Ethylene Control Technologies in Extending Postharvest Shelf Life of

Aug 2, 2017 - ... significant published works in this field. Special attention is given to 1-methylcyclopropene (1-MCP), which is effective in fruit p...
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Ethylene Control Technologies in Extending Postharvest Shelf Life of Climacteric Fruit Junhua Zhang,*,†,‡ Dong Cheng,‡,§ Baobin Wang,‡ Iqbal Khan,‡ and Yonghao Ni*,‡,§ †

Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China ‡ Limerick Pulp and Paper Centre, Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada § Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, Tianjin 300457, China ABSTRACT: Fresh fruit is important for a healthy diet. However, because of their seasonal production, regional specific cultivation, and perishable nature, it is essential to develop preservation technologies to extend the postharvest shelf life of fresh fruits. Climacteric fruit adopt spoilage because of ethylene, a key hormone associated with the ripening process. Therefore, controlling ethylene activity by following safe and effective approaches is a key to extend the postharvest shelf life of fruit. In this review, ethylene control technologies will be discussed aiming for the need of developing more innovative and effective approaches. The biosynthesis pathway will be given first. Then, the technologies determining the postharvest shelf life of climacteric fruit will be described with special attention to the latest and significant published works in this field. Special attention is given to 1-methylcyclopropene (1-MCP), which is effective in fruit preservation technologies. Finally, the encapsulation technology to improve the stability of 1-MCP will be proposed, using a potential encapsulation agent of 1-MCP, calixarene. KEYWORDS: fruit preservation, shelf life, ethylene, 1-MCP, encapsulation

1. INTRODUCTION There are a number of approaches: physical (temperature, light), chemical (oxidation), or biological (microorganisms), which can be adopted for fresh fruit preservation. Effective methods of fruit preservation make it possible to have fresh fruit available year-round regardless of their growing season and regional nature to meet our pursuit of various and diverse types of fresh fruit. Fresh fruit can be divided into climacteric and nonclimacteric fruit based on the ethylene production and cellular respiration in the stage of fruit ripening. For climacteric fruit, which including apple, banana, melon, apricot, tomato, and so on, their ethylene production and cellular respiration will be increased in their ripening stage. The main cause for their spoilage nature is the biochemical changes that happen because of ethylene, a key hormone associated with the ripening process. Therefore, controlling ethylene activity by following safe and effective approaches is the key to extend the postharvest shelf life of fruits.1 In the literature, many ethylene controlled technologies, including the ethylene synthesis suppression with controlled temperature/atmosphere2−7 or silver treatment,8−11 and the ethylene removal by vacuum ultraviolet radiation12/O3,13 KMnO4,14−16 or nano-TiO217,18 oxidation, have been reported to prolong the postharvest shelf life of climacteric fruits. The development of high efficiency processes/methods to control the ethylene formation/release/ acceptance of climacteric fruit is always in demand. In this review, the ethylene biosynthesis pathway will be discussed first. Then, the technologies of extending the postharvest shelf life of climacteric fruit as a result of the ethylene control/removal/inhibition will be discussed. 1Methylcyclopropene (1-MCP), a unique chemical for this © 2017 American Chemical Society

purpose will be particularly highlighted. Finally, the encapsulation technology related to the use of 1-MCP will be discussed and a potential encapsulation agent of 1-MCP, calixarene, will be proposed.

2. ETHYLENE BIOSYNTHESIS PATHWAY The effect of ethylene on plant growth can be traced back to 1864, it was found that a gaseous material leaking from the street lighting system could modify the growth of plants.19 The gaseous material was later proved to be ethylene.20 Then, ethylene as a natural compound generated from apples was discovered by Gane.21 Later, it was found that all parts of higher plants, including leaves, stems, roots, flowers, fruit, tubers, and seedlings can produce ethylene.22 The key function of ethylene as fruit ripener and plant developer, including seed germination, vegetative growth, vegetative senescence, leaf abscission, and plant flowering, was confirmed.23 During the growth process of fruit and other plants, there are many potential compounds that can be converted to ethylene. Among them, methionine (MET) was suggested as a possible precursor of ethylene.25−30 As shown in Figure 1, the generation of ethylene from MET includes the following key steps: (1) MET will first be activated by ATP to form Sadenosylmethionine (SAM) (step 1);24,31−33 (2) the generated SAM will react with pyridoxal phosphate to produce a Schiff base (step 2); (3) the Schiff base undergoes an elimination of α hydrogen, along with γ substituent to form a cyclopropane ring Received: Revised: Accepted: Published: 7308

