J.foodhyd.2013.06.00520211108 4503 1nep54b With Cover Page v2

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Accelerat ing t he world's research.

Edible films from pectin: Physical-


mechanical and antimicrobial
properties - A review
Roberto Avena
Food Hydrocolloids

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Food Hydrocolloids xxx (2013) 1e10

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

Review

Edible films from pectin: Physical-mechanical and antimicrobial


properties - A review
Paula Judith Pérez Espitia a, *, Wen-Xian Du b, Roberto de Jesús Avena-Bustillos b,
Nilda de Fátima Ferreira Soares a, Tara H. McHugh b
a
Food Packaging Laboratory, Food Technology Department, Federal University of Viçosa, Av. P. H. Rolfs s/n, Campus Universitário, Zip code 36570-000,
Viçosa, Minas Gerais, Brazil
b
Processed Foods Research Unit, Western Regional Research Center, U.S. Department of Agriculture, Agricultural Research Service, 800 Buchanan St., Albany,
CA 94710, USA

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

Article history: Pectin is one of the main components of the plant cell wall chemically constituted by poly a1e4-
Received 18 March 2013 galacturonic acids. According to its degree of esterification with methanol, pectin can be classified as
Accepted 9 June 2013 high methoxyl pectin or low methoxyl pectin. In food industry, pectin is listed as generally recognized as
safe (GRAS) by the Food and Drug Administration and is used as gelling, stabilizing, or thickening agent
Keywords: in food products such as jams, yoghurt drinks, fruity milk drinks, and ice cream. Due to its biodegrad-
Pectin
ability, biocompatibility, edibility, and versatile chemical and physical properties (such as gelation, se-
Biopolymer
lective gas permeability, etc), pectin is a suitable polymeric matrix for the elaboration of edible films
Active packaging
Mechanical resistance
intended as active food packaging. Active packaging is a packaging system which possesses attributes
Structural characterization beyond basic barrier properties that are achieved by adding active ingredients in the packaging material
Antimicrobial activity and/or using functionally active polymers. When the packaging system has antimicrobial activity, the
packaging limits or prevents the microbial growth by extending the lag period and reducing the growth
rate of microorganisms. This review describes the main methods for elaborating pectin edible films,
principal characterization techniques for determining their physical-mechanical properties, and appli-
cations of pectin edible films as antimicrobial food packaging. Finally, legislation and future trends
regarding the use of pectin edible films are also discussed.
Ó 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Pectin as polymeric matrix for elaboration of edible film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Pectin edible film elaboration by casting method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2. Pectin edible film elaboration by extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3. Pectin edible film elaboration by spraying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4. Pectin edible film elaboration by knife-coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Methods for improving the properties of pectin edible films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Emulsifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Physical-mechanical characterization of pectin edible films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Pectin films as antimicrobial food packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Legislation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
7. Future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

* Corresponding author. Tel.: þ55 31 38991796.


E-mail addresses: perez.espitia@gmail.com, espitia.paula@gmail.com (P.J.P. Espitia).

0268-005X/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodhyd.2013.06.005

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
2 P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10

Source(s) of support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction extraction are apple pomace and citrus peels (Videcoq, Garnier,
Robert, & Bonnin, 2011).
The current global market has experienced an increasing con- Chemically, pectin is poly a1e4-galacturonic acids (Fig. 1a), with
sumer demand for more natural foods meeting the criteria of high varying degree of methylation of carboxylic acid residues and/or
quality and safety. This has lead companies and researchers to amidated polygalacturonic acids (Fig. 1b) (Mishra, Banthia, &
explore different ways to improve their productivity in terms of Majeed, 2012; White, Katona, & Zodda, 1999).
maintaining quality, freshness, and food safety, such as using sus- Methoxylated carboxyl groups are obtained by esterification
tainable materials in food packaging (Mahalik & Nambiar, 2010). with methanol of carboxyl groups of galacturonic acid. On the other
Moreover, edible film research has undergone rapid expansion in hand, amidated carboxyl group are obtained when some of the
the past twenty years, due to increased consumer interest in health, galacturonic acid are converted with ammonia to carboxylic acid
nutrition, food safety, and environmental issues. World production amide.
of plastic resins increased around 25-fold, while less than 5% of all According to the degree of esterification (DE) with methanol,
plastics were recycled, leading to a rapid accumulation of plastics in which is the ratio of esterified galacturonic acid groups to total
the environment (Sutherland et al., 2010). In the United States galacturonic acid groups (Farris, Schaich, Liu, Piergiovanni, & Yam,
alone, the increased plastic production resulted in 31 million tons 2009; Sila et al., 2009), pectin can be classified as high methoxyl
of plastic waste in 2010, representing 12.4% of total Municipal Solid pectin (HMP) or low methoxyl pectin (LMP). HMP has over 50% of
Wastedmore commonly known as trash or garbage (EPA, 2011). their carboxyl groups esterified (DE > 50), while LMP have a
Food wraps account for million tons of waste in landfills every year, DE < 50. Their DE affects gelling properties of pectins. In this way,
putting a serious burden on the environment. As a result, research LMP forms gel in presence of multivalent ions, which acts as a
works related to the use of biopolymers has emerged as an alter- bridge between pairs of carboxyl groups of different pectin chains.
native, due to their biodegradability. Biopolymers have been On the other hand, HMP forms gel in acidic media with the addition
studied regarding their film-forming properties to produce edible of different sugars such as sucrose or glucose (Mishra et al., 2012;
films intended as food packaging (Azeredo et al., 2009). Videcoq et al., 2011).
Structuring biopolymers, such as polysaccharides, proteins, and Different intermolecular interactions are involved in the gela-
lipids have been used for the formulation of edible films. Recent tion of pectins. The gelation of LMP involves electrostatic in-
reviews have focused on edible films based on lipids (Debeaufort & teractions between the cations and the negative charged cavities
Voilley, 2009), protein (Ramos, Fernandes, Silva, Pintado, & Malcata, formed by polymer chains, where the cations are inserted. This is
2011) and on polysaccharides such as chitosan (Dutta, Tripathi, known as the egg box model (Fig. 2) and this process is similar to
Mehrotra, & Dutta, 2009), hemicelluloses (Hansen & Plackett, the gelation of alginates. Moreover, egg-boxes formed between two
2008) and starch (Jiménez, Fabra, Talens, & Chiralt, 2012). More-
over, extensive publications have presented very well and wide
reviews regarding the development and application of edible films
(Cagri, Ustunol, & Ryser, 2004; Campos, Gerschenson, & Flores,
2011; Falguera, Quintero, Jiménez, Muñoz, & Ibarz, 2011;
Gennadios, Hanna, & Kurth, 1997; Guilbert, Gontard, & Cuq, 1995;
Janjarasskul & Krochta, 2010). However, to the best of our knowl-
edge literature related to pectin-based edible films is quite scarce
and there is no review article solely devoted on pectin-based edible
films so far in the literature.
Thus, this review highlights specifically the development of
edible films made from pectin and the characterization of these
films. Antimicrobial activity, their application on food preservation,
and related legislation of pectin edible films are also discussed.
Finally, future trends regarding the use of pectin edible films are
presented.

