Food Hydrocolloids 106 (2020) 105862

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Food Hydrocolloids
journal homepage: http://www.elsevier.com/locate/foodhyd

Pectin films loaded with copaiba oil nanoemulsions for potential use as
bio-based active packaging
L.B. Norcino a, **, J.F. Mendes b, C.V.L. Natarelli a, A. Manrich c, J.E. Oliveira d, *, L.H.C. Mattoso c
a
Graduate Program in Biomaterials Engineering, Federal University of Lavras, Lavras, 37200-000, MG, Brazil
b
Graduate Program in Food Sciences, Federal University of Lavras, Lavras, 37200-000, MG, Brazil
c
National Laboratory of Nanotechnology for Agriculture (LNNA), Embrapa Instrumentation, S~ ao Carlos, 13560-970, SP, Brazil
d
Department of Engineering, Federal University of Lavras, Lavras, 37200-000, MG, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: The objective of this study was to prepare pectin films (PEC) activated by copaiba oil (CP) nanoemulsions (NE).
Biodegradable film CP-NE were added to film-forming formulations based on pectin and then dried into films by continuous casting.
Pectin Chemical, morphological, thermal, mechanical and antimicrobial properties were studied in addition to biode­
Nanoemulsion
gradability by the respirometer test. In general, the nanoemulsions were suitably dispersed in the PEC matrix,
Biodegradation
Copaiba oil
both phases showing good interaction and compatibility. The nanoemulsions caused large changes in PEC, such
as increased roughness with oil concentration, gradual reduction of the elastic modulus and tensile strength,
increased elongation at break, and antimicrobial activity against S. aureus and E. coli. Another important
observation was the maintenance of the biodegradation profile of the films after the addition of CP-NE. In
conclusion, the active pectin film manufactured with CP emulsions showed great potential for active food
packaging and is a promising alternative to reduce environmental impacts.

1. Introduction filmogenic capacity and potential application in active packaging (Nisar

et al., 2018).
In recent years, global concern about the amount of nonbiodegrad­ In recent years, interest in the development of active packaging by
able polymers discarded into the environment has been boosting the the food industry has increased considerably due to the desire to ensure
development of eco-compatible materials (Nisar et al., 2018). Biode­ extra the quality and safety of food products. Active agents, such as
gradable polymers have been gaining prominence due to the potential antioxidants or antimicrobials, are incorporated into the packaging
application of these materials in various industrial sectors and for sus­ rather than being added directly to the food, so these can be enriched
tainability and environmental protection issues. They have advantages through the migration of these substances. Recent studies have explored
due to their biodegradability and biocompatibility and because they are the potential of pectin films for the preparation of active food packaging
obtained from renewable sources such as lipids, proteins, and poly­ (Bayarri, Oulahal, Degraeve, & Gharsallaoui, 2014; Eça, Machado,
saccharides (Arfat, Benjakul, Prodpran, Sumpavapol, & Songtipya, Hubinger, & Menegalli, 2015; Mendes et al., 2016; Nisar et al., 2018;
2014; Müller, Renner, Mo �czo
�, Fekete, & Puka �nszky, 2014; Ortega-Toro, Otoni et al., 2014; Ranjbaryan, Pourfathi, & Almasi, 2019).
Jim�enez, Talens, & Chiralt, 2014). Oils extracted from plants are generally recognized as safe (GRAS)
Pectin (PEC) is a term used to describe a group of polysaccharides food additives. They have received much attention for use as active
found in cell walls and intercellular regions of plants and fruits. Its main agents in biodegradable films, mainly due to their safety and antimi­
sources are citrus fruit, sugarcane, and apple processing waste. It is crobial activity. Copaiba (CP) oil is an oil-resin native to tropical regions
anionic, amorphous, nontoxic, and easily solubilized in water poly­ and, in Brazil, is easily found in the Amazon and Central regions (Valdir
saccharides. Its chemical composition is mostly defined by helical chains F. Veiga & Pinto, 2002). Today, it is one of the most important natural
of poly [α-(1 → 4)-D-galacturonic acid] or homogalacturonan (Willats, commercial products of northern Brazil. According to the Brazilian
Knox, & Mikkelsen, 2006). Pectin is also known for its excellent Institute of Geography and Statistics (Instituto Brasileiro de Geografia

* Corresponding author. Engineering Department (DEG), Federal University of Lavras, Lavras, MG, 37200-000, Brazil.
** Corresponding author. Forest Sciences Department (DCF), Federal University of Lavras, Lavras, MG, 37200-000, Brazil.
E-mail address: laisnorcino@hotmail.com (J.E. Oliveira).

https://doi.org/10.1016/j.foodhyd.2020.105862
Received 10 December 2019; Received in revised form 13 March 2020; Accepted 13 March 2020
Available online 19 March 2020
0268-005X/© 2020 Elsevier Ltd. All rights reserved.
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

and Estatística), in 2017, 140 t of copaiba oil were produced, mainly in Pharmakos D’Amazo ^nia (Manaus, Brazil). Glycerol (>99.5% pure) and
the state of Amazonas (IBGE, 2017). This oil is also exported to the Tween 80 were purchased from Synth (Diadema, SP, Brazil). Deionized
United States, France, Germany, and England (Valdir F. Veiga & Pinto, water (ρ > 18.2 MΩ cm) was obtained by a purification system Barn­
2002). It has numerous important properties, such as analgesic, anti­ stead Nanopure Diamond™ (Thermo Fisher Scientific Inc, USA).
parasitic, anti-inflammatory, larvicide, expectorant, diuretic, and anti­
bacterial activity (Bonan et al., 2015; Dos Santos et al., 2008; Gelmini 2.2. Preparation of nanoemulsions
et al., 2013; Trindade, Stabeli, Pereira, Facundo, & Silva, 2013). The
bioactive compounds present in higher amounts in CP are the sesqui­ The emulsions were prepared following the method described by
terpenes and diterpenes. Since it is a natural product, CP has become Noori et al. (2018), with modifications. Direct oil-in-water (O/W)
attractive for use in the food industry because consumers look for emulsions were prepared by adding CP at 1, 3, and 6% (wt. of water) and
healthier alternatives to conventional additives. Morelli et al. (2015) Tween 80 (1% wt. of CP) to ultrapure water. Then, both oily and
studied the addition of CP to films based on poly (lactic acid) and paper aqueous phases were mixed under magnetic stirring at 3400 rpm for 1
produced by casting and impregnation techniques and found it had min at room temperature to obtain a coarse emulsion. Then the ultra­
antimicrobial activity against the gram-positive bacterium Bacillus sonic emulsification was used to convert the coarse emulsion to a
subtilis. nanoemulsion. A probe sonicator (Branson, Danbury, United States)
The incorporation of natural oils into filmogenic solutions presents operating at 20 kHz and 150 W was used for nanoemulsification. The
some challenges. Their low miscibility and phase separation during the probe of the apparatus, with a diameter of 15 mm, was dipped into the
film formation process, their adverse effects on film transparency, and coarse emulsion at the depth of 25 mm, and nanoemulsification went on
the sensitivity of bioactive compounds to environmental factors (e.g., for 5 min. The obtained nanoemulsions were stored in an amber glass
UV radiation, temperature, oxygen, pH, and humidity) are the most flask, covered with a screw-cap, and kept under darkness.
common deficiencies in the direct addition of bioactive compounds to
biodegradable active films (Atar� es & Chiralt, 2016). Natural oils are
2.3. Droplet size, size distribution, and short-term stability
usually emulsified in the film-forming dispersion to develop into a film
or active coating after drying. Therefore, it is expected that the particle
The droplet diameter (indicated by z-average) and diameter distri­
size of the emulsified oil has significant effects on the functional
bution (indicated by polydispersity index, PdI) were determined by
properties.
dynamic light scattering on a Zetasizer Nano ZS (Malvern Instruments
The nanoemulsions (NE) consist of colloidal dispersions composed of
Inc., Worcestershire, U.K.). Ultrapure water was used as a dispersant to
an oily phase (e.g., hydrocarbons or triglycerides) and an aqueous phase
avoid multiple scattering as well as interdroplet dispersion and inter­
(for example, water or water combined with an electrolyte or polyol),
action effects. Measurements were carried out soon after emulsification
which are present as droplets with smaller diameters (500 nm) (Otoni,
as well as after sitting at room temperature for 24 h to assess stability
Avena-Bustillos, Olsen, Bilbao-S� ainz, & McHugh, 2016). Due to the
during a typical film-forming period. All measurements were done in
small size of the particles, there is a reduction of the gravitational force,
triplicate and mean values were reported.
allowing the Brownian motion to be sufficient to overcome the force of
gravity, thereby avoiding coalescence or flocculation, interface defor­
mation and disruption, and sedimentation during storage (Espitia, 2.4. Pectin–copaiba oil film-forming protocol
Fuenmayor, & Otoni, 2019; McClements & Gumus, 2016).
Nanoemulsions have two significant properties: (i) high physico­ Solutions (6% wt.) of PEC was prepared by dissolving powdered
chemical activity and stability and (ii) improved biological properties, pectin in ultrapure water, and the mixture was totally homogenized with
such as high specific surface area and, therefore, low necessary amounts the aid of a T25 Ultra-Turrax mixer (IKAWerk GmbH & Co, Staufen,
of active components (McClements, 2012; Mcclements & Rao, 2011). A Germany) operating at 12,000 rpm for 10 min. Glycerol was then added
significant improvement in the antibacterial properties of the nano­ at 15 wt% (dry basis) and combined at 1:1 (weight ratio) with the
emulsions loaded with natural oils, compared to the respective con­ previously prepared nanoemulsions (1–6% w/w), homogenized in a T25
ventional emulsions, was reported by Liang et al. (2012), Noori, Zeynali, Ultra-Turrax mixer (IKAWerk GmbH & Co, Staufen, Germany) operating
and Almasi (2018), and Severino et al. (2015). at 12,000 rpm and vacuum-degassed for 20 min. Finally, the PEC and
The objective of this study, given the environmental problems caused PEC/nanoemulsion formulations were dried in a coating apparatus
by the use of nonbiodegradable materials previously surveyed, as well as (Mathis®, KTF-S-B, Switzerland) by continuous casting. Aqueous mix­
the trend towards the use of antimicrobial agents in active packaging, tures were poured in a coating device, where they were spread onto a
was to produce biodegradable pectin-based films containing CP nano­ polyester sheet conveyor using a doctor knife type B. The wet layer
emulsions. As far as we know, this is the first article on how the anti­ thickness was kept at 1.5 mm by accurately (�0.01 mm) setting the knife
microbial CP nanoemulsion affects the biodegradation process of active height above the conveyor. The wet layer was then conveyed at rolling
pectin films that were produced continuously using a pilot-scale lami­ speed of 10 cm min 1 across two oven-drying stages at 70 � C, conditions
nating unit. Finally, the antimicrobial, physico-chemical, and mechan­ which had been reported to allow complete drying (Lorevice, Otoni,
ical properties of the PEC films loaded with CP nanoemulsions were Moura, & Mattoso, 2016; Manrich et al., 2017; Otoni et al., 2016). Dried
evaluated. The results of this study may have important implications for films were allowed to equilibrate in a desiccator at 52 � 3% RH and 25
future applications in the food industry as active packaging as well as a � 2 � C for at least 48 h before further steps.
promising alternative for the reduction of environmental impacts caused
by conventional nonbiodegradable polymers. 2.5. Thermogravimetry

