Starchegelatin edible lms: Water vapor permeability and mechanical

properties as affected by plasticizers

A.A. Al-Hassan, M.H. Norziah
*
Food Technology Department, School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
a r t i c l e i n f o
Article history:
Received 20 May 2010
Accepted 14 April 2011
Keywords:
Edible lm
Sago starch
Fish gelatin
Glycerol
Sorbitol
DSC
Glass transition
a b s t r a c t
Physical and mechanical properties of edible lms based on blends of sago starch and sh gelatin
plasticized with glycerol or sorbitol (25%, w/w) were investigated. Film forming solutions of different
ratios of sago starch to sh gelatin (1:0, 2:1, 3:1, 4:1, and 5:1) were used and cast at room temperature.
Amylose content of sago starch was between 32 and 34% and the protein content of the sh gelatin was
found to be 81.3%. The ndings of this study showed that the addition of sh gelatin in starch solutions
has a signicant effect (p < 0.05), resulting in lms with lower tensile strength (TS) and higher water
vapor permeability (WVP). On the other hand, increasing protein content (from 10.9% to 21.6%) in lm
samples plasticized with sorbitol showed signicantly lower (p < 0.05) TS but no trend was observed in %
elongation-at-break (EAB) and no differences in WVP. However, TS decreased with higher protein
content in the samples when either plasticizers were used in general, but no signicance differences was
observed among the samples (p < 0.05) with glycerol with exception to lm with high protein content
(21.6%) only and no trend was observed in % EAB among samples as well. Signicant difference (p < 0.05)
was observed in TS and viscosity between different formulations with sorbitol. The morphology study of
the sago starch/sh gelatin lms showed smoother surfaces with decreasing protein in the samples with
either plasticizer. DSC scans showed that plasticizers and protein content incorporated with sago starch
lms reduced the glass transition temperature (T
g
) and melting temperature (T
m
) and the melting
enthalpy (DH
m
). In this study, observation of a single T
g
is an indication of the compatibility of the sago
starch and sh gelatin polymers to form lms at the concentration levels used.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Consumers demand higher quality and longer shelf life in foods,
while reducing disposable packaging materials and increasing
recyclability. Such demands have caused increased interest in
edible and biodegradable lms or materials that potentially are
used to extend the shelf life and improve the quality of almost any
food system by serving as mass transfer barriers to moisture,
oxygen, carbon dioxide, lipid, avor and aroma between food
components and the surrounding atmosphere (Jongjareonrak,
Benjakul, Visessanguan, Prodpran & Tananka, 2006). Such lms
may have the ability of decreasing the amounts of non-renewable
conventional synthetic polymer packaging materials, and use
ingredients of agricultural derived products (Soares, Lima, Oliveira,
Pires, & Soldi, 2005). Edible lms can be prepared from protein,
polysaccharides, lipids or the combination of these components
(Cao, Fu, & He, 2007; Cuq, Gontard, Cuq, & Guilbert, 1997). Starch
lms due to the hydrophilicity properties of the starch polymers,
provide a minimal barrier to moisture. Films of protein or poly-
saccharides have overall suitable mechanical and optical properties
but are highly sensitive to moisture and exhibit poor water vapor
barriers (Guilbert, Gontard, & Gorris, 1996). Thus, composite lms
and coatings can be formulated consisting of several biopolymers.
As an example, the lipid component in the lm formulation can
serve as a good barrier to water vapor permeability (Garcia,
Martino, & Zaritzky, 2000a) and polysaccharides and proteins can
be reasonably effective as gas barriers (O
2
and CO
2
)(Arvanitoyannis,
Psomiadou, & Nakayama, 1996; Baldwin, Nisperos-Carriedo, &
Baker, 1995). Lipids lms are more moisture resistance but
vulnerable to oxidation. Therefore, the new trend is to combine
different biopolymers for food packaging and coatings (Gomez-
Guillen et al., 2008). As a result of poor mechanical strength and
high moisture sensitivity exhibited by starch edible lms, several
studies have investigated various additives, types of modication,
sources of starch, and process parameters in order to improve these
weaknesses in properties (Mali, Grossmann, Garcia, Martino, &
* Corresponding author. Tel.: 60 46535200; fax: 60 46573678.
E-mail address: norziah@usm.my (M.H. Norziah).
Contents lists available at ScienceDirect
Food Hydrocolloids
j ournal homepage: www. el sevi er. com/ l ocat e/ f oodhyd
0268-005X/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodhyd.2011.04.015
Food Hydrocolloids 26 (2012) 108e117
Zaritzky, 2006; Viga-Santos, Oliveria, Cereda, & Scamparini, 2007).
Several studies have investigated the use of sorbitol and glycerol as
plasticizers in forming starch or gelatin based edible lms
(Arvanitoyannis, 2002; Arvanitoyannis et al., 1996; Sobral,
Menegalli, Hubinger, & Roques, 2001). Vanin, Sobral, Menegalli,
Carvalho, and Habitante (2005) concluded that glycerol was
compatible with gelatin and showed the highest plasticizing effect
on the mechanical properties of the lm producing a exible and
easy handling lm with no phase separation. Sobral et al. (2001)
reported that the effects of sorbitol on the water vapor perme-
ability, mechanical and thermal properties of edible lms based on
gelatin gave a reasonable plasticizing effect on the puncture force.
They also reported that the water vapor permeability increased
with the increase in sorbitol content and similarly the increase of
sorbitol content did not reduce the formation of junction zones in
the lms.
The objective of this study was to investigate the physical and
mechanical properties including tensile strength, elongation-at-
break, water vapor permeability, lm morphology and moisture
isotherm and the compatibility of edible lms made from
a combination of sago starch and sh gelatin plasticized with
glycerol and sorbitol.
2. Materials and methods
2.1. Materials and reagents
Sago starch (Metroxylon sagu) was purchased from Nitsei
Industrial Sdn. Bhd. (Malaysia). Fish gelatin was extracted fromsh
wastes provided by a local surimi processing plant. The extractions
and preparation of sh gelatin was carried out as described by
Norziah, Al-Hassan, Khairulnizam, Mordi, and Norita (2009).
Sorbitol was kindly donated by Rhodia, Malaysia, glycerol from Sim
Company Sdn. Bhd, Malaysia, sodium cacodylate trihydrate and
osmium tetroxide (4%) from Sigma, glutaraldehyde from Ajax
chemicals. All chemicals were of analytical grade.
2.2. Determination of amylose content
Amylose content in sago starch was determined according to the
method described by McGrance, Cornell, and Rix (1998) based on
the colorimetric measurement of the iodine complexes formed
with amylose and amylopectin. Absorbance was read at 600 nm
wavelength in a 1 cm path length quartz cell using a uvevis
spectrophotometer (UV-160A, Shimadzu). Amylose and amylo-
pectin from potato starch (Fluka Biochemika) were used to prepare
standards. All tests were conducted in triplicate.
2.3. Analysis of protein and amino acids content
Protein content was measured by Kjeldahl method (AOAC,
1999). Fish gelatin (1 g) was dissolved in 100 mL distilled water
at 60

