Food Packaging and Shelf Life 27 (2021) 100615

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Food Packaging and Shelf Life

journal homepage: www.elsevier.com/locate/fpsl

Starch-based films enriched with nanocellulose-stabilized Pickering

emulsions containing different essential oils for possible applications in
food packaging
Alana G. Souza a, Rafaela R. Ferreira a, Larissa C. Paula a, Sushanta K. Mitra b, Derval S. Rosa a, *
a
Centro de Engenharia, Modelagem e Ciências Sociais Aplicadas, CECS/Universidade Federal do ABC (UFABC), Avenida dos Estados, 5001, CEP: 09210-580, Santo
André, SP, Brazil
b
Waterloo Institute for Nanotechnology, Department of Mechanical & Mechatronics Engineering, University of Waterloo, Waterloo, ON, N2L 3G1, Canada

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

Keywords: Consumers are increasingly demanding biodegradable food packaging with a minimal amount of synthetic
Active packaging preservatives and, at the same time, worried about potential contaminants, particularly during any pandemic
Cardamom essential oil event. Plant essential oils (EO) are natural compounds with remarkable antimicrobial properties. This study
Ho wood (Cinnamomum camphora) essential
aimed to prepare thermoplastic starch films (TPS) containing nanocellulose-stabilized Pickering emulsions (PE)
oil
Cinnamon essential oil
of different essential oils: ho wood (Cinnamomum camphora), cardamom, and cinnamon, and investigate the
Biobased films suitability of biopolymer films as packaging material. The films were prepared via casting method and were
characterized concerning chemical interactions by FT-Raman and FTIR, mechanical, crystallinity, thermal, and
water vapor permeability properties. PE Ho wood-starch films showed strong chemical interactions, which
significantly improved the film’s mechanical resistance. The films with cardamom and cinnamon showed low
compatibility, with a decrease in tensile strength. All films showed less crystallinity than the pristine TPS, which
can be attributed to the starch chain organization’s changes. The films showed high thermal stability due to the
strong molecular interactions among starch chains and PE, as confirmed by TGA and DSC analysis. The films’
thermal stability is an indication that it can be safely applied in the food industry. Besides, the films showed a
lower water vapor transmission rate, and the water may act as a carrier for PE, improving the release of the active
compounds. This study reveals the differences between three essential oils incorporated into starch-based films.
The ho wood films are the most promising PE to be applied as biodegradable active packaging.

1. Introduction
In recent years, there is a growing need to replacing petroleum-based
plastics, such as polypropylene and polyethylene, due to the enormous
environmental concern due to their non-renewability, significant carbon
footprint, and low biodegradability (Valencia, Nomena, Mathew, &
Velikov, 2019). Therefore, there is a strong need to develop new prod­
ucts from sustainable raw materials. Starch is a common biopolymer
available in abundance, with low cost and ease of handling (Li, Ye, Lei, &
Zhao, 2018). This polymer is a potential food packaging candidate
because its films have good mechanical and thermal properties, biode­
gradability, and renewability (Zhou, Yang, Wang, & Chen, 2019).
Biopolymers like starch represent a challenge for food packaging due
to their chemical properties, that act as microbial food. To overcome this
limitation, it is possible to chemical functionalize the packaging films to
avoid microbial attack by releasing active components to the food. Be­
sides that, together with the demand for biodegradable packaging, there
is a need to functionalize the chosen biopolymer to prevent and decrease
bacterial and fungal attacks (Roy & Rhim, 2020). So, it is possible to
prolong biopolymers’ film shelf life and improve its functionality,
thereby obtaining an active packaging. The objective of active pack­
aging is to improve its functionality, and the main types include anti­
microbial, antifungal, and antioxidant. Antimicrobial films are usually
developed to increase the food shelf life through active agents interac­
tion either within the food or food package headspace, aiming to inhibit,
reduce, or retard microorganisms’ growth on food surface (De Oliveira

* Corresponding author.
E-mail addresses: alana.gabrieli@ufabc.edu.br (A.G. Souza), reis.f@ufabc.edu.br (R.R. Ferreira), larissa.canuto@aluno.ufabc.edu.br (L.C. Paula), skmitra@
uwaterloo.ca (S.K. Mitra), derval.rosa@ufabc.edu.br (D.S. Rosa).

