ICNTC-2019 Special Issue

J. Indian Chem. Soc.,

Vol. 96, September 2019, pp. 1211-1216

Development of chitosan-based edible biocomposite films incorporated with Kumquat peels

extract as food packaging
Fatmagül S, ahin, lknur Küçük* and brahim Doymaz
Department of Chemical Engineering, Yildiz Technical University, 34220 Istanbul, Turkey
E-mail: [email protected]
Manuscript received online 26 April 2019, revised and accepted 20 July 2019

Edible films incorporate with various ratio of Kumquat peel extract were prepared by using solvent casting techniques. In or-
der to determine the effect of Kumquat peel concentration, the biofilms have been characterized by physical properties such
as moisture content, swelling degree, water solubility, water vapor permeability, color and transparency as their structures
were confirmed by Scanning Electron Microscope (SEM). In addition, the mechanical properties have been determined with
the tensile strength and elongation in terms of breakage of the prepared films.
It has been observed that the amount of moisture, swelling, and solubility of the films changed between 30.95–22.05%,
177.96–24.8% and 34.58–54.47%, respectively. It has been observed that the amount of moisture and the degree of swell-
ing of the films decreased and the solubility values increased with the increase of Kumquat peel extract. The water vapor
permeability, thickness and density range values of the films have been as follows: 1.039 g H 2O Pa –1 s–1 m –1 and 0.989 g H2O
Pa –1 s–1 m –1, 0.0670 to 0.0554 mm, 0.86 g/cm 3 to 0.79 g/cm 3. It has been determined that the ratio of Kumquat bark extract
does not cause a significant change on the water vapor permeability, thickness and density values of the films. With the in-
creasing of the concentration of the Kumquat peel extract in the film structure and the films exhibit a more flexible property
and the tensile strength at 33.28–13.5 MPa has been observed to vary between 7.74% and 20.57%. Results indicate that
the chitosan-based films incorporated with Kumquat peel extract can be an alternative for food packaging.

Keywords: Chitosan, Kumquat, edible film, biopolymer, food packaging.

Introduction duced from fossil fuels and are practically un-degradable.

Biological origin-based polymers which are using for ed- For this, packaging materials for foodstuff, like any other short-
ible films and coatings, are newly undergoing remarkable term storage packaging material, represent a serious global
and prevalent researches1,2, as a promising alternative for environmental problem7. Therefore, innovative edible films
non-biodegradable synthetic products3, allowing the minimi- derived from agro-food industry wastes and renewable low
zation of waste removal issue. Currently, the edible or biode- cost natural resources have been explored as replacement
gradable films are made from natural polymers such as pro- for conventional plastics. Currently, the edible or biodegrad-
teins, lipids and polysaccharides. On the other hand, poly- able films are made from natural polymers such as proteins,
mer blending is one of the useful methods to obtain new lipids and polysaccharides8.
materials with desired functional properties and there has Chitosan is a linear polysaccharide consisting of (1,4)-
been great scientific and commercial progress made in the linked-2-amino-deoxy--d-glucan; it is obtained through the
area of food applications4,5. deacetylation of chitin, which, after cellulose, is the second
Packaging plays an important role in reducing food waste most abundant polysaccharide in nature7. This polysaccha-
because it can improve food preservation and optimize space ride is widely utilized not only for its film-forming ability but
during handling, shipping, and storage6. Nowadays, the larg- also to its antimicrobial properties. Indeed, the antimicrobial
est part of materials used in packaging industries are pro- properties of chitosan and its derivate (chitosan-oligo-sac-

