Trends in Food Science & Technology 68 (2017) 70e82

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Trends in Food Science & Technology

journal homepage: http://www.journals.elsevier.com/trends-in-food-science-
and-technology

Review

Edible and active lms and coatings as carriers of natural antioxidants

for lipid food
Sophie Ganiari, Evanthia Choulitoudi, Vassiliki Oreopoulou*
National Technical University of Athens, School of Chemical Engineering, Laboratory of Food Chemistry and Technology, 5 Iroon Polytechniou, Zografou,
15780 Athens, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Background: Lipid oxidation is one of the main causes of food spoilage. It can be delayed by the addition
Received 5 April 2017 of antioxidants to food or by using vacuum or modied atmosphere packaging. A recent approach is the
Received in revised form application of antioxidants in active packaging.
28 June 2017
Scope and approach: The scope of this review is to present and update all information about the
Accepted 17 August 2017
Available online 22 August 2017
incorporation of natural antioxidants in edible and active lms and coatings. Natural antioxidants can
replace chemical additives and are preferably accepted by the consumers. Their effect on the barrier,
mechanical and antioxidant properties of the various lms (chitosan, cellulose derivatives gelatin etc.)
Keywords:
Active packaging
are discussed. The ability to delay food oxidation is examined in relation to the active components.
Edible lm Key ndings and conclusions: Water or ethanol extracts from several herbs (rosemary, oregano, tea),
Natural antioxidant berries, or plant by-products increased the total phenolic content and the antiradical activity of the lms
Lipid oxidation and proved efcient in delaying the oxidation of sh and meat products. Also, a protective activity was
Phenolic compounds observed from the essential oils that were rich in carvacrol or thymol. The barrier properties of the lms
Essential oil were positively affected, due to interactions between the active groups of the additive (e.g. polyphenols)
and the lm matrix. On the contrary, hydrophilic additives increased water vapor and oxygen perme-
ability. The mechanical properties were in most cases adversely affected. Results are promising and
further research on the release of antioxidant compound into food, the effect on sensorial properties, and
application to other lipid foods may encourage practical application.
2017 Elsevier Ltd. All rights reserved.

1. Introduction
Lipid oxidation is one of the main causes of food spoilage. Foods
with a high lipid content, especially those with a high grade of
unsaturation, are susceptible to deterioration following this path.
The oxidation of lipids in foodstuffs results in the development of
off-avors, typical of rancidity, rendering the product unacceptable
for human consumption. Other negative effects are the formation of
Abbreviations: ABTS, 2,2-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid
radical; CD, conjugated dienes; CMC, carboxymethylcellulose; DPPH, 2,2-diphenyl-
1-picryl-hydrazyl-hydrate radical; EO, essential oil; EVOH, Ethylene vinyl alcohol
co-polymer; FRAP, ferric reducing activity power; HPMC, hydroxypropyl methyl
cellulose; LDPE, low-density polyethylene; MC, methylcellulose; MMT, montmo-
rillonite; OP, oxygen permeability; p-AV, p-anisidine value; PV, peroxide value;
TBARs, thiobarbituric acid reactive substances; TEAC, trolox equivalent antioxidant
capacity; TPC, total phenol content; TS, tensile strength; WVP, water vapor
permeability.
* Corresponding author.
E-mail address: vasor@chemeng.ntua.gr (V. Oreopoulou).
toxic aldehydes (Guillen & Goicoechea, 2008) and the loss of
nutritional quality because of polyunsaturated fatty acid (PUFA)
degradation. To reduce lipid oxidation, several strategies have been
applied, such as the direct addition of antioxidants to foods or the
design of a suitable packaging technology such as vacuum or
modied-atmosphere packaging combined with high-barrier
packaging materials (Lo ! pez de Dicastillo, Alonso, Catala
!, Gavara, &
Herna !ndez- Mun ~ oz, 2010). Food packaging has no longer just a
passive role in protecting and marketing a food product. New
concepts of active and intelligent packaging play an increasingly
important role by offering numerous and innovative solutions for
extending the shelf-life, maintain, improve or monitor food quality
and safety.
Every kind of material that is used for food packaging in order to
prolong its shelf life, while it can also be consumed with the food, is
called an edible lm or coating. Edible lms or coatings provide a
barrier to moisture, oxygen and solute movement from the food
(Bourtoom, 2008). They have a high potential to carry active in-
gredients such as anti-browning agents, colorants, avors,