2. Materials and methods Film samples (5–6 mg) were accurately weighed in a platinum pan
and heated from 25 to 600 � C at a rate of 10 � C min 1, within an at­
2.1. Materials mosphere comprising synthetic air (21% O2) flowing at 40 mL min 1.
Sample weight as a function of temperature was monitored by a high-
Citrus high-methoxyl pectin (PEC) with a poly (galacturonic acid) precision balance within an atmosphere of nitrogen flowing at 60 mL
content of 84%, a methoxylation degree (MD) of 8.4%, and a weight- min 1 on a TA Q500 (TA Instruments, Inc., New Castle, USA) to obtain
average molecular weight (Mw) of 1.3 � 105 g mol 1 was kindly pro­ thermogravimetric (TG) and derivative TG (DTG) curves. At least 2
vided by CP Kelco (Limeira, SP, Brasil). CP was purchased from replicates were performed for each sample.

2
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

2.6. FTIR vibrational spectroscopy

142:86 x b*
YI ¼ (3)
Fourier transform infrared spectroscopy measurements were ob­ L*
tained using a FTIR model Vertex 70 Bruker spectrophotometer (Bruker, qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Germany) equipped with a single-reflection diamond crystal ATR WI ¼ 100 ð100 L* Þ2 þ ða* Þ2 þ ðb* Þ2 (4)
module. Spectra were recorded at a spectral range between 400 and
All measurements were done in triplicate.
4000 cm 1 at a scan rate of 32 scans and spectral resolution of 4 cm 1.
At least 2 replicates were performed for each sample.
2.11. Water vapor permeability (WVP)

2.7. X-ray diffraction (XRD) The water barrier properties of the films were determined using a
modified ASTM method E96/16 (ASTM E96, 2016). The samples were
The crystalline structure of the films was analyzed through diffrac­ cut into circles and sealed on the top of permeation cells containing
tion patterns obtained on an XRD-6000 X-ray diffractometer (Shimadzu, dried silica gel to provide constant RH. Then, the cells were stored in a
Kyoto, Japan). Samples were scanned from 5 to 40� (2θ) at 1� min 1. desiccator containing distilled water (100% RH; 2.337 � 103 Pa vapor
Crystallinity index (CI) was determined based on the areas under the pressure at 20 � C). Afterwards, the amount of water vapor transferred
Gaussian-deconvoluted crystalline and amorphous peaks after baseline through the film was quantified gravimetrically over 8 h. WVP (g.mm.
correction. At least 2 replicates were performed for each sample. kPa 1.h 1.m 2) was calculated by Eq. (5):
Wxδ
2.8. Scanning electron microscopy (SEM) WVP ¼ (5)
A:t: ΔP

Morphological characterization was performed using a JSM-6510 Where W is change in cell weight [g], δ is average film thickness [m],
microscope (JEOL Ltd., Japan) running at 5 kV and a working dis­ and A, t, and ΔP are exposed film area [m2], time [s], and partial water
tance of 2–3 mm. Cross-sectional views of polymer samples were pre­ vapor pressure differential [Pa], respectively. The average WVP value
pared by freeze-fracturing in a liquid nitrogen bath ( 165 � C for 3 min). for each sample was obtained in triplicates.
All samples were coated with gold (~5 nm) in an argon atmosphere.
Samples were prepared by deposition of powders on conductive graphite 2.12. Contact angle measurements
paint (SPI Supplies, USA). All images were recorded in secondary elec­
tron mode. Contact angle was determined in a CAM 101 Optical Contact Angle
Meter (KSV Instruments) equipped with a CCD KSV-5000 digital camera.
2.9. Mechanical properties For each measurement, 5 μL of ultrapure water was dropped onto film
surface and 100 images were automatically recorded within an experi­
Films were submitted to a uniaxial tensile assay on a DL3000 uni­ mental time of 60 s using the KSV CAM2008 software. Contact angle
versal testing machine (EMIC, S~ ao Paulo-SP, Brazil). Tests were carried determinations were performed with 5 replicates as per ASTM D5725-99
out according to ASTM D822-09 (ASTM, 2009) and other studies (Abral (ASTM, 2009).
et al., 2019; Saricaoglu, Tural, Gul, & Turhan, 2018). At least six 15-mm
wide, 100-mm long, and ~0.8-mm-thick (measured using an IP65 2.13. Antimicrobial properties
Mitutoyo digital micrometer at five random positions) specimens per
treatment were stretched at 25 mm min 1 using an initial Stock cultures of E. coli (ATCC 11229) and S. aureus (ATCC 6538)
clamp-to-clamp distance of 50 mm and a 50-kgf load cell. The elastic were maintained at 80 � C until grown in tubes with tryptic soy broth
modulus (EM) was determined from the linear slope of the stress-ver­ (TSB) (Acumedia Manufactures, Inc., Lansing, MI) at 37 � C for 24 h, and
sus-strains curves. The tensile strength (TS) was calculated by dividing then in different tubes with TSB at 37 � C for 12 h. The suspensions were
the maximum force by the initial cross-sectional area. Elongation at streaked on solidified tryptic soy agar (Acumedia Manufactures, Inc.)
break (ε) was calculated by Eq. (1), wherein d is the final displacement and incubated at 37 � C for 18–24 h. Disk inhibition tests were performed
and d0 is the initial clamp-to-clamp distance: according to M07-A9 (CLSI, 2012). Colonies isolated from the cultures
were inoculated into 0.85% w/v) NaCl solutions until 0.5 McFarland
standard turbidity was matched (108 CFU mL 1). The suspensions were
d d0
εð%Þ ¼ x 100 (1)
d0 plated with swabs onto solidified Mueller–Hinton agar (Becton, Dick­
The elastic modulus (E) was determined from the linear slope of the inson and Co., Sparks, MD). Film discs (1 cm diameter) were exposed to
stress-versus-strain curves. At least 15 replicates were performed for each UV light (110 V and 254 nm) for 2 min on each side before being placed
sample. at the midpoint of the inoculated Petri dishes, which were incubated at
37 � C for 16–18 h. The diameters of the inhibition zones around the films
(colony-free areas) were measured to the nearest 0.01 mm with a digital
2.10. Optical properties
caliper (Mitutoyo Corp.), and the growth below the film discs was
visually evaluated.
Colorimetric parameters of the films were determined using a Konica
Minolta CM-5 colorimeter (Minolta Camera Co., Ltd, Osaka, Japan). A
white standard color plate (L* ¼ 91.76, a* ¼ 0.25, b* ¼ 0.40) was 2.14. Sensory evaluation
used for calibration and as background before luminosity (L*) as well as
the chromatic coordinates a* and b* were determined by reflectance The aroma and color sensory attributes of the pectin-based films
according to the CIE L*, a*, and b* scale. The color parameters were used were determined using an untrained panel constituted by 70 judges, in
to calculate total color difference (ΔE*, Eq. (2)), yellowness index (YI, accordance with the 9-point hedonic scale. Films were cut into 2 cm
Eq. (3)), and whiteness index (WI, Eq. (4)): diameter circles and the evaluations were performed in individual
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi booths under artificial daylight at temperatures ranging between 22 and
ΔE* ¼ ðΔL* Þ2 þ ðΔa* Þ2 þ ðΔb* Þ2 (2) 24 � C with air circulation and the samples were evaluated in a monadic
manner. The samples (one unit at a time) were served in disposable cups
coded with randomized 3-digit numbers. A 9- point structured hedonic

