Food Chemistry 337 (2021) 127750

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Ethylene scavengers for the preservation of fruits and vegetables: A review T

a a,⁎ a a b,⁎
Haiying Wei , Farzad Seidi , Tingwei Zhang , Yongcan Jin , Huining Xiao
a
Joint International Research Lab of Lignocellulosic Functional Materials and Provincial Key Lab of Pulp and Paper Sci & Tech, Nanjing Forestry University, Nanjing
210037, People’s Republic of China
b
Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3, Canada

ARTICLE INFO ABSTRACT

Keywords: The phytohormone ethylene is the main cause of postharvest spoilage of fruit and vegetables (F&V). To address
Ethylene scavengers the global challenge of reducing postharvest losses of F&V, effective management of ethylene is of great im­
Catalyst portance. This review summarizes the various ethylene scavengers/inhibitors and emerging technologies re­
Preservation cently developed for the effective removal of ethylene released, paying particular attention to the ethylene
Fruit and vegetables
scavenger/inhibitors containing catalysts to promote the in-situ oxidation of ethylene without inducing further
Packaging
pollution. Packing ethylene scavengers, such as zeolite, titanium dioxide and transition metals, in a small sachet
has been practically used and widely reported. However, incorporating ethylene scavenger into food packaging
materials or films along with the in-situ oxidation of ethylene has been rarely reviewed. The current review fills
up this gap, covering the latest research progress on ethylene scavengers/inhibitors and discussion on the me­
chanisms of ethylene elimination and oxidation associated with F&V packaging.

1. Introduction
Ethylene, released from fruits and vegetables (F&V), is associated
with the processes for growth, ripening, and germination for F&V (Dan
et al., 2018; Sun et al., 2019). The specific roles played by ethylene are
often governed by the nature of fruits, the state of maturity and extent
of exposure of fruits to ethylene (Pathak et al., 2017; Pathak, 2018).
Apart from accelerating fruit ripening, ethylene often leads to over-ri­
pening and even decay, thus reducing shelf life and causing losses.
Moreover, there are increasing demands for the long-term maintenance
of food quality and the minimization of food spoilage for both health
and economic benefits. Hence, utilizing ethylene synthesis inhibitors or
scavengers to slow down ripening of F&V is critical in postharvest
preservation (Pathak et al., 2017; Pathak, 2018).
Depending on the sources, the ripening of fruits and vegetables is
affected by two types of ethylene: endogenous ethylene which is pro­
duced by the plant itself through a biological pathway, and exogenous
ethylene which originates from adjacent crops, automobile exhaust,
plastics and smoke (Keller et al., 2013). Since fruits and vegetables will
ripen faster regardless of which ethylene they are exposed to, it is thus
essential to remove both types of ethylene (Pathak et al., 2017; Pathak,
2018; Saltveit, 1999). However, plants are very sensitive to ethylene
which tends to significantly affect plant growth and development even
at a concentration of 0.1 μL/L. According to the survey conducted by
Keller et al (2013), harmful impact of ethylene on F&V has been esti­
mated to cause significant product losses (as high as 10–80%), which
continues to be an incentive for us to investigate further to mitigate this
impact. Moreover, Xu et al (2020) reported that drop shock during
transport observably resulted in an increase for ethylene production in
harvested apple fruit. Thus, ethylene control strategies in the post­
harvest ripening processes are the key in diminishing the loss of pro­
ducts and maintaining food quality (Janjarasskul & Suppakul, 2018).
In order to protect postharvest commodities from the effects of
ethylene, many strategies such as low temperature (Wang et al., 2019b;
Yao et al., 2018), controlled atmosphere (CA) storage (Thewes et al.,
2015; Thewes et al., 2017; Weber et al., 2020), using of hydrogen
sulfide (Li et al., 2016), Pickering emulsion coating (Jung et al., 2020),
and LED lighting (Ballester & Lafuente, 2017), have been developed and
classified in different manners. As early as 1997, Indian scientist Raje
et al used Ethysord (ethylene adsorber), Stoprot (SO2 releaser), Ethy­
lene oxidizer, respectively, to extend the shelf life of mangoes at 32–36
℃, which showed that Ethysord was effective in maintaining the taste,
color and flavor of mangoes up to 16 days (Raje et al., 1997). 1-Me­
thylcyclopropene (1-MCP) is a commonly used endogenous ethylene
inhibitor that blocks the hormonal action of ethylene by competing
with ethylene for ethylene receptors (Janjarasskul & Suppakul, 2018),
mainly by inhibiting the synthesis of ethylene in fruit ethylene pro­
duction system II (Hoeberichts et al., 2002). Moreover, although

⁎
Corresponding authors.
E-mail addresses: f_seidi@njfu.edu.cn (F. Seidi), hxiao@unb.ca (H. Xiao).

