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Ethylene control technologies in extending post-harvest shelf life of climacteric fruit Junhua Zhang, Dong Cheng, Baobin Wang, Iqbal Khan, and Yonghao Ni J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b02616 • Publication Date (Web): 02 Aug 2017 Downloaded from http://pubs.acs.org on August 2, 2017
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Journal of Agricultural and Food Chemistry
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Ethylene control technologies in extending post-harvest shelf life of
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climacteric fruit
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Junhua Zhang *1, 2, Dong Cheng 2, 3, Baobin Wang 2, Iqbal Khan 2, Yonghao Ni *2, 3
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1
5
Education, Zhejiang Sci-Tech University, Hangzhou 310018, China.
6
2
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Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada.
8
3
9
300457, China.
Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of
Limerick Pulp and Paper Centre, Department of Chemical Engineering, University of New
Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, Tianjin
10 11
Contact information for Corresponding Author
12
*(Zhang JH) E-mail:
[email protected]. Tel.: +86-571-86843871. Fax: +86-571-86843250.
13
*(Ni YH) E-mail:
[email protected]. Tel.: +1-506-4516857. Fax: +1-506-4534767.
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Graphical abstract
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ABSTRACT:
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Fresh fruit is important for a healthy diet. However, due to their seasonal production, regional
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specific cultivation and perishable nature, it is essential to develop preservation technologies to
51
extend the post-harvest shelf life of fresh fruits. Climacteric fruit adopt spoilage because of
52
ethylene, a key hormone associated with the ripening process. Therefore, controlling ethylene
53
activity by following safe and effective approaches is a key to extend the post-harvest shelf life
54
of fruit. In this review, ethylene control technologies will be discussed aiming for the need of
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developing more innovative and effective approaches. The biosynthesis pathway will be given
56
firstly. Then, the technologies determining the post-harvest shelf life of climacteric fruit will be
57
described with special attention to the latest and significant published works in this field.
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Special attention is given to 1-methylcyclopropene (1-MCP), which is effective in fruit
59
preservation technologies. Finally, the encapsulation technology to improve the stability of 1-
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MCP will be proposed, using a potential encapsulation agent of 1-MCP, calixarene.
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Keywords: fruit preservation, shelf life, ethylene, 1-MCP, encapsulation
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1. Introduction
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There are a number of approaches: physical (temperature, light), chemical (oxidation) or
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biological (microorganisms), which can be adopted for fresh fruit preservation. Effective
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methods of fruit preservation make it possible to have fresh fruit available year-round
81
regardless of their growing season and regional nature to meet our pursuit of various and
82
diverse types of fresh fruit.
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Fresh fruit can be divided into climacteric and non-climacteric fruit based on the ethylene
84
production and cellular respiration in the stage of fruit ripening. For climacteric fruit, which
85
including apple, banana, melon, apricot, tomato, and so on, their ethylene production and
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cellular respiration will be increased in their ripening stage. The main cause for their spoilage
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nature is the biochemical changes that happen because of ethylene, a key hormone associated
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with the ripening process. Therefore, controlling ethylene activity by following safe and
89
effective approaches is the key to extend the post-harvest shelf life of fruits (1). In the
90
literature, many ethylene controlled technologies, including the ethylene synthesis suppression
91
with controlled temperature/atmosphere (2-7) or silver treatment (8-11), and the ethylene
92
removal by vacuum ultraviolet radiation (12) / O3 (13), KMnO4 (14-16) or nano-TiO2 (17, 18)
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oxidation, have been reported to prolong the post-harvest shelf life of climacteric fruits can be
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prolonged. The development of high efficiency processes/methods to control the ethylene
95
formation/release/acceptance of climacteric fruit is always in demand.
96
In this review, the ethylene biosynthesis pathway will be discussed first. Then, the
97
technologies of extending the post-harvest shelf life of climacteric fruit as a result of the
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ethylene control/removal/inhibition will be discussed. 1-methylcyclopropene (1-MCP), a unique
99
chemical for this purpose will be particularly highlighted. Finally, the encapsulation technology
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related to the use of 1-MCP will be discussed and a potential encapsulation agent of 1-MCP,
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calixarene will be proposed.
102
2. Ethylene biosynthesis pathway
103
The effect of ethylene on plant growth can be traced back to 1864, it was found that a
104
gaseous material leaking from the street lighting system could modify the growth of plants (19).
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The gaseous material was later proved to be ethylene (20). Then, ethylene as a natural
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compound generated from apples was discovered by Gane (21). Later, it was found that all
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parts of higher plants, including leaves, stems, roots, flowers, fruit, tubers and seedlings can
108
produce ethylene (22). The key function of ethylene as fruit ripener and plant developer,
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including seed germination, vegetative growth, vegetative senescence, leaf abscission, and
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plant flowering, was confirmed (23).