http://dx.doi.org/10.1016/j.tifs.2017.08.009
0924-2244/ 2017 Elsevier Ltd. All rights reserved.
 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82
nutrients, spices, antimicrobial and antioxidant compounds that
can extend product shelf-life, or even enhance the organoleptic
properties and nutritional value of the food. Another important fact
is the lower environmental impact, as these lms and coatings can
be consumed with the food, while additional external packaging
can be limited.
Aiming to the reduction of the use of chemical additives in the
food industry, growing interest has risen on the use of natural food
additives with antimicrobial and antioxidant properties. The
incorporation of functional ingredients in edible lms and coatings
for fresh-cut fruit and vegetables has been reviewed by Rojas-Gra,
Soliva-Fortuny, and Martn-Belloso (2009) and Ea, Sartori, and
Menegalli (2014). Essential oils (EOs) represent an interesting
ingredient for active food packaging, mainly due to their natural
origin and their antimicrobial properties. Their use along with
other synthetic chemical agents such as potassium sorbate or so-
dium benzoate to protect fresh and minimally processed fruits and
vegetables has been reviewed by Valencia-Chamorro, Palou, del Ro
and Pe !rez-Gago (2011). Extracts from herbs and spices, or agricul-
tural by-products have shown antioxidant properties too, which
make them interesting additives in food. In addition to their use
directly on food material, several research efforts focused on their
incorporation in packaging material, with promising results. The
main goal of this article is to review and update the information
available on the use of edible lms and coatings as carriers of
natural antioxidants to improve the shelf-life of lipid food.
2. Natural antioxidants
A food antioxidant may be dened as any substance, which is
capable of delaying, retarding or preventing the development of
rancidity in food or other avor deterioration due to oxidation. The
presence of synthetic antioxidants in food is questioned, owing to
the potential risks, and strict statutory controls are required. The
alternative approach that is being studied widely is the use of
natural antioxidants, particularly tocopherol, plant extracts and
EOs, or their constituents (Tovar, Salafranca, Sanchez, & Nern,
2005; Wessling, Nielsen, Leufve !n, & Ja
gerstad, 1999). Also, it is
relevant to mention the potential use of food industrial waste as
source of antioxidant agents (Barbosa-Pereira, Angulo, Paseiro-
Losada, & Cruz, 2013; Cruz, Conde, Domnguez, & Parajo !, 2007).
Spices and herbs, used in foods for their avor and in medicinal
mixtures for their physiological effects, often contain high con-
centrations of phenolic compounds that have strong H-donating
activity. Such compounds can be recovered and added to food
systems to prevent oxidation. Among them, rosemary, oregano,
thyme, marjoram, savory, sage, and other herbs belonging to the
Lamiaceae family have been broadly investigated. Another herb
that is widely examined as natural antioxidant is tea that belongs to
the Theaceae family. Antioxidant components of herbs and spices
may be recovered and concentrated as EOs, extracts, or oleoresins
(Fig. 1).
Chemically, EOs are extremely complex mixtures containing
compounds of every major functional group class (Bourtoom,
2008). They consist of volatile, lipophilic substances that are
mainly hydrocarbons or monofunctional compounds derived from
the metabolism of mono- and sesquiterpenes, phenylpropanoids,
amino acids and fatty acids (Bauer, Garbe, & Surburg, 2001). EOs
may be isolated by steam distillation, extraction (with organic
solvent or supercritical CO2), or mechanical expression. The
method selected depends on the botanical material, and is one of
the prime factors that determine the yield and quality of the EO.
Steam distillation is almost exclusively used for the recovery of the
EO from aromatic herbs and spices. EOs have been related mostly
with antimicrobial protection but they could also serve as potential
71
natural antioxidants. The constituents that have shown a noticeable
antimicrobial activity are carvacrol and thymol (Serrano et al.,
2008; Tongnuanchan & Benjakul, 2014), which also demonstrate
moderate antioxidant activities (Tsimogiannis, Bimpilas, &
Oreopoulou, 2017).
Extracts of many herbs and spices have a high total phenol
content (TPC). The most common techniques to extract phenolic
compounds from herbs and spices employ organic solvents or
mixtures with water. The nal yield can be inuenced by several
parameters including extraction solvent, time, temperature,
solvent-to-sample ratio, and number of sample extractions.
Furthermore, the recovery of phenolic compounds differs from one
sample to another and depends on the plant matrix and its active
components. The most commonly used solvents are water, acetone,
ethyl acetate, alcohols (methanol, ethanol, propanol) and their
mixtures (Oniszczuk et al., 2014). Ethyl acetate and acetone recover
the non-polar compounds, like avonoid aglycones (quercetin,
luteolin, apigenin, eriodictyol) and terpenoids (carnosol, thymol,
carvacrol) while alcohols, water, and hydro-alcoholic mixtures are
good solvents for phenolic acids (caffeic, rosmarinic, salvianolic)
and avonoid glycosides (rutin, apigenin glycoside).
Oleoresins are also recovered by spices and herbs and contain
nonvolatile, lipophilic compounds, such as resins, waxes and
essential or fatty oils (Rajamma, Bai, & Nambisan, 2012). They are
composed mainly of terpenes and derivatives and may contain
small amounts of volatile phenolic compounds and resin acids.
They are soluble in most organic solvents but not in water. Oleo-
resins are recovered by non-polar solvents including supercritical
carbon dioxide, ethyl acetate, hexane, or polar solvents (alcohols)
and are used mostly as avouring agents and antimicrobials (Singh
et al., 2014; Upadhyay & Niwas Mishra, 2014).
Additionally to herbs and spices, extracts obtained from plant
by-products like barley husks, pomegranate peel, olive leaves, etc.
have demonstrated good antioxidant activities (Marcos et al., 2014;
Qin et al., 2015; Pereira de Abreu, Villalba Rodriguez, & Cruz, 2012;
Yuan, Lv, Yang, Chen, & Sun, 2015). The ground raw materials may
be subjected to acid hydrolysis and treatment with alkaline solu-
tion for the release of phenolic compounds from bres and lignin.
Phenolic compounds may then be extracted from the liquid phase
with organic solvents like ethyl acetate (Pereira de Abreu et al.,
2012).
3. Active packaging
Active packaging is dened as a package system that deliber-
ately incorporates components, which release or absorb substances
into or from the packaged food or the environment surrounding the
food to extend the shelf-life or to maintain or improve the condi-
tion of the packaged food (Regulation (CE) No. 450/2009 (29/05/
2009)). The use of antioxidants in active packaging is of high in-
terest for food technologists since this process may reduce lipid
oxidation and can even increase food nutritional value (Barbosa-
Pereira et al., 2013; Pereira de Abreu et al., 2012).
There are two main modes of action for antioxidant packages:
the release of antioxidants to the food and the scavenging of un-
desirable compounds such as oxygen, radical oxidative species or
metal ions from the headspace or from the food. Scavengers are
substances that react with, modify or trap substances which are
involved in any step of the oxidation process. Since these sub-
stances are not released into the food, the package should be
designed to allow the access of the pro-oxidant substances to the
location where scavengers are incorporated.
Regarding the antioxidant releasing packaging materials, one of
the main benets, as compared to the direct addition of antioxi-
dants to food, is that active materials may act as a source of
72 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82
Fig. 1. Extraction procedures for the recovery of natural antioxidants.
antioxidants that are released to the food at controlled rates, so that
a predetermined concentration of the active compound is main-
tained in the food, compensating the continuous using up of anti-
oxidants during storage (LaCoste, Schaich, Zumbrunnen, & Yam,
2005; Mastromatteo, Mastromatteo, Conte & Del Nobile, 2010).
4. Edible lms and coatings
An edible coating is a thin layer of edible material formed as a
coating on a food product, while an edible lm is a preformed, thin
layer, made of edible material, which once formed can be placed on
or between food components (McHugh, 2000). The main difference
between these systems is that the edible coatings are applied in
liquid form on the food, usually by immersing the product in a
solution, while edible lms are rst molded as solid sheets, which
are then applied as a wrapping on the food product. An edible lm
or coating does not act as a package itself, but it may reduce the
barrier requirements of the package.
Edible lm and coating technology is close to active packaging
technology and may also be a means of reducing oxidative spoilage
in foods. The main mechanism of action is the reduction of the
oxygen transmission rate, as well as the possibility of incorporating
antioxidant compounds in the edible lm or coating matrix. With
regards to the latter case, this vehicle has the advantage of close
contact between coating and food.
The use of edible coating or edible lms in food applications,
depends on diverse characteristics such as cost, availability, func-
tional attributes, mechanical properties (exibility, tension), optical
properties (brightness and opacity), the barrier effect against gases
ow, structural resistance to water and microorganisms and sen-
sory acceptability. These characteristics are inuenced by param-
eters such as the kind of material implemented as structural matrix
(composition, molecular weight), the conditions under which lms
are preformed (type of solvent, pH, components concentration and
temperature) and the type and concentration of additives (plasti-
cizers, cross-linking agents, antimicrobials, antioxidants or emul-
siers) (Guilbert, Gontard, & Gorris, 1996; Rojas-Gra et al., 2009).
The structural materials used in the construction of edible lms
and coatings are based on proteins, lipids and polysaccharides and
are summarized in Table 1.
Combination of these materials may be also used for the con-
struction of composites. For example, a composite lm may consist
of lipids and hydrocolloids combined to form a bilayer or a cluster
(Krochta, Baldwin, & Nisperos-Carriedo, 1994). Oussalah, Caillet,
Salmie !ri, Saucier, and Lacroix (2004) and Go ! mez-Estaca, Montero,
Gime !nez, and Go !mez-Guille
!n (2007) considered the production
of edible and biodegradable lms by combining various poly-
saccharides, proteins and lipids, with the aim of taking advantage of
the properties of each compound and the synergy between them.
The mechanical and barrier properties of these lms not only
depend on the compounds used in the polymer matrix, but also on
their compatibility (Altenhofen, Krause, & Guenter, 2009). Addi-
tionally, the release of antioxidant additives may be better
controlled when using a blend of polymers instead of a single
polymer matrix. A new approach consists of using smart blending,
combined with the development of different lm morphologies, to
generate novel packaging materials capable to provide controlled
release of active compound for a wide range of food applications
(LaCoste et al., 2005).
During manufacturing, lm materials must be dispersed and
dissolved in a solvent such as water, alcohol or mixture of water and
alcohol solvents (Table 2). Plasticizers, antimicrobial or antioxidant
agents, colors or avors can be added in this process. The lm so-
lution is then casted and dried at a desired temperature and relative
humidity to obtain freestanding lms (Bourtoom, 2008). Different
technological approaches are used to incorporate antioxidants into
 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82
Table 1
Main compounds used in structural matrices of edible lms and edible coatings.
Category Compound Examples
Hydrocolloids Polysaccha- cellulose and derivatives, galactomannans, chitosan,
rides pectin, carrageenan, alginates, starch
Proteins gelatin (sh or meat origin), corn zein, wheat gluten,
milk proteins (casein, whey protein isolate)
Lipids Waxes and parafn, carnauba, candelilla, bee wax
parafn
Acetoglyceride acetylated monoglyceride
Shellac resins
Composites Several alginate & pectin, starch & sodium caseinate, calcium
caseinate & whey protein isolate with CMC, gelatin &
chitosan
the lms. Most of them consist either of direct blending of an
antioxidant agent with the plastic materials (LaCoste et al., 2005),
or co-extrusion of the antioxidant together with the lm-forming
plastic material (Granda-Restrepo, Peralta, Troncoso-Rojas, &
Soto-Valdez, 2009). Nern et al. (2006) prepared an active pack-
aging system by coating a plastic lm with a varnish containing the
natural extract.
The addition of plasticizing agents to edible lms is required to
overcome lm brittleness caused by extensive intermolecular
forces. Plasticizers such as glycerol, reduce these forces and in-
crease the mobility of polymer chains, thereby improving exibility
and extensibility, affecting water vapor permeability (WVP) oxygen
permeability (OP), and solute permeability of the lms (Bifani et al.,
2007). In some cases, higher plasticizer concentration may show
faster release of the antioxidant agent, due to the higher mobility of
the polymer chains (Lo !pez de Dicastillo, Navarro, Guarda & Galotto,
2015). Emulsiers such as Tween are used in order to improve lm-
forming emulsion stability (Abdollahi, Rezaei, & Farzi, 2012b). The
addition of montmorillonite (MMT), the most commonly used
layered silicate, could effectively improve mechanical properties
and decrease the WVP of biopolymer lms (Abdollahi et al., 2012b;
Qin et al., 2015; Quilaqueo Gutie
!rrez, Echeverra, Ihl, Bifani & Mauri,
2012) (Table 2).
5. Effect of the incorporation of antioxidants on the
properties of lms and coatings
Any incorporation of components in lms and coatings might
inuence the characteristics and properties of the lm itself and
also of the packaged food. Therefore, before adding antioxidants to
lms and coatings, it is necessary to evaluate rst of all their anti-
oxidant capacity, but also how they inuence the properties of the
packaging material and the characteristics of the food product.
Thus, many researchers have focused their studies on the me-
chanical and physical properties of lms and coatings and how they
have been affected by the incorporation of antioxidant agents. The
main results are summarized in Table 2.
Film properties can be affected even by small changes in the
extract used, as was demonstrated by Bifani et al. (2007). In their
experiment, two ecotypes of murta leaves with a different avonol
prole were used, the one having a higher concentration of myr-
icetin than the other. The addition of these extracts in carboxy-
methylcellulose (CMC) edible lms modied the WVP and gas
permeability of the lms in different ways for each ecotype. In some
cases the incorporation of an antioxidant may affect the lm
positively. For example, Siripatrawan and Harte (2010) noticed that
the incorporation of green tea extract in chitosan lms lowered the
WVP and improved the mechanical properties of the lm. Ac-
cording to FTIR analysis the observed results were attributed to
73
Reference
Dashipour et al. (2014), Cerqueira et al. (2010), Martins et al. (2012), Pe
!rez Espitia,
Du, Avena-Bustillos, Ferreira Soares, and McHugh (2014), Tavassoli-Kafrani,
Shekarchizadeh, and Masoudpour-Behabadi (2016), Batista Reis et al. (2015)
Matrucci et al. (2015), Oussalah et al. (2004), Arcan and Yemeniciog #lu (2011)
Zamudio, Pe
!rez, Salcedo, Gonza
!lez, and Violante (2017), Singh et al. (2016)
Bourtoom, 2008
Bourtoom, 2008
Altenhofen et al. (2009), Galus and Lenart (2013), Jime
!nez et al. (2013), Oussalah
et al. (2004), Go
!mez-Estaca et al. (2007)
interactions between the chitosan matrix and the added extract, i.e.
interactions of green tea polyphenolic compounds with hydroxyl
and amino groups in chitosan matrix. Among the main phenolic
compounds of green tea, catechin was reported to interact with the
amine functional groups of the chitosan (Zhang & Kosaraju, 2007),
while Curcio et al. (2009) observed the formation of covalent bonds
between catechin and chitosan, as well as gallic acid and chitosan.
The hydrogen and covalent interactions between the chitosan
network and polyphenolic compounds limit the availability of
hydrogen groups to form hydrophilic bonding with water, and
subsequently lead to a decrease in the afnity of chitosan lm to-
wards water. The same interactions seem to strengthen the me-
chanical properties of the lm. Also, green tea extract could form
hydrogen bond with functional groups of gelatin, and consequently
improve the water barrier and mechanical properties of the lm (Li,
Miao, Wu, Chen, & Zhang, 2014). Similar interactions were
observed between polyphenols and protein-based lms (Go !mez-
Estaca, Bravo, Go ! mez-Guille !n, Alem! an, & Montero, 2009; Orliac,
Rouilly, Silvestre, & Rigal, 2002), as well as anthocyanins and
hydroxypropyl methyl cellulose (HPMC) lms or gelatin lms
(Akhtar et al., 2012; Li et al., 2014). However, extracts from Lycium
barbarum fruit (that contain polysaccharides, carotenoids and a-
vonoids) improved the WVP of chitosan lms, due to bonding with
hydroxyl and amino groups of the matrix, but decreased the tensile
strength (TS) and elongation of the lm Wang et al. (2014), while a
similar result was observed by Peng, Wu, and Li (2013) with the
addition of extracts from green or black tea. The combination of
pomegranate rind extract or rosemary EP with MMT improved
signicantly the mechanical properties and WVP of chitosan lms,
while the same was not observed in CMC lms enriched with murta
leaves extract.
A cross-linking effect was induced to HPMC edible lm by the
addition of ascorbic or citric acid, which resulted in better me-
chanical properties and lower WVP and OP (Atare !s, Pe!rez-Masia!, &
Chiralt, 2011). Also, several authors reported on the cross-linking
properties of ferulic acid in edible lms of soy protein isolate (Ou,
Wang, Tang, Huang, & Jackson, 2005), gelatin (Cao, Fu, & He,
2007) or starch-chitosan blends (Mathew & Abraham, 2008). In
general the effect of phenolic acids incorporated into protein- or
carbohydrate-based lms is governed by two different attributes:
a) their ability to form hydrogen bonds or other interactions be-
tween the carboxyl groups and the amino acid of proteins or the
carboxyl groups of carbohydrates, thus promoting a cross linking
effect and b) their afnity for water that results in high water ab-
sorption. The cross-linking effect increases the TS and mechanical
resistance of the lms (Atare !s et al., 2011; Cao et al., 2007; Fabra,
Hambleton, Talens, Debeaufort, & Chiralt, 2011; Mathew &
Abraham, 2008), and decreases OP (Atare !s et al., 2011; Fabra
et al., 2011). However, the WVP depends on the dense structure
74 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82