https://doi.org/10.1016/j.fpsl.2020.100615
Received 22 April 2020; Received in revised form 27 October 2020; Accepted 29 November 2020
Available online 14 December 2020
2214-2894/© 2020 Elsevier Ltd. All rights reserved.
A.G. Souza et al.
Fig. 1. Schematic for the preparation of Pickering emulsion and active starch films, where PE is the Pickering emulsions obtained for each essential oil, and TPS is the
thermoplastic starch films.
et al., 2020). Various antimicrobial agents have been used in the pro­
duction of active packaging films, such as metal and metal oxides of
silver (Peighambardoust, Peighambardoust, Mohammadzadeh Pourna­
sir, & Pakdel, 2019), copper (Castro Mayorga, Fabra Rovira, Cabedo
Mas, Sánchez Moragas, & Lagarón Cabello, 2018), CuO (Dehghani,
Peighambardoust, Peighambardoust, Hosseini, & Regenstein, 2019),
ZnO (Azizi-Lalabadi, Ehsani, Ghanbarzadeh, & Divband, 2020), and
TiO2 nanoparticles (El-Gendy, Abou-Zeid, Salama, Diab, & El-Sakhawy,
2017). However, due to the effects of synthetic agents’ consumption on
human health and its toxicity, consumers are demanding more natural
agents (Fasihi et al., 2019).
Essential oils (EO) are natural substances that have stood out as
excellent antibacterial and antifungal agents due to the presence of al­
cohols, phenols, terpenes, esters, and others bioactive ingredients
(Gavahian, Chu, Lorenzo, Mousavi, & Barba, 2020; Shin et al., 2019).
Several studies were conducted to verify these OEs in active food
packaging (Ahmed et al., 2019; Ju et al., 2019; Silva, Caldera, Trotta,
Nerín, & Domingues, 2019). However, EOs have low surface energy and
high volatility and are highly sensitive to oxidation, light, and thermal
decomposition (Cossu, Wang, Chaudhari, & Nitin, 2015). These limita­
tions make the use of EO a challenge, and the high volatility reduces the
stability of its biological activity (Cossu et al., 2015; Shin et al., 2019).
For this reason, different approaches have been studied to improve the
applicability of EO. These include micro- and nanoemulsions, micro-
and nanoencapsulation using different wall materials, such as bio­
polymers, nanofibers, and nanosponges, and also the addition of the free
essential oils in polymeric matrices (do Vale et al., 2019; Hadidi,
2
Food Packaging and Shelf Life 27 (2021) 100615
Pouramin, Adinepour, Haghani, & Jafari, 2020; Hassanzadazar, You­
sefizadeh, Ghafari, Fathollahi, & Aminzare, 2019; Ribeiro-Santos,
Andrade, & Sanches-Silva, 2017; Simionato, Domingues, Nerín, & Silva,
2019; Wen et al., 2016). Prakash et al. prepared linalool nanoemulsions
and obtained a stable system with a mean droplet diameter of 10 nm,
with excellent antibacterial activity (Prakash, Vadivel, Rubini, &
Nithyanand, 2019). Hadidi et al. (2020) prepared chitosan nanoparticles
loaded with clove essential oil. Criado et al. (2019) prepared alginate
beads loaded with thyme essential oil containing nanocellulose and
observed that the system increased the oil stability, and showed good
antimicrobial properties.
The inherent stability issues related to EO can be circumvented by
applying the Pickering emulsions (PE) technique for its active in­
gredients. Pickering emulsions stabilize the oil-in-water solution by
using solid particles (metals, oxides, anisotropic particles, etc.) as sta­
bilizers accumulated at the interface between the phases, stabilizing oil
droplets by electrostatic and steric mechanisms (Pickering, 1906; Zou,
Sipponen, & Österberg, 2019). This stabilization method decreases the
droplets sizes and avoid the coalescence of the droplets (Mikulcová,
Bordes, & Kašpárková, 2016), and are prepared using sufficient energy,
such as homogenization, ultrasonication, and other. The studies
regarding incorporating this emulsion type as active compounds into
biopolymer-based films are rare (Almasi, Azizi, & Amjadi, 2020). A few
reported studies generally use only one type of EO and investigate its
influence in the polymer films (Cossu et al., 2015; Fasihi et al., 2019; Zou
et al., 2019) about packaging material.
There is no available literature that provides a clear picture in
A.G. Souza et al.
determining the ideal candidate for food packaging to the best of our
knowledge. This work aims to provide a guideline for using such film in
the food packaging industry. For this purpose, we prepared and char­
acterized starch biopolymer films containing nanocellulose-stabilized
Pickering emulsions of essential oils. Three different essential oils
were used to prepare the PE: cardamom, cinnamon cassia, and ho wood
(linalool active compound). The emulsions’ effect on the films was
evaluated through chemical properties (FTIR and FT-Raman), mechan­
ical properties, crystallinity, thermal analyses, and vapor permeability.
2. Materials and methods
2.1. Materials
Corn starch (AMISOL 3408) was supplied by Ingredion (São Paulo,
Brazil). Cellulose nanocrystals (CNC) were prepared according to the
methodology described in our previous work (Ferreira et al., 2019).
Chemical reagents with analytical grade were purchased from
Sigma-Aldrich (São Paulo, Brazil). The essential oils of Ho wood (Cin­
namomum camphora var. linalooliferum, CAS Number 92201-50-8), cin­
namon cassia (Cinnamomum cassia, CAS Number 84961-46-6), and
cardamom (Elettaria cardamomum, CAS number 8000-66-6) were pur­
chased from Ferquima (São Paulo, Brazil). The essential oil main char­
acteristics are presented in Table 1S (Supplementary material).
2.2. Preparation of Pickering emulsions
The oil-in-water (O/W) emulsions were prepared by dispersing
0.75 wt.% of CNC in distilled water. The O/W ratio was 80/20 (Lu et al.,
2019; Zhai, Lin, Liu, & Yang, 2018). Then, the different essential oils
(EO) were added to the solution, and the primary emulsions were pre­
pared using an Ultra-Turrax blender (IKA T25, Staufen, Germany) at
5000 rpm for 40 min. The adopted nomenclatures were PE-X, where PE
is assigned to "Pickering emulsions," and X is the essential oil
(cardamom, cinnamon cassia, or ho wood). The different essential oils
were chosen based on different chemical structures, which result in
different stabilizations and interactions with starch. Cardamom is
mainly composed of terphenyl acetate, which contains cyclohexene and
an ester end group, stable and low reactive due to the local resonance.
Cinnamon contains a highly stable benzene group and an aldehyde end
group, and the ho wood contains hydroxyls groups from the alcohol that
are highly reactive.
2.3. Preparation of active films
Thermoplastic starch-based films were prepared via casting method.
4 wt% of starch was dispersed in distilled water and continuously stirred
at 80 ◦ C to achieve the starch gelatinization. Then, 1 wt% of glycerol (to
the dry starch mass) was added, and the mixture was stirred at 800 rpm
for 5 min. The biopolymer films were prepared by mixing the starch and
PE containing CNC; concentrations of 2 wt% and 5 wt% of PE were
added, and the mixture was stirred at 50 ◦ C for 15 min. Finally, the
resulting solution was cast onto polystyrene plates and dried in an oven
at 35 ◦ C for 12 h. The adopted methodology is illustrated in Fig. 1. The
adopted nomenclatures were TPS-Y% PE-X, where Y is the Pickering
emulsion (PE) (2 or 5%) content, and X is the essential oil (cardamom,
cinnamon cassia, or ho wood).
2.4. Characterization
2.4.1. Fourier transform Raman (FT-Raman) spectroscopy
The films were analyzed with an FT-Raman – MultiRaman, Bruker
Optics, with a 1064 nm wavelength and 150 W power laser. The data
acquisition was carried out in a range of 600-4000 cm− 1, and 32 scans
were accumulated in each sample with 4 cm− 1 spectral resolution.
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Food Packaging and Shelf Life 27 (2021) 100615
2.4.2. Fourier transform infrared spectroscopy
Fourier transform infrared spectroscopy (FT-IR) was conducted using
a Frontier 94,942 (PerkinElmer, USA) in the range 4000− 500 cm− 1. 32
scans were accumulated in each sample with 4 cm− 1 spectra resolution.
It was used an attenuated total reflectance (ATR) accessory equipped
with diamond.
2.4.3. Mechanical tests
The tensile tests were investigated using an Instron 3367 (Norwood,
USA) equipment, at room temperature, following the standard ASTM
D638-14. It was used a load cell of 50 N and a test speed of 25 mm/
min− 1, and the film thickness was 0.15 ± 0.05 mm.
2.4.4. X-ray diffraction
X-ray diffraction measurements were conducted using a D8 Focus
diffractometer (Bruker AXS - Karlsruhe, Germany) at 40 kV and 40 mA.
Monochromatic CuKα1 radiation (λ =1.54056 Å) was used, at a step
width of 0.01◦ and counting time of 100 s at each 0.5◦ , from 2θ = 10 to
60◦ . Eq. (1) was used to estimate the crystallinity index (CI) of TPS films
by the ratio between the crystalline peak (Ic) and the amorphous halo
(Ia) (Mariano, Chirat, El Kissi, & Dufresne, 2016; Rocha et al., 2018).
Ic
CI = x 100% (1)
Ic + Ia
2.4.5. Thermogravimetric analysis
The thermal stability was evaluated using an equipment STA 6000
(PerkinElmer, USA). The samples were added to alumina pans and
heated from 30 to 600 ◦ C at the rate of 10 ◦ C min− 1 under nitrogen at­
mosphere (20 mL min− 1).
