Review

Natural Polymers Used in Edible Food Packaging—History,

Function and Application Trends as a Sustainable Alternative to
Synthetic Plastic
Barbara E. Teixeira-Costa 1,2, * and Cristina T. Andrade 1

1 Programa de Pós-Graduação em Ciência de Alimentos, Instituto de Química, Universidade Federal do Rio de

Janeiro, Avenida Moniz Aragão 360, Bloco 8G/CT2, Rio de Janeiro 21941-594, Rio de Janeiro, Brazil;
[email protected]
2 Faculdade de Ciências Agrárias, Universidade Federal do Amazonas, Avenida General Rodrigo Otávio 6200,
Manaus 69077-000, Amazonas, Brazil
* Correspondence: [email protected]

Abstract: In this review, a historical perspective, functional and application trends of natural polymers
used to the development of edible food packaging were presented and discussed. Polysaccharides
and proteins, i.e., alginate; carrageenan; chitosan; starch; pea protein, were considered. These natural
polymers are important materials obtained from renewable plant, algae and animal sources, as
well as from agroindustrial residues. Historically, some of them have been widely used by ancient
populations for food packaging until these were replaced by petroleum-based plastic materials after
World War II. Nowadays, biobased materials for food packaging have attracted attention. Their use
was boosted especially because of the environmental pollution caused by inappropriate disposal of



plastic packaging. Biobased materials are welcome to the design of food packaging because they


possess many advantages, such as biodegradability, biocompatibility and low toxicity. Depending
Citation: Teixeira-Costa, B.E.;
on the formulation, certain biopolymer-based packaging may present good barrier properties, an-
Andrade, C.T. Natural Polymers
timicrobial and antioxidant activities Thus, polysaccharides and proteins can be combined to form
Used in Edible Food
Packaging—History, Function and
diverse composite films with improved mechanical and biological behaviors, making them suitable
Application Trends as a Sustainable for packaging of different food products.
Alternative to Synthetic Plastic.
Polysaccharides 2022, 3, 32–58. Keywords: food packaging; biobased materials; biodegradable packaging; edible films; composite
https://doi.org/10.3390/ films; alginate; carrageenan; chitosan; starch; pea protein
polysaccharides3010002

Academic Editor: Rajkumar Patel

Received: 2 December 2021 1. Introduction

Accepted: 24 December 2021
Plants, algae and marine seafoods are important resources to obtain natural poly-
Published: 29 December 2021
mers that can be used for designing sustainable packaging. Historically, different natural
Publisher’s Note: MDPI stays neutral materials, e.g., plant and animal parts, shells, ceramics, and others, were the firstly used
with regard to jurisdictional claims in materials by the ancient populations for food packaging [1]. The Industrial Revolution
published maps and institutional affil- and the World War II were significant events that boosted the discovery, design of new
iations. packaging materials and novel processing strategies. Aluminum cans by canning operation
and the coming up of petroleum-based plastics are some typical examples [2,3]. Afterwards,
conventional plastics were extensively used for packaging. As their majority has a single
use only, usually ends up polluting landsites and aquatic environments. It was estimated
Copyright: © 2021 by the authors.
that, only in 2015, around five billion tons of plastic waste ended up in natural sites [4].
Licensee MDPI, Basel, Switzerland.
Because of this problem, reducing petroleum-based pollution should be top priority of all
This article is an open access article
nations around the world. More than 170 United Nations Member States have committed
distributed under the terms and
to reduce the use of plastics until 2030 [4]. In this way, replacing conventional plastics for
conditions of the Creative Commons
Attribution (CC BY) license (https://
biobased materials is a sustainable approach that contributes to reducing plastic pollu-
creativecommons.org/licenses/by/
tion. Consequently, the synthesis and use of biobased materials for packaging design has
4.0/). increased over the past few years.

Polysaccharides 2022, 3, 32–58. https://doi.org/10.3390/polysaccharides3010002 https://www.mdpi.com/journal/polysaccharides

Polysaccharides 2022, 3 33

Besides being environmentally friendly and emitting low greenhouse gases, natural
materials can be obtained from different renewable sources, such as plants, animals, mi-
croorganisms and their residues, making them extensively available [5]. This is also an
advantage when compared to conventional plastic polymers, since the latter are petroleum-
based, a nonrenewable resource. Natural polymeric materials, such as plant- or marine-
based polysaccharides and proteins, are naturally biodegradable, which means that they
can be degraded by local microorganisms and return to nature [6]. Natural polymers have
important technological and biological properties, which allow their utilization for food
packaging. Generally, these materials display good film-forming and gelling properties,
which leads to consider them distinguishable and sustainable choices to prepare edible
films and coatings. When applied to this end, biopolymeric films may exhibit some process-
ing challenges. They present brittleness, low water and gases barrier properties, inferior
mechanical behavior, characteristic of their nature [7]. The incorporation of hydrophobic
substances or blending two or more biopolymers to form composites consist of alternative
approaches to overcome these technological issues [8].
In this context, this review aims to summarize a historical perspective, technological
trends and physicochemical properties of five natural materials, as alginates, carrageenan,
chitosan, starch and pea protein, used to the design of edible films and coatings. Two
platforms, Web of Science® and Google Scholar® , were used to search published articles
within the last 10 years, although some older references may appear, mainly linked to the
historical point of view of food packaging and these natural polymers.

2. Historical Perspective of Food Packaging

It has been exceedingly difficult to study the firstly used materials for packaging
food supplies, since so little of them have survived along the centuries. These primitive
packaging used by the ancient populations thousands of centuries ago were made from
natural materials, such as wooden parts, bamboo, shells, animal skin, leaves, grasses, jute,
glass, and ceramic [1,9–11]. Some evidence of primitive pottery and glass used as packaging
is dated around 7000 B.C. [9,10].
When visiting museums, is common to find ancient ceramic jars named amphoras,
and potteries made from glass, which were frequently used in Mediterranean region as
packaging for different goods. Some of these, dating about 1500 B.C. to 500 A.D., were used
to transport and commercial trade of wine, oil, grains and other foods by Egyptians, Greek
and Roman civilizations [10,11]. On the other side of the Atlantic Ocean, Latin-American
indigenous populations also had used ceramic materials to prepare and dish their foods
during ritual events, dating around 1000 B.C. [12].
Limestone, sand, soda, and silica were the basic materials molded and used to make
glass potteries, cups and bowls in the 1200 B.C. [10,13]. These ingredients have not changed
in the glass-making process since their discovery. However, molding evolved with the
invention of the blowpipe by Phoenicians in 300 B.C., who improved the glass production
to make round vessels [13]. It was only in the 17–18th century that the split molding process
was developed, allowing the fabrication of irregular shapes and different decorations on
glass packaging [13]. From this period until the early 1900s, glass vessels with a wide range
of shapes and sizes gained the consumers attention and dominated the packaging market
up to the 1960s [13]. Even with the discovery and use of metals for different purposes
during the Iron Age, 500–332 B.C., their use as a packaging material was not common until
the development of stronger alloys and thinner coatings by the process of tin plating in
1200 A.D. [13].
The major packaging evolution occurred during the Industrial Revolution in the
18–19th centuries. During this period, an event stamps the beginning of the Modern
Packaging Era, the discovery of canning operation by Nicholas Appert, who used this
method to preserve food supplied to the French Army of Napoleon Bonaparte [2,3,10]. The
Appert’s method allowed that food products were heated during processing, consequently
improving their shelf-life and preserving it against microbial contamination [10]. This
Polysaccharides 2022, 3 34

technology was quickly employed in many places, especially in the USA, where it was
used in a continuous production in the early 1900s [3].
The development of aluminium cans, which years later was to be used for beer and
other drinking food, resulted from the tinplate shortage during World War II (WWII) [3].
Several of these technologies were especially designed to sustain a safe food supply to
the armies during WWII and are used until today. In the 19th century, different materials,
such as paper and paperboard, were continuously improved, folded into smaller packages,
cartons, and corrugated boxes and used for food packaging [10]. Additionally, the first
plastics derived from cellulose and petroleum were discovered in the 1800s [2,9]. The
petroleum-based plastics were firstly employed to protect munition during WWII and then
became packages used for cereals and biscuits [2]. The development of various polymers
in the early 1900s, such as polypropylene, polyester, and ethylene vinyl alcohol, pushed the
plastic packaging industry increasingly forward letting the metal, glass, and paperboard
industries [2,10].
The use of edible materials as food coating has also few historical reports. Back in the
ancient age, edible packaging was used in the production of sausages, preserving meat by
stuffing it in animal intestines, a process developed by Sumerians in Mesopotamia around
3000 B.C., and by Chinese settlers in China around 580 B.C. [14]. A particular type of edible
thin film made from the skin of boiled soy milk was used in Japan during the 15th century
to cover different foods [15]. In China and Europe, during the 16th century animal grease
(lard) and wax were used to coat fruits and other food products for their conservation and
later consumption [9,15]. And later, back on the 19th century, a coating made from gelatin
was patented by USA and used in meat products [15]. As synthetic plastics dominated the
packaging market after WWII, the use of edible resources for packaging were left behind
until recently.
After WWII, the synthesis of different plastic materials and their development for food
packaging were significantly enhanced. The plastic industry has profoundly expanded in
the 21st century. With a quick look at some aspects of our daily life is possible to identify
many different types of plastics surrounding us. In the food industry, this expansion was
also noticeable, mainly because the use of these materials has improved food preservation
and extended the storage period of a lot of products. Many advantages have contributed
to the extensive use of plastics in food packaging, such as low cost, good resistance to
solvents and processability, flexibility, lightweight, easiness to be molded in different sizes
and shapes, and others [1]. In the 1960s, more than 25% of bread sold were packaged in
low-density polyethylene bags [10]. It was estimated that in the period of 1950 to 2015 the
cumulative production of plastics reached more than 7.5 billion metric tons and, only in
2018, the global production of these materials has risen to 360 million tons [5,16]. Around
40% of the petrochemical-based plastics are used for packaging purposes and closely to
60% of plastic packaging are used to pack food and beverages [17].
Giant food industries and packaging companies have announced commitments to
the reduction of plastics waste and to practice a circular economy for them. For example,
Unilever® , the owner of the food brands Ben & Jerry’s® and Lipton® , has declared in
October 2019 an ambitious commitment with the reduction of the use of plastic packaging
in more than 100,000 tons and use at least 25% of recycled plastic packaging until 2025 [18].
In Brazil, the actions of the group are supported by a long-running partnership with the
retailer Grupo Pão de Açúcar® , which helps in the waste collection through drop-off sta-
tions [18]. Dasani® , a brand of bottled water commercialized by The Coca-Cola Company®
in USA, has announced the first fully recyclable polyethylene terephthalate (PET) bottle
50% plant-based, HydridBottleTM [19]. The Coca-Cola Company® has announced to make
100% of its packaging recyclable by 2025 and use at least 50% recyclable materials in their
packaging by 2030 [20]. Other food companies, such as Keurig Dr Pepper® , PepsiCo® and
Mondelez® , also have agreed to reduce the use of virgin plastic for its rigid plastic pack-
aging [21]. According to the non-profit organization As You Sow [21], Keurig Dr Pepper®
Polysaccharides 2022, 3, FOR PEER REVIEW 4