111 112
Fig.1 A mechanism for the biosynthesis of ethylene from methionine (MET: methionine, SAM:
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S-adenosylmethionine, MTAN: 5’-methylthioadenosine, ACC: 1-aminocyclopropane-1-carboxylic
114
acid, MTR: 5-methylthioribose). The scheme is modified from that of Yang and Adams (24).
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During the growth process of fruit and other plants, there are many potential compounds
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that can be converted to ethylene. Among them, methionine (MET) was suggested as a possible
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precursor of ethylene (25-30). As shown in Fig.1, the generation of ethylene from MET includes
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the following key steps: 1) MET will first be activated by ATP to form S-adenosylmethionine
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(SAM) (Step 1) (24, 31-33); 2) the generated SAM will react with pyridoxal phosphate to
120
produce a Schiff base (Step 2); 3) the Schiff base undergoes an elimination of α hydrogen, along
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with γ substituent to form a cyclopropane ring (A) and 5’-methylthioadenosine (MTAN) (24)
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(Step 3); 4) the generated Compound A will be converted to 1-aminocyclopropane-1-carboxylic
123
acid (ACC) and pyridoxal phosphate in the presence of H2O and H+ (Step 4), which is a
124
controlling step for the synthesis of ethylene; 5) ACC will be oxidized by ACC oxidase to form
125
ethylene via Compound B (Step 5) in the presence of oxygen and low levels of CO2 , both of
126
which are essential to activate ACC oxidase (34-37); 6) the obtained Compound B will be finally
127
converted to ethylene (Step 6); 7) MTAN can be regenerated to MET through an intermediate
128
of 5-methylthioribose (MTR) (Steps 7 and 8). This sulfur cycle is very important to maintain a
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substantial ethylene production rate (38, 39).
130
3. Current ethylene controlling strategies for climacteric fruit preservation
131
Ethylene is a key in the climacteric fruit ripening process, there are a number of
132
technologies reported in the literature to prolong the shelf life of climacteric fruit (showed in
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Table 1):
134
Table 1 the published ethylene controlling strategies for climacteric fruit preservation
135
(RH=relative humidity, CTHH=Controlled temperature and high humidity, CA=controlled
136
atmosphere). Method
Fruit
Storage conditions
Results
Ref.
Treated with 125 ppm Weight loss was reduced, chlorine water and then Tomato
remained green up to 40
(40)
stored at 12 °C under CA days.
CTHH storage with 98% RH Exposed to temperature of
Low amounts of CO2 and
33 °C under 70% RH
ethylene were produced
durian
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0 °C for 6 months, with a further 10 d shelf-life in air
Ethylene production,
at 20 °C were: 0.5 kPa O2 +
respiration was suppressed
Apple
(2) 6.0 kPa CO2 stored in air+12% CO2 or in
Pear
a 0.5% O2 atmosphere for 7
Respiration and ethylene production rates were
(3)
days at 2.5 °C followed by suppressed one day at 20 °C
Apple
Pre-treated with 2%
Respiration and ethylene
ascorbic acid and held in
production rates were
100% N2 at 10 °C
suppressed
(4)
Pre-dipped in ascorbic acid CA
Preserved their original and calcium chloride and color with minor changes
Apple stored under 100% N2 at 8-
(5)
for more than 1 month
10 °C Retained the quality and Honeydew
Stored under 2% O2+10%
retarded increased
melon
CO2 at 10 °C
metabolism and microbial
(6) growth
Treated with 1% CaCl2 or 2% Ca lactate and stored at 0Kiwifruit
2 °C, 90% RH in an C2H4-free Had a shelf-life of 9-12 days
(7)
atmosphere of 2 to 4 kPa O2 and/or 5-10 kPa CO2 Decreased the ethylene Banana
Treated with AgNO3
synthesis and delayed the
(9)
solution
Silver
ripening process treatment Treated with silver
Decreased the ethylene
thiosulfate
synthesis and delayed the
Banana
(10)
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ripening process Long-term silver treatment stimulated both the Treated with silver Tomato
conversion of ACC to
(11)
thiosulfate ethylene and the synthesis of ACC stored in sealed polyethylene bags
keep in firm green after 16
containing KMnO4 and
days
(14) Ca(OH)2 Treated with alkaline
Ethylene can be removed
KMnO4 in conjunction with
and green life of bananas
CA storage
can be extended
Banana Oxidize
(15)
ethylene to KMnO4 was present in the
CO2
stored polyethylene films or
Extended the shelf-life
(16)
bags Fruit softening, weight loss, browning and climatic
Chinese jujube
Packed with nano-TiO2
(18) evolution was inhibited after 12-day Ethylene action with plants tissue was blocked (2, 5NBD has an unpleasant
(42-
Block
smell and can lead to
45)
ethylene
cancer, so it was not be
action
used in fruit preservation)
Plants
Apple
Treated with 2, 5-NBD
DACP was applied as a gas