3
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

scale was used for quantifying acceptability, which ranged from “(1) nanoemulsion repel each other to prevent coalescence from occurring,
extremely disliked” to “(9) extremely liked” (Ferreira Saraiva et al., keeping them stable, and may be influenced by changes in the interface
2014). The study plan was previously evaluated by the Research Ethics with the dispersant medium (Roland, Piel, Delattre, & Evrard, 2003). In
Committee of the Federal University of Lavras (Lavras - MG, Brazil; general, the zeta potential did not change drastically during the storage
under resolution # 165 89319918.9.0000.5148), which endorsed the period (Table 1), keeping the system stable. The nanoemulsions pre­
development of this study (protocol # 166 2746637). pared in this study contained a nonionic surfactant (Tween 80). There­
fore, an electric charge close to zero would be expected. However, the
2.15. Biodegradation films containing CP had a highly negative zeta potential that may be
associated with the presence of ionizable groups on the surface of the CP
The polymer films were subjected to respirometry testing to quantify droplets, such as resin acids, which can be divided at the interface of
the production of carbon dioxide released by microbial respiration and nanoemulsions due to the power of ultrasonic energy (Acevedo-Fani,
to evaluate their biodegradation, according to the NBR 14283 - ABNT Salvia-Trujillo, Rojas-Graü, & Martín-Belloso, 2015; Dias et al., 2014;
(ABNT, 1999). Biometer flasks, used as originally suggested by Bartha Leandro et al., 2012).
and Pramer (1965), each containing 50 g of soil þ polymer sample Acevedo-Fani et al. (2015) also observed negative zeta potentials in
(duplicate), were incubated at 28 � C � 2 � C for 28 days. CO2 production sage essential oil nanoemulsions with Tween 80 and attributed this
was measured volumetrically at intervals of approximately 24 h. At least result to exposure of the emulsions to the severe mechanical stresses of
3 replicates were performed for each sample. ultrasonication, which may have caused the release of hydroxyl and
carboxyl groups from the oil that moved towards the surface of the
2.16. Statistical analyses droplets and bound to water (Chen, Gao, Yang, & Gao, 2013). The
electric charge of the droplets plays an important role in the stability of
The results were submitted to a one-way analysis of variance the nanoemulsions, and when the charge is sufficiently large, the
(ANOVA), and the means were compared by Tukey’s test at a confidence droplets are prevented from aggregating due to the electrostatic repul­
level of 95% (p < 0.05), using the software Origin, version 6.0 (Origin sion between them.
Lab, Northampton, MA, USA). The formulations containing CP during the observed period had PdI
values ranging from 0.2 to 0.5, indicating a unimodal behavior with a
3. Results and discussion narrow droplet size distribution in the formulations. Even though the
droplet size increased, the PdI value remained below 0.6, indicating the
3.1. Droplet size, zeta-potential and polydispersity index (PdI) homogeneity of the droplets in the formulations (Tang, Manickam, Wei,
& Nashiru, 2012).
The mean droplet diameter, zeta potential, and polydispersion index
of CP nanoemulsions are shown in Table 1. 3.2. Thermal properties
Ultrasonication can reduce droplet size in an oil-in-water emulsion to
the nanoscale because high energy inputs create deforming forces that The TGs and their first derivatives (DTG) for making PEC-based films
overcome Laplace pressure and break droplets up into smaller ones are shown in Fig. 1. The temperatures corresponding to the onset (Tonset)
(Noori et al., 2018; Ranjbaryan et al., 2019), and this was confirmed in and offset (Toffset) of the thermal degradation are shown in Table 2.
the present study: characterization of CP-NE revealed that a nanosized CP is a natural oil-resin composed of a solid, a resin, and a nonvol­
emulsion was successfully prepared (Table 1). atile fraction made of diterpenes. This resin and viscous fraction are
Curiously, the increase in CP content led to smaller droplets, sug­ diluted in another fraction, an essential oil, a volatile, and a fluid,
gesting that some CP amphiphilic components may contribute to droplet including sesquiterpenes such as α-humulene, α- and β-selinene,
size reduction (Bonilla, Atar�es, Vargas, & Chiralt, 2012). Particles are β-bisabolene, and β-caryophyllene (Veiga, Rosas, Carvalho, Henriques,
susceptible to gravitational forces regardless of their dimensions, but it & Pinto, 2007). Due to the existence of different types of oil resins, each
is less likely that sedimentation of nanoparticles occurs compared to fraction differs, and consequently, the CP has a varied composition,
conventional droplets because the Brownian motion of smaller droplets affecting its thermal stability.
is greater than the gravity-induced creaming rate (Huang, Yu, & Ru, The thermogram of CP indicated that the thermal decomposition
2010). This is in agreement with the observation that droplets smaller process was divided into three events. The first event (50–220 � C) is
than 1 μm are normally kinetically stable (Yi, Li, Zhong, & Yokoyama, related to vaporization of the volatile fraction, with sesquiterpenes
2014). Regarding our nanoemulsions, droplet size remained unchanged above 170 � C; the second (215–380 � C) was explained as the boiling
(p > 0.05) after 24 h of emulsification (Table 1), suggesting that stability point of the solid fraction, being for diterpenes above 260 � C; and the
would not be lost due to the coalescence of the droplets, because the third (T > 380 � C) was attributed to the degradation of the remaining
drying conditions allowed dry films to be obtained within minutes, so­ substances (Favvas, Kouvelos, Papageorgiou, Tsanaktsidis, & Mitro­
lidifying the emulsions (Manrich et al., 2017). poulos, 2015; Hazra, Alexander, Dollimore, & Riga, 2004; Svetlichny
The zeta potential is a measure of how strongly the droplets of a et al., 2017).

Table 1
Average diameter (z-average) (nm), polydispersity index (PdI) and Zeta potential (mV) of copaiba oil (CP)-pectin (PEC) nanoemulsion produced by ultrasonic ho­
mogenization (operating at 20 kHz and 150 W).
CP (wt.%) Zeta potential (mV) Droplet diameter (nm) PdI

0h 24 h 0h 24 h 0h 24 h

1 25 � 0.6a(a) 25 � 0.5a(a) 68.9 � 0.3a(a) 71.5 � 1.4a(a) 0.31 � 0.02a(b) 0.39 � 0.04a(a)
3 22 � 0.8b(a) 21 � 0.2b(a) 52.3 � 0.4b(a) 54.8 � 1.8b(a) 0.22 � 0.01b(a) 0.21 � 0.01b(a)
6 21 � 0.1b(a) 20 � 0.4b(a) 41.2 � 0.4c(a) 46.1 � 0.9c(a) 0.29 � 0.01b(a) 0.28 � 0.01c(a)

Values are reported as average values � standard deviations. Different letters on column (samples) and line (time, parenthesis) show that values were not statistically
significant (p > 0.05) using Turkey test.

4
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

Fig. 1. Thermogravimetric (TG; left) and derivative TG (right) profiles of films comprising pectin and/or copaiba oil (CP).

Table 2
Tensile attributes – elastic modulus (EM), tensile strength (TS), and elongation at break (ε) – as well as thermal parameters – initial (Tonset) and final degradation
temperatures (Toffset) and residual mass at 600 � C – of pectin (PEC) films as influenced by different concentrations of copaiba oil (CP).
CP /wt.% Thickness (μm) TS (MPa) ε (%) EM (MPa) Tonset (� C) Toffset (� C) R600 (%)

0 40.1 � 1.3a 41.8 � 6.5a 1.7 � 0.1d 1589 � 201a 215 450 0.4
1 41.2 � 1.0a 25.6 � 2.1b 2.0 � 0.5c 1347 � 135b 198 433 0.1
3 41.5 � 1.1a 20.1 � 1.4c 2.2 � 0.3b 1089 � 106c 201 427 0.2
6 40.4 � 0.9a 12.4 � 4.7d 2.4 � 0.5a 853 � 159d 200 435 0.1

Mechanical attributes are reported as average values and standard deviations. The same letters on the same column indicate that the values are not statistically
significant (p > 0.05) using Tukey’s test.

In general, the DTG curve for the pure film showed three defined
mass loss steps. The first occurred between 50 and 150 � C, corre­
sponding to the removal of water that is physically connected, and the
loss of volatiles of low molar mass. The second stage occurred between
180 and 300 � C and may be related to the thermal degradation of pectin
resulting from the depolymerization of the polymer chains; the release
of CO2, H2O, and CO; and the generation of aliphatic compounds. The
third stage (T > 400 � C) was related to the combustion of aromatic
carbon residues (Gorrasi, Bugatti, & Vittoria, 2012). The thermal
behavior of the films was modified after the addition of CP, particularly
the appearance of the degradation peak at approximately 370 � C, rela­
tive to the resin fraction of the oil.
PEC was thermally stable up to 215 � C (Table 2), while the nano­
emulsified PEC films were thermally stable up to 200 � C. The degrada­
tion onset temperature (Tonset) decreased for the emulsified films,
suggesting that the addition of the nanoemulsion decreased the molec­
ular interactions between the adjacent chains of pectin and strengthened
the hydrogen bonds between the hydroxyl groups of pectin and the polar
compounds (polyphenols) found in the CP-NE, as indicated by the FTIR
(Fig. 2) and XRD (Fig. 3). A decrease in the Tonset of films due to the
addition of emulsions or extracts was previously reported (Cerruti et al.,
2011; Medina Jaramillo, Guti�errez, Goyanes, Bernal, & Fama �, 2016;
Sanyang, Sapuan, Jawaid, Ishak, & Sahari, 2016).
Finally, regardless of composition, all films had a remarkably low
residual mass at 600 � C (Table 2). In general, the components that Fig. 2. Attenuated total reflectance Fourier transform infrared spectra of
copaiba oil (CP) and films comprising pectin (PEC) and copaiba oil (1–6 wt%).
comprised the aromatic rings in their chemical structures are stable up
Y-axis: transmittance/a.u.
to 600 � C (Medina Jaramillo et al., 2016; Patel et al., 2010).

5
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

40.14� (2θ) associated with the crystallinity of pure pectin (Meneguin,

Cury, & Evangelista, 2014; Chaichi, Hashemi, Badii, & Mohammadi,
2017). In the present study, pectin films exhibited a wide peak at 12.4�
(2θ), indicating that the pure pectin film had a semicrystalline structure
(Fig. 3).
The incorporation of CP, in turn, narrowed this diffraction peak and
led to another at 2θ ¼ 20.6� . These changes may be associated with the
inclusion of some CP compounds in the crystal structure, which would
modify the interplanar spacing and deform the lattice and is consistent
with the FTIR spectra (Fig. 2). In addition, the peak at 2θ ¼ 20.6� of the
films containing CP-NE was more intense than in the control. The
increased relative height indicates a different structure factor, which
could be caused by substitution of inter- and intramolecular hydrogen
bonds of pure pectin by CP-pectin hydrogen bonds, thereby increasing
the pectin intermolecular attraction. Similar results were reported by
Almasi, Azizi, and Amjadi (2020).

