Development and Characterization of Biodegradable Chitosan Films Containung Two Essential Oils
Development and Characterization of Biodegradable Chitosan Films Containung Two Essential Oils
Development and Characterization of Biodegradable Chitosan Films Containung Two Essential Oils
a r t i c l e i n f o a b s t r a c t
Article history: Active biodegradable films from chitosan containing 10% to 30% w/w of citronella essential oil (CEO)
Received 8 September 2014 and cedarwood oil (CWO) were developed by casting and solvent-evaporation method, and their phys-
Received in revised form 4 November 2014 ical, mechanical and thermal properties were investigated. Possible interactions between the chitosan
Accepted 21 November 2014
chains and the essential oils were confirmed using Fourier-transform infrared spectroscopy (FTIR). Vari-
Available online 24 December 2014
ous amounts of CEO or CWO had significant effects on the films’ mechanical properties, with the exception
of 10% of CEO, which did not significantly affect the tensile strength of the films. The incorporation of
Keywords:
the two tested oils provoked a remarkable reduction in the water-vapor permeability properties, with a
Essential oils
Biodegradable film
decrease of about 63% when 30% CEO was added in chitosan films. Thermogravimetric analysis showed
Chitosan that degradation temperatures of the films containing CEO and CWO improved only slightly in compari-
SEM son to control films without essential oils. FTIR spectra analysis provided some insights on the possible
Tensile properties. interactions between chitosan and the two essential oils used. This study suggests that active films can
be developed by including CEO and CWO in a chitosan matrix. Such films can provide new formula-
tion options for packaging industries in developing active packaging with potential food-technology
applications.
© 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ijbiomac.2014.11.046
0141-8130/© 2014 Elsevier B.V. All rights reserved.
290 Z. Shen, D.P. Kamdem / International Journal of Biological Macromolecules 74 (2015) 289–296
have been proposed to improve the barrier and mechanical proper- 2.2. Chitosan characterizations
ties of chitosan-based films. To improve water-barrier properties,
hydrophobic compounds, such as lipids, are usually included in the The number average molecular weight (Mn) and weight average
polymer matrix. Over recent years different works have studied molecular weight (Mw) were calculated by using data from the gel
the use of fatty acids as lipid components to be incorporated in permeation chromatography (GPC) analysis. The GPC system was
chitosan films to modulate the water vapor barrier [12–14]. The carried on an Agilent 1100 series HPLC equipped with two Waters
incorporation of plant essential oils into these films represents an Styagel HR 4 Column Waters Hydrogel 250 and Waters Hydrogel
interesting alternative to lipids. Essential oils extracted from plants 500, Milford, MA, USA. About 1% v/v acetic acid was used as eluent
or spices are rich sources of phenolic compounds, and have been at a flow rate of 0.65 mL min-1 at room temperature close to 30 ◦ C.
demonstrated to have a wide spectrum of antimicrobial activity The sample concentration was 1% (w/v). Six standard references
[15]. Despite the essential oils’ potential for food preservation, their with molecular weights ranging from 6000 to 2,000,000 gram per
usage is often restricted because of their intense aroma, toxicity mole (g/mole) were used for calibration following a method pre-
problems and possible changes in the organoleptic properties of viously described by Stoklosa et al. [29]. Mn and Mw of chitosan
the food [16]. To avoid this problem, an interesting approach to were calculated by using the elution time multiply by the flow rate
inhibit their diffusion into food products is to incorporate them of the eluent obtained from GPC following the procedure reported
into the chemical structure of the film [17]. Furthermore, compared by Wu [30]. The Mn and Mw are expressed in g/mol.
with direct application, use of edible coatings to carry essential oils
could reduce the required doses of essential oils by the encapsula-
tion effect in the polymer matrix, thus reducing the oils’ negative 2.3. Preparation of the film-forming dispersions
impact.