Had lower internal ethylene
in the light for 24 h to
concentrations than
apples harvested at a
untreated fruits
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mature, preclimacteric stage and held in air at 21 °C for 30 days red color development was
Tomato
Treated with fluorescent-
inhibited for 8 days in red,
light exposed DACP and
12 days in pink and 14–16
held in air at 22 °C
days in mature green
(47)
tomatoes Single application of 1-MCP Treated with 1-MCP
was able to give significant
followed by continuous
delays in the ripening of
treatment with propylene
suppressed-climacteric
(48)
plums Exposed to 0.5 μl/L 1-MCP Can easily be cold-stored and cold-stored at 2 °C and
(49) for 2 to 4 weeks
95% RH Plum
Decreased ethylene Treated with 1-MCP and
production during storage
stored at 0 °C
and shelf-life in fruits kept
1-MCP
(50)
treatment 30 days Ethylene production was Treated with 500 μl/L 1inhibited, skin color MCP for 24 h at 25 °C after changes was retarded,
(51)
removal from the cold firmness decline was storage at 0 °C for 4 weeks. delayed The ripening was Treated with 300 nmol/mol significantly blocked in Banana
1-MCP and held at 14 °C
(52) terms of physiological and
and 90% RH for 16 h technological parameters
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The ripening process was Treated with 50 μl/L significantly delayed and ethephon and 400 nl/L 1-
(53) the commodity value was
MCP maintained Immersed in 500 nl/L of aqueous 1-MCP
The postharvest ripening
microbubbles, then stored
was effectively delayed
(54) at 25 °C for 8 days Can extend the storage time in standard NA storage Treated with 937 nl/L 1for at least 3 months MCP and then stored in without significantly losing
(55)
normal atmosphere at 0freshness even two weeks 1 °C, 90-95% RH after removal from cold storage Total putrescine levels Treated with 1 μl/L 1-MCP,
decreased due to changes
then stored under 2.5 kPa
in the conversion of
O2+2.5 kPa CO2 at 3 °C for
putrescine into higher
46 weeks
polyamines and resulted in
(56) Apple
the delay of fruit ripening The 0.625 μl/L of 1-MCP treatment was applied after Increased fruit firmness in 6 days of pre-refrigeration comparison to the
(57)
for additional 24 h at 2.5 °C reference storage condition in a ventilated gas-tight stainless steel container 1 μl/L of 1-MCP was applied
Affect the volatile
to treat apples in a sealed
biosynthesis and gene
(58)
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container for 12 h at 20 °C
expression of apple 1-MCP maintained fruit
Exposed to 1 μl/L of 1-MCP acidity by regulating the in sealed airtight plastic tent balance between malate
(59)
fitted with a circulation fan biosynthesis and at 20 °C for 24 h degradation Energy use of apples was Treated with 625 nl/L 1-
reduced by 70% when
MCP for 24 h and then
compared to ULO (1.0 kPa
stored under 1 kPa O2+2.7
O2+2.5 kPa CO2) at 1 °C, the
kPa CO2 at 5 °C
fruits were firmer than
(60)
fruits under ULO Reduced ripening and Treated with 625 nl/L 1superficial scald, did not MCP after 3 days cold
(61) induce diffuse skin
storage browning 1 μl/L of 1-MCP was applied 2 days and then again to
Improved firmness
half of the fruit after 4
retention and extended the
months of CA storage (2.5
shelf-life
(62)
kPa O2+2 kPa CO2) Treated with 1-MCP at 0.15 Ethylene production was μl/L and stored at -1 °C for 7
(63) inhibited
months Pear
Inhibited ethylene Treated with 1-MCP at 0.3 production, flesh firmness μl/L for 24 h at 0 °C and and green color losses, stored at -1.1 °C for 6 senescence disorders, and months friction discoloration
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(64)
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Delayed the decrease of Treated with 10 ppm 1-MCP
firmness, total soluble
and then stored at 16 °C
solids contents and
(65) titratable acid contents Treated with 0.6 μl/L 1-MCP
Slowed fruit ripening and
at 0 °C for 24 h
extended postharvest life
(66) decreased respiration rates and ethylene production, inhibited core browning Treated with 1 μl/L 1-MCP development, lowered
(67)
and then stored at 25 °C chlorogenic acid content and polyphenol oxidase activity Exposed to 1-MCP at 4.2 μmol/m3 and then stored in
Delayed fruits ripening
(68)
air at 0.5 °C Showed delay in ripening, Treated with 0.3 mg/L 1-
less shrivel and maintained
MCP for 5 h and stored for
mitochondrial integrity
19 days at 13 °C
compared to the control
(69)
fruit Delayed fruit softening, Mango improved rheological properties, decreased level Treated with 1 ml/L 1-MCP of citric acid, malic acid,
(70)
for 12 h at 20 °C for 10 days succinic acid, total organic acids, total sugars and sucrose Kiwifruit
Treated with 20 μl/L 1-MCP
Could be stored up to 5
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for 16 h at 10 °C and then
weeks by maintaining
stored at 1 °C
higher fruit firmness, ascorbic acid and total phenolic contents Relieved the pulp softening
Treated with 1 μl/L 1-MCP
extent and inhibited total
combined with 0.02 M
chlorophyll content
Nisin-EDTA
decrease, maintained the
(72)
quality Treated with 5000 μl/L