3.5. Scanning electron microscopy

The microstructure of CP pectin films was studied to obtain some

Fig. 3. X-ray diffraction patterns of pectin (PEC)-based films containing understanding of the organization of the oil droplets throughout the
copaiba oil (CP; 1–6 wt%). Y-axis: intensity/a.u. matrix of biopolymer films and their possible influence on film prop­
3.3. Fourier transformed infrared spectroscopy (ATR-FTIR) erties, such as mechanical behavior. The scanning electron micrographs
of the surface and the cross sections of the pectin films incorporated into
ATR-FTIR spectroscopy was performed to elucidate possible in­ the CP are shown in Fig. 4.
teractions between PEC and CP. The spectra are shown in Fig. 2. PEC showed the most smooth, compact, and continuous surface and
The PEC spectrum exhibited typical vibration bands of 3370–3350 presented a homogeneous and cohesive internal structure. A smooth
cm 1 related to the O–H stretching of water molecules and hydroxyl surface was also observed in the films incorporated with CP. The surface
groups of pectin. The band centered at approximately 2937 cm 1 was micrographs of pectin/CP films proposed that CP was completely
attributed to the elongation of C–H bonds of pyranoid-ring carbons. The assimilated and well distributed in the matrix and did not cause irreg­
band at 1737 cm 1 was observed and was related to the C¼O vibration ularities. In the cross-section, the control film had smooth and compact
of the elongation of carboxylic groups and esters. The vibration bands structure. Nevertheless, CP 6% had some discontinuous zones and
below 1000 cm 1 were complex in nature and encompass the poly­ became rougher than others. This might be associated with the reduc­
saccharide “fingerprint” region. In addition, two additional vibration tion in tensile strength (Table 2). The increase in surface coarseness with
bands were observed related to the carboxylic groups in their carbox­ the presence of vegetable oil has been previously observed (Norajit, Kim,
ylate form: asymmetric elongation at 1633 cm 1 and symmetric & Ryu, 2010; Shojaee-Aliabadi et al., 2013). Sa �nchez-Gonza �lez, Chiralt,
stretching at 1438 cm 1. The spectral region of 1200–1000 cm 1 is Gonza �lez-Martínez, and Cha �fer (2011) attributed this fact to the
related to the vibrations of C–O and C–C of glycosidic bonds and pyra­ migration of oil droplets upwards the films and further volatilization
nose rings (Synytsya, Copíkov
� a, Mat�
� ejka, & Machovi�c, 2003). during water evaporation, resulting in a holey structure.
The infrared spectra of CP showed bands characteristic of its Even if microstructure of some formulations changed, in general, the
composition, highlighting the region between 2921 cm 1 and 2850 SEM result indicated that CP nanoemulsions had a stable emulsion
cm 1, attributed to the C–H-bonding axial deformations in aliphatic system, and no collapse of nanosized droplets occurred during film
hydrocarbons, such as sesquiterpenes and other organic compounds drying. The short processing times associated with continuous casting
found in CP (Bonan et al., 2017). The bands at 1693 cm 1 and 1637 did not lead to the formation of macroscopic defects in the film
cm 1 were related to the axial deformation of the carboxylic acid. Bands structure.
at 1445 cm 1 and 1369 cm 1 referred to the axial strains of C–H bonds.
Bands at 1380 and 1365 cm 1 were characteristic of the angular 3.6. Mechanical properties
deformation of CH3.
The spectra of PEC/CP-covered peaks were typical of all components. The study of mechanical behavior is essential to evaluate the per­
Specifically, the addition of CP caused the appearance of a peak at 885 formance of the material for a given application. For this purpose, it is
cm 1 (β-caryophyllene) as well as the increase in the intensity of the necessary to perform tests that simulate the real conditions to which it
bands 2921 cm 1 and 2850 cm 1 (sesquiterpenes), suggesting that the would be exposed (Grigoriadou et al., 2011). The effects of different CP
films retained the components that provide the antimicrobial action to concentrations on the mechanical properties of PEC-based films were
CP. Similar results were observed by Pelissari, Grossmann, Yamashita, investigated, and the results are presented in Table 2.
and Pined (2009). Furthermore, a decrease in the –OH stretching range There was no significant difference between the thickness of the PEC
(3500-3200 cm 1) was observed with the addition of CP, indicating the control film and the thickness of the active films. The incorporation of
reduction of pectin hydroxyl groups after reaction with fatty acid CP resulted in a gradual decrease in EM and TS, while increasing ε (p <
anhydrides. 0.05). A decrease of approximately 30% and 54% in TS and EM was
observed. For ε, there was an increase of approximately 41%. The
addition of CP at a concentration of 6 wt% resulted in significant de­
3.4. X-ray diffraction creases in EM and TS, with a concomitant increase in ε (p < 0.05),
implying a film with low stiffness and good flexibility (Bilbao-Sa �inz,
XRD was used to analyze the crystal structure and evaluate the Avena-Bustillos, Wood, Williams, & Mchugh, 2010; Gilfillan, Mog­
compatibility of PEC and CP. Fig. 3 shows the XRD patterns for pure haddam, & Doherty, 2014; Otoni et al., 2016; Zún ~ iga, Skurtys, Osorio,
films and pectin/CP. Aguilera, & Pedreschi, 2012). This result suggests a CP plasticizing ac­
Well-defined peaks were reported at 12.72� , 16.30� , 25.32� , and tion on the pectin matrix. According to Kokoszka, Debeaufort,

6
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

Fig. 4. SEM micrographs of the surface and cross-sections of the films: pectin (PEC) and films containing different percentages of copaiba oil (1–6% CP).

Hambleton, Lenart, and Voilley (2010), the plasticizers weaken the 2010; Basiak, Debeaufort, & Lenart, 2015; Galus & Kadzi, 2016).
intermolecular interactions between the polymer chains, causing an Red-green (a*), blue-yellow (b*) and YI parameters increased signifi­
increase in free volume and molecular mobility, leading to decreased cantly by increasing CP concentration compared to the control film. In
stiffness and improved film extensibility and flexibility. In the literature, addition, pectin films loaded with CP showed higher ΔE* than PEC. This
there are reports demonstrating the occurrence of TS reduction in films phenomenon could be attributed to the phenolic compounds of CP,
based on polysaccharides when hydrophobic compounds such as lipids which might show light absorption at lower wavelengths. The variance
are added to their matrix (Acevedo-Fani et al., 2015; Arrieta, Peltzer, in color parameters appears to be the consequence of natural yellow of
Garrigo�s, & Jim�enez, 2013; Ghani et al., 2018; Gim�enez, Lo �pez de Lacey, vegetal oils or lipids (Dashipour, Razavilar, Hosseini, &
P�erez-Santín, Lo�pez-Caballero, & Montero, 2013; Manrich et al., 2017; Shojaee-aliabadi, 2015; Shojaee-Aliabadi et al., 2013). All of these re­
Otoni et al., 2014). This effect on TS reduction may also be attributed to ports are in line with the results of Pająk, Przetaczek-Ro_znowska, and
the development of a heterogeneous filmogenic structure, with discon­ Juszczak (2019). On the other hand, the WI did not change with
tinuities in the polymer network triggered by the lipid dispersed phase increasing CP concentration. Similar results have been reported by
(Perez-Gago & Krochta, 2001; Sa �nchez-Gonza �lez, Cha�fer, Chiralt, & Hasheminya, Rezaei, and Ghanbarzadeh (2019) and Atef, Rezaei, and
Gonza �lez-Martínez, 2010; Sa �nchez-Gonz� alez et al., 2011; Shellhammer Behrooz (2014). Overall, the color of edible films is directly dependent
& Krochta, 1997). These results are in agreement with the micrographs on the kind and concentration of the vegetal oil which is added to the
presented above in Fig. 4. Similar behavior when analyzing the me­ film (Atar�es & Chiralt, 2016).
chanical properties of films based on polysaccharides combined with
oils was found in the literature (Kanmani & Rhim, 2014; Kavoosi,
Derakhshan, Salehi, & Rahmati, 2018; Nur Fatin Nazurah & Nur Hanani, 3.8. Water vapor permeability (WVP)
2017; Rodrigues et al., 2018).
Water vapor permeability is an essential parameter to estimate the
permeation of water vapors through film matrix at a certain tempera­
3.7. Optical properties ture. The water barrier properties of the PEC-based films added or not by
CP nanoemulsions were investigated through WVP measurements, and
Both color and transparency of food packaging materials play an the results are shown in Fig. 5.
important role in their appearance and acceptance by consumers (Ace­ The WVP of PEC films was significantly reduced (p < 0.05) by ca.
vedo-Fani et al., 2015). The effects of CP-NE additions on the color 60% upon nanoemulsification, but all PEC/CP films showed the same (p
parameters of the films are shown in Table 3. > 0.05) WVP, indicating that droplet size did not influence the barrier
PEC film had a higher (p < 0.05) luminosity than those containing properties. It is worth mentioning that WVP is directly related to the
CP. Increases in CP content resulted in further lower L* values but all quantity of polar (e.g., hydroxyl) groups in the molecular assembly
films presented high lightness (i.e., L* values close to 100), which is (Huber & Embuscado, 2009). CP addition provided PEC films with
recurrent for edible films (Araujo-Farro, Podadera, Sobral, & Menegalli, increased crystallinity (Fig. 3) due to the rearrangement of pectin chains

Table 3
Luminosity (L*), chromatic coordinates (a* and b*), and colorimetric parameters (ΔE*, total color difference; YI, yellowness index; WI, whiteness index) of pectin films
as influenced by different concentrations of copaiba oil (CP).
Sample L* a* b* ΔE* YI WI

PEC 89.9 � 0.2a 0.21 � 0.01c 0.58 � 1c 48.7 � 0.2d 1.1 � 0.1b 33.3 � 1a
CP1% 83.7 � 0.1b 0.27 � 0.01b 0.99 � 0.4b 51.3 � 0.3c 1.5 � 0.2c 33.7 � 2a
CP3% 82.6 � 0.2b 0.29 � 0.01b 1.04 � 0.2b 66.5 � 0.2b 1.9 � 0.2b 34.9 � 0.9a
CP6% 81.8 � 0.4b 0.36 � 0.02a 1.38 � 0.5a 71.5 � 0.1a 2.1 � 0.5a 33.8 � 0.3a
a-d
Different letters in the same column indicate a significant difference (p < 0.05).