C until clear solution was obtained and 0.3 mL gelatin
solution was poured into digestion tubes. The protein content was
determined using the nitrogen conversion factor for gelatin, which
is 5.55 (AOAC, 1984). The test was carried out in triplicate.
The amino acids composition of the gelatin was determined
using High performance liquid chromatography (HPLC, Agilent
1200) with a uorescence detector and a owrate of 2 mL/min. The
column used was ZORBAX Eclipse-AAA (4.6 75 mm, 5 mm). The
mobile phase was A: 40 mM Na
2
HPO
4
pH 7.8 and B: Acetone:
methanol: water (45:45:10 (v/v/v)). Each sample was hydrolyzed in
6 N hydrochloric acid at 110

C for 24 h.
2.4. Preparation of starch/gelatin edible lms
The lm forming solutions were prepared using blends of sago
starch and sh gelatin with added plasticizers (glycerol or sorbitol).
Different ratios of sago starch and sh gelatin solutions (1:0, 2:1,
3:1, 4:1 & 5:1) based on total weight basis (5 g) including 25% (w/w)
plasticizers (glycerol or sorbitol) in 200 mL distilled water were
prepared. Sago starch (db) was dissolved in distilled water and
heated with magnetic stirring in a water bath at 85

C for 30 min
until completely gelatinized. From previous DSC runs (data are not
shown here) in which sago starch powder (w7 mg) added with
distilled water (ratio 1:3 sago starch: water) was heated from 40 to
90

C, the gelatinization temperature was observed to be at 67.13

C
and complete gelatinization was achieved at 76e77

C. Fish gelatin
was dissolved in distilled water at 60

C for 30 min until a clear
solution was obtained. Fish gelatin solution was added to gelati-
nized sago starch at 60

C and stirring was continued for 30 min,
followed by addition of plasticizer with constant stirring for
another 30 min. The mixture was then cooled to roomtemperature.
The solution mixture (95 g) was cast onto polyacrylic plates
(16 cm 16 cm 3 mm) and dried in a ventilated oven at 35

C for
24 h. The dry lms obtained were peeled off and stored in a desic-
cator containing saturated sodium bromide (NaBr) solution with
56% (RH) at 30

C until for further analysis. Control lms were
prepared in the same way without the addition of sh gelatin. Each
lm formulation was prepared in triplicates.
2.5. Viscosity of lm forming solutions
Viscosity of sago starch/gelatin solutions was measured using
a digital viscometer (Model DV-E, Brookeld, middle Boro) with
speed 100 rpm and LV spindle no. 2 for all samples and values are
expressed in (centipoises, cP). The measurement was conducted at
room temperature (28

C). The spindle was immersed into the
solution for about 3 min for thermal equilibrium between solution
and spindle with continued shearing. Five readings of viscosity
were recorded for each solution, and average values were taken.
Tests were run in triplicate.
2.6. Determination of pH of lm forming solution
Measurement of pH value of sago starch and sago starch/gelatin
lm forming solutions was taken using a pH meter (Mettler Toledo,
FE20. China).
2.7. Film thickness and light absorption
Thickness of the lms was measured using a manual microm-
eter (Mitutoyo, Japan) with an accuracy of 0.001 mm. Six different
positions of the samples were measured and average thickness was
calculated. Films prepared were observed visually for homogeneity
without phase separation and with uniform colour.
The light barrier properties of the lms were measured by
exposing the lms to light absorption at wavelength 550 nm. Film
transparency was measured according to the method of Bao, Xu,
and Wang (2009) by placing rectangular lm samples into a spec-
trophotometer test cell directly. Absorbance was recorded using an
UV-160A uvevis spectrophotometer (Shimadzu, Japan). The
transparency (T) of lms was calculated according to the following
equation:
T A
550
/x
where A
550
is the absorbance at 550 nm and x is the lm thickness
(mm). According to this equation, a higher value of T would indicate
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 109
a lower degree of transparency. Tests were run in triplicates for
each type of lm.
2.8. Tensile strength and elongation tests
The mechanical properties of lms prepared were evaluated by
conducting tensile strength and elongation-at-break (EAB) tests
according to ASTMD882-00 method (ASTM, 2000a). Filmspecimen
strips (14 cm 2 cm) were cut and conditioned in a desiccator
containing saturated sodium bromide solution with 56% (RH) at
30

