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Advances in research and development of bioplastic for food packaging

Piyawanee Jariyasakoolroj, Pattarin Leelaphiwat and Nathdanai Harnkarnsujarit*

Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart

University, Bangkok 10900, Thailand

Center for Advanced Studies for Agriculture and Food (CASAF), KU Institute for Advanced
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Studies, Kasetsart University, Bangkok 10900, Thailand

*Corresponding author E-mail address: nathdanai.h@ku.ac.th

ABSTRACT

The paper reviews the recent developments in bioplastic food packaging. Several bioplastic

materials (polylactide, polyhydroxyalkanoates, and starch) have been successfully converted

into food packaging using conventional plastic conversion technologies including extrusion,

injection molding, and compression molding. This review emphasizes the advances in

bioplastic packaging with regard to active packaging applications and applications requiring

gas and water barrier. Recently, bioplastic packaging has been developed into active

packaging which can either control the release of active ingredients or scavenge undesirable

substances. The review shows that antioxidant and antimicrobial functions are major

developments for the control-release application in bioplastic packaging. Factors affecting the

release of active ingredients have been reviewed. The sorption of low molecular weight

substances such as humidity, aromas, and gases, also affects the properties of packaging

materials. Some patents are available for oxygen-scavenging bioplastic packaging. Moreover,

improved high-barrier packaging technologies (modified polymer, coating, and lamination)

have been developed to increase the shelf-life of food products.

Keywords: Bioplastic, Food Packaging, Packaging Technology, Release, Scavenging, Barrier

This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: 10.1002/jsfa.9497

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1. Introduction

In recent decades, there has been increased effort to develop bioplastics for food

contact materials, especially in the packaging field, because of environmental awareness and

the implementation of stringent environmental regulations [1]. Bioplastics can be categorized


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into two major groups, namely bio-based and bio-degradable plastics. The bio-based plastics

are made from renewable resources such as starch, cellulose, wheat gluten, polylactide

(PLA), and polyhydroxyalkanoates (PHAs). However, all bio-based plastics are not

necessarily biodegradable such as bio-based-polyethylene (Bio-PE), bio-based-polypropylene

(Bio-PP), and bio-based-poly(ethylene terephthalate) (Bio-PET), which are made by

converting renewable resources (e.g. sugarcane, sugar beet, corn, and cassava.) into building

blocks for PET. Conversely, the bioplastics in Group III and IV (Figure 1) can be

biodegradable after use by oxidation or photodegradation reactions. However, the rate of

biodegradation mainly depends on the types of bioplastics. Furthermore, after biodegradation

step, the desintegration level of bioplastics is another basic requirement to determine the

efficiency of composting process. In the case of Group III, not only they are able to be

biodegraded, but also produced from natural resources, so-called “compostable plastics” as

presented in Figure 1. The different resources used in bioplastics also trigger intrinsic

physical and chemical properties, which play important roles in designing their applications.

Table 1 presents a list of examples of bioplastics with their unique properties for food

packaging.

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1.1 Non-biodegradable bioplastics for food packaging

Generally, conventional plastics are polymers produced from monomers as products of the

petrochemical industry. The main chemical structures are covalently bound hydrocarbon
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molecules which are non-biodegradable. In the last decade, monomers of conventional

plastics have been successfully prepared using the fermentation of carbohydrate-based plants

which generates ethanol as a raw material for further conversion to various derivatives such

as ethylene and ethylene glycol (EG).

In 2009, Morschbacker [3] reported the manufacture of ethanol using sugarcane in Brazil as

feedstock for the fermentation process, including a catalytic dehydration reaction to prepare

an ethylene unit for Bio-PE. This was followed by Braskem launching their “I'm greenTM

Polyethylene” product (i.e. commercial grade Bio-PE) which retains the same properties and

performances of petroleum-based PE with relatively low cost, but reduced carbon dioxide

emission. Currently, Braskem offers a wide range of bio-based high-density polyethylene

(HDPE) and linear-low-density polyethylene (LLDPE). Therefore, Bio-PE facilitates

immediate use in the plastics production chain with similar processes to form package and

recycling [4,5]. The manufacturing process of Bio-PP is more complicated than that of Bio-

PE and has been commercialized under the name Biopolypropylene 109D, which was utilized

for injection-molding packaging in 2011. It is made using 20 percent post-industrial algae

biomatter and targets thin-walled applications [6].

Another non-biodegradable bioplastic is Bio-PET, having been already produced using resin

with further formation into a bottle shape at the industrial scale. PET is generally comprised

of 30% EG and 70% terphthalic acid (TPA). PlantBottle® from Coca-Cola is made of bio-

based EG (30% Bio-PET), and similar packaging is used by Dasani, Coca-Cola, Sprite, and

Fresca [7]. In 2010, Berti et al. [10] developed the viable process to produce bio-based-TPA

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on a commercial-scale, using isobutanol, n-butanol, isobutylene, limonene, muconic acid,

terpenes, and carbohydrates (glucose and fructose) as reactants. Recently, PepsiCo

successfully produced 100% Bio-PET from switchgrass, pine bark, and corn husks. The

performance of Bio-PET packaging is identical to other petroleum-based PET products [11].


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Bio-based-polyethylene furanoate (Bio-PEF), a technology of the Avantium company, has

been developed as an alternative for PET bottles. It can be obtained from bio-based EG and

furan dicarboxylic acid (FDCA). PEF has the predominantly favorable characteristics of

being a better gas and moisture barrier with lower carbon dioxide (CO2) emission than PET.

All non-biodegradable bioplastics as developed have the same structure as those of

petroleum-based plastics, allowing the same performance but reducing the carbon footprint of

the production process [12].

1.2 Biodegradable plastics for food packaging

Biodegradable plastics are classified into two categories according to resources, as presented

in Figure. 2. Natural biodegradable plastics can be divided into three subgroups by

production technologies. The high potential, natural biodegradable plastics for food

packaging are starch, PLA, and PHAs which have been up-scaled to industrial

manufacturing.