2.4.6. Differential scanning calorimetry (DSC)
The TPS films’ thermal behavior was determined using a DSC Q se­
ries (TA Instruments) under a nitrogen atmosphere (20 mL.min− 1). The
samples were heated to − 20 ◦ C to 150 ◦ C.
2.4.7. Water vapor permeability
Water vapor permeability (WVP) tests were carried out following a
modified version of the standard ASTM E96/E96M-16, as described by
Paula, De Melo, Camani, Rosa, and Carastan (2019). Films were placed
and sealed on the top of permeation cells (15 mm of internal diameter x
35 mm depth). The cells were placed in desiccators containing a satu­
rated NaCl solution (25 ◦ C, 75 % RH). The weight gain was monitored
every 24 for 7 days. The experiments were conducted in triplicate. The
water vapor transmission rate (WVTR) can be defined as:
G
WVTR = (2)
tA
G is the change in weight, t is the time, and A is the test balloon’s mouth
area. To calculate WVP, in g Pa− 1 m− 1 s− 1, the following equation was
used:
WPTR. L
WVP = x 100% (3)
ΔP
L is film thickness, and ΔP is the partial differential of the film’s water
vapor.
2.4.8. Statistical analysis
The statistical analysis was used to evaluate the water vapor
permeability (WVP) and mechanical properties variables. The samples
were measured in triplicate and quintuplicate, respectively. Results
were subjected to one-way variance analysis (ANOVA) and means were
compared by post-hoc analysis performed by the Tukey test multiple
range at significance level p < 0.05.
A.G. Souza et al.
Fig. 2. FT-Raman spectra of the thermoplastic starch films (TPS) without and with Pickering Emulsions (PE) with different essential oils: a) Ho wood (TPS-X% PE Ho
wood), b) Cardamom (TPS-X% PE Cardamom), and c) Cinnamon (TPS-X% PE Cinnamon), where X is the PE content (2 or 5%).
3. Results and discussion
3.1. Fourier transform Raman (FT-Raman) spectroscopy
The Raman spectroscopy was used to evaluate possible interactions
between starch and Pickering emulsions through specific signatures
depending on functional groups (Escamilla-García et al., 2017). The
Raman spectra of TPS films with and without the Pickering emulsions
are exhibited in Fig. 2a–c. The main key peaks and bands are observed in
the region 3400− 3000 cm− 1 (O–H vibration), 1500− 800 cm− 1 (the
fingerprint region), and below 800 cm− 1. The main starch peaks are:
3000− 2800 cm− 1 (C–H stretching vibration), 1460 cm− 1 (CH2
bending), 1390 cm− 1 (CH2 scissoring, C–H, and C–O–H deformation),
1340 cm− 1 (C–O–H bending, CH2 twisting), 1258 cm− 1 (CH2OH (side
chain) related mode), 1122 cm-1 (C–O stretching, C–O–H bending),
1076 cm− 1 (C–O–H bending), 946 cm− 1 (skeletal mode vibrations of
α-1,4 glycosidic linkage, (C–O–C)), and 851 cm− 1 (C(1)–H, CH2
deformation) (Kizil, Irudayaraj, & Seetharaman, 2002).
Considering the PE Ho wood, the films are presented in Fig. 2a (and a
detailed zoom of the spectra is presented in Fig. 1S); slight changes were
observed after adding the emulsions. TPS-5% PE Ho wood showed a new
peak at 1423 cm− 1 (CH2 and CH3 deformation) (Do, Hadji-Minaglou,
Antoniotti, & Fernandez, 2015). Fig. 3 shows a possible approximation
scheme between starch and cellulose, or starch and essential oil. Since a
possible interaction causes a change in the HO-CH3 starch group, the
new peak formed may be an indication that there is a tendency for the
components to approach and interact physically, changing the molecu­
lar vibrations of the compounds (Fig. 3a). This change is also reflected
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Food Packaging and Shelf Life 27 (2021) 100615
by peaks 1241 and 1048 cm-1, associated with e CH2OH (side chain)
related mode and the C–O–H deformation mode (Nobrega, Olivato,
Mueller, & Yamashita, 2012; Sindhu, Devi, & Khatkar, 2019). This
interaction between the components helps retain the essential oil in the
polymeric matrix, prolonging its release time and, consequently, the
food shelf life.
The TPS-PE Cardamom film spectra are presented in Fig. 2b. FT-
Raman spectra’s main changes were observed at 1397, 1342, 1235,
1144, 1125, 1108, and 910 cm− 1. The decrease in intensity at peaks
1235, 1144, 1155, and 1108 cm− 1 are attributed to variations in the
modes of vibration and deformation associated with the groups: CH2OH
(side chain), C–O–H, C–O stretching, and C–O–H bending (Nobrega
et al., 2012; Sindhu, Devi, & Khatkar, 2019). Also, peaks at 1397, 1287,
and 1235 cm− 1 practically disappeared. These peaks are associated with
CH2 scissoring, C–H and C–O–H deformation, and CH2OH (side chain)
related mode (Kizil et al., 2002; Nobrega et al., 2012). According to
Escamilla-García et al., the disappearance of some characteristic peaks is
indicative of the chemical bond between the components of the film, i.e.,
the starch and the cardamom oil (Escamilla-García et al., 2017).
Besides, the peak at 910 cm− 1 is associated with C–O–C vibrations
of α-1,4 glycosidic linkages. This peak’s disappearance can be related to
a conformational change in the starch chains (Kizil et al., 2002). Since
the cardamom chemical structure (Terpenyl acetate as a major com­
pound) has a cycle hexane group and a large spatial arrangement, the
PE-Cardamom addition can result in rotations and translations of the
TPS chain, reflecting a change in the peak at 910 cm-1 (Fig. 3b).
The TPS-PE Cinnamon films showed the poorest interaction between
starch and essential oil, which can be attributed to the cinnamon EO’s
A.G. Souza et al.
Fig. 3. Representative scheme of possible interactions between the EO major compounds with TPS: a) Ho wood (linalool), b) Cardamom (terphenyl acetate), c)
Cinnamon (cinnamaldehyde) and, d) cellulose (stabilizing agent).
chemical structure. The main spectral changes observed are the decrease
in intensity at peaks 1396 and 1144 cm− 1 and changes in 1356, 1262,
1460, 1047, 923, and 862 cm− 1. However, no new peaks were observed.
The cinnamaldehyde structure has a benzene ring in its structure and
oxygen with a double bond (Fig. 3c). This structure has no active groups
that tend to interact with starch, and therefore, a chemical interaction is
not expected. This approach can generate TPS chain rotation and
translation, resulting in vibrational changes. For PE-Cinnamon samples,
a possibility is that the interaction occurs between cellulose and starch
since cellulose is the stabilizer of emulsions (Fig. 3d).
3.2. Fourier transform infrared spectroscopy
The different samples’ FTIR spectra were reported in Fig. 4 and
Table 2S (Supplementary information). As the FTIR bands were similar
to FR-Raman, the details are presented in the Supplementary Informa­
tion. Briefly, PE Ho wood films (Fig. 4a) decreased the band 3400− 3000
intensity due to the competitive effect of new hydrogen bonding induced
by essential oil groups. Slight spectral differences were verified due to
the essential oil chemical vibrations. PE Cardamom films (Fig. 4b)
increased peaks 1460, 1417, and 1150 cm− 1 intensity due to the EO
components, such as caryophyllene, germacrene D, and isoborneol,
associated with the antimicrobial properties of cardamom oil (Abarca,
Rodríguez, Guarda, Galotto, & Bruna, 2016; Inan, Kaya, & Albu, 2013;
Kumar, Kumar, Bhandari, & Kumar, 2010; Rout, Sahoo, Jena, & Rao,
2003). PE cinnamon film spectra (Fig. 4c) showed new peaks due to
cinnamon essential oil’s aromatic structure. The small changes are
associated with low PE contents (2 and 5%), which are not enough to
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Food Packaging and Shelf Life 27 (2021) 100615
cause significant chemical changes.
3.3. Mechanical properties
Table 1 presents the measured mechanical properties of film sam­
ples, and the representative mechanical curves are shown in Fig. 2S
(Supplementary material). TPS films elastic modulus (E), tensile
strength (σ), elongation at break (ε) values were 223.7 ± 6.3 MPa,
6.4 ± 0.6 MPa, and 48.3 ± 7.6 %, respectively (Wang, Zhang, Wang, &
Copeland, 2016). Interestingly, the mechanical behavior was highly
dependent on the type of essential oil used, with TPS PE Ho Wood
showing the most significant mechanical results (highest σ and E
values), and TPS PE Cardamom films showing the lowest mechanical
values.
According to previous results, there was a strong interaction between
PE Ho wood and starch. This strong interaction and the newly formed
hydrogen bonds can be associated with a significant increase in E and σ
values. In this case, the emulsification process was possibly more effi­
cient since PE drops did not act as a plasticizer but as a reinforcing agent.
In this case, the internal structure of the starch was kept cohesive and
homogeneous. The literature generally reports the EO plasticizer effect,
verified by a significant increase in the elongation values (Almasi et al.,
2020; Escamilla-García et al., 2017; Li, Yang, Deng, Guo, & Xue, 2020;
Otoni, Pontes, Medeiros, & Soares, 2014). Our ε values decreased, and E
values increased, indicating that the Pickering emulsion method’s sta­
bilization was sufficient in stabilizing the droplets and avoided
coalescence.
TPS-PE Cardamom showed the lowest mechanical properties, with a
A.G. Souza et al. Food Packaging and Shelf Life 27 (2021) 100615

