polymers

Review
The Green Era of Food Packaging: General Considerations
and New Trends
Enrico Maurizzi 1, * , Francesco Bigi 1 , Andrea Quartieri 1 , Riccardo De Leo 1 , Luisa Antonella Volpelli 1,2
and Andrea Pulvirenti 1,2

1 Department of Life Sciences, University of Modena and Reggio Emilia, 41125 Modena, Italy
2 Interdepartmental Research Centre for the Improvement of Agro-Food Biological
Resources (BIOGEST-SITEIA), University of Modena and Reggio Emilia, 42124 Reggio Emilia, Italy
* Correspondence: enrico.maurizzi@unimore.it

Abstract: Recently, academic research and industries have gained awareness about the economic,
environmental, and social impacts of conventional plastic packaging and its disposal. This conscious-
ness has oriented efforts towards more sustainable materials such as biopolymers, paving the way
for the “green era” of food packaging. This review provides a schematic overview about polymers
and blends of them, which are emerging as promising alternatives to conventional plastics. Focus
was dedicated to biopolymers from renewable sources and their applications to produce sustainable,
active packaging with antimicrobial and antioxidant properties. In particular, the incorporation
of plant extracts, food-waste derivatives, and nano-sized materials to produce bio-based active
packaging with enhanced technical performances was investigated. According to recent studies,
bio-based active packaging enriched with natural-based compounds has the potential to replace
petroleum-derived materials. Based on molecular composition, the natural compounds can diversely
interact with the native structure of the packaging materials, modulating their barriers, optical and
Citation: Maurizzi, E.; Bigi, F.; mechanical performances, and conferring them antioxidant and antimicrobial properties. Overall,
Quartieri, A.; De Leo, R.; the recent academic findings could lead to a breakthrough in the field of food packaging, opening the
Volpelli, L.A.; Pulvirenti, A. The
gates to a new generation of packaging solutions which will be sustainable, customised, and green.
Green Era of Food Packaging:
General Considerations and New
Keywords: biopolymers; antioxidant compounds; antimicrobial compounds; essential oils; nanoparticles
Trends. Polymers 2022, 14, 4257.
https://doi.org/10.3390/
polym14204257

Academic Editor: Dariusz 1. Introduction

Kowalczyk
Food technologies have played a crucial role since the beginning of human civilisation.
Received: 15 September 2022 Throughout history, the evolution of food processing and packaging has led to a constant
Accepted: 5 October 2022 increase of food quality and safety, improving the quality of human life [1]. Recently,
Published: 11 October 2022 human society has gained awareness about the impact of agri-food practices on our world,
and these concerns have oriented the food sector towards the adoption of novel and
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
sustainable technologies.
published maps and institutional affil-
Among the main pillars of this multifaceted process, it is worth citing three lines of
iations. research that have deeply contributed to re-define the concept of “Food Technology” [2]:
1. Substitution of thermal techniques and chemical sanitisation with green alternatives
in order to reduce the consumption of resources and the impact on food quality.
2. Extraction of added-value compounds from renewable sources (e.g., food by-products)
Copyright: © 2022 by the authors. and their application as alternatives to conventional preservatives and additives.
Licensee MDPI, Basel, Switzerland.
3. Development of bio-based active packaging based on renewable biopolymers, aiming
This article is an open access article
to reduce the use of petroleum-derived plastics in the food packaging sector, and to
distributed under the terms and
prolong the shelf-life of the products, preventing the generation of food waste.
conditions of the Creative Commons
Attribution (CC BY) license (https:// This work provides a synthetic overview about the strategy trends which are leading
creativecommons.org/licenses/by/ the food-packaging industry towards green technology and sustainability criteria, reducing
4.0/). the energy consumption, waste generation, and footprints on the environment. A specific

Polymers 2022, 14, 4257. https://doi.org/10.3390/polym14204257 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 4257 2 of 40

focus was dedicated to biodegradable polymers from renewable sources (e.g., agri-food
by-products) and natural-derived compounds, and their application to produce active pack-
aging items with antimicrobial, antioxidant, and nano-reinforced properties as prospective
substitutes for conventional plastic materials.

2. Bio-Based Packaging: General Considerations

Food packaging is a coordinated system aiming to preserve the safety and quality
of the food products from their production to their end-use [3]. It plays a crucial role in
human society as a fundamental component of the food supply chain [4].
Worldwide, it is estimated that one-third of produced food is disposed every year
due to various factors including incorrect harvesting procedures, mechanical damage, and
inadequate storage conditions, which result in microbial decay, oxidation, the degradation
of nutrients, and loss of acceptability [5]. Therefore, the selection of adequate packaging
solutions able to protect each targeted product and to maintain its quality is crucial to
extend the food’s shelf life, thus preventing waste generation.
Conventional packaging is commonly constituted by a one-time use item, immedi-
ately discarded after reaching the intermediate or final user [4]. Over a broad variety of
materials, fossil-based plastics have dominated the food-packaging industry since their
appearance during the Second World War [6] thanks to their enhanced barrier and me-
chanical properties, chemical resistance, durability, lightweight nature, availability, and
cost-effectiveness [7].
Currently, the global production of plastics comprises about 320 million tons/year [8].
Data reveal that one-third of all produced plastic is dedicated to packaging materials [9].
Hence, the food-packaging industry is closely involved in the production of massive
amounts of plastics, generating severe economic burdens and ecological impacts.
The main concern of plastics is related to their non-sustainable nature since their
source (petroleum) is not renewable (PE, PET, PP, etc.) [10–12]. Besides, single-use plastics
are generally considered as not “environmentally friendly” due to their non-compostable
nature and low recycling rate [13]. This ends up causing the accumulation of tremendous
masses of waste in landfills and oceans, increasing wildlife mortality from ingestion and
entanglement [14].
In the last few years, the awareness about the environmental impacts of plastic has
grown both at personal and at community levels. On the one hand, consumers are increas-
ingly demanding natural, high-quality foods, and food packaging that does not create
pollution. On the other hand, governments are pushing towards the reduction of human
impact on the environment. For example, the European Parliament focused its Sustainable
Development Goals on the partial replacement of oil-based polymers with biodegradable
polymers from renewable resources by 2030 (European Commission, 2015). This prompted
researchers and companies to shift their efforts towards the exploration and exploitation
of novel renewable resources and the development of sustainable packaging solutions,
including films, coatings, and other items.
Specifically, films are thin layers of material prepared through different technologies
such as solution casting or extrusion as stand-alone structures. The prepared films are
used to wrap the foods or to be placed between the layers of food products. Coatings are
thin layers of material which are directly applied on the food surface, and act as a barrier
between the external environment and the product during transportation, processing, and
storage. Coatings are applied either by dipping the product in the coating solution or by
directly spraying them over the product’s surface.
These novel packaging systems are designed to perform multiple functions. Along
with the “classic” packaging activity, namely the interposition of a physical barrier between
food and environment, they may operate as carriers of bioactive compounds with antioxi-
dant, antimicrobial, or nutritional properties. These “active ingredients” aim to prolong
the shelf life or increase the nutritional value of the packaged product [15]. Moreover, the
addition of bioactive compounds can result in modified physicochemical, mechanical, and
Polymers 2022, 14, 4257 3 of 40

barrier properties since they chemically interact with the biopolymer structure. Hence,
their wide application may allow improving or even adapting the functional features of
packaging solutions for a broad variety of applications [16].

2.1. Compostable, Biodegradable, or Renewable?

Research and industries are pushing towards the usage of biodegradable polymers for
food-packaging purposes. Additionally, the extensive exploitation of renewable resources
has the potential to reduce the use of oil and other fuels. However, plastics produced by
renewable resources are not necessarily compostable or biodegradable, and vice versa [17].
For example, cellulose, starch, and gelatin also maintain their biodegradability when
obtained synthetically. Equally, when castor oil monomers are polymerised to produce
Nylon 9, they lose their biodegradability [18]. In fact, biodegradation is correlated to the
chemical structure of the compound rather that its origin. In this context, it is important
to clearly state the definitions of biodegradation and compostability, allowing further
introduction of the concept of biopolymers.
Biodegradation broadly defines an event in which a biomass is over 90% decomposed
within 6 months via the action of enzymes and/or chemical degeneration associated with
living organisms such as moulds, yeasts, and bacteria [(UNI EN 13432:2002)]. This process
can be conducted both in aerobic and anaerobic conditions [19]. Other processes such as
photodegradation, hydrolysis, and oxidation may also have an impact on the structure
of biomass prior to or during biodegradation [20]. Compostability involves a series of
processes (mainly conducted in industrial conditions) that exploit biodegradation to convert
organic matter into the so-called “compost”, which must completely degrade in soil within
3 months by producing water, carbon dioxide, and other inorganic compounds [21].
In light of these statements, it is worth noting that the large-scale synthesis of com-
postable bioplastic using 100% renewable resources has not been realised yet. Until now,
bioplastic usually comprises more than 50% (w/w) of renewable sources [18]. Several
bioplastics include mixtures of synthetic compounds to improve the technical properties
of the final product, extending its potential applications. Despite that, the current ten-
dency is to replace synthetic additives with natural compounds with comparable functional
properties and to enhance the use of biopolymers over fossil-derived materials to produce
approximately 100% renewable and biodegradable plastics.

2.2. Biopolymers
According to the European Bioplastics association, biopolymers are defined as biodegrad-
able, compostable, and biocompatible polymers derived from renewable resources [22]. They
are broadly regarded as the most promising sustainable alternative to petrol-based synthetic
polymers for food-packaging applications due to their compostable nature and film-forming
ability [20].
Thanks to their technical variability, biopolymers are adaptable to various packaging
technologies, offering a range of package products, including cups, covers, separation
layers, and food containers. In particular, they can be used to prepare composite films
and multi-layered coatings to prolong the shelf-life of food products. Moreover, biopoly-
mers are compatible with functional ingredients including nutraceuticals, antioxidants,
antimicrobials, probiotics, and additives [23].
Biopolymers have been classified into three categories according to their sources and
synthesis: (I) polymers extracted from renewable biomasses, including polysaccharides,
polypeptides, and lipids; (II) polymers synthetised from chemical polymerisation of bio-
monomers (e.g., polylactic acid); and (III) polymers derived from microbial fermentation
(e.g., polyhydroxy alkanoates) [19] (Figure 1). Besides, biopolymers can be distinguished
according to their hydroplastic or thermoplastic behaviour [3].
 monomers (e.g., polylactic acid); and (III) polymers derived from microbial fermentation
(e.g., polyhydroxy alkanoates) [19] (Figure 1). Besides, biopolymers can be distinguished
according to their hydroplastic or thermoplastic behaviour [3].  
Most biopolymers possess remarkable technical features for packaging application
Polymers 2022, 14, 4257 due to their chemical complexity, as shown by the studies in Table 1. A brief description
4 of 40
of the most common biopolymers is detailed in the following sub‐sections.  

 
Figure 1. Classification of biopolymers (reproduced with copyright permission from Chen et al. [24]).
Figure 1. Classification of biopolymers (reproduced with copyright permission from Chen et al. 
[24]).  Most biopolymers possess remarkable technical features for packaging applications
due to their chemical complexity, as shown by the studies in Table 1. A brief description of
Table 1. Cases of study of biopolymers and their effects in food‐packaging applications. 
the most common biopolymers is detailed in the following sub-sections.
Solvents for 
Polymers  Table 1. Cases of study
Additives  of biopolymers and their effects inThe Effects and Advantages 
Treatments  food-packaging applications. References
the Polymers 
Solvents for
Polymers Additives Treatments The Effects and Advantages References
Biodegradation  the Polymers
Polybutylene succinate 
Polybutylene succinate test of 10 test of
Biodegradation •  FastFast degradation of PCL in 8 weeks 
degradation of PCL in 8 weeks
(PBS), Polyhydroxybutyrate 
(PBS), Polyhydroxybutyrate ◦ C due to the activity of fungal
at 50at 50 °C due to the activity of fungal 
(PHB), Polycaprolactone / / 10 months at 25, 37, and
months at 25, 37,  /  / [21] [21] 
(PHB), Polycaprolactone 
(PCL), Polylactic acid (PLA)
50 ◦ C soil and compost strain of T. lanuginosus
and 50 °C soil  strain of T. lanuginosus 
(PCL), Polylactic acid (PLA)  • Isolated 63 bacterial strains that can
and compost 
produce PHAs
• Presence of Bacillus coagulans in
Poly-β-hydroxybutyrate / Fermentation Oily sludge 99.96% of the cases [25]
• Bacillus coagulans showed a produc-
tion yield with molasses of 6.36 g/L,
B. megaterium
• Polymer was not suitable for food
packaging because of the high migra-
PLLA-15% ZIF-8 MOF / Extrusion / tion level of Zn2+ [26]
• Zn2+ release was double in acidic
simulant
• GTA cross-linking enhanced gelatin
Glutaraldehyde (GTA)
Gelatin 6% (w/v) Cross-linking Distilled water thermal stability and mechanical [27]
50% (w/v of polymer)
properties with pH 4.5

 
Polymers 2022, 14, 4257 5 of 40

Table 1. Cont.

