Ethylene Control Technologies in Extending Postharvest Shelf Life of

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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

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Education, Zhejiang Sci-Tech University, Hangzhou 310018, China.

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2

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Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada.

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3

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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

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Contact information for Corresponding Author

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*(Zhang JH) E-mail: [email protected]. Tel.: +86-571-86843871. Fax: +86-571-86843250.

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*(Ni YH) E-mail: [email protected]. Tel.: +1-506-4516857. Fax: +1-506-4534767.

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ACS Paragon Plus Environment


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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

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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

55

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-

60

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

63 64 65 66 67 68 69 70 71 72 73 74 75 76



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1. Introduction

78

There are a number of approaches: physical (temperature, light), chemical (oxidation) or

79

biological (microorganisms), which can be adopted for fresh fruit preservation. Effective

80

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.

83

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

86

cellular respiration will be increased in their ripening stage. The main cause for their spoilage

87

nature is the biochemical changes that happen because of ethylene, a key hormone associated

88

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)

93

oxidation, have been reported to prolong the post-harvest shelf life of climacteric fruits can be

94

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

98

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).

105

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

107

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,

109

including seed germination, vegetative growth, vegetative senescence, leaf abscission, and

110

plant flowering, was confirmed (23).

111 112

Fig.1 A mechanism for the biosynthesis of ethylene from methionine (MET: methionine, SAM:

113

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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115

During the growth process of fruit and other plants, there are many potential compounds

116

that can be converted to ethylene. Among them, methionine (MET) was suggested as a possible

117

precursor of ethylene (25-30). As shown in Fig.1, the generation of ethylene from MET includes

118

the following key steps: 1) MET will first be activated by ATP to form S-adenosylmethionine

119

(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

121

with γ substituent to form a cyclopropane ring (A) and 5’-methylthioadenosine (MTAN) (24)

122

(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

129

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

133

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


(41)

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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


(46)

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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


(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


(71)

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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



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

143

ATP break and the ACC oxidation can be controlled, then, the ethylene synthesis can be


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144

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

159

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



172

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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174

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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201

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-



229

norbornadiene (2, 5-NBD) (42-45), diazocyclopentadiene (DACP) (46, 47), and cyclopropene

230

(CP) (87), have been reported to inhibit the ethylene reaction.

Page 18 of 30

231

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)


Page 19 of 30


254

, 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).



Page 20 of 30

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


Page 21 of 30


286

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



Page 22 of 30

315

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,


Page 23 of 30


344

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



366

Fig.3 Typical structures of calixarene (calix [4] and [6]) and their cavity dimensions based on

367

chem3D calculation.

Page 24 of 30

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


Page 25 of 30


395

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

References

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