Polysaccharides 2022, 3 35
plastic packaging [21]. According to the non-profit organization As You Sow [21], Keurig
Dr Pepper® used 208,000 metric tons of plastic packaging in 2018, and the company has
planned to cut by
used 208,000 20% the
metric tonsuse of virgin
of plastic plastics by
packaging 2025.and the company has planned to cut
in 2018,
byInnovative
20% the use packaging
of virgin designed
plastics byfor food products with differentiated characteristics,
2025.
such as Innovative
high moisture content,designed
packaging high pressure andproducts
for food modifiedwithatmosphere, natural
differentiated and fresh
characteristics,
foods,
suchamong
as highothers,
moistureandcontent,
with anhigh environmentally
pressure and friendly
modifiedapproach
atmosphere,are anatural
challenge andfor
fresh
thefoods,
researchamong
and others, and with
development an environmentally
in the packaging industry friendly approach are
[22]. Moreover, a challenge
these biobasedfor
the research
materials shouldandbedevelopment
from renewable in the packaging
sources, industry
recyclable and[22].
haveMoreover, these biobased
low greenhouse gas
materials
emissions should
in the be from
ecosystem renewable sources, recyclable and have low greenhouse gas
[5].
emissions
Biobasedinpackaging
the ecosystem [5]. wholly or partly materials from biological origin
contains
[23,24]. Biobased
Materialspackaging contains
from biological wholly
sources or partly
(e.g., plants,materials
animal, from biological origin
microorganisms, [23,24].
seafood,
Materials
woods, from biological
and agricultural sources
residues) (e.g.,
are plants,biodegradable
naturally animal, microorganisms, seafood,These
and compostable. woods,
and agricultural
materials when used residues) are naturally
for packaging can bebiodegradable
degraded by and the compostable.
action of livingThese materials
organisms
upon disposal and converted to CO2, CH4, H2O, inorganic compounds, or biomass, return-dis-
when used for packaging can be degraded by the action of living organisms upon
ingposal and converted
to nature [25–27]. Onceto CO 2 , CH
made 4, H
by 2 O, inorganic
biological compounds,
resources, such as or biomass,
proteins, returning to
polysaccha-
nature
rides and [25–27].
microbialOnce made bypackaging
polyesters, biological materials
resources,cansuch beasnamed
proteins, polysaccharides
as biobased plastics.and
microbial
Biobased polyesters,
materials packagingfrom
are obtained materials can becarbon
renewable namedresources,
as biobased as plastics.
plants orBiobased
biomass,ma-
terials
such are obtained
as chitosan, from
starch, renewable
cellulose, carbon resources,
hemicellulose, as plants
poly(lactic) acidororbiomass,
vegetablesuch
oilsas[28,29].
chitosan,
starch, cellulose, hemicellulose, poly(lactic) acid or vegetable oils
Besides renewable resources, biodegradable materials can be produced from petroleum- [28,29]. Besides renewable
resources,
based productsbiodegradable materials
[6,28]. Different can be produced
biodegradable materialsfromandpetroleum-based
their sources are products
displayed[6,28].
Different
in Figure 1. biodegradable materials and their sources are displayed in Figure 1.

Figure 1. Classification
Figure of biodegradable
1. Classification materials
of biodegradable used
materials in biobased
used packaging.
in biobased packaging.

Biobased, biodegradable, and composting plastics are terms frequently misunderstood

and cannot be considered synonymous [25,30]. Not all biobased material is biodegradable
Polysaccharides 2022, 3, FOR PEER REVIEW 5

Polysaccharides 2022, 3 Biobased, biodegradable, and composting plastics are terms frequently misunder- 36
stood and cannot be considered synonymous [25,30]. Not all biobased material is biode-
gradable and otherwise, not all biodegradable material is derived from biological sources
[31]. Different institutions
and otherwise, and experts material
not all biodegradable have diverted aboutfrom
is derived a unique definition
biological sourcesfor [31].
the
term biodegradable.
Different institutionsAccording to the
and experts havestandard
diverteddesignation,
about a uniqueD 996–04, from the
definition forAmerican
the term
biodegradable.
Society According
for Testing to the standard
and Materials, designation,
biodegradable can D be996–04,
definedfrom the American
as being capable Society
of de-
for Testing
compose and
into Materials,
carbon biodegradable
dioxide, methane, water, can be definedcompounds,
inorganic as being capable of decompose
or biomass, by pre-
into carbon dioxide,
dominantly microbialmethane,
enzymaticwater, inorganicwhich
mechanism, compounds,
should be or measured
biomass, by bypredominantly
standardized
microbial enzymatic mechanism, which should be measured by standardized
tests, in a specified period of time, reflecting available disposal conditions, compostable tests, is
in
a specified
the capacity period
of being ofbiologically
time, reflecting availableindisposal
decomposed particularlyconditions,
compostingcompostable is the
sites, breaking
itcapacity
down inofcarbon
being dioxide,
biologically decomposed
water, in particularly
inorganic compounds, andcomposting
biomass, at sites,
a ratebreaking
consistentit
down
with in carbon
known dioxide, materials
compostable water, inorganic
[32]. compounds, and biomass, at a rate consistent
withTheknown compostable materials
biodegradability [32]. materials is intrinsically linked to their chemi-
rate of biobased
The biodegradability rate of biobased
cal structure. For example, the biobased polypropylenematerials is intrinsically linked to their
(PP) and polyethylene chemical
(PE) (vinyl
polymers) obtained from the sugar cane processing are nonbiodegradable materials(vinyl
structure. For example, the biobased polypropylene (PP) and polyethylene (PE) and
polymers)
are obtainedtofrom
used similarly the sugar cane
the fossil-based PP processing
and PE [33]. areItnonbiodegradable materials
is critical to underline and are
that biodeg-
used similarly
radability do notto imply
the fossil-based PP process
a short time and PE [33]. It is should
and this critical be
to underline
expected to that biodegrad-
happen on a
ability do
specific not imply
ecosystem at aaparticular
short timetime
process
[25]. and this should be expected to happen on a
specific ecosystem
Nowadays, theatglobal
a particular time [25].
production of bioplastics, considered low, has reached a total
Nowadays, the global production
of 2.11 million tons in 2020 and is expected of bioplastics,
to grow 15% considered
until 2024low,
[33].has reached atototal
According the
of 2.11 million tons in 2020 and is expected to grow 15% until 2024
report published in November 2020 by Intrado Globe Newswire [34], the world bioplastic [33]. According to the
report published
market in November
has generated more than 2020 by Intrado
U$4.5 billion Globe
in 2019Newswire [34], the world
and it is estimated bioplastic
to reach more
market has generated more than U$4.5 billion in 2019 and it is estimated
than U$13 billion until 2027. To them, the starch-based bioplastics market should totalize to reach more
than U$13 billion until 2027. To them, the starch-based bioplastics
U$561 million until 2023, with an annual growth rate (CAGR) of more than 3.5%. The market should totalize
U$561 million until 2023, with an annual growth rate (CAGR) of more than 3.5%. The major
major contribution to the bioplastic market was from the Asia-Pacific region. Europe
contribution to the bioplastic market was from the Asia-Pacific region. Europe should
should have the highest CAGR, more than 16%, until 2027 [34]. The distribution by sector
have the highest CAGR, more than 16%, until 2027 [34]. The distribution by sector of the
of the bioplastics global production market in 2020 [35] is presented in Figure 2. Thus, the
bioplastics global production market in 2020 [35] is presented in Figure 2. Thus, the plastics
plastics and packaging markets are witnessing a significant increase on demand for ma-
and packaging markets are witnessing a significant increase on demand for materials from
terials from renewable resources.
renewable resources.

