Food Chemistry 127 (2011) 14961502

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Development and characterisation of a new biodegradable edible lm made

from keran, an exopolysaccharide obtained from ker grains
Mehran Ghasemlou a,, Faramarz Khodaiyan a, Abdulrasoul Oromiehie b, Mohammad Saeid Yarmand a
a
Department of Food Science, Engineering and Technology, Faculty of Agricultural Engineering and Technology, Campus of Agriculture and Natural Resources, University of
Tehran, P.O. Box 4111, Karaj 31587-77871, Iran
b
Iran Polymer and Petrochemical Institute, Pazhoohesh Street, P.O. Box 14965/159, Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 4 October 2010
Received in revised form 6 January 2011
Accepted 1 February 2011
Available online 25 February 2011
Keywords:
Keran
Edible lm
Plasticizer
Exopolysaccharide

a b s t r a c t
This study examined the feasibility of using keran, an exopolysaccharide obtained from ker grains, as a
new lm-forming material. Keran-based lms, with and without glycerol as plasticizer, were prepared
by a casting and solvent-evaporation method. To study the impact of the incorporation of glycerol into
the lm matrix, physical, mechanical, and thermal properties of the lms were investigated. As expected,
the increase of glycerol concentration from 15% to 35% w/w increased extensibility but decreased tensile
strength, implying higher mobility of polymer chains by the plasticizing effect of glycerol. Water vapour
permeability of lms was found to increase as the plasticizer content increased. Glass transition temperatures decreased as a result of plasticization as glycerol content increased. The properties of the lms
were related to their microstructure, which was observed by scanning electron microscopy. Thus, it
was observed that plasticizer is a signicant factor in the properties of these lms and their food technology applications.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, the food and packaging industries have been
joining their efforts to determine new ways to protect food from
environmental conditions and mechanical stresses. The use of synthetic polymers and plastics for packaging has grown tremendously in the last century; however, this increase has created
serious environmental problems due to the materials inability to
biodegrade. Moreover, the insecurity of oil and petroleum resources the raw materials from which such packaging is derived
is encouraging the food industry to explore the use of natural
bio-based materials and polymers in packaging (Debeaufort, Quezada-Gallo, & Voilley, 1998). Edible, biodegradable lms, by acting
as barriers to control the transfer of moisture, oxygen, lipids, and
avours, can prevent quality deterioration and increase the shelf
life of food products (Gontard, Guilbert, & Cuq, 1993).
Several studies have reported the use of polysaccharides from
different sources to prepare lms and coatings with different properties, and have indicated that these carbohydrates are promising
materials (Mali, Sakanaka, Yamashita, & Grossmann, 2005). Less
attention has been paid to microbial exopolysaccharides, mainly
due to their low production levels when compared to other polysaccharides, even though these materials can form gels and viscous
solutions at low concentrations (Paul, Morin, & Monsan, 1986).
Corresponding author. Tel.: +98 912 598 7860; fax: +98 261 2248804.
E-mail address: mghasemlou@ut.ac.ir (M. Ghasemlou).
0308-8146/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2011.02.003

Keran, a microbial polysaccharide obtained from the ora of

ker grains, is nding increasing use in the food industry as a texturing and gelling agent. It is a water-soluble polysaccharide containing approximately equal amounts of glucose and galactose
(Micheli, Uccelletti, Palleschi, & Crescenzi, 1999). Recent studies
have shown that high yields of these exopolysaccharides can be
easily isolated from the grains in deproteinized whey (Rimada &
Abraham, 2001). Thus exopolysaccharides from ker grains might
be an affordable alternative to synthetic packaging in food
applications.
In addition, when compared with other polysaccharides, keran
has several important advantages, such as antibacterial, antifungal,
and antitumour properties (Maeda, Zhu, Omura, Suzuki, & Kitamura, 2004; Murofushi, Shiomi, & Aibara, 1983). The literature data
and preliminary studies in our laboratory have shown that keran
can produce lms with good appearance and satisfactory mechanical properties: it appears to have excellent potential as a lmforming agent. However, to date there has been little information
available on its lm characteristics.
In general, natural packaging lms exhibit several disadvantages, such as a strong hydrophilic character and poor mechanical
properties, when compared to synthetic packaging lms. These
drawbacks make it unsatisfactory for some applications such as
packaging (Debeaufort et al., 1998).
Many researchers have studied the effects of various plasticizers on lm-based biopolymers as a way to overcome the lms brittleness. Plasticizers reduce intermolecular forces and increase the