2. Pectin as polymeric matrix for elaboration of edible film

An edible film is defined as a packaging material, which is a thin


layer of edible material placed on or between food components
(McHugh, 2000). Different structural materials have been used in
edible film elaboration, such as proteins, lipids and polysaccharides.
Polysaccharides include cellulose, chitosan, starch and pectin.
Pectin is one of the main components of the plant cell wall,
contributing to tissue integrity and rigidity and it is considered one Fig. 1. Chemical structure of polygalacturonic acid (a) and representative chemical
of the most complex macromolecules in nature (Jolie, Duvetter, Van structure of pectin showing typical repeating groups (b). With permission from White
Loey, & Hendrickx, 2010). The main industrial sources for pectin et al. (1999).

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10 3

and rhamnogalacturonan II (RG I and RG II) (Willats, McCartney,


Mackie, & Knox, 2001). HGA represents the backbone chain of the
pectin molecule, which contains a-1,4-linked residues of D-gal-
acturonic acid and constitutes the smooth region (Fig. 3). RG I is
located in the highly branched area containing large number of side
chains of a-1,2-linked residues of L-rahmnopyranose whereas the
more complex RG II structure has been identified in the primary cell
wall of some plants, both constitute the hairy region of pectin
(Yadav, Yadav, Yadav, & Yadav, 2009).
Moreover, pectin is an ingredient used in food industry with no
limitation other than current good manufacturing practice, is
considered as generally recognized as safe (GRAS) by the FDA (FDA,
2013b) and it has been used in food mainly as gelling, stabilizing, or
thickening agent in products such as jams, yoghurt drinks, fruity
milk drinks, and ice cream (Laurent & Boulenguer, 2003). Produc-
tion of edible films from pectin can be accomplished by various
methods such as casting, extrusion, spraying, and knife-coating.

2.1. Pectin edible film elaboration by casting method


Fig. 2. Representation of the “Egg Box” model. Polygalacturonic acid chains are rep-
resented by black lines, calcium ions and carboxyl groups by circles. With permission
from Fraeye et al. (2010). Casting method consists basically in spreading a prepared film-
forming solution onto a flat and nonstick surface, followed by
removal of the formed film, previously dried. In general, solvents
neighboring chains are stabilized by Van der Waals interactions and used for edible films production include water, ethanol, or a com-
hydrogen bonds in addition to electrostatic interactions (Fraeye, bination of both (Campos et al., 2011), with water being the solvent
Duvetter, Doungla, Van Loey, & Hendrickx, 2010). primarily used in the elaboration of pectin edible films.
On the other hand, the gelation of HMP takes place in conditions Another important component in the elaboration of pectin-
where electrostatic repulsions and water activity are reduced, in based edible film is the plasticizer. The plasticizer is generally a
the presence of co-solutes at low pH. The cross-linking results from small molecule of low volatility that, when added to polymeric
the formation of polymeric chain aggregates of varying sizes materials, modifies their three-dimensional organization, de-
(Alonso-Mougán, Meijide, Jover, Rodríguez-Nuñez, & Vázquez-Tato, creases attractive intermolecular forces, and increases free volume
2002). and chain mobility. These changes in molecular organization
In addition, treatment with ammonia generates amidated low caused by the plasticizer results in increased extensibility,
methoxyl pectin (ALMP) (Jug, Kosalec, Maestrelli, & Mura, 2012). dispensability, and flexibility of the developed film while at the
ALMP needs less calcium to gel than the non-amidated LMP, they same time cohesion and rigidity of the film are decreased
are less sensitive to precipitation by high amounts of calcium, and (Kokoszka, Debeaufort, Hambleton, Lenart, & Voilley, 2010). Food-
their gels are thermoreversible (Tho, Arne Sande, & Kleinebudde, grade plasticizers include glycerol and sorbitol, with glycerol be-
2005). ALMP are more tolerant to pH variations and fluctuation in ing the most popular plasticizer used in film-making techniques,
calcium levels than conventional pectins, characteristics that made due to stability and compatibility with hydrophilic biopolymeric
them useful in colonic delivery systems (Munjeri, Collett, & Fell, packaging chain (Chillo et al., 2008).
1997; Wakerly, Fell, Attwood, & Parkins, 1997). The commercial name of glycerol, glycerin, applies to purified
Three major pectic polysaccharides have been structurally well- products containing 95% or more of glycerol. Glycerin has various
characterized: homogalacturonan (HGA), rhamnogalacturonan I grades of uses in the United States and in Europe; however, the

Fig. 3. Hairy and smooth regions of pectin. With permission from Yadav et al. (2009).