https://doi.org/10.1016/j.foodchem.2020.127750
Received 21 February 2020; Received in revised form 15 June 2020; Accepted 31 July 2020
Available online 04 August 2020
0308-8146/ © 2020 Elsevier Ltd. All rights reserved.
H. Wei, et al.
exogenous ethylene scavenging agents such as potassium permanganate
(KMnO4) and ozone (O3) can be used for oxidizing ethylene into carbon
dioxide, it also has some disadvantages which will be discussed in the
following section. Some other types of ethylene absorbers/scavengers
such as activated carbon, zeolite, ZSM etc., were also reported and
utilized in small sachets, which, however, tend to cause interactions
among scavenging agents and packaging materials; meanwhile, ab­
sorption can easily reach saturation so that the replacement is often
needed once failure occurs (Janjarasskul & Suppakul, 2016, Keller
et al., 2013). The issues related to low efficiency, waste disposal and
prolonged exposure times remain as challenges.
Fortunately, emerging effective and environmental-friendly techni­
ques, based on catalytic oxidation of ethylene (e.g., photocatalysis in­
duced by metal catalysts), offer alternative approaches that could help
address some of these historical issues (Pathak et al., 2017; Pathak,
2018). It is well known that photocatalysis can lead to the degradation
of pollutants, regardless in aqueous or gaseous phase (Ibhadon &
Fitzpatrick, 2013). Among various photo-catalysts, TiO2 has been well
received and commonly used (Hussain et al., 2011). Upon exposure to
visible light or UV radiation, reactive oxygen species (ROS) are often
generated at the catalyst surface, which induce the oxidation of ethy­
lene, eventually producing carbon dioxide and water (Pathak et al.,
2017; Pathak, 2018). Over the past decades, porous materials with a
high specific surface, TiO2 nanoparticles and other materials, have
become increasingly important due to their unique properties and
feasibility in industrial applications (Wuttke et al., 2018).
The review presented herein consists of four main parts: 1) the
origin and impact of ethylene; 2) the classification and mechanisms of
ethylene inhibition/removal; 3) the preparation of ethylene sca­
vengers/adsorbent containing catalyst; and 4) the application of paper-
based or thin-film porous materials in F&V preservation. Particular
attention is paid to the emerging technologies associated with ethylene
scavengers/inhibitors with catalytic roles. Despite the fact ethylene
scavengers/inhibitors have been well documented (Vilela et al., 2018),
the application of ethylene scavengers containing catalysts, especially
metal oxide catalysts, in packaging films has rarely been reported; the
current review aims at filling up this gap.
2. Biosynthesis pathway and impacts of ethylene on ripening of
fruits and vegetables
The synthesis of endogenous ethylene is relatively complex com­
pared with exogenous ethylene, which is initiated by endogenous de­
velopmental signals such as growth, ripening, and senescence, and also
triggered by exogenous biotic and abiotic factors from the environment
(Steffens, 2014). The biosynthesis and signal transmission of ethylene
have been reviewed in detail (Zhou et al., 2019; Zhang et al., 2017).
Endogenous ethylene biosynthesis pathway that starts with the initial
precursor methionine has been found in plants. The process, shown in
Fig. 1, involves the conversion of methionine (MET) to S-adenosyl
methionine (SAM), which then reacts with pyridoxal phosphate to
produce a Schiff base. The resulting Schiff base forms a cyclopropane
ring and 5′-methylthioadenosine (MTAN) after undergoing an elim­
ination of α hydrogen, along with γ substituent. The cyclopropane ring
is further converted to 1-aminocyclopropane-1-carboxylate (ACC),
which is a key step for the synthesis of ethylene; and ACC is oxidized by
ACC oxidase to form ethylene finally (see Fig. 1). Parallelly, 5′-me­
thylthioadenosine (MTAN) is converted to methionine via a 5-methyl­
thioribose (MTR) compound (see Fig. 1), and a “methionine cycle”
enables methionine to be utilized efficiently (Yang & Hoffman, 1984;
Yao et al., 2018; Zhang et al., 2017; Zhou et al., 2019).
Fleshy fruits have been classified as climacteric and non-climacteric,
depending on respiration rate and ethylene production, which are de­
tailed in Table 1 (Hu et al., 2019; Yang, 2018). Moreover, as shown in
Fig. 2, the climacteric fruits exhibit a peak in respiration and ethylene
production during the ripening process and are able to ripen even after
2
Food Chemistry 337 (2021) 127750
harvest, while non-climacteric fruits do not show any peak in respira­
tion and cannot be fully ripened after harvest (Pitts, 2012).
The differences between the two types of fruits are detailed as fol­
lows:
First, climacteric fruit contain System I and System II while non-
climacteric fruits only produce ethylene by the so-called System I.
System II produces greater ethylene under several orders of magnitude,
including a relatively shorter time than some varieties of System I due
to its autocatalytic process. There are an obvious rising period and a
producing peak for climacteric fruit.
Secondly, climacteric fruits and non-climacteric fruits show little
difference during development stage, only producing trace amounts of
ethylene. However, during the full ripening period, the amount of
ethylene produced by the climacteric fruits is much more than that of
the non-climacteric fruits.
Third, exogenous ethylene is only effective in the early jump stages
for the climacteric fruit, which can lead to the rise of respiration and
autocatalysis of endogenous ethylene. This reaction is irreversible, even
after exogenous ethylene is removed, the respiration rate of the fruit
cannot reach its previous level. For non-climacteric fruits, exogenous
ethylene can react with ethylene receptors in both early and late stages.
When exogenous ethylene is removed, respiration returns to the level of
processing.
Finally, increasing the concentration of exogenous ethylene, the
occurrence time of the respiratory jump in the fruit of the climacteric is
advanced, but the intensity of the respiratory peak remains unchanged.
The change of ethylene concentration is roughly logarithmic with the
advance time of respiration. However, for non-climacteric fruit, in­
creasing the concentration of exogenous ethylene can improve the re­
spiratory intensity, but not the duration of respiratory peak. Although
extraneous treatment of ethylene can increase respiration intensity, it
does not increase the production of ethylene, indicating that ethylene
has no autocatalytic capacity (Yang et al., 2016).
Biochemical changes induced by ethylene are the main cause for F&
V spoilage, which accelerates aging and spoiling of fruits even in re­
frigerators at low temperature (Li et al., 2019; Li et al., 2018). Conse­
quently, we should take a dialectical view of the role of ethylene; while
also develop a proper strategy for ethylene management to prolong the
postharvest storage life of F&V and to lower postharvest losses (Wills &
Golding, 2015). Harvest of immature fruits is one of the solutions to
address this problem, which not only reduces the potential mechanical
damage during transport, but also delays the ripening process until they
are delivered to the final consumer (Bazzano et al., 2016). Moreover,
ethylene must be removed or inhibited for stored fruit even at lower
temperatures, since it plays an extremely important role in the reg­
ulation of fruit ripening (Liu et al., 2015).
For the sake of enhancing quality and extending shelf-life of F&V,
control of atmospheric ethylene levels during transportation, storage
and handling of fresh food is essential (Vilela et al., 2018). In order to
remove or inhibit ethylene effectively, the mechanism of F&V pre­
servation must be understood thoroughly.
3. Classification and preservation mechanisms of ethylene
scavengers
The fresh-keeping mechanisms of F&V mainly involve four aspects:
(1) Inhibiting or slowing down the ripening process of F&V: when the
content of ethylene is > 0.01 μL/L, it stimulates the respiratory
intensity of F&V (Hayama et al., 2006; Ozdemir & Floros, 2004),
which in turn speeds up the degradation of chlorophyll in F&V,
leading to the depletion of nutrients and the end of shelf life.
(2) Inhibiting the growth of bacteria in F&V.
(3) Modified atmosphere packaging (MAP) slows down the respiratory
intensity of F&V and puts them into hibernation. The synergistic
effects of low O2 and high CO2 are used to resist the ripening effect
H. Wei, et al. Food Chemistry 337 (2021) 127750

Fig. 1. Mechanism for the biosynthesis of ethylene from methionine (MET). Adapted from Hu et al. (2019).