JICS-15 1211
 J. Indian Chem. Soc., Vol. 96, September 2019

charides) have been largely reported in the literature, thereby (Fowler IP54) at five random spots of the film and the mean
encouraging its use as potential packaging material8. value was used for the determination of the physical and
Kumquat is an elliptical shaped fruit, closely related to mechanical properties. The density of the film samples were
Citrus9. Differently from most Citrus, Kumquat fruits are eaten calculated by using eq. (1).
whole, and they have a strong, sweet start, with a slightly m
bitter finish10. Health benefits of Citrus are well documented;  = ——— (1)
A×
aglycones of flavonoid C-glycosides in Kumquat, such as
phloretin and acacetin, exhibit a broad spectrum of biologi- where A is the film area,  the film thickness (cm), m is the
cal activities such as antioxidant activity, anti-inflammatory dry mass of film (g) and s is the dry matter density of the film
effect, and anticancer effect11. (g/cm3)14.
Although some studies dealing with chitosan and their Moisture content (MC) was analyzed gravimetrically by
composites have been performed, there is no previous re- drying equilibrated film sample (2 cm×2 cm) at 110ºC to a
port on the chitosan incorporated with Kumquat peal extract constant weight15.
films as a packing materials. This work focused on the po- To determine swelling degree (SD) and solubility (S), film
tential of being edible and biodegradable film that can be pieces (2 cm×2 cm) were dried at 110ºC to constant weight
used as food packaging with chitosan biopolymer and peel to obtain the initial dry mass (Wi). Then, they were immersed
extract of Kumquat fruit has been investigated. deionized water for 24 h. Next, the films were taken out from
the water and the weight of films were determined (Wf) after
Experimental removing the excess water on the films surface using a pa-
Chitosan with the degree of deacetylation of 75% was per tissue. Swelling degree (SD) and solubility (S) of films
supplied by Sigma-Aldrich. All the chemicals in this study were calculated by using following equations16:
were of analytical grade. Kumquat, was purchased from a
Wf – Wi
local market. After manual peeling, the separated peels were SD = ———— ×100 (2)
dried at 60ºC for 2 days and were pulverized in a blender. Wi
Chitosan solution (CH) (2% w/v) was prepared by dis- Initial dry weight – final dry weight
solving into 5% (v/v) acetic acid aqueous solution and after S = ———————————————— ×100 (3)
chitosan was dissolved glycerol was added (0.4 g g/g biopoly- Initial dry weight
mer) while stirring at 800 rpm for 30 min. Powdered Kum- Water vapor permeability (WVP) tests were conducted ac-
quat peels were extracted with distilled hot water at 80ºC for cording to ASTM method E96-00 (ASTM, 2004) with some
3 h under 600 rpm then was cooled to room temperature and modifications. Each film sample was sealed onto a circular
filtered. Film forming solution were obtained by mixing permeation cell (permeation area: 7×10–2 m2). To maintain a
chitosan solution and Kumquat peel extract (KPE) at 100:0, 75% relative humidity (RH), anhydrous silica (0% RHc) and
95:5, 90:10, 80:20, 60:40 Chitosan:Kumquat peel extracts a saturated NaCl solution (75% RHd) were used. All mea-
weight ratio and coded as CH, CHKPE5, CHKPE10, surements were made at steady-state conditions. Changes
CHKPE20, CHKPE40, respectively. The blends were homog- in the weight of the cell were recorded and plotted as a func-
enized with a stirrer at 800 rpm for 1 h. Edible films were tion of time. The slope of each curve (m/t, g H2O s–1)
produced by casting technique: film forming solutions were was obtained by linear regression and the water vapor trans-
poured into 12×12 cm Petri dishes and dried at room tem- mission rate (WVTR) was calculated from the slope divided
by the permeation cell area. WVP was calculated by using
perature for 96 h prior the characterization.
eq. (4):
Characterization:
WVP = [WVTR/(PVH2O.(RHd – RHc))].d (4)
Film thickness was measured using a digital micrometer
where WVTR, water vapor transmission rate (g H2O Pa–1 s–1

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 S, ahin et al.: Development of chitosan-based edible biocomposite films incorporated with Kumquat peels extract etc.

m–1), PVH2O: saturation water vapor pressure at test tem- LS 10) and analyzed using an accelerating voltage of 10 kV.
perature (2339.27 Pa at 20ºC), RHd-RHc, relative humidity Prior to the analysis, the film samples were coated with gold
gradient across the, A, permeation area (m2) and d, film thick- under a vacuum.
ness (m). Each WVP value represents the mean value of
Results and discussion
three samples taken from different films17.
Table 1 shows the basic film properties, including film
The film color was determined using a Miltona colorim-
density, thickness, moisture content, solubility, swelling de-
eter (CR-300, Japan). The white tile was used as standard
gree, and water vapor permeability.
during the color measurement. Lightness (L*) and chroma-
ticity parameters a* (red-green) and b* (yellow-blue) were The thickness of Chitosan:Kumquat peel extract
used to characterize the film color in the Hunter Lab scale (CH:KPE) based films ranged between 0.0554 and 0.0670
(CIE Lab scale)18. mm while density range between 0.79 and 0.86 g/cm3. The
films thickness is an important characteristic in determining
The opacity of the MP films was determined according to
the feasibility of edible films as packaging materials for food
a Hunterlab method, with the same equipment used for the products since the thickness of the films affects other char-
color measures, also operating in the reflectance mode. The acteristics of the films, such as tensile strength, elongation,
opacity (Y) of the samples was calculated as the relationship and water vapor permeability. Incorporating Kumquat peel
among the opacity of each sample on the black standard extract and concentration of KPE did not affect significantly
(Yb) and the opacity of each sample on the white standard on the film thickness and density and in this study, film thick-
(Yw)19. ness and density was controlled in a strait range.
Y black packing Packaging films should maintain moisture levels within
Opacity% = ———————— ×100 (5) the packaged product. Therefore, the knowledge of mois-
Y white packing
ture content of the films have to be determined for food pack-
Zwick Roell (Germany) Universal Testing Instrument was aging applications20.
used to measure tensile strength (TS) and percentage elon- The MC values of the CH and CH:KPE composite films
gation at break (%EB) of films. Film sample cut into 1.0×5 ranged between 30.95 and 22.05%. The MC values de-
cm strips before measurement and the thickness of the film creased significantly with the increasing KPE concentration.
samples was determined using a micrometer at random po- This could be explained by that chitosan is hydrophilic due
sition. The tensile strength (TS) and elongation at break to stronger interactions between water molecules and its func-
(%EB) were determined using initial grips separation of 25 tional groups (-OH, -NH2) by hydrogen bonds21. Swelling
mm, load cell 2 kN and cross-head speed of 5 mm/min with degree and solubility are both leading property of the edible
the testXpert software. Three sample of each film were evalu- films, affecting resistance of film to water and storage quality
ated. of food22.
The surface morphologies of the film samples were ex- The swelling degree of the films were significantly de-
amined using scanning electron microscopy (Zeiss EVO® creased with incorporating KPE and increasing KPE con-