Figure 2. Distribution by sector of the bioplastics global production market in 2020 (total of 2.11 million tons).
Figure 2. Distribution by sector of the bioplastics global production market in 2020 (total of 2.11
Even
million with this high demand for biobased materials, some challenges must be over-
tons).
come. Some examples may be cited.
• Even with this of
Improvement high demand
national andfor biobased materials,
international some
legislation challenges
to correctly must be
establish over-
the con-
come.cepts
Someand
examples may be cited.
required standards related to bioplastics.
• Revision of industrial facilities for the processability of these materials while maintain-
ing optimized and efficient performance.
• Maintaining the adequate quality of products and ensuring their biodegradability and
compostability.
 • Improvement of national and international legislation to correctly establish the con-
cepts and required standards related to bioplastics.
• Revision of industrial facilities for the processability of these materials while main-
taining optimized and efficient performance.
Polysaccharides 2022, 3 37
• Maintaining the adequate quality of products and ensuring their biodegradability
and compostability.
• Adjustments of the waste management system of each country/region to the collec-
• Adjustments of the
tion of biobased waste since
plastics management
each citysystem
has itsofown
eachprogram.
country/region to the collection
of biobased plastics since each city has its own program.
3. Some Natural and Renewable Macromolecules Used to Prepare Edible Films and
3. Some Natural and Renewable Macromolecules Used to Prepare Edible Films
Coatings
and Coatings
A wide
A wide range
range ofof natural
naturalpolymers
polymersfromfromrenewable
renewable sources
sourceshashas
been
beenused in the
used de-
in the
velopment of biobased food packaging. The main natural sources for this
development of biobased food packaging. The main natural sources for this purpose are purpose are de-
rived from
derived frompolysaccharides,
polysaccharides,proteins,
proteins,lipids,
lipids,or
orblends
blends of of these macromolecules [36,37]
these macromolecules [36,37]
(Figure3).
(Figure 3). The
The utilization
utilization of
of these
these natural
natural materials
materials is
is partly
partly linked
linked to
to its
its biodegradability
biodegradability
and renewability.
and renewability. However,
However, somesome other
other advantages
advantages are are expected
expected when
when usedused for
for food
food
packaging, e.g., as these materials
packaging, e.g., as these materials can can act as carriers of functional substances adding well-
being benefits,
being benefits, incorporating
incorporating flavorings
flavorings and
and colorings
colorings aspects,
aspects, enhancing
enhancing organoleptic
organoleptic
characteristics, improving
characteristics, improving mechanical
mechanical and
and barrier
barrierresistance,
resistance,and andothers
others[8].
[8].

Figure 3. Major
Figure 3. Major natural
natural biological
biological materials
materials used
used in
in food
food biobased
biobased packaging.
packaging.

Polysaccharides
Polysaccharides are are known
known to topossess
possessgood
goodoxygen
oxygen barrier
barrier and and to have
to have sitessites for
for hy-
hydrogen bonding formation, which can be used for incorporation of functional
drogen bonding formation, which can be used for incorporation of functional substances, substances,
e.g.,
e.g., coloring,
coloring,flavoring,
flavoring,andandantioxidants
antioxidants agents. ByBy
agents. contrast, these
contrast, materials
these do not
materials do exhibit
not ex-
good barrier to water vapor, which can be overcome by blending with other
hibit good barrier to water vapor, which can be overcome by blending with other hydro- hydrophobics
macromolecules, such as lipids
phobics macromolecules, [7,8].
such as Polysaccharides
lipids have been
[7,8]. Polysaccharides used
have to develop
been natural-
used to develop
based packaging [7,36].
natural-based packaging [7,36].
Plant-derived
Plant-derived proteins
proteins have
have gained
gained remarkable
remarkable attention
attention of
of food
food manufactures
manufactures and and
consumers
consumers in search for natural food resources and alternative materials to
in search for natural food resources and alternative materials to vegetarian,
vegetarian,
vegan,
vegan,and andfood
foodallergy
allergydiet restrictions.
diet restrictions.Protein-based
Protein-based film packaging
film packagingexhibit extraordinary
exhibit extraordi-
mechanical
nary mechanicaland barrier properties,
and barrier especially
properties, to oxygen
especially and carbon
to oxygen dioxide
and carbon gases, gases,
dioxide when
compared to polysaccharides [7,38]. Besides being eco-friendly materials, these films can
when compared to polysaccharides [7,38]. Besides being eco-friendly materials, these
nutritionally improve food quality and preservation. Moreover, the amphiphilic attribute
films can nutritionally improve food quality and preservation. Moreover, the amphiphilic
of proteins contributes to their utilization as emulsifiers by stabilizing oil/water interface
attribute of proteins contributes to their utilization as emulsifiers by stabilizing oil/water
due to changes in interfacial tension [39]. Nowadays, a great variety of plant proteins have
interface due to changes in interfacial tension [39]. Nowadays, a great variety of plant
been used in food industry and packaging, such as from soybean, wheat, corn, sunflower,
proteins have been used in food industry and packaging, such as from soybean, wheat,
and pea [40].
corn, sunflower, and pea [40].
Edible films can be defined as a thin layer of a material coating or placed between
Edible films can be defined as a thin layer of a material coating or placed between
foods, in which act as a barrier ad that can be consumed without any health risk [8,38]. Both
foods, in which act as a barrier ad that can be consumed without any health risk [8,38].
are a primary food packaging and can be thought similar, although they differ substantially.
Both are a primary food packaging and can be thought similar, although they differ sub-
Mainly, films are solid laminates, separately prepared, dried, processed and then used
stantially.
to cover food Mainly, films
surface, are solid
placed laminates,
between separately
food parts, or used prepared, dried,
as an edible processed
sealed and
bag [7,41].
Differently, coatings are prepared as a solution, directly sprayed or dipped on the food
surface and then dried [42]. Thus, coatings can be considered as a part of the food product,
since they are not made to be removed [8]. Moreover, films can be prepared as a mono, bi
or multilayers. The latter provide a better water barrier to food but are less commonly used
as they need two or more processing steps of casting and drying [7].
 then used to cover food surface, placed between food parts, or used as an edible sea
bag [7,41]. Differently, coatings are prepared as a solution, directly sprayed or dipped
the food surface and then dried [42]. Thus, coatings can be considered as a part of the fo
Polysaccharides 2022, 3 product, since they are not made to be removed [8]. Moreover, films can be prepared 38 a
mono, bi or multilayers. The latter provide a better water barrier to food but are less co
monly used as they need two or more processing steps of casting and drying [7].
Both films and coatings should be composed only by food-grade components, GR
Both films and coatings should be composed only by food-grade components, GRAS
(Generally Recognized as Safe), including any additives, such as plasticizers [42]. As a
(Generally Recognized as Safe), including any additives, such as plasticizers [42]. As
other packaging, these materials must protect the food integrity and maintain its qua
any other packaging, these materials must protect the food integrity and maintain its
[8,41,42].
quality [8,41,42]. In Figure
In Figure 4 is4 presented
is presented the
the mainpurposes
main purposesofofedible
ediblefood
foodpackaging.
packaging. Althou
it is not expected that the edible films could replace completely all conventional pack
Although, it is not expected that the edible films could replace completely all conventional
ing, they can be used to significantly reduce the use of petroleum-based
packaging, they can be used to significantly reduce the use of petroleum-based plastics, plastics, decre
food
decrease food losses,
losses, andand reduce
reduce thethe environment
environment pollution
pollution over
over a long-term.
a long-term.

Figure 4. Main purposes of edible food packaging.

Figure 4. Main purposes of edible food packaging.
Edible films and coatings may have in their composition two main based materials,
Edible films and coatings may have in their composition two main based materi
a biomacromolecule matrix and additives, such as plasticizers, cross-linkers, other rein-
a biomacromolecule
forcements substances and functional matrix and additives,
ingredients such as
[14]. These plasticizers,
materials cross-linkers,
can be used alone other re
forcements substances and functional ingredients [14]. These
or blended. Edible packaging composed by natural-based materials can be classified materials canasbe
a used alo
or blended. Edible packaging composed by natural-based materials
subgroup of biobased and biodegradable packaging [8]. Generally, polysaccharides, pro- can be classified a
subgroup of biobased and biodegradable packaging [8]. Generally, polysaccharides,
teins, lipids, and their mixtures are used for the development of edible films and coatings. p
teins, lipids,
The classification and someand examples
their mixtures are used
of these formaterials
natural the development
commonlyof edible films
used for and coatin
this
The classification
purpose are presented in Table 1. and some examples of these natural materials commonly used for t
purpose are presented in Table 1.
Polysaccharides 2022, 3 39

Table 1. Natural materials used in edible films and coatings.

Biomacromolecules Raw Materials References

Agar [43]
Alginate [44]
Cellulose [45]
Chitosan [46]
Polysaccharides Gums [47]
K-carrageenan [48,49]
Pectin [50]
Pullulan [51]
Starch [52,53]
Casein [54]
Collagen [55]
Corn zein [56]
Gelatin [45]
Proteins Pea protein [57]
Sodium caseinate [50]
Soy protein [58]
Wheat gluten [59]
Whey protein [60]
Candelilla wax [61]
Lipids Bee wax [62]
Vegetable oils [63]
Blends [5,51,54,55,60]
Composites Residues and by-products from agriculture [64–66]
Fruit pulps [67]

Edible coatings can be used to decrease weight loss, color changing, inhibit ethylene
production and delay softening related to the postharvest ripening of fruits [68]. Different
natural polymers, such as chitosan, carrageenan, alginates, gums, starches, their blends,
and a wide range of additives can be used to prepare edible coatings and to be applied on
fruits, as listed in Table 2.

Table 2. Edible coatings applied on fruits.