Table 2
Edible lm composition and effect of additives on mechanical and barrier properties.

Main Film composition Mechanical properties Barrier properties Reference

component
Compounds (%) in the Additives Thickness Moisture TS E (%) WVP*1011 OP*1010
initial solution* (%) in the initial solution (mm) content (%) (MPa) (g(m*s*Pa)!1) (cm3(m*s*Pa)!1)

Cellulose and CMC: 2 None 0.016 n.d.** n.d. n.d. 7.14 8.10 Bifani et al. (2007)
derivatives Glycerol: 0.4 Murta leaves extract (MLE) e0.046 7.19 5.94
sunower oil: 0.5 (Soloyo Chico): 100
in water MLE (Soloyo Grande): 100 5.66 4.38

CMC: 2 None n.d. 23.20 25.50 23.50 10.50 1.40 Quilaqueo Gutie
!rrez
glycerol: 0.4 MMT: 0.1 19.65 36.50 12.50 6.50 0.25 et al. (2012)
in water MMT: 0.2 20.52 40.00 13.50 5.00 0.25

MLE: 80 n.d. 29.26 17.50 55.00 11.50 0.35

MMT: 0.1, MLE: 80 20.22 25.50 32.50 5.00 0.45
MMT: 0.2, MLE: 80 20.13 18.50 17.50 5.20 0.20

MC: 1 None 0.075 n.d. 5.30 53.40 1.05 n.d. Lo

! pez de Dicastillo
polyethylene glycol: 0.65 Glutaraldehyde: 0.025 e0.090 10.30 69.10 1.03 et al. (2016)
in 70% ethanol/water Glutaraldehyde: 0.075 6.30 55.50 0.79

Maqui berry extract: 0.3 0.075 n.d. 6.50 89.00 0.59 n.d.
Glutaraldehyde: 0.025 maqui e0.090 6.20 69.50 0.55
berry extract: 0.3

MC: 2 None 0.051 7.00 66.00 15.00 87.00 0.015 Pastor et al. (2013)
in water Resveratrol: 0.02 0.051 6.73 65.00 10.00 77.00 0.014
Resveratrol: 0.2 0.058 5.90 49.00 4.00 60.00 0.014