of aging hormones such as ethylene, so as to reduce the consump­
tion of nutrients and extend the life span of F&V.
(4) Anti-fog: since common-used film for packaging is hydrophobic, the
evaporation phenomenon of F&V can induce the condensation of
water vapor on the surface of film, forming water droplets that are
not conducive to the observation of F&V from outside the film, and
leading to the reproduction of bacteria. Under such circumstances,
the addition of anti-fog agents is necessary.
The regulatory effect of ethylene is achieved by regulating bio­
synthesis and receptor. Therefore, the biosynthesis and signal trans­
duction of ethylene have been the central problems in ethylene re­
search. The regulatory role of ethylene is described in detail below.
(1) Biosynthetic pathway: According to the biosynthetic pathway of
ethylene (Fig. 1), ACC synthase (ACS) and ACC oxidase (ACO) are
the key enzymes to promote the series reaction of ethylene pro­
duction, where ACS is the rate-limiting enzyme. Systems I and II of
climacteric fruits are the same in the synthesis pathway. They have
different response patterns towards exogenous ethylene, which may
be related to the different properties of ACS and ACO isoenzymes.
(2) Development of fruit cells: The effect of ethylene is not only influ­
enced by the content of ethylene in fruit tissues, but also affected by
the development of fruit cells. During the ripening process, the
sensitivity of fruits to ethylene is gradually enhanced, and the
sensitivity of fruits to ethylene is also different (Table 1).
(3) Biofilm permeability: In addition to regulating protein synthesis
and altering metabolic pathways, the physiological role of ethylene
may also be related to improving biofilm permeability (Yang,
2018). Plant cell intima are mostly composed of lipids and proteins,
and ethylene is much more soluble in lipids than in water. It has
been speculated that the cell membrane may be the starting point
for ethylene action. The biosynthesis of ethylene is closely
associated with the maturation of fruit cell, the increase of per­
meability of cell intima, and the increase of material exosmosis rate.
The ethylene synthesized during fruit ripening is likely to stimulate
the formation of peroxide and thus affect the integrity of the
membrane. Large amounts of ethylene produced during the re­
spiratory jump are probably involved in the ripening and senes­
cence of the fruit in this way.
Synthetic pathways and ripening mechanisms of ethylene in plants
have been extensively studied (Liu et al., 2015). The elimination of
ethylene by inhibitor is divided into two strategies according to its
source: 1) plant level actions (endogenous ethylene); and 2) environ­
ment level actions (exogenous ethylene) (Keller et al.,2013). The in­
hibition of endogenous ethylene is mainly governed by genetic mod­
ifications and chemical treatment; while the removal of exogenous
ethylene mainly relies on physical adsorption, oxidation, catalysis and
biofiltration.
Ethylene scavenger is used to preserve F&V by inhibition, absorp­
tion and oxidation. The roles of ethylene inhibitors (1-MCP), ethylene
absorbents (zeolites) and ethylene catalytic oxidants (KMnO4, Ozone,
TiO2 and so on) are detailed as follows.
3.1. 1-Methylcyclopropene as ethylene inhibitor
1-Methylcyclopropene (1-MCP), a small molecule, belongs to the
small ring hydrocarbons, and has been widely used in F&V preservation
because of its non-toxic, high efficiency and easy handling character­
istics (Lim et al., 2016; Lv et al., 2020; Xu et al., 2019). As shown in
Fig. 3 (Liu et al., 2019), 1-MCP prevents the over-ripening of post­
harvest fruits by competing with ethylene for ethylene receptors (Ad-
ERS1a, Ad-ETR2 and Ad-ETR3) and inhibiting expression of several
transcription factors (Ad-ERF4, Ad-ERF6, Ad-ERF10 and Ad-ERF14).
Moreover, 1-MCP inhibits kiwifruit softening by reducing cell wall-

Table 1
Common classification of different fruits (Hu et al., 2019).
Product type Product Ethylene sensitivity (μL/L)

Climacteric fruits Apples, kiwis, Pears (0.03 ~ 0.1)

Cantaloupe, Passion fruit (> 0.4)
Apricot, Banana, Mango (0.03 ~ 0.1)
Nectarine, Papaya, Peach, Plum, Tomato (0.01 ~ 0.02)
Non-climacteric fruits and Vegetables Cucumber, Persimmon, Orange, (0.01 ~ 0.02)
Carrot, Cabbage, Broccoli, Potato (0.01 ~ 0.02)
Citrus, Celery, Bean, Eggplant (0.04 ~ 0.2)
Berries, cherries, Grapes, (> 0.2)
Pineapples, Pepper (> 0.2)

3
H. Wei, et al.
Fig. 2. Schematic of growth, ripening and aging stages of fruits. Adapted from Yang, 2018.
related gene expression, such as polygalacturonase (PG) and expansin
(EXP) (Ilina et al., 2010). Two structural analogues of 1-MCP, 1-pen­
tylcyclopropene (1-PentCP) and 1-octylcyclopropene (1-OCP) (Wang
et al., 2015), can also superiorly suppress ethylene action of respiratory
climacteric fruits by competitively bonding to ethylene receptors (Xu
et al., 2019; Zhang et al., 2017). Inhibiting the binding of ethylene to its
specific receptor tends to weaken the roles played by ethylene. Once it
works, the ethylene inhibiting effect remains stable even when the 1-
MCP gas environment is removed (Pathak et al., 2017; Pathak, 2018;
Sisler & Serek, 2003).
1-MCP has a stronger effect, compared to ethylene, on the ethylene
receptor, given the whole molecule has a planar structure, a lower
dissociation constant, higher double bond tension, and combination
energy that facilitates its binding to the receptor and thus, preventing
ethylene from normal binding (Tsantili et al., 2007). When 1-MCP binds
to the receptor metal by its own double bond, it causes the rearrange­
ment of the electron cloud and structure of ethylene receptor, which is
different from the rearrangement after ethylene binding. The binding
state of the receptor may also hinder the formation of physiologically
Fig. 3. Schematic diagram of 1-MCP degradation of ethylene. Adapted from Yang Liu et al., 2019; Yang, 2018.
4
Food Chemistry 337 (2021) 127750
active substances in plants, thus disrupting the signal transduction of
ethylene and inhibiting the physiological effects of ethylene. More
studies have shown that 1-MCP not only inhibits ethylene, but also
plays other direct physiological roles, however, the mechanism of de­
laying aging and quality deterioration has not been fully elucidated.
There are many reports about using 1-MCP to preserve F&V. Yarilgac
et al (2019) used modified-atmosphere packaging (MAP) technology to
keep quality attributes of cherry fruit at 22 ± 0.5 ℃ and 80 ± 5%
relative humidity (RH) over 3 days. MAP-treated fruits had better fruit
firmness, lower ethylene concentration and lower decay rate than un­
treated ones, suggesting that MAP was an appropriate approach for the
preservation of cherry fruit. Wang et al. (2018) treated ‘Changkou’
hawthorn fruits with 1.0 μL/L 1-MCP combined with controlled
freezing-point storage at −1.0 ℃. The results showed that ethylene
production and respiratory rate were lowered and the corresponding
production peak and respiratory peak were delayed, so that the pre­
servation time of hawthorn were significantly prolonged. Zhou et al.
(2017) also treated “Wujiuxiang” pear with 1.0 μL/L 1-MCP at 0 ℃ for
120 days, and then transferred to 25 ± 2 ℃. Results showed that 1-
 Table 2
H. Wei, et al.

The application of ethylene scavengers in the preservation of fruits and vegetables.

Method Presentation Food Application Storage conditions Benefits Reference

1-MCP Sachet Tomato 10 ℃, 7 days Reduce both ethylene production and respiration rate and in turn retard the changes in parameters Guillén et al. (2007)
20 ℃, 4 days related to fruit ripening
1-MCP Sachet Avocado 20 ℃, 18 days Delay accumulation of total soluble phenolics, flavonoids, and total antioxidant capacity although Zhang et al. (2013)
levels eventually reached control fruit maxima
1-MCP Sachet Apples 2 ℃, 14 days Suppress the internal ethylene concentrations (IECs) of the fruit during the 14 days period Watkins and Nock
(2012)
1-MCP Sachet Kiwifruit 4 ± 1 °C, 20 days An efficient way to improve the postharvest quality and prolong the shelf life of kiwifruit Xu et al. (2019)
1-MCP Sachet Melon 20 °C, 9 days Melons treated with 1-MCP for 20 and 30 min had reduced ethylene and CO2 production and Nguyen et al. (2019)
slower softening
1-MCP Sachet Pear 0 ℃,120 days 1-MCP inhibited the pear appearance of scald Zhou et al. (2017)
25 ± 2 ℃
1-MCP Sachet Pear 4 months 1-MCP repressed the expression of enzyme polyphenol oxidase gene Giné-Bordonaba et al.
(2020)
Ozone gas kiwifruit 20 °C, 12 days Ozone blocked ethylene production and depressed protein carbonylation in kiwifruit induced by Minas et al. (2012)
ripening
Ozone gas kiwifruit 20 °C, 8 days Ozone treatment reduced the activities of the cell wall enzymes, which lowered ethylene Minas et al. (2014)
concentration, extending shelf life of kiwifruits
Ozone gas kiwifruit 0 °C, 6months Kiwifruit treated with ozone inhibited ACC and MACC concentrations and ACS and ACO enzyme Minas et al. (2018)
activities during ripening
Ozone gas Melon 6 °C, 13 days Melons treated with ozone limited the production of ethylene and the microbial growth of total Toti et al. (2018)
mesophiles
KMnO4 Sachet Apple 0 °C, 5 months Delayed degreening process and flesh firmness loss Sardabi et al. (2014)