Matrix Concentration Additives Food Product Reference

Different mixing ratio of
Carboxymethyl 8% galangal essential oil and
5:0, 4:1, 3:2, 2.5:2.5, 2:3 Mangoes [51]
chitosan/pullulan 20% glycerol (w/w)
and 1:4 (w/w)
Chitosan 1% (w/v) 40 mmol L−1 of ascorbic acid Plums (Prunus salicina) [69]
K-carrageenan 0.2–0.8% (w/v) 0–1% glycerol (w/v) Papaya (Carica papaya) [48]
Sodium alginate 0, 1 and 3% (w/v) 20% glycerol (v/v) Plum (Prunus salicina) [70]
Ficus hirta extract, 0.7% citric
Nanfeng mandarin
Sodium alginate 1.5% (w/v) acid and 1.0% sucrose ester [71]
(Citrus reticulata)
(w/v)
Starch/chitosan 2%/0.5–1.0% (w/v) 2% glycerol (w/v) Apples Fuji cultivar [53]
Starch/gelatin 3–5%/10% (1:1) 10% sorbitol Red Crimson grapes [72]
Pears (Pyrus pyrifolia
Xantham gum 2.5 g L−1 1.0 g L−1 cinnamic acid [47]
and P. communis)

Moisture and oxygen absorption as well as lipids, flavor and odor change due to
degradation or migration between packaging, food and the environment are important
factors that impact food quality. These aspects are tightly correlated to the mass transfer
phenomena during shelf-life of food products and cannot be dissociated from packaging
properties [8]. Because of this, films and coatings should be developed accordingly to their
Polysaccharides 2022, 3 40

application purpose, e.g., layers for fruits should have lower water vapor permeability to
reduce weight loss and reduce respiration.
The investigation of the water vapor permeability (WVP) of edible films are a valuable
information to comprehend the mass transfer phenomenon since it implies diffusion and
solubility of water moieties through the polymeric matrix. WVP represents the amount of
water that infiltrates per unit of area of the film and time (kg m−1 s Pa), considering the film
thickness and differential pressure [36]. Usually, polysaccharide-based films and coatings
exhibit higher values of WVP than petroleum-based plastics. Natural polysaccharide-based
films may present WVP value ranging from 6.6 × 10−13 to 1.7 × 10−8 than synthetic poly-
mers, ranging from 1.1 × 10−14 to 0.5 × 10−11 [36,73]. The addition of lipids, plasticizers,
and emulsifiers constitutes a useful method to overcome high values of WVP in edible
films and coatings since this may decrease hydrophilicity.
The processing methods used to obtain films or coatings will be influenced by many
factors, such as matrix composition, solubility, thermal behavior, flexibility, as well as
their compatibility and cohesion forces, e.g., ionic, covalent and H-bonding, between
polymer chains, and presence of additives [8,38,41]. Coatings can be applied on foods
using dipping, spraying, fluidized bed processing, brushing, and panning methods. For the
films production, mainly two types of methods are used, wet and dry processes. In the wet
process, also known as casting, polymers are solubilized and dispersed onto a flat surface,
then dried under specific conditions until film formation. In the dry processing, different
methods, extrusion, injection, blow-molding, and heat-pressing, can be used without the
use of liquid solvents. By these methods, high viscous polymers may be processed [8].
However, the dry method could not be used in the case of thermosensitive substances to be
present in the matrix composition.
A composite edible film packaging commonly will consist of a blend of two or more
hydrocolloids aiming to improve their individual properties and application [74]. Protein
and lipid can be supported on a polysaccharide matrix, or the lipid material may be en-
capsulated on hydrocolloids and dispersed on the polysaccharide film matrix [8]. This
configuration may be used to improve mechanical and thermal properties, and to over-
come some processing limitations. Furthermore, the incorporation of natural or chemical
additives, such as plasticizers, may also contribute to improve mechanical, thermal, func-
tional, sensorial, and nutritional features of edible films [75,76]. The use of plasticizers to
improve those properties of edible films have been well reported in the literature [56,77–79].
Nanofibers prepared by electrospinning have also been incorporated in edible films to
reinforce their mechanical and thermal properties [14]. This nanofillers change the molecu-
lar mobility and relaxation of the matrix, thus leading to significant influence on thermal
behavior of nanocomposite films [14]. The incorporation of essential oils in poly(lactic acid)
films had a relevant effect in the results of their thermogravimetric curves and thermal
stability, due to the formation of hydrogen bonds between poly(lactic acid) and essential
oil, which could be linked to its delayed degradation behavior [29].

3.1. Alginates
Alginates are natural anionic polysaccharides from marine origin. These biopoly-
mers are widely used in the food and pharmaceutical/cosmetic industries because of its
biodegradability, biocompatibility, bioavailability, nontoxicity, and low price [80,81]. Algi-
nates are largely isolated from different brown seaweeds. Laminaria digitata, Macrocystis pyrifera
and Ascophyllum nodosum are the most important sources of alginates [82]. As expected,
the seaweed source has influence on their properties. Although they can be obtained from
microorganisms (e.g., Azotobacter and Pseudomonas genera) processing is not economically
feasible [80,83]. The main advantage to their use may be attributable to their functional
properties. They present crosslinking capacity, good gelling and film-forming properties,
fine water absorption, pH-sensitivity, mucoadhesiveness and others [68,81,83]. Moreover,
alginic acid and its salts are classified by the U.S. Food and Drug Administration (FDA) and
Polysaccharides 2022, 3, FOR PEER REVIEW 10

Polysaccharides 2022, 3 41
fine water absorption, pH-sensitivity, mucoadhesiveness and others [68,81,83]. Moreover,
alginic acid and its salts are classified by the U.S. Food and Drug Administration (FDA)
and European
European Commission
Commission (EC)(EC) as a food
as a food gradegrade
additiveadditive and approved
and approved to beasused
to be used as
gelling,
gelling, emulsifier, and thickener
emulsifier, and thickener agents [75]. agents [75].
Alginates
Alginatescancanbe beextracted
extractedfromfromseaweeds
seaweedswith withaahothotalkali
alkalisolution,
solution,usually
usuallysodium
sodium
carbamate.
carbamate. Afterwards, alginates dissolve as sodium alginate forming a verydense
Afterwards, alginates dissolve as sodium alginate forming a very denseslurry,
slurry,
which
whichmay maycontain
containundissolved
undissolvedalgae algaecellulose
celluloseparts,
parts,and
andneed
needto tobe
bediluted,
diluted,pressed
pressedandand
filtered.
filtered.Finally,
Finally,thethealginate
alginatesample
sampleisisprecipitated
precipitatedfrom fromthe thefiltered
filtered solution,
solution,either
eitherasas
alginic acid or calcium alginate. To improve this process, to obtain a
alginic acid or calcium alginate. To improve this process, to obtain a less colored product less colored product
and
andreduce
reducethetheloss
lossof of
viscosity, an acid
viscosity, an acidpretreatment
pretreatment can becanperformed
be performed [68,82]. The mon-
[68,82]. The
ovalent
monovalent salts from alginic acid are water-soluble [75]. It can be highlighted thatsodium
salts from alginic acid are water-soluble [75]. It can be highlighted that sodium
alginate
alginateisisthe
themost
mostused usedsalt
saltfrom
fromalginic
alginicacid.
acid.
Structurally,
Structurally,alginates
alginatesarearelinear copolymers
linear copolymers of α-1,4-L-guluronic
of α-1,4-L-guluronic acid (G)acidand(G)β-1,4-
and
D-mannurunic
β-1,4-D-mannurunic acid (M) repeating
acid units. These
(M) repeating units
units. mayunits
These be arranged
may be as G and Masblocks,
arranged G and
and as regions
M blocks, of regions
and as alternating G and M units
of alternating G and(Figure
M units5.(Figure
[80]. The molecular
5) [80]. weight ofweight
The molecular algi-
nates varies from 32 to 400 kDa, according to their source, and processing
of alginates varies from 32 to 400 kDa, according to their source, and processing meth- methods [84].
In
odsthe[84].
1960s,
In different
the 1960s,researchers using partial
different researchers hydrolysis
using were able towere
partial hydrolysis separate
able the alginic
to separate
the alginic
acid in threeacid in threewhere
fractions, fractions,
twowhere
of themtwocontained
of them contained
units of units
G or M,of Gwhereas
or M, whereas
the thirdthe
third fraction
fraction contained
contained balanced balanced proportions
proportions of bothofblocks,
both blocks,
MG dimersMG dimers
residues.residues. Later
Later on, it
on, it
was was elucidated
elucidated that alginates
that alginates have no have no regular
regular repeating
repeating unitthat
unit and andthe thatmonomers
the monomers dis-
distribution
tribution along
along the backbone
the backbone chainchain cannot
cannot be predicted
be predicted by statistical
by statistical analysis,
analysis, Markov
Markov or
or Bernoullian’s models [83]. These models were used to assign
Bernoullian’s models [83]. These models were used to assign the structure of alginates the structure of alginates
frombacteria,
from bacteria,though
thoughthey theydodonot
notfitfitfor
forascribing
ascribing thethe algal
algal monomer
monomer sequences
sequences [82].[82].

Chemicalstructures
Figure5.5.Chemical
Figure structures
ofof mannuronic
mannuronic acids
acids diads
diads (MM),
(MM), guluronic
guluronic acidacid diads
diads (GG),
(GG), and and
al-
alternated mannuronic acid/guluronic acid/mannuronic acid triad (MGM) in
ternated mannuronic acid/guluronic acid/mannuronic acid triad (MGM) in alginate.alginate.