Chitosan Chitosan: 2, glycerol: 0.6 None 0.062 n.d. 23.66 54.62 0.30 n.d. Siripatrawan and
in 1% acetic acid Green tea extract (GTE): 2 25.00 54.76 0.26 Harte (2010)
GTE: 10 28.35 60.39 0.21
GTE: 20 27.55 60.73 0.10

Chitosan: 2, Tween 80: 0.2 None n.d. 14.50 60.80 3.56 7.00 n.d. Abdollahi et al.
in 1% acetic acid Rosemary EO: 0.5 19.50 68.51 4.97 8.00 (2012a, 2012b)
Rosemary EO: 1.5 18.50 65.46 4.61 6.80

MMT: 0.06 0.050 n.d. 72.54 3.44 3.90

MMT: 0.06, Rosemary EO: 0.5 0.050 73.48 4.11 4.70
MMT: 0.06, Rosemary EO: 1.5 0.052 71.33 4.83 3.10

Chitosan 2, glycerol 0.6 None 0.072 28.91 32.50 32.00 13.39 n.d. Peng et al. (2013)
in 1% acetic acid GTE: 0.5 0.096 19.81 26.50 5.00 8.34
GTE: 2.0 0.132 10.78 28.00 1.00 5.07
Black tea extract: 0.5 0.098 23.20 24.50 7.50 11.51
Black tea extract: 2.0 0.131 11.73 28.00 1.00 5.82

Chitosan 2 None n.d. 22.17 23.00 22.00 6.48 n.d. Wang et al. (2014)
in acetic acid solution and Lycium barbarum extract: 0.4 20.82 19.50 13.00 4.86
water Lycium barbarum extract: 1.2 20.69 15.00 9.50 4.74
Lycium barbarum extract: 2.0 19.96 10.00 7.00 3.82

Chitosan 1.5, glycerol 0.1 None 0.065 n.d. 20.80 12.70 218.00 n.d. Qin et al. (2015)
in 2% acetic acid MMT: 0.015 0.069 26.30 15.90 193.00
MMT:0.015 Pomegranate 0.084 35.00 14.90 171.00
extract: 2
MMT: 0.075 0.074 32.30 16.70 173.00
MMT:0.075 Pomegranate 0.085 40.90 16.60 147.00
extract: 2

Chitosan: 2 None 0.105 n.d. 22.23 31.51 27.77 n.d. Yuan et al. (2015)
Glycerol: 1 Carvacrol: 1 0.091 8.54 17.37 9.72
Tween 80: 0.5 Pomegranate extract: 1 0.111 23.50 30.76 22.21
in 1% acetic acid Carvacrol:1 Pomegranate 0.126 15.91 21.67 13.88
extract:1

Chitosan: 1.5 None 0.094 12.60 34.00 52.00 6.02 n.d. Martins et al. (2012)
Tween 80: 0.1 a-tocopherol: 0.1 0.115 11.80 23.00 44.00 6.71
In 1% lactic acid a-tocopherol: 0.2 0.120 11.40 18.00 23.00 7.38

Alginates Sodium alginate: 2 CaCl2: none 0.070 29.64 22.20 19.32 0.20 n.d. Norajit et al. (2010)
0.01, glycerol: 3 50% Red ginseng 0.114 25.29 13.81 27.95 0.24
in water 50% White ginseng 0.105 24.87 8.05 24.39 0.23

Galactomannans Galactomannan: 1.5, none 0.052 n.d. n.d. n.d. 6.54 n.d. Cerqueira et al.
glycerol: 0.5 Gleditschia 1.0% 0.105 9.31 (2010)
in water
 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82 75

Table 2 (continued )

Main Film composition Mechanical properties Barrier properties Reference

component
Compounds (%) in the Additives Thickness Moisture TS E (%) WVP*1011 OP*1010
initial solution* (%) in the initial solution (mm) content (%) (MPa) (g(m*s*Pa)!1) (cm3(m*s*Pa)!1)

Gelatin Gelatin: 5 none 0.110 n.d. 17.70 10.80 14.60 n.d. Matrucci et al.
PG 8 Oregano EO: 0.2 0.100 14.00 8.30 12.10 (2015)
in buffer phosphate Oregano EO: 0.6 0.130 11.30 10.00 8.40
Lavender EO: 0.2 0.070 8.80 4.30 12.70
Lavender EO: 0.6 0.110 12.80 7.30 6.80

Gelatin: 3 none 0.123 14.40 23.42 62.86 2.63*** n.d. Li et al. (2014)
Glycerol: 0.9 GTE: 0.1 0.148 24.43 20.79 44.62 1.81
in water Grape seed 0.140 16.47 19.46 45.10 2.42
extract(proanthocyanidins):0.1
Grape seed 0.156 19.77 14.64 30.86 2.49
extract(polyphenols): 0.1

Composites Corn starch: 2 sodium none n.d. n.d. 6.10 19.00 251.31 0.0013 Jime
!nez et al. (2013)
caseinate: 2 a-tocopherol: 0.4 9.40 8.00 199.94 0.0017
Glycerol: 1
in water
*
The processing method for the lm preparation was casting in all cases.
**
n.d.: non-determined.
***
WVP measured in g*m/(m2*d*kPa).

of the lm but also on the ability to absorb water molecules. Thus it
may remain unaffected or slightly decrease or increase, depending
on the concentration of the acid in the lm (Cao et al., 2007; Fabra
et al., 2011; Ou et al., 2005). In general, polar compounds enhance
the hydrophilic properties of the lms, leading to an increase in
WVP (Cerqueira, Souza, Martins, Teixeira, & Vicente, 2010).
A major factor that inuences the enriched lm properties is the
relative humidity of the lm environment. Lo !pez de Dicastillo,
Go! mez-Estaca, Catala !, Gavara & Herna !ndez-Mun ~ oz (2012) studied
the effect of ascorbic acid, ferulic acid, quercetin, and green tea
extract on the permeability of ethylene vinyl alcohol (EVOH) lms
at different relative humidities. At low relative humidity (35%), the
incorporation of ferulic acid, quercetin, or green tea extract caused
an increase of about 20% WVP, probably due to the presence of
foreign substances in the polymer matrix. On the other hand, the
lm with ascorbic acid produced an unexpected barrier improve-
ment, probably due to interactions between the acid and the hy-
droxyl groups of the polymer. At high relative humidity (90%), the
addition of quercetin and green tea extract provided an improve-
ment of the water barrier, attributed to the lower afnity of these
agents for water, which reduced the hydrophilic capacity of the
composite matrix. On the contrary, the high afnity of ascorbic acid
for water resulted in its solubilization, breakage of the interaction
with polymer chains, and consequently higher plasticization and
increase of WVP. With respect to OP it was inuenced by ascorbic
acid in a similar manner to WVP. The authors also reported that the
added antioxidants lowered the melting point of the EVOH lm, a
fact associated with a more decient crystalline structure. They
commented that the presence of antioxidants probably produces
two antagonistic effects: a nucleating effect on the polymer, which
induces the growth of a large number of crystals, and a decrease in
crystal size because of imperfections (Lo !pez de Dicastillo et al.,
2012).
Carvacrol, a hydrophobic substance, decreased the WVP of chi-
tosan lms but, also, the mechanical properties (TS and elongation
at break) (Lo!pez-Mata et al., 2013; Rubilar et al., 2013; Yuan et al.,
2015). The same effect was observed with the addition of
carvacrol-rich essential oils in gelatin lms (Matrucci, Gende, Neira,
& Ruseckaite, 2015). These effects were attributed to the develop-
ment of a structure with less mobility and therefore less exibility
and resistance to fracture when the hydrophobic molecule was
incorporated.
Alpha-tocopherol is another antioxidant that has been incor-
porated in edible lms. Having few active groups, it does not seem
to present cross-linking effects and showed moderate improve-
ment in WVP of the lms, apparently attributed to its hydrophobic
nature (Fabra et al., 2011; Jime !nez, Fabra, Talens, & Chiralt, 2013;
Mei & Zhao, 2003). Also, it did not signicantly enhance the OP
of a whey protein lm (Han & Krochta, 2007), while it affected
controversially the mechanical properties of a chitosan lm
(Martins, Cerqueira, & Vincente, 2012) and a composite lm
(Jime!nez et al., 2013).
Resveratrol (3,5,40 -trihydroxystilbene found in grapes and other
plant species) caused different microstructural and barrier changes
to chitosan and methylcellulose (MC) lms. It modied the possi-
bility of the hydrogen bond formation between chitosan chains,
limiting the growth of crystalline zones, whereas it formed crystals
separated and randomly distributed as the concentration increased
in MC lms. These changes resulted in an increase in lm thickness
and decrease in TS in both cases but controversially affected the
elasticity of the lms. The OP and WVP were slightly improved, as
concentration of the compound increased probably due to its hy-
drophobic nature (Pastor, Sa !nchez-Gonza !lez, Chiralt, Cha
!fer, &
Gonza !lez-Martnez, 2013).
Other compounds, like triterpene saponins, which are abundant
in ginseng extract, did not inuence signicantly the WVP and the
moisture content values of lms (alginate). However, they caused
the formation of small pores and signicant reduction in TS and
elastic modulus values (Norajit, Myong Kim, & Hyung Ryu, 2010).
The active phenolic or glycoside OH groups of an extract may also
interact with cross-linking agents (e.g. glutaraldehyde) and disturb
the crosslinking effect (Lo !pez de Dicastillo, Rodrguez, Guarda &
Galotto, 2016).
The addition of herb or fruit extracts affect the color and
transparency of the lms. Tea extracts and fruit extracts increased
the darkness and imparted some red and yellow colorations to
chitosan lms, while green tea and borage extracts increased the
opacity of chitosan- and protein-based lms, respectively (Go !mez-
Estaca, Gime !nez, Montero, & Go !mez-Guille !n, 2009; Siripatrawan &
Harte, 2010; Wang et al., 2014; Yuan et al., 2015). EVOH copolymer
lms also became darker after the incorporation of green tea
extract (Lo !pez-de-Dicastillo et al., 2012) and the same was
76 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82