C for 48 h prior to testing. Films were tested for sorption
isotherm in 2 h interval and equilibrium was achieved in 6 h in
most ratios where water content in the lms did not change up to
24 h. Tensile strength and EAB were performed as a tension test
using a Texture analyzer TA XT2 (Stable Microsystems, Surrey, UK)
with a load cell of 30 kg and crosshead speed of 60 mm/min. The
samples were mounted between grips with initial grip gap of
100 mm and lm width of 2 cm. The results of tensile and elon-
gation tests were expressed by MPa and percentage (%), respec-
tively. Each test trial per lm consisted of ve replicate
measurements.
2.9. Water vapor permeability
Water vapor permeability (WVP) of the lms was determined
according to the ASTM E96-00 method (ASTM, 2000b). Gas
permeation cells with diameter 4.5 cm and height 2.8 cm were
used. Glass permeation cell contained 25 g silica gel (0% RH) that
was dried in oven at 120

C for 1 day initially and the headspace for
the cell was 1.0 cm fromthe opening of the cell. The test lms were
sealed on top of the permeation cells. These cells were then placed
in a desiccator containing distilled water (100% RH) and kept at
30

C. The cells were weighed at 24 h intervals over a 7-day period.
The cells were recorded to the nearest 0.0001 g and plotted as
a function of time. The slope of each line was calculated by linear
regression (r
2
0.99). The measured WVP of the lms was deter-
mined as follows:
WVP (WVTR L)/DP
where WVTR is the water vapor transmission rate (g m
2
h
1
)
through a lm, calculated fromthe slope of the straight line divided
by the exposed lm area (m
2
), L is the mean lm thickness (mm),
and DP is the partial water vapor pressure difference (Pa) across the
two sides of the lm. For each type of lm, WVP measurements
were replicated three times for each batch of lms.
2.10. Moisture sorption isotherm
The sorption isotherm of sago starch and sago starch/gelatin
lms was determined at 30

C according to Chang, Cheah, and Seow

(2005) with slight modications. Samples of sago starch and sago
starch/sh gelatinwere cut into small pieces (1 2 cm) and dried in
a desiccator over Phosphorus pentoxide (P
2
O
5
) for 7 days. The dried
samples were weighed to the nearest 0.0001 g into pre-weighed
bottles and equilibrated versus saturated salt solutions with
known relative humidity (RH) in air-tight containers in an incu-
bator at 30

C in duplicate. Seven super saturated salt solutions,
lithium chloride, potassium acetate, magnesium chloride, potas-
sium carbonate, sodium bromide, sodium chloride, and potassium
chloride with relative humidity (RH) of 11%, 22%, 32%, 43%, 56%, 75%
and 84% at 30

C respectively, were used and the equilibrium was
assumed to be achieved when changes in weight did not exceed
0.1% for 3 consecutive measurements.
2.11. Scanning electron microscopy (SEM)
Films were observed by SEMfollowing the procedures described
by Denavi et al. (2009) using a Modal Leo Sipra So Vp Field Emis-
sion, CaH-Zeiss SMT, Oberkochen, Germany. Films were pretreated
prior to SEM analysis. They were cut into small strips and xed in
a solution of 2% (v/v) glutaraldehyde and 0.1 M sodium cacodylate
buffer (pH 7.2) for 2 h, washed with 0.1 M sodium cacodylate buffer
(3 times in 10 min) and post xed in 0.4% (w/v) osmium tetroxide
(O
5
O
4
) and 0.2 M sodium cacodylate buffer (pH 7.2) for 2 h, then
washed with 0.1 M sodium cacodylate buffer (3 times in 10 min).
Samples thenwere dehydrated for 15 min through a graded ethanol
series: 30, 50, 70 and 90%, (v/v) and nally (3 times; 15 min) at
99.5% (v/v) then were dried overnight. The dried samples were
mounted on aluminum stubs and then coated with a layer of gold
by Baizer SCD SPUTTER coater, allowing surface visualization
using an accelerated voltage of 5 kV.
2.12. Analysis on thermal properties of lms
Thermal properties of lms were determined by using differ-
ential scanning calorimetry. Measurements on a TA Instruments
Calorimeter Q200 (TA Instruments Ltd., Leatherhead, UK) with
a refrigerated cooling system(RCS) and a nitrogen DSC cell purge at
50 ml/min was used to achieve temperatures of 0

C. T-zero
hermetic aluminum pans were used with a conventional MDSC
with a modulation of (1/min). Samples (w15 mg 2 mg) were
conditioned over P
2
O
5
for 7 days, then at 56% RHand 30

C for 48 h.
Samples were then hermetically sealed and heated from0 to 200

C
at 3

C/min. The reference was an empty pan and the equipment
was calibrated with indium (T
m
156.6