Starch is a polysaccharide mostly found in carbohydrate-plants. It consists of a large number

of glucose units linked by 1,4- and 1,6-glycosidic bonds, leading to linear and helical

structures of amylose (amorphous and crystalline phases) and a branching structure of

amylopectin (amorphous phase), respectively. The ratio of amylose/amylopectin mainly

influences the properties of starch. Nevertheless, starch is highly crystalline with strong inter-

and intramolecular hydrogen bonding among starch polymers, resulting in a very high

melting temperature, close to the degradation temperature and this obstructs the melting

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process to form film packaging. Therefore, the modification of starch is required for

bioplastic production using chemical and physical pathways [13-15].

Plasticization or thermoplastic formation of starch is a promising approach to deal with the

limitation of processability. Polyhydric alcohols (glycerol, sorbitol, carboxylic acid), polyols,


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and epoxides have been widely investigated as reagents to plasticize starch to form

thermoplastic starch (TPS). Utilization of TPS for packaging is mostly blended with other

polymers (PE, PS, PVOH, PLA, PCL) due to its intrinsic moisture absorption and poor

mechanical properties [9, 17-22]. The content of plasticizers plays an important role in the

blend characteristics of controlling the flexibility or elongation and toughness. Flexibility can

be readily improved by increasing the plasticizer content. TPS also provides finer phase

dispersion in the blend system compared to pure starch or chemically modified starch.

Commercial PLA is produced through the ring-opening polymerization of lactide which can

be obtained from the fermentation of corn and sugar cane among other raw materials. PLA

has high transparency and tensile strength, melt processability, and biocompatibility.

Interestingly, the performance of PLA is similar to PET; thus, there has been much effort to

replace PET with PLA in bottles, films and pouches, among other products. However, the

limitations of PLA are its high cost and the fact that it is a poor gas barrier, with low thermal

distortion, and it is brittle, resulting in a narrow processing window. These attributes are

consequences of its high glass transition temperature and low crystallization rate due to the

long time required for the formation of the helical packing structure [23].

PLA has been blended with various polymers to enhance its ductility and accelerate

crystallization for packaging applications. For example, Mallet and coworkers [24] studied

the processability and mechanical and thermomechanical properties of PLA blended with

epoxy-functionalized chain extender, nucleating agent (talc and N, N‟-ethylenbis

(stearamide)), and plasticizer (polyethylene glycol). A semi-crystalline structure during the

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blowing process was successfully induced using PLA-based blending, leading to an

improvement in film flexibility.

Polyhydroxybutyrate (PHB) is the first polymer of the PHA family, produced using bacteria

and algae. PHB is brittle and stiff which limits its application. The different pendant groups
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can be used to design the properties of the PHAs obtained; for instance, having an ethylene

group of polyhydroxyvalerate (PHV) instead of the methyl group of PHB generates

flexibility. Moreover, PHA has been blended with other biodegradable polymers to reduce

the cost and increase flexural strength and complex viscosity such as in PLA, PBS

(polybutylene succinate), and PBAT (polybutylene adipate-co-terephthalate) [25].

PBS is produced using condensation polymerization of succinic acid and butanediol which

can be sourced from both petrochemical and natural resources. PBS film has high heat

deflection and is tough, but it is not transparent and furthermore it is expensive. However,

PBS still cannot be utilized in flexible or rigid packaging; it has a relatively low melt strength

and can be easily hydrolyzed [26]. Several reports have discussed improvement of the

mechanical properties of PBS such as using stress treatment to improve the gas barrier

property of PBS [27] and adding silicate nanoclays to increase barrier properties against the

diffusion of oxygen, carbon dioxide, flavor compounds, and water vapor [28].

Bioplastic packaging has been successfully produced using conventional packaging

conversion including extrusion, blow molding, compression molding, injection molding,

blown film extrusion, and thermoforming (Figure 3). This review emphasizes the advances in

bioplastic packaging with regard to active packaging applications and applications requiring

gas and water barrier.

2. Release and desorption activity in bioplastics

Active packaging has been utilized to extend food shelf-life and preserve food quality.

Among others, antioxidant and antimicrobial functions are major developments for control-

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release application in bioplastic packaging. Microbial growth causes spoilage and affects

safety in high aw food products. Lipids, proteins, vitamins, and pigments are prone to

oxidation which contributes to nutritional and quality losses such as denaturation, rancidity,

and discoloration. A direct reaction of molecular oxygen with organic compounds or so


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called „autoxidation‟ causes free radical inducing oxidation [29]. This deterioration occurs

mainly on the food surface exposed to the outer environment and therefore, active antioxidant

and antimicrobial packaging has been applied to extend the shelf-life of packaged products. A

direct addition of antioxidants and antimicrobials to food and/or food surface coating,

possibly causes neutralization or too rapid diffusion with bulk food. Instead, the use of

control-release packaging can prolong the migration of antimicrobial and antioxidizing

compounds from the packaging material to the food surface, thereby maintaining their

required concentrations for long-term storage [30-32].

2.1 Antioxidant packaging

The development of antioxidant release bioplastic packaging is shown in Table 2. Both

natural and synthetic antioxidants as well as nanoparticles have been successfully developed

into single and multilayer films [55]. These active components are directly compounded with

the polymer matrix via conventional extrusion. The addition of active components varies

between 0.02 to 12% with most being in the range 1-5%. The stability of these active

ingredients varies during severe thermo-mechanical extrusion; for example, there have been

reported losses of 52% for BHT [52], 16% for α-tocopherol [50], 30% for thymol [53], and

82% for astaxanthin [55] in PLA. Accordingly, the synthetic antioxidants have no higher heat

and shear resistance than natural compounds. Instead, their properties, including thermal

stability and volatility, govern their loss. These active compounds may be added in the last

processing step to avoid thermal degradation. Fabra et al. [38] showed that though

electrospinning did not affect β-carotene in PCL, the heat treatment (annealing at 50 and 60

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°C) near the PCL melting temperature caused substantial β-carotene loss. Moreover, the

improved thermal stability of antioxidants can be achieved by coupling onto polymers [35].

The loss was mainly caused by poor mixing and dispersion, evaporation, thermal

degradation, and their antioxidant action with free radicals formed during the process [52-53].
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The release kinetics for the active ingredients have been investigated in different food

simulants at various temperature. Fick‟s behavior describes well the migration into different

ethanol concentrations of active compounds such as α-tocopherol, olive leaf extract [50-51],

merkén spice [44], BHT at 13, 23, and 43 °C [52], astaxanthin at 30 and 40 °C [55], and a

synthetic phenolic mixture at 20 °C and 40 °C [46]. Accordingly, the derived diffusion

coefficients for release were compared in different studies. Moreover, the Arrhenius equation

was a good predictor of faster release at elevated temperature in these simulants [43,46].