Citronella essential oil (CEO), from Cympobogon spp (Poaceae), A chitosan solution with concentration of 1% (w/v) was prepared
is popular in mosquito-repellent formulations [18]. Candles and by dissolving the chitosan powder in a 1% (w/v) aqueous acetic
incense containing CEO have been reported to be sold as insect acid while stirring at 250 rpm on a magnetic stirrer set at 45 ◦ C,
repellents in several countries [19]. Pires et al. [20] demonstrated following the method of Ojagh et al. [31]. The chitosan solution
that the main chemical components of CEO can be categorized as was stirred overnight at room temperature to achieve complete
38.3% sesquiterpenes hydrocarbons (-elemene, ␦-cadinene and dispersion. The emulsions were obtained by adding either CEO or
eremophilene), 27.6% monoterpene hydrocarbons (3 -carene and CWO to the chitosan solution to reach final concentrations of 10%,
␥-terpinene) and 22.5% oxygenated monoterpenes (-citronellal 20% and 30% w/w. Tween 80 was added as an emulsifier in quanti-
and -citronellol). Huang et al. [21] reported that citronellal is ties proportional to the essential oils (0.1%, 0.2% and 0.3% w/w) to
the main component of CEO. Cedarwood oil (CWO) is an essen- help distribute and completely incorporate the oil. Finally, emul-
tial oil generally obtained from Juniperus species. The main sions were homogenized for 4 min at 2500 rpm with a Dual-Range
chemical components of CWO have been found to be cedrol Mixer (IKA, Canada) and then degassed under vacuum to remove
(13–15%), widdrol (9–12%), 8,14-cedranoxide (7–8%), 14-hydroxy- dissolved air bubbles. The quantities of Tween 80, CEO and CWO
(E)-caryophyllene (5–9%), cis-thujopsene (10–11%) and ␣-cedrene were defined according to our preliminary tests and based on liter-
(6–8%) [22]. CWO is reported to be produced in China (Cupres- ature data, taking into account the maximum levels of two essential
sus funebris) [23]. Studies have indicated inhibitory effects of oils which could be incorporated into the matrix without oil phase
CEO on ectoparasites and pathogenic microorganisms, includ- separation during film drying. Composite film without essential oil
ing bacteria and fungi [24–26]. CWO has also been reported to and emulsifier was also produced and considered as control. The
have antifungal, antitermite and anti-inflammatory effects [27,28]. suspension were then poured in polystyrene petri dishes measur-
These two essential oils have received approval from the FDA ing 65 mm diameter, which was placed on a leveled surface and
for use as food additives, and could be considered as potential allowed to dry for approximately 48 h at 30% RH and 22 ◦ C. Uni-
alternatives to synthetic additives in antimicrobial food pack- form film thicknesses were achieved by casting the same amount
aging. However, there is as yet little information about their of film-forming solution onto each plate. After drying, the films
possible application as components of edible films. Considering were peeled off the casting surface and maintained at 22 ◦ C and 53%
that CEO and CWO are gaining importance for their consid- relative humidity (produced with saturated Ca(NO3 )2 solution) in a
erable antimicrobial activities, this study focuses on two main conditioning desiccator until further evaluation. For each test, three
specific objectives: (1) to develop an antimicrobial–antioxidant different samples were prepared by taking three portions from each
film based on chitosan and two essential oils – CEO and film at different positions (two at the edges and one at the center)
CWO; and (2) to evaluate some characteristics of these films, with the exception of the water vapor permeability analysis, where
such as their physical, mechanical, thermal and structural prop- the whole sample was used, and replicates of each type of film were
erties, to examine their potential applications as packaging evaluated.
material.
20 days and weighed. Dry-matter densities were calculated using 0.8 mm/min. A microcomputer was used to record the stress-strain
Eq. (1): curves. Tensile strength (TS and elongation at break (EAB) were
m calculated. Four replicates were used for the tensile testing.
s = (1)
A×ı
2.4.6. Thermogravimetric (TGA) analysis
where A is the film area (1 cm2 ), ı is the film thickness (cm),
Thermogravimetric (TGA) analysis was performed to evaluate
m is the film dry mass (g) and s is the dry-matter density of the
the thermal stabilities of composite films using a TGA 2950 running
film (g/cm3 ). The film density was expressed as the average of three
with the Universal Analysis Software package V.3.9a (TA Instru-
determinations.