C, and enthalpy
DH 28.3 J/g). The transition temperature (T
m
) was calculated as
the temperature where the endothermic peak occurs, and the
enthalpy (DH) of the transition was calculated as the area over the
endothermic peak. The glass transition temperature (T
g
) was
calculated using a TA Instrument Universal analysis 2000 software
as the shifting down of the reversible heat ow curve.
2.13. Statistical analyses
SPSS 12.0 was used in this study to analyze the data. One-way
variance analysis was carried out using Duncans test with con-
dence level as p 0.05.
3. Results and discussion
3.1. Amylose content
The amylose content in the sago starch was found to be in the
range of 32e34%. Most native starches like corn, tapioca, potato and
sago have high percentage of amylopectin. Generally, most starches
contain 15e30% amylose (Wong, Muhammad, Dzulkiy, Saari, &
Ghazali, 2007).
3.2. Protein content and amino acids prole
Protein content of sh gelatin was found to be 81.3% soluble
protein. Therefore sago starch/sh gelatin lms contained different
protein mixtures which are 21.6%, 16.3%, 13.0%, and 10.9% (w/w)
protein in 2:1, 3:1, 4:1 and 5:1 lm ratios, respectively. Amino acids
composition of the sh gelatin is shown in Table 1. The result shows
that the gelatin has high contents of glutamic acid, glycine, alanine
and arginine. Proline and hydroxyproline are present in low
amounts (5.72 and 5.94 residues/100) compared to bovine-hide
and tuna skin gelatins as reported by (Gmez-Estaca, Montero,
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 110
Fernndez-Martn, & Gmez-Guilln, 2009). They reported proline
content of 12.7 and 10.7 residues/100 and hydroxyproline of (8.3
and 7.8 residues/100 residues) for bovine-hide and tuna skin
gelatin respectively.
3.3. Viscosity and pH of lm forming solutions
The pH of the lm forming solutions ranged between pH 4.54
and 4.61. The viscosity of lm forming solutions of sago starch/sh
gelatin added with either sorbitol or glycerol increased signicantly
(p < 0.05) with decreasing gelatin protein content in the samples.
Film samples 2:1 and 3:1 with glycerol added showed higher
viscosity than those added with sorbitol of the same lm ratio,
however as the gelatin content decreased in lm ratios of 4:1 and
5:1, there was no signicant difference between lms added with
sorbitol or glycerol (Fig. 1). Moreover, signicant difference was
observed in comparing sago starch/sh gelatin lm forming solu-
tions to sago starch lm forming solution plasticized as controls
with either glycerol or sorbitol. Sago starch lm forming solutions
showed higher viscosity from other sago starch/sh gelatin lm
forming solution. Dickinson (1998) reported that pro-
teinepolysaccharides interaction between two biopolymers is
made up from an average over the large number of different
intermolecular forces arising between the various segments and
side-chains on the two macromolecules. Depending on the aqueous
environmental conditions and the distribution of the different
kinds of groups (charged, hydrophobic, hydrogen bonding, etc.).
The overall proteinepolysaccharide interaction maybe net attrac-
tive or net repulsive.
3.4. Thickness and light absorption of lms
Thickness of sago starch/sh gelatin lms ranged between 0.05
and 0.07 mm for all lms with plasticizers. Films of sago starch/sh
gelatin prepared were transparent and homogeneous. All lms
were found to be exible and easily removed from the acrylic plate
with the exception of lms (2:1) that contain glycerol which was
found to be soft, sticky and easily shrink when removed from
casting plates and left outside for short time at lab environment
(RH% z 65) and this was due to being more hygroscopic with
higher protein content than other lms. This observation was
similarly reported by Thomazine, Carvalho, and Sobral (2005) in
those lms with glycerol tend not to be as strong and are more
stretchable than lms that contain sorbitol.
The UVeVis absorption of sago starch/sh gelatin lms and sago
starch lms plasticized with 25% glycerol or sorbitol is shown in
Table 2. Higher transparency values indicate higher absorbance
values. The results showed that no signicant differences in the
level of light absorption at 550 nmwere found in both control lms
with either plasticizer. Glycerol plasticized lms exhibited higher
absorbance values compared to sorbitol plasticized lms. In glyc-
erol plasticized sago starch/sh gelatin lms, further increase of
gelatin concentration did not have any signicant effects on the
degree of transparency or light absorption, however all lms
exhibited signicantly higher absorbance than control. In general,
all sago starch/sh gelatin lms with glycerol showed signicantly
higher light absorbance (p < 0.05) compared to lms with sorbitol.
Higher light absorbance of lms could be an excellent barrier to
prevent light-induced lipid oxidation when applied in food system
(Gomez-Guillen, Ihlb, Bifanib, Silvab, & Montero, 2007).
3.5. Mechanical properties of starchegelatin lms
The tensile strength (TS), percentage of elongation-at-break (%
EAB) and Youngs modulus (E) values of the starch (as control) and
sago starch/sh gelatin edible lms prepared in this study are
Fig. 1. Viscosity of lm forming solutions of different ratios of sago starch and sh
gelatin plasticized with 25% glycerol [ ] or 25% sorbitol [ ].
Table 2
Mechanical properties, Youngs modulus and transparency of sago starch/sh
gelatin lms plasticized with 25% glycerol or 25% sorbitol.
Films
(starch:
gelatin)
TS (MPa) % EAB Youngs
modulus,
(E)(N/m
2
) 10
7
Transparency
1:0 (G) 9.87 0.64
a
17.11 6.11
ad
6.17 0.01
a
1.34 0.09
a
1:0 (S) 25.03 0.88
b
4.33 0.78
e
59.35 0.01
b
1.24 0.10
a
2:1 (G) 1.28 0.25
c
102.31 20.78
c
0.12 0.04
c
2.00 0.18
b
3:1 (G) 1.57 0.30
cd
95.15 10.99
bc
0.16 0.03
c
1.91 0.02
b
4:1 (G) 1.70 0.08
d
84.14 2.77
b
0.20 0.01
c
2.12 0.09
b
5:1 (G) 1.67 0.12
d
93.11 12.34
bc
0.18 0.02
c
1.85 0.17
b
2:1 (S) 10.27 0.90
ae
11.94 2.07
a
0.91 0.09
d
0.86 0.06
c
3:1 (S) 17.59 1.71
f