5
KMnO4 Filter Peach 0 °C, 36 days Reduced firmness and weight loss. Delayed pH Emadpour & Kalaj
Increase and mantained good appearance. (2015)
KMnO4 Sachet Tomato 4 °C Reduced weight loss, delayed ascorbic acid degradation rate and antioxidant capacity loss Frígola (2016)
‘Cherry’ 25 days
‘Rama’
‘Raf’
‘Pera
KMnO4 nanofibers avocados * Membrane absorption of ethylene generated by avocados was totally quenched in 21 h, and a Tirgar et al. (2018)
nearly zero ethylene concentration was observed for more than 5 days
TiO2/SiO2 Particles Tomatoes 15 °C Prolong fresh fruit and vegetable quality and reduce waste without an excessive increase in costs. Hussain et al. (2011)
CT-TiO2 Film cherry tomatoes 20 °C, 14 days. Exhibit better tensile strength and barrier properties as well as ethylene photodegradation ability Kaewklin et al. (2018)
0.75%GO/TiO2/Bi2WO6 Particles * 20 ± 2 °C High catalytic activity and reusability Lv et al. (2019)
Tourmaline-nitrogen-doped-TiO2 particles * * The SN-TiO2 catalyst containing 4 wt% tourmaline has higher photocatalytic activity for the Tzeng et al. (2019)
(S-NTiO2) oxidation of ethylene than pure TiO2 and N-doped-TiO2
Bi2WO6-TiO2(BT)/starch Film * 25 ± 1 °C Exhibit higher visible-light catalytic activity and the degradation rate of C2H4 reached 12.47% Wang et al. (2019a)
Pt-TiO2 Nanosheets * * Decoration of Pt nanoparticles improve the photocatalytic performance. Within 8 or 12 min, Pan et al.(2016)
200 ppm of C2H4 is completely removed by Pt-TiO2-NS under UV or visible light irradiation
Pt-MCM-41 Particles * 0 °C The conversion of 50 ppm ethylene over 1 wt% Pt/MCM-41 at 0 °C was over 99.8%. To our Jiang et al. (2013)
knowledge, this is the highest conversion of ethylene oxidation at low temperature.
Pt-SBA-15 Particles * 0 °C The SBA-15 supported Pt catalyst (1.8 wt% Pt loading) exhibited an ethylene conversion higher Satter et al. (2018)
than 99% at the initial stage
ZSM-5/WO3‑Pt Nanorod Tomatoes 5 °C,14 days It can be catalyzed efficiently under visible light Kim et al. (2019)
Pt-Loaded Silica Membranes/fibers Flower 5 °C, 9 days Ethylene decomposition activities of 99.8%, at low temperature (5 °C) Na et al. (2019)
Bananas 5 °C, 14 days
Avocado 5 °C, 8 days
Pd-ZSM-5 Pellets kiwi fruit and room temperature 7 days 100% degraded ethylene Mok et al. (2019)
broccoli and 5 days
Au-Co3O4 Particles * 0 °C Ethylene oxidation to achieve a 76% conversion at 0 °C Ma et al. (2010)
Food Chemistry 337 (2021) 127750
H. Wei, et al.
MCP inhibited the appearance of scald due to the influence of gene
expression related to ethylene metabolism and several glutathione S-
transferase and glutathione peroxidase genes in pears. Very recently
Giné-Bordonaba et al. (2020) elucidated the physiology of pear scald
with 1-MCP after 4-months of cold storage, and found that 1-MCP
treatments prevented the development of scald via inhibiting the pro­
duction of ethylene and a common repression effect on the enzyme
polyphenol oxidase gene. Hotchkiss et al. (2007) proposed the release
of 1-MCP from heat-pressed polymer films at a predictable rate into the
package headspace to suppress the effect of ethylene instead of con­
ventional removal methods. Although 1-MCP is an effective, low-cost
option and intended to be hazardous-free without residue issues, it may
still create some disorders leading to diseases in various fruits (Watkins,
2006). Moreover, Xu et al. (2019) found that 1-MCP and lysozyme
coatings have more profound effect on the preservation of kiwi fruit in
postharvest storage compared with 1-MCP alone. Table 2 summarizes
the various applications of 1-MCP in the preservation of F&V. Other
ethylene inhibitors, such as melatonin (Hu et al., 2019), Selenium(Lv
et al., 2017; Zhu et al., 2017), Aloe vera gel (AV) and Aloe arborescens
gel (AA) (Martinez-Romero et al., 2017), have also been used in the
preservation of F&V. Melatonin (N-acetyl-5-methoxytryptamine), an­
other ethylene inhibitor, was reported for postharvest preservation of
bananas and pears (Hu et al., 2017; Liu et al., 2019). Liu et al. (2019)
treated pears with melatonin via nitric oxide (NO) regulation to inhibit
ethylene production and remove ROS, and found that melatonin mainly
induced NO production via regulation of nitric oxide synthase (NOS)
activity while NO may be involved in melatonin scavenging ROS during
softening, which delay postharvest senescence in pears. Moreover, Se­
lenium has been reported for the preservation of F&V (Lv et al., 2017;
Zhu et al., 2017). Zhu et al. (2017) used selenium (Se) to delay the
ripening of tomato fruit and enhance the antioxidant defense system.
The results indicated that pre-treatment of tomato plants with Se could
delay fruit ripening and maintain fruit quality. The possible mechanism
may be Se could repress ethylene biosynthesis genes and inhibit ROS
generations. Ozone plays an important role in the preservation of F&V,
which can directly oxidize ethylene (the details are described in the
following sections). Minas et al. (2018) inhibited ripening of kiwifruit
by 1-MCP, O3, and combination of 1-MCP and O3 at 20 ℃, respectively.
Result showed that all postharvest treatments lowered ACC and 1-
malonyl-aminocyclo-propane-1-carboxylic acid (MACC) concentrations
and ACS and ACO enzyme activities during ripening. In addition, 1-
MCP + O3 suppressed kiwifruit softening more than the individual
treatments alone, which suggested 1-MCP + O3 can function as a ro­
bust regulator of kiwifruit ripening. Bailén et al. (2006) treated toma­
toes by MAP with palladium catalyst impregnated granular-carbon ac­
tivated (GAC-Pd). The results indicated that the addition of GAC-Pd
resulted in lower ethylene concentration, which delayed the ripening
process of tomato. For example, sweetness, firmness, color and flavor
are much better than those packed in MAP without catalysts. In addi­
tion, Khan and Singh (2008) treated Japanese plum with 1-MCP
(1.0 μL/L) and MAP, alone or in combination at 0 ± 1 ℃ and
90% ± 5% RH, and found that the content of ACC, activities of ACS,
ACO cell wall-associated enzymes (exo-polygalacturonase (exo-PG),
endo-polygalacturonase (endo-PG), pectin esterase (PE), and endo-1,4-b-
D-glucanase (EGase)) were reduced, leading to a reduction in ethylene
production. The application of MAP technology can enhance ethylene
inhibition of 1-MCP, slow down the fruit softening and extend the
storage life of plums up to 7 weeks without affecting the quality of ripe
fruit.
Although 1-MCP has some disadvantages, the overall studies de­
monstrate that 1-MCP is indeed effective in prolonging the shelf life of F
&V.
3.2. Zeolite as ethylene adsorbent
Due to the high specific surface area of porous materials, ethylene
6
Food Chemistry 337 (2021) 127750
adsorbents including zeolites, activated carbon, carbon nanospheres,
porous metal oxide, silica gel, halloysite nanotubes and montmor­
illonite are capable of absorbing ethylene released from F&V effectively
(Janjarasskul & Suppakul, 2018). However, the main drawbacks of
these materials are as follows: 1) ethylene only adsorbs on the surface
or inside pores of adsorbents but cannot be completely decomposed; 2)
desorption phenomena may occur; 3) with the prolonging of adsorp­
tion, the adsorption efficiency tends to be decreased; 4) adsorption
reaches the saturation easily and adsorbents need to be replaced in time
(Kim et al., 2019).
Thus, these mental-coated porous materials are often used as fillers
or active ingredients to be added to packaging films/paper or as carriers
for other ethylene scavengers to be incorporated. Esturk et al. (2014)
prepared low-density polyethylene bags containing zeolite-based active
ingredients, which extend the shelf life of broccoli up to 20 days,
compared to a 5-day shelf-life for the unpackaged product. The dis­
advantages of such packaging dispersed with powdered mineral are
that the resulting films are opaque and grainy. Moreover, the films
typically have low efficacy for absorbing ethylene since only a limited
amount of mineral is incorporated to avoid negative impact on the
mechanical properties of the package. Alternative systems reported for
effectively capturing ethylene by adsorption, followed by catalytic de­
composition of ethylene include the activated carbon-based sachets in
conjunction with various metal catalysts and bromine-type inorganic
chemicals (Janjarasskul & Suppakul, 2018; Smith et al., 2016).
Mansourbahmani et al. (2017) treated tomato fruits with several sys­
tems: palladium-promoted nano zeolite (0,1,2.5 and 5 wt%), KMnO4-
promoted nano zeolite (0,10,15 and 20 wt%), 1-MCP (30 ppm), CaCl2
(0,1,1.5 and 2 wt%), salicylic acid (SA;0,0.1,0.5 and 1 wt%) and UV-C
(0,5,10 and 15 min). The fruits were stored at 7 ± 0.5 °C and
90 ± 2% RH over 35 days of cold storage. The results showed that
palladium-promoted nano zeolite 5%, KMnO4-promoted nano zeolite
20%, 1-MCP 30 ppm, CaCl2 2%, SA 1% and UV-C 15 min levels had the
most ethylene scavenging function. Effectiveness of the treatments in
ethylene scavenging was in the order: palladium > KMnO4 > 1-
MCP > SA = CaCl2 > UV-C (Mansourbahmani et al., 2017), sug­
gesting that metal catalysts are most effective in removing ethylene
compared with other ethylene scavenger or inhibitor. Coincidentally,
Jiang et al. (2013) also investigated the effect of the support using Pt
catalysts supported on MCM-41, SiO2, Al2O3, ZrO2, and TiO2. The
catalytic activities were ranked as follows: Pt/MCM-41 > Pt/
SiO2 > Pt/Al2O3 > Pt/TiO2; and Pt/ZrO2, 1 wt% Pt/MCM-41 could
almost completely degrade ethylene.
Overall, metal or metal oxide catalysts which are supported on
porous materials have unique advantages in ethylene removal.
3.3. Ethylene catalytic oxidants
There are several types of ethylene catalytic oxidants such as po­
tassium permanganate (KMnO4), ozone (O3) and titanium dioxide
(TiO2). Among them, the purple KMnO4 is the most widely used ex­
ternal ethylene scavenge, because of its high oxidizing ability, which
decomposes ethylene via the following reactions (Kim et al., 2019).
3CH2CH2 + 2KMnO4 + H2O → 2MnO2 + 3CH3CHO + 2KOH (1)
CH3CHO + 2KMnO4 + H2O → 3CH3COOH + 2MnO2 + 2KOH (2)
3CH3COOH + 8KMnO4 → 6CO2 + 8KOH + 2H2O (3)
The reactions above are activated by the moisture from transpira­
tion and respiration of fresh products, and change color of KMnO4 from
purple to brown, which also implies the effectiveness of KMnO4-based
C2H4-scavenging in preservation of F&V (Janjarasskul & Suppakul,
2018). The overall reaction is illustrated in Eq. (4) below, in which
ethylene is oxidized into CO2 and H2O; and meanwhile MnO2 and KOH
are produced from KMnO4.
H. Wei, et al. Food Chemistry 337 (2021) 127750