June 6, 2017 August 1, 2017 August 2, 2017 August 2, 2017 DOI: 10.1021/acs.jafc.7b02616 J. Agric. Food Chem. 2017, 65, 7308−7319

Review

Journal of Agricultural and Food Chemistry

Figure 1. Mechanism for the biosynthesis of ethylene from methionine (MET, methionine; SAM, S-adenosylmethionine; MTAN, 5′methylthioadenosine; ACC, 1-aminocyclopropane-1-carboxylic acid; MTR, 5-methylthioribose). The scheme is modified from that of Yang and Adams.24

(A) and 5′-methylthioadenosine (MTAN)24 (step 3); (4) the generated compound A will be converted to 1-aminocyclopropane-1-carboxylic acid (ACC) and pyridoxal phosphate in the presence of H2O and H+ (step 4), which is a controlling step for the synthesis of ethylene; (5) ACC will be oxidized by ACC oxidase to form ethylene via compound B (step 5) in the presence of oxygen and low levels of CO2, both of which are essential to activate ACC oxidase;34−37 (6) the obtained compound B will be finally converted to ethylene (step 6); (7) MTAN can be regenerated to MET through an intermediate of 5-methylthioribose (MTR) (steps 7 and 8). This sulfur cycle is very important to maintain a substantial ethylene production rate.38,39

conversion of ACC to ethylene. The ATP break and the ACC oxidase activation are mainly affected by the fruit respiration and the O2 content, respectively. On the basis of the above, if we reduce the respiration rate and O2 content during storage, the ATP break and the ACC oxidation can be controlled, then the ethylene synthesis can be decreased. Three main technologies have been reported to control the fruit respiration and O2 content. 3.1.1. Controlled Temperature and High Humidity (CTHH) Technology. The CTHH technology refers to fruit storage in lower temperatures and higher humidity to prolong their shelf life and reduce their weight loss. As shown in Figure 1, the fruit respiration consists of the ethylene biosynthesis and sulfur recycling, which includes the conversion of MET to SAM, SAM to Schiff base, Schiff base to compound A and MTAN, compound A to ACC and then to ethylene, MTAN to MTR and then back to MET. At room temperature, the fruit respiration is maintained at the normal level. However, if the fruit is stored at a lower temperature, the fruit respiration will be reduced resulting in a decreased ATP break, thus, decreased ethylene biosynthesis.82 The essence of the CTHH technology is to control fruit respiration by suspending the ethylene biosynthesis, thus, extending the fruit shelf life.

3. CURRENT ETHYLENE CONTROLLING STRATEGIES FOR CLIMACTERIC FRUIT PRESERVATION Ethylene is a key in the climacteric fruit ripening process, and there are a number of technologies reported in the literature to prolong the shelf life of climacteric fruit (shown in Table 1): 3.1. Suppression of Ethylene Synthesis. There are two key steps for the generation of ethylene (Figure 1): (1) the ATP break, which will affect the conversion of MET to SAM and (2) the ACC oxidase activation, which will affect the 7309

DOI: 10.1021/acs.jafc.7b02616 J. Agric. Food Chem. 2017, 65, 7308−7319

7310

1-MCP treatment

block ethylene action

oxidize ethylene to CO2

silver treatment

CA

CTHH

method

apple

banana

plum

tomato

apple

plants

Chinese jujube

banana

banana banana tomato

apple apple honeydew melon kiwifruit

keep in firm green after 16 days ethylene can be removed and green life of bananas can be extended extended the shelf life fruit softening, weight loss, browning and climatic evolution was inhibited after 12-day

stored in sealed polyethylene bags containing KMnO4 and Ca(OH)2 treated with alkaline KMnO4 in conjunction with CA storage KMnO4 was present in the stored polyethylene films or bags packed with nano-TiO2