Theindustry
The industryofofseaweed
seaweedhydrocolloids,
hydrocolloids,which
which includes
includes alginates,
alginates, agars,
agars, andand car-
carra-
geenans, has been growing in the order of 2–3% per year, mainly in Asia [85]. China is theis
rageenans, has been growing in the order of 2–3% per year, mainly in Asia [85]. China
the major
major manufacturing
manufacturing market
market of seaweeds,
of seaweeds, reaching
reaching 10 million
10 million tonstons in 2014,
in 2014, especially
especially of
of Laminaria (Saccharina) japonica, followed by Indonesia and Philippines in Asia [85,86]. In
the Americas and Europe, the seaweed market is dominated by Chile (Lessonia spp. and
Polysaccharides 2022, 3 42

Macrocystis), with more than 20,000 dry tons in 2015 and Norway and France (Laminaria ssp.
and Ascophyllum ssp.), respectively, with a production of more than 32,000 dry tons in
2015 [85]. Besides the fact that this market is expanding, only a small fraction of the global
biomass supply of seaweeds is produced. Some researchers suggest that the cultivation of
seaweeds offshore could provide an alternative source of biomass, leading to a sustainable
production of food, chemicals, and biofuels [86].
The utilization of seaweeds for food and feed by mankind dates back to antiquity.
The earliest written report was tracked in China and dated from about 1700 years ago [86].
For many centuries, harvesting and consumption of seaweeds were linked to costal in-
habitants, until their scaleup industrial utilization in the 19th century. The first extraction
reports of alginic acid extracted from kelps are from the 1880s, by the British chemist
Edward C. Stanford [83]. He patented and published a paper with his discovery in 1883 in
The Chemical News and Journal of Physical Science, entitled ‘On Algin: A new substance
obtained from some of the commoner species of marine algae’. Later, alginate was firstly
used as a food gelling agent to the production of artificial cherries in 1946 [87]. Since then,
alginates have been widely used in different industries, such as in textile, pharmaceutical,
cosmetic, food and other fields.
Alginate solubility depends on 4 main factors, G and M distribution blocks, solvent pH,
ionic strength, and presence of gelling ions. It can go through sol-to-gel transformation by
ionotropic gelation, resulted of the addition of multivalent ions that will act as crosslinking
agents, e.g., calcium, magnesium, aluminium, manganese, and iron, or by lowering the
pH below the pKa value of the guluronic residue [82,88]. Alginate is greatly sensible to
pH changes due to the presence of carboxylic acids along its chain. At pHs < 3.4 (below
pKa of M = 3.38 and G = 3.65), the carboxylic groups are nonionized (−COOH) making
alginate insoluble, whereas, at a pH > 4.4, these groups become ionized (−COO− ), resulting
in chain expansion by the electrostatic repulsion of these negative charges, reaching the
highest point at pH 7.4 [80]. Alginate affinity for divalent ions decreases in the following
order: trivalent cations > Pb2+ > Cu2+ > Cd2+ > Ba2+ > Sr2+ > Ca2+ [68,80]. For alginate
gels formation, a three-dimensional network is diaxially formed by the interaction of
carbonyl groups from the G blocks with multivalent cations, such as calcium, resulting in
the formation of a cavity or binding site, commonly named as “egg-box” conformation or
zipping mechanism [68,84]. Preparation, characteristics, and binding mode of alginate with
different ions were critically reviewed by Hu et al. [84]. The flexibility of alginate matrices
can be increasingly influenced by their segment blocks according to the following order:
MG > MM > GG [82]. Besides this interchain interactions, it is known that alginate as an
anionic polyelectrolyte can be combined with a cationic polyelectrolyte, such as chitosan
via complexation of their opposite charges, complex coacervation, aiming the formation of
micro/nanoparticles to encapsulate bioactive substances [89].

3.2. Carrageenans
Carrageenans are linear polysaccharides also obtained from marine sources, the
red seaweeds that belong to the Rhodophyceae family. They are mainly extracted from
Kappaphycus alvarezii and Eucheuma denticulatum, although other species (e.g., Chondrus crispus)
from Ireland and England have been used [68]. Historically, this seaweed has been known
since 400 A.D., especially in Ireland, as a homemade medicine to treat respiratory diseases,
and as a gelling agent. Moreover, the first reports on the use of Chondrus crispus to produce
carrageenan dates from 1862, by the British chemist Edward C. Stanford, who also worked
with alginates back then [68,83]. The name carrageenan and its utilization as we know
nowadays have been proposed after the 1950s [68].
Obtaining macromolecules from seaweeds has many advantages, since these algae
have a fast growing, thus producing large amounts of renewable biomass that are available
in abundance to many industrial purposes [90]. Besides, these materials are biodegradable,
biocompatible, present low or no toxicity, as well as have many biological properties.
These biopolymers are used in the development and formulation to a wide range of
Polysaccharides 2022, 3, FOR PEER REVIEW 12

Polysaccharides 2022, 3 43
biodegradable, biocompatible, present low or no toxicity, as well as have many biological
properties. These biopolymers are used in the development and formulation to a wide
range of pharmaceutical
pharmaceutical and food and food products
products because because of its emulsifying,
of its emulsifying, gelling,
gelling, and and stabi-
stabilizing
lizing properties
properties [91]. [91].
Carrageenans
Carrageenansare aresulfated
sulfatedwater-soluble
water-solublepolymers
polymersconsisting
consistingofofof
of1,3-linked-β-D-
1,3-linked-β-D-
galactopyranose
galactopyranose and 1,4-linked-α-D-galactopyranose alternating units[7].
and 1,4-linked-α-D-galactopyranose alternating units [7].Industrially,
Industrially,
the
themost
mostemployed
employedtypes
typesareareκ-(kappa),
κ-(kappa),ι-(iota)
ι-(iota)and
andλ-(lambda)
λ-(lambda)carrageenans,
carrageenans,being
beingclas-
clas-
sified
sifiedaccording
accordingto totheir
theirmolecular
molecularstructures,
structures,which
whichinclude
includethe
thesulfation
sulfationarrangements
arrangements
as
aswell
wellasasthe
theexistence
existenceoror absence
absenceof of
3,6-anhydro-α-galactopyranose
3,6-anhydro-α-galactopyranose on on
thethe
1,4-linked α-
1,4-linked
galactopyranose unit [92]. Figure 6 shows the main types of carrageenans
α-galactopyranose unit [92]. Figure 6 shows the main types of carrageenans used for used for indus-
trial purposes.
industrial purposes.

Figure
Figure6.6.Chemical
Chemicalstructures
structuresof
ofthe
thethree
threetypes
typesof
ofcarrageenans.
carrageenans.

Kappa-carrageenanand
Kappa-carrageenan andiota
iotacarrageenan
carrageenanexhibit
exhibitabout
about25–30%
25–30%and and28–30%
28–30%of ofsulfate
sulfate
content,respectively
content, respectively [93]. These carrageenans
carrageenans are arenaturally
naturallyhydrophilic
hydrophilicpolymers
polymersbelonging
belong-
to one
ing of of
to one thethe
major
majorgroups
groupsofofgalactans,
galactans,extracted
extracted from
from cell walls of of red
redseaweeds
seaweeds[68]. [68].
Thissulfated
This sulfatedwater-soluble
water-solublebehavior,
behavior,as aswell
wellasastheir
theirchemical
chemicalstructure,
structure,which whichcancanform
form
aahelical
helicalassembly,
assembly,isisresponsible
responsiblefor forits
itsgreat
greatpotential
potentialtotoprepare
preparefilm-forming
film-formingsolutions,
solutions,
thus having good employment to the design of edible films and
thus having good employment to the design of edible films and coatings [68,93]. coatings [68,93].
To the
To the design
design of
of edible
edible packaging,
packaging,carrageenans
carrageenanshave havebeen
beenused
usedto toreplace
replacecasings
casings
madefrom
made fromanimals’
animals’gut
gutforfor sausage
sausage making,
making, andand as coatings
as coatings in solid
in solid oily foods,
oily foods, meat,meat,
fish
fishpoultry
and and poultry for preventing
for preventing their superficial
their superficial dehydration
dehydration [91]. In a [91].
recentIn a recent
study, Tran study,
et al.
Trandeveloped
[49] et al. [49] developed and optimized
and optimized a composite a composite
film based filmonbased
sodiumon sodium
alginate,alginate, kappa-
kappa-carra-
carrageenan, Momordica cochinchinensis pulp and glycerol. These authors
geenan, Momordica cochinchinensis pulp and glycerol. These authors noted that the optimal noted that the
optimal film composition was 1.03% of sodium alginate, 0.65%
film composition was 1.03% of sodium alginate, 0.65% of kappa-carrageenan, 0.4% of M.of kappa-carrageenan,
0.4% of M. cochinchinensis
cochinchinensis pulp, and 0.85%pulp,ofand 0.85%(w/v).
glycerol of glycerol (w/v). Their
Their composite filmcomposite
exhibited film
goodexhib-
me-
ited good mechanical and physical properties, and low water vapor
chanical and physical properties, and low water vapor permeability, which demonstrated permeability, which
demonstrated
potential for foodpotential for food application.
application.
Jancikova et al. [93] studied the addition of 5–20% of lapacho extract (LE) in edible
films also containing ι- and κ-carrageenan as matrices. These authors observed that the use
 Jancikova et al. [93] studied the addition of 5–20% of lapacho extract (LE) in edible
films also containing ι- and κ-carrageenan as matrices. These authors observed that the
Polysaccharides 2022, 3
use of those different gelling agents in the composite films resulted in significant statistical44
differences (p < 0.05. in their tensile strength and breaking strain properties. Besides this,
these authors also evaluated the antioxidant properties of the produced films and noted
of those
the different
best results gelling
20% agents
for the in the
lapacho composite films resulted
extract-κ-carrageenan film. in
Insignificant statistical
another work, Simona dif-
etferences
al. [94](pinvestigated
< 0.05. in their
thetensile strength
properties and breakingfilms
of carrageenan straintoproperties.
which orange Besides this, these
essential oil
authors
and also evaluated
trehalose the antioxidant
were incorporated. Theirproperties of the produced
results showed films and noted
that the incorporation the best
of orange
essential oil with trehalose had a decreasing effect in UV-Vis transmittance for the al.
results 20% for the lapacho extract-κ-carrageenan film. In another work, Simona et [94]
carra-
investigated the properties of carrageenan films to which orange essential
geenan-based films, thus producing a UV protector coating. These authors also observed oil and trehalose
were
that theincorporated.
films exhibited Their resultsto
resistance showed that the bacteria
Gram-positive incorporation of orange
(Staphylococcus essential
aureus subsp.oil
with trehalose had a decreasing effect in UV-Vis transmittance for the carrageenan-based
Aureus).
films, thus producing a UV protector coating. These authors also observed that the films
exhibited
3.3. Chitosan resistance to Gram-positive bacteria (Staphylococcus aureus subsp. Aureus).