M. Ghasemlou et al. / Food Chemistry 127 (2011) 14961502

mobility of polymer chains, decreasing the glass transition temperature (Tg); unfortunately, they also decrease the lms water vapour permeability (Gontard et al., 1993). Glycerol is one of the
most widely used plasticizers in lm-making techniques. It is a
high-boiling-point plasticizer that is water-soluble, polar, and nonvolatile; these properties make glycerol a suitable plasticizer for
use with a compatible water-soluble polymer (Cheng, Karim, &
Seow, 2006).
There is only one paper on the use of keran as an edible lm
(Piermaria, Pinotti, Garcia, & Abraham, 2009), and, to the best of
our knowledge, there is no specic study on the effect of various
concentrations of plasticizer on lm properties. In the recent years,
a major emphasis has been placed on the search for new microbial
biopolymers with different compositions and properties, and several of them have been under investigation. In the current research,
varying levels of glycerol were used in keran-based lms. The aim
of this work was to study some selected characteristics of glycerol
plasticized keran lms intended for use as edible or biodegradable lms. These results are not available in the literature but are
very important to evaluate possible applications of these lms as
packaging material.
2. Materials and methods
2.1. Starter culture
Ker grains, used as a starter culture in this study, were obtained from a household in Tehran, Iran. The grains were kept in
skimmed milk at room temperature for short periods and the medium was exchanged daily for new culture to maintain the grains
viability. After the culture was continued for seven subsequent
days, the grains were considered active.
2.2. Isolation and purication of keran
Exopolysaccharides in the ker grains were extracted by the
method of Piermaria et al. (2009). In brief, a weighed amount of ker grains was treated in boiling water (1:100) for 1 h and stirred
vigorously. The mixture was centrifuged (Sigma 316 k Frankfurt,
Germany) at 10,000g for 15 min at 20 C and an equal volume of
chilled ethanol was added to precipitate the polysaccharide and
kept at 20 C overnight. The pellets were collected by centrifuging at 10,000g for 20 min at 4 C. The precipitates were re-dissolved in hot distilled water and the precipitation method was
repeated twice. The resulting solution was concentrated, yielding
a crude polysaccharide. The samples were tested for the absence
of other sugars and proteins by high-performance liquid chromatography and the phenolsulphuric acid method (Dubois, Gilles,
Hamilton, Rebers, & Smith, 1956), respectively.
2.3. Preparation of lms
Aqueous solutions of 1%, 2%, and 3% keran were prepared by
weighing the amount of lm-forming solution under constant stirring via the use of a magnetic stirrer for 15 min. Preliminary experiments had showed that lmogenic solutions containing 2% keran
were easily removed from the plate. On the other hand, lms formulated with 1% had low thickness values and were difcult to
handle. Also, the lms prepared without plasticizer were brittle,
and cracked on the casting plates during drying. Thus, plasticizer
was incorporated into the lm-forming solutions to achieve
more-exible lms.
Glycerol (Sigma Chemical Co., St. Louis, MO, USA) was added as a
plasticizer at various levels (1535% w/w based on keran weight).
Following the addition of plasticizers, stirring was continued for a