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
4 P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10

desirable grade for food applications and edible film elaboration is properties comparable to those obtained by casting from solutions
the USP glycerin. The designation USP is an abbreviation of U.S. containing the same materials. In similar conditions, pectin films
Pharmacopeia and means that the glycerin designated meets or were developed with various combinations of orange albedo and
exceeds the standards established in the U.S. Pharmacopeia. USP starch (Fishman, Coffin, Onwulata, & Konstance, 2004). Moreover,
glycerin is a clear, almost colorless product of high purity of glycerin films from pectin, poly(vinyl alcohol) (PVOH) and starch blends
with taste and odor characteristics desirable for pharmaceutical were elaborated using two stage extrusion process (Fishman,
and food purposes (SDA, 1990). Also, glycerin is considered by the Coffin, Onwulata, & Willett, 2006). The first stage extrusion was
FDA as a multiple purpose GRAS food substance (FDA, 2013a). done in a twin screw extruder in order to pelletize all film-forming
Casting method for pectin-based edible films elaboration can be ingredients. In the second stage, the pelletized ingredients were
sub-classified in two methods: by solution casting process (in extruded both as flat sheet and as blown film using a single screw
batches) or by a continuous casting method. In both methods a extruder, with a screw speed of 20 rpm for the film blowing, and
film-forming solution is prepared by mixing pectin with the sol- 30 rpm for the sheet extrusion. Results showed that pectin, starch
vent, plasticizer and other ingredients. However, both methods and PVOH plasticized with glycerol can be successfully extruded in
differ in the volume scales at which films are prepared, as well as a two stage process using both a twin screw extruder and a single
drying time necessary to obtain edible films. screw extruder to form strong extruded sheets with a thickness of
The method of casting process is commonly used to elaborate 0.4 mm or less, and blown into films with thicknesses of less than
edible films at laboratory scale. In this method, drying conditions 0.15 mm.
can vary from 12 min with hot air to 12 h at room temperature (Du, In addition, Liu et al. (2005) studied the optimal conditions of
Avena Bustillos, Hua, & McHugh, 2011). This process is also known extrusion parameters for the elaboration of edible packaging films
as batch casting. derived from food-based polymers. The experiment was done in a
Moreover, the continuous casting method is mainly used at in- twin screw extruder with a cylindrical die (Fig. 4), which resulted in
dustrial scale. Previous work have indicated the use of a Mathis the formation of a hollow continuous casing. The authors indicated
Labcoater unit (Werner Mathis AG, Zürich, Switzerland) to produce that optimal conditions for pectin films were temperatures at
edible films from pectin and apple puree by using the continuous extruder zone 3 and zone 4 at 125  C and 110  C, respectively. Also,
casting method (Du et al., 2008a). According to the authors, the the feeder speed was optimal at 18.49 g/min, with 50% of glycerol
continuous casting unit was set spreading 41 mil (1 mil ¼ 0.001 in.) concentration and screw speed of 225 rpm. These conditions were
thickness apple solution on a Mylar sheet conveyor moving at determined according to the assessment of film physical-
0.11 m/min. The casted edible film was first partially dried by an mechanical properties, such as tensile strength, elongation, punc-
infrared heater adjusted to 0 and 90% energy emission at the bot- ture resistance, color, Young’s modulus, tear resistance, turbidity
tom and top, respectively. The convective heating stage was and thickness (Liu et al., 2005).
controlled at 132  C and 1500 m/min air velocity. Further studies used these parameters to develop edible casings
The continuous casting method is considerable more practical for breakfast pork sausage (Liu, Kerry, & Kerry, 2007). Casings from
due to reductions in drying times, usually takes few minutes, which pectin and incorporated with 2.5% corn oil and 5% olive oil were
enable the rapid formation of films without any microbial compared with gelatin/sodium alginate blends with same con-
contamination from surrounding ambient (Du et al., 2011). centration of corn oil and olive oil. Sensory analysis of sausages
showed that pectin casings were more preferred than gelatin/so-
2.2. Pectin edible film elaboration by extrusion dium alginate blend casing for sausage manufacture. This result
was coherent with results of color analysis. However, water losses
Extrusion is used for the production of conventional commercial from sausages using pectin casings were higher than those using
plastic packaging. This process uses one or two rotating screws gelatin/sodium alginate blend casing, probably due to the fact that
fitted in a barrel in order to progressively increase the pressure and gelatin/sodium alginate blend casing have higher ability to trap and
push forward and mix the ingredients required to manufacture the absorb water compared to pectin casings.
commercial polymer through a die where expansion may take In general, edible films do not pretend to replace traditional
place (Nur Hanani, Beatty, Roos, Morris, & Kerry, 2012). Extrusion is packaging materials (Campos et al., 2011). Instead, they are devel-
often preferred to casting as the method of fabricating films oped to be used as carrier for additive with specific function over
because the throughput of the process is faster and less energy is the contained food, such as anti-browning, antimicrobial agents,
required for the removal of water (Fishman, Coffin, Konstance, & texture enhancers, nutrients, probiotics and flavors, among others,
Onwulata, 2000). so they can provide an additional stress factor to be applied for the
The successful application of extrusion depends upon the main maintenance of food quality and preservation.
variables that should be controlled during the extrusion process.
These variables include food polymer selection, liquid feed rates,
screw configuration, screw speed, zone temperatures, product
inlet/outlet pressures (and their differentials), as well as die
configuration (Liu, Kerry, & Kerry, 2005).
Although extrusion is a promising approach for the elaboration
of edible films, there are a limited number of studies related to the
use of this technology on pectin edible film elaboration. Probably,
this is due to the behavior and chemical interaction of food in-
gredients during extrusion, which is difficult to understand along
with many processing variables that need to be controlled.
In this way, Fishman et al. (2000) used extrusion for the
development of edible films from pectin/starch blends plasticized
with glycerol. They used a twin screw extruder provided with nine
heating zone. As a result, the authors observed that extruded edible Fig. 4. Configuration of extrusion die used in the extrusion of pectin films. With
films have microstructure and thermal dynamic mechanical permission from Liu et al. (2005).