Solvents for
Polymers Additives Treatments The Effects and Advantages References
the Polymers
Murta berry extract
(MU) 25% (w/w of the
poly-
mer)Glutaraldehyde • Cross-linking decreased the swelling
Methyl cellulose (MC) 1%
(GA) 10–20% (w/w of / Distilled water index of the materials and increased [28]
(w/v)
polymer) mechanical properties
Polyethylene glycol
(PEG) (25% w/w of the
polymer)
Binary blend of polymers at
a final concentration of 5% of • Pure OSA film had low plasticity
gelatin (GEL) and different • GAR film was weak from a mechani-
polysaccharides: gum arabic cal point of view
(GAR), methylcellulose Glycerol 1% (w/w) / Distilled water • Incompatibility between GEL and [29]
(MC), octenyl succinic MC, especially at a 50/50 ratio
anhydride modified starch • GEL improved the durability and
(OSA), and water-soluble stiffness of the film
soy polysaccharides (WSSP)
• Maximum improvement of E0 and
Nanocomposite
glass transition temperature at 3% of
films containing 1−5%
Cationic exchange DCNP loading level
(w/w of the polymer) of
Polylactic acid (PLA) reaction between a Chloroform • Oxygen permeability and WVP de- [30]
dye−clay hybrid nano
cationic dye and C20A creased in comparison to neat PLA
pigments
• Optimum of 3% for optical property
(DCNP)
and UV barrier
• The plasticising effect of the
sesquiterpenoid plant metabolite
Polylactic acid (PLA) 1% α-costic acid (α-CA) 7:1
/ Chloroform induced better thermal degradation [31]
(w/v) (w/w of the polymer)
• Homogeneous and efficient inclu-
sion of α-CA in PLA
• PLA reacted with NCFHL at nearly
Nanocellulose fibrils 50% of the total area
Extraction of Thuja Aqueous
with high lignin content • NCFHL until 10% enhanced elastic
PLA latex plicata bark and suspensions of [32]
(NCFHL) from 5 to 20% modulus and tensile strength
fibrillation NCFHL
(w/w) • NCFHL increased thermal stability
and hydrophobicity
• Bio-based PC had weak thermal re-
sistance and low viscosity
Fossil-based and bio-based
/ Moulding / • Good optical property but lower bire- [7]
polycarbonate (PC)
fringence compared with the fossil
PC
200–800 mg/L of
• Best performance of immobilisation
Sodium alginate 1–3.5% protease from Bacillus
/ Milli-Q water at 2.5–3% of Na-alginate and CaCl2 , [33]
(w/v) brevis
with 400–600 mg/L of protease
1–3.5% CaCl2
• Best crosslinking rate with 20% SB
and 180 min of UV and 0.2% gelatin,
associated with exposure of GLA sat-
Sodium benzoate 5–30%
UV irradiation at urate vapour for 90 min
CMC 0.5% (w/v), gelatin (w/v), Aqueous
(253.7 nm, 30 W) for • Photo-crosslinking enhanced hy- [34]
(GEL) 0.05–0.25% (w/v) saturate vapour of solution
30–180 min drophobicity
glutaraldehyde (GLA)
• Both crosslinking methods improved
the tensile strength and contact angle
of CMC film
Glycerol 30% (w/w of
• HAE’s gave light barrier properties,
the polymer) and tween
Chitosan 1.5% (w/v) / Distilled water higher water content and solubility [35]
80 0.2% (w/v of
• EOs enhanced tensile strength
essential oil)
• TE modified the microstructural ap-
Lyophilised tannic acid
pearance of CH, due to crosslinking
Chitosan (CH) 2% (w/w), pea (TA) 1:0.04 (w/w on
Water effect of polyphenols
starch (S) 2% (w/w), CH:S 1:4 polymer) or thyme / [36]
dispersion • TA and TE gave higher resistance
(w/w) extract (TE) 1:0.15 (w/w
at the break but poor elasticity and
on polymer)
opaque films
Epoxidised cardoon oil • Compatibility between ECO and
Corn starch and polylactic (ECO) 3% (w/w of PLA PLA, which gave higher WVP and
acid (PLA) blended at a ratio fraction) and glycerol at Melt blending process / barrier to O2 [37]
of 80:20 30% (w/w of starch • Poor mechanical property of the
fraction) films
Polymers 2022, 14, 4257 6 of 40

Table 1. Cont.

Solvents for
Polymers Additives Treatments The Effects and Advantages References
the Polymers
• Zein/gelatin ratio influenced me-
Zein (Z) 15% (w/v), gelatin
Tea polyphenol Acetic acid chanical property in multilayer films
(G) 10% (w/v), blend ZG at
2.5%–7.5% (w/v), / (AA) and • Multilayers were more transparent [38]
different ratios (2:1, 1:1, 1:2)
glycerol 0.4–0.8 mL water and had a higher UV barrier than
15% (w/v)
neat polymers
Microcrystalline cellulose 3% • Transparent Zn-cellulose film
68% ZnCl2 (w/w) / Distilled water [39]
(w/w) crosslinked with Ca2+
• Cross-linking process permitted to
Heat cross-linking with
reach a swelling degree above 400%
citric acid (CA) 3–12%
Polyvinyl alcohol (PVA) Electrospinning and • Microfibers treated with CA were
(w/w of the polymer), Distilled water [40]
5–12.5% (w/v) cross-linking highly hygroscopic
Clove oil (CO) 20% (w/w
• Cross-link improved mechanical
of the polymer)
property and thermal stability
Whey protein isolate
(WPI) 4% (w/v), • Compatibility between polymer and
microcrystalline additives
Chitosan(CS) 4% (w/v) / Distilled water [41]
cellulose (MCC) 4% • Better WVP at 1.5:1 CS/MCC ratio
(w/v) and glycerin with 30% glycerin and 3.6 of pH
10–50%
• GCE worked as a crosslinker for
Galla chinensis extract gelatin hydrogel
Gelatin 6% (w/v) powder (GCE) / Distilled water • The maximum concentration of GCE [42]
0.03–0.12 g/100 mL improved thermal stability and gel
strength

2.2.1. Polysaccharides
Polysaccharides are complex macromolecules consisting of repeated mono or disac-
charide units linked via glycosidic bonds [43]. They are natural, easily accessible, non-toxic,
and renewable.
Due to their complex structure, polysaccharides exhibit adequate mechanical resistance
and high barrier to oxygen (O2 ) and carbon dioxide (CO2 ). The presence of hydroxyl groups
lead to the formation of hydrogen bonds, responsible for inter–intra macromolecular
association and thus film-forming ability. However, their hydrophilic nature entails poor
moisture resistance and reduced capacity to hinder water vapour transmission [23]. To
overcome these drawbacks, polysaccharides are modified through chemical pathways to
obtain derivatives with enhanced performances or by blending them with hydrophobic
materials and nanofillers.

Chitosan
Chitosan, or β-(l-4)-2-amino-2-deoxy-D-glucopyranose, is a cationic linear polysaccha-
ride consisting of N-acetyl-glucosamine and N-glucosamine units. It derives from alkaline
N-deacetylation of chitin, the second most abundant natural polysaccharide after cellulose.
The primary sources of chitin are shellfish waste, insect cocoons, and fungi [44].
Chitosan is biodegradable, non-toxic, bio compatible, and broadly available. It is
widely used for many applications in the biomedical, cosmetic, agricultural, and food
sectors. The biodegradable property of chitosan results from the sensitivity of glycosidic
bonds to chemical and physical breakdown, mainly due to oxidation and reactivity with
enzymes (hydrolases), acids, and alkali compounds. Due to the absence of nearly positively
charged amino groups, the A-A and A-D glycosidic sections are the preferred targets of
hydrolysis in acidic conditions [45]. In general, it appears that as the acetylation levels
increase, so does the degradation rate. This concept is true even for lysozyme, an enzyme
present in human saliva and tears [46].
Chitosan is insoluble in water but soluble in acid aqueous solutions due to the proto-
nation of the NH2 groups. It exhibits good antimicrobial activity against Gram-positive
and Gram-negative bacteria, filamentous fungi, and yeasts [47].
Chitosan shows excellent film-forming abilities. However, extrusion technology is
inadequate to produce chitosan-based films due to the low degradation temperature of this
Polymers 2022, 14, 4257 7 of 40

polymer and its non-thermoplastic behaviour. As a result, the production of films is mainly
conducted through the solution-casting method.
These films have good mechanical properties and effectively obstruct O2 and CO2
transmission [48]. Meanwhile, they are highly sensitive to moisture transmission, which
compromises their use to preserve fresh or fatty food products. To overcome this criticism,
authors investigated different strategies including chemical crosslinking and grafting
with secondary components [49]. These methods provide an interpenetrated structural
network to the resulting films, improving their hydrophobicity. Another suitable technique
is blending chitosan with compatible polymers to induce a strong inter–intramolecular
hydrogen bonding, which results in improved barrier and mechanical performances of the
blend films [50].

Cellulose and Derivatives

Cellulose, or (1→4)-β-D-glucopyranosyl, is a linear chain polysaccharide in which
anhydrous glucose rings ((C6 H10 O5 ) n) are bound through β1-4 glycosidic bonds, and
the number of repeat units depends on the source material [51]. It constitutes the most
abundant biopolymer in nature and can be degraded by cellulolytic microorganisms. In
nature, the synergism between cellulolytic and non-cellulolytic microorganisms leads to the
complete degradation of this polymer. These microorganisms are mainly aerobic and can
synthesise cellulases enzymes (cellobiohydrolases and endoglucanases), which hydrolyse
the β1-4 glycosidic bonds [52,53].
Native cellulose is water-insoluble due to its structural complexity, high crystallinity,
and tightly packed hydrogen bonds, and is thus unable to form stable gels. This limitation
is overcome by applying an alkali treatment followed by acidification using hydrophilic
agents such as chloroacetic acid, methyl chloride, or propylene oxide to produce cellulose
hydroplastic and thermoplastic derivatives. Cellulose derivatives are commonly isolated
from wood, hemp, cotton, and other plant components [39]. These derivatives have been
extensively investigated to develop biodegradable composites and films
Polymers 2022, 14, x FOR PEER REVIEW  due to their high
8 of 43 
 
abundance, non-toxicity, and stability (Figure 2).

 
Figure 2. Examples of possible applications of monomers of cellulose for polymer production 
Figure 2. Examples of possible applications of monomers of cellulose for polymer production
(reproduced with copyright permission from Shaghaleh et al. [54]). 
(reproduced with copyright permission from Shaghaleh et al. [54]).
Hydroplastic polymers obtained from cellulose are highly hydrophilic and possess 
excellent gelling capacity. They include carboxy methylcellulose (CMC), methylcellulose 
(MC),  hydroxypropyl  methylcellulose  (HPMC),  hydroxypropyl  cellulose  (HPC),  and 
others  [55].  Films  and  coatings  based  on  these  polymers  are  transparent,  odourless, 
resistant  to  oxidation,  and  show  enhanced  mechanical  and  gas  barrier  properties  [19]. 
However, they are highly sensitive to water vapour transmission due to their hydrophilic 
nature, which limits their application to dried and low‐fat foods. In this context, several 
strategies have been investigated to confer hydrophobicity to cellulose‐based films, thus 
Polymers 2022, 14, 4257 8 of 40

Hydroplastic polymers obtained from cellulose are highly hydrophilic and possess
excellent gelling capacity. They include carboxy methylcellulose (CMC), methylcellulose
(MC), hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), and oth-
ers [55]. Films and coatings based on these polymers are transparent, odourless, resistant
to oxidation, and show enhanced mechanical and gas barrier properties [19]. However,
they are highly sensitive to water vapour transmission due to their hydrophilic nature,
which limits their application to dried and low-fat foods. In this context, several strategies
have been investigated to confer hydrophobicity to cellulose-based films, thus reducing
their WVP value. Shahbazi et al. [34] applied surface modification of CMC based films via
reaction with sodium benzoate and glutaraldehyde vapour, followed by photo-crosslinking
or chemical-crosslinking with gelatin. Authors observed that photo-crosslinking improved
hydrophobicity and water barrier property more than the chemical crosslinking. Another
study tested cellulose-based films obtained via chemical crosslinking of CMC with hydroxy
ethylcellulose (HEC) using citric acid [56].
Cellulose acetate is the most researched thermoplastic polymer derived from native
cellulose. This derivative is obtained treating technical-grade cellulose with a methylene
chloride-acetic acid solution to substitute hydroxyl groups with acetyl groups [57]. FDA
tagged cellulose acetate as GRAS, which prompted the food-packaging industry to develop
and test novel applications of this polymer [54]. Cellulose acetate is commonly used to
wrap fresh products and baked goods. Cellulose acetate films and coatings are tough and
resistant to puncture. Conversely, they possess relatively poor moisture barrier properties,
high rigidity, and lower thermal resistance compared with conventional thermoplastics [58].
These criticisms can be partially solved by adding plasticisers, which impart clarity and
tailored rigidity. Moreover, when employed for prolonged applications, cellulose acetate
may undergo partial hydrolysis to produce acetic acid [59].

Starch
Starch represents the primary energy reserve biosynthesised in the plants and one of
the most plentiful renewable feedstocks. Native starch consists of two types of glucose
polymers: amylose, a linear polysaccharide with (1→4)-α-D-glucopyranosyl units, and
amylopectin, branched amylose with (1→6)-α-D-glucopyranosyl side units. Starch has
been extensively studied as a biodegradable plastic and food hydrocolloid component
thanks to its renewability, biodegradability, and excellent film-forming capacity. This
polymer can be easily degraded in water, since amyloglucosidase or α- and β-amylase can
form complexes with starch and hydrolyse the glycosidic linkages [60]. This process is
strongly influenced by pH, the degree of crystallinity of starch, and its retrogradation [61].
Starch-based films and coatings exhibit remarkable mechanical strength, elasticity,
transparency, and low oxygen permeability [15]. The major challenges related to native
starch films are brittleness and high hydrophilicity, which results in poor water vapour
barrier properties. These drawbacks preclude the application of starch-based films and
coatings to package foods sensitive to moisture and oxidation [20]. To enhance the flexibil-
ity and water resistance, food-grade plasticisers (e.g., glycerol, glycol) and hydrophobic
substances can be incorporated into the film-forming solution [47].

Pectin
Pectin is an anionic, hydro soluble, and high-molecular-weight heteropolysaccharide.
It is one of the main components of the plant cell wall, contributing to tissue rigidity
and integrity.
Pectin is chemically composed by poly α-(1→4)-D-galacturonic acid chains [62], com-
monly known as homogalacturonan. Its linear structure is interrupted by rhamnose
residues, on which secondary chains containing galactose, xylose, and arabinose are grafted.
Consequently, pectin is composed of three different polysaccharide domains. The first
domain is the homogalacturonan, which is the smooth component of the molecule. The
second domain is named rhamnogalacturonan I and it is constituted by a chain of α-(1,2)-
 to tissue rigidity and integrity.  
Pectin  is  chemically  composed  by  poly  α‐(1→4)‐D‐galacturonic  acid  chains  [62], 
commonly known as homogalacturonan. Its linear structure is interrupted by rhamnose 
residues,  on  which  secondary  chains  containing  galactose,  xylose,  and  arabinose  are 
Polymers 2022, 14, 4257 grafted. Consequently, pectin is composed of three different polysaccharide domains. The  9 of 40
first domain is the homogalacturonan, which is the smooth component of the molecule. 
The second domain is named rhamnogalacturonan I and it is constituted by a chain of α‐
(1,2)‐linked  L‐rhamnopyranose 
linked L-rhamnopyranose residues.residues. 
The third The  third  one,  rhamnogalacturonan 
one, rhamnogalacturonan II,  is 
II, is characterised
characterised  by  a  complex  and  heterogeneous  structure.  The  second 
by a complex and heterogeneous structure. The second and the third domains form theand  the  third 
domains form the hairy regions of pectin [63] (Figure 3). 
hairy regions of pectin [63] (Figure 3).