0.625 μL/L of 1-MCP treatment was applied after 6 days of prerefrigeration for additional 24 h at 2.5 °C in a ventilated gastight stainless steel container

treated with 1 μL/L 1-MCP, then stored under 2.5 kPa O2+2.5 kPa CO2 at 3 °C for 46 weeks

exposed to 0.5 μL/L 1-MCP and cold-stored at 2 °C and 95% RH treated with 1-MCP and stored at 0 °C treated with 500 μL/L 1-MCP for 24 h at 25 °C after removal from the cold storage at 0 °C for 4 weeks. treated with 300 nmol/mol 1-MCP and held at 14 °C and 90% RH for 16 h treated with 50 μL/L ethephon and 400 nl/L 1-MCP immersed in 500 nl/L of aqueous 1-MCP microbubbles, then stored at 25 °C for 8 days treated with 937 nl/L 1-MCP and then stored in normal atmosphere at 0−1 °C, 90−95% RH

treated with 1-MCP followed by continuous treatment with propylene

DACP was applied as a gas in the light for 24 h to apples harvested at a mature, preclimacteric stage and held in air at 21 °C for 30 days treated with fluorescent-light exposed DACP and held in air at 22 °C

single application of 1-MCP was able to give significant delays in the ripening of suppressed-climacteric plums can easily be cold-stored for 2 to 4 weeks decreased ethylene production during storage and shelf life in fruits kept 30 days ethylene production was inhibited, skin color changes was retarded, firmness decline was delayed ripening was significantly blocked in terms of physiological and technological parameters ripening process was significantly delayed and the commodity value was maintained postharvest ripening was effectively delayed can extend the storage time in standard NA storage for at least 3 months without significantly losing freshness even two weeks after removal from cold storage total putrescine levels decreased due to changes in the conversion of putrescine into higher polyamines and resulted in the delay of fruit ripening increased fruit firmness in comparison to the reference storage condition

red color development was inhibited for 8 days in red, 12 days in pink and 14−16 days in mature green tomatoes

ethylene action with plants tissue was blocked (2, 5-NBD has an unpleasant smell and can lead to cancer, so it was not be used in fruit preservation) had lower internal ethylene concentrations than untreated fruits

decreased the ethylene synthesis and delayed the ripening process decreased the ethylene synthesis and delayed the ripening process long-term silver treatment stimulated both the conversion of ACC to ethylene and the synthesis of ACC

treated with AgNO3 solution treated with silver thiosulfate treated with silver thiosulfate

treated with 2, 5-NBD

had a shelf life of 9−12 days

treated with 1% CaCl2 or 2% Ca lactate and stored at 0−2 °C, 90% RH in an C2H4-free atmosphere of 2 to 4 kPa O2 and/or 5−10 kPa CO2

respiration and ethylene production rates were suppressed preserved their original color with minor changes for more than 1 month retained the quality and retarded increased metabolism and microbial growth

ethylene production, respiration was suppressed respiration and ethylene production rates were suppressed

0 °C for 6 months, with a further 10 d shelf life in air at 20 °C were: 0.5 kPa O2 + 6.0 kPa CO2 stored in air + 12% CO2 or in a 0.5% O2 atmosphere for 7 days at 2.5 °C followed by one day at 20 °C pretreated with 2% ascorbic acid and held in 100% N2 at 10 °C predipped in ascorbic acid and calcium chloride and stored under 100% N2 at 8−10 °C stored under 2% O2+10% CO2 at 10 °C

apple pear

results weight loss was reduced, remained green up to 40 days low amounts of CO2 and ethylene were produced

storage conditions

treated with 125 ppm chlorine water and then stored at 12 °C under CA storage with 98% RH exposed to temperature of 33 °C under 70% RH

tomato durian

fruit

Table 1. Published Ethylene Controlling Strategies for Climacteric Fruit Preservationa ref