3CH2CH2 + 12KMnO4 → 12MnO2 + 12KOH + 6CO2 (4) ethylene degradation, which is mainly attributed to its unique photo­
chemical reactivity and physical properties including ultrahigh bright­
It is worth noting that the intermediates could be generated due to
ness (due to high refractive index) and resistance to discoloration (Alex
incomplete oxidation reaction, which might be bound to the residues,
et al., 2012). Ethylene photo-degradation induced by TiO2 starts with
thus raising disposal issues potentially (Pathak et al., 2017; Keller et al.,
the radiation of UV light generating oxidizing agents, including hy­
2013). Due to the large specific surface area of porous materials, em­
droxyl radical (OH•) and reactive oxygen species (ROS), which are
bedding KMnO4 into porous materials can not only achieve a good
highly reactive and convert ethylene into CO2 and H2O (Kaewklin et al.,
ethylene removal effect, but is also beneficial in the removal of un­
2018; Kim et al., 2019). Its reaction mechanism is described as follows:
desirable byproducts (Janjarasskul & Suppakul, 2018, Pathak, 2018).
First, TiO2 is irradiated via photons at UV wavelengths (e.g., around
Once physically adsorbed by the porous medium, KMnO4 oxidizes
380 nm) to generate the electrons which create holes in the valence
ethylene to ethylene glycol–forming manganese oxide, potassium hy­
band due to UV-induced excitation, as shown in Eq. (6). The resulting
droxide and CO2. KMnO4 is often used in the form of a highly perme­
electron–hole pairs are capable of initiating the reduction and oxidation
able sachet blanket or tube to be placed inside packaging, or in storage
reactions (Lin et al., 2014; Pathak, 2018). This produces electron (e − )
warehouses (Janjarasskul & Suppakul, 2018), allowing the diffusion of
and hole (h + ) species on the TiO2 surface. The hole reacts with water
ethylene through blanket. A membrane composed of alumina nanofi­
or hydroxide ions (OH−) adsorbed on the TiO2 surface to produce
bers produced by electrospinning as efficient KMnO4 carriers was re­
highly reactive hydroxyl radicals (OH•) and e − reduces oxygen to
ported by Tirgar et al. (2018). Results showed that the membrane with
produce superoxide ions (O2−), which further oxidize ethylene to CO2
high surface area oxidized 73% of C2H4 in 25 min, and its high capacity
and H2O as its end product (Kaewklin et al., 2018). The decomposition
for C2H4 absorption could last over a prolonged period. Additionally,
of ethylene by TiO2 is given in the following equations:
Sammi and Masud (2009) packed freshly harvested mature green to­
In Eq. (6), hν, e- and h+ represent radiation, electrons and holes,
matoes at room temperature in polyethylene (PE) packaging with
respectively.
KMnO4, demonstrating the use of KMnO4 contributed to the production
of CO2 and water in the package atmosphere, which helped lower the TiO2 + hν → TiO2 + e-+ h+ (6)
respiration and ripening processes. The application of KMnO4 in the • •
The hydroxyl radical (OH ) and superoxide ion ( O2−)
are generated
preservation of F&V is summarized in Table 2.
from the oxidation of water molecules and the reduction of oxygen
One of the challenges associated with KMnO4 is how to maintain its
induced by the electron–hole pairs, using the following equations, re­
efficiency which is often lowered, following saturation over time.
spectively (Pathak et al., 2017; Pathak, 2018):
Therefore, KMnO4-based C2H4-scavengers need to be replaced fre­
quently for high ethylene-producing commodities due to longer storage H2O + h+ → OH• + H+ (7)
durations (Pathak, 2018). Moreover, KMnO4 is not typically integrated - •
into food contact surfaces of packaging due to its high toxicity and O2 + e → O2– (8)
inherent deep purple color, with the possibility of migrating onto fresh The resulting radicals are highly reactive, able to readily decompose
product (Kim et al., 2019; Yildirim, et al., 2018). organic compounds (Pathak et al., 2017). The reaction between hy­
Ozone, as a strong oxidant, is another substance for ethylene droxyl radical and ethylene is presented in Eq. (9):
scavenging (Kim, et al., 2019), which has been reported for fruit pre­
servation. The decomposition of ethylene by ozone is given in Eq. (5): OH• + C2H4 → xCO2 + yH2O (9)