The release behavior in food simulants can be controlled by several factors such as polymer

integrity, affinity between the active components, and food simulants. A higher penetration of

food simulant into film matrices and film hydrolysis mainly accelerates the release of

antioxidant [42,50]. Though BHT has greater affinity with hydrophobic matrices, the release

from PLA films in coconut oil was much lower than in 95% ethanol [52]. This suggested the

importance on the release mechanism of matrix disintegration due to ethanol. Moreover,

plasticization effects of active ingredients also improved the release of antioxidant [40]. The

higher simulant temperature increased PLA crystallization providing two diverse effects on

antioxidant release. The crystallization produced a more tortuous matrix which reduced the

rate of antioxidants release; however, it possibly increased the mobility of antioxidant and

hastened the release [46]. A fast release is required for short shelf-life product, whereas, a

longer release is needed for slower release kinetics. Cellulose nanofiber has been shown to

delay the release of TBHQ from PLA films due to increased matrix hydrophobicity and hence

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reduces plasticization by water adsorption, an increased tortuous path, decreased porosity,

induced matrix crystallization, and interaction between nanocellulose and TBHQ [43,46].

The properties of antioxidant, bioplastic, food simulant, and the temperature determine the

rate and quantity of antioxidant release. The release rate also depends on the size and shape
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of the antioxidants in relation to the size and number of the voids within the matrix where the

migration occurs. Accordingly, several factors influence antioxidant diffusion through a

polymer including [39, 46, 56]:

 Polymer properties, including polymer morphology, crystallinity, molecular weight

distribution, density, cross-linking, branching, and orientation which subsequently

impact the size and shape distribution of void spaces within the matrices. More void

space possibly accelerates diffusion and hence matrix accessibility to simulants which

enhance the release rate.

 Antioxidant properties, including molecular size, shape, density, polarity, affinity with

matrix and simulants, and solubility.

 Interaction between the bioplastic and antioxidant, for example the plasticizing effect

which affects the free volume and increases deformability of the matrices. Therefore,

the plasticizers hasten the release.

 Temperature related factors, such as Tg and Tm of the polymer, and the diffusion

coefficient of the antioxidant. The increased temperature increases release due to

increased molecular mobility and hydrolysis of the matrices. Nevertheless, it should

be noted that heating possibly destroys antioxidant and modified polymer properties

leading to delayed release.

The mechanism of action for antioxidant food packaging possibly differs between simulant

testing and food products. For example, with the storage in oil, whole milk powder and

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buttermilk powder, showed no antioxidant-PLGA film degradation but the GC analysis of

headspace volatility showed reduced lipid oxidation in dry milk products. Accordingly, there

was migration of the antioxidant (α-tocopherol, BHA, and BHT) into dry milk products due

to both volatization and direct surface contact with the PLGA films [42]. Scavenging activity
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of volatile free radicals in the headspace of the package was also possible without direct

contact with food product [32].

2.2 Antimicrobial packaging

Antimicrobial packaging has already been extensively reviewed elsewhere [30, 57-59].

However, these reviews mostly considered antimicrobial packaging in the forms of edible

films or coating on petroleum-based packaging. There are still limited publications on

antimicrobial packaging based on commercial bioplastic such as TPS, PLA, PBAT as shown

in Table 3. Most researchers suggested that antimicrobial packaging had more efficacy on

Gram-positive than Gram-negative bacteria [72]. The extruded PBAT/TPS films containing

sorbate effectively reduced the yeast and mold counts and inhibited darkening in fresh pasta

stored at 10 °C for 43 days. The films were placed layer-by-layer with fresh pasta sheets and

sealed in LDPE bags [68]. PBAT films with oregano oil reduced the total coliform,

psychrotroph and Staphylococcus aureus counts in fish fillets stored at 7 ºC [70]. Moradian et

al. [73] produced bacterial cellulose‐ based active membranes placed on the tray bottom of

button mushrooms giving antioxidant and antimicrobial activity against Escherichia

coli and Staphylococcus aureus. The color, ascorbic acid, and polyphenol contents were more

preserved in the active package due to: i) the reduction in microbial enzymes that catalyzed

the loss of polyphenol and ii) the reduced O2 concentration in the package and thus reduced

PPO activity. In addition, the volatility of the active ingredients also modified the vapor

pressure inside the package and reduced the rate of water evaporation from the mushroom.

Lorite et al. [61] developed a novel PLA package using nanoclays and surfactants to extend

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the shelf-life of ready-to-eat fresh cut fruit. The fruit packed in PLA-nanoclay-surfactant

system showed better qualities and the shelf-life was expected to be longer than commercial

PET packaging (15 days) [61].

Added nanoparticles such as Ag, montmorrilonite nanoclays, TiO2 and ZnO have been
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reported to limit microbial growth due to both antimicrobial activity and modified package

permeability associated with CO2, O2, water vapor, and other gases [60-61, 74]. The presence

of a negative charge and the quaternary ammonium group in modified nanoclays produced

strong antimicrobial activity against Gram-positive bacteria such as Listeria monocytogenes

and Staphylococcus aureus [69,72]. The nanoparticles also served as a carrier for long-term

and delayed release of antimicrobials and increased the surface area to enhance contact

frequency which induced cell disruption [60, 70].

An essential oil (carvacrol) was successfully incorporated via conventional extrusion in

bioplastic to serve as antimicrobial packaging. The volatility of the essential oil provides the

extra benefit of indirect contact with foods, such as in the reduction of mycelial and fungi

growth on the surface of strawberries [70]. Encapsulation is necessary to stabilize volatile

compounds in polymeric packaging. Jash & Lim [75] enhanced the antimicrobial and

phospholipase D inhibition properties of PLA with hexanal using an electrospinning process.