Fig. 4. FTIR Spectra of starch films without and with Pickering emulsions (PE) with different oils: a) Ho wood (TPS-X% PE Ho wood), b) Cardamom (TPS-X% PE
Cardamom), and c) Cinnamon (TPS-X% PE Cinnamon), where X is the PE content (2 or 5%).

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A.G. Souza et al. Food Packaging and Shelf Life 27 (2021) 100615

Table 1 resistance and the polymer’s segmental mobility (Almasi et al., 2020).
Mechanical properties of starch films without or with Pickering emulsions: The addition of cardamom or cinnamon weakened the starch molecules’
elastic modulus (E) (MPa), tensile strength (σ) (MPa), elongation at break (ε) hydrogen bonding, destroying the internal network and cohesiveness of
(%), and crystallinity index (CI), calculated by XRD. starch films, which decreased the σ values (Li et al., 2020).
Sample E (MPa) σ (MPa) ε (%) ANOVA and Tukey tests were applied to investigate the PE concen­
TPS 223.7 ± 6.3 6.4 ± 0.6 39.8 ± 6.3 tration influence (2, and 5 wt%) on the elastic modulus (E) of active
TPS 2% PE Ho wood 479.5 ± 11.8 12.9 ± 0.5 26.9 ± 5.3 films containing PE. The ANOVA results (Table 2) indicate that the PE
TPS 5% PE Ho wood 491.7 ± 48.6 10.8 ± 2.7 29.5 ± 7.8 incorporation increased the active film stiffness compared to the pristine
TPS 2% PE Cardamom 130.2 ± 7.3 2.4 ± 0.6 9.1 ± 1.8 TPS. The addition of 2% PE showed a little interaction, which was more
TPS 5% PE Cardamom 71.4 ± 1.3 1.7 ± 0.2 44.7 ± 3.8
TPS 2% PE Cinnamom 361.2 ± 8.5 5.7 ± 0.5 12.8 ± 0.1
intense to the 5% PE addition, revealing a disturbance in the system, and
TPS 5% PE Cinnamom 208.6 ± 22.4 5.1 ± 1.1 32.4 ± 6.8 confirming the statistical difference on the studied mechanical proper­
ties, i.e., the PE addition influenced the films stiffness. Besides, the high
p-values were observed for cinnamon > ho wood > cardamom.
Table 2
ANOVA and Tukey test results comparing the effect of PE addition into starch 3.4. X-ray diffraction
films, considering the elastic modulus values.
The crystalline structure of starch films without and with PE was
Ho wood Cardamom Cinnamon
investigated by XRD analysis; XRD diffractograms are shown in Fig. 5.
Interaction p-value Interaction p-value Interaction p-value
The TPS diffractogram showed characteristic peaks at 15.0◦ , 17.1◦ ,
0-2 0.004541 0-2 0.04903 0-2 0.03613 19.7◦ , and 22.1◦ (2θ) (Nawab, Alam, Haq, Lutfi, & Hasnain, 2017;
0-5 0.003966 0-5 0.01295 0-5 0.03613 Sandhu & Lim, 2008). Corn starch shows typical type A-structure, which
2-5 0.8892 2-5 0.1489 2-5 1
presents an arrangement of helices in unit cells with monoclinic sym­
metry (Jiménez, Fabra, Talens, & Chiralt, 2013; Nawab et al., 2017).
significant decrease in stiffness, tensile strength, and elongation at Type B can be obtained from the recrystallization of gelatinized starch,
break. In this case, the plasticizer effect occurred only with 5% PE with three well-defined peaks at ~17◦ , 19◦ , and 22◦ (Tian et al., 2019).
Cardamom. The droplets of PE Cardamom probably interfered in the From Fig. 5, it is possible to observe a mix of starch types A and B.
hydrogen bonds of starch-based films, restricting the stiffness and From XRD patterns, the crystallinity index was calculated, and the
values are presented embedded in Fig. 5. The PE droplets addition

Fig. 5. Diffractograms of starch films without and with Pickering Emulsions (PE) with different essential oils: a) Ho wood (TPS-X% PE Ho wood), b) Cardamom (TPS-
X% PE Cardamom), and c) Cinnamon (TPS-X% PE Cinnamon), where X is the PE content (2 or 5%).

7
A.G. Souza et al. Food Packaging and Shelf Life 27 (2021) 100615

Table 3 According to dos Santos Caetano et al., the EO aromatic structure occurs
Results of TGA (T10) and DTG (Tmax) analysis, followed by DSC (Tm and ΔHm). at higher temperatures (dos S. Caetano et al., 2018). Besides, the thermal
SAMPLES T10% (◦ C) Tmax (◦ C) Tm (◦ C) ΔHm (J/g) stability improvement can be associated with the strong molecular in­
teractions among starch chains, which were reorganized with the PE
TPS 103.2 318.5 99.0 88.1
TPS-2 % PE Ho Wood 149.3 328.7 83.1 80.3 addition, and the hydrogen bonding between the hydroxyl groups of
TPS-5 % PE Ho Wood 112.3 320.0 85.8 100.3 starch and active groups of the essential oils, as indicated by FTIR
TPS-2 % PE Cardamom 139.1 328.8 83.5 161.7 (Mendes et al., 2020). These results are different from those reported in
TPS-5 % PE Cardamom 148.5 326.4 81.9 93.7 the literature, in which there is usually a decrease in Tonset and Tmax
TPS-2 % PE Cinnamom 153.1 325.1 77.3 134.9
TPS-5 % PE Cinnamom 245.2 332.3 94.51 79.44
(Assis et al., 2017; De Camargo Andrade-Molina, Shirai, Victória Eiras
Grossmann, & Yamashita, 2013; Leal et al., 2019; Li et al., 2018;
Peighambardoust et al., 2019). The essential oils act as plasticizers,
changes the starch chains’ organization, modifying the interplanar similar to the glycerol, and both materials are known to be exudation
spacing, and deforming the lattice (Mendes et al., 2020). During the susceptible during film storage or use due to their migration to the film
pasting process, the intermolecular forces between the starch and the surface. Exudation is highly undesirable and results in greater fragility,
essential oils may promote starch granules’ disintegration. All the films less extensibility, and changes in films’ appearance. Even though we did
showed similar results (Tian et al., 2019). not investigate such properties as a function of time, exudation can be
expected to be less in the materials produced here due to the more
significant interactions between the components and the starch, as well
3.5. Thermal stability analyzes
as the significant increases in thermal stability (Mendes et al., 2020).
The films showed excellent thermal stability until the temperature of
The thermogravimetric analysis of the starch films without and with
50 ◦ C, thus having thermal stability to be safely applied in the food in­
Pickering emulsions are shown in Fig. 3S, and the main results are
dustry (Silva-Pereira, Teixeira, Pereira-Júnior, & Stefani, 2015).
summarized in Table 3. All the films showed two weight loss stages, as
The DSC thermograms of all the films are shown in Fig. 6. An
described in the literature. At a temperature between 90 and 120 ◦ C, the
endothermic process can be observed in the range of 50− 120 ◦ C,
first event of weight loss corresponds to the residual moisture and
attributed to the melting of starch crystals formed during the retrogra­
glycerol loss (dos S. Caetano et al., 2018). The second event, between
dation (Medina-Jaramillo, Ochoa-Yepes, Bernal, & Famá, 2017). The
300 and 350 ◦ C, is associated with the starch’s thermal decomposition
addition of PE slightly changed the Tm values (Table 3), which means
and loss of molecular weight fraction (Assis, Lopes, Costa, Flôres, & Rios,
that the essential oil can affect the retrogradation process due to the
2017).
interactions between each mixture component. According to Mathew
TPS-PE films showed higher T10 % and Tmax values (Table 3).