 
Figure 3. Comparison between (a) the traditional and (b) the modern pectin model (reproduced with
Figure 3. Comparison between (a) the traditional and (b) the modern pectin model (reproduced 
copyright permission from Willats et al. [64]).
with copyright permission from Willats et al. [64]). 

The carboxyl groups of galacturonic acid are partially esterified with methanol to
form methoxylated groups, and can be converted to amide groups via reaction with
ammonia [44]. According to the esterification degree (DE), pectin can be classified as
 
low-methoxyl (<50%) and high-methoxyl (>50%) pectin. DE strongly influences the gelling
properties of pectin [65].
The main industrial sources of pectin are orange pulp and apple pomace [47]. Pectin
is widely applied in the food industry as a gelling, thickening, and stabilising agent for
jam, drinks, and ice cream. It is recognised as safe (GRAS) by the FDA (2013) and it is
well known for its biocompatibility, good gelling ability, and biodegradability. Degrada-
tion of pectin can be performed through physical (ultrasonication, radiation, photolysis,
high-pressure treatment, etc.), chemical (pH differences of 3.5 allow either acid or alkali
hydrolysis), and enzymatic processes (mainly pectate lyase, pectin lyase, and endo- and
exo-polygalacturonase) [66,67].
The ability of pectin to form edible films and coatings has been largely investigated [63].
Some researchers suggested the scarce potential of pectin as a film-forming polymer due
to its limited physicochemical and mechanical performances [68]. Despite that, several
investigations have been conducted to improve pectin-based filming and coating properties.
To enhance the mechanical stability of the film and the surface adhesion on the food
substrate, pectin has been blended with food-grade plasticisers (e.g., glycerol, polyethylene
glycol, and sucrose) and polymers (e.g., polyvinyl alcohol and cellulose derivatives). As
well, pectin has been combined with hydrophobic compounds such as lipids to enhance its
resistance to moisture and water vapour transmission.

2.2.2. Proteins
Proteins are complex macromolecules characterised by variable molecular structures
and exertion of different functional properties [69]. Protein derivatives are commonly iso-
lated from natural resources and represent promising biopolymers to produce biodegrad-
able packaging with excellent physicochemical, optical, mechanical, and barrier perfor-
Polymers 2022, 14, 4257 10 of 40

mances. In particular, the enhanced capacity of protein-based packaging to control gas

transmission allows hindering the loss of flavours and restricting the migration of ac-
tive components [70]. Besides, protein-based packaging can be easily degraded in the
environment, and acts as a good biofertiliser due to the high nitrogen content [24].
The film-forming ability of protein derivatives strongly depend on their structure (e.g.,
sequence of amino acids, amount of intra-protein interactions), molecular weight, solubility,
and charge [69]. Besides, proteins can be combined with other biopolymers, resulting in
composite films with improved features [71].

Gelatin
Gelatin is a water-soluble protein obtained through the partial hydrolysis of native
collagen, a primary component of bones and connective tissues of animals. This protein
consists of a triple helix structure with repeated glycine-proline-hydroxyproline units. It is
composed by a mixture of α-chains (one polymer/single chain), β-chains (two crosslinked
α-chains), and γ-chains (three crosslinked α-chains), with relevant variability depending on
the source [24]. According to the synthesis method, gelatin is broadly classified as (I) Type A,
derived from acid-treated collagen, and (II) Type B, obtained from alkali-treated collagen.
Among biopolymers, gelatin has the peculiar capacity to form thermo-reversible gels
with a melting point close to 40 ◦ C. This attribute, along with the abundance, prompted
its widespread use in food and pharmaceutical industries as stabilising agent and for the
production of biodegradable packaging [29].
Gelatin-based films exhibit low O2 permeability and acceptable mechanical proper-
ties [72]. Additionally, gelatin can act as a carrier for natural antioxidants and antimicrobial
agents. However, these films are highly sensitive to moisture and permeable to water
vapour due to their hygroscopic behaviour.
Numerous studies have been conducted evaluating the incorporation of crosslinkers,
strengthening nanofillers, plasticisers, vegetable oils (e.g., corn, sun flower, essential oils),
and natural polyphenolic antioxidants as promising methods to improve the performances
of gelatin-based films and to support their bioactivity [42]. In particular, the cross-linking
reaction was found to affect the intermolecular forces within the triple helix structure,
resulting in an interpenetrated network structure of the film matrix (IPN) [27]. More-
over, gelatin has been blended with other biopolymers including chitosan [27] and zein
protein [38] to produce a series of unique hybrid active films. Some studies have found
that crosslinking reduces the biodegradability of gelatin. Instead, blending with highly
hydrophilic polymers enhances the degree of degradability with respect to pure gelatin. In
general, the molecular weight of gelatin typically affects the rate of degradation [27].

Corn Zein
Zein is a prolamin protein mainly isolated from corn seeds. It is an alcohol-soluble
and biodegradable protein, whose hydrophobic nature relies on the high density of non-
polar amino acids [73]. Moreover, it exerts a thermoplastic behaviour and outstanding
film-forming properties [3]. These characteristics make zein a good candidate for the
development of biodegradable packaging items. This protein can be easily degraded in
specific environmental conditions (neutral pH, 50–60% of humidity, temperature over
40 ◦ C) or in presence of proteases, such as trypsin, thermolysin, and pepsin [74].
Zein-based films are smooth, thermally stable, and possess low WVP values [75]. These
attributes are mainly related to the formation of hydrogen and disulfide bonds between
zein chains during solvent evaporation. For this reason, zein-based films can be tailored
to act as selective barriers to oxygen, carbon dioxide, and oils. Despite that, these films
generally exhibit poor mechanical properties and fragility, which can compromise their
wide application. Thus, many strategies have been explored to improve their structural
properties, including the addition of plasticisers and combination with other polymers to
produce bilayer and composite films [15].
Polymers 2022, 14, 4257 11 of 40

2.2.3. Polylactic Acid (PLA)

Polylactic acid (PLA) is a compostable (under industrial conditions), biocompatible,
and thermoplastic aliphatic polyester. This polymer can be completely degraded through
a slow cleavage reaction of ester bonds. The process of biodegradation is carried out by
microorganisms (Actinomycetes, other bacteria, fungi) or by degrading enzymes (proteases,
cutinases, and esterases) [76].
PLA is obtained either through direct polycondensation of L- and/or D-lactic acid
monomers or from the ring-opening polymerisation of lactide monomers. The first pathway
is generally followed to produce low-molecular weight PLA, while the second method is
applied to produce high-molecular weight PLA [20].
PLA is mainly synthetised by microbial fermentation from agricultural renewable
sources such as corn, cassava, sugar beet pulp and sugarcane. Although 90% of total PLA
is obtained by bacterial fermentation, the remaining 10% is synthetically produced by the
hydrolysis of lactonitrile [77]. Currently, the annual production of PLA is estimated to be
140,000 tons, with an increasing trend due to its potential as a substitute for petroleum-based
materials [78].
PLA properties include tensile strength, thermal stability, and gas permeability, and
are comparable to those of synthetic polymers such as polypropylene, polyethylene, and
polystyrene [30]. Moreover, PLA exhibits a better thermal processability compared with
other thermoplastic biopolymers, and thus can be processed through conventional blow
filming, injection moulding, fibre spinning, thermoforming, and cast filming [79].
PLA has been accepted as GRAS by the FDA [31]. As a result, this polymer has been
increasingly employed in the food-packaging industry to produce disposable cutlery, plates,
lids, and other items. Despite that, the high cost and the technical drawbacks, such as
brittleness, low resistance to oxygen, and low degradation rate still deter the mass use of
this polymer [3].
Considerable efforts have been made to improve PLA performances. Different blends
of PLA with other natural biopolymers were tested. For example, blending with thermo-
plastic starch (TPS) enhanced the mechanical properties and the biodegradability rate of
the biopolymer and reduced the production cost [37]. On the other hand, the PLA/PHB
blend obtained by melt blending showed improved oxygen barrier and water resistance
compared with pure PLA.
The addition of plasticisers represents another suitable strategy to improve the PLA
mechanical performances. Thus, the demand for new “green” plasticisers based on natural
and renewable resources such as vegetable oils is rapidly increasing [31].

2.2.4. Polycaprolactone (PCL)

Polycaprolactone (PCL) is a semicrystalline biodegradable but non-renewable biopoly-
mer of synthetic origin. This polymer is synthesised through the polymerisation of ε-
caprolactone at high temperature (over 120 ◦ C) or polycondensation of hydroxycarboxylic
acid, yielding PCL with different degrees of molecular weight based on the alcohols used
as catalysts. The final molecular weight affects the polymer’s properties: low molecular
weight results in a crystalline, brittle, and hard film; high molecular weight results in a
more elastic, tough, and poorly crystalline film [80].
PCL is characterised by its good solubility in organic solvents (i.e., chloroform,
dichloromethane, benzene, tetrahydrofuran, toluene, etc.) at ambient temperature, insolu-
bility in water, and partial solubility in other organic solvents, such as acetone, acetonitrile,
ethyl acetate, and dimethyl formamide. However, the solubility in these last solvents can
be enhanced through heat thanks to the low melting point temperature (60–65 ◦ C) [81]. Al-
though the physical and mechanical qualities are low and influenced by molecular weight,
the barrier properties to oxygen and water vapour are excellent. These characteristics
prompt the possibility to combine this polymer with others to improve its gas barrier
properties for applications in food packaging. Therefore, PCL has attracted the attention
Polymers 2022, 14, 4257 12 of 40

of medical research due to its non-toxicity and potential applications in drug-delivery

systems [82].
PCL is a biodegradable polymer that can be easily degraded through chemical and
enzymatic hydrolysis thanks to the presence of ester groups [81]. The enzymatic method is
preferable due to the rapid reactions that result in a complete polymer degradation in a few
days [83]. The composting of this polymer is particularly efficient due to the heat of the
process, which can support the biodegradation process, and to the enzymes (in particular,
lipase, and esterases) generated by the microorganisms involved in the process [80].

2.2.5. Polyhydroxy Butyrate (PHB)

Polyhydroxy butyrate (PHB) belongs to the family of the polyhydroxy-alkanoates
(PHAs), a series of biodegradable, crystalline, and thermoplastic polyesters synthesised
from microbial fermentation of organic biomass. It is produced by the Gram-positive
bacterium Bacillus megaterium [25].
This polymer cannot be easily degraded by chemical treatments. Instead, it is more
susceptible to thermo-mechanical degradation, oxidation, photodegradation, and enzyme
and biotic degradation. The enzymes usually involved in this process are esterases, lipases,
and proteases, which work through hydrolysis of ester linkage of the polymer. Biotic degra-
dation is carried out mainly by PHB depolymerase, synthesised by Alcaligenes, Pseudomonas,
Comamonas spp., and other species of bacteria, fungi, and algae [84].
PHB exhibits remarkable technical performances, comparable to those of polyethylene
and polypropylene. Moreover, owing to its lamellar structure, it has superior water vapour
barrier properties and a lower carbon footprint than conventional plastics. In fact, it
is easily biodegraded by the action of PHA hydrolases depolymerases, which form (R)-
and (S)-hydroxybutyrates and other non-toxic compounds under aerobic or anaerobic
conditions [85].
These attributes make PHB a sustainable candidate for the replacement of fossil com-
modity polymers for short-term applications. Despite that, some criticisms, i.e., high brit-
tleness, low thermal stability, and reduced processability still limit its widespread use [86].
Many attempts have been made to overcome these limitations. Arrieta et al. [87] blended
PHB with PLA thanks to their comparable melting point temperatures, showing improved
flexibility with respect to pure PHB. Additionally, extensibility can be enhanced by incor-
porating plasticiser or by fabricating composites through the addition of nanofillers [86].

3. Bio-Active Packaging
Food packaging has evolved beyond its use as simple containers and barriers against
external factors. The consumer demand for healthy, safe, and more sustainable products
has prompted scientists and industries to develop packaging materials able to actively
ensure food safety and extend the shelf-life, thus maintaining food quality and taste [88].
This new packaging approach is known as “active packaging” [89].
Active packaging items are designed as “materials and articles that are intended to
extend the shelf-life or to maintain or improve the condition of packaged food; they are
designed to deliberately incorporate components that would release or absorb substances
into or from the packaged food or the environment surrounding the food” (European
regulation [EC] No. 450/2009).
Active food packaging expands the features of traditional packaging, including con-
tainment, protection, preservation, and communication, shifting from a passive defensive
role towards an active role. It acts as a medium of interaction among product, environment,
and packaging itself, altering the native environment of the packed product [90]. Depend-
ing on its functioning mode, active packaging can be classified under two major categories:
scavenging and emitting systems. Scavengers are materials that absorb undesirable sub-
stances from the internal packaging environment, including moisture, oxygen, carbon
dioxide, ethylene, and odours/flavours. Conversely, emitters are designed to discharge
specific substances with desirable properties to produce a positive impact in the packaging
Polymers 2022, 14, 4257 13 of 40

headspace [91]. These active compounds can be either part of the packaging material or
enclosed inside the package, separated from the packed food. The advantages related to
the first solution are (I) no possible manipulation by the consumer, decreasing the chance
of contamination; and (II) the packaging is produced with conventional equipment, de-
creasing the complexity of the process (Figure 4). Some substances commonly added to the
packaging system are antioxidant and antimicrobial agents, enzymes, aromatic compounds,
nutraceuticals, and pre- or pro-biotics. Among these, antimicrobial and antioxidant active
compounds (either synthetic or natural-based) have been recognised as the most attrac-
tive ones to be incorporated into packaging systems, since microbial spoilage and lipid
Polymers 2022, 14, x FOR PEER REVIEW  14 of 43 
 
oxidation are considered as the two major causes of food deterioration [92].