The hexanal was first entrapped in N,N′-dibenzylethane-1,2-diamine to form a stable hexanal

precursor compound of 1,3-dibenzylethane-2-pentylimidazolidine prior to homogeneously

dispersed in PLA using electrospinning. Hexanal is highly volatility and susceptibility to

oxidation were successfully entrapped in the PLA fiber. The release of hexanal was triggered

by citric acid. Dai & Lim [76] entrapped a volatile allyl isothiocyanate from mustard seed

meal powder in electrospun fiber of PLA-poly(ethylene oxide). Accordingly, the use of

volatile antimicrobial agents may not require the direct contact, while the non-volatile

substance need to contact directly with food surface.

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The release and diffusion of active compounds through polymer layers are key factors in

antimicrobial activity. A tightly bonded antimicrobial in the packaging matrices has restricted

release and hence lacks microbial inhibition [63]. Plasticizers such as lactic acid oligomers

increase the free volume and promote molecular mobility that enhances the diffusion and
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release of active agents [39]. Moreover, swelling of the starch layer in contact with wet agar

media increased swelling which accelerated diffusion of cinnamaldehyde through surface and

hence provided greater antimicrobial activity in bilayer films [64]. The addition of other

components also modified matrix microstructures and increased discontinuity. The

absorption/binding of the active compounds was subsequently modified and this may have

provided a synergistic antimicrobial effect [62]. Santagata et al. [77] found that cavoxin

enhanced PBS crystallization and induced hydrolysis which subsequently enhanced the

release of antifungal agents against Penicillium roqueforti and Aspergillus niger. Water

diffusion into a PLA-poly(ethylene oxide) polymer triggered the hydrolysis and hence the

release of volatile allyl isothiocyanate. The modified hydrophilicity of the matrix carrier

effectively controls the release kinetics [76]. The study showed a potential active packaging

application based on the humidity-triggered volatile release.

The antimicrobial activity of bioplastic films has often been investigated using standard disc

diffusion methods and microbial counts in food. The in-vitro detection of an inhibition zone

in the disc diffusion methods is based on the release of active agents from the composite film

into the agar media. Several factors govern the antimicrobial activities that were determined

using these methods. The rate of active compound diffusion from the polymer to the food or

agar media is governed by polymer disintegration, film matrix swelling, humidity, affinity

between the films, and the contact materials, among other factors. Consequently, the

antimicrobial activity determined from the colony counts in active packaged foods can be

different from the in-vitro study. Moreover, the amount of the active compound released is

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time- and temperature-dependent which is determined by the Arrhenius equation [46]. For

example, the temperature difference between food storage and the in-vitro microbial

incubation possibly can contribute to a difference in antimicrobial activity [62].

Previous findings pointed out that the active ingredients also affected mechanical, barrier, and
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physical properties including heterogeneity and discontinuity of the polymer organization,

increased free volume, plasticization effects, and hydrogen bonding or other molecular

interactions causing rigid structures [33, 36-37, 40]. Small amounts of essential oil (2.5 to

10%) possibly weakened the PBAT network [36]. Marcos et al. [51] also showed that α-

tocopherol and olive leaf extract modified the melt viscosity and increased the melt flow

index of PLA resins. The incorporated nanometal or metal oxides such as TiO2 and ZnO

produced antimicrobial activity but altered package permeability and strength [66-67].

Moreover, it should be noted that package discoloration, clarity, and taint may adversely

increase consumer dissatisfaction. Therefore, the concentration of added antioxidants and

antimicrobials is limited by adverse changes in the optical, mechanical, and barrier properties

[33, 50-51, 70, 74].

3. Absorption and scavenging of bioplastic

The sorption of small molecules through bioplastic materials is an important phenomenon

leading to changes in polymer properties. The sorption behavior is attributed to the

interaction between small molecules (sorbate) and packaging materials. Small molecules,

including gas, water, and organic compounds can be absorbed in the polymer on the higher

concentration side and desorbed on the lower concentration side. The affinity between the

compounds and the polymers is involved in describing the solubility of a compound present

in the gas phase which is in contact with a polymer phase. The greater the difference between

the polymer surface concentration and the atmospheric concentration, the higher the

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desorption rate. In many simple cases, it is assumed that the sorption of the compounds into

the polymers follows the Henry‟s law which is applicable for the ideal solution at a low

concentration. Whereas the sorption as a function of polymer–permeant interaction follows

the Flory-Huggins model. In such cases, the sorption process of small molecules occurs in the
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glassy state of the polymer, which is much more complex than that in the rubbery state. This

sorption behavior is generally described by the dual−mode sorption model combination of

Henry‟s law dissolution in an equilibrium region and Langmuir-type sorption in a non-

equilibrium region [78].

3.1 Sorption of gases and humidity

In the sorption study of bioplastics, most researchers in the last decade have worked with the

PLA polymer as it is made from renewable resources and is commercially available in

various applications. The sorption of gases in the PLA was determined using a quartz crystal

microbalance (QCM) [79-82] The kinetics process of sorption follows different models

depending on the type of sorbate. The sorption of gases (O2 and CO2) usually occurs in the

glassy state and can be described by the dual-mode sorption model [79,82] There are two

mechanisms involved in the sorption of gases in glassy bioplastics that describe the sorption

at equilibrium and non-equilibrium. However, the Flory-Huggins model [80] and the

Langmuir model [82] can describe the predominant control of carbon dioxide and oxygen

sorption, respectively, in PLA films. The predicted results from these models provided good

correlation with the experimental data for gas sorption in the PLA.These predicted

coefficients were higher using the time-lag method, which could be explained by the time-lag

method including only the diffusion of gas through the films while the other models take into

account both molecules that diffuse through and those that are trapped in the void occurring

in the case of glassy polymer [79]. Not only oxygen and carbon dioxide gases but also

ethylene gas has been studied for sorption in PLA films. The results showed that the

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experimental data correlated well with the Langmuir model for the sorption of ethylene gas in

PLA [83]. Moreover, the sorption of gas in the bioplastics was also measured using the

gravimetric method. The sorption of carbon dioxide was found in poly(3-hydroxybutyrate-co-

3-hydroxyvalerate) (PHBV) [84] and PBAT [85] presenting the Fickian behavior.
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QCM was used to measure the sorption of water in a bioplastic which tended to follow

Henry‟s law [83]. The humidity absorption possibly modified polymer properties such as

TPS and PLA causing crazing and crystallinity evolution as well as hydrolysis leading to

weight loss in the PLA films [86].