ments, New Castle, DE, USA). Samples of approximately 5 mg were
heated from 50 to 500 ◦ C at 10 ◦ C/min heating rate under a nitrogen
2.4.3. Moisture uptake
flow of 70 mL/min. Weight losses of samples were measured as a
Moisture uptake was measured as described in our previous
function of temperature. TGA was run in duplicate.
study [32]. Prior to testing all specimens were cut to a square piece
of 2.0 cm × 2.0 cm and conditioned using anhydrous calcium sul-
phate at 0% RH for 48 h. The films were accurately weighed to 2.4.7. Differential scanning calorimetry (DSC)
give the dried film (Wi ). After weighing, they were conditioned at A differential scanning calorimetry was performed using a DSC
23±1 ◦ C in a desiccator containing potassium sulphate saturated Q100 (TA Instrument, New Castle, DE, USA) in accordance to ASTM
solution to ensure a relative humidity of 97%. The samples were D3418 [35] with some modifications as described below. An empty
removed from the desiccator after 48 h and weighed (W1 ). The pan was used as an inert reference and the calibration was per-
moisture uptake values of the samples were calculated using the formed using the indium standard. Samples were heated up at a
following equation (2): heating rate of 10 ◦ C/min between temperature ranges of 0 and
350 ◦ C under a nitrogen flow of 70 mL/min. The data obtained
(W1 − Wi )
% moisture uptake = × 100 (2) was then analyzed by using the Thermal Analysis Universal 2000
Wi
version 4.5A software (TA Instrument, New Castle, DE, USA). DSC
where W1 is the weight of the film sample after exposure to 97% analysis was conducted in duplicate.
RH for 48 h, and Wi is the initial weight of the sample. Each test con-
sisted of triplicate measurements and expressed as the mean value. 2.4.8. Fourier-transform-infrared spectroscopy (FT-IR)
FTIR spectra were obtained using ATR accessory. The used of ATR
2.4.4. WVP (Water vapor permeability) to collect IR spectra on solids and liquids has been widely reported
The WVP of films was determined gravimetrically in accordance by Subirade et al. [36]. Other advantages of ATR are the reduced
with ASTM E96/E96 M [33] with some modifications. Films with- time and efforts for sample preparation.
out pinholes or defects were cut into discs with a diameter slightly The Fourier transformed infrared (FT-IR) spectra in the wave-
larger than the diameter of special glass cups with a circular open- length range of 500–4000 cm−1 . were recorded with a Shimadzu
ing of 0.000324 m2 . Each cup was completely filled with calcium IR-Prestige 21 (Columbia, MD., USA) equipped with Miracle ATR
sulphate desiccant (0% RH) and covered with a disc, leaving an accessory from Pike Madison, WI., USA. ATR accessory was
air gap of 1 cm between the film underside and the desiccant. The equipped with a ZnSe crystal and a clamp to optimize the contact
whole system was then placed in a desiccator containing a satu- between the sample and the crystal to control the spectrum qual-
rated sodium chloride solution (75% RH). The RH inside the cell was ity. FT-IR was performed on films measuring about 25 m thick by
always lower than outside, and water-vapor transport was deter- 5 mm width and 5 mm long with a resolution of 8 cm−1 on 64 scans
mined from the weight gain of the permeation cell at a steady state for each spectrum on reflectance mode. Prior to data analysis, all
of transfer. The cups were weighed to the nearest 0.0001 g. Changes the FTIR spectra were normalized by ratioing the intensity of peaks
in the weight of the cup were recorded six times at 1 h interval to the intensity of the highest peak in the region between 2000 and
before a steady state was reached. The slope of each line was calcu- 500 cm−1 .