2O3 + C2H4 → 2CO2 + 2H2O (5) The overall reaction can be summarized below:

The mechanism of using ozone to keep F&V fresh is mainly reflected C2H4 + 3O2 → 2CO2 + 2H2O (10)
in two aspects: blocking ethylene biosynthesis during ripening by in­
Although the mechanism of photocatalytic oxidation has been elu­
hibiting ACS and ACO gene expression and enzymatic activity; and
cidated previously (Augugliaro et al., 2012; Pathak et al., 2017; Pathak,
modulating cell wall of fruits. Minas et al kept kiwifruits at 0 ℃ for 1, 3,
2018), the exact reaction mechanism still remains a subject under de­
and 5 months with or without treatment of ozone (0.3 μL/L) and then
bate owing to the presence of various reaction intermediates which
allowed them to ripen at 20 ℃ for 12 days. Results showed that ozone
have not been clarified completely. Maneerat and Hayata (2008) coated
blocked ethylene production and depressed protein carbonylation in
TiO2 on polypropylene film for packing tomatoes, which significantly
kiwifruit induced by ripening, which indicated ozone improved post-
increased the preservation time of tomatoes due to the photocatalytic
harvest behavior of kiwifruit (Minas et al., 2012). Moreover, O3 treat­
oxidation of ethylene. TiO2 coating on degradable cellulose paper was
ment maintained the firmness of kiwifruit by blocking swelling of cell
also reported by Liu et al. (2016a), which appears to be a better choice
wall, solubilization of pectin and neutral sugar and activity of cell wall-
compared to petroleum-based polypropylene film. Kim et al (2019)
degrading enzymes (Minas et al., 2014). Toti et al (2018) treated can­
proved that ethylene scavenger coupling with zeolite adsorbents via
taloupe melons via O3 at 6 ℃ for 13 days. Results showed that O3
photocatalytic oxidation can be considered as a favorable process for
treatment reduced the activities of the cell wall enzymes, thus lowering
prolonging the shelf life of fruits. In addition, Chiara et al (2015) also
ethylene concentration and extending shelf life of kiwifruits. The var­
successfully used mesoporous TiO2/SiO2 nanocomposites for ethylene
ious applications of O3 in the preservation of F&V are included in
photodegradation to prolong the shelf life of tomato fruit. The appli­
Table 2.
cation of TiO2 in the preservation of F&V is shown in Table 2.
Generally Recognized as Safe (GRAS) is the safety index for food
The key drawback in photocatalytic systems is the readiness of
additive as evaluated by the FDA (Food and Drug Administration).
catalyst deactivation as well as low efficiency. Effective utilization of
Despite the fact O3 is regarded safe as a food additive according to
photons and prevention of electron–hole recombination are important
GRAS (Pathak, 2018), it is still rather difficult to handle because of its
issues that should be addressed in an attempt to improve photocatalytic
facilitative decomposition into oxygen (Janjarasskul and Suppakul,
efficiency (Pathak et al., 2017; Pathak, 2018; Tytgat et al., 2012).
2018; Kim et al., 2019). Currently, there are reports on the integration
Therefore, modification of catalysts is in high demand, as reviewed by
of ozone and 1-MCP treatment for prolonging the quality of post-har­
Pathak et al (Pathak et al., 2017; Pathak, 2018). Moreover, the negative
vested fruits, which have been described in detail in 3.1.
effect of UV exposure on food quality should be taken into account
Photocatalysis is another approach to degrade ethylene (Ibhadon &
(Yildirim, et al., 2018).
Fitzpatrick, 2013, Keller et al., 2013; Kim et al., 2019). TiO2 is a typical
semiconductor material and one of the most popular photocatalysts for