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10 5

2.3. Pectin edible film elaboration by spraying They decrease intermolecular forces between polymer chains, thus
increasing flexibility and extendibility. Generally, plasticizers act by
Spraying is a wet processing, where polymers are dispersed or entering between polymeric molecular chains, physical-chemically
solubilized into a liquid phase, cast and dried (Talja, 2007). In the associating with the polymer, reducing cohesion within the film
spraying process a film forming solution is sprayed onto the network, and effectively extending and softening the film structure
product surface or a support material, such as a non-sticky surface, (Arnold, 1968; Banker, 1966; Guilbert & Gontard, 1995). Examples of
on which droplets formed by a sprayer form uniform films. In food-grade plasticizers incorporated into edible films are polyols
spraying, solvent evaporates to some extent after leaving the nozzle (e.g., glycerol, sorbitol, and polyethylene glycol), sugars (e.g.,
of the sprayer allowing a shorter drying time for film coating. glucose and honey), and lipids (e.g., monoglycerides, phospho-
Recently, Jindal, Kumar, Rana, and Tiwary (2013) extracted lipids, and surfactants). Commonly used plasticizers are liquid
pectin from Bael fruit (Aegle marmelos) and used this method for organic compounds such as polyols, mono/di/oligosaccharides,
the development of pectinechitosan cross-linked films. They used lipids, and lipid derivatives (Padua & Wang, 2002; Reiners, Wall, &
a spray gun (1 mm nozzle) with the help of peristaltic pump using a Inglett, 1973).
non-sticky surface of a rotating drum with hot air blown at 50  C for Glycerol, acetylated monoglycerides, polyethylene glycol, and
solvent evaporation. The authors observed that film-forming so- sucrose are some of the most common plasticizers incorporated
lution of Aegle marmelos pectin (AP) alone did not produce any film, into the polymeric matrix to decrease glass transition temperature
whereas, the films formed by using chitosan (CH) alone were brittle and increase film flexibility (Guilbert and Gontard, 1995). Plasti-
and hard. On the other hand, they observed that 30:70, 40:60, cizers are usually hygroscopic and attract water molecules. Water
50:50, 60:40 and 70:30 ratios of CH:AP yielded acceptable films, can also function as plasticizer, but it is easily lost due to dehy-
which were subjected to evaluation of physical-mechanical and dration in low relative humidity environments (Guilbert and
electrical properties. Gontard, 1995). In addition to improving mechanical properties,
plasticizers also affect the resistance of films to the permeation of
2.4. Pectin edible film elaboration by knife-coating vapors and gases (Sothornvit & Krochta, 2000, 2001), where hy-
drophilic plasticizers usually increase the water vapor permeability
Casting is a simple method to produce films, but has the of film. Unfortunately, plasticizers generally also decrease the
disadvantage of being a batch procedure only used for the pro- ability of films to act as barriers to the transport of moisture, gases,
duction of films in a very small-scale. Knife-coating process is a and aroma compounds (Krochta, 2002).
continuous industrial film making procedure (Larotonda, 2007).
In this method, knifes spread a precise layer of solution onto a 3.2. Emulsifiers
surface moving under the knife. Micrometer adjustments are pro-
vided to adjust height of the knife above the surface to increase/ Emulsifiers are surface-active compounds with both polar and
decrease the film thickness. This process is known as knife-over- non-polar molecular structures, which absorb at the water-lipid or
roll coating (Rossman, 2009). watereair interface reducing surface tension (Krochta, 2002; Lin &
This method allows an effective control of the thickness and Zhao, 2007). Polysaccharides are polymeric and hydrophilic in na-
application speed over a suitable support that can be chosen for ture, thus they possess excellent oxygen, aroma, and lipid barriers
each biopolymer solution used. The important advantage of films at low relative humidity. However, they are poor moisture barriers
produced by knife coating results from their improved uniformity compared to synthetic films such as low-density polyethylene.
due to a strict thickness control, leading to a better property On the other hand, lipids are hydrophobic with better moisture-
reproducibility, mainly in the tensile tests. Another advantage of barrier properties than those of polysaccharides. However, their
the films produced by knife coating is that this method uses a de- non-polymeric nature limits their cohesive film-forming capacity.
vice simple to operate with little maintenance required. Also, there As a result polysaccharide-lipid composite films have been devel-
is an important reduction of drying time from 24 to 48 h, for casting oped, in which the polysaccharide provides the film integrity and
method, to just 2 h. Thus, knife coating is a good method to produce entraps the lipid component, and the lipid component imparts the
films in a large scale. moisture-barrier property (Krochta, 1997). Without the presence of
an effective emulsifier the lipid often separates from the poly-
3. Methods for improving the properties of pectin edible saccharide film.
films Composite film can be categorized as bilayer or stable emulsion.
For bilayer composite films, lipid generally forms an additional
Numerous studies have been carried out to improve the prop- layer over the polysaccharide layer, while the lipid in the emulsion
erties of pectin edible films by incorporating functional ingredients, composite films is dispersed and entrapped in the polysaccharide
such as plasticizers (for improving mechanical properties) or matrix. Emulsified films improve moisture barrier properties and
emulsifiers (for increasing stability and better adhesion), into the can be manufactured in a single step in contrast to a layer-by-layer
pectin matrix. process for multilayer films (Hambleton, Fabra, Debeaufort, Dury-
Brun, & Voilley, 2009). Polysaccharides stabilize emulsions by
3.1. Plasticizers strongly attaching to the surface of the lipid and significantly pro-
truding into the continuous phase to form a polymeric layer or a
Plasticizers, such as glycerol, acetylated monoglycerides, poly- network of appreciable thickness (Callegarin, Quezada Gallo,
ethylene glycol, and sucrose are often used to modify the me- Debeaufort, & Voilley, 1997).
chanical properties of the film. Incorporation of these additives To produce polysaccharide-lipid composite films from aqueous
may cause significant changes in the barrier properties of films. solution, it is often necessary to add an emulsifier to allow
A plasticizer, in most cases, is required for making edible films, dispersion of the hydrophobic lipid material in the solution to
especially for polysaccharide- and protein-based films since the improve emulsion stability and increase the particle distribution in
structure of these is often brittle and stiff due to extensive in- emulsion composite edible films (Debeaufort & Voilley, 1995). Se-
teractions between polymer molecules (Gennadios, 2004; Krochta, lection of emulsifiers for formulation of composite films can be
2002). Plasticizers are added to polymers to reduce brittleness. facilitated using the hydrophilic-lipophilic balance and phase