7
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

capacity of plasticizer (glycerol) and functional groups of pectin. Ac­

cording to Fig. 5, addition of CP increased water contact angle of films
and resulted in decreasing hydrophilicity of the pectin-based films
which might be due to the loss of free functional groups (amino and
hydroxyl groups) and to the hydrophobic nature of the oil (Shojaee-A­
liabadi et al., 2013). Besides surface composition, the outmost (mono­
layer) surface structure affects the wettability properties of the film,
whereas a dense external structure contributes for higher contact angle
values (Basiak, Debeaufort, & Lenart, 2015). Similar behavior was
observed in films prepared with the incorporation of cinnamon essential
oil (Ojagh, Rezaei, Rezavi, & Hosseini, 2010), Zataria multiflora Boiss
essential oil (Moradi et al., 2012), olive oil (Pereda, Amica, & Marco­
vich, 2012) and grape pomace wax and oil (Ferreira, Nunes, Castro,
Ferreira, & Coimbra, 2014). In addition, the fast solvent removal rate of
Fig. 5. Water vapor permeability (WVP) and contact angle of films based on
the continuous casting process may have less phase separation effects in
pectin (PEC), either added or not with copaiba oil (CP). Equal letters in pa­
copaiba/pectin films, thereby imparting hydrophobicity to films,
rentheses indicate equal values (p > 0.05).
particularly those containing 6 wt% CP. These results are in agreement
with the SEM (Fig. 4), ATR-FTIR (Fig. 2) and WVP (Fig. 5) analyses,
and substitution of inter- and intramolecular hydrogen bonds of pure
which revealed a homogeneous distribution and a uniform dispersion
pectin by CP-pectin hydrogen bonds, thereby increasing the pectin
inside the film matrix.
intermolecular attraction. The polymeric chains become less mobile due
to addition of oil in the film matrix leading to reduce diffusibility of
3.10. Antimicrobial activity
water vapors via the interface with the polysaccharide chains which lead
to decrease in WVP (Hosseini, Razavi, & Mousaviousavi, 2009; Mo €ller,
The inhibitory effects against E. coli and S. aureus of pectin (PEC)
Grelier, Pardon, & Coma, 2004; Park & Zhao, 2004). These results are in films and those prepared with CP nanoemulsions are shown in Fig. 6.
agreement with the uniform and interconnected matrix presented above
As expected, the films without the addition of CP had no antimi­
in Fig. 4 and may be associated with those found in the contact angle test
crobial effect, indicating that pectin has no antimicrobial properties
(Fig. 5).
against the tested bacteria. In the antibacterial test, the samples con­
Our findings are in accordance with the results obtained by Nisar
taining CP showed no zone of inhibition around the discs. However, no
et al. (2018), who also observed that WVP values tended to decrease
bacteria spread on the agar in the region directly below the film samples
when the clove bud essential oil was incorporated into pectin-based
for the three concentrations studied. This result indicates that bacterial
films. According to that work clove bud essential oil could entered
inhibition probably occurred by direct contact with the surface of the
into the structural matrix of films, which further limit the passage of
biopolymers combined with CP, indicating that the oil diffusion in the
liquid molecules through them. Considering the WVP levels, the herein
film was small. Therefore, a bacteriostatic effect was observed on the
produced films are appropriate for use as moisture barriers in food
films keeping them in the stationary growth phase (Pankey & Sabath,
packaging (Bedane, Xiao, Farmahini, & Xiao, 2015; Jim�enez, Fabra, &
2004).
Talens, 2012; Lorevice et al., 2016; Park & Zhao, 2004).
The use of packaging with bacteriostatic action by the food industry
is a viable strategy because it can prolong the shelf life of a food,
3.9. Contact angle measurements maintaining its integrity and preventing the presence of these bacteria
from putting the food at risk. Similar results were reported by Morelli
The contact angle is a simple way to evaluate the affinity between the et al. (2015) when studying films of polylactic acid and CP. The results
solvent and the surface of the material, which is generally used to assess on the E. coli and S. aureus cultures corroborate those presented by the
the wettability of the films (Hambleton, Fabra, Debeaufort, Dury-brun, FTIR (Fig. 2) because they showed inhibition by contact, showing that
& Voilley, 2009; Mahmood, Zuber, Mahboob, Sultana, & Sultana, the active compounds present in CP can act on the microorganisms.
2010; Pereda, Aranguren, & Marcovich, 2010). Fig. 5 shows the mean
contact angle values for films produced by continuous casting.
The higher hydrophilicity of PEC is attributed to the water binding

Fig. 6. Antibacterial test done in petri dishes with pectin coated with copaiba oil.

8
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

samples in soil.
The results obtained in the respirometric tests over 28 days show that
the four materials analyzed underwent aerobic biodegradation in soil,
which was indicated by the rapid evolution of CO2—mineralization—in
the flasks containing them compared to those containing only the con­
trol sample (soil), which showed less evolution. It can be seen that PEC
exhibited higher CO2 evolution than the other samples. This was due to
the presence of carbohydrates, such as glucose, fructose, and sucrose,
which are more easily assimilable by microorganisms (Cinelli et al.,
2014; Medina Jaramillo et al., 2016). Degradation of pectic substances
can follow two main routes: depolymerization by β-elimination re­
actions under the action of pectin lyase and pectin lyases of microbio­
logical origin or by demethylation with the aid of pectin-esterase,
followed by acid hydrolysis of the α(1 → 4) bonds by polygalacturonases
Fig. 7. Sensory outcome of color and aroma for PEC and PEC/CP). Equal letters (Singthong, Cui, Ningsanond, & Douglas Goff, 2004). Thus, it is sug­
in parentheses indicate equal values (p > 0.05). (For interpretation of the ref­ gested that the biodegradation process followed these routes.
erences to color in this figure legend, the reader is referred to the Web version
Fig. 8 shows two distinct phases of the biodegradation process: an
of this article.)
initial phase in which there was a marked increase in the formation of
3.11. Sensory evaluation carbon dioxide and, after 20 days, a phase that tended to stabilize the
production of CO2. The inclusion of CP caused a gradual decrease in the
It is generally accepted that color and aroma are importance char­ evolution of CO2 as its concentration increased, delaying the biodegra­
acteristics in determining the sensory of food for customers (Gotow, dation of the biopolymers.
Kobayashi, & Kobayakawa, 2013). This sensory test was constituted by According to Pepper, Gerba, & Brusseau (2011), in the soil, there is a
untrained judges, comprised by 65% female and 35% male consumers. predominance of bacteria of the genera Arthrobacter, Streptomyces,
According to the statistical analysis performed in the sensory evaluation Pseudomonas, and Bacillus and of the fungi Penicillium, Aspergillus,
of the films by different concentrations of CP, significant differences Fusarium, Rhizoctonia, Alternaria, and Rhizopus. CP has antimicrobial
were observed (p < 0.05) between the treatments for each of the sensory potential against several microorganisms, including Pseudomonas spp.
attributes evaluated (Fig. 7). (Marangon et al., 2017; Masson, Salvador, Polizello, & Frade, 2013),
The treatments containing copaiba oil were significantly more Aspergillus flavus (Deus, Alves, & Arruda, 2011), Bacillus subtilis (Dos
satisfying compared to the control samples in all sensory properties. The Santos et al., 2008; Morelli et al., 2015), Fusarium spp. (Dos Santos
sensory attribute of aroma to CP1% and CP6% presented an average et al., 2013), Penicillium spp. (Dos Santos et al., 2013), and Rhizopus
sensory score of 6 meaning “Like slightly”, while CP3% score was 7 spp. (Dos Santos et al., 2013). This antibacterial activity of CP is
meaning “Like moderately”. This result suggested that CP3% showed attributed to a combination of diterpenes and sesquiterpenes that affect
better balance levels in the volatile compounds and promoted a signif­ the integrity of the cell wall of the microorganism, causing a decrease in
icant higher score. cell volume and subsequent release of cytoplasmic compounds (Dos
In relation to color, no significant differences (p > 0.05) were Santos et al., 2008; Dos Santos et al., 2013). Thus, it is suggested that the
observed among the tested edible films, with average score of 8, presence of CP active compounds has caused some inhibition of micro­
meaning “like very much”. These results are in agreement with the SEM bial growth, decreasing the evolution of CO2 in the biodegradation
(Fig. 4) and optical properties (Table 3) analyses, which revealed a good process. These results may be associated with those found in the anti­
homogeneity distribution, uniform dispersion inside the film matrix and microbial and FTIR tests. This result is relevant because it indicates that
high lightness, which is meaningful for the consumer’s acceptance of the it was possible to produce new polymer-based materials with active
product based on the appearance. properties but still be biodegradable.

4. Conclusion
3.12. Biodegradation
Addition of CP nanoemulsions to PEC-based films affected their
The influence of the incorporation of CP on the biodegradation of the matrices, providing active functionality, preserving or even improving
pectin film was investigated. Fig. 8 shows the CO2 evolution of the

Fig. 8. Cumulative CO2 production and pictures of PEC and PEC/CP during biodegradation in soil for 28 days.