57

56

52 53 54 55

49 50 51

48

47

46

42−45

14 15 16 18

9 10 11

7

4 5 6

2 3

40 41

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a

7311

treated with 600 mg/L 1-MCP and then stored at 18 °C with 75% RH treated with 0.5 μL/L 1-MCP for 24 h and then stored at 0 °C with 90% RH for 40 days

treated with CaCl2 (1% w/v) + 1-MCP (312.5 ppb) and then stored at 4 °C with 90% RH treated with 0.4 μL/ 1-MCP for 24 h at 0 °C and then stored under 21% O2 + 0.03% CO2 at 0 °C with 95% RH for 60 days

pitahaya nectarine

mulberry medlar

peach

tomato

treated with 5000 μL/L propylene for 24 h, followed by 5 μL/L 1-MCP treatment for 12 h treated with 500 nl/L 1-MCP for 12 h at 25 °C and then stored at 15 °C

durian

treated with hot water at 48 °C for 10 min and then with 10 μL/L 1-MCP for 12 h and stored at 20−25 °C with 80−90% RH treated with 1 μL/L 1-MCP for 20 h

treated with 1 μL/L 1-MCP combined with 0.02 M Nisin-EDTA

treated with 20 μL/L 1-MCP for 16 h at 10 °C and then stored at 1 °C

treated with 1 mL/L 1-MCP for 12 h at 20 °C for 10 days

exposed to 1-MCP at 4.2 μmol/m3 and then stored in air at 0.5 °C treated with 0.3 mg/L 1-MCP for 5 h and stored for 19 days at 13 °C

treated with 10 ppm 1-MCP and then stored at 16 °C treated with 0.6 μL/L 1-MCP at 0 °C for 24 h treated with 1 μL/L 1-MCP and then stored at 25 °C

treated with 625 nl/L 1-MCP after 3 days cold storage 1 μL/L of 1-MCP was applied 2 days and then again to half of the fruit after 4 months of CA storage (2.5 kPa O2+2 kPa CO2) treated with 1-MCP at 0.15 μL/L and stored at −1 °C for 7 months treated with 1-MCP at 0.3 μL/L for 24 h at 0 °C and stored at −1.1 °C for 6 months

ethylene production was inhibited inhibited ethylene production, flesh firmness and green color losses, senescence disorders, and friction discoloration delayed the decrease of firmness, total soluble solids contents and titratable acid contents slowed fruit ripening and extended postharvest life decreased respiration rates and ethylene production, inhibited core browning development, lowered chlorogenic acid content and polyphenol oxidase activity delayed fruits ripening showed delay in ripening, less shrivel and maintained mitochondrial integrity compared to the control fruit delayed fruit softening, improved rheological properties, decreased level of citric acid, malic acid, succinic acid, total organic acids, total sugars and sucrose could be stored up to 5 weeks by maintaining higher fruit firmness, ascorbic acid and total phenolic contents relieved the pulp softening extent and inhibited total chlorophyll content decrease, maintained the quality extended “eating window” and shelf life with the suppression of endogenous ethylene inhibited ethylene production by preventing an increase in ACC oxidase activity in the peel postponing the respiration, enhancing firmness, increasing Glutathione peroxidases activity and up-regulating PpaGPXs expression climacteric ethylene peak was delayed by approximately 12 days and polygalacturonase activity was strongly inhibited reduced the ethylene action and slowed the ripening maintained firmness, reduced incidence of chilling injury and polyphenol oxidase, polygalacturonase and pectin methylesterase activities, total soluble solid contents and respiration rates reduced the browning rate by maintaining the L color value extended the storage life, decreased weight loss and delayed the rate of softening, loss of taste, browning incidence in skin color