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
6 P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10

inversion temperature criteria (Hernandez, 1994; McClements, amorphous tie points due to the interaction of Ca2þ with acidic
2005). groups, which forms a complex with sodium alginate and pectin.
The barrier and mechanical properties of the composite films This complex, known as “Egg Box” model results in non-crystalline
are affected by the composition and distribution of the hydrophobic physical crosslinks in the molecular network.
substances in the film matrix (Debeaufort, Martin-Polo, & Voilley, In addition to the analysis of structural changes on pectin edible
1993; Kamper & Fennema, 1985). In general, bilayer films are more films, the study of their performance is important as well. The study
effective water vapor barrier than emulsion films due to the exis- of packaging performance, such as mechanical and barrier prop-
tence of a continuous hydrophobic phase in the matrix, and their erties, and how it is related to the primary functions of food
moisture-barrier property can be improved by increasing the de- packaging, including physical integrity have become increasingly
gree of lipid saturation and chain length of fatty acids (Hagenmaier relevant and more frequently studied.
& Shaw, 1990; Kamper & Fennema, 1984a, 1984b). For emulsion Chambi and Grosso (2011) proposed to mimic biological struc-
composite films, the type of lipid, location, volume fraction, poly- tures such as the cell wall of plant tissues as an alternative to obtain
morphic phase, and drying conditions significantly impact biodegradable films with improved mechanical resistance. Biode-
moisture-barrier property (Gontard, Duchez, Cuq, & Guilbert, 1994). gradable films were elaborated using methylcellulose, gluco-
mannan, pectin, and gelatin mixture. The mechanical properties of
4. Physical-mechanical characterization of pectin edible films developed films were determined according to the ASTM D882 and
they observed that the film with the best mechanical performance
Characterization of active packaging involves two processes, (72.63 MPa tensile strength and 9.85% elongation) was obtained
which are the structural analysis of the packaging materials and from methylcellulose-glucomannan-pectin at 1:4:1 ratio.
measurement of their properties. Structural analysis is carried out The effect of cellulose nanofibers (CNF) on mechanical resistance
using a variety of microscopic and spectroscopic techniques, while of edible films based on pectin and mango puree have been studied
property characterization is more diverse and depends on the in- (Azeredo et al., 2009). This study indicated that CNF were effective in
dividual application (Espitia et al., 2012). increasing tensile strength, and its effect on Young’s modulus was
Some of the techniques used in the structural analysis of pectin even more noticeable at increasing CNF concentrations, suggesting
edible films are scanning electron microscopy (SEM), confocal laser the formation of a fibrillar network within the matrix.
scanning microscopy (CLSM), wide-angle X-ray diffraction (WAXD) In addition, the effect of antimicrobial incorporation on me-
and small- angle X-ray scattering (SAXS). chanical properties of edible films, based on pectin and fruit puree,
Microscopic techniques have been widely used to evaluate has been also studied. Du et al. (2009a) studied the effects of allspice,
morphological changes in the surface of pectin edible films. cinnamon, and clove bud essential oils on physical properties of
Bierhalz, Da Silva, and Kieckbusch (2012) used SEM to study the edible films based on apple puree and pectin. They observed that the
effect of nantamycin in composites of alginate/pectin films for food incorporation of essential oils caused a significant reduction
packaging applications. These authors observed that control films (p < 0.05) in tensile strength and elastic modulus of the developed
presented a homogeneous structure. On the other hand, nanta- edible films, and this effect was more pronounced in films con-
mycin incorporation caused dramatic changes on film surface, with taining clove bud oil, which displayed lower tensile strength and
the presence of nantamycin crystals. This may be due to the low elastic modulus values than films with allspice and cinnamon
solubility of natamycin in the film-forming solution, leading to the essential oils. Moreover, mechanical resistance of edible films made
formation of a second phase during film drying. from apple puree and high methoxyl pectin incorporated with apple
SEM technique has also been used by Giancone et al. (2011), who skin polyphenols was studied (Du, Olsen, Avena-Bustillos, Friedman,
studied the effect of surface density on the surface of high methoxyl & McHugh, 2011). According to the authors, the tensile strength and
pectin edible films. They observed that pectin films presented percent elongation of developed films did not significantly change
heterogeneous structure as a result of pectin clusters; however, when apple skin polyphenol concentration increased from 0% to 3%.
differences in surface density have no effect on film microstructure. However, incorporation of apple skin polyphenols caused a signifi-
Moreover, Jin, Liu, Zhang, and Hicks (2009) used the CLSM tech- cant increase (p < 0.05) in tensile strength, elastic modulus, and
nique to study the surface of pectin and polylactic acid (PLA) elongation of the resulting apple films when the concentration of
composite films incorporated with nisin. This technique allows apple skin polyphenols increased from 4.5% to 6%.
obtaining high-resolution optical images with depth selectivity. Other emerging characterization technique, such as thermog-
The key feature of this technique is the ability to acquire three- ravimetry, has been used. Thermogravimetry allows knowing the
dimensional reconstructions of topologically complex objects. Ac- thermal resistance of packaging materials, due to the determination
cording to Jin, Liu, Zhang, et al. (2009) CLSM revealed a relatively of weight variation of studied material (loss or gain) as a function of
rough morphology of pectin/PLA films. The film rough morphology temperature and/or time, while the sample is subjected to a
was related to nisin activity in composite films, since the access and controlled temperature increase. Thermogravimetric analysis (TGA)
sorption of nisin was facilitated by the rough and hydrophilic na- enables to know the temperature range at which the packaging
ture caused by pectin. This indicated that pectin in developed material starts to decompose. In this way, Giancone et al. (2011)
composite films played an important role in embedding nisin studied the thermal stability of high methoxyl pectin edible films
during the diffusion coating process. with different surface densities by means of TGA. TGA curves of
Moreover, X-ray diffraction (XRD) techniques, such as WAXD developed films presented twoestep behavior: the first step, be-
and SAXS, use the scattered intensity of an X-ray beam on the tween 30  C and 150  C, due to water loss; the second step was above
sample, revealing information about the crystallographic structure, 250  C, caused by thermal degradation of samples. Regarding to the
chemical composition and physical properties of the material difference in surface density, no effect was observed (p > 0.05),
studied (Koo, 2006). Gohil (2011) studied the crystallographic indicating no difference in the structure of evaluated samples.
structure of low methoxyl pectin and sodium alginate films treated
with CaCl2 using WAXD and SAXS. The authors observed that so- 5. Pectin films as antimicrobial food packaging
dium alginate is amorphous while pectin has low crystallinity; thus
crystalline character of blended films increases with pectin content. In general, one of the most important aspects of edible films is
Furthermore, treatment with CaCl2 results in the formation of their ability to carry and release a variety of active compounds,