Relative humidity (RH) and temperature are the main factors affecting the sorption of

bioplastic as shown in the study by Holm et al. [87] and Sato et al. [88]. Sorption of water in

PLA film at 98% RH was higher than at 11% RH, especially at a higher temperature. The

hydrolysis and plasticization effects were observed under high RH conditions though a

decrease in the average molecular weight leading to the loss of tensile strength [87]. Whereas

the sorption of carbon dioxide in PBS and PBSA increased with the decrease of temperature

[88]. Furthermore, the film composition also affects the sorption of gases as determined at

different pressure and temperature. The carbon dioxide sorption of PLA (D/L:80/20) is larger

than that of (D/L:98/2) at high pressure. The effect of the thermal treatment was observed

only in PLA (D/L:98/2) [82].

3.2 Sorption of organic compounds

The sorption of organic compounds has been widely investigated in petroleum-based

polymers but rarely in bioplastics where sorption is often determined using gravimetric

methods [89]. Many researchers have shown the effect of the sorption of organic compounds

on the mechanical properties of amorphous bioplastic films. Colomines et al. [90] reported

that a recrystallized sample sorbed the smallest quantity of ethyl acetate because the sorption

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mostly occurred in the amorphous region. Widiastuti et al. [91] recorded decreased modulus

strength with the sorption of organic material in PLA.Furthermore, ethyl esters

(benzaldehyde and 2-nonanone) sorbed in PLA acted as plasticizer decreasing the glass

transition temperature (Tg) and increasing crystallinity [92].


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Volatile scalping possibly has adverse effects on the aroma concentration in foods. PLA was

shown to be a better barrier to the aroma compounds d-limonene and ethyl acetate than other

major packaging films [89]. Greater sorption of the key aromatic compounds in herbs

(eucalyptol, linalool, and estragol) was observed in PLA compared to petroleum-based

polymers [93]. It was found that the sorption of organic compounds in the polymers

depended on the affinity between the organic compounds and the polymers; therefore, the

sorption of organic compounds in polymers can be estimated using the solubility parameter

[89, 93].

3.3 Oxygen-scavenging bioplastic

Oxygen absorbers or scavengers have been used to remove oxygen from the headspace of

packaged food products and/or to absorb oxygen entering the package. They are

commercially available in many forms including sachets, films, and labels. Oxygen-

scavenging agents can be metallic, organic, polymer based, and enzyme-based agents [94] in

the forms of a polymer blend or laminate, especially in petroleum-based polymers.

Nowadays, bioplastic packaging has been incorporated with oxygen scavengers as well. The

material surface coating of the oxygen scavenger effectively remove oxygen from the

headspace of packaged food products and/or to absorb oxygen entering the package [95]. The

incorporation of an organic-scavenging agent (-tocopherol) in PLA films was studied by

Gonçalves et al. [96] and Scarfato et al. [97]. The encapsulation technique of 40% (wt) -

tocopherol in PLA films was efficient for oxygen removal [97]. Gallic acid was also used as

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an organic oxygen-scavenging agent in bio-based packaging films. The highest oxygen

absorption of 1 g of gallic acid powder was 447 mg O2 at 21 °C and 100% RH. The capacity

of oxygen absorption of gallic acid was reduced after it was incorporated into films because

of the barrier property of the packaging films that limited oxygen exposure. However, the rate
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of oxygen absorption increased with increased RH in the packaging system [98]. The

increasing rate of oxygen absorption with increasing RH was investigated in thermoplastic

starch (TPS) films incorporating ascorbic acid (AA) and iron powder (Fe) [99]. Furthermore,

iron act as oxygen scavengers with a particle size less than 25 µm incorporated in a

biopolymer foam tray for meat packaging [100]. The development of oxygen-scavenging

materials is very important to the food product, especially for oxygen-sensitive foods, as it

can protect against quality change and extend the shelf-life of oxygen-sensitive products.

4. Permeation and high barrier bioplastic packaging

For non-biodegradable bioplastics (Bio-PE, Bio-PP, Bio-PET, and Bio-PA), the permeability

of gases (water vapor, O2, and CO2) is the same as in petroleum-based plastics (PE, PP, PET,

PA, respectively) because of the same chemical structures. For the bioplastics Groups III and

IV, the key to biodegradability is the rate of hydrolysis or oxidation in which sensitivity to

moisture or O2 in the surrounding environment is necessary to initiate the reaction. However,

this intrinsic property leads to the poor gas barrier property of biodegradable plastics.

Therefore, biodegradable plastics are mostly formed composites or blends in order to increase

the degree of crystallinity and consequently, acceptable barrier properties were obtained.

Table 4 presents examples of several bio-composites reported to reduce the permeation of

various gases and which have potential for use in food packaging and related fields [101-

110]. Additionally, the compatibilizers (e.g. modified kaolinite or phyllosilicate derivative

[107], maleic anhydride [108], and cellulose nanocrystals modified with phosphate ester

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[110]) were applied to bioplastic-based composites and blends in order to enhance the

effectiveness of both mechanical and barrier properties.

There are alternative approaches to adjust the barrier or permeation of gases in bioplastic

films such as induced chain alignment, multilayer structure formation, and coating
Accepted Article

lamination. In 2016, a report and a patent claimed that the stretching and temperature control

during the secondary film-forming process can precisely induce polymer orientation,

especially in PLA film, which triggered toughness and improved gas barrier capability

[111,112].

Gao and coworkers [113] prepared alternating multilayer films of neat PLA and

PLA/graphite nanoplatelets (GNPs) using a coextrusion technique. The forced assembly

during the process reduced the thickness of the GNPs and also induced in-plane orientation of

platelet-like GNPs with a high degree of planar alignment, resulting in improved strength and

water vapor barrier capability while being lightweight for food packaging [113].

Additionally, many patents claimed that laminated PLA film with a good barrier layer (metal

primed and metalized films) or an adhesion layer coated with metal oxide, was effective

moisture barriers [114-118]. PLA film was also used as a first-core layer and coated on one

side of the receiving-layer with polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVOH), a

blend of crosslinked EVOH/PVOH, vinyl alcohol-vinyl lamine (PVAm) copolymer, and

anionic carboxylated styrene-butadiene copolymer (SBR) emulsion. This dried coating layer

can be further metalized, resulting in superior gas and moisture barrier properties with

excellent appearance and metal adhesion [115]. PLA and PHA films can be coated as thin

barrier layer or adhesive layer onto paper or conventional plastics as substrates, since these

biodegradable plastics are safe for direct food contact [116].