results affect the volatile biosynthesis and gene expression of apple 1-MCP maintained fruit acidity by regulating the balance between malate biosynthesis and degradation energy use of apples was reduced by 70% when compared to ULO (1.0 kPa O2+2.5 kPa CO2) at 1 °C, the fruits were firmer than fruits under ULO reduced ripening and superficial scald, did not induce diffuse skin browning improved firmness retention and extended the shelf life

storage conditions

1 μL/L of 1-MCP was applied to treat apples in a sealed container for 12 h at 20 °C exposed to 1 μL/L of 1-MCP in sealed airtight plastic tent fitted with a circulation fan at 20 ° C for 24 h treated with 625 nl/L 1-MCP for 24 h and then stored under 1 kPa O2+2.7 kPa CO2 at 5 °C

kiwifruit

mango

pear

fruit

RH = relative humidity, CTHH = controlled temperature and high humidity, CA = controlled atmosphere.

method

Table 1. continued ref

80 81

78 79

77

76

73 74,75

72

71

70

68 69

65 66 67

63 64

61 62

60

58 59

Journal of Agricultural and Food Chemistry Review

DOI: 10.1021/acs.jafc.7b02616 J. Agric. Food Chem. 2017, 65, 7308−7319

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Journal of Agricultural and Food Chemistry

did not affect the biological conversion of ACC to ethylene, while long-term treatment blocked the ethylene synthesis in pericarp tissue, which stimulated both the conversion of ACC to ethylene and the synthesis of ACC. However, silver ions have negative environmental consequences and the high STS concentration has a toxic effect on the organism, thus, their application in the inhibition of ethylene synthesis in fruit preservation is rather limited. 3.2. Oxidation of Ethylene to CO2. Another method to extend the shelf life of climatic fruits is to remove ethylene immediately once it is generated. Up to now, many chemical methods/processes have been reported to remove ethylene to prolong the fruit shelf life, among them, the oxidation of ethylene to CO2 is a popular method. The reported oxidants include O3, KMnO4, and nano-TiO2. Although O3 can be used to remove ethylene from the atmosphere, the effect of O3 on fruit can be harmful, which limits its commercial use.13 KMnO4 is an effective oxidant to convert ethylene to CO2 and H2O, which can be used in fruit preservation. An early research revealed that bananas, which were stored in sealed polyethylene bags containing KMnO4 and Ca(OH)2 can keep in firm green after 16 days due to the oxidation of ethylene to CO2.14 In another study, a commercial “Purafil”, which is alkaline KMnO4 on silicate carrier produced by Mabson Chemical Co., in conjunction with CA storage in polyethylene bags, can be used to remove ethylene and extend the green life of bananas.15 It was also reported by Elamin16 that the bananas’ ripening can be delayed significantly when KMnO4 was present in their stored polyethylene films or bags. Nano-TiO2 can also be used as an oxidant to remove ethylene due to its light catalyzing capability.17 It was also reported that the fruit softening, weight loss, browning, and climatic evolution of Chinese jujube packed with nano-TiO2 material in lower relative humidity, the fruit softening, weight loss, browning, and climatic evolution can be evidently inhibited after 12-day storage.18 3.3. Blocking the Ethylene Receptor. Using some chemicals to block the reaction between ethylene and its receptor on fruit cells is an effective method to prolong the fruit shelf life. Three typical chemicals, including 2,5-norbornadiene (2,5-NBD),42−45 diazocyclopentadiene (DACP),46,47 and cyclopropene (CP),87 have been reported to inhibit the ethylene reaction. The inhibitory effects of 2,5-NBD on ethylene action in plants was first described by Sisler and Pian.43 After that, a number of physiological studies with 2,5-NBD were performed and the ability of 2,5-NBD to block ethylene action in a number plants was confirmed.42−45 However, 2,5-NBD has an unpleasant smell and can lead to cancer; therefore, the commercial application is limited. DACP was first verified as an ethylene receptor label.88 It was studied to reduce tissue responses to ethylene among, apples46 and tomatoes.47 However, DACP is an explosion hazard under strong light conditions; therefore, the discovery of new chemicals for the blocking of ethylene receptor is always in demand. For the past few years, a great number of work has been done related to the use of CP to block ethylene receptor, which include CP, 1-methylcyclopropene (1-MCP), and 3,3-dimethylcyclopropene (3,3-DMCP).87,89 As observed in Table 2, CP and 1-MCP are about 1000 times more active than 3,3DMCP.87 In addition, 1-MCP is more stable than CP;