 
Figure 4. Application of different bioactive compounds in active packaging (reproduced with
Figure 4. Application of different bioactive compounds in active packaging (reproduced 
copyright permission from Vilela et al. [93]).
with copyright permission from Vilela et al. [93]). 
3.1. Antimicrobial Packaging
3.1. Antimicrobial Packaging 
Antimicrobial packaging has received increasing attention from food and packaging
industries as a valuable alternative to thermal treatments to control the growth and avoid
Antimicrobial packaging has received increasing attention from food and packaging 
the spread of targeted pathogenic and spoilage microorganisms [20].
industries as a valuable alternative to thermal treatments to control the growth and avoid 
Concisely, antimicrobial packaging is obtained by incorporating an antimicrobial agent
the spread of targeted pathogenic and spoilage microorganisms [20].  
in the packaging material [18]. This represents a potential alternative to the direct addition
Concisely,  antimicrobial  packaging  is  obtained  by  incorporating  an  antimicrobial 
of bioactive agents into or on the surface of food, which could lead to the immediate deple-
agent in the packaging material [18]. This represents a potential alternative to the direct 
tion of the antimicrobial functionality [94]. In this sense, antimicrobial packaging can exert a
addition  of  bioactive  agents  into  or  on  the  surface  of  food,  which  could  lead  to  the 
controlled release of the antimicrobial compounds, whose migration kinetics depend upon
immediate  depletion 
different factors such as of the
the molecular
antimicrobial functionality  [94].  In and
structures of the polymer this antimicrobial
sense,  antimicrobial 
com-
packaging  can  exert  a  controlled  release  of  the  antimicrobial 
pounds, the physicochemical characteristics of the packaging item, and the environmental compounds,  whose 
migration kinetics depend upon different factors such as the molecular structures of the 
conditions, both internal and external [18]. In this context, the design of an antimicrobial
polymer  and 
packaging system antimicrobial  compounds, 
is complex, since it requires the  physicochemical 
a thorough knowledge of characteristics  of  the 
five major factors:
packaging item, and the environmental conditions, both internal and external [18]. In this 
the food product; the internal package atmosphere; the targeted microorganisms; the pack-
context, the design of an antimicrobial packaging system is complex, since it requires a 
aging material; and the antimicrobial agent [95]. Different approaches have been explored
thorough 
for knowledge 
the development of  five  major 
of bio-based factors: packaging,
antimicrobial the  food  asproduct; 
shown in the  internal 
Table package 
2 (Figure 5).
According to their structure and production process, antimicrobial packaging systems can
atmosphere; the targeted microorganisms; the packaging material; and the antimicrobial 
be categorised
agent  into fiveapproaches 
[95].  Different  classes [91].have 
The first
been class consists
explored  ofthe 
for  antimicrobial
development  sachets which
of  bio‐based 
are included in the package, and gradually release the active compound
antimicrobial packaging, as shown in Table 2 (Figure 5). According to their structure and during the storage
period. In the second class, the active molecules are directly blended in the polymer matrix
production process, antimicrobial packaging systems can be categorised into five classes 
to produce antimicrobial items. The third class of antimicrobial packages are obtained
[91]. The first class consists of antimicrobial sachets which are included in the package, 
by adsorbing a specific matrix, serving as a carrier of the antimicrobial additive, onto
and gradually release the active compound during the storage period. In the second class, 
the active molecules are directly blended in the polymer matrix to produce antimicrobial 
items.  The  third  class  of  antimicrobial  packages  are  obtained  by  adsorbing  a  specific 
matrix, serving as a carrier of the antimicrobial additive, onto the packaging surface. This 
production  method  overcomes  the  disadvantages  related  to  the  second  class,  since  the 
Polymers 2022, 14, 4257 14 of 40

the packaging surface. This production method overcomes the disadvantages related to
the second class, since the active compounds are not exposed to high temperatures and
shearing forces related to the production process. In the fourth class, the antimicrobial
agent is immobilised on the polymer matrix through ionic or covalent bonds between their
functional groups. In this case, polymers and additives should share compatible functional
groups, and the release of the active agent from the matrix largely depends on the type of
bonding. The fifth class of antimicrobial packaging involves the application of polymers
with intrinsic antimicrobial properties (e.g., chitosan). This approach requires direct contact
between the packaging material and the food product for effective inhibition, which could
be considered a limiting factor for two reasons: inhibition process is restricted to superficial
contact layers; and the polymer must be approved as a food additive [96].

Table 2. Antimicrobial compounds and their efficacy against food-borne pathogenic micro-organisms.

Solvents for the

Antimicrobial Compounds Polymers The Effects and Advantages Microorganisms Efficacy References
Antimicrobial Compounds
• The active coating decreased the microbial charge by 3 logs
after 4 days of storage
Citric acid 0.5–1% (w/w) Gelatin 2% (w/v) Distilled water Total bacterial count(TBC) + [88]
• Citric acid helped avoiding lipid oxidation and keeping the
pH at values lower than the control
• The bacteriocins were effective against L. innocua but did not Lactobacillus plantarum -
L. curvatus CRL705 Wheat gluten Distilled water affect L. plantarum CRL691, probably due to the high concen- [97]
bacteriocins Listeria innocua +
tration of fat in wieners
Listeria monocytogenes -
Microfluidiser apple skin • The ASP/CMC film showed good inhibition zone against
extract (ASP) 1:1 (v/v of the Salmonella enterica and Shigella flexneri regardless of the con- Staphylococcus aureus -
0.75% CMC Distilled water [98]
polymer) and tartaric acid centration
(TA) 0.5–1% Salmonella enterica +

Shigella flexneri +

HPMC 3% (w/w) in a • The film of HPMC with nanoparticles showed antibacterial Escherichia coli +
PVA-coated silver properties against gram-positive S. aureus
AgNPs of 41 and 100 nm Distilled water [99]
nanoparticles solution • The size of nanoparticles seemed to be influenced by this Staphylococcus aureus +
property

Nisin (N), glutaraldehyde Stainless steel • Antimicrobial activity of SDGN and SDAN against L. mono-
/ Listeria monocytogenes + [100]
(G) and succinic acid (A) (S)/polydopamine (D) cytogenes

Murta berry extract (MU)

25% (w/w of the polymer), Methyl cellulose (MC) 1% • All the films were effective against Listeria
Ethanol solution 70% • In the presence of MU, the reduction percentage of the mi- Listeria innocua + [28]
glutaraldehyde (GA) (w/v)
10–20% (w/w of polymer) croorganism was 99.9%

S. aureus +

E. coli +
• The best results were represented by CS and CT1-UV, due
TiO2 nanopowders 0–2% to the intrinsic antimicrobial property of CS and the photo- P. aeruginosa +
Chitosan 2% (w/v) Distilled water [101]
(w/w) catalysis of TiO2 that happens in presence of UV-light
S. typhimurium +

Aspergillus spp. +

Pennicillium spp. +
• The percentage of clay composite did not influence the an- Listeria monocytogenes +
timicrobial effect
Whey Protein Isolate (WPI) Clay composite 5–20% Distilled water [102]
• WPI had a bacteriostatic effect on gram-positive bacteria Escherichia coli -
such as Listeria monocytogenes

Nisin (N) 0.25–0.5% (w/w) Corn distarch phosphate 3% • N showed a better antimicrobial property against S. aureus, S. aureus +
and ε-polylysine (PL) 0.2% (w/w),nanocellulose 0.5% Distilled water PL against E. coli [103]
(w/w) (w/w), CMC 0.8% (w/w) • The combination of the two compounds gave the better re- E. coli +
sult

Nisin 105 IU/mL in 0.02 M Chitosan 1% (v/v), gelatin • The blend between chitosan and gelatin showed a good an-
HCl, Grape seed extract Distilled water timicrobial property related to the polymers Total Viable Count (TVC) + [104]
3% (v/v)
0.5% (w/v)

Cellulose nanocrystal (CNC) • LNP was effective against P. syringae pv. omato (Pst), even at
PLA grafted with GMA at Pseudomonas syringae pv.
1% and lignin nanoparticle / + [105]
15% (w/w of the polymer) the concentration of 106 CFU/mL tomato
(LNP) 3%

Polyvinyl alcohol (PVA) • CO was particularly effective against S. aureus, slowing S. aureus +
Clove oil (CO) 20% (w/w of
5–12.5% (w/v) cross-linked Distilled water down the growth of 0.13 OD with respect to the control [40]
the polymer) E. coli +
with citric acid (CA) 3–12% • CO was less effective against E. coli
(w/w of the polymer)

Escherichia coli +
Cedrus deodara pine needle
extract (PNE) 15% (w/w • SL film had good activity against all the pathogens tested in
Soy protein isolate (SPI) 6% Salmonella typhimurium +
of SPI) and cellulose Distilled water this experiment, gram-positive and negative. [106]
(w/v) • PNE showed a significant antimicrobial property
nanofibril (CNF) 15% (w/w Staphylococcus aureus +
of SPI)
Listeria monocytogenes +

Escherichia coli +
• Synergistic effect between CS- TiO2 - BPPE with the highest
Nanosized TiO2 1% (w/v) Staphylococcus aureus +
value of antimicrobial activity
and black plum peel extract Chitosan 2% (w/v) Distilled water [75]
• All the compounds showed good efficiency against all the
(BPPE) 1% (w/v) Salmonella spp. +
tested microorganisms
Listeria monocytogenes +
 nanofibril (CNF) 15%   PNE showed a significant 
(w/w of SPI)  antimicrobial property  Listeria 
+ 
monocytogenes 
 Synergistic effect between CS‐  Escherichia coli  + 
Nanosized TiO2 1%  TiO2‐ BPPE with the highest  Staphylococcus 
+ 
(w/v) and black plum  value of antimicrobial activity  aureus 
Chitosan 2% (w/v)  Distilled water  [75] 
peel extract (BPPE) 1% 
Polymers 2022, 14, 4257  All the compounds showed  Salmonella spp.  +  15 of 40
(w/v)  good efficiency against all the  Listeria 
tested microorganisms   + 
monocytogenes 

 
Figure 5. Different applications of green antimicrobial compounds to polysaccharide-based packaging
Figure 5. Different applications of green antimicrobial compounds to polysaccharide‐based 
(reproduced with copyright permission from Zhao et al. [107]).
packaging (reproduced with copyright permission from Zhao et al. [107]). 

Antimicrobial compounds belong to several categories of molecules, either synthetic

or extracted from plant, animal, and microbial biomasses [33]. All these classes of molecules
have been successfully integrated into bio-based packaging, with promising results against
  pathogenic and spoilage bacteria and fungi [3].

3.1.1. Essential Oils (EOs)

Essential oils (EOs) are aromatic secondary metabolites which are present in various
plants. They consist in complex oily blends of 20–60 components, extracted from different
plant parts including roots, leaves, flowers, and bark. They are extracted through solvent
extraction, distillation, cold pression, and non-conventional technologies (e.g., microwaves;
ultrasounds; supercritical fluids) [108]. The composition of EOs includes monoterpenes and
sesquiterpenes as the predominant components, followed by phenolic acids, aldehydes,
ketones, and terpenoids. Due to the presence of various active molecules, EOs have been
reported to exert a broad number of biological activities [3].
The biocidal action of EOs is exerted through different pathways. However, it is
commonly agreed that the main target of EOs is the cytoplasmic membrane of the microbial
cell [109]. Since EOs are hydrophobic, their presence induces a change in the structure and
fluidity of the cell membrane (Figure 6). This process triggers a cascade of chain reactions,
resulting in internal pH disorder, electrical potential alteration, and impairment of the
sodium-potassium pump, ultimately culminating in cell death [110].
Several studies, listed in Table 3, investigated the ability of EOs, either free or incorpo-
rated in biodegradable packaging, to impede the growth of Gram-positive bacteria (e.g.,
S. aureus; L. monocytogenes), Gram-negative bacteria (e.g., Aeromonas hydrophila; E. coli, S.
enterica, Campylobacter jejuni, Pseudomonas aeruginosa) and fungi (Fusarium spp.; Aspergillus
spp.; Penicillium spp.) [50,111,112]. These studies highlighted that the antimicrobial effec-
tiveness of EOs depends on their specific composition and source, as well as the defensive
strategies fielded by the microorganisms [18].
 acids,  aldehydes,  ketones,  and  terpenoids.  Due  to  the  presence  of  various  active 
molecules, EOs have been reported to exert a broad number of biological activities [3].  
The  biocidal  action  of  EOs  is  exerted  through  different  pathways.  However,  it  is 
commonly  agreed  that  the  main  target  of  EOs  is  the  cytoplasmic  membrane  of  the 
microbial cell [109]. Since EOs are hydrophobic, their presence induces a change in the 
Polymers 2022, 14, 4257 structure and fluidity of the cell membrane (Figure 6). This process triggers a cascade of  16 of 40
chain  reactions,  resulting  in  internal  pH  disorder,  electrical  potential  alteration,  and 
impairment of the sodium‐potassium pump, ultimately culminating in cell death [110].  

 
Figure 6. Effect of EOs on cellular membrane and target sites (reproduced with copyright permission
Figure 6. Effect of EOs on cellular membrane and target sites (reproduced with copyright 
from Nazzaro et al. [109]).
permission from Nazzaro et al. [109]). 

Several  studies,  listed  in  Table  3,  investigated  the  ability  of  EOs,  either  free  or 
Table 3. EOs and their activity through incorporation in packaging.
incorporated in biodegradable packaging, to impede the growth of Gram‐positive bacteria 
EOs and Plants Extracts (e.g.,  S.  aureus;  L.  monocytogenes), 
Polymers Solvents forGram‐negative 
EOs bacteria 
The Effect(e.g.,  Aeromonas  hydrophila; 
and Advantages E. 
References
coli,  S.  enterica,  Campylobacter  jejuni,  Pseudomonas  aeruginosa)  and  fungi  (Fusarium  spp.; 
Rosemary EO at 0.5, 1.0, and • Significant antioxidant activity of EO
1.5% (v/v)
Aspergillus 
Chitosan spp.;  Penicillium 
2% (w/v) spp.) 
Distilled water [50,111,112]. 
• These 
EO studies 
increased WVP andhighlighted 
transparency that  the 
[113]
• EO reduced UV transmittance
antimicrobial effectiveness of EOs depends on their specific composition and source, as 
Extracts of cinnamon, • Extracts increased gloss and mechanical
well as the defensive strategies fielded by the microorganisms [18].  
Blend of gelatin 4% and property
guarana, rosemary and Absolute ethanol [114]
  boldo-do-chile   1% (w/v)
chitosan • GEL50:CH50 enhanced antioxidant and
antimicrobial properties.
• E improved UV-vis light barrier and me-
Eugenol (E) and ginger (G) Blend of gelatin 4% and chanical properties
Distilled water [115]
EOs (0.5 g/g biopolymer) chitosan 1% (w/v) • E showed the greatest resistance to oxi-
dation
• EOs inhibited more than 95% of mycelial
EOs of Cinnamomum ssp.
Chitosan Ethanol growth of M. canis at 200 µg mL−1 , 100% [116]
and Syzygium aromaticum
  over 400 µg mL−1

D-Limonene and terpenes • Nanoencapsulated terpenes at 1.0 g/L

from Melaleuca alternifolia / Sunflower oil and palm oil delayed the microbial growth of L. del- [117]
(25 g/L to 0.1 g/L) brueckii, at 5.0 g/L and completely inac-
tivated the microorganism in fruit juices
• Compatibility between polymers and
Cinnamon, citronella, pink EOs
clove, nutmeg and thyme Chitosan 2%, gelatin 2% (w/v) Distilled water • EOs improved UV barrier properties [111]
EOs at 1% (v/v) • Efficient antimicrobial properties for
thyme EO against common food
pathogens.
• EO gave antimicrobial properties
Cinnamon essential oil (EO) Sodium alginate 0.75%, CMC against E. coli and S. aureus
Distilled water [55]
5–15 g/L 0.25% • EO enhanced hydrophobicity of the film,
thickness, E%, and decreased TS
Polymers 2022, 14, 4257 17 of 40

Table 3. Cont.