Fig. 6. DSC thermograms recorded in the first heating scan of the starch-based films without and with Pickering Emulsions (PE) with different oils: a) Ho wood (TPS-
X% PE Ho wood), b) Cardamom (TPS-X% PE Cardamom), and c) Cinnamon (TPS-X% PE Cinnamon), where X is the PE content (2 or 5%).

8
A.G. Souza et al. Food Packaging and Shelf Life 27 (2021) 100615

Table 4 coupling forces between the amorphous matrix and the crystallites.
Water vapor permeability results of WVR and WVRT for TPS films without and These interactions can change the starch chains’ alignment, decreasing
with Pickering emulsion addition. the crystallinity of the starch-based films, as reported in the XRD section.
11 1 1 -1 1
Samples WVR (10− g m− Pa− s ) WVTR (g day− m− 2)

TPS 2.6 ± 0.1 1.0 × 10− 5 3.6. Water vapor permeability

5
TPS-2% PE Ho Wood 2.8 ± 0.2 1.2 × 10−
5
TPS-5% PE Ho Wood 2.9 ± 0.2 1.3 × 10− The water vapor barrier property of a packaging film plays an
5
TPS-2% PE Cardamom 2.9 ± 0.0 1.2 × 10−
TPS-5% PE Cardamom 2.6 ± 0.3 1.1 × 10− 5 essential role in preventing or decreasing the moisture exchange be­
TPS-2% PE Cinnamom 2.6 ± 0.1 1.1 × 10− 5 tween the packaged products and the surrounding atmosphere (Ren,
TPS-5% PE Cinnamom 2.7 ± 0.1 1.2 × 10− 5
Yan, Zhou, Tong, & Su, 2017). TPS films have a hydrophilic nature,
resulting in low barrier capacity against water vapors (Nawab et al.,
2017). The WTRP for starch-based films without and with Pickering
Table 5 emulsion are presented in Table 4.
Unidirectional ANOVA test results for water vapor permeability properties with As the WVP is directly proportional to the water vapor transmission
a 95.0 % confidence level. rate (WVTR) values, the same trend is expected in the results shown in
Water vapor permeability Table 4. The TPS WVTR value was 2.6 g day− 1 m-2 (dos S. Caetano et al.,
2018; Silva-Pereira et al., 2015), and this phenomenon is governed by
Samples Sum of df Mean F p-value
Squares Square
two mechanisms i) vapor diffusion through the film and ii) vapor solu­
bility in the starch hydrophilic parts (Mansour et al., 2020). The incor­
Between
109594 2 54796.8 porating of the different Pickering emulsions slightly changed the water
TPS + PE Ho Groups
wood 2, and Within 3.352 0.1719 vapor permeability of the film. WTRP depends on the hydrophilic:hy­
49041.1 6 16347
5 wt% Groups drophobic ratio of the film constituents. There is a balance in this ratio in
Total 158635 8 this work due to the oils and the nanocellulose, which are hydrophobic
and hydrophilic, respectively (dos S. Caetano et al., 2018). Considering
Between
117172 2 58585.8 that both starch and nanocelluloses structures are highly hydrophilic,
TPS + PE Groups
Cardamom 2, Within 1.842 0.3007
the films tend to interact with water (Han et al., 2019). The slight in­
95411.6 6 31803.9 creases in WVP values can be attributed to − OH cellulose groups that
and 5 wt% Groups
Total 212583 8 improve the attraction of water molecules. According to Dai, Zhang, and
Cheng (2019), the TPS film may undergo a growing tendency to WVP as
Between the amylose content is found in the structure, the base of our films is
46174.7 2 23087.4
TPS + PE Groups
Cinnamom 2, Within 1.617 0.3338
approximately 28 % (Corradini, Lotti, De Medeiros, & Curvelo, 2005),
42822.4 6 14274.1 resulting in a homogeneous and flat film.
and 5 wt% Groups
Total 88997.1 8 Table 5 shows ANOVA results considering the water vapor perme­
ability analysis; ANOVA-Tukey of p-value did not indicate any variance
between the studied samples, indicating that Pickering emulsions did
and Abraham, some components or additives can decrease the Tm values
not significantly influence the starch films WVP properties (Mendes
of thermoplastic materials (Mathew & Abraham, 2008). Wu, Chen, Li, &
et al., 2020; Paula, Lamsal, Luiz, Magalhães, & Mottin, 2019). However,
Li, 2009 reported a decrease of Tm values attributed to the essential oil
this slight change is a good indicator. Since starch-based materials are
polyphenols’ interaction with the amylopectin side chains, changing the
already available in the packaging sector, even with WVP rates, the

Fig. 7. Schematic representation of the developed films’ main properties, with a brief summarization of the main properties for each essential oil incorporated in the
TPS films.