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For Bio-PE, Bio-PP, and Bio-PET, the lamination technique was combined with biaxial

orientation to improve the oxygen and moisture barrier properties. Generally, biaxially

oriented PE, PP, or PET (BOPE, BOPP, or BOPET, respectively) films have a high degree of

crystallinity and an ordered packing structure which play a key role in obstructing gas
Accepted Article
permeation. Practically, the biaxially oriented Bio-PE, Bio-PP, and Bio-PET films have been

further metalized to increase barrier properties [117-118].

Surface treatment using various coating techniques has effectively improved the barrier

properties of bioplastic. Not only metallic compounds but also silica derivatives have been

deposited on bioplastic films. For example, Iotti et al. [119] reported an organic-inorganic

hybrid coated PLA film for food packaging which had improved oxygen barrier properties.

The inorganic phase was based on silica whereas polyethylene glycol (PEG),

polycaprolactone (PCL), or PLA was used as the organic phase. These compounds provided

good adhesion for the PLA substrate and can be further exploited by inducing new

functionality to PLA films [119]. Song et al. [120] presented a poly (L-lactic acid) (PLLA)

film that was coated with silicon oxide molecules (SiOx) using plasma-enhanced chemical

vapor deposition. The permeabilities of various gases (e.g. O2, CO2, N2, and H2O) were

significantly decreased by about 30-50% compared to pure PLLA. Additionally, the

deposition of SiOx on PLLA film can increase gas permselectivity ratios of CO2/O2, O2/N2,

and CO2/N2 [120]. Furthermore, the PLLA/SiOx film can be applied to equilibrium-modified

atmosphere packaging (EMAP) to extend the shelf life of chilled meat, and the gas

composition reached its dynamic equilibrium state with 6% to 11% CO2 and 8% to 13% O2.

This PLLA/SiOx film combined with tea polyphenol pads, provided effective microbial

growth inhibition [121].

Modified atmosphere packaging (MAP) is of wide interest to prolong the shelf-life of fresh

produce. PLA film has great potential for the development of an equilibrium-MAP (EMAP)

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system. Briassoulis and coworkers used the multilayer structure of laser micro-perforated 30

µm PLA/non-perforated Mater-Bi® films for EMAP. This film was designed to be able to

adjust suitable barrier properties for cherry tomatoes and peaches [122]. Peelman et al. [123]

evaluated the shelf-life of rump steak, ham sausage, filet desaxe, grated cheese, and pre-fried
Accepted Article
fries which were MAP-packed in multilayer trays using commercial cellulose-based film/

PLA and/or paper/AlOx/PLA films. Up to the present, bioplastic products, particularly PLA,

have proven to be versatile and this allows for proper design and better control of the in-

package atmosphere than for conventional materials with their higher permeability to water

vapor combined with their poorer barrier properties with respect to CO2 and O2. The

successful application of laser micro-perforation technology in bioplastics further enhances

their possibilities in the development of optimal EMAP systems fitting the exact needs of

specific, high-value horticultural products [124].

5. Concluding remarks

Bioplastic including biodegradable and non-biodegradable materials, has been widely

developed into food packaging using conventional plastic processing. The review reflects that

PLA is the major bioplastic investigated and developed for food package. In recent decade,

several new material technologies have been investigated to fabricate functional and high-

barrier bioplastic packaging. These have included control-release (desorption), scavenging

(absorption) and permeation technology. The active ingredients derived from organic and

inorganic materials were incorporated into the packaging in the form of dispersion,

lamination, and coating to improve the functional and barrier properties. The antioxidant and

antimicrobial capacities of the packaging are major considerations in a controlled-release

application which has widely been shown in in-vitro study. However, the investigations of

food-package interactions in real food systems, containing e.g. multicomponent, mix

microbial load and headspace, are still very limited. For example, the dispersion of functional

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ingredients into polymer matrices also altered package permeability and hence environment

of packaged-products. Nevertheless, only few studies pointed out these modified packaging

conditions that could directly impact shelf-life of products. Moreover, oxygen-scavenging

multilayer packaging based on bioplastic materials has been investigated and patented. The
Accepted Article
previous investigations also showed that bioplastic materials are more sensitive to humidity,

gas, and other environmental factors than petroleum-based materials, which modified

package properties and hence possibly gave diverse effects on food qualities. Accordingly,

the food products and packaging conditions greatly influence the stability and functional

properties of bioplastic packaging. Investigation of food-package interactions will need to be

emphasized strongly to achieve commercial utilization.

ACKNOWLEDGEMENT

The authors are grateful for financial support from the Kasetsart University Research and

Development Institute (KURDI), Bangkok, Thailand as well as the Center for Advanced

Studies for Agriculture and Food (CASAF), KU Institute for Advanced Studies and the

Faculty of Agro-Industry.

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Accepted Article

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Accepted Article
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Accepted Article
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113 Gao Y, Picot OT, Tu W, Bilotti E, Peijs T. Multilayer coextrusion of graphene polymer

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117 Chang KP, Brandmeier MF, inventors; Toray Plastics (America) Inc, assignee. Biaxially
Accepted Article
oriented bio-based polyolefin films and laminates. United States patent application

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122 Briassoulis D, Mistriotis A, Giannoulis A, Giannopoulos D. Optimized PLA-based

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Accepted Article
vegetables by using micro-perforated poly-lactic acid (PLA) films. Postharvest

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Captions for FIGURES AND TABLES
Figure 1 Categories of bioplastics according to resources and biodegradability, adapted from [2].

Figure 2 Classification of biodegradable polymers by different resources and production

technologies, adapted from [16].


Accepted Article
Figure 3 Bioplastic packaging and conversion technologies

Courtesy of the Department of Packaging and Materials Technology, Kasetsart University,

Bangkok, Thailand.