lated by linear regression using Microsoft® Office Excel 2010 (the
lines’ regression coefficients were >0.998). The water vapor trans-
mission rate (WVTR) was obtained by dividing the slope (g/h) by 2.4.9. Scanning electron microscopy (SEM)
the effective film area (m2 ). This was multiplied by the thickness of A focused ion beam scanning electron microscope cross beam
the film and divided by the pressure difference between the inner (FIB-SEM) from Carl Zeiss Auriga (Tescan Mira 3 XMU, Cranberry
and outer surfaces to obtain the WVP value, which was expressed Township, USA) was used to scan the cross section of the film to
as [g m−1 s−1 Pa−1 ] and calculated according to Eq. (3): examine the microstructure and the morphology. Film was placed
in liquid nitrogen and hand fractured using a pair of plies to gen-
m X erate cross section. Cross sections were tungsten coated at 3 nm
WVP = (3)
At p thickness under vacuum level of 10−5 Torr. Imaging was collected
using a dual column focused ion beam with Gallium as ion source.
where m is the weight of moisture gain per unit of time (g/s),
t The ion and electron columns were set at a fixed angle of 36◦ . Film
X is the average film thickness (m), A is the area of the exposed
samples were tilted to 54◦ so that the surface is perpendicular to
film surface (m2 ) and p is the water vapor pressure difference
the ion beam. A 5 kV beam energy was used.
between the two sides of the film (Pa). WVP was measured for three
replicated samples for each type of film.
2.4.10. Statistical analysis
2.4.5. Mechanical properties The results were presented as the mean ± standard deviation of
The mechanical properties of the composite films were deter- each treatment. The experiments were factorial with a completely
mined at 22 ◦ C and 30% RH with an Instron 5565 Universal Testing randomized design using analysis of variance (ANOVA), analyzed
machine (Instron, Canton, MA, USA) according to ASTM standard using SAS software (version 9.3; Statistical Analysis System Insti-
method D882 [34]. Films were cut in rectangular strips of 50 mm tute Inc., Cary, NC, USA). Duncan’s multiple range tests were used
long and 6.35 mm wide. The films were fixed with an initial to compare the differences among the mean values for the films’
grip separation of 25 mm and stretched at an extension speed of properties at the level of 0.05.
292 Z. Shen, D.P. Kamdem / International Journal of Biological Macromolecules 74 (2015) 289–296
Table 1
Physical and mechanical properties of chitosan films containing CEO and CWO essential oils.
Film type Essential oil conc. (% w/w) Moisture uptake (%) Density (g/cm3 ) Tensile strength (MPa) Elongation at break (%)
Values represent the mean ± standard deviation of four replicates for tensile strength and three replicates for other test
Values in a column having different superscript letters are significantly different (P < 0.05).
in EAB was shown after adding 30% CWO; the greatest reduc- 100
tion of EAB was when 30% of CWO was incorporated. This effect
could primarily be explained by the partial replacement of stronger (a)
polymer–polymer interactions by weaker polymer–oil interactions
80
in the film network when essential oil components are present,
which may reduce the cohesion of the polymer network forces, thus
Weight (%)
decreasing the TS. Values of mechanical properties obtained for CH
films were similar to those found by some investigators [41,45], 60
but differed from those obtained in other works [46,47]. Due to the
differences in reactivity in binding or interacting with the polymer
network, different essential oils affected the mechanical properties Chitosan
40
of the films differently. Moreover, the source of chitosan, the acid CWO 10 %
medium used to disperse the polymer and the experimental condi- CWO 20 %
tions (pH, concentration, RH used during equilibration of the film, CWO 30 %
presence of emulsifiers) can explain the observed differences [47]. 20
50 150 250 350 450 550
3.5. Thermal stability Temperature (oC)
100
TGA thermograms showing thermal degradation behavior of CH
films with or without CEO and CWO are shown in Fig. 2. (b)
The films’ corresponding degradation temperatures (Td), weight
80
loss (w) and residue are presented in Table 2. The control CH
film generally exhibited three main stages of weight loss. Previ-
Weight (%)
Table 2
Thermal degradation temperature (Td, ◦ C) and weight loss (w, %) of chitosan films incorporated different concentrations of citronella essential oil (CEO) and cedarwood oil
(CWO).