7
H. Wei, et al.
4. Metal oxide catalysis supported by micro-mesoporous material
as ethylene scavenger
In terms of pore size, porous materials are typically divided into
three categories: microporous (pore widths exceed 50 nm), mesoporous
(pore widths between 2 and 50 nm) and microporous (widths smaller
than 2 nm). These porous materials have been used extensively owing
to their unique structures and excellent performance (Wuttke et al.,
2018). Among various porous materials, zeolite is most commonly used
due to its large vacant spaces or cages for capturing or accommodating
ethylene upon adsorption (Ichiura et al., 2003). The excellent perfor­
mance of zeolite-based is attributed to its porous 3-dimensional struc­
ture with cation exchange, adsorption, and molecular sieving properties
(Yildirim et al., 2018). Nanocomposites composed of visible-light active
Pt-loaded monoclinic WO3 nanorods on ZSM-5 (ZSM-5/WO3-Pt) was
developed by Kim et al (2019), which displayed a synergistic effect for
ethylene removal. Tomato fruits were packaged after 12 days with and
without photocatalytic module to determine its efficacy for maintaining
fruits quality. Results showed that with the application of photo­
catalytic module (temperature 20–25 °C, humidity 45–55%.), tomatoes
were more consistent with less-red color. Catalytic activity relies on
hydroxyl radicals created by WO3-Pt loaded in the micropores of the
ZSM-5 matrix, thus enabling the adsorption and decomposition of
ethylene during fruit storage without requiring a circulation device. In
addition, silica is also a commonly used support material due to its high
specific surface area. Chiara et al (2015) also used TiO2/SiO2 nano­
composites to successfully prolong the shelf life of tomatoes. A com­
plete oxidation of ethylene used silica-supported Pt catalyst with a high
catalytic activity was reported by Jiang et al (2013), in which trace
amounts of ethylene were conversed over 99.8% at 0 °C by 1% silica-
supported Pt under practical conditions. However, physisorption of
water molecules formed during complete ethylene oxidation decreases
the initial activity gradually with reaction time, which results in the
partial blockage of active species on Pt nanoparticles. In order to deal
with the effects of water molecules, Satter et al. (2018) increased the
hydrophobicity of mesoporous silica SBA-15 by a simple high tem­
perature calcination in air, and found that Pt catalysts after calcination
showed higher ethylene conversion and CO2 yield than the untreated
catalyst. This is attributed to the release of water molecules formed on
Pt nanoparticles incorporated into hydrophobic mesopores, thus pre­
venting Pt sites from being deactivated by water. Gloria et al (2006)
also reported that the activated carbon loaded with 1% palladium (Pd)
was more effective than activated carbon used alone in maintaining the
quality of tomatoes (Pathak et al., 2017; Pathak, 2018). Moreover,
zeolite impregnated with Pd was more effective than untreated zeolite
in removing of ethylene, extending the shelf life while maintaining
color of fruits such as green banana and avocado (Pathak et al., 2017;
Pathak, 2018; Smith et al., 2016; Terry et al., 2007). The application of
metal catalysts in the degradation of ethylene is shown in Table 2.
Several other solid catalysts such as Ag/Zeolites (Cisneros, Gao, &
Corma, 2019), Au/CO3O4 (Wen et al., 2011), and Ag/ZnO (Zhu et al.,
2018) have also been widely studied for ethylene oxidation. Malshe and
Malshe (2010) reported a simple and economical process for prepara­
tion of Ag-coated non-metallic nano/microparticles and found that
silver-coated nano/micro particles enabled the conversion of ethylene
to ethylene oxide effectively.
However, owing to health concerns and regulations against their
food-contact applications, these ethylene capturing materials are
usually used in the form of sachets placed inside packaging, which
consequently appears to have limited acceptance for end users. To cope
with this problem, the incorporation of scavengers in packaging films
has emerged as an appropriate approach.
There are five main methods for preparing microporous films, i.e.,
mechanical perforation, inorganic fill drawing technique, semi-crys­
talline stretching, Chemical foaming process and phase separation.
Among them, the inorganic fill drawing technique is one of the most
8
Food Chemistry 337 (2021) 127750
optimal choices as fruit fresh keeping technology.
5. Film-based packaging containing ethylene scavenger
As mentioned previously, the integration of scavenger into packa­
ging film might be promising to tackle sachet-related problems.
Ethylene scavengers could either be embedded into a solid, dispersed in
plastic, or incorporated into various layers of the packaging (Ozdemir &
Floros, 2004).
However, there has only been limited research on incorporating
ethylene absorbers/scavengers in the structure of packaging films. As
one of the limited examples, zeolite molecular sieve (ZMS) was found
applicable to be incorporated into packaging films as an ethylene-ab­
sorbing additive (Zi et al., 2011). Various reports have proved that
incorporation of zeolites increases gas permeability of packaging films
due to their crystalline porous-3-dimensional framework structure
(Yildirim et al., 2018; Zi et al., 2011). The incorporation of additives for
active packaging can be accomplished by coating, immobilization or
surface modification of substrate materials and its effect on the quality
of different foods has been well documented by Yildirim et al. (2018).
Malshe and Malshe (2018) filed a patent for the incorporation of coated
nano/micro particles in kinds of packaging films. Moreover, these
materials could also be fabricated in various forms, commensurate with
the needs of fruit and other supply chains, which can retain freshness,
extend usable life and reduce the degrading effects on the environment.
Some preservative materials based on adsorption or removal of ethy­
lene have been commercialized. For example, commercial silver cata­
lyzed bags (Freshness Plus Bags) (lasting for three years) was used for
the preservation of F&V, which help destroy ethylene gas while slowing
down their ripening process without losing nutritional value. Lifeline
Technologies has also been manufacturing nano silver-based additives
for preservation of F&V for several years. In addition, Debbie Meyer
green bags have been available since last 40 years, which, however,
used zeolites to adsorb ethylene, and had a limited life due to the sa­
turation of zeolite.
Maneerat and Hayata (2008) reported TiO2-coated polypropylene
film for the photocatalytic oxidation of ethylene; the resulting film
extended the shelf life of tomatoes significantly. From a practical point
of view, thin films are required for packaging, which has driven the
adoption of nanotechnology for film products (Wuttke et al., 2018).
Blending nano-powders (nano-Ag, nano-TiO2, and kaolin) with PE for
reduction of ethylene in packaged vegetables was reported by Li et al.
(2009); meanwhile, the results showed that the incorporation of na­
noparticles into polyethylene film significantly prevented fruit from
softening and browning even after 12-day storage. Moreover, an im­
portant index of rate of browning of Chinese jujube was reduced from
0.7 to 0.6 on day 12, which indicated that nano-powders with PE
composite film are a good choice to maintain the quality of the fruit.
Similarly, Hu et al (2011) investigated the effect of active packaging
prepared by blending nano-Ag, nano-TiO2, and montmorillonite with
PE on the quality of ethylene-treated mature kiwifruit at 4 °C for
42 days. Weight loss, softening, color variation, and Brix degrees (°Brix)
of kiwifruit were significantly reduced by 22.7%, 124.8%, 23.5%, and
14.4%, respectively, however, the specific shelf life was not reported.
The effects of four kinds of packing film including non-perforated
highly gas-permeable film (HNP), non-perforated ethylene-absorbing
highly gas-permeable film (HNPE), microperforated highly gas-perme­
able films (HMP) and common non-perforated polyethylene film (LNP)
on the preservation of ‘Nam Dok Mai’ mango was revealed by
Boonruang et al (2012). Results showed that the shelf life of mangoes
was extended to 40 days with HNPE, 35 days with HNP, 30 days with
HMP, and 5 days with LNP, as compared with 20 days without
packaging film at 12 °C. In addition, HNPE films incorporated with MFI-
type zeolites can further delay ripening of mangoes. Moreover, Esturk
et al (2014) tested the influence of low-density polyethylene (LDPE)
bags containing Tazetut (an inorganic product containing 50% of
H. Wei, et al.
various aluminosilicate minerals (zeolite)) on the preservation of
Broccoli florets. Results showed that composite films containing the
scavenger prolonged storability of broccoli up to 20 days at 4 °C;
broccoli only lasted 5 days with unpackaged control. The oxygen con­
centration in the LDPE bags without ethylene scavenger was found to
be less than 1% after 5 days of storage, leaving them susceptible to the
growth of anaerobic fermentation. Therefore, it has become one of the