Table 1. Density, thicknesses, moisture contents (MC), water solubility (S), swelling degree (SD) and water vapor permeability of CH and
KPE incorporated CH films
CH:KPE Density Thickness MC% S% SD% WVPx1011
ratio (g/cm3) (mm) (g H2O Pa–1 s–1 m–1)
CH 0.86±0.13 0.0670±0.001 30.95±0.88 34.58±0.15 177.96±2.55 0.997±0.286
CHKPE5 0.79±0.02 0.0554±0.004 28.43±0.64 42.06±0.60 43.57±1.46 1.099±0.738
CHKPE10 0.86±0.07 0.0612±0.003 27.18±0.59 43.55±0.97 34.9±2.08 1.124±0.397
CHKPE20 0.78±0.06 0.0632±0.004 26.39±0.34 50.25±0.77 25.31±2.94 0.951±0.200
CHKPE40 0.79±0.039 0.0554±0.002 22.05±0.95 54.47±0.94 24.28±7.31 0.951±0.151

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 J. Indian Chem. Soc., Vol. 96, September 2019

Fig. 1. Tensile strength (TS) and elongation at break (EB)% of CH and KPE incorporated CH films.

centration within the films. The highest SD of pure CH film The values of L, a, b and opacity are shown in Table 2. It
was around 177.96% which is similar to literature23. Although is clear that all the parameters were observed to be affected
chitosan has hydrophilic groups, such as carboxylic groups, by KPE. After the addition of KPE, the opacity and a* values
these groups could easily interact with water, resulting in were significantly increased, while the L value decreased,
swelling of the films, upon being enriched with the extract indicating a tendency towards redness and darkness. This
intermolecular interaction between chitosan and the extract may help to protect the packaged foods from visible and ul-
developed and this resulted in a decrease in the film swell- traviolet light that lead to nutrient losses, discoloration and
ing. In addition, a lower level of swelling could be attributed off-flavour27.
to the hydrophobic properties of the extract24.
The solubility values of the CH and CH:KPE films ranged Table 2. Color parameters including L, a, b and opacity of CH and
between 34.58 and 54.47% which were very closed to re- KPE incorporated CH films
ported by Rodriquez-Nunez et al.25. The lowest S values of CH:KPE ratio L a b Opacity %
pure chitosan films was observed 34.58%. The results CH 93.2±0.33 0.31±0.16 5.45±0.42 10.45±0.49
CHKPE5 90.5±1.25 1.08±0.23 16.3±1.72 13.22±0.40
showed that incorporating KPE and increasing KPE concen-
CHKPE10 86.84±0.97 1.25±0.25 31.52±0.35 16.45±0.28
tration into the chitosan films, significantly increased in wa-
CHKPE20 84.62±0.90 3.26±1.32 44.67±2.36 20.39±0.76
ter solubility. The reduction of the solubility was not observed
CHKPE40 81.8±0.95 6.46±0.40 53.88±0.81 26.14±1.37
indicating that the interaction between chitosan and the ex-
tracts was not hydrophobic. A similar phenomenon was also
observed by Souza et al.26 for chitosan films incorporated Tensile strength is the ability of a material to resist under
with natural antioxidants. tensile stress until it breaks and is one of the most important
and widely measured properties of materials used in struc-
WVP controls the transfer of water from the food to its
tural applications. Elongation-at-break of a material is the
environment and to keep foods fresh, the WVP value should
percentage increase in length that occurs before it breaks
be maintained as low as possible. As shown in Table 1, in-
under tension. As shown in Fig. 1, TS values decreased while
corporating KPE did not significantly influence the WVP val-
EB values increased with the increasing KPE concentration
ues of pure chitosan film which remain around 1011 g H2O
within the CH film. The results indicate that CH:KPE film more
Pa–1 s–1 m–1. This results could be associated with the den-
flexible compare to pure CH films. These behaviors suggest
sity of the CH:KPE films.

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