3.3. Chitosan
Chitosan is a polysaccharide derived from chitin, which is found in crustaceans
shells, in the exoskeleton of insects or produced by microorganisms [95,96]. After cellu-
Chitosan is a polysaccharide derived from chitin, which is found in crustaceans shells,
lose, chitin is the second most abundant polysaccharide in the world, exhibiting a global
in the exoskeleton of insects or produced by microorganisms [95,96]. After cellulose, chitin
turnover around 1011 tons per year [97]. The earliest works with chitin and chitosan date
is the second most abundant polysaccharide in the world, exhibiting a global turnover
from the 1850s with Charles Rouget and later in 1890s with Felix Hoppe-Seyler [95]. Since
around 1011 tons per year [97]. The earliest works with chitin and chitosan date from the
then, chitosan has been used to a wide range of purposes, mainly because of its renewable
1850s with Charles Rouget and later in 1890s with Felix Hoppe-Seyler [95]. Since then,
sources, relevant biological properties (e.g., as antioxidant, antimicrobial, and anticancer
chitosan has been used to a wide range of purposes, mainly because of its renewable
activities), as well as to its biodegradability, biocompatibility and nontoxicity [31] (Figure
sources, relevant biological properties (e.g., as antioxidant, antimicrobial, and anticancer
7).
activities), as well as to its biodegradability, biocompatibility and nontoxicity [31] (Figure 7).

Figure 7. Diverse biological, functional and technological properties of chitosan.

Figure 7. Diverse biological, functional and technological properties of chitosan.
Chitin is composed by (1,4)-β-2-acetamido-2-deoxy-D-glucopyranose units and low
Chitin
amounts ofis(1,4)-β-2-amino-2-deoxy-D-glucopyranose
composed by (1,4)-β-2-acetamido-2-deoxy-D-glucopyranose units
units, whereas chitosan and low
is composed
amounts of (1,4)-β-2-amino-2-deoxy-D-glucopyranose
of N-acetyl-D-glucosamine units, whereas(D-units)
(A-units) and deacetylated D-glucosamine chitosanunitsis com-
[98].
posed of N-acetyl-D-glucosamine (A-units) and deacetylated D-glucosamine
The main difference is that chitosan is deacetylated (Figure 8), which makes it soluble (D-units)
units [98].acidic
in mild The main difference
solutions, is that
whereas chitosan
chitin is deacetylated
is insoluble in many (Figure
organic8),
andwhich makessol-
inorganic it
soluble in mild acidic solutions, whereas chitin is insoluble in many organic and
vents [99]. The presence of hydroxyl and amine groups in chitosan chains allows the occur- inorganic
rence of chemical changes under pronation, which can influence significantly its biological,
mechanical, and physical-chemical properties [46,96]. The NH2 groups located at C-2 of
rings on the D-glucosamine repeating units promote a polycationic behavior of the chitosan
chains [46]. This polycationic characteristic allows the formation of electrostatic interactions
between chitosan and other polyanionic biopolymers, such as sodium alginate, and some
 solvents [99]. The presence of hydroxyl and amine groups in chitosan chains allows the
occurrence of chemical changes under pronation, which can influence significantly its bi-
ological, mechanical, and physical-chemical properties [46,96]. The NH2 groups located at
C-2 of rings on the D-glucosamine repeating units promote a polycationic behavior of the
Polysaccharides 2022, 3 chitosan chains [46]. This polycationic characteristic allows the formation of electrostatic 45
interactions between chitosan and other polyanionic biopolymers, such as sodium algi-
nate, and some amphiphilic proteins. The formation of such complexes is used to encap-
sulate bioactive substances and to form micro- or nanoparticles by complex coacervation
amphiphilic proteins. The formation of such complexes is used to encapsulate bioactive
[100–102]. The protonated amino groups are responsible for chitosan interaction with neg-
substances and to form micro- or nanoparticles by complex coacervation [100–102]. The
ative cell membranes
protonated of microorganisms,
amino groups altering
are responsible for its interaction
chitosan permeability andnegative
with metabolism, che-
cell mem-
late trace metals and microorganism’s spores, thus leading to cell death and inhibiting
branes of microorganisms, altering its permeability and metabolism, chelate trace metals
microbial
and growth [31].
microorganism’s spores, thus leading to cell death and inhibiting microbial growth [31].

Figure 8. Deacetylation
Figure8. Deacetylation of
of chitin
chitin to
to chitosan.
chitosan.
Due to its physicochemical and biological properties, chitosan has been widely ex-
Due to its physicochemical and biological properties, chitosan has been widely ex-
ploited to the design of different food packaging. Besides, chitosan-based films and coatings
ploited to the design of different food packaging. Besides, chitosan-based films and coat-
are environmentally friendly materials because they are biodegradable in many landsites
ings are environmentally friendly materials because they are biodegradable in many
and aquatic environments [103,104]. In a recent work, Hiremani et al. [105] studied the
landsites and aquatic environments [103,104]. In a recent work, Hiremani et al. [105] stud-
physicochemical and biological properties of a bioactive film of chitosan/white turmeric
ied the physicochemical and biological properties of a bioactive film of chitosan/white
starch prepared by the solvent casting technique. These authors observed that the produced
turmeric
films starchgood
exhibited prepared
tensileby the solvent
properties, castingsurface,
a smooth technique. These
as well as aauthors observed
fine miscibility, that
water
the produced
resistance and films exhibited
UV barrier good tensile
behavior. properties,
They found that thea smooth surface, as
chitosan/white well asstarch
turmeric a fine
miscibility, water resistance and UV barrier behavior. They found that the
blended films were more than 60% degraded within 15 days, confirming its well-reported chitosan/white
turmeric starch blended
biodegradability. films
In another wereSady
study, moreetthan 60% degraded
al. [106] incorporatedwithin 15 days, pomace
chokeberry confirming
ex-
tracts into chitosan-based films for potential food application. Their films showedchoke-
its well-reported biodegradability. In another study, Sady et al. [106] incorporated good
berry pomace
antioxidant extracts into
properties, chitosan-based
as well as enhanced films for potential
UV–vis light andfood application.
water Their films
vapor barrier, and
showed oxygen
reduced good antioxidant properties, as well as enhanced UV–vis light and water vapor
permeability.
barrier, and reducedfilms
Chitosan-based oxygen permeability.
plasticized with 30% of glycerol were used to coat strawberries
by Pavinatto et al. [107]. These authors found that the produced film had a bacterici-
dal behavior against gram-positive and gram-negative bacteria and a fungal resistance,
which protected the strawberries from microbial degradation without altering its senso-
rial properties. Chitosan and curcumin grafted with 2,2,6,6-tetramethylpiperidine-1-oxyl
(TEMPO)-oxidized cellulose nanofiber were used to prepare nanocomposite films by cast-
ing [108]. These films presented increased crystallinity due to the addition of nanofibers,
as well as oxidation resistance and an improved UV blocking property, although the me-
chanical strength and water vapor permeability decreased. In another recent study from
Polysaccharides 2022, 3 46

Qiao et al. [109], the physicochemical and structural behavior of chitosan films prepared
with different solvents were investigated. These authors noted changes in the crystallinity
of the chitosan films, which presented an amorphous structure in lactic and citric acids,
whereas a partial crystalline structure was present when the films were prepared with
hydrochloric and acetic acids. Their observations highlight the importance to choose a
proper solvent to the design of chitosan-based films aiming target applications. Moreover,
chitosan films can be affected not only by the solvent used and pH of the media, but also
by chitosan molecular weight, deacetylation degree, type and content of plasticizer, film
matrix and composites.

3.4. Starch
Starch is a natural polysaccharide obtained from different renewable vegetable sources
and their byproducts. This biopolymer has gained great attention due to its diverse
industrial and biotechnological applications, abundance, world-wide availability, low-
cost, biodegradability, edibility, and good processability in conventional plastic processing
equipments [110–112]. Cereals and tubers, e.g., maize, cassava, wheat and potato, are the
main sources of the worldwide industrial production of starch, although other vegetable
sources and their residues such as sorghum, rice, sweet potato, yams, barley, sago, and some
nonconventional fruits, tubers, legumes and pseudo-cereals can also be exploited [113–115].
This diverse botanical sources as well as many environmental factors can lead to differences
in the molecular structure, composition, shape, and size of starch granules, which will
significantly influence its processing properties [111,112].
Native starch is a heterogeneous material, chemically composed by two polyglucans,
amylopectin and amylose, forming semicrystalline granules [111,115–117], as can be vi-
sualized in Figure 9. The first is the major component, comprised by a highly branched
short chains of (1,4)-α-linked D-glucosyl units connected by (1,6)-α-linkages. The other
is amylose, which has linear longer chains and is a minor component (up to 35%) in
starches [115,116]. Generally, starches can contain around 20–25% of amylose and 75–80%
of amylopectin [111]. Some mutant plants may have high content of amylose, i.e., amylo-
maize or Hylon, whereas others may have little or no amylose, e.g., waxy corn and waxy
potato [115]. Amylose has a molecular weight 10 times higher than conventional synthetic
petroleum-based polymers, e.g., polyethylene and polypropylene, while has a much lower
Polysaccharides 2022, 3, FOR PEER REVIEW 16
molecular weight than amylopectin, which can reach millions [110].