important trends to prepare composite packaging films that can adsorb
ethylene while simultaneously resisting bacteria. Li et al (2016) used
LDPE as base material, ZSM-5 zeolite as ethylene adsorbent, TiO2 as
photocatalyst to scavenge ethylene and the antimicrobial agent to
successfully prepare a kind of packaging film with the function of
ethylene scavenging and antimicrobial.
The composite films, however, tend to be opaque and grainy, which
are the key disadvantages; moreover, owing to the limited amount of
active agents (such as zeolite, SiO2) that can be incorporated into
packaging film to minimize negative impact on the mechanical prop­
erties of film, the efficiency of capturing ethylene in the composite films
is not sufficiently high (Janjarasskul & Suppakul, 2018). Moreover,
other petroleum-based plastics containing active substances such as
LDPE and polyvinyl chloride films (Boonruang et al., 2012; Tas et al.,
2017; Wang et al., 2010; Yang et al., 2010; Zi et al., 2011), have also
been widely reported for the preservation of F&V, as reviewed by
Yildirim et al (2018); although the review was only focused on tradi­
tional petroleum-based materials. Nowadays, in order to guarantee
sustainability and to provide consumers high quality foods with the
least amounts of chemical preservatives, food packaging industries are
seeking natural source-based and biodegradable packages that can re­
duce the use of petroleum-based materials (Ballesteros et al., 2018).
Natural polymers for such applications were reviewed by Malhotra et al
(2015), as shown in Fig. 4(a). In fact, based materials, cellophane and
paper, originating from biodegradable lignocellulosic materials, are still
commonly used in food packaging nowadays. Chitosan (CH), the second
Fig. 4. (a). The origin and renewable sources of biobased polymers. Adapted from Malhotra et al., 2015; (b). Cellulosic paper products for fruit/vegetable packaging,
download from internet; (c). A schematic diagram of the possible mechanism of photocatalytic degradation of ethylene and antimicrobial activity of the chitosan-
TiO2 nanocomposite film. Reprinted from (Siripatrawan & Kaewklin, 2018), with permissions from Elsevier.
9
Food Chemistry 337 (2021) 127750
most abundant natural biopolymer next to cellulose, is also used to pack
food products due to its antimicrobial behavior (Youssef et al., 2016).
On the other hand, polylactic acid (PLA) is one of the most widely used
biopolymers because of its biocompatibility and environmental
friendliness (Pan et al., 2016).
Specifically, Peelman et al (2014) used PLA and a cellulose-based
multilayer package as modified atmosphere packaging (MAP) to pack
various foods such as steak, sausage, cheese and pre-fried fries at 4 °C.
The high gas-barrier, particularly the oxygen barrier contributed by
cellulose film, might be the key reason for prolonging the shelf-life of
MAP-packed food products. Completely based on cellulose fibers, paper
products are also suitable for food packaging. Apart from the cost-ef­
fectiveness and reasonably high mechanical strength, paper packaging
allows good airflow and prevents products from drying out compared to
polyolefin-based plastics. In the presence of ethylene scavengers, anti­
microbial agents or other functional active substances, paper products
can further improve their performance in the preservation of fruits
(cellulosic paper products in Fig. 4(b)). For starch-based film, 4% of
Bi2WO6–TiO2 (BT) was used to prepare starch nanocomposite films for
the oxidation of ethylene (Wang et al., 2019), which promoted the rate
of ethylene degradation up to 12.4%. Chitosan and nano-sized TiO2
nanocomposite film was prepared by Kaewklin et al (2018) in an at­
tempt to induce the ethylene photodegradation, thus maintaining the
quality of fruits (e.g., tomatoes) by delaying the ripening process.
In addition to the ethylene scavenging effect, the antibacterial
properties of the film must also be taken into account in order to
achieve the maximum preservation effect. As one type of antimicrobial
agents, ZnO nanoparticles were incorporated into the composite film
consisting of chitosan and carboxymethyl cellulose (CMC) for the pre­
servation of soft white cheese (Youssefet al., 2016). The resulting film
increased the shelf-life of the cheese at 7 °C up to 30 days owing to the
improved bacterial barrier contributed by ZnO nanoparticles. An ideal
antimicrobial agent should be highly effective against a broad spectrum
H. Wei, et al.
of bacteria, including both Gram-positive (S. aureus) and Gram-negative
(Pseudomonas aeruginosa, E. coli) bacteria as well as fungi (e.g., Candida
albicans). Lavoine et al (2015) used a chlorhexidine digluconate (CHX)
and microfibrillated cellulose (MFC) to prepare an antimicrobial ma­
terial for surface coating of paperboard which was used for the pre­
servation of pork liver. CHX/MFC coated paperboard preserved the
freshness of pork liver, better than polyethylene-coated paperboard. Liu
et al. (2016b) coated CNC (cellulose nanocrystals)/Ag/beeswax com­
posites on paper surface. When the coating weight was 21.53 g/m2, the
dynamic contact angle and the growth inhibition of E. coli reached 113◦
and 99.96%, respectively. Moreover, Ni et al. (2018) coated filter paper
using a composite film including ZnO nanoparticles, carboxymethyl
cellulose and guanidine-based starch for the preparation of anti­
bacterial paper, with excellent inhibition towards E. coli. These results
suggested that the developed method was effective for the production
of multi-functional paper with enhanced antibacterial and water re­
sistance properties.
The shelf life of F&V can be improved significantly by the synergetic
effect of ethylene scavenging and antibacterial enhancing, thus max­
imizing the preservation. This was also demonstrated from work con­
ducted by Siripatrawan and Kaewklin (2018) on TiO2/chitosan nano­
composite films, which exhibited great potential as active packaging for
postharvest applications. A schematic revealing the possible mechanism
is illustrated in Fig. 4(c) (Siripatrawan & Kaewklin, 2018). Moreover,
CS-TiO2-BPPE (black plum peel extract) films were used as antioxidant,
ethylene scavenging, antimicrobial and pH-sensitive food packing ma­
terial, thus rendering the composite film multi-functional (Zhang et al.,
2019).
Cezar et al (2019) reported antimicrobial packages containing the
inclusion complexes (ICs) of ß-cyclodextrin (ß-CD) with essential oils of
palmarosa (ICp) or star anise (ICsa) as antibacterial agents. The results
indicated that antimicrobial packaging prolonged the shelf-life of apple
to 12 days partly due to the slowing of Penicillium expansum growth
Pan et al (2019) recently reviewed guanidine-based polymers for
rendering polysaccharide-based materials antimicrobial, which are
highly applicable in fabricating antimicrobial cellulose-based or paper
products for F&V packaging. The overall performance of guanidine-
based polymers is better than those of conventional QAS (quanternary
ammonium salt) or phosphonium type polymers in terms of minimum
inhibitory concentration (MIC). Moreover, the production of anti­
microbial packaging with guanidine-modified starch can be readily
scaled up (Khan et al. 2016). Therefore, integrating guanidine polymer
and ethylene scavenger into the package structure would be an ex­
cellent choice.
6. Conclusions
Catalytic scavengers are effective in eliminating ethylene associated
with F&V preservation, but usually prepared as large particles in sto­
rage space in the form of a pouch that can be hazardous to human
health. Mixing ethylene scavenger into film is one of the promising
approaches to alleviate this problem. However, packaging materials
integrated with ethylene-scavengers in the packaging structure still
remains challenging in commercial applications. Literatures about the
use of these materials for various fresh products are also limited. The
successful packaging of food produce should allow gas permeability of
the packaging film to correspond to respiration and enable to remove or
capture ethylene from the package environment. Moreover, packaging
parameters designed for specific products should be varied or optimized
based on respiration rate, ethylene sensitivity, and ethylene production
rate. The composite films that can adsorb ethylene efficiently and resist
bacteria without sacrificing the transparency of films are in high de­
mand as one of the particularly hot topics for research. In addition, the
interactions among food, environment and packaging materials must be
further explored from a fundamental point of view. These findings will
not only provide an important guideline on emerging technology to be
10
Food Chemistry 337 (2021) 127750
developed for F&V packaging, but also enhance consumer’s acceptance
towards new packaging materials and packing manners.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgement
The work is supported by the funding from the Joint International
Research Lab of Lignocellulosic Functional Materials at Nanjing
Forestry University and NSERC Canada.
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