9
A.G. Souza et al.
developed materials have maintained the TPS intrinsic properties. Be­
sides, the effect of the ratio between groups/total was conducted, and it
was observed that the PE addition with different essential oils of ho
wood, cardamom, and cinnamon influenced about 69.0, 55.1, and 51.8
%, respectively, the WVP properties.
Although the increase in permeability is not expected, this result can
be promising since water can act as a carrier for essential oils, with a
release of the active compounds present in the emulsion, resulting in the
films’ more significant biological activity, as represented in Fig. 7.
4. Conclusions
Starch-based films without and with nanocellulose-stabilized Pick­
ering Emulsions (PE) with three different essential oils were prepared by
casting method. The films with PE-Ho wood showed strong chemical
interactions via a hydrogen bond, which resulted in excellent mechan­
ical properties. The cardamom and cinnamon essential oil showed weak
interactions, which is associated with their chemical structures. All the
films presented low crystallinity (~2%) and good thermal stability,
associated with the molecular interactions among starch chains. The
films with PE showed low melting temperatures related to the in­
teractions of the polyphenols of essential oils with the amylopectin
chains, changing the coupling forces between the amorphous matrix and
the crystallites. The films showed a slight decrease in water vapor
permeability values. However, this result can be promising since water
can act as a carrier for essential oils, releasing the EO active compounds,
resulting in the film’s greater biological activity. In general, the starch-
based films with nanocellulose stabilized Pickering emulsion containing
Ho wood essential oil could be applied as packaging material, consid­
ering mechanical, thermal, and permeability properties. Our findings
showed that the developed films could be applied in food packaging
material, and further studies should be done to evaluate the biode­
gradability of these films and their effects on food systems.
CRediT authorship contribution statement
Alana G. Souza: Conceptualization, Methodology, Formal analysis,
Investigation, Writing - original draft, Visualization. Rafaela R. Fer­
reira: Methodology, Validation, Formal analysis, Investigation, Writing
- original draft, Visualization. Larissa C. Paula: Validation, Investiga­
tion, Visualization. Sushanta K. Mitra: Conceptualization, Writing -
review & editing, Supervision. Derval S. Rosa: Conceptualization, Re­
sources, Writing - review & editing, Supervision, Project administration,
Funding acquisition.
Acknowledgments
The authors thank the financial support provided by CNPQ (305819/
2017-8) and FAPESP (2018/11277-7), FAPESP-CALDO (2019/006576),
Revalores Strategic Unit, and Multiuser Experimental Center of the
Federal University of ABC (CEM-UFABC).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.fpsl.2020.100615.
References
Abarca, R. L., Rodríguez, F. J., Guarda, A., Galotto, M. J., & Bruna, J. E. (2016).
Characterization of beta-cyclodextrin inclusion complexes containing an essential oil
component. Food Chemistry, 196, 968–975. https://doi.org/10.1016/j.
foodchem.2015.10.023
Ahmed, J., Mulla, M., Jacob, H., Luciano, G., Bini, T. B., & Almusallam, A. (2019).
Polylactide/poly(ε-caprolactone)/zinc oxide/clove essential oil composite
antimicrobial films for scrambled egg packaging. Food Packaging and Shelf Life, 21
(July), 100355. https://doi.org/10.1016/j.fpsl.2019.100355
10
Food Packaging and Shelf Life 27 (2021) 100615
Almasi, H., Azizi, S., & Amjadi, S. (2020). Development and characterization of pectin fi
lms activated by nanoemulsion and Pickering emulsion stabilized marjoram
(Origanum majorana L.) essential oil. Food Hydrocolloids, 99, Article 105338.
https://doi.org/10.1016/j.foodhyd.2019.105338
Assis, R. Q., Lopes, S. M., Costa, T. M. H., Flôres, S. H., & de O. Rios, A. (2017). Active
biodegradable cassava starch films incorporated lycopene nanocapsules. Industrial
Crops and Products, 109, 818–827. https://doi.org/10.1016/j.indcrop.2017.09.043
Azizi-Lalabadi, M., Ehsani, A., Ghanbarzadeh, B., & Divband, B. (2020). Polyvinyl
alcohol/gelatin nanocomposite containing ZnO, TiO2 or ZnO/TiO2 nanoparticles
doped on 4A zeolite: Microbial and sensory qualities of packaged white shrimp
during refrigeration. International Journal of Food Microbiology, 312, Article 108375.
https://doi.org/10.1016/j.ijfoodmicro.2019.108375
Castro Mayorga, J. L., Fabra Rovira, M. J., Cabedo Mas, L., Sánchez Moragas, G., &
Lagarón Cabello, J. M. (2018). Antimicrobial nanocomposites and electrospun
coatings based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and copper oxide
nanoparticles for active packaging and coating applications. Journal of Applied
Polymer Science, 135(2), 1–11. https://doi.org/10.1002/app.45673
Corradini, E., Lotti, C., De Medeiros, E. S., & Curvelo, A. A. S. (2005). Estudo
Comparativo de Amidos Termoplásticos Derivados do Milho com Diferentes Teores
de Amilose. Polímeros: Ciência e Tecnologia, 15(4), 268–273.
Cossu, A., Wang, M. S., Chaudhari, A., & Nitin, N. (2015). Antifungal activity against
Candida albicans of starch Pickering emulsion with thymol or amphotericin B in
suspension and calcium alginate films. International Journal of Pharmaceutics, 493
(1–2), 233–242. https://doi.org/10.1016/j.ijpharm.2015.07.065
Criado, P., Fraschini, C., Jamshidian, M., Salmieri, S., Desjardins, N., Sahraoui, A., …
Lacroix, M. (2019). Effect of cellulose nanocrystals on thyme essential oil release
from alginate beads: Study of antimicrobial activity against Listeria innocua and
ground meat shelf life in combination with gamma irradiation. Cellulose, 26(9),
5247–5265. https://doi.org/10.1007/s10570-019-02481-2
Dai, L., Zhang, J., & Cheng, F. (2019). Effects of starches from different botanical sources
and modification methods on physicochemical properties of starch-based edible
films. International Journal of Biological Macromolecules, 132(3), 897–905. https://
doi.org/10.1016/j.ijbiomac.2019.03.197
De Camargo Andrade-Molina, T. P., Shirai, M. A., Victória Eiras Grossmann, M., &
Yamashita, F. (2013). Active biodegradable packaging for fresh pasta. LWT - Food
Science and Technology, 54(1), 25–29. https://doi.org/10.1016/j.lwt.2013.05.011
De Oliveira, T. V., Augusto, P., De Freitas, V., Pola, C. C., Osvaldo, J., Silva, R., …
Soares, N. D. F. F. (2020). Development and optimization of antimicrobial active
films produced with a reinforced and compatibilized biodegradable polymers. Food
Packaging and Shelf Life, 24, Article 100459. https://doi.org/10.1016/j.
fpsl.2019.100459
Dehghani, S., Peighambardoust, S. H., Peighambardoust, S. J., Hosseini, S. V., &
Regenstein, J. M. (2019). Improved mechanical and antibacterial properties of active
LDPE films prepared with combination of Ag, ZnO and CuO nanoparticles. Food
Packaging and Shelf Life, 22, Article 100391. https://doi.org/10.1016/j.
fpsl.2019.100391
Do, T. K. T., Hadji-Minaglou, F., Antoniotti, S., & Fernandez, X. (2015). Authenticity of