Table 1 Types of bioplastics and intrinsic properties with packaging forms

Table 2 Previous investigations on antioxidant bioplastic for food packaging

Table 3 Previous investigations on antimicrobial bioplastic for food packaging

Table 4 Improved barrier properties in different bio-nanocomposites

This article is protected by copyright. All rights reserved.


Accepted Article

Figure 1 Categories of bioplastics according to resources and biodegradability, adapted from [2]

Figure 2 Classification of biodegradable polymers by different resources and production


technologies, adapted from [16].

This article is protected by copyright. All rights reserved.


Accepted Article

Figure 3 Bioplastic packaging and conversion technologies


Courtesy of the Department of Packaging and Materials Technology, Kasetsart University,
Thailand.

This article is protected by copyright. All rights reserved.


Table 1 Types of bioplastics and intrinsic properties with packaging forms
Intrinsic properties
Bioplastics Packaging form References
Advantages Disadvantages
Bio-PE  Recyclable  Non-degradable  Bottle (HDPE) [3,5]
Accepted Article
 Less carbon footprint (as  Bags, pouches,
compared to petroleum-based wrap (LLDPE)
PE, according to ISO 14040
and ISO 14044)
 Chemical and physical
properties, similar to
Group II

petroleum-based PE
Bio-PET  Recyclable  Non-degradable  Bottle [5]
 Less carbon footprint (as  Film
compared to petroleum-based  Fiber
PET, determined by ASTM
D6866)
 Chemical and physical
properties, similar to
petroleum-based PET
TPS  High Flexibility  Sensitive to moisture  Film, edible film [9]
 Natural abundance  High melt viscosity  Bubble wrap
 Cost effectiveness  Sheet
 Compostable  Foam
PLA  Transparency  Brittleness  Bag [8, 9]
 High strength  Low barrier and heat  Film, metalized
 Production capability in distortion film, shrink film
Group III

industrial-scale  Required specific  Clamshells, tray


 Less carbon footprint (as extreme conditions to  Foam
compared to petroleum-based degrade and compost
PE, PP and PET films,
determined by EN 16640)
PHAs  Relatively high impact strength  Brittleness  Tray [9]
 Compostable (EN13432  High production cost  Bag
standard)  High CO2 emission  Bottle (personal
(as compared to cares)
petroleum-based PP  Film coating
bag, by EN 16640)
PBAT  High flexibility  Low processability  Bag (polymer [9]
 Biodegradable  High production cost blends or
 Less carbon footprint (as  Low transparency composites)
compared to petroleum-based
LDPE bag, determined by
Group IV

ASTM D6866)
PBS  High flexibility  Low processability  Film coating [9,26]
 Biodegradable  High production cost  Film (polymer
 Compostable (depending on  Low transparency blends or
resources, EN13432 standard) composites)
 Less carbon footprint (as
compared to petroleum-based
LDPE films, by EN 16640)

This article is protected by copyright. All rights reserved.


Accepted Article
Table 2 Previous investigations on antioxidant bioplastic for food packaging
Food Antioxidant
Antioxidant Converting Packaging
Bioplastic Antioxidants products/ food capacity References
content technology Form
simulants measurement
PLA α-tocopherol 1 % (w/w) α- Methanol Extrusion Film DPPH [33]
tocopherol
PLA Lignin nanoparticles 1, 3% (w/w) Methanol Extrusion Film DPPH [34]
(LNP)
PLA/TPS/PBA Ferulic acid-coupled 0.02-0.16 % Ethanol Extrusion Film DPPH [35]
T chitosan (w/w) FRAP

PBAT Oregano essential oil 0.0, 2.5, 5.0, Fish Extrusion Film DPPH [36]
7.5 and
10.0 % (w/w)
TPS/PBAT Tocopherol 0.3-0.8 % 50:50 Extrusion Film DPPH [37]
Avocado peel extract (w/w) Ethanol/water
Corn TPS/PCL β-carotene 50 % (w/w) TCM Electrospinnin Film ABTS [38]
g
PLA/PHB Carvacrol 10 % (w/w) Methanol Compression Film DPPH [39]
molding
PLA/PHB Catechin 5 % (w/w) 50% ethanol Extrusion Film DPPH [40]
Bio Lignin 5 % (w/w) - Injection Composite Oxidation [41]
HDPE/cellulos molding s material induction time
e (OIT)

PLGA α-tocopherol 2% α- Water Solution Film UV [42]


BHA tocopherol Oil casting spectrophotom
BHT 1 % BHA, eter
1% BHT

This article is protected by copyright. All rights reserved.


Accepted Article Food Antioxidant
Antioxidant Converting Packaging
Bioplastic Antioxidants products/ food capacity References
content technology Form
simulants measurement
PLA TBHQ 3 % (w/w) Soybean oil Solution Film DPPH [43]
casting Oxidative
stability index
(OSI)
PLA Merken (Chilean spice) 3, 5 % (w/w) Ethanol Extrusion Film DPPH [44]
50% ethanol ABTS
Water FRAP
Total phenolic
content
PLLA Piperidine (PPD) 0.03 % (w/w) - Compression Sheet Free radical [45]
molding scavenging
ability by EPR
sprectra
1
PLA BHA 2 % (w/w) CDCL3 Extrusion Film H-NMR [46]
BHT HPLC
Propyl gallate
TBHQ
PLA/poly Oregano essential oil 0, 3, 6, 9 and Water Solution Film DPPH [47]
(trimenthylene 12 % (w/w) Methanol casting Total phenolic
carbonate) content
PLA Allium spp. extract 2, 5, and 6.5% Methanol Extrusion Film DPPH [48]
(w/w) ABTS

PLA Oregano essential oil 2, 5 and 10 % Methanol Extrusion Film DPPH [49]
(w/w) ABTS
PLA α-tocopherol 2.58 % (w/w) Ethanol Extrusion Film HPLC [50]

Ecoflex and α-tocopherol 10 % (w/w) Methanol Extrusion Film DPPH [51]


Ecoflex- Olive leaf extract
PLA

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Accepted Article Food Antioxidant
Antioxidant Converting Packaging
Bioplastic Antioxidants products/ food capacity References
content technology Form
simulants measurement
PLA BHT 1.5 % (w/w) Water Extrusion Film HPLC [52]
95% ethanol
Coconut oil
PLA Thymol 8 % (w/w) Methanol Compression Film DPPH [53]
molding
PLA Sorbic acid 0.5 % (w/w) Methanol Extrusion Film HPLC [54]