CWO 10 117.67 8.94 278.67 18.99 334.43 21.76 423.74 9.75 472.95 9.36 31.19
20 103.04 9.18 274.33 17.22 338.43 24.71 443.16 6.38 480.04 12.46 30.05
30 119.87 6.40 260.51 20.30 342.31 22.73 440.96 9.84 477.86 12.49 28.24
1, 2, 3, 4 and 5 indicate the first, second, third, fourth and fifth stage weight loss, respectively, of film during heating scan
3.6. Thermal properties exothermic peak at the higher temperature was associated with
polymer decomposition. As shown in Fig. 3, the exothermic tem-
Typical DSC thermograms (Fig. 3) show that all CH film (with peratures of those films containing 10% w/w CEO and CWO were
or without essential oils) produces one broad endothermic peak higher than the control films. This clearly showed that both CEO
at approximately 140 ◦ C and one exothermic peak at 290 ◦ C. As and CWO contributed to an improvement in the thermal stability
we commented in the TGA results, the endothermal effect can be of the CH films. However, adding more of either CEO or CWO did
related to the evaporation of residual solvent used in the prepa- not further improve the films’ thermal stability.
ration of the films. With the 10% w/w increase of either CEO or
CWO, no difference was found in this endothermic peak. However, 3.7. Structural properties
the peak tended to shift to lower temperatures with the increase
of oil concentration to 30% w/w. This change could be explained To identify possible molecular interactions between CH func-
by the crystallinity of film samples. The results suggested that tional groups and the two essential oils studied in this work, FTIR
adding high concentrations of CEO or CWO into CH film changes the spectroscopy analysis was performed. The FT-IR spectra of control
film’s intermolecular interactions, leading to the observed changes
in the degree of crystallinity. Similar behavior was observed 1022
Chitosan
when ␣-tocopheryl acetate adding into chitosan film [49]. The (a) 1060
CWO 10 % 894
CWO 20 % 1149
1647
Endo
Chitosan
CWO 10 %
CWO 20 %
CWO 30 % 3600 3100 2600 2100 1600 1100 600
Wave number (cm-1)
0 50 100 150 200 250 300 350
Temperature (oC)
1149
Chitosan 894
(b) CEO 10%
(b) CEO 20% 1562
3352
2870 CEO 30%
Endo
1647
Absorbance
Chitosan
CEO 10 % 1022
CEO 20 % 1257
CEO 30 %
0 50 100 150 200 250 300 350 3600 3100 2600 2100 1600 1100 600
Temperature (oC) Wave number (cm-1)
Fig. 3. Results of thermal stability of chitosan composite films containing various Fig. 4. FTIR spectra of chitosan composite films including various concentrations
concentrations of (a) cedarwood oil (CWO) and (b) citronella essential oil (CEO) of (a) cedarwood oil (CWO) and (b) citronella essential oil (CEO). Please see online
analyzed through TGA. Please see online edition for color images. edition for color images.
Z. Shen, D.P. Kamdem / International Journal of Biological Macromolecules 74 (2015) 289–296 295
CH films and those incorporated with CEO and CWO at different of CEO and CWO-containing films were analysed and compared,
concentrations are shown in Fig. 4. it was hard to find any difference; this that little chemical inter-
All FTIR spectra showed quite similar general features, with action had taken place during the film preparation. However, the
most of the peaks characteristic of CH films as reported by Silva- addition of more CEO (30% w/w) resulted in a marked increase in
Weiss et al. [50]. The peaks at 894, 1022, 1060 (C O stretching) the intensity of the CH stretching peak at around 2870 cm−1 , sug-
and 1149 cm−1 (asymmetric stretching of C O C bridge, glycosidic gesting an increase in the content of ester groups, which might
linkage) were associated with the structure of pure CH, and were come from the CEO molecule. A new peak at 1257 cm−1 was
common to all films. The band located at 1378 cm−1 is assigned to observed at higher concentrations of CEO, which can be related
the acetamide groups, indicating that CH is not completely deacety- to the bending vibration of the OH groups from the phenol group
lated [51]. The absorption peak at 1647 cm−1 was attributed to present in the essential oil structure [40]. Besides, the new peak