19.04 1.00
d
1.47 0.14
e
1.43 0.04
ad
4:1 (S) 18.06 0.55
f
5.53 0.42
e
1.71 0.05
f
1.20 0.09
ae
5:1 (S) 13.44 0.73
g
11.76 2.98
a
1.20 0.10
g
1.60 0.18
d
Values were given as mean standard deviation. Values with the same superscript
letters within a column are not signicantly different (p < 0.05). G: glycerol; S:
sorbitol; TS: tensile strength; EAB: Elongation-at-break.
Table 1
Amino acids composition in gelatin sample.
Amino acids Residues/100 residues
Aspartic acid 6.20
Glutamic acid 11.61
Serine 4.21
Histidine 0.67
Glycine 21.08
Threonine 4.24
Arginine 7.36
Alanine 16.63
Tyrosine 0.32
Valine 3.12
Methionine 2.06
Phenylalanine 2.12
Isoleucine 1.46
Leucine 2.74
Lysine 4.43
Hydroxyproline 5.94
Proline 5.72
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 111
shown in Table 2. Films with glycerol at all sago starch/sh gelatin
ratios showed lower tensile strength (between 1.28 MPa and
1.67 MPa) than the sago starch control lmwith glycerol (9.87 MPa)
and lms of the same ratios that contain sorbitol (varied from
10.27 MPa to 18.06 MPa). According to Sothornvit and Krochta
(2001) glycerol is a smaller molecular weight and more hygro-
scopic (at constant a
w
from adsorption and desorption isotherms)
compared to sorbitol and therefore, glycerol increase its effective-
ness as plasticizer. Glycerol contributes more plasticization effect
compared to sorbitol when used at the same mass content in
protein, polysaccharides and proteinepolysaccharides based lms.
Thus protein, polysaccharides and proteinepolysaccharides based
lms with glycerol are more stretchable and exible due to the
plasticization effect that increases the mobility of polymer chains.
Plasticizers have been used to overcome the brittleness of lms
resulting from high intermolecular forces by increasing the
mobility of polymer chains which makes lms stretchable and
exible. Films with sorbitol at all ratios had signicantly lower
(p < 0.05) TS than lms containing sago starch (1:0) with sorbitol
only (25.03 MPa). However, in all formulations, the presence of
protein signicantly reduced the TS as a result of the interaction
between hydroxyl groups between starch and protein that may
reduce the interaction between starch chains since polyols did not
vary in all samples. Polyols such as sorbitol are often cited as good
plasticizers due to their ability to reduce intermolecular hydrogen-
bonding while increasing intermolecular spacing (Vanin et al.,
2005). Sorbitol interacts with water by hydrogen bonding due to
the present of more hydroxyl groups in the molecule (Mali,
Sakanaka, Yamashita, & Grossmann, 2005). Garcia, Martino, and
Zaritzky (2000b) reported that the chances of sorbitol to interact
with polymeric starch chains are higher than glycerol due to
sorbitol being more similar to the molecular structure of glucose
units therefore; lms plasticized with sorbitol presented higher
intermolecular forces and showed a lower capacity to interact with
water. Higher tensile strength leads to stronger lms. It was
observed that reducing the gelatin content in lms with glycerol
(ratio from 2:1 to 5:1) did not have much effect on the TS values. In
general, for lms with sorbitol, tensile strength increased signi-
cantly from lm ratios of 2:1 to of 4:1, however for a lm ratio of
5:1, the tensile strength was much lower. This indicated that tensile
strength increased with decreasing content of gelatin from 21.6% to
13.0%. However with further reduction in gelatin content, no
further increase in TS was observed for lms with sorbitol in the
ratios used in this study. Arvanitoyannis, Psomiadou, Nakayama,
Aiba, and Yamamoto (1997) reported that tensile strength and
elongation-at-break are greatly affected by preparation tempera-
ture and relative humidity of conditioning. From the results
(Table 2), in general % elongation-at-break (% EAB) increased with
gelatin content in lms with glycerol with highest % EAB value
(102.31%) for a starch to gelatin ratio of (2:1) which indicated that
in these lms, gelatin seemed to act as a plasticizer which enhanced
lmexibility and reduced brittleness. Su, Huang, Yuan, Wang, and
Li (2010) concluded that glycerol is a small size molecule plasticizer
that can penetrate between the polymer chains, and weaken the
interaction between polysaccharides and proteins as in carbox-
ymethyl cellulose and soy protein isolate lms. Moreover,
increasing the concentration of glycerol at constant poly-
saccharideseprotein composition reduces the mechanical proper-
ties. However, for sago starch/sh gelatin lms with sorbitol, no
trend was observed in % EAB (varied from 5.53 to 19.04%). Varying
gelatin content in the lms had both negative and positive effects
on % EAB. Samples with sorbitol with ratios of 3:1 and 4:1 showed
the highest (19.04%) and the lowest % EAB (5.53%), respectively. In
general, the % EAB depends as TS on many factors in a mixed system
between polysaccharides and protein including the hydroxyl
groups that are available for forming hydrogen bonding between
gelatinestarchepolyolewater. Sorbitol has higher molecular
weight with more hydroxyl groups than glycerol, which may react
with starch and gelatin molecules and give less plasticizing affect
compare to glycerol. Mali et al. (2005) reported that glycerol-con-
taining lms of cassava starch affected the mechanical properties
and resulted in the lowest values for tensile stress due to its
hygroscopic character that tends to provide additional water into
the lm matrix. Moreover, they reported that lower molecular
weight of the plasticizer such glycerol has a plasticization affect
than the higher molecule ones like sorbitol when used at the same
mass basis where the number of moles of glycerol incorporated in
the lms would be higher than the sorbitol ones. Pranoto, Lee, and
Park (2007) reported that the polysaccharide macromolecules with
relatively long chains can cross-link with gelatin, leading to
increased TS, and also possibly macromolecular relaxation leading