EOs and Plants Extracts Polymers Solvents for EOs The Effect and Advantages References
• High temperature activated the film for
Cinnamaldehyde 5.33% Chitosan 1.5% Ethanol 96% the release of the antimicrobial com- [49]
pound that effectively inhibited L. mono-
cytogenes in milk
• EO increased elasticity of the film and
Origanum vulgare L. EO Chitosan nanoparticles ensured a good antimicrobial property
Distilled water against S. aureus, L. monocytogenes, S. en- [118]
0.4–1.2%, (w/v) (CSNPs) and fish gelatin 4%
teritidis, and E. coli at the concentration
of 1.2%

Mucilage from quince seeds • Antimicrobial activity against gram-

Oregano EO 0–2% (v/v) Distilled water positive bacteria (S. aureus, L. monocyto- [119]
1%
genes) at a concentration higher than 1%

• 10% concentration was effective against

gram-positive and gram-negative bacte-
ria and did not change the film charac-
Carvacrol 0–10% (w/v of the Cellulose acetate (CA) 5% teristics, except for the degree of crys-
Acetone [120]
polymer) (w/v) tallinity and glass transition tempera-
ture
• CA-carvacrol enhanced three times the
shelf life of cooked ham
• EO at different percentages modulated
Oregano essential-oil the mechanical property of the film
Hydroxypropyl
nanoemulsion (ORNE) Distilled water • ORNE improved UV barrier property [121]
methylcellulose (HPMC) 2.5%
0–7.5% (v/v) and showed activity against all the
tested microorganisms
• EO gave antioxidant and antimicrobial
Oregano essential-oil properties to the film
nanoemulsion (ORNE) Fish gelatin 3%, Chitosan 2% Distilled water • EO positively influenced light barrier [122]
0–7.5% (v/v) and water vapour barrier property
(WVP), elasticity and thickness

Chitosan nanofibre (CSNF) • CSNF and EO synergised together, giv-

Molten cocoa ing a hydrophobic characteristic to the
Cinnamon EO emulsified in Nanostructured [123]
butter film
lipid carriers (NLC)
• EO opacified the film
• EO improved the thermal stability of the
Clove bud EO 0–1.5% Pectin 3% (w/v) Distilled water film. [124]
• Efficiency of EO against gram-positive
bacteria in agar disc-diffusion assay.
Lecithin:cholesterol (60:0,
50:10, 40:20, and 30:30) • Nano-encapsulated EO provided a good
Satureja khuzestanica Jamzad dissolved in extension of the shelf-life of meat lamb
Methanol products, decreasing the microbial count [125]
EO 1% dichloromethane/methanol
(1:1), added to chitosan 2% during storage
(w/v) • EO provided antioxidant property

• High antioxidant activity due to the

presence of EOs of plants related to Thy-
mus spp., with a higher value for the TP
T. moroderi (TM) and T.
extract
piperella (TP) extracted EOs Chitosan 2% (w/v) Distilled water [126]
• Concentrations of 1–2% were effective
0.5–2% (v/v)
against all the microorganisms, probably
due to the presence of carvacrol or cam-
phor in the EOs, as bioactive compounds

• Thyme oil was the best option among

Clove bud, tagetes, thyme, the tested EOs, giving a good antimicro-
poly(3-hydroxybutyrate-co-4- bial property to the film at 30% with the
eucalyptus, neem, cinnamon
hydroxybutyrate) Chloroform absence of mould [127]
leaf, himalayan pine needle,
4% • EOs acted as a plasticiser for the poly-
tea tree EOs 0–40% (v/w)
mer and increased the WVP and elonga-
tion at break (%).
Plant EOs extracted from
Cinnamomum cassia Presl,
Litsea cubeba, Cymbopogon • Cinnamomum cassia Presl,
martini, Thymus mongolicus • Litsea cubeba, Cymbopogon martini
Ronn, Syringa Linn., and Thymus mongolicus Ronn were the
/ / EOs with the best antifungal activities, [112]
Lavendula angustifolia Mill.,
Foeniculum uulgare Mill, Citrus probably due to the presence of trans-
reticulata Banco, Mentha cinnamaldehyde, citral, trans-geraniol,
haplocalyx Briq., Allium and carvacrol, respectively.
sativum and Artemisia argyi
 Cinnamomum cassia Presl, Litsea 
cubeba, Cymbopogon martini,   Cinnamomum cassia Presl, 
Thymus mongolicus Ronn, Syringa   Litsea  cubeba,  Cymbopogon  martini  and  Thymus 
Linn.,  mongolicus  Ronn  were  the  EOs  with  the  best 
/  /  [112] 
Lavendula angustifolia Mill.,  antifungal activities, probably due to the presence 
Foeniculum uulgare Mill, Citrus  of  trans‐cinnamaldehyde,  citral,  trans‐geraniol, 
Polymers 2022, 14, 4257 18 of 40
reticulata Banco, Mentha haplocalyx  and carvacrol, respectively. 
Briq., Allium sativum and 
Artemisia argyi 

The most common EOs which are applied as active agents in food packaging include
The most common EOs which are applied as active agents in food packaging include 
cinnamon (cinnamaldehyde) [123], rosemary [128], ginger [115], oregano [121], tea tree [35],
cinnamon (cinnamaldehyde)  [123],  rosemary [128],  ginger  [115],  oregano  [121],  tea tree 
citrus [122], and thyme [127] (Figure 7).
[35], citrus [122], and thyme [127] (Figure 7). 

 
Figure 7. Radial disk diffusion assay on (A) lettuce microflora film of control; (B) film with 10%
Figure  7. Radial  disk  diffusion  assay  on  (A)  lettuce  microflora  film  of control;  (B) film with  10% 
thyme essential oil in the presence of Escherichia coli and (C) film with 15% thyme essential oil against
thyme essential oil in the presence of Escherichia coli and (C) film with 15% thyme essential oil against 
broccoli microflora (reproduced with copyright permission from Chen et al. [24]).
broccoli microflora (reproduced with copyright permission from Chen et al. [24]). 

All these studies demonstrated that the presence of EOs can remarkably affect the
All these studies demonstrated that the presence of EOs can remarkably affect the 
structure of the
structure  of  the packaging
packaging material,
material, either
either improving
improving oror worsening
worsening the technical
the  perfor-
technical 
performances by interacting with the polymer matrix and the plasticisers [111]. Besides,  their
mances by interacting with the polymer matrix and the plasticisers [111]. Besides,
antimicrobial effect can be compromised by the fast release of volatile compounds. Fur-
their antimicrobial effect can be compromised by the fast release of volatile compounds. 
thermore, EOs may also influence the organoleptic attributes of foods [129]. A strategy to
solve these issues is represented by the micro or nanoencapsulation of EOs and subsequent
addition to the polymer matrix. This process allows performing a controlled delivery of
 
the bioactive compounds and avoiding an excessive impact on the sensorial profile of
food [121].

3.1.2. Animal-Derived Polypeptides

Polypeptides are the most common animal-derived antimicrobial compounds. They
are mainly secreted as a defence mechanism against bacterial spread [130].
Lysozyme is an animal-derived enzyme which was recognised as GRAS for direct
inclusion in food matrices [131]. It is stable over broad ranges of temperature (4–95 ◦ C)
and pH (2–10). The biocidal activity of lysozyme has been tested against a wide range of
pathogens and spoilage bacteria, finding its main effectiveness on Gram-positive bacteria
such as Clostridium tyrobutyricum and L. monocytogenes [132].
Lysozyme expresses its antibacterial activity by disrupting the peptidoglycan layer
of bacterial cell walls, achieved through the hydrolysis of the bond between N-acetyl-d-
glucosamine and N-acetyl-muramic acid [133]. This specific mechanism makes lysozyme
extremely effective against gram-positive bacteria, while the lipo-polysaccharidic layer
of Gram-negative bacteria inhibits its access to the site of action. Many studies have
suggested the possibility to expand the lysozyme activity by modifying its molecular
structure through different pathways including covalent attachment of saturated fatty acids
to lysine residues, thermal denaturation, glycosylation, reduction of disulfide linkages, and
application of chelating molecules [134]. Nowadays, lysozyme is mainly used to challenge
undesired butyric fermentation and late blowing caused by C. tyrobutyricum in semi-hard
cheeses [135].
Lactoperoxidase is another animal-derived enzyme, secreted in the epithelial cells
of the mammary gland and largely present in cow’s milk [136]. It is extremely effective
against enteric bacteria including Salmonella spp., Shigella spp., and E. coli. It catalyses the
oxidation of thiocyanate groups by hydrogen peroxide to yield thiocyanogen, which is
then hydrolysed to hypothiocyanite. These unstable molecules react with the sulfhydryl
groups of the bacterial cell membrane proteins, causing microbial death. This enzyme can
Polymers 2022, 14, 4257 19 of 40

be applied at ambient temperature, and thus is recommended for the preservation of raw
milk [137].
Lactoferrin is a globular glycoprotein exerting antioxidant, anti-carcinogenic, anti-
obesity, and antibiotic properties. It is found in secretions of humans and other mammalians
and in colostrum milk [138]. The antimicrobial activity of lactoferrin is due to its ability to
chelate iron, disrupting the external membrane of gram-negative bacteria. Along with the
biocidal activity, lactoferrin exerts a bacteriostatic action, decreasing the microorganisms’
proximity to nutrients. It resulted as effective against many pathogenic bacteria such as E.
coli, Klebsiella spp., and L. monocytogenes [139].

3.1.3. Antagonistic Microorganisms and Bacteriocins

Some microorganisms and their metabolites can prevent the growth of others. This
ability has attracted the attention of researchers and industries, eager to apply them as a
“natural shield” to the growth of pathogenic and spoilage microorganisms in food. Nowa-
days, the application of “antagonistic microorganisms” and their derivatives for preserving
food has become widespread, and it is commonly referred to as “bio-preservation” [140].
The prominent class of antagonistic microorganisms employed in food systems are
the Lactic Acid Bacteria (LAB). LAB have been defined as GRAS by the FDA and have
obtained the Qualified Presumption of Safety (QPS) by the European Food Safety Authority
(EFSA) [141].
The use of LAB to compete against undesired microorganisms has been investigated,
along with their ability to produce nutrients and metabolites with antimicrobial properties.
Successful results were achieved by applying them to fruit and vegetables [142], fresh dairy
products [143], and cooked meat [144]. In these studies, different species of Lactobacillus
showed their capacity to thrive in competition with bacterial (e.g., L. monocytogenes) and
fungal (e.g., Penicillium spp.) populations.
Bacteriocins are proteinaceous metabolites mainly produced by LAB as a defence
mechanism against other microbial strains. Their promising application has been assessed
on a wide range of food products, including minimally processed fruits and vegetables,
dairy products, meat and fish. In particular, their maximal potency is expressed when com-
bined with other technologies through a hurdle approach [110]. Nisin and pediocin are the
major bacteriocins that have received attention as promising food bio-preservatives [133].
Nisin is a heat-stable protein produced by specific Lactococcus lactis strains. It possesses
a strong antibacterial activity against Gram-positive bacteria such as Staphylococcus, Bacillus
cereus, Clostridium spp., L. monocytogenes, and others. However, it exhibits a lower inhibiting
activity against Gram-negative bacteria and fungi [145]. In fact, nisin hinders the growth
of Gram-positive cells by binding to specific groups of the cell wall, which results in the
poration of the cell membrane and the loss of intracellular constituents [146]. Nisin found
one of its most promising applications in controlling the populations of L. monocytogenes
and Clostridium spp. in dairy products [147].
Pediocin is produced by different species of Pediococcus, a group of Gram-positive,
homofermentative bacteria belonging to the family of Lactobacillaceae. Pediocin acts by
generating holes in the cytoplasmic membrane of the target cells, reducing the intrinsic pH
and inhibiting the proteins responsible for energy production [148]. The addition of con-
centrated pediocin has been tested for the preservation of vegetables, dairy products [149],
and processed meat [150]. The activity of pediocin in food is mainly influenced by pH,
osmotic equilibrium, enzyme activity, and temperature.
Bacteriocins have been applied as antimicrobial additives incorporated in active pack-
aging. For example, nisin has been successfully employed in antimicrobial films (both
petroleum-derived and bio-based), used to wrap raw and processed meat, and tested
against Listeria spp. [97]. Moreover, its impact on the technical properties of biodegradable
films was evaluated in a recent study [103].
Polymers 2022, 14, 4257 20 of 40

3.2. Antioxidant Packaging

Antioxidant packaging represents another trend category of active packaging. In this
case, packaging is enriched with active compounds able to delay the oxidation rate of the
packed products [16].
With respect to the food sector, the activity of an antioxidant agent is mainly addressed
to suppress the ignition of lipid oxidation chain reactions, which naturally occurs within
biological matrices. This process causes the gradual alteration and decay of colour (en-
zymatic oxidation), odour, and flavour (oxidative rancidity), structure (softening), and
nutrients [151]. Antioxidants strongly differ from each other for their reaction pathways.
Some molecules act as “direct” antioxidants, reacting with intermediate peroxyl radicals
and blocking the subsequent reactions (e.g., glutathione, ascorbic acid, polyphenols). Other
molecules act as “preventative” antioxidants, binding cationic metals such as Fe (II) and
Cu (II) (e.g., albumin) [4]. According to their molecular nature and reactive mechanism,
antioxidants can be employed to produce release-type packaging, which transfers the active
substance to the food surface at a sustainable rate, or scavenging-type packaging, which
sequesters target radicals and ions without affecting the food composition [23].
The development of an antioxidant packaging system starts with the selection of
the bioactive agent, which must comply with two requirements: (I) suitability for the
target product to-be-preserved, and (II) compatibility with the polymer matrix to achieve a
homogeneous distribution of the substance in the packaging item [152]. Focusing on bio-
based and edible packaging, antioxidant films and coatings are mainly obtained through
direct incorporation of the active molecule in the biopolymer matrix. Other techniques
involve the functionalisation of the packaging material via physical (e.g., encapsulation) or
chemical (e.g., crosslinking, plasticiser addition) processes, which affect the adhesion of
the active compounds to the polymer matrix. These processes allow tailorising the rate of
release and/or the scavenging mechanism of the active molecule, adapting the materials
for a broad range of applications [153].
A broad variety of antioxidants have been evaluated for the development of active
packaging, as shown in Table 4. The current trend is focused on replacing synthetic
additives with natural and harmless alternatives.