1497

further 15 min. The lm solution was left for several minutes to naturally remove most of the air bubbles incorporated during stirring.
Films were cast by pouring the mixture onto Teon-coated plates
resting on a levelled granite surface for approximately 18 h at room
temperature and room relative humidity. Dried lms were peeled off
the casting surface and stored inside desiccators at 25 1 C until
evaluation. Saturated magnesium nitrate (Merck, Darmstadt, Germany) solution was used to meet required relative humidity.
2.4. Determination of physical properties of lms
2.4.1. Film thickness
Thickness of the lms was measured using a manual digital
micrometre (Mitutoyo No. 293-766, Tokyo, Japan) to the nearest
0.001 mm. Measurements were made in at least ten random locations for each lm, and an average value was calculated. The average value was used in calculations for tensile properties and WVP
tests.
2.4.2. Moisture content
The lms moisture content (approximately 1  3 cm2) was
determined by measuring the weight loss of lms before and after
drying in a laboratory oven (Blue M Electric Co., Blue Island, IL) at
103 2 C until constant weight was reached (dry sample weight).
Three replications of each lm treatment were used for calculating
the moisture content.
2.4.3. Film solubility in water
For this study, solubility in water was dened as the ratio of the
water-soluble dry matter of lm that is dissolved after immersion
in distilled water (Gontard, Duchez, Cuq, & Guilbert, 1994). A circular lm sample was cut from each lm, dried at 103 2 C for 24 h
in a laboratory oven, and weighed to determine the initial dry
weight. The solubility in water of the different keran lms was
measured from immersion assays in 50 ml of distilled water with
periodic stirring for six hours at 25 C. After that period, the
remaining pieces of lms were taken out and dried at 103 2 C
until constant weight (nal dry weight).
The percentage of the total soluble matter (% TSM) of the lms
was calculated using Eq.(1):

%TSM initial dry weight

 final dry weight=initial dry weight  100

TSM tests for each type of lm were carried out in three replicates.
2.4.4. Contact angle measurements
The contact angle is dened as the angle between the baseline
of the drop and the tangent line at the point of contact of the water
droplet with the surface (Ojagh, Rezaei, Razavi, & Hosseini, 2010).
Contact angle measurements were performed with water using a
goniometer (Kruss G10, Germany). To perform the measurements
of the contact angles, a syringe was lled with 5 ml of distilled
water and a drop was placed on the lm surface. For each lm type,
at least ve measurements at different positions on the lm surface were taken and the average was calculated.
2.5. Surface colour measurements
Film colour was determined using a colourimeter (Minolta CR
300 Series, Minolta Camera Co., Ltd., Osaka, Japan). Film specimens
were placed on a white standard plate (L = 93.49, a = 0.25 and
b = 0.09) and the lightness (L) and chromaticity parameters a
(redgreen) and b (yellowblue) were measured. L values range
from 0 (black) to 100 (white); a values range from 80 (greenness)
to 100 (redness); and b values range from 80 (blueness) to 70

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M. Ghasemlou et al. / Food Chemistry 127 (2011) 14961502

(yellowness). All measurements were performed in triplicates. Total colour difference (DE) and whiteness index (WI) were calculated using Eqs. (2) and (3) (Bolin & Huxsoll, 1991).

q

DE L  L2 a  a2 b  b2

where L, a, and b are the colour parameter values of the standard

and L, a, and b are the colour parameter values of the sample.

WI 100 

q
2
100  L2 a2 b

2.6. Water vapour permeability

The lms water vapour permeability (WVP) was measured
gravimetrically according to the standard method E96 (ASTM,
1995) and corrected for the stagnant air gap inside test cups
according to the equations of Gennadios, Weller, and Gooding
(1994). Special glass cups with wide rims were used to determine
WVP. The cups, which contained approximately 50 g anhydrous
calcium chloride desiccant (0% RH, assay cup) or nothing (control
cup), were covered with lms of varying plasticizer concentration.
Films without pinholes or defects were cut circularly (0.00287 m2
lm area) and sealed to the cup mouths using melted parafn. Each
cup was placed in a desiccator maintained at 75% RH with a sodium-chloride-saturated solution (Merck, Darmstadt, Germany).
This difference in RH corresponds to a driving force of
1753.55 Pa, expressed as water vapour partial pressure. After the
lms were mounted, the weight gain of the whole assembly was
recorded every 1 h during the rst nine hours and nally after
24 h (with an accuracy of 0.0001 g). The cups were shaken horizontally after every weighing. The slope of the weight-versus-time
plot (the lines regression coefcients were >0.998) was divided
by the effective lm area to obtain the water vapour transmission
rate. This was multiplied by the thickness of the lm and divided
by the pressure difference between the inner outer surfaces to obtain the WVP (Eq. (4)).