to increase % EAB. Chambi and Grosso (2006) concluded that the
mechanical properties of lms are largely associated with distri-
bution and density of intermolecular and intra-molecular interac-
tions, which depend on the arrangements, and orientation of
polymer chains in the network.
Youngs modulus (E) signicantly decreased with incorporation
of protein in all lms with either plasticizer (Table 2). Control lms
(1:0) showed the highest in Youngs modulus (6.17 Pa) and
(59.35 Pa) for glycerol and sorbitol lms, respectively. Higher TS
and lower % EAB results in higher Youngs modulus. However,
generally Youngs modulus (E) increased with decrease in protein
content (from 21.6% to 13.0%) with highest E value for lm ratio of
4:1 in both types of lms. However, when the protein content was
decreased further to 10.9% (in lm ratio of 4:1) E values did not
increase further in both types of lms. The addition of more protein
showed lower E values compared to lms with no protein added in
both cases with glycerol or sorbitol. The ndings of this study
suggested that among the different formulations plasticized with
glycerol or sorbitol; there was a certain level where the interaction
between the two biopolymers i.e. starch and protein that affected
TS, % EAB and Youngs modulus (E). However, no linear trend was
observed in TS, % EAB and E with different ratios when protein
content was increased in all samples with either plasticizers. Values
obtained in this study showed that there might be an optimum
level of interactions between polysaccharides and protein that may
affect TS and % EAB as in (4:1) and (5:1) with both glycerol or
sorbitol. Pranoto et al. (2007) reported that there was an optimum
level for interaction between polysaccharides and gelatin where
gelatin was the major and dominant phase in the lm system they
used, and concluded that 2% was found to be beyond the optimum
level of interaction between polysaccharides and gelatin. Fonkwe,
Narsimhan, and Cha (2003) reported that the polysaccharides
could form networks with gelatin molecules between anionic
domains of the polysaccharides and cationic domains of the gelatin,
which strengthen the lm structures as a result. Lee, Shim, and Lee
(2004) found that TS was improved by increasing the gellan
(polysaccharides) to gelatin ratio, with highest TS at the lm made
from gellan indicating that there is a certain level of optimum
interaction between polysaccharides and gelatin in general. Thus,
concluded that the strength and exibility of the composite lms
could be modied by changing the ratio of polysaccharides to
protein. Tolstoguzov (1994) reported that interactions in gelatin/
water or gelatin/starch/water/polyol systems are between hydroxyl
groups of starch chains, starchewater and starchepolyol mole-
cules, as well as between polyolepolyol or waterepolyol molecules.
The possibilities of gelatin or starch hydrogen-bonding within the
blends are greatly enhanced by the introduction of comparatively
small molecules such as water and polyols. Mali et al. (2005)
reported lower stress and Youngs Modulus values were obtained
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 112
with lms plasticized with glycerol, indicating that glycerol exerted
a more effective plasticization.
3.6. Water vapor permeability of lms
As shown in Fig. 2, water vapor permeability (WVP) of different
ratios of starch/gelatin lms plasticized with glycerol did not show
any signicant differences. There was no clear trend observed in
WVP for lms with sorbitol. However, higher WVP was observed
with the incorporation of sorbitol into lms compared to glycerol
for sh gelatinesago starch lms. Control starch lms exhibited
higher WVP with glycerol added compared to sorbitol however,
both types of lms with either sorbitol or glycerol added showed
lower WVP. Adding gelatin to starch lms leads to interaction with
starch chains breaking the intact network of starch inter chain
hydrogen-bonding. Since gelatin is more hygroscopic than starch,
the afnity for water molecules will be higher in these lms and
therefore resulting in higher water diffusion giving lms with
higher WVP. The results also showed that increasing protein
content in the lms i.e. varying the starch to gelatin ratio from 5:1
to 2:1 did not affect the WVP of both lms with added sorbitol or
glycerol. This result is in contrast with results obtained by
Jongjareonrak, Benjakul, Visessanguan, and Tanaka (2006) who
reported that higher WVP was found with gelatin lms containing
greater protein content. McHugh, Avena-Bustillos, and Krochta
(1993) also reported that since gelatin contained a wide range of
hydrophilic amino acids, lms with a higher amount of protein and
thickness could absorb more water molecules from the environ-
ment. Thus, the lmwith higher protein content was most likely to
be hygroscopic, compared with that containing the lower protein
content. Bourtoom, Chinnan, Jantawat, and Sanguandeekul (2006)
concluded that plasticizers modify the protein network structure
and increase the water vapor permeability (WVP) of edible water-
soluble sh proteins lm when both plasticizers sorbitol or glyc-
erol increased from 25% to 75%. Plasticizers modify the molecular
organization of the protein network and increase the free volume
resulting in less dense network that results in more lms that are
permeable to water. The hydrophilicity nature of plasticizer mole-
cules could be the cause of permeability increase with an increase
in plasticizer. Hydrophilic plasticizers such glycerol and sorbitol are
known to enhance the water vapor permeability of hydrocolloid-
based lms. Arvanitoyannis, Nakayama, and Aiba (1998) reported
that increasing the total plasticizer content (water and polyols) in
the polymer matrix results in a proportional increase of water
vapor transfer rate. However, they reported that sorbitol showed
higher WVP than glycerol in hydroxypropyl starch and gelatin lms
produced by both methods of high temperature casting and drying
(60