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10 7

including antioxidants, flavorings, antibrowning and antimicrobial activity against Escherichia coli, with oregano edible film being the
compounds, among others (Falguera et al., 2011). Most active most effective against tested microorganism. Moreover, the anti-
compounds incorporated in pectin edible films are antimicrobials. microbial activity was the highest for edible films with oregano,
Pectin edible films have been incorporated with several antimi- intermediary for the films with lemongrass oil and the lowest for
crobial substances in order to obtain antimicrobial active packaging the films with cinnamon oil. Similarly, Du et al. (2009b) tested the
that contributes to extend product shelf life and reduce the risk of antimicrobial activity of three different essential oils incorporated
pathogen growth on food surfaces. Antimicrobial active packaging in edible films. They incorporated allspice, garlic or oregano
is a type of packaging that alters conditions surrounding the food to essential oils in edible films based on pectin and tomato puree and
maintain product quality by the controlled diffusion of one or more tested their antimicrobial activity against E. coli, Salmonella enterica
antimicrobial agents from the packaging material to the product and L. monocytogenes. The results indicated that developed edible
(Cagri et al., 2004). The main advantage of antimicrobial edible films presented antimicrobial activity against tested pathogens.
films is that they target post-processing foodborne pathogens or Likewise, edible film incorporated with oregano essential oil pre-
spoilage microorganisms on food surfaces by the diffusion of the sented higher antimicrobial activity when compared to edible film
antimicrobial into the food product without increasing excessively with allspice, which was followed by the film incorporated with
the global concentration of the additive in the food (Campos et al., garlic essential oil.
2011). In addition, pure main components of essential oils, such as
Antimicrobial compounds incorporated into pectin edible films carvacrol which is the major constituent of oregano and thyme
are from natural sources. Selected antimicrobials are generally essential oils, or cinnamaldehyde, the major constituent of cinna-
recognized as safe (GRAS) compounds which satisfy consumer mon essential oil, have been used as antimicrobials in active
demands for healthy foods and free of chemical additives. Anti- packaging made from pectin films. Edible films based on pectin and
microbials with these characteristics include bacteriocins, essential tomato puree incorporated with carvacrol presented antimicrobial
oils and polyphenols. activity against E. coli O157:H7. Also, the content of carvacrol was
Bacteriocins are an interesting alternative to the use of tradi- stable at 5 and 25  C over a period of 98 days while incorporated in
tional chemical preservatives for the control of foodborne patho- the edible films (Du et al., 2008b).
gens or spoilage bacteria. Bacteriocins are antimicrobial peptides, In addition, the antimicrobial activity of developed pectin edible
ribosomally synthesized by bacteria and have the ability to kill films incorporated with essential oils and their main constituents
closely related bacteria. However, the bacterium that secretes the have been tested in simulation of real packaging conditions by their
peptide is immune to the produced bacteriocin (Cleveland, application on food matrixes. Cinnamaldehyde or carvacrol was
Montville, Nes, & Chikindas, 2001). Nisin is the most studied incorporated in edible films based on pectin and apple puree at
bacteriocin, currently considered as the only bacteriocin licensed as 0.5%, 1.5%, and 3% (w/w) and their antimicrobial activity was tested
GRAS food additive and is commercially used as natural preserva- on chicken breasts and ham stored at either 23 or 4  C for 72 h
tive (Acuña, Morero, & Bellomio, 2011). Nisin is also widely (Ravishankar, Zhu, Olsen, McHugh, & Friedman, 2009). Results