WVP

Dm X
ADt Dp

where Dm/Dt is the weight of moisture gain per unit of time (g/s), X
is the average lm thickness (mm), A is the area of the exposed lm
surface (m2), and Dp is the water vapour pressure difference between the two sides of the lm (Pa). WVP was measured for three
replicated samples for each type of lm.
2.7. Determination of lms mechanical properties
The lms mechanical properties, including tensile strength
(MPa) and elongation at break (%), were determined at 25 C using
a Testometric Machine M350-10CT (Testometric Co., Ltd., Rochdale, Lancs., England) according to ASTM standard method D882
(ASTM, 2001). Films were cut in rectangular strips of 38 mm long
and 5.79 mm wide. All lm strips were equilibrated at 51% RH
for 48 h in a desiccator using saturated magnesium nitrate solution. The lms were xed with an initial grip separation of
50 mm and stretched at a cross-head speed of 50 mm/min. A
microcomputer was used to record the stressstrain curves. Tensile strength was calculated by dividing the maximum load on
the lm before failure by the cross-sectional area of the initial lm
specimen. Percentage elongation was dened as the percentage of
a change in the length of the specimen when compared to the original length between the grips. At least ve replicates of each lm
were tested.

2.8. Differential scanning calorimetry (DSC)

The thermal properties of the lms were carried out using DSC
equipment (PL Polymer Laboratories, UK). A 10 mg lm sample
was cut as small pieces and placed into a sample pan of DSC equipment. An empty aluminum pan was used as reference. Samples
were scanned at a heating rate of 10 C/min between temperature
ranges of 50 and 150 C. Nitrogen was used as the purge gas at a
ow rate of 20 ml/min. The glass transition temperatures (Tg) of
the different lms were determined from resulting thermograms
as the midpoint temperature of a step-down shift in baseline,
due to the discontinuity of the specic heat of the sample. The
melting point (Tm) was calculated as the temperature where the
peak of the endotherm occurs. The enthalpy (DHm) of the solgel
transition was determined as the area over the endothermic peak.
All these properties were determined in duplicates and the results
were averaged.
2.9. Scanning electron microscopy
Microstructural analysis of the surface and cross-sections of the
dried lms was conducted by scanning electron microscopy (Oxford Instruments INCA Penta FETX3). The lms containing 25%
glycerol were fractured in liquid nitrogen, mounted on aluminum
stubs using a double-sided adhesive tape, and sputtered with a
thin layer of gold using a BAL-TEC SCD 005 sputter coater (BALTEC AG, Balzers, Liechtenstein). All samples were examined using
an accelerating voltage of 20.0 kV. Samples were photographed
at an angle of 90 to the surface to allow observation of the lms
cross-section.
2.10. Statistical analysis
Statistics on a completely randomized design were performed
with the analysis of variance (ANOVA) procedure using SAS software (Version 9.1; Statistical Analysis System Institute Inc., Cary,
NC, USA). Duncans multiple range tests were used to compare
the difference among mean values of lms properties at the level
of 0.05.
3. Results and discussion
3.1. Physical properties of lms
Preliminary studies were carried out to determine the glycerol
concentration range for the lm formulation. The lowest effective
glycerol concentration was 10% (w/w, lm dry weight basis); below this concentration, the lms tended to be brittle and difcult
to handle, whereas lms with more than 35% glycerol were exible
but sticky. This stickiness may have resulted from phase separation
and diffusion of glycerol to the lm surface.
For a constant concentration of keran (2%), lms prepared with
different concentrations of glycerol (15%, 25%, and 35% by weight),
had thickness values ranging from 0.058 to 0.067 mm (Table 1).
These thickness values were higher than those reported by Piermaria et al. (2009), which may have been due to the differences in
lm-forming solution formulations and lm-making procedures.
The moisture content increased signicantly from 17.95% to
37.04% as the plasticizer content increased (P < 0.05) (Table 1).
Glycerol acts as a water-holding agent, with the higher number
of water molecules in glycerol-plasticized lms increasing plasticity (Gontard et al., 1993).
The solubility of the lms generally increased with increasing
concentrations of glycerol. In glycerol-plasticized lms, glycerol
can diminish interactions between biopolymer molecules and

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M. Ghasemlou et al. / Food Chemistry 127 (2011) 14961502

Table 1
Physical properties of keran lms incorporated with various concentration of glycerol as plasticizer

A
B

A,B

Glycerol conc.% (w/w) (based on keran

content)

Thickness
(mm)

Moisture content (%
d.b.)