Extended “eating window”
propylene for 24 h, followed and shelf-life with the (73) by 5 μl/L 1-MCP treatment
suppression of endogenous
for 12 h
ethylene Inhibited ethylene
Treated with 500 nl/L 1Durian
production by preventing
(74,
an increase in ACC oxidase
75)
MCP for 12 h at 25 °C and then stored at 15 °C activity in the peel Postponing the respiration, Treated with hot water at enhancing firmness, 48 °C for 10 min and then increasing Glutathione
Peach
with 10 μl/L 1-MCP for 12 h
(76) peroxidases activity and up-
and stored at 20-25 °C with regulating PpaGPXs 80-90% RH expression The climacteric ethylene peak was delayed by Treated with 1 μl/L 1-MCP
approximately 12 days and
for 20 h
polygalacturonase
(77)
Tomato activity was strongly inhibited
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Pitahaya
Treated with 600 mg/L 1-
Reduced the ethylene
MCP and then stored at
action and slowed the
18 °C with 75% RH
ripening
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(78)
Maintained firmness, reduced incidence of chilling injury and Treated with 0.5 μl/L 1-MCP polyphenol oxidase, for 24 h and then stored at Nectarine
polygalacturonase and
(79)
0 °C with 90% RH for 40 pectin methylesterase days activities, total soluble solid contents and respiration rates Treated with CaCl2 (1% w/v)
Reduced the browning rate
+ 1-MCP (312.5 ppb) and Mulberry
by maintaining the L color
(80)
then stored at 4 °C with value 90% RH Extended the storage life, Treated with 0.4 μl/ 1-MCP decreased weight loss and for 24 h at 0 °C and then delayed the rate of Medlar
stored under 21% O2 + 0.03% CO2 at 0 °C with 95%
(81) softening, loss of taste, browning
RH for 60 days incidence in skin color 137
3.1 Suppression of ethylene synthesis
138
There are two key steps for the generation of ethylene (Fig.1): 1) the ATP break, which will
139
affect the conversion of MET to SAM; 2) the ACC oxidase activation, which will affect the
140
conversion of ACC to ethylene. The ATP break and the ACC oxidase activation are mainly
141
affected by the fruit respiration and the O2 content, respectively.
142
Based on the above, if we reduce the respiration rate and O2 content during storage, the
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ATP break and the ACC oxidation can be controlled, then, the ethylene synthesis can be
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decreased. Three main technologies have been reported to control the fruit respiration and O2
145
content:
146
3.1.1 Controlled temperature and high humidity (CTHH) technology
147
The CTHH technology refers to fruit storage in lower temperatures and higher humidity to
148
prolong their shelf life and reduce their weight loss. As shown in Fig.1, the fruit respiration
149
consists of the ethylene biosynthesis and sulfur recycling, which includes the conversion of MET
150
to SAM, SAM to Schiff base, Schiff base to Compound A and MTAN, Compound A to ACC and
151
then to ethylene, MTAN to MTR and then back to MET. At room temperature, the fruit
152
respiration is maintained at the normal level. However, if the fruit is stored at a lower
153
temperature, the fruit respiration will be reduced resulting in a decreased ATP break, thus,
154
decreased ethylene biosynthesis (82). The essence of the CTHH technology is to control fruit
155
respiration by suspending the ethylene biosynthesis, thus, extending the fruit shelf life.
156
The CTHH technology has been used in the preservation of tomatoes (40) and durians (41)
157
before. It was revealed by Bhowmik and Pan (40) that tomatoes remained green up to 40 days
158
when they were stored at 98% relative humidity at 12 °C. It was also reported by Ketsa and
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Pangkool (41) that low amounts of CO2 and ethylene were produced for durian fruits at 33 °C
160
and 70% relative humidity. The CTHH technology can decrease the ethylene formation and the
161
response rate of the tissue to ethylene action in two aspects (83, 84): 1) the respiratory
162
intensity of fruit in the preservation period can be controlled, so that the ethylene formation
163
can be decreased; 2) the water evaporation can be abated effectively and the weight loss of
164
fruit can be reduced, so that the fruit can stay fresh.
165
3.1.2 Controlled atmosphere (CA) technology
166
The CA technology refers to fruit storage in a controlled atmosphere to prolong their shelf
167
life. As stated above, the conversion of ACC to Compound B (Fig.1, Step 5) is a key step for the
168
ethylene biosynthesis, which mainly depends on the activation of ACC oxidase. However, ACC
169
oxidase need to be activated in the presence of O2 and low levels of CO2. If we can control the
170
oxygen content of the fruit storage atmosphere at a low level, the ACC oxidase activation will
171
be decreased. The essence of the CA technology is to control the O2 concentration in the
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storage atmosphere so that the activation of ACC oxidase is retarded, as a result, the fruit shelf
173
life can be extended.