C O stretching (amide I), and the one at 1554 cm−1 corresponded appeared at 1562 cm−1 which might be due to the interaction of the
to N H bending (amide II) [52]. At the same time, these bands amine group with a functional group of the essential oil. Another
showed stronger peak intensity in those films containing oils com- important change was found with a new peak at 1647 cm−1 , indi-
pared with those of pure CH. The bands appearing at 2930 and cating an ester linkage, which could be attributed to the more
2870 cm−1 in the spectrum of CH film occur because of stretching intensive interaction between CH and essential oil. The absorp-
vibrations of the C H bond in CH2 and CH3 groups, respec- tion intensity increased with increasing oil concentration. A shift
tively [53]. These peaks became more flattened when 30% essential of the peak at 1026 cm−1 to 1022 cm−1 was noted for the 10%
oil was included. This may be due to hydrogen bonding between w/w CEO-containing film; this could be ascribed to C O stretching
the OH group in functional groups in oil ingredients and the of hydroxyl and ether bonds. Such a shift toward lower wave-
NH and OH groups in CH. Moreover, the CH film exhibited a number values indicates weaker interactions with these essential
strong absorption band between 3190 and 3352 cm−1 that cor- oils. All these changes led to an assumption that intermolecular
responded mainly with the stretching vibration of free hydroxyl interaction and molecular compatibility between the essential-oil
and to the asymmetric and symmetric stretching of the N H bonds ingredients’ functional groups and hydroxyl and amino groups in
[46]. When the band intensities of the spectra of 10% and 20% w/w the CH matrix could exist. This information may explain the weaker
Fig. 5. Scanning electron microscopy micrographs of the cross section of films (a) chitosan film, (b) film containing 10% essential oil, (c) film containing 20% essential oil, and
(d) film containing 30% essential oil viewed at a magnification of 6500×.
296 Z. Shen, D.P. Kamdem / International Journal of Biological Macromolecules 74 (2015) 289–296
mechanical properties of these films reported in the previous sec- [7] M. Ghasemlou, N. Aliheidari, R. Fahmi, S. Shojaee-Aliabadi, B. Keshavarz, M.J.
tion. Cran, R. Khaksar, Carbohydr. Polym. 98 (2013) 1117–1126.
[8] M. Rinaudo, Prog. Polym. Sci. 31 (2006) 603–632.
[9] M.N. Ravi Kumar, React. Funct. Polym. 46 (2000) 1–27.
3.8. Microstructure [10] P. Dutta, S. Tripathi, G. Mehrotra, J. Dutta, Food Chem. 114 (2009) 1173–1182.
[11] I. Leceta, P. Guerrero, K. de la Caba, Carbohydr. Polym. 93 (2013) 339–346.
[12] Y. Ruiz-Navajas, M. Viuda-Martos, E. Sendra, J. Perez-Alvarez, J. Fernández-
Fig. 5 shows SEM micrographs of the cross-sections of the films López, Food Control 30 (2013) 386–392.
containing various essential oil concentrations. Films containing [13] Á. Perdones, M. Vargas, L. Atarés, A. Chiralt, Food Hydrocoll. 36 (2014) 256–264.
[14] Y. Peng, L. Yin, Y. Li, Int. J. Food Sci. Technol. 48 (2013) 44–50.
CWO and CEO show a similar microstructure. While a continuous
[15] S. Burt, Int. J. Food Microbiol. 94 (2004) 223–253.
structure was observed for the chitosan film (Fig. 5a), the pres- [16] M. Viuda-Martos, Y. Ruiz-Navajas, J. Fernández-López, J.A. Pérez-Álvarez, Int. J.
ence of essential oil (Fig. 5b–d) caused a heterogeneous structure in Food Sci. Technol. 43 (2008) 526–531.
which oil droplets were entrapped in the continuous carbohydrate [17] A.G. Ponce, S.I. Roura, C.E. del Valle, M.R. Moreira, Postharvest Biol. Technol. 49
(2008) 294–300.
network. The number and size of the lipid droplets were increased [18] L.S. Nerio, J. Olivero-Verbel, E. Stashenko, Biores. Technol. 101 (2010) 372–378.
with the essential oil concentration. Little creaming was observed [19] M. Arancibia, A. Rabossi, P.A. Bochicchio, S. Moreno, M. López Caballero, G.
in the emulsified films at 10% and 20% w/w essential oil concentra- Guillén, P. Montero García, Food Control 44 (2014) 7–15.