Table 3
Reports about the antioxidant properties of lms enriched with natural antioxidants.

Composition of the lm Additive Method of Effect of natural additives on lm properties References

Measurement

Chitosan with Tween Rosemary EO TPC TPC increased with the use of the EO. Abdollahi et al.
(2012a)
Chitosan-MMT nanocomposite Rosemary EO TPC TPC was the same with the one observed by Abdollahi et al. (2012a), but the Abdollahi et al.
with Tween WVP decreased after incorporation of MMT (2012b)
Chitosan with glycerol Green tea water extract TPC, DPPH TPC and DPPH scavenging activity signicantly increased with increasing GTE Siripatrawan
(GTE) concentration in the lms. and Harte
(2010)
Chitosan with glycerol GTE and black tea DPPH The addition of tea extracts signicantly improved the DPPH radical scavenging Peng et al.
extract (BTE) activity of lms. The higher the GTE and BTE concentration, the faster the release (2013)
of the tea antioxidants from the lm.
Chitosan with glycerol Indian gooseberry TPC The percentage of antioxidant released decreased with the increase of the Mayachiew and
ethanol extract extract incorporated, possibly due to higher intermolecular interaction. Devahastin
(2010)
Chitosan Lycium barbarum DPPH Lycium barbarum fruit extract enhanced the antioxidant activity of chitosan Wang et al.
extract powder lms. (2014)
Chitosan with glycerol Lyophilized Maqui TPC, DPPH, All assays indicated signicant antioxidant properties correlated with TPC. Genskowsky
berry extract FIC, FRAP et al. (2015)
Chitosan-MMT with glycerol Pomegranate rind TPC, DPPH Pomegranate rind extracts imparted excellent antioxidant activities to the lm. Qin et al. (2015)
ethanol extract
Chitosan with glycerol and Carvacrol and TPC, FRAP An additive effect was observed between carvacrol and pomegranate peel Yuan et al.
Tween Pomegranate peel extract. (2015)
methanol extract
Chitosan with Tween a-Tocopherol DPPH Two concentrations of the antioxidant were incorporated in the lms and Martins et al.
affected the radical scavenging activity in the same way. (2012)
MC or chitosan Resveratrol DPPH Some loss of the antioxidant activity of resveratrol was observed after its Pastor et al.
incorporation in MC lms. (2013)
CMC with glycerol and Tween Clove EO TPC, DPPH The antioxidant capacity increased with an increase in EO concentration. Dashipour et al.
(2014)
HPMC with glycerol Purple carrot extract ABTS, TEAC TEAC of the antioxidant agent decreased slightly during lm preparation. Films Akhtar et al.
stored in light had the lowest antioxidant activity. (2012)
MC cross-linked with Maqui berry ethanol FTIR The extract disturbed the crosslinking effect of GA, probably because phenolic Lo
!pez de
glutaraldehyde (GA) with and water extracts compounds of the extract reacted with GA. Dicastillo et al.
polyethylene glycol (2016)
Cellulose acetate with triethyl Onion ethanol, acetone TPC, DPPH, The highest antioxidant capacity was found for the 85% ethanol in water and Lo
!pez de
citrate or water extracts FRAP, ABTS absolute ethanol extracts. Dicastillo et al.
(2015)
CMC-MMT nanocomposite Murta leaves water ABTS The addition of MMT to CMCemurta leaves extract formulations resulted in a Quilaqueo
with glycerol extract signicant increase of the antioxidant activity. Gutie!rrez et al.
(2012)
Gelatin with propylene glycol Oregano and lavender ABTS Oregano-based lms exhibited the most effective antioxidant properties. Matrucci et al.
EOs (2015)
Tuna-skin gelatin or bovine- Oregano and rosemary TPC, DPPH, The potential antioxidant activity of the lms was not affected by the source of Go! mez-Estaca
hide gelatin, with sorbitol water extracts FRAP, ABTS the gelatin employed, however the supplemented lms did release differing et al. (2009)
and glycerol amounts of phenols.
Sole skin gelatin with glycerol Borage ethanol extract TPC, FRAP, The antioxidant activity of the borage extract was better than that of BHT and a- Go! mez-Estaca
and sorbitol ABTS tocopherol and also higher than oregano and rosemary extracts from another et al. (2009)
experiment by Go !mez-Estaca et al. (2009).
Alginate with glycerol White (WG) and red DPPH, FRAP The ginseng extract can be successfully incorporated into biodegradable alginate Norajit et al.
(RG) ginseng ethanol lms and retain excellent antioxidant activity. The lm with RG showed better (2010)
extracts DPPH radical scavenging activity than WG.
Galactomannan with glycerol Gleditsia triacanthos TPC, DPPH, The water extracts imparted the highest TPC content to the lm, meaning that G. Cerqueira et al.
ethanol and water triacanthos phenolic compounds are mostly water soluble. (2010)
extracts
EVOH copolymer GTE HPLC, DPPH, The process that was used for lm preparation (extrusion) resulted in a 20% Lo!pez de
ABTS degradation of the extract, due to the potential polymerization of phenols and Dicastillo et al.
the degradation of some catechins. (2011)
Corn starch-sodium caseinate Oleic acid and a- ABTS, TEAC Film antioxidant capacity was reduced after incorporation of oleic acid probably Jime!nez et al.
and glycerol tocopherol due to oxidation reactions. a-Tocopherol improved the antioxidant capacity of (2013)
the lms.
Ecoex1 and Ecoex1- Olive leaves extract and DPPH The lms containing a-tocopherol exhibited higher antioxidant activity than the Marcos et al.
polylactic acid (PLA) a-tocopherol lms containing olive leaf extract. (2014)
LDPE Barley husks ethyl HPLC-UV, The extract showed more than 2-fold the antioxidant capacity of BHT. Pereira de
acetate extract DPPH Abreu et al.
(2012)