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Generally, 2%-3% of O2 content and 5%-15% of CO2 content are often used in the CA
175
storage, and many studies have been devoted to investigate the inhibition of ethylene
176
generation under the CA condition (2-7). It was reported by Saquet and Streif (2) that the ACC-
177
oxidase activity, ethylene production, and respiration of ‘Jonagold’ apple will be affected by the
178
controlled atmosphere. As a result, the CA condition of 0.5 kPa O2 + 6.0 kPa CO2 showed the
179
strongest suppression in ethylene production, respiration and generated higher values in the
180
respiratory quotient. In addition, the effect of CA storage on sliced partially ripe pears also
181
revealed that their respiration and ethylene production rates can be suppressed under the CA
182
condition. The firmness of pear slices can be kept in the storage atmosphere of 12% CO2 and
183
0.5% O2 (3). The low O2 atmosphere effect on the storage of bananas and ’Fuji’ apples showed
184
that these fruits can be effectively preserved for a long time under the CA condition (4). Similar
185
results were also obtained on apple slices (5), honeydew melons (6), kiwifruit (7) under low O2
186
atmosphere or elevated CO2 level, or their combination.
187
The CA storage exhibits an effective preservation of climacteric fruit, and there is no
188
harmful effect for the human body (85). It is practiced in the industry for the post-harvest
189
storage of climacteric fruit.
190
A low O2 atmosphere condition can not completely inhibit the senescence and tissue
191
breakdown. In addition, under extremely low O2 or extremely high CO2 conditions (beyond the
192
tolerance limit), an anaerobic respiration may occur, resulting in unexpected metabolites
193
products and other physiological disorders (86).
194
3.1.3 Silver treatment
195
There are a number of studies in the literature regarding the use of silver as an inhibitor of
196
ethylene formation. Beyer (8) found that plants treated with 25 mg/L of AgNO3 decreased the
197
time required to reach 100% leaf abscission by 2 days. Saltveit Jr, Bradford and Dilley (9) and
198
Veen (10) reported that AgNO3 solution and silver thiosulfate (STS) can decrease the ethylene
199
synthesis, thus delaying the ripening process of banana slices. Atta-Aly, Saltveit and Hobson
200
(11) further reported that a short-term silver treatment did not affect the biological conversion
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of ACC to ethylene, while long-term treatment blocked the ethylene synthesis in pericarp
202
tissue, which stimulated both the conversion of ACC to ethylene and the synthesis of ACC.
203
However, silver ions have negative environmental consequences, and the high STS
204
concentration has a toxic effect on the organism, thus, their application in the inhibition of
205
ethylene synthesis in fruit preservation is rather limited.
206
3.2 Oxidation of ethylene to CO2
207
Another method to extend the shelf life of climatic fruits is to remove ethylene
208
immediately once it is generated. Up to now, many chemical methods/processes have been
209
reported to remove ethylene to prolong the fruit shelf life, among them, the oxidation of
210
ethylene to CO2 is a popular method. The reported oxidants include O3, KMnO4, and nano-TiO2.
211
Although O3 can be used to remove ethylene from the atmosphere, the effect of O3 on fruit can
212
be harmful, which limits its commercial use (13).
213
KMnO4 is an effective oxidant to convert ethylene to CO2 and H2O, which can be used in
214
fruit preservation. An early research revealed that bananas, which were stored in sealed
215
polyethylene bags containing KMnO4 and Ca(OH)2 can keep in firm green after 16 days due to
216
the oxidation of ethylene to CO2 (14). In another study, a commercial 'Purafil', which is alkaline
217
KMnO4 on silicate carrier produced by Mabson Chemical Co., in conjunction with CA storage in
218
polyethylene bags, can be used to remove ethylene and extend the green life of bananas (15). It
219
was also reported by Elamin (16) that the bananas’ ripening can be delayed significantly when
220
KMnO4 was present in their stored polyethylene films or bags.
221
Nano-TiO2 can also be used as an oxidant to remove ethylene due to its light catalyzing
222
capability (17). It was also reported that the fruit softening, weight loss, browning and climatic
223
evolution of Chinese jujube packed with nano-TiO2 material in lower relative humidity, the fruit
224
softening, weight loss, browning and climatic evolution can be evidently inhibited after 12-day
225
storage (18).
226
3.3 Blocking the ethylene receptor
227
Using some chemicals to block the reaction between ethylene and its receptor on fruit
228
cells is an effective method to prolong the fruit shelf life. Three typical chemicals, including 2, 5-
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norbornadiene (2, 5-NBD) (42-45), diazocyclopentadiene (DACP) (46, 47), and cyclopropene
230
(CP) (87), have been reported to inhibit the ethylene reaction.
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The inhibitory effects of 2, 5-NBD on ethylene action in plants was first described by Sisler
232
and Pian (43). After that, a number of physiological studies with 2, 5-NBD were performed and
233
the ability of 2, 5-NBD to block ethylene action in a number plants was confirmed (42-45).