9
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

their physico-mechanical and antimicrobial properties. In particular, the Bartha, R., & Pramer, D. (1965). Features of flask and method for measuring the
persistence and biological effects of pesticides in soil. Soil Science, 100, 68–70.
nanoemulsions altered the mechanical properties of the films, increasing
https://doi.org/10.1097/00010694-196507000-00011.
their extensibility and decreasing their stiffness. The sensory acceptance Basiak, E., Debeaufort, F., & Lenart, A. (2015). Effect of oil lamination between
of the films by panelists was good. Finally, the PEC/CP films showed plasticized starch layers on film properties. Food Chemistry, 195. https://doi.org/
adequate trends for degradation in the soil, ensuring that they will 10.1016/j.foodchem.2015.04.09.
Bayarri, M., Oulahal, N., Degraeve, P., & Gharsallaoui, A. (2014). Properties of
remain biodegradable even after the incorporation of the antimicrobial lysozyme/low methoxyl (LM) pectin complexes for antimicrobial edible food
agent CP. In summary, the addition of nanoemulsions in PEC-based films packaging. Journal of Food Engineering, 131, 18–25. https://doi.org/10.1016/j.
provided relevant functional properties for potential application in the jfoodeng.2014.01.013.
Bedane, A. H., Xiao, H., Farmahini, M., & Xiao, H. (2015). Water vapor transport
food industry, in addition to directly contributing to the reduction of the properties of regenerated cellulose and nanofibrillated cellulose films. Journal of
environmental impact caused by conventional plastic packaging. Membrane Science, 493, 46–57. https://doi.org/10.1016/j.memsci.2015.06.009.
Bilbao-S�ainz, C., Avena-Bustillos, R. J., Wood, D. F., Williams, T. G., & Mchugh, T. H.
(2010). Composite edible films based on hydroxypropyl methylcellulose reinforced
CRediT authorship contribution statement with microcrystalline cellulose nanoparticles. Journal of Agricultural and Food
Chemistry, 58(6), 3753–3760. https://doi.org/10.1021/jf9033128.
Bonan, R. F., Bonan, P. R. F., Batista, A. U. D., Perez, D. E. C., Castellano, L. R. C.,
L.B. Norcino: Visualization, Writing - review & editing, Conceptu­
Oliveira, J. E., et al. (2017). Poly(lactic acid)/poly(vinyl pyrrolidone) membranes
alization, Methodology. J.F. Mendes: Visualization, Writing - review & produced by solution blow spinning: Structure, thermal, spectroscopic, and
editing, Conceptualization, Methodology. C.V.L. Natarelli: Data cura­ microbial barrier properties. Journal of Applied Polymer Science, 134(19), 1–9.
https://doi.org/10.1002/app.44802.
tion. A. Manrich: Formal analysis. J.E. Oliveira: Project administra­
Bonan, R. F., Bonan, P. R. F., Batista, A. U. D., Sampaio, F. C., Albuquerque, A. J. R.,
tion, Supervision. L.H.C. Mattoso: Project administration, Supervision. Moraes, M. C. B., et al. (2015). In vitro antimicrobial activity of solution blow spun
poly(lactic acid)/polyvinylpyrrolidone nanofibers loaded with Copaiba (Copaifera
sp.) oil. Materials Science and Engineering: C, 48. https://doi.org/10.1016/j.
Acknowledgments msec.2014.12.021.
Bonilla, J., Atar�es, L., Vargas, M., & Chiralt, A. (2012). Effect of essential oils and
The authors are grateful to the Brazilian Agricultural Research Cor­ homogenization conditions on properties of chitosan-based films. Food Hydrocolloids,
26(1), 9–16. https://doi.org/10.1016/j.foodhyd.2011.03.015.
poration (Embrapa), in particular Embrapa Instrumentaç~ ao, for the fa­ Cerruti, P., Santagata, G., Gomez d’Ayala, G., Ambrogi, V., Carfagna, C.,
cilities and equipment; to Coordination of Superior Level Staff Malinconico, M., et al. (2011). Effect of a natural polyphenolic extract on the
Improvement - CAPES (grant # 1744107/2016-8); and to the National properties of a biodegradable starch-based polymer. Polymer Degradation and
Stability, 96(5), 839–846. https://doi.org/10.1016/j.polymdegradstab.2011.02.003.
Council for Scientific and Technological Development - CNPq (grant # Chaichi, M., Hashemi, M., Badii, F., & Mohammadi, A. (2017). Preparation and
141823/2017-8; 302469/2018-4) and the Minas Gerais Research characterization of a novel bionanocomposite edible film based on pectin and
Foundation - FAPEMIG (grant # APQ-00906-17; APQ-01505-15) for the crystalline nanocellulose. Carbohydrate Polymers, 157, 167–175. https://doi.org/
10.1016/j.carbpol.2016.09.062.
financial support.
Chen, J., Gao, D., Yang, L., & Gao, Y. (2013). Effect of microfluidization process on the
functional properties of insoluble dietary fiber. Food Research International, 54(2),
Appendix A. Supplementary data 1821–1827. https://doi.org/10.1016/j.foodres.2013.09.025.
Cinelli, P., Schmid, M., Bugnicourt, E., Wildner, J., Bazzichi, A., Anguillesi, I., et al.
(2014). Whey protein layer applied on biodegradable packaging film to improve
Supplementary data to this article can be found online at https://doi. barrier properties while maintaining biodegradability. Polymer Degradation and
org/10.1016/j.foodhyd.2020.105862. Stability, 108, 151–157. https://doi.org/10.1016/j.polymdegradstab.2014.07.007.
CLSI. (2012). Methods for Dilution Antimicrobial Susceptibility Tests f or Bacteria That Grow
Aerobically; Approved Standard. Wayne, PA: CLSI.
References Dashipour, A., Razavilar, V., Hosseini, H., & Shojaee-aliabadi, S. (2015). International
Journal of Biological Macromolecules Antioxidant and antimicrobial carboxymethyl
cellulose films containing Zataria multiflora essential oil. International Journal of
Abnt. (1999). Resíduos em solos - determinaç~ ao da biodegradaç~ao pelo m�etodo respirom�etrico
Biological Macromolecules, 72, 606–613. https://doi.org/10.1016/j.
(Vols. 1–8).
ijbiomac.2014.09.006.
Abral, H., Hartono, A., Hafizulhaq, F., Handayani, D., Sugiarti, E., & Pradipta, O. (2019).
Deus, R. J. A., Alves, C. N., & Arruda, M. S. P. (2011). Avaliaç~ao do efeito antifúngico do
Characterization of PVA/cassava starch biocomposites fabricated with and without
o
�leo resina e do o �leo essencial de copaíba (Copaifera multijuga Hayne). Revista
sonication using bacterial cellulose fiber loadings. Carbohydrate Polymers, 206,
Brasileira de Plantas Medicinais, 13(1), 1–7. https://doi.org/10.1590/S1516-
593–601. https://doi.org/10.1016/j.carbpol.2018.11.054.
05722011000100001.
Acevedo-Fani, A., Salvia-Trujillo, L., Rojas-Graü, M. A., & Martín-Belloso, O. (2015).
Dias, D. de O., Colombo, M., Kelmann, R. G., Kaiser, S., Lucca, L. G., Teixeira, H. F., et al.
Edible films from essential-oil-loaded nanoemulsions: Physicochemical
(2014). Optimization of Copaiba oil-based nanoemulsions obtained by different
characterization and antimicrobial properties. Food Hydrocolloids, 47, 168–177.
preparation methods. Industrial Crops and Products, 59, 154–162. https://doi.org/
https://doi.org/10.1016/j.foodhyd.2015.01.032.
10.1016/j.indcrop.2014.05.007.
Almasi, H., Azizi, S., & Amjadi, S. (2020). Development and characterization of pectin
Dos Santos, E. C. G., Donnici, C. L., da Silva Camargos, E. R., de Rezende, A. A., de Aguiar
films activated by nanoemulsion and Pickering emulsion stabilized marjoram
Andrade, E. H., Soares, L. A. L., et al. (2013). Effects of Copaifera duckei Dwyer
(Origanum majorana L.) essential oil. Food Hydrocolloids, 99, 105338. https://doi.
oleoresin on the cell wall and cell division of Bacillus cereus. Journal of Medical
org/10.1016/j.foodhyd.2019.105338. June 2019.
Microbiology, 62(PART7), 1032–1037. https://doi.org/10.1099/jmm.0.060046-0.
Araujo-Farro, P. C., Podadera, G., Sobral, P. J. A., & Menegalli, F. C. (2010).
Dos Santos, A. O., Ueda-Nakamura, T., Dias Filho, B. P., Veiga, V. F., Pinto, A. C., &
Development of films based on quinoa ( Chenopodium quinoa , Willdenow ) starch.
Nakamura, C. V. (2008). Antimicrobial activity of Brazilian copaiba oils obtained
Carbohydrate Polymers, 81(4), 839–848. https://doi.org/10.1016/j.
from different species of the Copaifera genus. Memorias Do Instituto Oswaldo Cruz,
carbpol.2010.03.051.
103(3), 277–281. https://doi.org/10.1590/S0074-02762008005000015.
Arfat, Y. A., Benjakul, S., Prodpran, T., Sumpavapol, P., & Songtipya, P. (2014).
Eça, K. S., Machado, M. T. C., Hubinger, M. D., & Menegalli, F. C. (2015). Development of
Properties and antimicrobial activity of fish protein isolate/fish skin gelatin film
active films from pectin and fruit extracts: Light protection, antioxidant capacity,
containing basil leaf essential oil and zinc oxide nanoparticles. Food Hydrocolloids,
and compounds stability. Journal of Food Science, 80, 2389–2396. https://doi.org/
41. https://doi.org/10.1016/j.foodhyd.2014.04.023.
10.1111/1750-3841.13074.
Arrieta, M. P., Peltzer, M. A., Garrig�os, M. D. C., & Jim�enez, A. (2013). Structure and
Embuscado, M. E., & Huber, K. C. (Eds.). (2009). Edible films and coatings for food
mechanical properties of sodium and calcium caseinate edible active films with
applications (p. 403). NY: Springer.
carvacrol. Journal of Food Engineering, 114(4), 486–494. https://doi.org/10.1016/j.
Espitia, P. J. P., Fuenmayor, C. A., & Otoni, C. G. (2019). Nanoemulsions: Synthesis,
jfoodeng.2012.09.002.
characterization, and application in bio-based active food packaging. Comprehensive
ASTM. (2009). ASTM D882-09, standard test method for tensile properties of thin plastic
Reviews in Food Science and Food Safety, 18(1), 264–285. https://doi.org/10.1111/
sheeting. West Conshohocken, PA.
1541-4337.12405.
ASTM E96. (2016). ASTM E96- standard test methods for water vapor transmission of
Favvas, E. P., Kouvelos, E. P., Papageorgiou, S. K., Tsanaktsidis, C. G., &
materials.
Mitropoulos, A. C. (2015). Characterization of natural resin materials using water
Atar�es, L., & Chiralt, A. (2016). Essential oils as additives in biodegradable films and
adsorption and various advanced techniques. Applied Physics A, 119(2), 735–743.
coatings for active food packaging. Trends in Food Science & Technology, 48, 51–62.
https://doi.org/10.1007/s00339-015-9022-6.
https://doi.org/10.1016/j.tifs.2015.12.001.
Ferreira, A. S., Nunes, C., Castro, A., Ferreira, P., & Coimbra, M. A. (2014). Influence of
Atef, M., Rezaei, M., & Behrooz, R. (2014). International Journal of Biological
grape pomace extract incorporation on chitosan films properties. Carbohydrate
Macromolecules Preparation and characterization agar-based nanocomposite film
Polymers, 113, 490–499. https://doi.org/10.1016/j.carbpol.2014.07.032.
reinforced by nanocrystalline cellulose. International Journal of Biological
Macromolecules, 70, 537–544. https://doi.org/10.1016/j.ijbiomac.2014.07.013.