essential oils. TrAC – Trends in Analytical Chemistry, 66, 146–157. https://doi.org/
10.1016/j.trac.2014.10.007
do Vale, J. P. C., de F. Ribeiro, L. H., De Vasconcelos, M. A., Sá-Firmino, N. C.,
Pereira, A. L., do Nascimento, M. F., … Teixeira, E. H. (2019). Chemical
composition, antioxidant, antimicrobial and antibiofilm activities of Vitex
gardneriana schauer leaves’s essential oil. Microbial Pathogenesis, 135(June 2018),
103608. https://doi.org/10.1016/j.micpath.2019.103608
dos S. Caetano, K., Lopes, N. A., Costa, T. M. H., Brandelli, A., Rodrigues, E., Hickmann
Flôres, S., & Cladera-Olivera, F. (2018). Characterization of active biodegradable
films based on cassava starch and natural compounds. Food Packaging and Shelf Life,
16, 138–147. https://doi.org/10.1016/j.fpsl.2018.03.006
El-Gendy, A., Abou-Zeid, R. E., Salama, A., Diab, M. A., & El-Sakhawy, M. (2017).
TEMPO-oxidized cellulose nanofibers/polylactic acid/TiO2 as antibacterial
bionanocomposite for active packaging. Egyptian Journal of Chemistry, 60(6),
1007–1014. https://doi.org/10.21608/ejchem.2017.1835.1153
Escamilla-García, M., Reyes-Basurto, A., García-Almendárez, B. E., Hernández-
Hernández, E., Calderón-Domínguez, G., Rossi-Márquez, G., … Regalado-
González, C. (2017). Modified starch-chitosan edible films: Physicochemical and
mechanical characterization. Coatings, 7(12), 1–15. https://doi.org/10.3390/
coatings7120224
Fasihi, H., Noshirvani, N., Hashemi, M., Fazilati, M., Salavati, H., & Coma, V. (2019).
Antioxidant and antimicrobial properties of carbohydrate-based films enriched with
cinnamon essential oil by Pickering emulsion method. Food Packaging and Shelf Life,
19, 147–154. https://doi.org/10.1016/j.fpsl.2018.12.007
Ferreira, R. R., Souza, A. G., Nunes, L. L., Shahi, N., Rangari, V. K., & dos S. Rosa, D.
(2019). Use of ball mill to prepare nanocellulose from eucalyptus biomass:
Challenges and process optimization by combined method. Materials Today
Communications, 101773. https://doi.org/10.1016/j.marmicro.2019.101773.
online.
Gavahian, M., Chu, Y., Lorenzo, J. M., Mousavi, A., & Barba, F. J. (2020). Essential oils as
natural preservatives for bakery products: Understanding the mechanisms of action,
recent findings, and applications. Critical Reviews in Food Science and Nutrition, 60(2),
310–321. https://doi.org/10.1080/10408398.2018.1525601
Hadidi, M., Pouramin, S., Adinepour, F., Haghani, S., & Jafari, S. M. (2020). Chitosan
nanoparticles loaded with clove essential oil: Characterization, antioxidant and
antibacterial activities. Carbohydrate Polymers, 236(February), 116075. https://doi.
org/10.1016/j.carbpol.2020.116075
A.G. Souza et al.
Han, L., Wang, W., Zhang, R., Dong, H., Liu, J., & Kong, L. (2019). Effects of preparation
method on the physicochemical properties of cationic nanocellulose and starch
nanocomposites. Nanomaterials, 9(11), 1–16.
Hassanzadazar, H., Yousefizadeh, S., Ghafari, A., Fathollahi, M., & Aminzare, M. (2019).
Antimicrobial effects of the nanoemulsion of rosemary essential oil against
important foodborne pathogens. Journal of Human, Environment, and Health
Promotion, 5(2), 79–85. https://doi.org/10.29252/jhehp.5.2.6
Inan, M., Kaya, D. A., & Albu, M. G. (2013). The effect of lavender essential oils on
collagen hydrolysate. Revista de Chimie, 64(9), 1037–1042.
Jiménez, A., Fabra, M. J., Talens, P., & Chiralt, A. (2013). Phase transitions in starch
based films containing fatty acids. Effect on water sorption and mechanical
behaviour. Food Hydrocolloids, 30(1), 408–418. https://doi.org/10.1016/j.
foodhyd.2012.07.007
Ju, J., Xie, Y., Guo, Y., Cheng, Y., Qian, H., & Yao, W. (2019). Application of edible
coating with essential oil in food preservation. Critical Reviews in Food Science and
Nutrition, 59(15), 2467–2480. https://doi.org/10.1080/10408398.2018.1456402
Kizil, R., Irudayaraj, J., & Seetharaman, K. (2002). Characterization of irradiated starches
by using FT-Raman and FTIR spectroscopy. Journal of Agricultural and Food
Chemistry, 50(14), 3912–3918. https://doi.org/10.1021/jf011652p
Kumar, U., Kumar, B., Bhandari, A., & Kumar, Y. (2010). Phytochemical investigation
and comparison of antimicrobial screening of clove and cardamom. International
Journal of Pharmaceutical Sciences and Research, 1(12), 138–147.
Leal, I. L., Silva Rosa, Y. C., Silva Penha, J., Cruz Correia, P. R., Silva Melo, P.,
Guimarães, D. H., … Machado, B. A. S. (2019). Development and application starch
films: PBAT with additives for evaluating the shelf life of Tommy Atkins mango in
the fresh-cut state. Journal of Applied Polymer Science, 136(43), 48150. https://doi.
org/10.1002/app.48150
Li, J., Ye, F., Lei, L., & Zhao, G. (2018). Combined effects of octenylsuccination and
oregano essential oil on sweet potato starch films with an emphasis on water
resistance. International Journal of Biological Macromolecules, 115, 547–553. https://
doi.org/10.1016/j.ijbiomac.2018.04.093
Li, X., Yang, X., Deng, H., Guo, Y., & Xue, J. (2020). Gelatin films incorporated with
thymol nanoemulsions: Physical properties and antimicrobial activities. International
Journal of Biological Macromolecules, 150, 161–168. https://doi.org/10.1016/j.
ijbiomac.2020.02.066
Lu, Y., Qian, X., Xie, W., Zhang, W., Huang, J., & Wu, D. (2019). Rheology of the sesame
oil-in-water emulsions stabilized by cellulose nanofibers. Food Hydrocolloids, 94,
114–127. https://doi.org/10.1016/j.foodhyd.2019.03.001
Mansour, G., Zoumaki, M., Marinopoulou, A., Tzetzis, D., Prevezanos, M., &
Raphaelides, S. N. (2020). Characterization and properties of non-granular
thermoplastic starch—Clay biocomposite films. Carbohydrate Polymers, 245(May),
116629. https://doi.org/10.1016/j.carbpol.2020.116629
Mariano, M., Chirat, C., El Kissi, N., & Dufresne, A. (2016). Impact of cellulose
nanocrystal aspect ratio on crystallization and reinforcement of poly(butylene
adipate- co -terephthalate). Journal of Polymer Science, 54, 2284–2297. https://doi.
org/10.1002/polb.24139
Mathew, S., & Abraham, T. E. (2008). Characterisation of ferulic acid incorporated
starch-chitosan blend films. Food Hydrocolloids, 22(5), 826–835. https://doi.org/
10.1016/j.foodhyd.2007.03.012
Medina-Jaramillo, C., Ochoa-Yepes, O., Bernal, C., & Famá, L. (2017). Active and smart
biodegradable packaging based on starch and natural extracts. Carbohydrate
Polymers, 176, 187–194. https://doi.org/10.1016/j.carbpol.2017.08.079
Mendes, J. F., Norcino, L. B., Martins, H. H. A., Manrich, A., Otoni, C. G.,
Carvalho, E. E. N., … Mattoso, L. H. C. (2020). Correlating emulsion characteristics
with the properties of active starch films loaded with lemongrass essential oil. Food
Hydrocolloids, 100(June 2019), 105428. https://doi.org/10.1016/j.
foodhyd.2019.105428
Mikulcová, V., Bordes, R., & Kašpárková, V. (2016). On the preparation and antibacterial
activity of emulsions stabilized with nanocellulose particles. Food Hydrocolloids, 61,
780–792. https://doi.org/10.1016/j.foodhyd.2016.06.031
Nawab, A., Alam, F., Haq, M. A., Lutfi, Z., & Hasnain, A. (2017). Mango kernel starch-