Solubility in water
(%)

Water contact angle

(degree)

Without plasticizer
15
25
35

0.058 0.0041a
0.064 0.0098a
0.062 0.0070a
0.067 0.0095a

17.95 1.69d
23.59 2.11c
32.47 2.89b
37.04 1.56a

21.28 1.33c
25.30 0.64b
27.91 1.11a
28.88 0.85a

106.41 2.61a
103.06 2.22a
97.15 1.51b
95.44 0.93b

Means within each column with same letters are not signicantly different (P < 0.05).
Data are means SD.

The L values generally increased as the concentration of glycerol

increased; this increase was statistically signicant (P < 0.05). The
overall colour of the lms was lightened with incorporation of
glycerol. These results agreed with visual observation.
Colour changes due to incorporation of plasticizer can be more
fully described using other colour functions (Ghanbarzadeh, Almasi, & Entezami, 2010), such as DE, which indicates the degree of
total colour difference from the standard colour plate, and WI,
which indicates degree of whiteness. Incorporating glycerol revealed DE values that were signicantly (P < 0.05) lower than that
of unplasticized ones (increased clearness). In contrast, WI increased with increasing glycerol content.

increase solubility due to its hydrophilic nature, giving the polymer

molecules a greater ability to attract water (Cuq, Gontard, Aymard,
& Guilbert, 1997).
3.2. Water contact angle
Surface-tension characterisation through contact angle measurements can be a good way to determine how hydrophilic a lm
is (Pearoval, Debeaufort, Desprea, & Voille, 2002). Table 1 shows
the water contact angle measurements for the samples. There
was signicant difference among contact angles for lms with different glycerol content (P < 0.05). It is accepted that water contact
angle will increase with increasing surface hydrophobicity. The results in this study showed that the addition of plasticizers diminished the lms water contact angle. Plasticization, therefore,
resulted in decreasing hydrophobicity of the lms. The higher
hydrophilicity of the samples is attributable to the hygroscopicity
(water-binding capacity) of the plasticizer. In comparison with
other polysaccharide-based lms, keran lms have a higher contact angle with water, suggesting a higher surface hydrophobicity.
This means that these lms were less readily wetted.

3.4. Water vapour permeability (WVP)

Table 3 shows the water vapour permeability (WVP) values of
different keran lms. The WVP was 4.95  1011 g s1 m1Pa s1
for the unplasticized sample (0% w/w glycerol); this increased to
5.55 and 5.88  1011 g s1 m1Pa s1 for the lms containing
25% and 35% w/w glycerol, respectively. There was a signicant difference between the WVP values of lms made with different glycerol concentrations (P < 0.05). WVP values were in the range of
those reported by other authors in lms based on keran (Piermaria et al., 2009).
An increase in glycerol concentration normally causes an increase in the WVP of hygroscopic or hydrophilic lms. Glycerol is
a relatively small hydrophilic molecule, which can be inserted between adjacent polymeric chains, decreasing intermolecular forces
and increasing molecular mobility in the lm matrix. The increased
mobility results in greater free volume and segmental motions,
which facilitates the migration of water vapour molecules through

3.3. Colour measurement

Film colour is an important factor in a products acceptability to
consumers. Table 2 shows the L, a, and b Hunter Lab colour values,
total colour difference (DE), and whiteness index (WI) of lms. The
main differences in colour values among the keran lms for different concentrations of glycerol were increased L values and decreased b values. However, no signicant (P > 0.05) difference in
values for a were detected.

Table 2
Hunter colour values (L, a, and b), total colour difference (DE) and whiteness index (WI) of keran lms as a function of glycerol concentration

A
B

A,B

Glycerol conc.% (w/w) (based on keran content)

DE

WI

Without plasticizer
15
25
35

77.87 0.40b
79.68 1.37b
82.82 1.66a
84.47 1.41a

0.66 0.01a
0.65 0.11a
0.61 0.21a
0.60 0.07a

2.52 0.06c
2.51 0.15c
2.76 0.12b
3.09 0.11a

15.84 1.04a
14.05 2.70ab
11.04 2.73b
9.57 1.03b

77.71 0.40b
79.51 1.35b
82.58 1.61a
84.15 1.39a

Means within each column with same letters are not signicantly different (P < 0.05).
Data are means SD.