observed for galactomannan lms enriched with G. triacanthos
extract (Cerqueira et al., 2010). However, some extracts (e.g. ex-
tracts rich in anthocyanes) may function as colorant, providing also
protection of the lms from photo degradation (Akhtar et al., 2012).
6. Antioxidant activity of enriched edible and active
packaging lms
Many researches have focused on the antioxidant properties of
the enriched lms themselves, without using them to coat food.
Reports about the increase in TPC and the antioxidant properties
 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82
(measured by radical scavenging assays) of lms enriched with
natural antioxidants are summarized in Table 3.
It can been noticed that chitosan lms have been studied most
widely. Chitosan is the second most abundant polysaccharide after
cellulose, and is a deacetylated derivative of chitin. Its good lm-
forming ability and intrinsic antimicrobial and antioxidant prop-
erties have made it attractive for food packaging (Abdollahi, Rezaei,
& Farzi, 2012a). Although, chitosan has antioxidant potential, there
are some limitations in it being a practical antioxidant. In all ref-
erences, TPC as well as radical scavenging activity of chitosan lms
increased after the incorporation of natural antioxidants. Abdollahi
et al. (2012a) made chitosan active lms enriched with rosemary
EO (0.5, 1.0 and 1.5% v/v) and measured their TPC. As expected, the
TPC of chitosan lm increased signicantly and was not affected by
the addition of MMT (Abdollahi et al., 2012b). Similarly, the addi-
tion of a pomegranate rind ethanol extract to a composite lm of
chitosan and MMT increased the TPC of the lm proportionally to
the amount of the added extract and was not affected by the
combination of MMT in the lm (Qin et al., 2015). Genskowsky
Puente, Pe !
!rez-Alvarez, Fernandez-Lo! pez and Mun ~ oz (2015) re-
ported a signicant correlation (R2 > 0.959) of TPC and total
avonoid content (TFC) with the antioxidant capacity as measured
by the DPPH radical scavenging, the ferrous ion-chelating capacity
(FIC), and the ferric reducing activity power (FRAP) values of chi-
tosan lms enriched with maqui berry extracts. Tea or fruit extracts
(obtained with water or ethanol extraction) could be easily incor-
porated in the lm, in a liquid form or after lyophilization and
increased signicantly the DPPH scavenging activity of the lm
(Peng et al., 2013; Qin et al., 2015; Siripatrawan & Harte, 2010),
approximating up to a 10-fold increase when the weight ratio of the
extract to chitosan was 1:1 (Wang et al., 2014).
The antioxidant activity of the lm is related to its ability to
release the entrapped active polyphenols. Peng et al. (2013) re-
ported that the increase of the concentration of tea extracts in
chitosan lm resulted in a faster release of the antioxidant com-
pounds, and consequently in higher radical scavenging activity,
something which was also observed by Cerqueira et al. (2010) and
Lo! pez de Dicastillo et al. (2015) with different lm materials and
additives. However, Mayachiew and Devahastin (2010) observed
that the percentage of release of total phenols from chitosan lms
decreased as the phenolic extract concentration increased, prob-
ably due to stronger functional group interaction, and consequently
to a lower degree of swelling of the lm. Also, the drying methods
and conditions have a signicant effect on the residual content of
incorporated compounds in the lm and on the interactions of
between the functional groups of the antioxidants and the lm
matrix (Mayachiew & Devahastin, 2010).
Go! mez-Estaca et al. (2009) used bovine-hide and tuna-skin
gelatin, to prepare biodegradable and edible lms supplemented
by polyphenol-rich oregano or rosemary water extracts. Interest-
ingly, while the potential antioxidant activity of the lms was not
clearly affected by the source of the gelatin employed (as indicated
by the FRAP and ABTS methods), the supplemented lms did
release differing amounts of phenols, with the bovine hide gelatin
lms releasing larger amounts, presumably because pro-
teinepolyphenol interactions were formed to a higher extent in the
sh gelatin lms. Although this fact did not clearly affect the anti-
oxidant properties of the lms, it could affect the phenol diffusion
from lm to food. The authors commented that the more extensive
polyphenol-protein interaction could affect the antioxidant ca-
pacity negatively. Also, the antioxidant activity was affected by the
additive, with the oregano extract presenting 5.5- and 7-fold higher
antioxidant activity than the rosemary extract in the FRAP and
ABTS assays, respectively. This higher antioxidant activity of the
77
oregano was attributed to its higher phenol content.
Matrucci et al. (2015), added oregano and lavender EOs
(2000e6000 ppm) in gelatin lms and determined the DPPH
radical scavenging activity. The results suggested that the addition
of 6000 ppm of oregano EO made the lm more active against
DPPH radical, while with lavender EO, the radical scavenging ca-
pacity of the lm was negligible. These results could be attributed
to the different activity of the EO components of each plant or to
interactions between the gelatin matrix and the EO components.
Clove EO has also made CMC lms more active against the DPPH
radical and has caused an increase in the TPC of the lms
(Dashipour, Khaksar, Hosseini, Shojaee-Aliabadi, & Kiandokht,
2014).
Quilaqueo Gutie !rrez et al. (2012) incorporated a water extract of
murta leaves in CMC-MMT nanocomposite lms. The antioxidant
capacity (estimated through the ABTS radical scavenging assay)
increased more than 18-fold compared to the CMC control lm. The
water extracts of murta leaves are rich in derivatives of gallic acid,
myricetin and quercetin, and these compounds could be respon-
sible for the antioxidant activity of the lms studied. The addition of
MMT to CMC-murta extract formulations resulted in a signicant
increase of the antioxidant activity, an effect not observed in the
absence of the extract. On the contrary Qin et al. (2015) reported
that the addition of MMT in lms of chitosan enriched with
pomegranate rind ethanol extract did not affect their DPPH radical
scavenging activity.
Extracts have also been added in biodegradable lms to be used
for active, non-edible packaging. Marcos et al. (2014) produced
biodegradable lms based on Ecoex1 and Ecofex1-polylactic acid
(PLA) and incorporated olive leaves extract and a-tocopherol. By
using the DPPH radical assay, they noticed that membranes
enriched with a-tocopherol had a better antioxidant activity than
those with the leaf extract. Ginseng extract was successfully
incorporated in a biodegradable alginate lm and retained
completely its radical scavenging capacity (Norajit et al., 2010).
Additionally, Pereira de Abreu et al. (2012) used a low-density
polyethylene (LDPE) lm as a carrier for barley husk extract. The
dry extract was dissolved in methanol and dispersed on the lm.
The barley husk extract lost some of its antioxidant activity after the
incorporation in LDPE lms; still, the remaining antioxidant ca-
pacity was even higher than the one of the synthetic antioxidant
BHT. The extract also remained in the LDPE surface after tests with
various food simulants, something that makes this enriched lm
ideal for a wide variety of foods.
As discussed above, in most of the cases, the antioxidant ca-
pacities of the lms are proportional to the concentration of the
active compound in the lm. The activity loss during lm formation
and conditioning is not remarkable in most cases (Akhtar et al.,
2012; Leo ! n & Rojas, 2007; Pastor et al., 2013; Pereira de Abreu
et al., 2012), although signicant losses were reported in case an
extrusion process was followed at 170 # C (Soto-Valdez, Auras, &
Peralta, 2011). However, few studies evaluated the active com-
pound stability during storage of the enriched lm. During a period
of 5-week storage, Jime !nez et al. (2013) observed that starch-
sodium caseinate lms incorporated with oleic acid lost part of
their antioxidant capacity, while lms incorporated with a-
tocopherol showed an increased antioxidant activity. Leo !n and
Rojas (2007) observed an increasing loss of ascorbic acid entrap-
ped in gellan gum lms, as the relative humidity increased. Similar
result was observed by DeNobili, Pe !rez, Navarro, Stortz and Rojas
(2013) in low methoxyl pectin lms. The increase of temperature
increases signicantly the degradation of ascorbic acid, whereas
light impacts this reaction only slightly (Ea et al., 2014).
78 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82

Table 4
Reports about the application of antioxidant-enriched edible lms and coatings on food products.