234
However, 2, 5-NBD has an unpleasant smell and can lead to cancer, therefore, the commercial
235
application is limited.
236
DACP was first verified as an ethylene receptor label (88). It was studied to reduce tissue
237
responses to ethylene among, apples (46) and tomatoes (47). However, DACP is an explosion
238
hazard under strong light conditions, therefore, the discovery of new chemicals for the blocking
239
of ethylene receptor is always in demand.
240
For the past few years, a great number of work has been done related to the use of CP to
241
block ethylene receptor, which include CP, 1-methylcyclopropene (1-MCP), and 3, 3-
242
dimethylcyclopropene (3, 3-DMCP) (87, 89). As observed in Table 2, CP and 1-MCP are about
243
1000 times more active than 3, 3-DMCP (87). In addition, 1-MCP is more stable than CP,
244
therefore, most of the studies have been done with 1-MCP for fruit preservation (87).
245
Table 2. Minimum concentration and time of insensitivity in Musa sapientum fruit (1-MCP: 1-
246
methylcyclopropene, CP: cyclopropane, 3, 3-DMCP: 3, 3-dimethylcyclopropene). This table is
247
cited from Sisler and Serek (87). Compound
Concentration, nl/l
Insensitivity, days
1-MCP
0.5
12
CP
0.5
12
3, 3-DMCP
500
7
248
Many studies are available in the literature regarding the use of 1-MCP for different fruit
249
preservation. Abdi, McGlasson, Holford, Williams and Mizrahi (48) found that 1-MCP effectively
250
delayed the ripening process of plums, and a single application of 1-MCP would suffice for non-
251
climacteric plum cultivar, while a continuous low dose of 1-MCP would be needed for the
252
climacteric cultivar to reach a similar result. Other researches have shown a similar result (49-
253
51). 1-MCP was also applied to other fruit, including banana (52-54), apple (55-62), pear (63-68)
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, mango (69, 70), kiwifruit (71-73), durian (74, 75), peach (76), tomato (77), pitahaya (78),
255
nectarine (79), mulberry (80), and medlar (81). These studies support the conclusion that 1-
256
MCP is effective to prolong the shelf life of these fruits.
257
4. Mechanism of 1-MCP on fruit preservation
258
It was reported that the ethylene induced fruit ripening process involves the withdrawing
259
of electrons from a metal in the ethylene receptor, and a model involving ligand substitution
260
has been proposed to account for their experimental observations (87), which is shown in Fig.2:
261
1) ethylene approaches the metal (M) on the ethylene receptor to withdraw the electrons; 2)
262
another ligand in a trans position to it moves away from M; 3) yet another ligand moves toward
263
M and as it does, ethylene is lost, and an active complex is formed. In this model, the proposed
264
L1, L2, L3, L4, and L5 ligands are unknown, but it is probable that one or more of them is localized
265
on the ETR1 gene product, a protein thought to be part of the ethylene receptor (90).
266
However, if 1-MCP is also present, it will win the competition with ethylene in withdrawing
267
electrons from the metal on the ethylene receptor, 1-MCP will act on the ethylene receptor in a
268
similar way to ethylene. On the other hand, the formed 1-MCP- receptor complex, is not active
269
in the respiratory process, blocking the fruit ripening process (87).
270
The competing reactions between ethylene or 1-MCP and the ethylene receptor can be
271
elaborated graphically, which is shown in Fig.2. The ethylene receptor is like a ‘lock’ and
272
ethylene is a ‘key’, when an ethylene molecule attaches to the receptor, the ‘lock’ will turn and
273
a door will open, thus the ethylene induced fruit ripening process takes place. However, if 1-
274
MCP is available, it will preferentially (over ethylene) connect with the ethylene receptor, which
275
would ‘fill’ into the ‘lock’ so that the ethylene ‘key’ is unable to go into the ‘lock’ to open it, and
276
the fruit ripening process can thus be blocked (86, 91).
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277 278
Fig.2 A model for ethylene to induce the fruit ripening process and 1-MCP to block the ethylene
279
action with the ethylene receptor, this model is modified from Sisler and Serek (87).
280
5. Encapsulation technologies of 1-MCP for fruit preservation
281
1-MCP is unstable and easy to be polymerized at the ambient conditions. Therefore, it is
282
often used as an inclusion complex/encapsulation. Fillers/dusts, including some inorganic
283
minerals (calcium carbonate, lime, synthetic fine silica, talc, and chalk, etc.) and organic
284
powders (soy bean flour pumice, wheat flour, cottonseed hulls, and wood flour, etc.) were
285
reported for the encapsulation of 1-MCP (92). However, In these cases 1-MCP can easily escape
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from their inner structures of the encapsulation materials (92, 93). Others, such as molecular
287
sieve and supramolecular materials are promising, and have been reported in the literature.
288
5.1 Molecular sieve
289
Various molecular sieves have been studied to encapsulate 1-MCP . Among them, two
290
types of molecular sieve, 13X and 5A molecular sieve, were systematically investigated (93).
