.31
10.23
36.65
6.10
3.84
14.99
4.84
2.91
13.87
3.93
2.31
13.17
3.37
1.99
12.23
2.67
1.72
24.17
24.54
24.92
10.93
9.07
8.57
8.39
6.44
5.96
7.14
4.80
4.09
6.49
3.94
3.15
5.68
2.97
2.26
Transparency (A/mm) = log T/x (A, absorbance at each wavelength; T, transmittance (%) at each wavelength; x, lm thickness (mm)).
Value could not be determined.
1101
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