accepted as a food preservative in the European Community where showed that edible films containing carvacrol exhibited stronger
it is classified as a safe preservative for food contact, coded as E 234 activity against S. enterica and E. coli on chicken breast surface at
(FSA, 2010), as well as in Brazil where the use of nisin is permitted 4  C than those edible films with cinnamaldehyde. Similarly, edible
by Brazilian law as a natural preservative for biological products films with carvacrol showed higher reductions of E. coli O157:H7
(ANVISA, 1996). compared to cinnamaldehyde at 23  C, while the reduction of
The antimicrobial activity of pectin edible films incorporated Salmonella enteritidis was similar for both carvacrol and cinna-
with nisin and its combination with treatment of ionizing radi- maldehyde at the same temperature. Moreover, films with carva-
ation was used to control Listeria monocytogenes on a ready-to- crol exhibited stronger activity against L. monocytogenes on ham
eat (RTE) turkey meat (Jin, Liu, Sommers, Boyd, & Zhang, 2009). than cinnamaldehyde.
Results showed that treatment of pectin films with nisin and In addition, carvacrol or cinnamaldehyde incorporated in apple-
without irradiation reduced L. monocytogenes by 1.76 log CFU/ pectin edible films has shown antimicrobial activity against
cm2. Moreover, the combination of irradiation with pectin film Campylobacter jejuni, one of the leading causes of bacterial diar-
containing nisin resulted in a 3.95 log CFU/cm2 reduction at rheal illness worldwide, on chicken breast (Mild et al., 2011). Ac-
1 kGy and a 5.35 log CFU/cm2 reduction at 2 kGy; indicating a cording to the authors, incorporation of both carvacrol and
synergistic effect on Listeria viability on the surface of RTE turkey cinnamaldehyde in edible films showed bactericidal activity against
meat. C. jejuni when tested on chicken, with the cinnamaldehyde edible
Moreover, pectin-PLA composite films incorporated with nisin film being most effective against this foodborne pathogen. Mild
were tested against L. monocytogenes (Jin, Liu, Zhang, et al., 2009). et al. (2011) indicated that differences in antimicrobial activity
Developed composite films were tested in three different media, between cinnamaldehyde and carvacrol may be due to the fact that
brain heart infusion (BHI) broth, orange juice and liquid egg white. both antimicrobials operate by different mechanisms. Carvacrol is
Results showed that L. monocytogenes was reduced by 2.1, 4.5 and reported to disrupt bacterial cell membranes by non-covalent in-
3.7 log CFU/mL in BHI broth, liquid egg white and orange juice, teractions, whereas cinnamaldehyde reacts chemically with the
respectively by composite films containing nisin. membrane surfaces resulting in cell death.
Furthermore, pectin edible films have been used as carriers of Moreover, edible films based on pectin and apple, carrot or hi-
plant essential oils. Essential oils are natural flavoring substances biscus were incorporated with carvacrol or cinnamaldehyde and
with GRAS status (López, Sánchez, Batlle, & Nerín, 2007). Their their antimicrobial activity was tested against L. monocytogenes on
biological effects, including antibacterial and antifungal activity, as contaminated ham and bologna (Ravishankar et al., 2012). Results
well as pharmaceutical and therapeutic potentials, have been well showed that films with carvacrol exhibited better antimicrobial
documented (Bakkali, Averbeck, Averbeck, & Idaomar, 2008; Burt, activity against L. monocytogenes than films with cinnamaldehyde,
2004; Edris, 2007). with developed films being more effective on ham than on bologna.
Edible films based on pectin and apple puree were incorporated Moreover, the use of apple-pectin edible film resulted in a higher
with oregano, cinnamon or lemongrass essential oils (Rojas-Graü inactivation of this pathogen when compared to carrot or hibiscus-
et al., 2006). Developed edible films presented antimicrobial pectin films.