291
The results demonstrated that 13X molecular sieve was able to carry 15 ppm of 1-MCP
292
according to the chromatographic results but no measurable amount of 1-MCP was found on
293
5A molecular sieve. The modified starch combined with 3A molecular sieve was also used as a
294
microcapsules agent for the encapsulation of 1-MCP, and 0.5%-3.5% 1-MCP can be caught with
295
20%-30% 3A molecular sieve, 60%-65% modified starch, 1%-2% ammonium chloride, and 3%-
296
18% sodium bicarbonate (94). However, the encapsulated 1-MCP was difficult to release for the
297
structure of molecular sieve, which would negatively affect the commercial application.
298
5.2 Metal-organic frameworks (MOFs)
299
Metal-organic frameworks (MOFs) are a new class of synthetic porous materials which
300
have been developed to capture gases in fuel and chemical industries due to their highly-
301
ordered, porous crystalline structure (Kuppler et al., 2009). It was revealed that several MOFs
302
termed metal coordination polymer networks including calcium-4,4’-sulfonyldibenzoic acid,
303
copper-2,4,6-tris(3,5-dicarboxyl-phenylaminl)-1,3,5-triazine, and zinc-tcbpe [reaction product of
304
tetra(4-bromo-phenyl)ethylene and 4-(methoxycarbonyl)phenylboronic acid] can be used for
305
the adsorb and desorb of 1-MCP (95). In addition, the copper-based MOF with a trimesic acid
306
linker group also displayed a good perform to encapsulate 1-MCP, and a 17.6% w/w basis of 1-
307
MCP can be loaded, however, it was unable to release the 1-MCP (96).
308
5.3 Supramolecular materials
309 310
Some supramolecular materials, such as cucurbit uril and cyclodextrin, have been used as the encapsulation agent of 1-MCP.
311
Cucurbit urils is a kind of barrel-like macrocyclic molecule generated from formalin and
312
glycoluril (97-101). Cucurbit [6] urils can host/ absorb alkylammonuium ions (102), short
313
polypeptides (103), Et2O (104), metal cations (105), and some small-molecule gases (106) to
314
produce stable inclusion complexes (107-109). It was also reported by Zhang, Zhen, Jiang, Li and
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Liu (97) that cucurbit urils can be used as an absorbent to encapsulate 1-MCP due to the cavity
316
structure, and 4.5% 1-MCP by weight can be encapsulated by cucurbit [6] uril at the initial 1-
317
MCP concentration of 75 ml/l, the cucurbit [6] uril concentration of 30 mM at 20 °C in 8 hrs. The
318
encapsulated 1-MCP can be easily released in distilled water, benzoic acid, and sodium
319
bicarbonate solutions.
320
Cyclodextrin compounds are the favorable encapsulation materials for 1-MCP (93, 110-
321
116). Among them, α-cyclodextrin (α-CD) is the most popular due to its high encapsulation
322
capacity, reasonable cost and easy release capability (112, 113). Procedures for 1-MCP
323
encapsulation in α-CD have been patented (93, 110, 111). For example, Trinh (110) described a
324
carrier material which suspended perfume/CD complexes in polyalkylene glycol to encapsulate
325
1-MCP. The powder composition that contained one or more 1-MCP can retard the release of
326
1-MCP compound, however, it did not entirely prevent the release of 1-MCP compound. Daly
327
and Kourelis (93) developed the procedure to prepare α-CD/1-MCP complex, which was made
328
by trapping 80000 ppm of 1-MCP in a 5 gallon mixing vessel with 1.3 kg of α-CD in 0.575 l of
329
buffer solution (0.2 mol sodium acetate and 0.2 mol acetic acid solutions); the vessel was
330
chilled to 4 °C for 24 hrs so that 1- MCP was trapped into α-CD, which was crystalized; the α-
331
CD/1-MCP crystals/cakes were obtained by filtering, air dried, and ground to powder. Ghosh
332
(111) also reported a method which used α-CD as the capsulation agent to catch 1-MCP in a
333
stable water-in-oil-water double emulsion, which disclosed can provide prolong or controlled
334
release of 1-MCP.
335
A continuous process for the encapsulation of 1-MCP with α-CD was invented, the product
336
formation was evident by the generation of a slurry of white precipitate (116). During the α-
337
CD/1-MCP preparation, fresh 1-MCP gas was passed through a condenser held at a
338
temperature less than its boiling point; then, contacting an α-CD containing solution to give a
339
precipitate of the encapsulated α-CD/1-MCP; separating the precipitate from the solution by
340
filtering and allowed to air dry, and the 1-MCP contents in the encapsulated product ranged
341
from 0.5% to 2.8%.