C) with glycerol or sorbitol (15% and 25%) and lowtemperature

casting and drying (20

C) with glycerol (5% and 25%); and sorbitol
(3% and 24%). Similarly, Arvanitoyannis and Biliaderis (1998) found
that sorbitol increased WVP compared to glycerol at all concen-
trations used (5, 15 and 25%) in sodiumcaseinate and soluble starch
lms.
Garcia et al., 2000a reported that WVP depends on many factors
such as the ratio between crystalline and amorphous zone, poly-
meric chain mobility and specic interaction between the func-
tional groups of the polymers and the gases in the amorphous zone.
Slight differences in WVP values maybe related to the difference in
water molecule diffusion and hydrophilicehydrophobic ratio
(Arvanitoyannis, Kalichevsky, Blanshard, & Psomiadou, 1994;
Garcia et al., 2000a). However, Pranoto et al. (2007) reported that
Fig. 2. Water vapor permeability (WVP) of sago starch/sh gelatin lms with 25%
plasticizers [glycerol or sorbitol].
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70 80 90
M
o
i
s
t
u
r
e

c
o
n
t
e
n
t


(
d
r
y

b
a
s
i
s
)


(
%
)
Relative humidity (%RH)
1:0 G
2:1 G
3:1 G
4:1 G
5:1 G
Fig. 3. Moisture sorption isotherm for sago starch/sh gelatin lms (ratios 1:0, 2:1, 3:1,
4:1 & 5:1) with 25% glycerol, conditioned at different relative humidity.
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70 80 90
M
o
i
s
t
u
r
e

c
o
n
t
e
n
t

(
d
r
y

b
a
s
i
s
)

(
%
)
Relative humidity (%RH)
1:0 S
2:1 S
3:1 S
4:1 S
5:1 S
Fig. 4. Moisture sorption isotherm for sago starch/sh gelatin lms (ratios 1:0, 2:1, 3:1,
4:1 & 5:1) with 25% sorbitol, conditioned at different relative humidity.
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 113
the addition of gellan to gelatin lms signicantly reduced the WVP
that may due to the ionic interaction between gelatin and gellan
that formed a denser polymeric matrix, thus hindering water
molecule transfer through the lm. K-carrageenan was also found
to form ionic complexes with gelatin but weaker than that of gel-
lanegelatin matrix.
3.7. Moisture sorption isotherm
Figs. 3 and 4 show the water sorption isotherms of sago starch
and sago starch/sh gelatin edible lms as a function of sago starch
and sh gelatin ratio with added sorbitol or glycerol. The sorption
isotherm curves of sago starch and sago starch/sh gelatin lms
showed a typical behavior of water vapor sensitive hydrophilic
biopolymers when the relative humidity (% RH) increased. These
lms behaved as in gluten, starch and cellulose lms (Gontard,
Guilbert, & Cuq, 1993; Mali, Grossmann, Garca, Martino, &
Zaritzky, 2002) which presented a relatively slight slope at low
water activity (a
w
), and an exponential increase at high a
w
, (above
0.75). Such non-linear water sorption isotherms were possibly due
to the swelling of hydrophilic matrix that resulted in different
structural changes in the lms.
Glycerol sago starch/sh gelatin lms presented higher equi-
librium moisture contents than those of sago starch lms only
(Fig. 3). In general, moisture content of these lms increased
slowly at RHs lower than 40%, followed by a steep increase in
moisture content when RH% changed from 56% to 84%. The
equilibrium moisture content curves of the lms plasticized with
Fig. 5. Scanning electron microscopy images (500) of sago starch/sh gelatin lms plasticized with 25% glycerol (a) 2:1, (b) 3:1, (c) 4:1, (d) 5:1 and (e) 1:0.
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 114
25% sorbitol show similar sorption isotherm proles (Fig. 4) i.e.
low equilibrium moisture contents at low a
w
then increased at
higher a
w
. However, sago starch lms at 84% RH showed slightly
lower equilibrium moisture content than those of sago starch/sh
gelatin lms. Generally, the equilibrium moisture content was
higher in lms with added glycerol than those lms plasticized
with sorbitol due to the fact that glycerol is more hydrophilic than
that of sorbitol. Due to the presence of more hydroxyl groups in
the molecule, sorbitol interacted with water by hydrogen bonding
resulting in less plasticizing effect compared to glycerol (Mali
et al., 2005). Hu, Chen, and Gao (2009) also reported that
oxidized potato starch lms with higher glycerol level showed
higher moisture absorbability with increase of % RH due to glyc-
erol having excellent water-retaining ability. A lower water
binding capacity of lms with sorbitol has also been reported and
this behavior was due to the molecular structure of sorbitol
facilitating interactions with the polymeric chains (Garcia et al.,
2000b).
Fig. 6. Scanning electron microscopy images (500) of sago starch/sh gelatin lms plasticized with 25% sorbitol (a) 2:1, (b) 3:1, (c) 4:1, (d) 5:1 and (e) 1:0.
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 115
3.8. Film morphology
Figs. 5 and 6 show the scanning electron micrographs of sago
starch and sago starch/sh gelatin lms plasticized with glycerol
and sorbitol, respectively. It was observed that there were some
differences in surface and internal structure morphology between
glycerol and sorbitol lms at the various starch to gelatin ratios.
Glycerol lms were observed to have rougher surfaces with pres-
ence of pores or cavities that could be related to the formation of
channels whereas sorbitol lms showed a more compact and
homogeneous surface. However, smoother lm surfaces were
observed in both glycerol and sorbitol lms that has less protein
content (Figs. 5 and 6aed). Nevertheless, surface roughness and
formation of channels disappeared in samples of sago starch lms
only (1:0) with either plasticizer. Liu, Liu, Fishman, and Hicks
(2007) worked on pectin lms with addition of two different
types of proteins (sh skin gelatin or soybean protein) and obtained
pectin lms that showed relatively smoother surfaces than those
lms with the protein addition which produced rough, dense, and
brittle in appearance surfaces with some irregular particles
distributed uniformly within the pectin phase. Pranoto et al. (2007)
also found in lms with sh gelatin and gellan or k-carrageenan
mixtures produces lms that showed discontinuous zones with
noticeable cracks randomly distributed along the network.
However, they also concluded that addition of gellan to sh gelatin
lms contributed to eliminating those cracks thus giving a more
compact surface appearance, while addition of k-carrageenan had
no contribution in eliminating those cracks. Moreover, De Carvalho
and Grosso (2004) mentioned that gelatin lms plasticized with
glycerol have the presence of discontinuous zones characterized by
cracks distributed along the length of the network, however those
discontinuous zones possibly present as a result of the preferential
channels that occurred through drying.
3.9. Differential scanning calorimetry
Differential scanning calorimetry (DSC) results obtained for the
different ratios of sago starch/sh gelatin lms unplasticized and
plasticized with 25% (w/w) glycerol or sorbitol are given in Table 3.
The variation of glass transition temperature (T
g
) is another
effective indicator of the compatibility of polymers. Although
polysaccharides and protein materials have been widely studied,
still there is poor understanding of the dynamic interaction
between the molecules of such polymers. The ndings of this study
showed that unplasticized sago starch lms had a T
g
value of about
(84.04 0.8