[20] C. Pires, C. Ramos, B. Teixeira, I. Batista, M. Nunes, A. Marques, Food Hydrocoll.
tion, probably due to the reduction of oil droplet mobility induced 30 (2013) 224–231.
by the highly viscous effect of chitosan, which, increased when dry- [21] X.-w. Huang, Y.-c. Feng, Y. Huang, H.-l. Li, J. Essent. Oil Res. 25 (2013) 315–323.
ing progressed [52]. Nevertheless, the great oil phase concentration [22] Z. Tunalier, N. Kirimer, K. Baser, J. Essent. Oil Res. 16 (2004) 233–235.
[23] R.P. Adams, S. Li, J. Essent. Oil Res. 20 (2008) 235–242.
(30% w/w) contributes to visible creaming in the micrograph; it was [24] M.Y. Arancibia, M.E. López-Caballero, M.C. Gómez-Guillén, P. Montero, Food
possibly due to the high concentration of essential oil facilitate the Control 44 (2014) 7–15.
aggregation of lipid, which led to flocculation of essential oil in the [25] Q. Chen, S. Xu, T. Wu, J. Guo, S. Sha, X. Zheng, T. Yu, J. Sci. Food Agric. 94 (2014)
2441–2447.
polymer.
[26] P. Tongnuanchan, S. Benjakul, T. Prodpran, Int. J. Food Sci. Technol. 48 (2013)
2143–2149.
4. Conclusion [27] F. Eller, C.A. Clausen, F. Green, S. Taylor, Ind. Crops Prod. 32 (2010) 481–485.
[28] I. Tumen, I. Süntar, F.J. Eller, H. Keleş, E.K. Akkol, J. Med. Food 16 (2013) 48–55.
[29] R.J. Stoklosa, J. Velez, S. Kelkar, C.M. Saffron, M.C. Thies, D.B. Hodge, Green Chem.
This study was the first to explore the physical, thermal and 15 (2013) 2904–2912.
structural properties of CH-based films containing CEO or CWO. [30] C.-S. Wu, Handbook of Size Exclusion Chromatography and Related Techniques:
Revised and Expanded, CRC Press, Boca Raton Florida, 2003.
The addition of either of two essential oils at the lowest concen-
[31] S.M. Ojagh, M. Rezaei, S.H. Razavi, S.M.H. Hosseini, Food Chem. 122 (2010)
tration did not significantly affect the film properties. However, 161–166.
an improvement was observed for the highest concentration of [32] Z. Shen, M. Ghasemlou, D.P. Kamdem, J. Appl. Polym. Sci. (2014).
either essential oil particularly CEO, resulting in a CH film with bet- [33] ASTM Standard E96, Standard Test Methods for Water Vapor Transmis-
sion of Materials, ASTM International, West Conshohocken, PA, 2013,
ter barrier properties than the control film. TGA analysis clearly http://dx.doi.org/10.1520/C0033-13, www.astm.org.
showed that CEO and CWO at various concentrations led to differ- [34] ASTM Standard D882, Standard Test Method for Tensile Properties of
ent thermal stabilities for the resulting CH films. The FTIR spectra Thin Plastic Sheeting, ASTM International, West Conshohocken, PA, 2009,
http://dx.doi.org/10.1520/C0033-09, www.astm.org.
analysis indicated that a strong interaction occurred between CH [35] ASTM Standard D3418, Melting Point by DSC Testing Services, ASTM Inter-
and each essential oil. This may answer the question of how to pro- national, West Conshohocken, PA, 2003, http://dx.doi.org/10.1520/C0033-03,
duce extremely flexible CH films when essential oil is included in www.astm.org.
[36] M. Subirade, I. Kelly, J. Guéguen, M. Pézolet, Int. J. Biol. Macromol. 23 (1998)
the matrix. Overall, this study suggests that it is possible to formu- 241–249.
late CH films having CEO or CWO. Nevertheless, in vivo studies are [37] M. Islam, S.M. Masum, M.M. Rahman, M. Molla, A. Islam, A. Shaikh, S. Roy, Int.
required to evaluate the possible interactions between the film con- J. Basic Appl. Sci. 11 (2011).