342
To date, the 1-MCP/α-CD complexes are commercially available, and a commercial product
343
with the trade name of SmartFresh has been on the global market (51, 55, 58, 59, 62, 63, 66,
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68-71, 74, 76, 79, 112, 113, 117-120). For example, 1-MCP was reported as an agent to prolong
345
the shelf life of ‘Granny Smith’ apples, and the results showed that the treatment of ‘Granny
346
Smith’ apples with 1-MCP can extend the storage time in standard NA storage for at least 3
347
months without significantly losing freshness (55). It was revealed that the 1-MCP-treated
348
‘Kensington Pride’ mango showed improved rheological properties (firmness, springiness and
349
stiffness), decreased level of citric acid, malic acid, succinic acid, total organic acids, total sugars
350
and sucrose than other treatments (70). Their research results showed that 1-MCP can inhibit
351
the activities of fruit softening enzymes and then delay the ripening and ripening related
352
changes in ‘Kensington Pride’ mangoes. 1-MCP also has been used to treat Actinidia aruguta
353
hardy kiwifruits to prolong their shelf life, which were treated with 20 μl/l 1-MCP for 16 hrs at
354
10 °C and subsequently stored at 1 ± 0.5 °C (71). The results displayed that the hardy kiwifruits
355
without 1-MCP treatment showed increases in both respiration and ethylene production rates
356
during fruit storage. However, the 1-MCP treated kiwifruits could be stored up to 5 weeks and
357
maintained higher fruit firmness, ascorbic acid and total phenolic contents compared to the
358
control. The 1-MCP effect on Yali pear (Pyrus bretschneideri Rehd.) also displayed a delayed
359
decrease in firmness, total soluble solids, titratable acid content (65).
360
6. Calixarene, a potential supramolecular compound encapsulation agent
361
Calixarenes are a class of polyphenolic cyclo-oligomers, which can be synthesized via a
362
phenol-formaldehyde condensation. They have a defined upper and lower rim and a central
363
annulus, which exist in a “cup” like shape, and have similar structure to Cucurbit urils and CD
364
(Fig.3) (121).
365
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Fig.3 Typical structures of calixarene (calix [4] and [6]) and their cavity dimensions based on
367
chem3D calculation.
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368
As can be seen in Fig.3, the cavity size of the two typical calixarenes are 0.13-1.32 nm
369
(Calix [4] arene) and 0.28-1.55 nm (Calix [6] arene) respectively based on the distance
370
measurement of chem3D, therefore, they possess ideal inclusion ability to bind guest ions and
371
molecules (122, 123). For example, calixarenes were used for complexing metal ions due to
372
their selective inclusion ability with metal ions, such as the alkali metal ions (Li+, K+, Na+) (124,
373
125), the transition metal ions (Ru2+) (126), and the subgroup metal ions (U3+) (127, 128). Some
374
small organic molecules, such as toluene, nitrobenzene, butane, pentane and hexane can also
375
be encapsulated by calixarenes with the ratio of 1:1 (129). In addition, para-Octanoyl-calix [4]
376
arene was also an excellent adsorbent for saturated and unsaturated hydrocarbons, polarizable
377
inert gases, and carbon dioxide and two typical calixarenes, calix [4] and [6] have been reported
378
to encapsulate CO2 and ethylene (130-136).
379
The cup ring size of calixarene is rather flexible, which can be controlled through the
380
change of conformation and different substituting groups on the ring. Therefore, calixarene
381
may be a good candidate for the encapsulation of 1-MCP, because: 1) one calixarene can host
382
one 1-MCP through the adapting of its cavity size; 2) calixarene has a lypophilic inner cavity,
383
facilitating lypophilic interactions with 1-MCP; 3) calixarene has a hydrophilic external surface,
384
which can absorb water for the release of 1-MCP.
385
7. Conclusion
386
This review elaborated the mechanism of ethylene formation in climacteric fruit and its
387
role in the ripening process. The current ethylene controlling strategies for fruit preservation
388
were further discussed. Moreover, the applications of 1-MCP, which mimics ethylene structure
389
and competes favorably in reaction with the ethylene acceptors, have been especially
390
highlighted to extend the post-harvest shelf life of climacteric fruit. The 1-MCP encapsulation
391
technologies have been described. Finally, as a potential novel encapsulation agent of 1-MCP,
392
calixarene has been put forward and elaborated based on: 1) calixarene can host one 1-MCP
393
due to its unique structure of adapting its cavity size by different conformations/ substituting
394
groups; 2) its lypophilic inner cavity can facilitate the interactions with 1-MCP; 3) its hydrophilic
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external surface can adsorb water for the release of 1-MCP. Its feasibility for the encapsulation
396
of 1-MCP will be confirmed in our future research.
397
Acknowledgments
398
This work is financially supported by the National Natural Science Foundation of China
399
(21406208), the Natural Science Foundation of Zhejiang province (LY17C160008), China
400
Scholarship Council (201508330154), the open Foundation of the Most Important Subjects in
401
Colleges and Universities in Zhejiang Province (2015YXQN13), Zhejiang Provincial Top Key
402
Academic Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University
403
(YR2015005),
404
(11110132521309).
405
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