The CTHH technology has been used in the preservation of tomatoes40 and durians41 before. It was revealed by Bhowmik and Pan40 that tomatoes remained green up to 40 days when they were stored at 98% relative humidity at 12 °C. It was also reported by Ketsa and Pangkool41 that low amounts of CO2 and ethylene were produced for durian fruits at 33 °C and 70% relative humidity. The CTHH technology can decrease the ethylene formation and the response rate of the tissue to ethylene action in two aspects:83,84 (1) the respiratory intensity of fruit in the preservation period can be controlled, so that the ethylene formation can be decreased; (2) the water evaporation can be abated effectively and the weight loss of fruit can be reduced, so that the fruit can stay fresh. 3.1.2. Controlled Atmosphere (CA) Technology. The CA technology refers to fruit storage in a controlled atmosphere to prolong their shelf life. As stated above, the conversion of ACC to compound B (Figure 1, step 5) is a key step for the ethylene biosynthesis, which mainly depends on the activation of ACC oxidase. However, ACC oxidase need to be activated in the presence of O2 and low levels of CO2. If we can control the oxygen content of the fruit storage atmosphere at a low level, the ACC oxidase activation will be decreased. The essence of the CA technology is to control the O2 concentration in the storage atmosphere so that the activation of ACC oxidase is retarded; as a result, the fruit shelf life can be extended. Generally, 2−3% of O2 content and 5−15% of CO2 content are often used in the CA storage, and many studies have been devoted to investigate the inhibition of ethylene generation under the CA condition.2−7 It was reported by Saquet and Streif2 that the ACC-oxidase activity, ethylene production, and respiration of “Jonagold” apple will be affected by the controlled atmosphere. As a result, the CA condition of 0.5 kPa O2 + 6.0 kPa CO2 showed the strongest suppression in ethylene production, respiration and generated higher values in the respiratory quotient. In addition, the effect of CA storage on sliced partially ripe pears also revealed that their respiration and ethylene production rates can be suppressed under the CA condition. The firmness of pear slices can be kept in the storage atmosphere of 12% CO 2 and 0.5% O 2 . 3 The low O 2 atmosphere effect on the storage of bananas and “Fuji” apples showed that these fruits can be effectively preserved for a long time under the CA condition.4 Similar results were also obtained on apple slices,5 honeydew melons,6 kiwifruit7 under low O2 atmosphere or elevated CO2 level or their combination. The CA storage exhibits an effective preservation of climacteric fruit, and there is no harmful effect for the human body.85 It is practiced in the industry for the postharvest storage of climacteric fruit. A low O2 atmosphere condition cannot completely inhibit the senescence and tissue breakdown. In addition, under extremely low O2 or extremely high CO2 conditions (beyond the tolerance limit), an anaerobic respiration may occur, resulting in unexpected metabolites products and other physiological disorders.86 3.1.3. Silver treatment. There are a number of studies in the literature regarding the use of silver as an inhibitor of ethylene formation. Beyer8 found that plants treated with 25 mg/L of AgNO3 decreased the time required to reach 100% leaf abscission by 2 days. Saltveit, Jr., Bradford, and Dilley9 and Veen10 reported that AgNO3 solution and silver thiosulfate (STS) can decrease the ethylene synthesis, thus delaying the ripening process of banana slices. Atta-Aly, Saltveit, and Hobson11 further reported that a short-term silver treatment 7312