[38] G.J. Tsai, W.H. Su, H.C. Chen, C.L. Pan, Fish. Sci. 68 (2002) 170–177.
stituents and the food matrix. Additional work is in progress in our
[39] J.Z. Knaul, M.R. Kasaai, V.T. Bui, K.A. Creber, Can. J. Chem. 76 (1998) 1699–1706.
research group to study the antimicrobial and antifungal activity of [40] D. Salarbashi, S. Tajik, M. Ghasemlou, S. Shojaee-Aliabadi, M. Shahidi Noghabi,
these films. R. Khaksar, Carbohydr. Polym. 98 (2013) 1127–1136.
[41] J.T. Martins, M.A. Cerqueira, A.A. Vicente, Food Hydrocoll. 27 (2012) 220–227.
[42] M. Hosseini, S. Razavi, M. Mousavi, J. Food Process. Preserv. 33 (2009)
Acknowledgments 727–743.
[43] S. Shojaee-Aliabadi, H. Hosseini, M.A. Mohammadifar, A. Mohammadi, M.
Ghasemlou, S.M. Ojagh, S.M. Hosseini, R. Khaksar, Int. J. Biol. Macromol. 52
The authors gratefully acknowledge the financial assistance pro-
(2013) 116–124.
vided by the School of Packaging, Michigan State University. We are [44] N. Aliheidari, M. Fazaeli, R. Ahmadi, M. Ghasemlou, Z. Emam-Djomeh, Int. J.
also thankful to Muyang Li for GPC analysis. Biol. Macromol. 56 (2013) 69–75.
[45] W. Thakhiew, S. Devahastin, S. Soponronnarit, J. Food Eng. 119 (2013) 140–149.
[46] M. Vargas, A. Albors, A. Chiralt, C. González-Martínez, Food Hydrocoll. 23 (2009)
References 536–547.
[47] L. Sánchez-González, M. Cháfer, A. Chiralt, C. González-Martínez, Carbohydr.
[1] R. Tharanathan, Trends Food Sci. Technol. 14 (2003) 71–78. Polym. 82 (2010) 277–283.
[2] G. Robertson, in: E. Chiellini (Ed.), Environmentally Compatible Food Packaging, [48] D. Altiok, E. Altiok, F. Tihminlioglu, J. Mater. Sci.: Mater. Med. 21 (2010)
Woodhead Publishing, Cambridge, UK, 2008, pp. 3–28. 2227–2236.
[3] A. Lopez-Rubio, E. Almenar, P. Hernandez-Muñoz, J.M. Lagarón, R. Catalá, R. [49] S.-i. Park, Y. Zhao, J. Agric. Food Chem. 52 (2004) 1933–1939.
Gavara, Food Rev. Int. 20 (2004) 357–387. [50] A. Silva-Weiss, V. Bifani, M. Ihl, P. Sobral, M. Gómez-Guillén, Food Hydrocoll.
[4] S. Shojaee-Aliabadi, H. Hosseini, M.A. Mohammadifar, A. Mohammadi, M. 31 (2013) 458–466.
Ghasemlou, S.M. Hosseini, R. Khaksar, Carbohydr. Polym. 101 (2014) 582–591. [51] I. Leceta, P. Guerrero, I. Ibarburu, M. Dueñas, K. De la Caba, J. Food Eng. 116
[5] D. Salarbashi, S. Tajik, S. Shojaee-Aliabadi, M. Ghasemlou, H. Moayyed, R. Khak- (2013) 889–899.
sar, M.S. Noghabi, Food Chem. 146 (2014) 614–622. [52] J. Brugnerotto, J. Lizardi, F. Goycoolea, W. Argüelles-Monal, J. Desbrieres, M.
[6] E. Almenar, R. Catala, P. Hernandez-Muñoz, R. Gavara, LWT-Food Sci. Technol. Rinaudo, Polymer 42 (2001) 3569–3580.
42 (2009) 587–593. [53] M. Abdollahi, M. Rezaei, G. Farzi, Int. J. Food Sci. Technol. 47 (2012) 847–853.