Type of lm or coating Additive Food Method of Measurement Main results References

Gelatin lms Oregano and Cold- TBARs, PV, Free fatty acids Phenolic compounds from rosemary released during storage and, Go!mez-
Gelatin-chitosan lms with rosemary water smoked (FFA), FRAP thus, rosemary extract showed better protection of smoked sardines Estaca et al.
sorbitol and glycerol extracts sardine than oregano. (2007)
Gelatin with glycerol GTE, ginger, Lard DPPH, PV Higher antioxidant activity was observed with the increase of Li et al.
gingko leaf extract concentration. Green tea extract, gingko leaf extract, grape (2014)
extracts, grape seed polyphenols and proanthocyanidins showed excellent
seed antioxidant activities.
CMC coating with Tween Rosemary EO and Smoked DPPH, TPC, PV, CD, p-AV The increase in extract concentration led to increased protection Choulitoudi
ethanol extract eel llets against oxidation. EO showed very low activity. et al. (2017)
Calcium caseinate and Oregano and Beef TBARs, TPC, (N,N-diethyl- Pimento-based lms presented the highest antioxidant activity. The Oussalah
whey protein isolate pimento EOs p-phenylenediamine) lms allowed a progressive release of phenolic compounds during et al. (2004)
lms with CMC, glycerol colorimetric method storage.
Sodium alginate coating Oregano or Beef TBARs, DPPH, FRAP, ABTS Coatings enriched with EOs (especially those enriched with Vital et al.
crosslinked with rosemary EOs steaks oregano) had an effect on consumer acceptance. Oregano EO (2016)
calcium chloride showed the highest antioxidant activity in all analyses.
Sodium caseinate lms Cinnamon or Sunower ABTS, TEAC, PV Cinnamon EO showed a higher antioxidant capacity than ginger oil Atare
!s et al.
with glycerol ginger EOs oil although their incorporation in the lms did not increase the (2010)
antioxidant activity and showed PV values similar to non-enriched
lms.
HPMC lm with Tween Ascorbic acid, Toasted PV Ascorbic and citric acid protected the almond oil against oxidation, Atare
!s et al.
citric acid and almonds while ginger EO had no effect. (2011)
ginger EO
CMC coating with glycerol Thyme and basil Roasted DPPH, PV, CD, p-AV Improved sensory stability of roasted sunower seeds during Riveros et al.
EOs sunower storage, but only thyme EO increased their chemical stability. (2015)
seeds
CMC coating with Tween Winter savory Seabream TPC, PV, p-AV The ethanol extract (rich in rosmarinic acid and other polyphenols) Choulitoudi
EO, llets showed remarkable antioxidant activity. EO also showed activity et al. (2016)
ethyl acetate and attributed to carvacrol.
ethanol extracts
Chitosan lms with GTE Pork TBARs Incorporation of green tea into chitosan lm enhanced the Siripatrawan
glycerol sausages antioxidant properties of the lm thus maintained the qualities and and Noipha
prolonged the shelf life of the sausages. (2012)
Chitosan coating with GTE Walnut TBARs, TPC, PV GTE into chitosan reduces oxidation of the product. No differences Sabaghi et al.
glycerol kernel were observed in antioxidant activity of lms enriched with (2015)
different GTE concentrations.
Cassava starch lms with Yerba mate Palm oil PV, Total carotenoids Yerba mate extracts had high antioxidant efcacy, likely due to Batista Reis
mango pulp and glycerol water extract phenolic compounds and avonoids. Film formulations with higher et al. (2015)
concentrations of this additive exhibited lower rates of oxidation.

7. Applications of enriched edible and active packaging lms
for the antioxidant protection of lipid foods
Research reports about the use of lms enriched with antioxi-
dants in real foods are rather recent (Tables 4 and 5). Oregano and
rosemary extracts prevail as the most efcient antioxidants for sh
and meat products. More specically, water extracts of both herbs
have been added to edible lms made of gelatin or gelatin-chitosan
and proved effective to retard the oxidation of smoked sardines
(Go!mez-Estaca et al., 2007). Similarly, the ethanol extract of rose-
mary incorporated in CMC coating protected smoked eel llets and
retarded the accumulation of both primary and secondary oxida-
tion products with an effect increasing with concentration
(Choulitoudi et al., 2017). Bolumar, Andersen, and Orlien (2011) and
Bolumar, LaPen ~ a and Skibsted and Orlien (2016) incorporated an
ethanol extract of rosemary in LDPE lms and covered chicken or
pork patties, which were then vacuum packaged in a plastic pack-
aging and treated by high pressure. The active packaging was able
to delay the oxidation induced by high pressure processing and,
thus extended the shelf life of the products. Another observation
that was made during this research was that active packaging
enriched with natural extracts offers greater protection against
lipid oxidation than oxygen scavenging packaging.
Go
! mez-Estaca et al. (2007) examined the transfer of total phe-
nols from gelatin lms enriched with oregano or rosemary extracts
to cold smoked sardines, from the beginning of the storage. In the
case of oregano the phenols did not show any signicant increase
through time, while on the other hand a phenol increase was
noticed in the samples packaged with rosemary-enriched lms in
the following days of storage. This proves that the antioxidant ca-
pacity of rosemary is being released gradually. Comparing the re-
sults of the thiobarbituric acid reactive substances (TBARs) assay for
the samples coated with the oregano and rosemary enriched lms
revealed that the rosemary extract lowered the oxidation rate more
than oregano did, despite the fact that rosemary had lower TPC
values. This is indicative of quantitative and qualitative differences
in the nature of the phenolic compounds present in the extracts
from these two plants.
In general, both rosemary and oregano extracts are rich in
phenolic substances and effective when incorporated in edible or
non-edible lms, although, the different extraction procedures, the
lm matrix used to incorporate the antioxidants, or the food itself
may result in somehow different results. Thus, contrary to the
above presented results of Go !mez-Estaca et al. (2007), Camo,
Beltra
!n, and Roncale !s (2008) found oregano more effective than
rosemary extracts to protect lamb steaks packaged in active poly-
propylene lm. In a following research, Camo, Lore !s, Djenane,
Beltra
!n, and Roncale !s (2011) proved that there is a correlation be-
tween oregano extract concentration and antioxidant capacity and
with higher concentrations, the protection against lipid oxidation
increased. This nding seems to agree with the results of Batista
Reis, Oliveira de Souza, Alves da Silva, Martins, Nunes, and
Druzian (2015), who incorporated yerba mate extract in different
concentrations in starch lms. On the contrary, Nern et al. (2006)
did not nd differences in the antioxidant activity of poly-
propylene lms enriched with different rosemary extract
 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82 79

Table 5
Reports about the application of antioxidant-enriched non-edible active packaging lms on food products.

Type of lm or Additive Food Method of Measurement Main results References

coating

Polypropylene Oregano and Lamb steaks TBARs, metmyoglobin analysis In a high-oxygen modied atmosphere (to delay microbial Camo et al. (2008)
lm rosemary growth), active lms with oregano were more efcient than
extracts those with rosemary, exerting an effect similar to that of direct
(Amexol) addition of the rosemary extract to the meat surface.
Rosemary Beef steaks TBARs, metmyoglobin analysis Surface metmyoglobin and TBARs formation were depressed by Nern et al. (2006)
extract active packaging, although the increase of rosemary
(Amexol) concentration on the lm did not cause signicant differences
Oregano Beef steaks TBARs, metmyoglobin analysis At least 1% oregano was needed for obtaining an increase of Camo et al. (2011)
extract display life from 14 to 23 days. A concentration of 4% resulted in
unacceptable oregano smell. Most suitable oregano extract
concentrations for optimum active packaging should be within
the range of 1e2%.
LDPE Rosemary Chicken TBARs Antioxidant active packaging was able to delay (up to 25 days) Bolumar et al. (2011)
ethanol extract the oxidation induced by high pressure processing and, thus
extended the shelf-life.
Rosemary Pork patties TBARs Rosemary active packaging was effective to protect pork patties, Bolumar, LaPen~ a,
ethanol extract contrary to oxygen scavenger packaging that could not suppress Skibsted, and Orlien
the high pressure induced lipid oxidation. (2016)
Barley husk Atlantic TBARs, PV, CD, conjugated triene The oxidation indices showed that the active packaging with Pereira de Abreu et al.
ethyl acetate salmon hydroperoxides, p-p-AV, Free fatty the antioxidant slowed down lipid hydrolysis and oxidation, (2010a)
extract acids (FFA), Totox values with a concentration dependent effect.
Atlantic The results conrmed the ability of active packaging to increase Pereira de Abreu,
halibut the oxidative stability of the sh. Paseiro Losada,
Maroto, and Cruz
(2010b)
Blue shark The active packaging slowed down lipid hydrolysis and Pereira de Abreu,
oxidation (especially PV and TBARs) of blue shark, too. Paseiro Losada,
Maroto, and Cruz
(2011)
EVOH Ascorbic acid, Brined TBARs, PV The lms with GTE were the most effective, slowing down the Lo ! pez de Dicastillo
copolymer ferulic acid, sardines PV, and also reducing TBARs. Ferulic acid and quercetin had also et al. (2012)
lms quercetin, GTE a good protective action, while ascorbic acid had no effect.
Ethylene vinyl Horseradish Pork and TBARs, DPPH, PV Changes in PV of pork were insignicant but in the case of the Jung et al. (2009)
acetate methanol Japanese sh llets the extract inhibited early lipid oxidation according
lms extract Spanish to PV. Enriched lms also inhibited malondialdehyde
mackerel generation.
1)PET trays Citrus extract Turkey meat TBARs TBARS values of meat stored at 4 # C on the citrus-coated trays Contini et al. (2011)
with extract were signicantly lower than those of samples on the control
2) PET trays trays and a-tocopherol-coated trays, which did not show
with a- antioxidant properties.
tocopherol