Table 3
Effect of various concentrations of glycerol as plasticizer on the WVP and mechanical properties of keran lms

A
B

11

Glycerol conc.% (w/w) (based on keran content)

WVP (10

Without plasticizer
15
25
35

4.95 0.13c
5.04 0.18c
5.55 0.21b
5.88 0.10a

1 1

gm

pa)

A,B

Tensile strength (MPa)

Elongation at break (%)

11.18 2.24a
8.85 1.64ab
6.18 2.72b
5.04 2.10b

39.56 11.13c
50.73 10.60c
94.38 3.25b
162.45 6.09a

Means within each column with same letters are not signicantly different (P < 0.05).
Data are means SD.

M. Ghasemlou et al. / Food Chemistry 127 (2011) 14961502

the lm (Rodriguez, Oses, Ziani, & Mate, 2006). Additionally, at a

high glycerol concentration, glycerol could cluster with itself to
open polymer structures, enhancing the permeability of a lm to
moisture (Yang & Paulson, 2000). The same behaviours were
shown in research by Ghanbarzadeh et al. (2006), who found that
increasing glycerol concentration, increased the WVP of zein lms.
Values have been reported for WVP values of a corn starch lm, sodium casein lm, a sh myobrilar lm, a high-density polyethylene lm, a cellophane lm, wheat gluten lm, and a chitosan lm
of 8.68, 1.51, 6.4, 0.23, 8.4, 4.52, and 2.25  1011 g s1 m1Pa s1,
respectively (Cuq et al., 1997; McHugh & Krochta, 1994; Ojagh
et al., 2010; Smith, 1986). The WVP of the keran lms was better
than those of corn starch, cellophane, and sh myobrilar lms,
but worse than those of the other lms.

0%
Endothermal heat flow

1500

15%
25%

35%

3.5. Mechanical properties

Mechanical properties reect lms durability and ability to enhance the mechanical integrity of foods. Table 3 shows the effect of
incorporating glycerol on the mechanical properties of keran
lms. Films without glycerol presented greater tensile strength
(TS) and lower elongation at break (E). The presence of GLY in lms
caused signicant differences in TS and E values (P < 0.05). Overall,
the TS decreased as the concentration of glycerol increased. A tendency to be higher than E was observed as the concentration of
glycerol increased (P < 0.05). This effect of incremental increases
in plasticizer concentration on mechanical properties has been
broadly discussed in the literature (Cuq et al., 1997; McHugh &
Krochta, 1994). However, Lourdin, Coignard, Bizot, and Colonna
(1997) have well discussed it. They stated that a small quantity
of plasticizer could be easily inserted between polymer chains,
producing a cross-linker effect that decreases the free volume
of the polymer, causing the mechanical strength of the lms to
be decreased and the extensibility enhanced. The TS values of keran-based lms were 5.0411.18 MPa, which were lower than
those of synthetic polymers such as LDPE, Low-density polyethylene, (917 MPa), polystyrene (3555 MPa), and cellophane
(114 MPa) (Smith, 1986). However, keran lm plasticized with
glycerol showed extremely high elongation values higher, for
example, than cellophane (20%) and polystyrene (1%) but could
not be stretched nearly as far as LDPE (500%).
3.6. Thermal properties
DSC studies of the keran lms containing different glycerol
contents were performed to further understand the structure and
interaction between polymer and plasticizer. Fig. 1 presents the
DSC curves of these lms. The glass transition temperature (Tg) is
the temperature at which the material undergoes a structural transition from an amorphous solid state (glassy state) to a more viscous rubbery state (Ghanbarzadeh & Oromiehi, 2009). In all
cases, only one glass transition (Tg) followed by an endothermic
peak was observed.
Table 4 shows the glass transition temperatures (Tg), melting
temperatures (Tm), and enthalpies of fusion (DHm). All Tg values
were in the range of 14 to 21 C depending on the lms glycerol
concentrations, which are close to those of the most commonly
used synthetic lms (e.g. 18 C for polypropylene, 25 C for
low-density polyethylene), but higher than the Tg of high-density
polyethylene (125 C) (Robertson, 1993) and pure glycerol liquid
(93 C) (Cherian, Gennadios, Weller, & Chinachoti, 1995). The low
Tg values of keran lms could be attributed to their inherent
structural characteristics (high chain mobility) and to their relatively high hydrophilicity, which lets them absorb more water
molecules than other lms and thus markedly depresses the Tg
due to the plasticizing effect of the absorbed water molecules