3.2.1. Natural Antioxidants

Natural antioxidant molecules can be mainly categorised into three sub-groups: (I) vi-
tamins (e.g., ascorbic acid; α-tocopherol), (II) carotenoids (e.g., carotenes; xantophylls), and
(III) phenolic compounds.
Polyphenols constitute the most popular and important group of naturally occurring
antioxidant compounds employed for the production of active packaging due to their
strong free-radicals scavenging effect [154].
The antioxidant activity of polyphenols is commonly ascribed to single-electron trans-
fer and hydrogen transfer mechanisms, which allow the active molecule to react with active
radical species of the matrix, producing stable and harmless oxidised molecules.
Related to their composition, polyphenols can be classified into (ii) non-flavonoids
and (ii) flavonoids. Among them, flavonoids are the most largely studied for packaging
applications due to their strong antioxidant activity. Flavonoids are present in the form of
flavonols, flavones, isoflavones, anthocyanins, and others. Most of them are polar, which
makes them compatible with most of the hydroplastic polymers, and extracted through
protic solvents (e.g., water, ethanol, methanol, isopropanol) from non-edible portions of
fruit and vegetable by-products, such as peels and seeds [155].
Polymers 2022, 14, 4257 21 of 40

Table 4. Case studies of antioxidant compounds applied to food packaging for the prolongation of
the shelf-life.

Solvents of Antioxidant
Antioxidant Compounds Polymers The Effects and Advantages References
Compounds
Catechin (2% or 5%) or green • Better stability against thermal oxida-
Polypropylene / [153]
tea extract (2% or 5%) tion 6 times higher than the control
Microfluidiser apple skin
extract (ASP) 1:1 (v/v of the • ASP enhanced the antioxidant activity at
0.75% CMC Distilled water every concentration, but 2% was the best [98]
polymer) and tartaric acid
(TA) 0.5–1% one

• Absence of radical scavenging activity

Murta berry extract (MU) 25% for control without MU
(w/w of the polymer), Methyl cellulose (MC) 1% • GA decreased antioxidant activity at
Solution in ethanol 70% (v/v) [28]
glutaraldehyde (GA) (w/v) higher concentration
10–20% (w/w of polymer) • MU increased the release of antioxidants
from films by up to 50%
Chitosan 2% (w/w) and pea
Thyme extract (TE) with a starch 2% (w/w) solutions • TE had an antioxidant activity of
Ethanol 50% [36]
ratio of 0.04:1 on the polymer blended together in a ratio of 0.26 ± 0.02 kg TE/mol DPPH
1:4 w/w
Zein (Z) 15% (w/v), gelatin (G)
10% (w/v), blend ZG at • Tea polyphenol-loaded film inhibited
Tea polyphenol 2.5–7.5% w/w Acetic acid (AA) and water microbial growth and improved water [38]
different ratios (2:1, 1:1, 1:2)
15% (w/v) retention on freshly cut fruits.

• PNE is rich in phenolic compounds,

Cedrus deodara pine needle such as 2R,3R-dihydromyricetin,
extract (PNE) 15% (w/w of Soy protein isolate (SPI) 6% myricetin-3-O-ß-D-glucopyranoside
Distilled water [106]
SPI) and cellulose nanofibril (w/v) and protocatechuic acid, that gave
(CNF) 15% (w/w of SPI) antioxidant activity to SLE and SLEC
films
• CS and CS-TiO2 showed only a slight an-
tioxidant activity
Anthocyanins from black • CS-BPPE showed a better radical scav-
Chitosan 2% (w/v)Nanosized
plum peel extract (BPPE) Distilled water enging activity due to the anthocyanins [75]
TiO2 1% (w/v)
1% (w/v) • CS-TiO2 - BPPE exhibited an intermedi-
ate result due to the antagonistic interac-
tion between TiO2 and BPPE

Generally, polyphenols are not employed in active packaging singularly, but mostly
exist as complex mixtures which include aqueous and alcoholic plant extracts, essential
oils from spices and herbs, and a broad variety of phenolic concentrates obtained from
various waste bio-sources [156]. For this reason, the overall antioxidant activity of these
products not only refers to their polyphenolic content, but it strongly depends on their
source, chemical composition, and extraction process [157].

3.2.2. Plant Extracts

The inclusion of plant extracts, as complex systems containing numerous molecular
components, has the potential to functionalise bio-based packaging materials with an-
tioxidant bioactivity. These mixtures are isolated from several botanical sources through
solvent-extraction technology. The extraction efficiency, and thus the phenolic content of the
extracts, can be varied by changing the operational parameters, such as time, temperature,
solvent type, solvent concentration, and pH [155]. Moreover, physical processes such as
microwave, ultra-sonication, and milling allow further enhancing the extraction rate of
these antioxidants [158].
The main vegetal sources of polyphenolic extracts used in food packaging comprise
medical plants (leaves, roots, and stems), and various parts of fruits and vegetables. Among
medical plants, extracts from thyme [36], black tea [159], green tea [160], mint [161], rose-
mary [114], and sage [162] have been added to film-forming solutions to produce antioxi-
dant films for packaging purposes. Edible fruits, grape seed [104], pomegranate peel [163],
thinned apple [164], and others have been evaluated as sources of polyphenolic extracts.
All these studies highlighted the ability of the extracts to enhance the radical scavenging
capacity of the polymer, mainly due to their high phenolic component.
Polymers 2022, 14, 4257 22 of 40

The polyphenolic prolife of an extract strongly changes in relation to its source. Ac-
cording to their composition, different extracts diversely interact with the polymer matrix,
creating variable hydrogen-bonding patterns [160]. This fact not only influences the final
antioxidant property of the film but can alternatively affect the mechanical and barrier
properties of the packaging item. For example, in some cases the large number of viable hy-
droxyl groups induce an increase of the free volumes in the blend matrix, leading to highly
flexible films [114]. In contrast, the rigid aromatic and heterocyclic rings of flavonoids can
act as physical crosslinkers of the polymer chains, improving the tensile strength and elastic
modulus of the film [2].

4. Nanotechnology in Biodegradable Packaging

Nano-technology represents one of the major research topics of the packaging sector
due to the huge number of prospective applications and advantages [165].
The use of nano-materials traditionally covers many aspects of the food sector, in-
cluding food safety, nano-sensors, nutrients delivery, and pathogen detection [4]. Lately,
nano-technologies have been utilised to improve the technical performances of conventional
bio-based materials, and to give them additional features. Besides, this novel approach
is laying the basis for the development of a new generation of smart and intelligent food
packaging systems, able to localise, sense, and remote control the food items [166].
The use of nano-structures (i.e., nano-fillers, bio-nanocomposites, and nano-capsules)
is expected to broadly enhance the potentialities of bio-based packaging, and extend the
number of smart packaging solutions in the next few years.

4.1. Bio-Nanocomposite Materials

Nanoparticles are characterised by nanoscale dimensions, usually <100 nm. When
nanoparticles are incorporated into a biopolymer material with specific technological
purposes, they take the name of “nanofillers”, and the resulting item is called a “bio-
nanocomposite” [167]. Bio-nanocomposite materials may be defined as a multiphase mate-
rial in which a continuous phase (i.e., a biopolymer) is embedded with a non-continuous
nano-dimensional phase (i.e., a nanofiller), either inorganic or organic [168].
Due to their small size, high aspect ratio, and large interfacial areas, nanofillers
have been firstly explored as structural reinforcing agents, with the function to improve
the technological properties of packaging materials. When uniformly distributed in the
polymer matrix, nanofillers are able to interact with the polymer chains, creating a tangled
network of hydrogen bonds that fill the free spaces within the matrix and restricts its
molecular mobility [91]. In this way, nanoparticles provide an overall enhancement of
the mechanical, barrier, and thermal properties of the material with respect to traditional
non-composite systems [169]. In particular, it was demonstrated that low concentrations of
fillers (<5%) are able to significantly improve biopolymer properties, which is economically
advantageous in view of their large-scale application [170].
Along with the structural function, the incorporation of nanofillers also represents a
suitable strategy to confer additional functions to the packaging material. On the one hand,
nanofillers can serve as bioactive additives, since some of them exhibit inner antimicrobial,
antioxidant, and scavenging properties [166]. On the other hand, nanofiller incorporation
can tailorise the retainment and release kinetics of bioactive compounds from the polymer
matrix, and adapt the barrier performances of the packaging item [152]. As a result,
the correct selection of a nanofiller (nature, quantity) and suitable process parameters to
customising the bio-nanocomposite materials for countless potential applications [171].
Some case studies are shown in Table 5.
Polymers 2022, 14, 4257 23 of 40

Table 5. Application of nanoparticle technologies to food packaging.

Nanoencapsulated or
Polymers Solvent The Effects and Advantages References
Nanofiller Molecules
Silver nanoparticles (AgNPs)
Hydroxypropyl
of 79 mM silver nitrate • AgNPs helped to increase tensile strength
methylcellulose (HPMC) 3% Distilled water [99]
incapsulated in 45 mM of • NPs decreased the WVP
(w/w)
Poly(vinyl alcohol) (PVA)
• Opacity increased
Potato starch (PS) and • MMT improved thermal stability at higher
Montmorillonite clay (MMT) concentration
Microcrystalline cellulose Distilled water [172]
1–10% • Compatibility between MMT and PSMCC
(MCC)
that increased WVP and mechanical property
• MMT influenced dielectric property

• The addition of nanopowders improved the

mechanical and water barrier properties
TiO2 nanopowders • TiO2 lowered the transmittance through the
Chitosan 2% (w/v) Distilled water film [101]
0–2% (w/w)
• Nanocomposites gave ethylene-
photodegradation property to the film

Corn distarch phosphate

Nisin (N) 0.25–0.5% (w/w) and 3% (w/w),nanocellulose 0.5% • Good compatibility of N and PL with CN to
Distilled water [103]
ε-polylysine (PL) 0.2% (w/w) (w/w), form a compact and homogeneous film
CMC 0.8% (w/w)

Amine functionalised mullite Polypropylene-grafted-maleic • Improved thermal stability

fibres(AMUF) from 0.5 to anhydride o-xylene • Up to 5%, AMUF enhanced the Young’s mod- [173]
10 %wt (PP-g-MA) ulus and gave better crystallisation and less
fracture in the structure of PP

Nanofibril of cellulose • Solid state shearmilling process (SSSM) per-

10–40 % w/w from wheat Polylatic acid (PLA) / mitted to maintain good thermal stability for [174]
straw cellulose but decreased the crystallinity index

Cellulose nanofibril (CNF) Soy protein isolate (SPI) 6% • CNFs and PNE gave opacity to the film, im-
Distilled water proving the barrier to UV-light and prevent- [106]
15% (w/w of SPI) (w/v)
ing photo-oxidation
Microcrystalline cellulose Cellulose 3% in 68% ZnCl2 • Developed a transparent Zn-cellulose film
Distilled water [39]
3% (w/w) (w/w) crosslinked with Ca2+

Chitosan • Compatibility between polymer and addi-

Microcrystalline cellulose (CS) 4% (w/v), whey protein tives, rough surface, no sign of pores and
Distilled water cracks [41]
(MCC) 4% (w/v) isolate (WPI) 4% (w/v) and
glycerin 10–50% • Better WVP at 1.5:1 CS/MCC ratio with 30%
glycerin and 3.6 of pH
• Nanoencapsulation of TiO2 and antho-
Nanosized TiO2 1% (w/v) and cyanins of BPPE improved mechanical,
black plum peel extract Chitosan 2% (w/v) Distilled water UV-vis, WVP and light barrier properties [75]
(BPPE) 1% (w/v) • Compatibility between molecules that form
the film

4.1.1. Nano-Clays
Clays have gained remarkable interest as reinforcing fillers to improve the mechanical,
thermal, and barrier properties of biopolymers [173]. These siliceous compounds mainly
exist in the form of laminated one-dimensional (1D) or two-dimensional (2D) fibrous struc-
tures that can be easily dispersed into a polymer through two possible mechanisms, namely
intercalation or exfoliation [175]. The latter mode represents the best strategy to incorporate
these compounds into a polymer matrix, since it allows the complete delamination of the
particles and their homogeneous diffusion [165].
Some widespread nano-clays applied to develop bio-nanocomposite materials are
montmorillonite, bentonite, palygorskite, and sepiolite. Among these, montmorillonite
have been largely tested due to its excellent technical behaviour, abundance, low cost,
and compatibility with a wide range of biopolymers [176]. It consists of a hydrated
aluminium silicate layered structure, with a modest negative charge which varies from
layer to layer [175]. It possesses a high surface ratio and interfacial area, which contributes
to its uniform distribution.
The features of a clay-reinforced film strongly depend on the polymer matrix, nature
of the clay, the clay–polymer interactions, and the processing conditions [102]. Besides,
surface-modification methods have been tested on clays to enhance their capacity of in-
Polymers 2022, 14, 4257 24 of 40

terfacial interaction, including the use of alkylammonium cation surfactants. However,

these surfactants are not appropriate for modifying clay surfaces in bio-applications due
to their toxicity [177]. As a result, most clay-composites are prepared using unmodified
clay materials.