PLA Marigold flower extract 2 % (w/w) Methanol Extrusion Film HPLC [55]
containing astaxanthin
EVOH Clove essential oil 3 % (w/w) Water Extrusion Film HPLC [60]
3% acetic acid
10% ethanol
95% ethanol

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Accepted Article
Table 3 Previous investigations on antimicrobial bioplastic for food packaging
Analysis of
Antimicrobial Antimicrobial Food product Packaging Microorganisms
Bioplastic antimicrobial References
agent content
activity
PLA Copper modified MMT-Cu2+: 3.0% - Film Staphylococcus aureus Agar disc [60]
montmorillonite (wt) diffusion
(MMT-Cu2+) PP-g-MA: 0.0, method
PP-graft-maleic 10.0% (wt)
anhydride
(PP-g-MA)
Nanoclays 1.0% Unpeeled Tray Lactic acid bacteria Colony count [61]
melons Pseudomonasaeruginosa by microbial
Yeasts and moulds kits
Total mesophilic microorganism
Total coliforms
Psychrotrophic microorganism
Enterobacteriaceae
Zatariamultiflora ZME: Refrigerated Film Listeria monocytogenes (ATCC Agar disc [62]
Bioss. essential 0.5,1.0%(v/v) vacuum 19111) diffusion
oil (ZME) PEE: 2.0% (v/v) packed Staphylococcus aureus (ATCC method
Propolisethanolic cooked 25923) Colony count
extract (PEE) sausages Escherichia coliO157:H7 (ATCC
43895)
Vibrio parahaemolyticus (ATCC
43996)
Aerobic plate count
Lactic acid bacteria
Molds and yeasts
Enterobacteriaceae
Psychrotrophic bacteria
Clove essential Clove essential - Film Escherichia coli (ATCC25922) Liquid [63]

This article is protected by copyright. All rights reserved.


Accepted Article Analysis of
Antimicrobial Antimicrobial Food product Packaging Microorganisms
Bioplastic antimicrobial References
agent content
activity
oil (CLO) oil: 15.0– Staphylococcus aureus (ATCC culture test
Graphene oxide 30.0%(w/w) 6538)
(GO) nanosheets Graphene oxide:
nanosheets1.0%
(w/w)
Carvacrol Carvacrol:0.0,10. Ethanol 10% Film Escherichia coli (CECT 434) Agar disc [39]
Oligomer lactic 0% (wt) (v/v) Staphylococcus aureus (CECT diffusion
acid (OLA) Oligomer lactic Isooctane 239) method
acid:0.0,15.0,
20.0% (wt)
Cinnamaldehyde 2.5% (wt) Ethanol: 10% Film Escherichia coli Bacterial [64]
(v/v) Listeria Innocua counts
Acetic acid:
3% (w/v)
Ethanol: 50%
(v/v)
Isooctane
Cinnamaldehyde 1.0 mL - Film Escherichia coli (O157:H7) ASTM E [65]
Presure condition: Staphylococcus aureus (ATCC 2149
9.0,12.0 (Mpa): 25923), Determining
Depressurization under
rate: 0.1, 1.0, 10.0 dynamic
(min−1) contact
conditions
PBAT TiO2 0.0, 1.0, 3.0, 5.0, - Film Escherichia coli Agar disc [66]
7.0, 10.0% (wt) Staphylococcus aureus diffusion
method
ZnO 0.0, 1.0, 3.0, 5.0, - Nanocom- Escherichia coli Agar disc [67]
10.0% (wt) posite film Staphylococcus aureus diffusion
method

This article is protected by copyright. All rights reserved.


Accepted Article Analysis of
Antimicrobial Antimicrobial Food product Packaging Microorganisms
Bioplastic antimicrobial References
agent content
activity
Potassium sorbate 0.0, 1.5, 3.0, 4.5% Fresh pasta Film Yeast and mould Colony count [68]
(wt)
Oregano 0.0, 2.5, 5.0, 7.5, Fish fillet Film Total coliforms Colony count [36]
(Origanum 10.0% (wt) Staphylococcus aureus
vulgare) Psychrotrophic microorganisms.
essentialoil
(OEO)
PCL Cloisite 30B clay 0.0, 1.0, 3,5% - Film Staphylococcus haemolyticus Agar disc [69]
(polycapro (wt) Staphylococcus epidermidis diffusion
lactones) method
Tissueculture
plate method
(TCP)
Starch/ Essential oil Carvacrol: thymol Strawberries Film Botrytis cinerea Image [70]
TPS Carvacrol 50:50 analysis of
Thymol infected area

PVOH Sodium benzoate 0.1% (wt) - Film Escherichia coli (ATCC 25922), Agar [71]
(SB) Salmonella spp. diffusion
Sodium benzoate- Penicillium spp method with
UV Candida spp Image
analysis
Montmorillonite 5.0% (wt) - Nanocomp Listeria monocytogenes Colony count [72]
(MMT) nanoclay osite film Staphylococcus aureus
Salmonella enteric
Escherichia coli (O157:H7)
Pomegranate peel 25.0, 50.0% (wt) Mushroom Film for Staphylococcus aureus (ATCC- Agar disc [73]
extract (PPE) (Agaricus tray cover 19111) diffusion
Green tea extract bisporus) Escherichia coli (O157:H7ATCC- method
(GTE 11775)

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Accepted Article Analysis of
Antimicrobial Antimicrobial Food product Packaging Microorganisms
Bioplastic antimicrobial References
agent content
activity
Rosemary extract
(RE)

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Table 4 Improved barrier properties in different bio-nanocomposites

Dispersed phase/
Polymer matrices Improved barrier References
nucleating agents
Clay (cloisite 30B,
Accepted Article
PLA Water vapor [101]
Cloisite Na+)
Starch Water vapor [102]
TPS Water vapor [103]
PBS/TPS Water vapor [104]
PLA O2, N2, CO2 [105-106]
Amorphous PLA/PCL O2 [107]
PLA/PCL O2 [108]
Cellulose nanofiber Starch Water vapor [109]
Cellulose nanocrystals PLA/PHB O2, Water vapor [110]

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