DOI: 10.1021/acs.jafc.7b02616 J. Agric. Food Chem. 2017, 65, 7308−7319

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4. MECHANISM OF 1-MCP ON FRUIT PRESERVATION It was reported that the ethylene induced fruit ripening process involves the withdrawing of electrons from a metal in the ethylene receptor, and a model involving ligand substitution has been proposed to account for their experimental observations,87 which is shown in Figure 2: (1) ethylene approaches the metal (M) on the ethylene receptor to withdraw the electrons; (2) another ligand in a trans position to it moves away from M; (3) yet another ligand moves toward M and as it does, ethylene is lost, and an active complex is formed. In this model, the proposed L1, L2, L3, L4, and L5 ligands are unknown, but it is probable that one or more of them is localized on the ETR1 gene product, a protein thought to be part of the ethylene receptor.90 However, if 1-MCP is also present, it will win the competition with ethylene in withdrawing electrons from the metal on the ethylene receptor, 1-MCP will act on the ethylene receptor in a similar way to ethylene. On the other hand, the formed 1-MCP−receptor complex, is not active in the respiratory process, blocking the fruit ripening process.87 The competing reactions between ethylene or 1-MCP and the ethylene receptor can be elaborated graphically, which is shown in Figure 2. The ethylene receptor is like a “lock” and ethylene is a “key”; when an ethylene molecule attaches to the receptor, the “lock” will turn and a door will open, thus the ethylene induced fruit ripening process takes place. However, if

Table 2. Minimum Concentration and Time of Insensitivity in Musa Sapientum Fruita compound

concentration, nL/L

insensitivity, days

1-MCP CP 3,3-DMCP

0.5 0.5 500

12 12 7

a

1-MCP, 1-methylcyclopropene; CP, cyclopropane; 3,3-DMCP, 3,3dimethylcyclopropene. This table is cited from Sisler and Serek.87

therefore, most of the studies have been done with 1-MCP for fruit preservation.87 Many studies are available in the literature regarding the use of 1-MCP for different fruit preservation. Abdi, McGlasson, Holford, Williams, and Mizrahi48 found that 1-MCP effectively delayed the ripening process of plums, and a single application of 1-MCP would suffice for nonclimacteric plum cultivar, while a continuous low dose of 1-MCP would be needed for the climacteric cultivar to reach a similar result. Other researches have shown a similar result.49−51 1-MCP was also applied to other fruit, including banana,52−54 apple,55−62 pear,63−68 mango,69,70 kiwifruit,71−73 durian,74,75 peach,76 tomato,77 pitahaya,78 nectarine,79 mulberry,80 and medlar.81 These studies support the conclusion that 1-MCP is effective to prolong the shelf life of these fruits.

Figure 2. Model for ethylene to induce the fruit ripening process and 1-MCP to block the ethylene action with the ethylene receptor. This model is modified from Sisler and Serek.87 7313