10
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

Galus, S., & Kadzi, J. (2016). Food Hydrocolloids Whey protein edible fi lms modi fi ed Masson, D. S., Salvador, S. L., Polizello, A. C. M., & Frade, M. A. C. (2013). Antimicrobial
with almond and walnut oils ska, 52, 78-86 https://doi.org/10.1016/j.foodhyd.20 activity of copaíba (Copaifera langsdorffii) oleoresin on bacteria of clinical
15.06.013. significance in cutaneous wounds. Revista Brasileira de Plantas Medicinais, 15(4),
Gelmini, F., Beretta, G., Anselmi, C., Centini, M., Magni, P., Ruscica, M., et al. (2013). 664–669. https://doi.org/10.1590/S1516-05722013000500006.
GC-MS profiling of the phytochemical constituents of the oleoresin from Copaifera McClements, D. J. (2012). Nanoemulsions versus microemulsions: Terminology,
langsdorffii Desf. and a preliminary in vivo evaluation of its antipsoriatic effect. differences, and similarities. Soft Matter. https://doi.org/10.1039/c2sm06903b.
International Journal of Pharmaceutics, 440(2), 170–178. https://doi.org/10.1016/j. McClements, D. J., & Gumus, C. E. (2016). Natural emulsifiers — biosurfactants,
ijpharm.2012.08.021. phospholipids, biopolymers, and colloidal particles: Molecular and physicochemical
Ghani, N. A. A., Channip, A. A., Chok Hwee Hwa, P., Ja’afar, F., Yasin, H. M., & basis of functional performance. Advances in Colloid and Interface Science, 234, 3–26.
Usman, A. (2018). Physicochemical properties, antioxidant capacities, and metal https://doi.org/10.1016/j.cis.2016.03.002.
contents of virgin coconut oil produced by wet and dry processes. Food Sciences and Mcclements, D. J., & Rao, J. (2011). Critical reviews in food science and nutrition food-
Nutrition, 6(5), 1298–1306. https://doi.org/10.1002/fsn3.671. grade nanoemulsions: Formulation, fabrication, properties, performance, biological
Gilfillan, W. N., Moghaddam, L., & Doherty, W. O. S. (2014). Preparation and fate, and potential toxicity food-grade nanoemulsions: Formulation, fabrication,
characterization of composites from starch with sugarcane bagasse nanofibres. properties, performance, biological fate, and potential toxicity. Critical Reviews in
Cellulose, 21(4), 2695–2712. https://doi.org/10.1007/s10570-014-0277-4. Food Science and Nutrition, 51, 285–330. https://doi.org/10.1080/
Gim� enez, B., L�
opez de Lacey, A., P� erez-Santín, E., L�
opez-Caballero, M. E., & Montero, P. 10408398.2011.559558.
(2013). Release of active compounds from agar and agar-gelatin films with green tea Medina Jaramillo, C., Guti�errez, T. J., Goyanes, S., Bernal, C., & Fam� a, L. (2016).
extract. Food Hydrocolloids, 30(1), 264–271. https://doi.org/10.1016/j. Biodegradability and plasticizing effect of yerba mate extract on cassava starch
foodhyd.2012.05.014. edible films. Carbohydrate Polymers, 151, 150–159. https://doi.org/10.1016/j.
Gorrasi, G., Bugatti, V., & Vittoria, V. (2012). Pectins filled with LDH-antimicrobial carbpol.2016.05.025.
molecules: Preparation, characterization and physical properties. Carbohydrate Mendes, J. F., Paschoalin, R. T., Carmona, V. B., Sena Neto, A. R., Marques, A. C. P.,
Polymers, 89(1), 132–137. https://doi.org/10.1016/j.carbpol.2012.02.061. Marconcini, J. M., et al. (2016). Biodegradable polymer blends based on corn starch
Gotow, N., Kobayashi, T., & Kobayakawa, T. (2013). Retronasal aroma allows feature and thermoplastic chitosan processed by extrusion. Carbohydrate Polymers, 137,
extraction from taste of a traditional Japanese confection. 1–9. 452–458. https://doi.org/10.1016/j.carbpol.2015.10.093.
Grigoriadou, I., Paraskevopoulos, K. M., Chrissafis, K., Pavlidou, E., Stamkopoulos, T. G., Meneguin, A. B, Cury, B. S, & Evangelista, R. C. (2014). Films from resistant starch-pectin
& Bikiaris, D. (2011). Effect of different nanoparticles on HDPE UV stability. Polymer dispersions intended for colonic drug delivery. Carbohydrate Polymers, 99, 140–149.
Degradation and Stability, 96(1), 151–163. https://doi.org/10.1016/j. https://doi.org/10.1016/j.carbpol.2013.07.077.
polymdegradstab.2010.10.001. M€oller, H., Grelier, S., Pardon, P., & Coma, V. (2004). Antimicrobial and
Hambleton, A., Fabra, M., Debeaufort, F., Dury-brun, C., & Voilley, A. (2009). Interface physicochemical properties of Chitosan HPMC-based films. Journal of Agricultural
and aroma barrier properties of iota-carrageenan emulsion – based films used for and Food Chemistry, 52(21), 6585–6591. https://doi.org/10.1021/jf0306690.
encapsulation of active food compounds. Journal of Food Engineering, 93(1), 80–88. Moradi, M., Tajik, H., Mehdi, S., Rohani, R., Rasoul, A., Malekinejad, H., et al. (2012).
https://doi.org/10.1016/j.jfoodeng.2009.01.001. LWT - food Science and Technology Characterization of antioxidant chitosan fi lm
Hasheminya, S., Rezaei, R., & Ghanbarzadeh, B. (2019). Development and incorporated with Zataria multi fl ora Boiss essential oil and grape seed extract.
characterization of biocomposite films made from kefiran , carboxymethyl cellulose Lebensmittel-Wissenschaft und -Technologie- Food Science and Technology, 46(2),
and Satureja Khuzestanica essential oil. Food Chemistry, 289(March), 443–452. 477–484. https://doi.org/10.1016/j.lwt.2011.11.020.
https://doi.org/10.1016/j.foodchem.2019.03.076. Morelli, C. L., Mahrous, M., Belgacem, M. N., Branciforti, M. C., Bretas, R. E. S., & Bras, J.
Hazra, A., Alexander, K., Dollimore, D., & Riga, A. (2004). Characterization of some (2015). Natural copaiba oil as antibacterial agent for bio-based active packaging.
essential oils and their key components. Journal of Thermal Analysis and Calorimetry, Industrial Crops and Products. https://doi.org/10.1016/j.indcrop.2015.03.036.
75, 317–330. https://doi.org/10.1023/B:JTAN.0000017352.86803.6d. Müller, P., Renner, K., M� ocz�o, J., Fekete, E., & Puk�
anszky, B. (2014). Thermoplastic
Hosseini, M. H., Razavi, S. H., & Mousaviousavi, M. A. (2009). Antimicrobial, physcial starch/wood composites: Interfacial interactions and functional properties.
and mechanical properties of chitosaan-based films incorporated with thyme, clove Carbohydrate Polymers, 102(1), 821–829. https://doi.org/10.1016/j.
and cinnamon essential oils. Journal of Food Processing and Preservation, 33(6), carbpol.2013.10.083.
727–743. https://doi.org/10.1111/j.1745-4549.2008.00307.x. Nisar, T., Wang, Z.-C., Yang, X., Tian, Y., Iqbal, M., & Guo, Y. (2018). Characterization of
Huang, Q., Yu, H., & Ru, Q. (2010). Bioavailability and delivery of nutraceuticals using citrus pectin films integrated with clove bud essential oil: Physical, thermal, barrier,
nanotechnology. Journal of Food Science, 75(1), R50–R57. https://doi.org/10.1111/ antioxidant and antibacterial properties. International Journal of Biological
j.1750-3841.2009.01457.x. Macromolecules, 106, 670–680. https://doi.org/10.1016/J.IJBIOMAC.2017.08.068.
IBGE. (2017). Número de estabelecimentos agropecu� arios e Quantidade produzida, por Noori, S., Zeynali, F., & Almasi, H. (2018). Antimicrobial and antioxidant efficiency of
produtos da extraç~ao vegetal. IBGE. https://www.ibge.gov.br/estatisticas/economica nanoemulsion-based edible coating containing ginger (Zingiber officinale) essential
s/agricultura-e-pecuaria/21814-2017-censo-agropecuario.html?edicao¼25757&t¼r oil and its effect on safety and quality attributes of chicken breast fillets. Food
esultados. Control. https://doi.org/10.1016/j.foodcont.2017.08.015.
Jim�enez, A., Fabra, M. J., & Talens, P. (2012). Edible and biodegradable starch Films : A Norajit, K., Kim, K. M., & Ryu, G. H. (2010). Comparative studies on the characterization
review. https://doi.org/10.1007/s11947-012-0835-4, 2058–2076. and antioxidant properties of biodegradable alginate films containing ginseng
Kanmani, P., & Rhim, J. W. (2014). Antimicrobial and physical-mechanical properties of extract. Journal of Food Engineering, 98(3), 377–384. https://doi.org/10.1016/j.
agar-based films incorporated with grapefruit seed extract. Carbohydrate Polymers, jfoodeng.2010.01.015.
102(1), 708–716. https://doi.org/10.1016/j.carbpol.2013.10.099. Nur Fatin Nazurah, R., & Nur Hanani, Z. A. (2017). Physicochemical characterization of
Kavoosi, G., Derakhshan, M., Salehi, M., & Rahmati, L. (2018). Microencapsulation of kappa-carrageenan (Euchema cottoni) based films incorporated with various plant
zataria essential oil in agar, alginate and carrageenan. Innovative Food Science & oils. Carbohydrate Polymers, 157, 1479–1487. https://doi.org/10.1016/j.
Emerging Technologies, 45, 418–425. https://doi.org/10.1016/j.ifset.2017.12.010. carbpol.2016.11.026.
Kokoszka, S., Debeaufort, F., Hambleton, A., Lenart, A., & Voilley, A. (2010). Protein and Ojagh, S. M., Rezaei, M., Rezavi, S. H., & Hosseini, S. M. H. (2010). Development and
glycerol contents affect physico-chemical properties of soy protein isolate-based evaluation of a novel biodegradable film made from chitosan and cinnamon oil with
edible films. Innovative Food Science & Emerging Technologies, 11(3), 503–510. low affinity toward water. Food Chemistry, 122, 161–166. https://doi.org/10.1016/j.
https://doi.org/10.1016/j.ifset.2010.01.006. foodchem.2010.02.033.
Leandro, L. M., De Sousa Vargas, F., Barbosa, P. C. S., Neves, J. K. O., Da Silva, J. A., & Da Ortega-Toro, R., Jim� enez, A., Talens, P., & Chiralt, A. (2014). Properties of starch-
Veiga-Junior, V. F. (2012). Chemistry and biological activities of terpenoids from hydroxypropyl methylcellulose based films obtained by compression molding.
copaiba (Copaifera spp.) oleoresins. Molecules, 17(4), 3866–3889. https://doi.org/ Carbohydrate polymers. https://doi.org/10.1016/j.carbpol.2014.03.059.
10.3390/molecules17043866. Otoni, C. G., Avena-Bustillos, R. J., Olsen, C. W., Bilbao-S� ainz, C., & McHugh, T. H.
Liang, R., Xu, S., Shoemaker, C. F., Li, Y., Zhong, F., & Huang, Q. (2012). Physical and (2016). Mechanical and water barrier properties of isolated soy protein composite
antimicrobial properties of peppermint oil nanoemulsions. Journal of Agricultural and edible films as affected by carvacrol and cinnamaldehyde micro and nanoemulsions.
Food Chemistry, 60(30), 7548–7555. https://doi.org/10.1021/jf301129k. Food Hydrocolloids, 57, 72–79. https://doi.org/10.1016/j.foodhyd.2016.01.012.
Lorevice, M. V., Otoni, C. G., Moura, M. R. de, & Mattoso, L. H. C. (2016). Chitosan Otoni, C. G., Moura, M. R. de, Aouada, F. A., Camilloto, G. P., Cruz, R. S., Lorevice, M. V.,
nanoparticles on the improvement of thermal, barrier, and mechanical properties of et al. (2014). Antimicrobial and physical-mechanical properties of pectin/papaya
high- and low-methyl pectin films. Food Hydrocolloids, 52, 732–740. https://doi.org/ puree/cinnamaldehyde nanoemulsion edible composite films. Food Hydrocolloids,
10.1016/j.foodhyd.2015.08.003. 41, 188–194. https://doi.org/10.1016/j.foodhyd.2014.04.013.
Mahmood, K., Zuber, M., Mahboob, S., Sultana, T., & Sultana, S. (2010). Surface Pająk, P., Przetaczek-Ro_znowska, I., & Juszczak, L. (2019). Development and
characteristics of UV-irradiated chitin-based shape memory polyurethanes. physicochemical, thermal and mechanical properties of edible films based on
Carbohydrate Polymers, 80(1), 229–234. https://doi.org/10.1016/j. pumpkin, lentil and quinoa starches. International Journal of Biological
carbpol.2009.11.015. Macromolecules, 138, 441–449. https://doi.org/10.1016/j.ijbiomac.2019.07.074.
Manrich, A., Moreira, F. K. V., Otoni, C. G., Lorevice, M. V., Martins, M. A., & Pankey, G. A., & Sabath, L. D. (2004). Clinical relevance of bacteriostatic versus
Mattoso, L. H. C. (2017). Hydrophobic edible films made up of tomato cutin and bactericidal mechanisms of action in the treatment of gram-positive bacterial
pectin. Carbohydrate Polymers, 164, 83–91. https://doi.org/10.1016/j. infections. Clinical Infectious Diseases, 38(6), 864–870. https://doi.org/10.1086/
carbpol.2017.01.075. 381972.
Marangon, C. A., Martins, V. C. A., Leite, P. M. F., Santos, D. A., Nitschke, M., & Park, S., & Zhao, Y. (2004). Incorporation of a high concentration of mineral or vitamin
Plepis, A. M. G. (2017). Chitosan/gelatin/copaiba oil emulsion formulation and its into chitosan-based films. Journal of Agricultural and Food Chemistry, 52(7),
potential on controlling the growth of pathogenic bacteria. Industrial Crops and 1933–1939. https://doi.org/10.1021/jf034612p.
Products, 99, 163–171. https://doi.org/10.1016/j.indcrop.2017.02.007. Patel, P., Hull, T. R., McCabe, R. W., Flath, D., Grasmeder, J., & Percy, M. (2010).
Mechanism of thermal decomposition of poly(ether ether ketone) (PEEK) from a