4.1.2. Metal Nanoparticles

Metal nanoparticles such as copper (Cu), silver (Ag), gold (Au), and their alloys have
been widely applied to produce nanocomposite active films and coatings due to their
strong antimicrobial activity [178].
Different mechanisms have been postulated to explain the antimicrobial action of
metal nanoparticles. In particular, Tamayo et al. [179] suggested a three-step mechanism to
explain the antimicrobial activity of Cu-nanoparticles on the bacterial cell in Cu/polymer
nanocomposites: (I) the biopolymer gradually releases Cu2+ ions, which permeate the cell
wall and interact with the membrane proteins and lipopolysaccharides; (II) the cell wall
collapses due to the weakening of the membrane, which leads to the loss of cell organelles;
(III) ions interact with the bacterial DNA, causing its rupture and producing reactive oxygen
species (ROS), which lead to oxidative damage and bacterial death (Figure 8). A similar
mechanism was also proposed to describe the activity of Ag-doped edible packaging [178].
Despite their antimicrobial activity, metal nanoparticles possess a certain antioxidant
activity, exerted via the radical scavenging mechanism [180]. Moreover, they are compatible
with various natural antioxidant extracts and EOs, and thus can be used in synergy with
them to produce films with enhanced performances [181]. Additionally, the incorporation
of metal nanoparticles can alter the barrier properties of the material by filling the voids in
the porous matrix [99].

4.1.3. Metal Oxides

Metal oxides have been extensively studied for food-packaging applications due to
their strong antimicrobial properties, which makes them promising alternative to organic
agents. They include titania (TiO2 ), silica (SiO2 ), magnesium oxide (MgO), zinc oxide
(ZnO), and others. Among these, TiO2 and ZnO are the most widely tested in the food
packaging sector due to their specific physicochemical characteristics, chemical stability,
and biocompatibility [182]. These nanoparticles have been tested both as a reinforcing
agent to improve the technical properties of edible films, and as antimicrobial additives.
Specifically, they possess a remarkable photocatalytic activity in the near-UV region, since
they generate reactive oxygen species (ROS) that can directly damage the cell walls [183].
As an example, Siripatrawan et al. [101] developed TiO2 -enriched chitosan films. The
authors showed that increasing concentrations of TiO2 enhanced the photodegradation rate
of ethylene. Besides, the film exhibited broad antimicrobial activity against Gram-negative
and Gram-positive bacteria.
 permeate the cell wall and interact with the membrane proteins and lipopolysaccharid
(II) the cell wall collapses due to the weakening of the membrane, which leads to the l
of  cell  organelles;  (III)  ions  interact  with  the  bacterial  DNA,  causing  its  rupture  a
Polymers 2022, 14, 4257
producing reactive oxygen species (ROS), which lead to oxidative damage and bacte 25 of 40
death (Figure 8). A similar mechanism was also proposed to describe the activity of A
doped edible packaging [178].  

 
Figure 8. Mechanism of action against bacteria of copper nanoparticles (reproduced with copyright
Figure 8. Mechanism of action against bacteria of copper nanoparticles (reproduced with 
permission from Tamayo et al. [179]).
copyright permission from Tamayo et al. [179]). 
4.1.4. Bio-Nanofillers
Despite their antimicrobial activity, metal nanoparticles possess a certain antioxid
Bio-nanofillers are ultrathin structures produced by different methods (e.g., electro-
activity, acid
spinning; exerted  via  etc.)
hydrolysis the  [184,185]
radical  from
scavenging  mechanism 
organic materials. They [180].  Moreover,  they 
are biodegradable,
compatible with various natural antioxidant extracts and EOs, and thus can be used
renewable, and possess a high surface-to-volume ratio and low density. These particles
have been extensively tested in the food packaging sector as reinforcing agents, and to
synergy with them to produce films with enhanced performances [181]. Additionally, 
modulate the delivery
incorporation  of bioactive
of  metal  compounds
nanoparticles  can [186].
alter  the  barrier  properties  of  the  material
Cellulose derivatives are the most widespread bio-nanofillers to fabricate biodegrad-
filling the voids in the porous matrix [99]. 
able composites [187]. Cellulose nanoparticles can be classified into three types, related to
their structure: (I) cellulose nanocrystals (CNCs), which are rod-like crystals with 5–70 nm
4.1.3. Metal Oxides 
width and 100–250 nm length; (II) cellulose nanofibre (CNFs), which possess a fibrous
structure with a width of 5–60 nm and length of several nanometers; and (III) bacterial
Metal oxides have been extensively studied for food‐packaging applications due
cellulose (BNCs), which consists of ribbon-shaped fibrils with 70–80 nm width [188].
their strong antimicrobial properties, which makes them promising alternative to orga
Many researchers have focused their attention on the extraction of nanocellulose from
agents.  They  include  titania  (TiO2),  silica  (SiO2),  magnesium  oxide  (MgO),  zinc  ox
different sources of biomass and wastes, such as agricultural wastes, forest residues, algae
(ZnO), and others. Among these, TiO
residues, and industrial by-products [189–191]. 2 and ZnO are the most widely tested in the fo
The extraction methods can be divided into
packaging sector due to their specific physicochemical characteristics, chemical stabil
three different kinds of treatments: chemical, physical, and biological [189].
and The
biocompatibility 
chemical method[182].  These 
represents thenanoparticles 
most conventionalhave  been 
way tested 
to extract both  as  a  reinforc
nanocellulose.
Itagent to improve the technical properties of edible films, and as antimicrobial additiv
employs a bleaching treatment (e.g., oxidation by NaClO in water at pH10, in presence
of NaBr and TEMPO for catalysts), alkaline treatment (80 ◦ C for 2 h, 4.5% w/v NaOH), and
Specifically, they possess a remarkable photocatalytic activity in the near‐UV region, si
acid hydrolysis (45 ◦ C for 40 min, H2 SO4 60–64% w/v) [192–194]. The physical method
they generate reactive oxygen species (ROS) that can directly damage the cell walls [1
represents an effective treatment, which allows obtaining the highest yields of extraction.
The main drawback related to this method is that it is highly energy-consuming. Grinding,
homogenisation, ultrasound, high-pressure, and screw extrusion processes are widely
employed for this purpose [189]. Last but not least, the biological approach involves
 
the treatment of the cellulosic matrix through microorganisms, which can synthesise
Polymers 2022, 14, 4257 26 of 40

enzymes for the degradation of cellulosic materials [189], or through the direct application
of cellulases enzymes (such as cellobiohydroalases and endoglucanases) [185,190].
The combination of these techniques can overcome the drawbacks related to every
single method.
BCN is produced mainly by Komagataeibacter xylinum (but also Agrobacterium tume-
faciens, Dickeyadadantii, Salmonella enterica, Pseudomonas putida, Rhizobium leguminosarum,
Escherichia coli) bacteria, through molecular pathways that involve the presence of glucose
or different other sources of carbon [195].
Cellulosic nanofillers exhibit a characteristic self-association property, deriving from the
inter- and intramolecular hydrogen bonding involving their surface hydroxyl groups [196].
This promotes the strong adhesion of these materials on and within the polymer matrix,
enhancing the mechanical characteristics of the composite material by creating tortuosity,
crystal nucleation, and chain immobilisation [105]. In addition, the highly tortuous structure
induced by crystalline fibres can hamper the water vapour diffusion, resulting in28 of 43 
Polymers 2022, 14, x FOR PEER REVIEW  low WVP
 
values. Due to their surface reactivity, they can also serve as bio-scaffolds.
Cellulosic nanoparticles possess an enormous amount of active surface hydroxyl
groups that can be modified by chemical reactions such as cationisation, silylation, car-
Oyeoka et al. [198] demonstrated the fast water absorption rate and biodegradation 
boxylation, polymer grafting, and hybridation with metals and metal oxides [23]. In
of films incorporated with cellulose nanocrystals (CNCs). The behaviour of the CNCs at 
particular, surface-modified nanofillers possess higher interfacial compatibility with a
different concentrations was interesting: at lower levels of incorporation, the films tended 
range of biopolymers compared with un-modified ones (Figure 9). Surface-modification
to absorb more water (until 516% in 50 min) and be more resistant to degradation in soil; 
also influences the polarity and hydrophilic behaviour of the material, enhancing its ability
conversely, at higher levels of CNCs, the degree of absorption of water decreased (until 
to hinder vapour diffusion throughout the packaging system [197].
373% in 50 min), and the resistance to degradation was slightly reduced. 

 
Figure 9. Popular modifications of cellulose nanocrystals (reproduced with copyright permission 
Figure 9. Popular modifications of cellulose nanocrystals (reproduced with copyright permission
from Dufresne et al. [196]). 
from Dufresne et al. [196]).
4.2. Nano‐Encapsulation and Nano‐Emulsions 
Oyeoka et al. [198] demonstrated the fast water absorption rate and biodegradation
Encapsulation 
of films incorporatedis  a with
technology  which 
cellulose consists  of 
nanocrystals packing 
(CNCs). a  target 
The substance 
behaviour into 
of the CNCsa  at
solid  envelope, 
different with  the was
concentrations double  purpose atto lower
interesting: protect  it  from 
levels external  interactions 
of incorporation, the filmsand 
tended
provide  a  controlled  release  under  specific  conditions  [125].  Commonly,  hydrophilic 
materials (i.e., polysaccharides, proteins) are used to encapsulate hydrophobic substances, 
and vice versa.  
According  to  their  size,  capsules  can  be  categorised  as  macro‐,  micro‐,  and  nano‐ 
[117]. Specifically, nano‐capsules have been widely applied as carriers of nutraceuticals 
Polymers 2022, 14, 4257 27 of 40

to absorb more water (until 516% in 50 min) and be more resistant to degradation in soil;
conversely, at higher levels of CNCs, the degree of absorption of water decreased (until
373% in 50 min), and the resistance to degradation was slightly reduced.

4.2. Nano-Encapsulation and Nano-Emulsions

Encapsulation is a technology which consists of packing a target substance into a solid
envelope, with the double purpose to protect it from external interactions and provide a
controlled release under specific conditions [125]. Commonly, hydrophilic materials (i.e.,
polysaccharides, proteins) are used to encapsulate hydrophobic substances, and vice versa.
According to their size, capsules can be categorised as macro-, micro-, and nano- [117].
Specifically, nano-capsules have been widely applied as carriers of nutraceuticals (macronu-
trients, enzymes, prebiotic, probiotic, vitamins, omega-3-fatty acids) and technological
additives (antioxidant, antibacterial, and antifungal chemicals; colourants; flavours) to
produce functional food with enhanced safety and stability [199]. In addition, they were
used to dope biodegradable films and coatings to fabricate nanocomposite packaging
solutions [118]. As an example, Liu et al. [200] developed films based on gelatin and
enriched with different concentrations of tea polyphenols/chitosan nanoparticles. The
incorporation of nanoparticles decreased the WVP of the resultant films. Moreover,
Polymers 2022, 14, x FOR PEER REVIEW  29 of 43  the
 
release kinetics of tea polyphenols from the film surface were evaluated by means of two
food simulants (i.e., 50% ethanol at 4 ◦ C; 95% ethanol at 25 ◦ C). The study highlighted a
slow releasing rate of the polyphenols for both the simulants, which was probably due
slow releasing rate of the polyphenols for both the simulants, which was probably due to 
to film’s 
the  the film’s tortuosity
tortuosity  and increased
and  increased  diffusion
diffusion  pathways
pathways  induced
induced  by  the by the nanoparticles.
nanoparticles. 
Similar results were obtained by Cui et al. [201] for zein films doped with pomegranate
Similar results were obtained by Cui et al. [201] for zein films doped with pomegranate 
polyphenols/chitosan nanoparticles.
polyphenols/chitosan nanoparticles. 
Nano-emulsification
Nano‐emulsification  representsanother 
represents  anothertechnique 
techniquewhich 
which allows 
allows toto increase
increase the bioavail-
the 
ability and stability
bioavailability  of bioactive
and  stability  compounds,
of  bioactive  and to guarantee
compounds,  their proper
and  to  guarantee  their delivery
proper  in the
delivery in the surrounding environment [202]. 
surrounding environment [202].
A nano‐emulsion is a system composed by two immiscible liquids in which one is 
A nano-emulsion is a system composed by two immiscible liquids in which one is
homogenously dispersed in the other, forming nano‐sized globules (50–500 nm). Due to 
homogenously dispersed in the other, forming nano-sized globules (50–500 nm). Due
their  high 
to their ratio 
high of ofdroplet 
ratio dropletsurface/mass 
surface/massunit, unit,nano‐emulsions 
nano-emulsionspossess 
possessa a high 
high deliv-
delivery/encapsulation ability [203].  
ery/encapsulation ability [203].
The most widespread application of nano‐emulsions in the food industry consists of 
The most widespread application of nano-emulsions in the food industry consists of
the retainment and controlled delivery of active agents to solid foods. Bioactive molecules 
the retainment and controlled delivery of active agents to solid foods. Bioactive molecules
such 
suchas 
asEOs 
EOscan 
canbe 
bedirectly 
directlyincorporated 
incorporatedinto 
intoa afood 
foodsystem  or entrapped 
system or  entrapped in in polymer 
polymer matri-
matrices  to  produce  active  packaging  [50].  In  particular,  the  incorporation 
ces to produce active packaging [50]. In particular, the incorporation of nano-emulsified of  nano‐
emulsified EOs into biodegradable materials has the double advantage to minimise the 
EOs into biodegradable materials has the double advantage to minimise the concentration
concentration of active agent required to perform a valuable antimicrobial activity and to 
of active agent required to perform a valuable antimicrobial activity and to reduce its
reduce its sensory impact (Figure 10).  
sensory impact (Figure 10).

 
Figure10. 
Figure  Schematicrepresentation 
10.Schematic  representationof ofnanoemulsion 
nanoemulsionand 
andrelated 
relatedproperties 
propertiesat 
at different 
different sizes 
sizes (repro-
(reproduced with copyright permission from Donsì [199]). 
duced with copyright permission from Donsì [199]).

5. Biodegradable Packaging from Agri‐Food Waste 
To  date,  about  30%–50%  of  food  is  wasted  from  post‐harvesting  to  processing, 
storage, and consumer usage. Typical examples of food by‐products are vegetable peels, 
fruit pomace, seeds, and low‐quality whole fruits and vegetables [204]. The large part of 
Polymers 2022, 14, 4257 28 of 40

5. Biodegradable Packaging from Agri-Food Waste

To date, about 30–50% of food is wasted from post-harvesting to processing, storage,
and consumer usage. Typical examples of food by-products are vegetable peels, fruit
pomace, seeds, and low-quality whole fruits and vegetables [204]. The large part of these
matrices is still discarded in landfills, while a small portion is valorised for bioprocess-
ing [205].
A feasible strategy to valorise food waste and by-products consists of their use for
the production of bio-based packaging materials. This approach involves two remarkable
benefits. On the one side, food by-products constitute a cheap, renewable, and under-
utilised source of polysaccharides, lipids, proteins, and many other components [206].
These components can be either employed as the major constituent of packaging or as
minor additives, resulting in the reduction of the production costs. In particular, the
inclusion of by-products components has been demonstrated to improve the engineering
properties of the packaging material, thus conferring it additional activity [207].