Please cite this article in press as: Espitia, P. J. P., et al., Edible films from pectin: Physical-mechanical and antimicrobial properties - A review,
Food Hydrocolloids (2013), http://dx.doi.org/10.1016/j.foodhyd.2013.06.005
8 P.J.P. Espitia et al. / Food Hydrocolloids xxx (2013) 1e10

In addition to antimicrobial activity test, the effect of pectin consumer awareness of health benefits associated with consump-
edible films incorporated with volatile compounds has been tested tion of fruits and vegetables has led to the study of fruit and
on the sensory properties of packaged food. The effect of cinna- vegetable purees as part of the edible film-forming materials.
maldehyde or carvacrol incorporated in apple or tomato-pectin Previous works reported the use of fruit puree, such as apple and
based edible films on baked chicken was assessed by sensory mango together with pectin in edible films. Recently, Schreckinger,
analysis of paired preference test (Du et al., 2012). Results indicated Lotton, Lila, and Mejia (2010) indicated that tropical fruits such as
that adding 0.5% (w/w) carvacrol in tomato-pectin edible film berries from South America, including açaí (Euterpe oleracea),
formulation did not affect the preference of chicken. However, chilean wineberry (Aristotelia chilensis), wild crepemyrtle or acerola
increased concentration of carvacrol (0.75% w/w) in tomato-pectin (Malpighia emarginata), strawberry myrtle (Ugni molinae), among
films reduced drastically their preference choice. Moreover, the others, possess a rich and diversified composition of bioactive
addition of 0.5% (w/w) and 0.75% (w/w) carvacrol into apple-pectin compounds with health-promoting properties. Thus, in the next
edible film reduced the preference of baked chicken when few years this research could expand to use these tropical fruits as
compared to the control. Furthermore, baked chicken packaged part of film-forming ingredients in order to combine their biolog-
with apple-pectin films containing 0.5% cinnamaldehyde was ical activities as well as the color and flavor provided by their
equally preferred over chicken in control apple-pectin films. pigments and volatile compounds with the mechanical and barrier
Increasing concentration of cinnamaldehyde (0.75e1% w/w) in properties from the film-forming components.
edible films resulted in low preference for the baked chicken. When Moreover, researches related to the application of nanotech-
comparing the effect of both antimicrobial in sensory preference of nology to pectin edible film are scarce. Azeredo et al. (2009)
baked chicken, results showed that chicken packaged with apple- reported the use of cellulose nanofibers as potential nano-
pectin films with 0.75% (w/w) cinnamaldehyde was less preferred reinforcements in edible films based on pectin and mango puree.
than using the same film at same concentration of carvacrol. In This limitation is probably due to the current gap for completely
contrast, baked chicken wrapped with tomato films containing understanding the toxicological effects of nanoparticles in hu-
0.75% (w/w) carvacrol was more preferred (Du et al., 2012). man system after ingestion, which allows for determining the
overall impact on consumers. However, when more toxicological
6. Legislation studies are published in the coming years, the application of
nanotechnology may lead research toward the incorporation of
Edible films, including all of its components must be safe to eat nanoscale materials in pectin edible films and study their po-
or must have the GRAS status (Rossman, 2009). Moreover, edible tential synergistic effects on films antimicrobial activity as well
films when incorporated with antimicrobials are considered as as their contribution to the improvement of physical-mechanical
active food packaging. Active food contact materials means mate- properties of edible film.
rials that are intended to extend the shelf-life, maintain or improve
the condition of packaged food. They are designed to act as carriers 8. Conclusions
for control and release of active compounds from the packaging
material to the food (Arvanitoyannis, Choreftaki, & Tserkezou, Consumer demand for minimally processed foods and products
2005). free of additive has led to the development of new packaging ma-
Edible films can be classified as food products, food ingredients, terials. Pectin edible films are an environmental friendly alternative
food additives, food contact substances or food packaging mate- to petroleum-based polymers due to its low cost, availability,
rials, thus their elaboration should follow all required regulations biodegradability, and its feasibility to produce films alone or in
pertinent to food ingredients, since they are an integral part of the combination with other polymeric matrixes. When incorporated
edible portion of food products (Martín-Belloso, Rojas-Graü, & with natural bioactive compounds, pectin edible films showed
Soliva-Fortuny, 2009). Moreover, besides the GRAS status of all antimicrobial properties against foodborne pathogens. However,
ingredients used, production of pectin edible films should be done more studies need to be done in order to optimize concentration of
in food processing facilities following with good manufacturing antimicrobials to obtain materials with appropriate antimicrobial
practice (GMP). activity and desired physical-mechanical performance.
In addition, the development of edible films based on pectin and
other biodegradable polymers is encourage by “green-packaging”
Source(s) of support
initiatives such as the US EPA (US Environmental Protection
Agency) suggested plan to reduce the initial amount of packaging.
Doctoral scholarship from Coordenação de Aperfeiçoamento de
The suggestion consisted on designing packaging systems that
Pessoal de Nível Superior (CAPES).
could reduce the amount of environmental toxic materials used in
packaging and make them easier to reuse or compost. The Agency
also suggested using packaging that could reduce the amount of Acknowledgments
damage or spoilage to food products which eventually could
improve the quality and extend the shelf life of packaged foods Financial support for this research was provided by a doctoral
(Falguera et al., 2011). scholarship from Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior (CAPES) through PEC-PG agreement.
7. Future trends
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