11
L.B. Norcino et al. Food Hydrocolloids 106 (2020) 105862

review of decomposition studies. Polymer Degradation and Stability, 95(5), 709–718. Escherichia coli O157:H7 and Salmonella Typhimurium on green beans. Food
https://doi.org/10.1016/J.POLYMDEGRADSTAB.2010.01.024. Control, 50, 215–222. https://doi.org/10.1016/j.foodcont.2014.08.029.
Pelissari, F. M., Grossmann, M. V. E., Yamashita, F., & Pined, E. A. G. (2009). Shellhammer, T. H., & Krochta, J. M. (1997). Whey protein emulsion film performance as
Antimicrobial, mechanical, and barrier properties of cassava starch-chitosan films affected by lipid type and amount. Journal of Food Science, 62(2), 390–394. https://
incorporated with oregano essential oil. Journal of Agricultural and Food Chemistry, doi.org/10.1111/j.1365-2621.1997.tb04008.x.
57(16), 7499–7504. https://doi.org/10.1021/jf9002363. Shojaee-Aliabadi, S., Hosseini, H., Mohammadifar, M. A., Mohammadi, A.,
Pepper, I., Gerba, C., & Brusseau, M. (2011). Biotic Characteristics of the Environment. In Ghasemlou, M., Ojagh, S. M., et al. (2013). Characterization of antioxidant-
Environmental and Pollution Science (2nd). Academic Press. antimicrobial κ-carrageenan films containing Satureja hortensis essential oil.
Pereda, M., Aranguren, M. I., & Marcovich, N. E. (2010). Food Hydrocolloids Caseinate fi International Journal of Biological Macromolecules, 52(1), 116–124. https://doi.org/
lms modi fi ed with tung oil, 24, 800–808 https://doi.org/10.1016/j.foodhyd.2010.0 10.1016/j.ijbiomac.2012.08.026.
4.007. Singthong, J., Cui, S. W., Ningsanond, S., & Douglas Goff, H. (2004). Structural
Pereda, M., Amica, G., & Marcovich, N. E. (2012). Development and characterization of characterization, degree of esterification and some gelling properties of Krueo Ma
edible chitosan/olive oil emulsion films. Carbohydrate Polymers, 87, 1318–1325. Noy (Cissampelos pareira) pectin. Carbohydrate Polymers, 58(4), 391–400. https://
https://doi.org/10.1016/j.carbpol.2011.09.019. doi.org/10.1016/J.CARBPOL.2004.07.018.
Perez-Gago, M. B., & Krochta, J. M. (2001). Lipid particle size effect on water vapor Svetlichny, G., Külkamp-Guerreiro, I. C., Dalla Lana, D. F., Bianchin, M. D.,
permeability and mechanical properties of whey protein/beeswax emulsion films. Pohlmann, A. R., Fuentefria, A. M., et al. (2017). Assessing the performance of
Journal of Agricultural and Food Chemistry, 49(2), 996–1002. https://doi.org/ copaiba oil and allantoin nanoparticles on multidrug-resistant Candida parapsilosis.
10.1021/jf000615f. Journal of Drug Delivery Science and Technology, 40, 59–65. https://doi.org/10.1016/
Ranjbaryan, S., Pourfathi, B., & Almasi, H. (2019). Reinforcing and release controlling j.jddst.2017.05.020.
effect of cellulose nanofiber in sodium caseinate films activated by nanoemulsified Synytsya, A., Copíkov�
� a, J., Mat�ejka, P., & Machovi�c, V. (2003). Fourier transform Raman
cinnamon essential oil. Food Packaging and Shelf Life, 21(April). https://doi.org/ and infrared spectroscopy of pectins. Carbohydrate Polymers, 54(1), 97–106. https://
10.1016/j.fpsl.2019.100341. doi.org/10.1016/S0144-8617(03)00158-9.
Rodrigues, D. C., Cunha, A. P., Silva, L. M. A., Rodrigues, T. H. S., Gall~ ao, M. I., & Tang, S. Y., Manickam, S., Wei, T. K., & Nashiru, B. (2012). Formulation development
Azeredo, H. M. C. (2018). Emulsion films from tamarind kernel xyloglucan and and optimization of a novel Cremophore EL-based nanoemulsion using ultrasound
sesame seed oil by different emulsification techniques. Food Hydrocolloids, 77, cavitation. Ultrasonics Sonochemistry, 19(2), 330–345. https://doi.org/10.1016/j.
270–276. https://doi.org/10.1016/j.foodhyd.2017.10.003. ultsonch.2011.07.001.
Roland, I., Piel, G., Delattre, L., & Evrard, B. (2003). Systematic characterization of oil-in- Trindade, F. T. T., Stabeli, R. G., Pereira, A. A., Facundo, V. A., & Silva, A. de A. (2013).
water emulsions for formulation design. International Journal of Pharmaceutics, 263 Copaifera multijuga ethanolic extracts, oil-resin, and its derivatives display larvicidal
(1–2), 85–94. https://doi.org/10.1016/S0378-5173(03)00364-8. activity against Anopheles darlingi and Aedes aegypti (Diptera: Culicidae). Brazilian
S�
anchez-Gonz� alez, L., Ch�
afer, M., Chiralt, A., & Gonz� alez-Martínez, C. (2010). Physical Journal of Pharmacognosy, 23(3), 464–470. https://doi.org/10.1590/S0102-
properties of edible chitosan films containing bergamot essential oil and their 695X2013005000038.
inhibitory action on Penicillium italicum. Carbohydrate Polymers, 82(2), 277–283. Veiga, V. F., & Pinto, A. C. (2002). O G^enero Copaifera L. Quimica Nova. https://doi.org/
https://doi.org/10.1016/j.carbpol.2010.04.047. 10.1590/S0100-40422002000200016.
S�
anchez-Gonz� alez, L., Chiralt, A., Gonz�
alez-Martínez, C., & Ch� afer, M. (2011). Effect of Veiga, V. F., Rosas, E. C., Carvalho, M. V., Henriques, M. G. M. O., & Pinto, A. C. (2007).
essential oils on properties of film forming emulsions and films based on Chemical composition and anti-inflammatory activity of copaiba oils from Copaifera
hydroxypropylmethylcellulose and chitosan. Journal of Food Engineering, 105(2), cearensis Huber ex Ducke, Copaifera reticulata Ducke and Copaifera multijuga
246–253. https://doi.org/10.1016/j.jfoodeng.2011.02.028. Hayne-A comparative study. Journal of Ethnopharmacology, 112(2), 248–254.
Sanyang, M. L., Sapuan, S. M., Jawaid, M., Ishak, M. R., & Sahari, J. (2016). Effect of https://doi.org/10.1016/j.jep.2007.03.005.
plasticizer type and concentration on physical properties of biodegradable films Willats, W. G., Knox, J. P., & Mikkelsen, J. D. (2006). Pectin: New insights into an old
based on sugar palm (arenga pinnata) starch for food packaging. Journal of Food polymer are starting to gel. Trends in Food Science & Technology, 17(3), 97–104.
Science & Technology, 53(1), 326–336. https://doi.org/10.1007/s13197-015-2009-7. https://doi.org/10.1016/j.tifs.2005.10.008.
Saricaoglu, F. T., Tural, S., Gul, O., & Turhan, S. (2018). High pressure homogenization Yi, J., Li, Y., Zhong, F., & Yokoyama, W. (2014). The physicochemical stability and in
of mechanically deboned chicken meat protein suspensions to improve mechanical vitro bioaccessibility of beta-carotene in oil-in-water sodium caseinate emulsions.
and barrier properties of edible films. Food Hydrocolloids, 84, 135–145. https://doi. Food Hydrocolloids, 35, 19–27. https://doi.org/10.1016/j.foodhyd.2013.07.025.
org/10.1016/j.foodhyd.2018.05.058. Zú~niga, R. N., Skurtys, O., Osorio, F., Aguilera, J. M., & Pedreschi, F. (2012). Physical
Severino, R., Ferrari, G., Vu, K. D., Donsì, F., Salmieri, S., & Lacroix, M. (2015). properties of emulsion-based hydroxypropyl methylcellulose films: Effect of their
Antimicrobial effects of modified chitosan based coating containing nanoemulsion of microstructure. Carbohydrate Polymers, 90(2), 1147–1158. https://doi.org/10.1016/
essential oils, modified atmosphere packaging and gamma irradiation against j.carbpol.2012.06.066.

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