Figure
Figure 9. Chemical 9. Chemical
structure structure
of amylose andof amylopectin
amylose and amylopectin
as the mainasmolecules
the main molecules constituting
constituting starches.
starches.

The amylose/amylopectin ratio is influenced by the starch origin and, consequently,

leads to different crystallinity degrees. The technological properties of starches depend on
their crystallinity, which can vary from 20% to 45% [110,111,117,118]. Mainly because of
the presence of strong intermolecular hydrogen bonds, starches are not solubilized in cold
water. In hot water, these bonds are weakened by the interaction between water molecules
and hydroxyl groups of amylose and amylopectin, which leads to partial starch solubili-
Polysaccharides 2022, 3 47

The amylose/amylopectin ratio is influenced by the starch origin and, consequently,

leads to different crystallinity degrees. The technological properties of starches depend on
their crystallinity, which can vary from 20% to 45% [110,111,117,118]. Mainly because of
the presence of strong intermolecular hydrogen bonds, starches are not solubilized in cold
water. In hot water, these bonds are weakened by the interaction between water molecules
and hydroxyl groups of amylose and amylopectin, which leads to partial starch solubiliza-
tion [111]. When in solution, amylose can crystallize, forming left-handed double helices,
which are packed in, either A- or B-type allomorphs [115]. This phenomenon is called
retrogradation. The temperature, solvent and starch/solvent ratio used for solubilizing
starch are significant factors that can influence its gelatinization, a relevant process in the
production of starch-based films and coatings [111]. Different physicochemical reactions
occur during the thermal processing of starches, such as water diffusion, granule swelling,
gelatinization, decomposition, melting and crystallization, though the gelatinization is
among the most important [110]. Physicochemical techniques, e.g., X-ray diffraction, po-
larized microscopy, nuclear magnetic resonance, and differential scanning calorimetry are
commonly used to investigate the gelatinization process of starch [110].
Starch-based films can be prepared by using a wet or dry process. In the first,
the films are made by film-forming dispersion using the casting technique. In the sec-
ond, by thermoplastic or thermal processing using extruders, thermoplastic starch is
produced [110,111,117]. Starches form suspensions with good film-forming capability. Sim-
ilar to other natural polymer films, the starch-based films exhibit several advantages. Starch
films are tasteless, colorless and odorless. They present good oxygen barrier properties,
nutritional value, edibility and others [105,118]. However, due to their hydrophilic nature,
starch films have some disadvantages, mainly related to their low water vapor barrier
capacity and mechanical properties [114,117].
To overcome these limitations, some plasticizers and other hydrophobic substances
(e.g., polyols, as well as the incorporation of other natural polysaccharides and proteins to
form composite films) can be added to improve the water vapor barrier and mechanical
properties [77,111,117,119]. Glycerol is among the most used and best plasticizer for starch-
based films. Recently, some ionic liquids or deep eutectic solvents have been used to this
end [77]. These alternative plasticizers have been used because they interact with hydroxyl
groups of starch chains, exhibit high thermal stability, and low density, vapor pressure,
toxicity and viscosity at room temperature [77,79]. Table 3 shows some starch-based films
and coatings.

Table 3. Some starch-based films and coatings.

Biopolymer
Matrix Additives Reference
Component
Potato, or corn, or wheat starches - 1-ethyl-3-methylimidazolium acetate (1.5 wt%) [77]
White turmeric (Curcuma zedoaria)
Chitosan Glycerol [105]
starch
Purple yam starch Chitosan Glycerol [53]
Corn or cassava starches Chitosan Lactic acid (1%, v/v), Glycerol (0.9 g 100 mL−1 ) [120]
Potato starch Chitosan Citric acid (5–20%) [121]
Arrowroot starch - Blackberry pulp (0–40%) [122]
Babassu starch - Glycerol, sorbitol, glucose, or urea [78]
Pea starch Guar gum Glycerol (25%) [123]
Wheat starch - Glycerol (0–50%) [124]
Rice starch Glutelin Sorbitol (40%) [125]
Cassava starch Yam starch Glycerol (20%) [126]

3.5. Pea Protein

Plant-derived proteins have gained remarkable attention of food manufactures and
consumers in the search for natural food resources and alternative materials for vegetarian,
Polysaccharides 2022, 3 48

vegan, and food allergy diet restrictions. Protein-based film packaging exhibits extraor-
dinary mechanical and barrier properties, especially to oxygen and carbon dioxide gases,
when compared to polysaccharides [7,38]. Besides being an eco-friendly material, these
films can nutritionally improve food quality and preservation. Moreover, the amphiphilic
attribute of proteins contributes to their utilization as emulsifiers by stabilizing oil/water
interface due to changes in interfacial tension [39]. Nowadays, a great variety of plant
proteins have been used in food industry and packaging, such as from soybean, wheat,
corn, sunflower, and pea [40].
Pea, Pisum sativum L. ssp. sativum, is a notable grain legume that belongs to Fabaceae
(or Leguminosae) and Papilionoïdeae botanical families, such as soybean [127]. It is
known by several common names such as common pea, green pea, garden pea, field pea,
yellow field pea, spring pea, English pea, and Austrian winter pea (Pisum sativum L. ssp.
sativum var. arvense) [128]. Pea is a cool-season pulse crops largely cultivated for protein
and feed purposes, being one of the most important food harvests, reaching around 11 Mt
per year worldwide [127]. The major producers in 2014 were Canada and USA in the
Americas, France in the European Union, Russia in Eastern Europe, and Australia in
Oceania regions [128]. Nowadays, the major producing regions, in ascending order, are
Asia, Europe, Africa, Americas, and Oceania, reaching more than 21 million tons of green
pea production worldwide in 2019 [129].
Up to 30% of proteins can be found in peas, which contains 65–80% of globulins and
up to 20% of albumins [39]. Moreover, peas exhibit a good-balanced amino acid profile,
highlighting higher amounts of lysine, around 6%, and tryptophan than cereal grains. By
contrast, peas are deficient in methionine and cysteine, in relation to cereal grains [130–132].
Five proteins fractions can be found in peas. Besides globulins and albumins, prolamins,
glutelin are found in peas [128,133]. Albumins are water-soluble metabolic and enzymatic
proteins involved in cytosolic functions. Unlikely, globulins are salt-soluble proteins, which
are used on seeds germination to provide nutrients for plant growing [130].
The major storage proteins found in pea seeds are globulins, which consists of legu-
min (11S, Mw ~380 kDa) and vicilin (7S, Mw ~60 kDa) and convicilin (7S). Legumin is a
hexameric molecule containing six subunits held together by noncovalent interactions, that
contains 4–5 acidic (α) (40 kDa) and 5–6 basic (β) (20 kDa) polypeptides from several gene
families’ precursors, linked by disulfide bonds. Vicilin is a trimeric protein containing
three subunits each 50 kDa in size, that lacks cysteine residues and cannot form disulfide
bonds. Convicilin, a third major storage protein in peas, has a subunit of ~71 kDa and a Mw
in its native form of 290 kDa [130,134,135]. The variations in content, composition, and
structure of both globulins, vicilin and legumin, reflect in their nutritional and functional
properties, e.g., higher globulins content may result in better emulsification properties [39].
The pea proteins, as well as other proteins in seeds are considered bioactive proteins,
as they can contribute to wellness and health. Nevertheless, the food applications of
pea proteins are related to their nutritional value, distinguishable functional properties,
low allergenicity, non-GMO status, and biological activities, such as reducing the risk of
cardiovascular disease and lowering blood pressure effect [132]. The extraction methods
used to obtain pea proteins have a significant impact on its functionalities. A diverse
number of methods have been used to extract plant proteins, which can be classified as
conventional (solvent and alkali-based), physical (ultrasound, microwave, high-pressure
and pulse electric field-assisted extraction), and green extraction technologies [136].
For pea protein isolation, two processes (dry or wet extractions) can be used. The
dry process is based on air classification, in which the pea seeds are milled into a flour,
and separated in light and heavy fractions, protein and starch-rich respectively, by the
application of a spiral air stream. For the wet process, the proteins are extracted according
to their solubility in solutions, alkaline or saline, and further isolated by dialysis, micellar
precipitation, or ultrafiltration [128,137]. Recent studies have found that the methods used
for pea protein recovery influence its composition and gelling properties. Ultrafiltration
and dialysis let to higher albumin fraction, whereas alkaline-isoelectric and micellar precip-
Polysaccharides 2022, 3 49