gum composite films: Physical, mechanical and barrier properties. International
Journal of Biological Macromolecules, 98, 869–876. https://doi.org/10.1016/j.
ijbiomac.2017.02.054
Nobrega, M. M., Olivato, J. B., Mueller, C. M. O., & Yamashita, F. (2012). Biodegradable
starch-based films containing saturated fatty acids: Thermal, infrared and Raman
spectroscopic characterization. Polimeros-Ciencia E Tecnologia, 22(5), 475–480.
https://doi.org/10.1590/s0104-14282012005000068
Otoni, C. G., Pontes, S. F. O., Medeiros, E. A. A., & Soares, N. D. F. F. (2014). Edible films
from methylcellulose and nanoemulsions of clove bud (Syzygium aromaticum) and
oregano (Origanum vulgare) essential oils as shelf life extenders for sliced bread.
Journal of Agricultural and Food Chemistry, 62(22), 5214–5219. https://doi.org/
10.1021/jf501055f
Paula, A., De Melo, S., Camani, P. H., Rosa, S., & Carastan, D. J. (2019). Combined effects
of clay minerals and polyethylene glycol in the mechanical and water barrier
properties of carboxymethylcellulose films. Industrial Crops and Products, 140, Article
111644. https://doi.org/10.1016/j.indcrop.2019.111644
Paula, A., Lamsal, B., Luiz, W., Magalhães, E., & Mottin, I. (2019). Cassava starch films
reinforced with lignocellulose nanofibers from cassava bagasse. International Journal
11
Food Packaging and Shelf Life 27 (2021) 100615
of Biological Macromolecules, 139(8), 1151–1161. https://doi.org/10.1016/j.
ijbiomac.2019.08.115
Peighambardoust, S. J., Peighambardoust, S. H., Mohammadzadeh Pournasir, N., &
Pakdel, P. (2019). Properties of active starch-based films incorporating a
combination of Ag, ZnO and CuO nanoparticles for potential use in food packaging
applications. Food Packaging and Shelf Life, 22, Article 100420. https://doi.org/
10.1016/j.fpsl.2019.100420
Pickering, S. U. (1906). Emulsions. Journal of the Chemical Society, 2001–2021. https://
doi.org/10.1002/9781119220510.ch15
Prakash, A., Vadivel, V., Rubini, D., & Nithyanand, P. (2019). Antibacterial and
antibiofilm activities of linalool nanoemulsions against Salmonella typhimurium.
Food Bioscience, 28(May 2018), 57–65. https://doi.org/10.1016/j.fbio.2019.01.018
Ren, L., Yan, X., Zhou, J., Tong, J., & Su, X. (2017). Influence of chitosan concentration
on mechanical and barrier properties of corn starch/chitosan films. International
Journal of Biological Macromolecules, 105, 1636–1643. https://doi.org/10.1016/j.
ijbiomac.2017.02.008
Ribeiro-Santos, R., Andrade, M., & Sanches-Silva, A. (2017). Application of encapsulated
essential oils as antimicrobial agents in food packaging. Current Opinion in Food
Science, 14, 78–84. https://doi.org/10.1016/j.cofs.2017.01.012
Rocha, D. B., Souza de Carvalho, J., de Oliveira, S. A., dos Santos Rosa, D., De
Carvalho, S., De Oliveira, S. A., & Rosa, S. (2018). A new approach for flexible PBAT/
PLA/CaCO3 films into agriculture. Journal of Applied Polymer Science, 135(35), 1–9.
https://doi.org/10.1002/app.46660
Rout, P. K., Sahoo, D., Jena, K. S., & Rao, Y. R. (2003). Analysis of the oil of large
cardamom (amomum subulatum roxb,) growing in sikkim. Journal of Essential Oil
Research, 15(4), 265–266. https://doi.org/10.1080/10412905.2003.9712138
Roy, S., & Rhim, J. (2020). Carboxymethyl cellulose-based antioxidant and antimicrobial
active packaging film incorporated with curcumin and zinc oxide. International
Journal of Biological Macromolecules, 148, 666–676. https://doi.org/10.1016/j.
ijbiomac.2020.01.204
Sandhu, K. S., & Lim, S. T. (2008). Digestibility of legume starches as influenced by their
physical and structural properties. Carbohydrate Polymers, 71(2), 245–252. https://
doi.org/10.1016/j.carbpol.2007.05.036
Shin, J., Na, K., Shin, S., Seo, S. M., Youn, H. J., Park, I. K., & Hyun, J. (2019). Biological
activity of thyme white essential oil stabilized by cellulose nanocrystals.
Biomolecules, 9(12), 1–13. https://doi.org/10.3390/biom9120799
Silva, F., Caldera, F., Trotta, F., Nerín, C., & Domingues, F. C. (2019). Encapsulation of
coriander essential oil in cyclodextrin nanosponges: A new strategy to promote its
use in controlled-release active packaging. Innovative Food Science & Emerging
Technologies, 56(May), 102177. https://doi.org/10.1016/j.ifset.2019.102177
Silva-Pereira, M. C., Teixeira, J. A., Pereira-Júnior, V. A., & Stefani, R. (2015). Chitosan/
corn starch blend films with extract from Brassica oleraceae (red cabbage) as a visual
indicator of fish deterioration. LWT – Food Science and Technology, 61(1), 258–262.
https://doi.org/10.1016/j.lwt.2014.11.041
Simionato, I., Domingues, F. C., Nerín, C., & Silva, F. (2019). Encapsulation of cinnamon
oil in cyclodextrin nanosponges and their potential use for antimicrobial food
packaging. Food and Chemical Toxicology, 132(January), 110647. https://doi.org/
10.1016/j.fct.2019.110647
Sindhu, R., Devi, A., & Khatkar, B. S. (2019). Physicochemical, thermal and structural
properties of heat moisture treated common buckwheat starches. Journal of Food
Science and Technology, 56, 2480–2489. https://doi.org/10.1007/s13197-019-
03725-6
Tian, Y., Zhang, K., Zhou, M., Wei, Y. J., Cheng, F., Lin, Y., … Zhu, P. X. (2019). High-
performance starch films reinforced with microcrystalline cellulose made from
eucalyptus pulp via ball milling and mercerization. Starch/Staerke, 71(3–4), 1–8.
https://doi.org/10.1002/star.201800218
Valencia, L., Nomena, E. M., Mathew, A. P., & Velikov, K. P. (2019). Biobased cellulose
nanofibril-oil composite films for active edible barriers [Research-article]. ACS
Applied Materials & Interfaces, 11(17), 16040–16047. https://doi.org/10.1021/
acsami.9b02649
Wang, S., Zhang, X., Wang, S., & Copeland, L. (2016). Changes of Multi-Scale Structure
During Mimicked DSC Heating Reveal the Nature of Starch Gelatinization (pp. 1–9).
Nature Publishing Group. https://doi.org/10.1038/srep28271 (March).
Wen, P., Zhu, D. H., Wu, H., Zong, M. H., Jing, Y. R., & Han, S. Y. (2016). Encapsulation
of cinnamon essential oil in electrospun nanofibrous film for active food packaging.
Food Control, 59, 366–376. https://doi.org/10.1016/j.foodcont.2015.06.005
Wu, Y., Chen, Z., Li, X., & Li, M. (2009). Effect of tea polyphenols on the retrogradation of
rice starch. Food Research International, 42(2), 221–225. https://doi.org/10.1016/j.
foodres.2008.11.001
Zhai, X., Lin, D., Liu, D., & Yang, X. (2018). Emulsions stabilized by nanofibers from
bacterial cellulose: New potential food-grade Pickering emulsions. Food Research
International, 103, 12–20. https://doi.org/10.1016/j.foodres.2017.10.030
Zhou, X., Yang, R., Wang, B., & Chen, K. (2019). Development and characterization of
bilayer films based on pea starch/polylactic acid and use in the cherry tomatoes
packaging. Carbohydrate Polymers, 222(January), 114912. https://doi.org/10.1016/
j.carbpol.2019.05.042
Zou, T., Sipponen, M. H., & Österberg, M. (2019). Natural shape-retaining microcapsules
with shells made of chitosan-coated colloidal lignin particles. Frontiers in Chemistry, 7
(May), 1–12. https://doi.org/10.3389/fchem.2019.00370