concentrations. Camo et al. (2011) also noticed, that with an in-
crease in extract concentration, the oregano aroma became more
obvious, something which is likely to have a negative impact on
consumers. So they arrived to the conclusion that the ideal oregano
extract concentration in active packaging should be around 1e2%.
The EOs of aromatic plants have been also used in active pack-
aging with promising results as antimicrobial agents, but contra-
dictory as antioxidant ones. Oussalah et al. (2004) incorporated
oregano and pimento EOs in whey protein isolate lms and studied
their antioxidant capacity on packaged beef. The results of the
TBARs analysis showed that the incorporation of EOs in the lms
did not improve the protection of the meat samples against lipid
oxidation. Nevertheless, it is known that pimento oil is rich in
phenolic compounds such as eugenol, which are unstable and
could generate phenolic aldehydes. These aldehydes could provoke
a similar reaction to malonaldehyde that is determined by the
TBARS method, and would probably increase the obtained values,
i.e. mask the antioxidant effect of EOs. Cinnamon and ginger EOs
were inactive when incorporated in sodium caseinate lms for the
protection of sunower oil (Atare !s, Bonilla, & Chiralt, 2010).
In a recent research, Riveros, Nepote, and Grosso (2015), incor-
porated thyme and basil EOs in CMC coatings, which were used to
coat roasted sunower seeds. The results of the oxidation chemical
indicators (peroxide value (PV), conjugated dienes (CD) and p-
anisidine value (p-AV)) during storage evidenced that the CMC
edible coating helps to preserve the roasted sunower seeds
against lipid oxidation but, also, the addition of EOs (especially
thyme EO) improves the protection. Similar results were observed
in the protection of seabream llets with winter savory EO
entrapped in CMC coating (Choulitoudi et al., 2016). The fact should
be attributed to the presence of carvacrol or thymol, the main
components of thyme and winter savory EOs. On the contrary, CMC
coatings enriched with rosemary EOs provided minor protection to
smoked eel (Choulitoudi et al., 2017). It was also interesting to note
that the winter savory EO demonstrated antagonistic effect with
the ethanol extract of the same plant, probably because of the
antagonistic interactions of carvacrol and rosmarinic acid (the main
component of the ethanolic extract). Such an antagonistic effect has
been reported by Tsimogiannis et al. (2017). On the contrary,
rosemary EO that contains only traces of carvacrol, resulted in a
possible synergistic effect with rosemary ethanol extract, retarding
the formation of primary and secondary oxidation products
(Choulitoudi et al., 2017). The incorporation of EOs for the enrich-
ment of edible lms may present some difculties concerning
consumer acceptance because they have an intense aroma (Rojas-
Gra et al., 2009; Vital et al., 2016).
Green tea is another herb that demonstrated remarkable anti-
oxidant activity when incorporated in edible or non-edible lms.
80 S. Ganiari et al. / Trends in Food Science & Technology 68 (2017) 70e82
Siripatrawan and Noipha (2012) incorporated green tea water
extract (20% w/v) in chitosan lms and packaged pork sausages
with it. Lipid oxidation was measured with TBARs and proved that
green tea extract is a strong antioxidant. According to Sabaghi,
Maghsouldou, Khomeiri, and Ziaiifar (2015) the antioxidant activ-
ity of chitosan increases with increasing the concentration of tea
extract, due to: (1) increasing the active groups of the lm, (2)
reinforcing the network of the coating and thus enhancing the
oxygen barrier properties of the coating.
Lo
!pez de Dicastillo, Nern, Alfaro, Gavara and Herna !ndez-Mun ~ oz
(2011), studied the development of an active packaging based on
EVOH and green tea extract and the results of brined sardines
packaging showed that the enriched lms were very effective,
slowing down the PV and TBARs during storage to a greater extent
than ascorbic acid, ferulic acid and quercetin (Lo ! pez de Dicastillo
et al., 2012). Exposure of the lms to various food simulants
showed that the release of active agents depended on the afnity of
the antioxidants for the food simulants: the release of ascorbic and
ferulic acid were higher in aqueous simulants, and the release of
quercetin and green tea extract higher in ethanolic simulant. Jung
et al. (2009) also effectively protected sh from oxidation with
the incorporation of horseradish extract in ethyl vinyl acetate
copolymer lm.
Active packaging for sh protection was also examined by
Pereira de Abreu, Paseiro Losada, Maroto, and Cruz (2010a,2010b,
2011) who used LDPE lms coated with barley husk ethyl acetate
extract in two different concentrations. The main phenolic com-
pounds identied by HPLC were p-coumaric and ferulic acid. The
active lm proved effective in protecting salmon, halibut and blue
shark samples against oxidative processes during frozen storage.
The peroxide value was lowered, and the measurement of sec-
ondary oxidation products (TBARs and p-AV) showed that the
higher the extract concentration on the packaging, the more ef-
cient the protection of the food against oxidation, although differ-
ences were observed among the three sh species.
In order to create a material for use in an active packaging
application, transfer of the antioxidant must be allowed to take
place between the packaging and the food. The antioxidant should
migrate into the food product or to the surface of the packaging
material, where it can help to inhibit oxidation, thereby extending
the shelf-life of the product. It is clear that the lm material and
morphology might have an effect on phenol release, and antioxi-
dant capacity. Also, the chemical structure and polarity of the
antioxidant, in relation to the packaged food plays a major role. The
release rate of the antioxidant compounds from the lm to food is
slow when migration is governed by diffusion in the polymer
matrix, and it is fast when governed by swelling or dissolution that
is mainly affected by the nature of the food in contact with the
packaging material. Also, the microstructure of the polymer lm
can greatly inuence the mobility of active compound in the lm.
(LaCoste et al., 2005). Contini et al. (2011) commented that the
active hydrophilic phenolic groups of bioavonoids from citrus
extracts were effective antioxidants for meat because they were
oriented towards the surface of the lm and were in contact with
meat, contrary to a-tocopherol that is oriented with its hydropho-
bic side chain at the surface of the lm, and consequently, its active
part is not in contact with meat and cannot protect it. Wessling
et al. (1999) examined the transfer of a-tocopherol from low den-
sity polyethylene or polypropylene lms to foodstuffs and food
simulants. The antioxidant was easily transferred from LDPE lms
to products with a high fat or alcohol content. Unlike LDPE, poly-
propylene (PP) did not show any interactive tendencies towards
any of the foods. The a-tocopherol content in the PP lm remained
more or less unaffected and might be able to scavenge oxygen at the
surface of a packaged food.
8. Conclusions
Natural antioxidants are promising additives for lms and
coatings to delay oxidation of lipid foods. They act by increasing the
phenolic content and antiradical activity and improving the barrier
properties of the lm through interactions with the active groups.
The interactions of specic natural ingredients (avonoids,
phenolic acids, etc.) and the distribution of the additive in the
polymer matrix have also an effect on the mechanical properties of
the lm and should be carefully examined. Another factor that
needs further examination is the stability of the antioxidants dur-
ing storage of the lm, their release during storage of the packaged
food, and the inuence on the sensorial properties of food, a major
factor to decide for industrial application. Natural antioxidants can
be obtained by several herbs and agricultural by-products and are
well accepted by the consumers. Their incorporation in active
packaging may result in innovative solutions for extending the shelf
life, maintain or monitor the quality of lipid foods.
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