-100

-50

50

100

150

200

Temperature ( C)
Fig. 1. Representative examples of DSC curves of keran-based lms without
glycerol and plasticized with glycerol. The glycerol concentration (% w/w based on
keran weight) is indicated for each curve.

Table 4
DSC data of keran-based lm as a function of various glycerol concentrations

A,B

Glycerol conc.% (w/w)

(based on keran
content)

Tg (C)

Tm (C)

DHm (J/g)

Without plasticizer
15
25
35

14.88 1.25a
18.93 0.77b
20.68 0.58c
21.77 0.61c

73.29 1.01a
71.20 1.59ab
70.84 1.24ab
68.36 2.67b

73.14 4.29d
122.72 2.08c
167.50 2.12b
174.85 4.83a

A
Means within each column with same letters are not signicantly different
(P < 0.05).
B
Data are means SD.

(Yang & Paulson, 2000). The DSC thermograms of the studied lms
exhibited sharp endothermic peaks at the range of 6873 C. These
endothermic peaks have been attributed to the melting of keran
during retrogradation. The temperature position of the melting
peak decreased signicantly from 73.2 to 68.3 C as glycerol content increased from 0% to 35% w/w keran. The decrease of Tg
and Tm with increased plasticizer content was expected, and had
been observed in other studies (Ghanbarzadeh & Oromiehi, 2009;
Gontard et al., 1993). Similar results were obtained by Arvanitoyannis, Psomiadou, Nakayama, Aiba, and Yamamoto (1997) with
lms of gelatin/starch blends plasticized with glycerol or sorbitol.
Thermograms indicated partial miscibility of glycerol and keran
at the molecular level for any given concentration ratio. They remained homogeneous throughout the heating cycle, as no phase
separation (separated glass transition temperature or melting
peaks) was observed. If blends of polymer and plasticizers are
immiscible, the mixture will exhibit two Tg and Tm corresponding
to the two pure phases (Ghanbarzadeh et al., 2010).

3.7. Film microstructure

In an attempt to study microstructural changes in the lms,
scanning electron microscopy was used to depict the surface

M. Ghasemlou et al. / Food Chemistry 127 (2011) 14961502

1501

Fig. 2. Scanning electron micrographs of the surface (left) of keran-based lms viewed at a magnication of 500, and cross-section (right) viewed at a magnication of
1000; (A) unplasticized, (B) plasticized with 25% w/w glycerol.

and section topography of all prepared keran lms. Microscopic

views indicated smooth and uniform surface morphology without obvious cracks, breaks, or openings on the surfaces after
the incorporation of glycerol as a plasticizer. Fig. 2 shows scanning electron micrographs of the outer surface (left) and crosssection (right) for both the control and glycerol-containing lms.
Scanning electron microscopy observations of lms with different glycerol concentrations did not present any obvious differences in structure.
4. Conclusions
On the basis of the results obtained in this study, keran could be
used as a new lm-forming material. The physical, mechanical, and
thermal properties, which are important in food packaging applications, were examined as a function of glycerol concentration.
Generally, the TS of the lms decreased and % E increased with
increased concentrations of glycerol. Based on DSC thermograms,
the glass transition temperature (Tg) of the lms decreased with
the glycerol content. Keran lm exhibited a potential application
as an edible food lm and coating. The properties of keran-based
lm can be further improved for food-packaging applications. The
methods investigated and developed in this study are expected to
be very useful for future research in this area.
Acknowledgements
The authors wish to express their gratitude to Iran Polymers
and Petrochemical Institute and the University of Tehran for supporting the facilities for this research work, and for technical
assistance.

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