C), T
m
(167.41 3.2) and DH of (219.63 13.7).
Incorporating plasticizer (25% glycerol or sorbitol) into the starch
lms signicantly decreased T
g
, T
m
and DH. However, greater
decrease in the values was noticed when sorbitol was used
compared to glycerol. Plasticizing sago starch lms with glycerol
makes lms more hydrophilic and retain higher moisture
compared to unplasticized lms when conditioned at the same
humidity (RH %) and temperature. Mali et al. (2005) also reported
that glycerol-containing lms of cassava starch affected lms
properties due to the hygroscopic character of glycerol that tends to
provide additional water into the lm matrix. In this study, sorbitol
showed lower T
g
, T
m
and DH when added to sago starch lms
compared to unplasticized ones. Addition of glycerol to sago starch/
sh gelatin lms showed an increase inT
g
for all ratios (1:0, 2:1, 3:1,
4:1 & 5:1) but a signicant decrease (p 0.05) inT
m
for ratios (3:1 &
5:1) and DH for all ratios which indicated that plasticizers reduced
the intermolecular forces and increased the mobility of polar
polymer chains. Su et al. (2010) concluded that plasticizers like
glycerol reduce T
g
values when incorporated into carboxymethyl
cellulose and soy protein isolate lms that was probably due to the
ability of glycerol to penetrate between the polymer chains and
therefore weaken the interaction between polysaccharides and
proteins. Sago starch/sh gelatin lms plasticized with sorbitol
showed signicantly lower (p 0.05) T
g
, T
m
and DH for all ratios
with the exception of ratio (3:1) for T
m
values that showed no
signicant change compared to unplasticized lms of the same
ratio. The reduction in T
g
, T
m
and DH when sorbitol was used as
plasticizer maybe due to the interaction between sorbitol hydroxyl
groups with the polymers present in lms which may reduce the
interaction between the starch and gelatin. The presence of only
one T
g
could indicate that the sago starch and gelatin lms are
compatible. This phenomena with only one T
g
observed in
starchecaseinate blends plasticized with glycerol or sorbitol was
also reported by Arvanitoyannis and Biliaderis (1998) in their DTA
runs. Su et al. (2010) also reported that normally, a single T
g
for
blended polymers in a DSC scan indicates good compatibility of the
component polymers.
4. Conclusion
The physical and mechanical properties of edible lms from
sago starch and sago starch/sh gelatin plasticized by glycerol and
sorbitol were evaluated. Starch/gelatin solution with ratios of 3:1,
4:1 and 5:1 appear to form good exible lms with added glycerol
but not at higher gelatin content (2:1). The results obtained show
that different ratios of sago starch and sh gelatin blends plasti-
cized with glycerol or sorbitol affected physical, mechanical and
water vapor permeability of the lms produced. Changing the ratio
of two polymers can modify the strength and extensibility of the
composite lms. SEM micrographs show uneven surfaces in glyc-
erol lms compared to sorbitol lm surfaces. However, less protein
in the samples gave smoother lms with either sorbitol or glycerol.
Based on the concentration levels used and the polymers sources,
DSC runs revealed a single T
g
which maybe an indication of the
compatibility of sago starch and sh gelatin polymers in this study.
Acknowledgments
The authors wish to express their thanks to the Ministry of
Science, Technology and Innovation, Malaysia and the Saudi
Table 3
DSC thermal characterization of sago starch/sh gelatin lms unplasticized and
plasticized with glycerol or sorbitol (25%).
Films T
g
T
m
DH
1:0 NP 84.04 0.81
a
167.41 3.23
a
219.63 13.70
f
2:1 NP 52.82 2.28
d
159.15 16.84
hi
240.73 25.31
h
3:1 NP 55.32 1.43
ef
144.91 15.57
fg
239.63 9.22
h
4:1 NP 55.71 0.87
f
151.64 11.51
gh
227.00 2.96
g
5:1 NP 53.81 1.41
de
163.76 6.82
ai
217.73 11.40
f
1:0 G 60.08 1.1
gh
133.90 12.3
bd
171.83 8.3
de
1:0 S 53.10 0.8
d
112.70 5.4
c
148.33 1.2
b
2:1 G 62.28 0.8
i
157.61 10
hi
177.43 11.1
e
3:1 G 61.36 1.1
hi
133.15 10.5
bdh
172.50 27.3
de
4:1 G 58.50 0.5
g
143.12 4.1
efg
171.65 2.2
de
5:1 G 61.95 1.4
i
139.04 3.1
def
161.08 6.8
c
2:1 S 49.85 4.4
c
129.01 8.4
b
162.50 4.5
c
3:1 S 40.88 6.7
b
151.36 16.5
g
168.08 8.3
cd
4:1 S 48.15 4.9
c
135.20 15.2
bde
140.13 15.5
a
5:1 S 49.60 7.7
c
143.72 16.9
fg
151.97 2.3
b
Values are given as mean standard deviation. Values with the same superscript
letters within a column are not signicantly different (p < 0.05). G: glycerol; S:
sorbitol, NP: no plasticizer added.
A.A. Al-Hassan, M.H. Norziah / Food Hydrocolloids 26 (2012) 108e117 116
Arabia Government for the nancial support given for this
research work.
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