itation result in the retention of globulins [137]. In that work, gels formed by pea proteins
with higher compressive strength resulted from micellar precipitation and ultrafiltration
extractions. When considering the isolated protein yield and protein solubility, the best
results can be achieved by salt extraction-dialysis, followed by alkali extraction/isoelectric
precipitation and micellar precipitation, as found by Stone et al. [138]. In that same work,
the authors found that salt-extracted isolates displayed the highest oil holding capacities
and lowest water holding capacities. Additionally, pea protein isolate (PPI) is commonly
obtained using isoelectric precipitation with pH around 4.5 followed by membrane sep-
aration, e.g., ultrafiltration or diafiltration, to increase protein concentration [130]. Thus,
the technological understanding involving pea protein extraction and composition helps
to achieve their best functional physicochemical properties and meticulously design of
formulated products.
Generally, functional properties of proteins can be categorized as related to: (a) hydra-
tion (absorption of water and lipids, solubility, wettability, and thickening); (b) structure
and rheological behavior (adhesiveness, viscosity, elasticity, gelation and aggregation); (c)
protein surface (emulsification, foaming, whipping and formation of protein-lipid-based
films) [131]. From these, solubility, water- and lipid-binding capacities, rheological, emul-
sifying and gel forming properties, can be cited as the most significant properties for
application of pea proteins in food products.
Beyond processing factors, environmental conditions, e.g., temperature, pH, ionic
strength, and type of solvent, can significantly affect the functional properties of pea pro-
teins, especially its solubility. The solubilization of pea protein isolate is deeply influenced
by pH variation, presenting minimum solubility between pH 4–6 [131]. In another work, at
neutral pH, pea protein exhibited the highest surface hydrophobicity value, low surface,
and low solubility, resulting in a lower emulsion capacity when compared to chickpea, fava
bean and lentil proteins produced by isoelectric precipitation and salt extraction [139]. To
overcome these issues, the use of polysaccharides forming stable complexes with proteins
have gained interest. It prevents proteins aggregation and precipitation and improve
functionalities. Furthermore, protein-polysaccharides plays important roles controlling
food systems stability and forming film/coating and composite packaging materials.
Differently from polysaccharides, proteins-based films exhibited better mechanical
and optical properties, as well as good barrier against gases permeability, especially O2
and CO2 . The use of protein in food packaging provides a wide range of interactions and
chemical reactions with other substances, through covalent (peptide and disulfide) and
noncovalent (ionic, hydrogen and van der Waals) bonds [38]. They can be prepared as a
mono or multilayer food packaging and blended with other polymers as a composite film.
Some of the most used proteins in edible films are collagen, zein, gelatin, soy protein, milk
protein and pea protein [140].

3.6. Improvements by the Incorporation of Natural Bioactive Substances into Edible Films
The incorporation of bioactive agents into packaging films is a growing strategy that
aims to extend shelf-life, to increase lipid and microbial stability and safety when it is
applied to food products. Furthermore, the use of active packaging to extend the food shelf-
life and safety is an emerging and dynamic technology in food processing, since this coating
can actively interact with the food surface and the environment based on the intrinsic prop-
erty of their constitutional biopolymers or incorporated additives [141]. Moreover, using
natural bioactive compounds have become a good alternative for traditional packaging and
replace synthetic additives commonly used, e.g., butylated hydroxytoluene (BHT) [142].
Besides this, the addition of bioactive substances has been associated to microbial and
physical improvements in film properties as well as health beneficial activities, such as
antioxidant and probiotic, to consumers intake [143]. Some uses of different bioactive
substances on chitosan-based films are listed in Table 4.
Natural bioactive materials can be obtained from plants, animals, marine organisms,
and microorganisms using biotechnological methods [38]. Plant-based bioactive substances
Polysaccharides 2022, 3 50

are widely found in nature and is mainly secondary metabolites that presents inherent
biological functions. They can be obtained from renewable plant parts, such as, leaves,
flowers, fruits, seeds, grains, roots, and other vegetable portions, as extracts, resins, essential
oils, or vegetable oils and fats. In these materials, a wide number of natural phytochemicals,
such as phenolic acids, carotenoids, flavonoids, vitamins, isoflavones, indoles, saponins,
monoterpenes, bioactive peptides, phytosterols, essential fatty acids, and others can be
categorized as bioactive compounds [144].

Table 4. Incorporation of bioactive substances in chitosan-based films.

Additives Biological Properties Main Results Reference

− Effective against seven bacteria species.
Maqui berry extracts [145]
− Higher antioxidant activity.
Grape seed extract and − Improvement of total phenolic content,
Ziziphora clinopodioides antibacterial and antioxidant activities, [146]
essential oil thickness, and water vapor barrier property.
− Inhibition all tested bacteria on contact
surface.
Propolis extract Antimicrobial and − Tensile strength, elongation at break, total [147]
antioxidant phenolic content and antioxidant activity
increased.
− Improvement of the film physical properties
Apple peel polyphenols − Antioxidant and antimicrobial activities were [148]
significantly increased.
− Gelatin-nanochitosan films containing
Zataria multiflora Boiss
Zataria multiflora Boiss. essential oil delayed [149]
essential oil
the growth of bacteria in chicken meat.
Zataria multiflora Boiss
− Wettability of the surface, total phenol and
essential oil and grape [150]
antioxidant activity increased.
seed extract
Antioxidant
− Green tea films presented stronger
Green tea and black tea
antioxidant activity than that of black tea [151]
extracts
films in all food simulants.
− Incorporation of carvacrol was not effective
Carvacrol Antibacterial activity [5]
against bacterial activity.

Natural bioactive substances present many advantages for food preservation when
added into packaging. Some disadvantages may persist, such as off-flavors, thermosensi-
tivity and early loss of functionality, which may take place during processing and storage.
Furthermore, the bioactive efficiency decreases when exposed to oxidative conditions of
the surrounding environment (air, humidity, heat, light, oxygen, and others) [152]. Thus,
encapsulation of bioactive substance onto biopolymeric matrices, followed by incorporation
of these active particles in the food packaging is an effective strategy, which can improve
durability and maintenance of biological properties [153,154]. Some examples of the incor-
poration of lipid materials onto different hydrocolloid matrices are listed in Table 5.
Polysaccharides 2022, 3 51

Table 5. Incorporation of lipids onto different hydrocolloid matrixes.

Hydrocolloids Lipids Form Application Reference

Microcapsules by Potential application to
Chitosan and sodium alginate Açaí pulp oil [101]
complex formation biobased packaging
Microcapsules by Functional lipids and
Gelatin and gum Arabic Methyl oleate [155]
complex coacervation lipophilic food ingredients
Gluten and gelatin plasticized Incorporated in
Fatty acids Biobased packaging [156]
with glycerol or sorbitol edible films
Mesquite seed gum Palm fruit oil Emulsion edible film Biobased packaging [63]
Chitosan/xanthan or Microcapsules by
Palm oil Yogurt preparation [157]
chitosan/pectin complex formation
Chitosan/sodium
Food systems under
tripolyphosphate or Palm oil and Microcapsules by
gastrointestinal simulant [158]
chitosan/carboxymethyl β-carotene complex formation
conditions
cellulose
Chitosan plasticized with
Olive oil Emulsion film Biobased packaging [159]
glycerol

Furthermore, vegetable oils are a feasible source of essential fatty acids and sterols,
particularly, alpha-linolenic acid and linoleic fatty acids and phytosterols, which are related
to health benefit effects in reducing the risks of heart diseases, displaying antioxidant
activity and others associated to their incorporation in food products [160]. Besides, they
are obtained from renewable sources, edible, effortlessly available, generally display low
cost, are nontoxic, nondepletable and nonvolatile. Lipid materials can be used to promote
a desirable smooth effect, improve water, and gas barrier, as well as enhance cohesivity
when incorporated in biobased films [38,141].
The functionality of these bioactive materials may be different, as each component
introduces a wide range of properties to the matrix. Besides, functionality depends not
only on intrinsic characteristic of each component, but significantly on their compatibility
and cohesivity. Different approaches to this can be pursued, e.g., incorporation of the
encapsulated particles on the external surface of films or in the interface between the film
and the food and dispersed among the film [38]. It is expected that these incorporated
active compounds will be released from the package or absorb substances from food and
surrounding environment, as well as make changes in food composition and sensorial
characteristics [141].

4. Conclusions
Research on novel biobased food packaging has been growing over the last decade
mainly boosted because of concern with the global environmental plastic pollution. Inno-
vative strategies to develop biodegradable and sustainable packaging materials based on
natural resources are welcome to reduce the use of plastics. The present review highlighted
a historical timeline, functionality and application trends of alginate, carrageenan, chitosan,
starch and pea protein, as natural biopolymers for the design of food packaging. Using
these polymers from agroindustrial residues to this end are also an interesting strategy
to close the wheel of a circular and sustainable economy. These materials have valuable
potential in the chemistry and packaging industries, especially due to its renewability,
biodegradability, compatibility, as well as good technological and functional properties.
Therefore, many challenges related to its processability, proper ways of disposal and leg-
islations need to be overcome to increase their industrial application. It is known that a
full replacement of plastics for biobased packaging is not quite easy and is far from being
a reality in many countries, though any degree of substitution is welcome to achieve a
significant reduction of environmental pollution. This replacement is a challenge to be
Polysaccharides 2022, 3 52

overcome by packaging industries, especially because there is lack of legislation about

it, the adequacy of industrial processing facilities is costly and the disposal of packaging
residues is not well known by consumers or not available to all, especially in low-income
countries. Despite those difficulties, replacing petroleum-based plastics should be top
priority of all food packaging industry around the world.

Author Contributions: Conceptualization, B.E.T.-C. and C.T.A. Literature data collection, B.E.T.-C.
Writing—original draft, B.E.T.-C. Writing—review and editing, B.E.T.-C. and C.T.A. Supervision:
C.T.A. All authors have read and agreed to the published version of the manuscript.
Funding: The authors acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico-
Brazil (CNPq) (Grant n◦ 306482/2019-3), Fundação de Amparo à Pesquisa do Estado do Rio de
Janeiro-Brazil (FAPERJ) (Grant n◦ E-26/010.000984/2019. and Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior-Brasil (CAPES), Finance Code 001.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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