5.1. Life Cycle Assessment LCA

According to estimates by “Plastic Europe 2022”, the packaging sector is responsible
for 33.5% of plastic consumption worldwide, but only 6.6% of this plastic is recycled [208].
Due to this circumstance, it is necessary to determine the carbon footprint of these materials
to obtain an in-depth report about possible environmental damage to both production and
potential recycling.
For this reason, is important not only to replace non-biodegradable materials, but
also to estimate through a holistic approach the impact on the environment of the new
compounds chosen to be the new green polymers [209]. LCA is an analytical and systematic
methodology to estimate the ecological footprint of the entire process of modification,
transformation, transportation, emissions, and waste of a product. Life Cycle Assessment,
regulated by ISO 14040:2006, has developed into a legitimate area of study in the field
of research, becoming mandatory for efficient organisational, commercial, and disposal
process analysis.
Numerous studies have been recently conducted to highlight the issues related to the
production of plastics from non-renewable and poorly biodegradable sources [210–212].
These issues should be understood and exploited with a view towards a greener recycling
process for petroleum-based materials, with the hope of eventually replacing them entirely.

5.2. Pre-Treatments of By-Products and Application for Packaging Production

The most common way to prepare bio-based packaging containing food by-products
involves to directly blend the whole by-product or its components with biopolymers and
additional additives [213]. A necessary step to apply by-products for packaging production
is represented by their pre-treatment.
The first step of pre-treatment usually involves drying and milling processes. The
drying stops the microbiological decay and enhances the handling of the product. Milling
process reduces the size of the product particles, improving the processability, uniformity,
and dispersibility for blending [214].
A further step of treatment can involve the isolation of specific components through
conventional or non-conventional (e.g., microwave or ultrasound) extraction techniques [75].
This process allows isolating and purifying specific fractions of the raw material, which is
subsequently added to the film-forming solution for specific purposes such as technical
properties enhancement (e.g., polysaccharides to improve mechanical properties; lipids
to improve water-barrier properties) and providing additional features to the packaging
material (e.g., polyphenols for antioxidant capacity; essential oils for antimicrobial activity).
In recent years, some novel approaches have shown their potential as valuable ways
to valorise food by-products for packaging development. Among these strategies, it is
worthy to cite the extraction of fibres and cellulose from different by-products [215], the
isolation of nano-sized cellulose and their employment to improve the mechanical and
Polymers 2022, 14, 4257 29 of 40

water-related properties of packaging material [174], the production of cellulose by bacteria

from different foods by-products [216], chemical modifications of the raw material by
Polymers 2022, 14, x FOR PEER REVIEW 
different methods (e.g., grafting) [217], and fermentation of fruit juice pulp to obtain 31 of 43 
 
thermoplastic biodegradable polymers such as poly-hydroxy alkanoates [218] (Figure 11).

 
Figure 11. Flow chart for the recycling of polymers in the circular economy (reproduced with
Figure 11. Flow chart for the recycling of polymers in the circular economy (reproduced with 
copyright permission from Tyagi et al. [57]).
copyright permission from Tyagi et al. [57]). 
5.3. Impact on the Engineering Properties of Packaging
5.3. Impact on the Engineering Properties of Packaging  
In recent years, particular attention has been dedicated to by-products (both whole
and fractionated) as sustainable and green bio-fillers to produce materials with enhanced
In recent years, particular attention has been dedicated to by‐products (both whole 
technical characteristics.
and fractionated) as sustainable and green bio‐fillers to produce materials with enhanced 
Taking into account the mechanical properties, Nair et al. [32] showed that inclu-
technical characteristics.  
sion of 5–15% of wood-based CNCs led to a significant increase in the tensile strength of
Taking into account the mechanical properties, Nair et al. [32] showed that inclusion 
PLA films, mainly ascribed to the densified volume fraction of fibrils. Yang et al. [174]
of 5%–15% of wood‐based CNCs led to a significant increase in the tensile strength of PLA 
observed that, according to the treatments performed on nano-sized cellulose (e.g., pres-
films, mainly ascribed to the densified volume fraction of fibrils. Yang et al. [174] observed 
ence/absence of solid-state shear milling), their addition to the polymer matrix can either
that,  according  to  the  treatments  performed  on  nano‐sized  cellulose  (e.g., 
decrease or increase the tensile strength of the final film. This effect mainly depends on
presence/absence of solid‐state shear milling), their addition to the polymer matrix can 
the interfacial contact area achieved between the nano-sized fibres and the polymer chains.
either decrease or increase the tensile strength of the final film. This effect mainly depends 
Overall, it is interesting to note that many bio-based materials enriched with nano-sized
on the interfacial contact area achieved between the nano‐sized fibres and the polymer 
cellulose have tensile strength comparable to commonly used low-density polyethylene
chains. Overall, it is interesting to note that many bio‐based materials enriched with nano‐
(7.0–25.0 MPa), while the elongation percentage of most films are significantly lower. Be-
sized cellulose-based
sides cellulose  have  tensile  strength 
bio-fillers, comparable 
other compounds to  commonly 
derived used  low‐density 
from by-products can help
polyethylene 
improve (7.0–25.0 properties
the mechanical MPa),  while  the  elongation 
of packaging materials.percentage 
As an example,of  most  films  are 
pomegranate
significantly lower. Besides cellulose‐based bio‐fillers, other compounds derived from by‐
peel extract was found to enhance the elongation percentage of protein-based (from 81%
products 
to 173%) andcan  help 
PVA improve 
films the  to
(from 48% mechanical 
182%) basedproperties  of  packaging 
on the polyphenol materials. 
interaction As  an 
with the
material matrices, which chemically strengthened the composite [213].
example,  pomegranate  peel extract  was  found  to enhance  the  elongation  percentage of 
The addition
protein‐based  of by-products
(from  can and 
81%  to  173%)  reduce thefilms 
PVA  water(from 
vapour permeability
48%  of a pack-
to  182%)  based  on  the 
aging material
polyphenol  by altering
interaction  its the 
with  overall hydrophilicity
material  matrices, (reducing the available
which  chemically  hydrogen the 
strengthened 
groups) and the structure of the biopolymer (increasing the tortuosity for the passage of
composite [213].  
waterThe 
molecules).
addition  of  by‐products  can  reduce  the  water  vapour  permeability  of  a 
Grape seed extract [219], lime peel extract [207], and other extracts were found to
packaging material by altering its overall hydrophilicity (reducing the available hydrogen 
improve the water barrier properties of the tested materials when applied at specific
groups) and the structure of the biopolymer (increasing the tortuosity for the passage of 
concentrations (excessive or not sufficient concentrations can either have no significant
water molecules).  
effect or worsen the properties).
Grape  seed  extract  [219],  lime  peel  extract  [207],  and  other  extracts  were  found  to 
Aside from the above-mentioned properties, some researchers highlighted the changes
improve  the  water  barrier  properties  of  the  tested  materials  when  applied  at  specific 
in oxygen barriers, optical properties, thermal properties, and the morphology of bio-based
concentrations 
materials induced (excessive  or  not sufficient concentrations 
by the addition can  either 
of food by-products. For example, thehave  no  significant 
introduction of
effect or worsen the properties).  
Aside  from  the  above‐mentioned  properties,  some  researchers  highlighted  the 
changes in oxygen barriers, optical properties, thermal properties, and the morphology of 
bio‐based  materials  induced  by  the  addition  of  food  by‐products.  For  example,  the 
introduction of discarded balsamic vinegar or tea leaf waste extract remarkably decreased 
Polymers 2022, 14, 4257 30 of 40

discarded balsamic vinegar or tea leaf waste extract remarkably decreased the oxygen per-
meability of PVA films [220]. As well, thermal stability could be enhanced by strengthening
the chemical bonding pathways within the biopolymer matrix [219], or by including high
thermal-stable components such as lignin [32].

5.4. Impact on Antioxidant and Antimicrobial Capacities of Packaging

Food by-products contain a large number of bioactive compounds (i.e., polyphe-
nols, organic acids, EOs). Recently, the application of these compounds has caught the
interest of many researchers as an appealing strategy to confer targeted capacities to
packaging systems.
Regarding the antioxidant activity, the addition of pomegranate peel extracts [213]
apple skin powder [98], and black plum peel extract [75] resulted in a significant increase
of the antioxidant capacity of the final films. Some researchers applied various by-product
extracts to prevent the oxidation of lipid-rich foods. As an example, chitosan films enriched
with olive pomace resulted in significantly lower peroxide values in walnuts compared
with control (without extract) and polyethylene plastic films after 31 days of storage [221].
Along with antioxidant capacity, various by-products can also confer antimicrobial
properties to the packaging material, especially in the form of extracts. Two examples are
pine needle extract [106] and black plum peel extract [75].
The variable antimicrobial activities of extracts from by-products mainly result from
the mixed active compounds that characterise their specific composition. Moreover, the
antimicrobial efficacy strongly depends on the applied concentration and the interaction
with other components, which can be either synergistic or contrasting.

6. Future Challenges and Concluding Remarks

Much effort has been devoted to developing bio-based active packaging solutions
(Table 6). However, there is still a deep gap between laboratory-scale research and real-time
applications and commercialisation.
The first root of this gap is technological. It is worthy to cite some practical examples:
• EOs possess a strong biocidal efficacy on a broad range of microorganisms, which
virtually makes them suitable alternatives to conventional preservatives. However,
each of them also possesses a peculiar aromatic profile, which could negatively affect
the flavour of food, and this hinders their broad usage [222];
• Most of the biodegradable packaging films still do not provide a sufficient water
barrier for moisture-sensitive foods, and so their feasible applications are mainly
restricted to disposable food wrappers for fast foods that do not require improved
water barrier properties [174];
• To date, most of the studies focused on packaging with antimicrobial and antioxidant
properties are still performed at the in vitro level. For the future, it would be worthy
to extend the achieved findings to in vivo experiments in order to provide the food
industry with more specific data about the impact of these extracts on food safety,
quality, and shelf life.
• Industrial production of biopolymers for the replacement of plastic is still an im-
possible path to pursue due to the cost of production of these molecules compared
with plastics.
The second root is economical. For example, authors suggested reducing the sensory
impact of EOs by entrapping them in nano-emulsions. However, these approaches suffer
economic restrictions since they are not cost-effective [223]. Besides, talking about natural
metabolites, their production relies on the availability of their resource, on the extraction
procedure, and the purification steps, etc. All these aspects contribute to increase the
final price.
Polymers 2022, 14, 4257 31 of 40

Table 6. Advantages and disadvantages of essential oils, LABs, biopolymers, nanotechnology, and
natural antimicrobials.

Topics Advantages Disadvantages References

• Volatility
Essential oils
• Antimicrobial effect
[109,129,224]
• Hydrophobicity
• Antioxidant property
• Modify the flavour of the products
• Does not affect the flavour of the • Different characteristics and effec-
LABs products tiveness for every strain [141,150]
• Produce bacteriocins • Viability
• Biodegradable
• Water-soluble
• Renewable [3,15,17–19,24,45–47,51–54,57,60,63,65–67,69,71–
Biopolymers • Poor mechanical property
• Non-toxic 74,76,79–84,91,168,199,225,226]
• Scarce heat resistance
• Can be extracted from industry agri-
• Expensive industrialisation
cultural wastes
• Enhancing water vapour property
• Good barrier to gas • Decrease of elongation %
• Improvement of mechanical prop- • Potential toxicity
Nanotechnology erty [90,167,170,178,179,182,187,188,196,203,227]
• Lack of data about migration from
• Improvement of thermal stability packaging to food
• Wide application in food packaging
• Antimicrobial and antifungal activity

• Generate ROS to inactivate the bacte- • Poor knowledge of possible inter-

ria actions between antimicrobial com-
• Considered GRAS and non-toxic pounds and food
Natural
• Biodegradable • Oscillating stability of the effective- [1,5,19,20,50,90–92,96,107,108,110,133,139,145,147,
Antimicrobials
• The one derived from plants usually ness of these molecules 148,154,179,203,222,228]
are good antioxidant compounds • Could give undesirable flavours
• Can be encapsulated for a slow re- • Only a few natural antimicrobics
lease of antimicrobial compounds compounds have a wide range of ap-
and a better thermal stability plications against microorganisms

The third root is related to the impact of these compounds on human health and the
environment. In this sense, the composition of each active agent, its specific migration rate
from the packaging material, and the interactions with the food product should be fully
characterised to avoid any possible hazard for human health and to ensure the quality of
the whole package. This is particularly the case of nano-technology application in food
packaging [23]. The risks related to nanomaterials are mainly due to the lack of knowledge
about their mechanisms of migration from the packaging to the food product and the
environment. In this sense, food regulatory bodies such as FDA and EFSA have expressed
their reservations about the extensive application of these materials and established strict
regulations on the transfer threshold of these compounds. For example, EFSA established
that the upper limit for silver migration in food packaging is 0.05 mg/L in water and
0.05 mg/kg in food (EFSA, 2021). In this sense, further and in-depth research about
the migration pathways of these particles is strictly required to sustain their regulatory
approval [167].
These concerns are certainly a significant drawback for the pilot and industrial ex-
ploitation of natural compounds as additives in novel, upgraded, bioactive food packaging
materials. However, environmental pollution connected to the disposal of foods, agro-
industrial by-products, and conventional plastic packaging are becoming significant issues.
For this reason, it is necessary to encourage research in the field of biopolymers based on
sustainable production (i.e., use of by-products from the industry as extracting matrices;
utilisation of green solvents and physical treatments; microbiological processes) to fulfil
the market demands and to achieve the goals outlined in the 2030 Agenda (UN).
Overall, further efforts will be needed to strengthen our knowledge about all the
branches of this field. These novel studies will allow the green era of food packaging to
move a step forward towards the future.
Polymers 2022, 14, 4257 32 of 40

Author Contributions: E.M.: Visualisation, writing—original draft, review and editing; F.B.: con-
ceptualisation, writing—original draft; A.Q.: supervision and reviewing; R.D.L.: supervision and
reviewing; L.A.V.: project administration, supervision, and reviewing; A.P.: project administra-
tion, supervision, and reviewing. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding; the APC was funded by Dariusz Kowalczyk
and Andrea Pulvirenti.
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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