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easily released in distilled water, benzoic acid, and sodium bicarbonate solutions. Cyclodextrin compounds are the favorable encapsulation materials for 1-MCP.93,111−117 Among them, α-cyclodextrin (αCD) is the most popular due to its high encapsulation capacity, reasonable cost, and easy release capability.113,114 Procedures for 1-MCP encapsulation in α-CD have been patented.93,111,112 For example, Trinh111 described a carrier material which suspended perfume/CD complexes in polyalkylene glycol to encapsulate 1-MCP. The powder composition that contained one or more 1-MCP can retard the release of 1-MCP compound; however, it did not entirely prevent the release of 1-MCP compound. Daly and Kourelis93 developed the procedure to prepare α-CD/1-MCP complex, which was made 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 buffer solution (0.2 mol of sodium acetate and 0.2 mol of acetic acid solutions); the vessel was chilled to 4 °C for 24 h so that 1-MCP was trapped into α-CD, which was crystalized; the α-CD/1-MCP crystals/ cakes were obtained by filtering, air-dried, and ground to powder. Ghosh112 also reported a method which used α-CD as the capsulation agent to catch 1-MCP in a stable water-in-oil− water double emulsion, which disclosed can provide prolong or controlled release of 1-MCP. A continuous process for the encapsulation of 1-MCP with α-CD was invented, the product formation was evident by the generation of a slurry of white precipitate.117 During the α-CD/ 1-MCP preparation, fresh 1-MCP gas was passed through a condenser held at a temperature less than its boiling point; then, contacting an α-CD containing solution to give a precipitate of the encapsulated α-CD/1-MCP; separating the precipitate from the solution by filtering and allowing it to airdry, and the 1-MCP contents in the encapsulated product ranged from 0.5% to 2.8%. To date, the 1-MCP/α-CD complexes are commercially available, and a commercial product with the trade name of SmartFresh has been on the global market.51,55,58,59,62,63,66,68−71,74,76,79,113,114,118−121 For example, 1MCP was reported as an agent to prolong the shelf life of “Granny Smith” apples, and the results showed that the treatment of “Granny Smith” apples with 1-MCP can extend the storage time in standard NA storage for at least 3 months without significantly losing freshness.55 It was revealed that the 1-MCP-treated “Kensington Pride” mango showed improved rheological properties (firmness, springiness, and stiffness), decreased level of citric acid, malic acid, succinic acid, total organic acids, total sugars, and sucrose than other treatments.70 Their research results showed that 1-MCP can inhibit the activities of fruit softening enzymes and then delay the ripening and ripening related changes in “Kensington Pride” mangoes. 1MCP also has been used to treat Actinidia aruguta hardy kiwifruits to prolong their shelf life, which were treated with 20 μL/L 1-MCP for 16 h at 10 °C and subsequently stored at 1 ± 0.5 °C.71 The results displayed that the hardy kiwifruits without 1-MCP treatment showed increases in both respiration and ethylene production rates during fruit storage. However, the 1MCP treated kiwifruits could be stored up to 5 weeks and maintained higher fruit firmness, ascorbic acid and total phenolic contents compared to the control. The 1-MCP effect on Yali pear (Pyrus bretschneideri Rehd.) also displayed a delayed decrease in firmness, total soluble solids, titratable acid content.65

1-MCP is available, it will preferentially (over ethylene) connect with the ethylene receptor, which would “fill” into the “lock” so that the ethylene “key” is unable to go into the “lock” to open it, and the fruit ripening process can thus be blocked.86,91

5. ENCAPSULATION TECHNOLOGIES OF 1-MCP FOR FRUIT PRESERVATION 1-MCP is unstable and easy to be polymerized at the ambient conditions. Therefore, it is often used as an inclusion complex/ encapsulation. Fillers/dusts, including some inorganic minerals (calcium carbonate, lime, synthetic fine silica, talc, and chalk, etc.) and organic powders (soy bean flour pumice, wheat flour, cottonseed hulls, and wood flour, etc.) were reported for the encapsulation of 1-MCP.92 However, in these cases 1-MCP can easily escape from their inner structures of the encapsulation materials.92,93 Others, such as molecular sieve and supramolecular materials are promising and have been reported in the literature. 5.1. Molecular Sieve. Various molecular sieves have been studied to encapsulate 1-MCP . Among them, two types of molecular sieve, 13X and 5A molecular sieve, were systematically investigated.93 The results demonstrated that 13X molecular sieve was able to carry 15 ppm of 1-MCP according to the chromatographic results but no measurable amount of 1MCP was found on the 5A molecular sieve. The modified starch combined with 3A molecular sieve was also used as a microcapsules agent for the encapsulation of 1-MCP, and 0.5− 3.5% 1-MCP can be caught with 20−30% 3A molecular sieve, 60−65% modified starch, 1−2% ammonium chloride, and 3− 18% sodium bicarbonate.94 However, the encapsulated 1-MCP was difficult to release for the structure of molecular sieve, which would negatively affect the commercial application. 5.2. Metal−Organic Frameworks (MOFs). Metal−organic frameworks (MOFs) are a new class of synthetic porous materials which have been developed to capture gases in fuel and chemical industries due to their highly ordered, porous crystalline structure.95 It was revealed that several MOFs termed metal coordination polymer networks including calcium-4,4′-sulfonyldibenzoic acid, copper-2,4,6-tris(3,5-dicarboxyl-phenylaminl)-1,3,5-triazine, and zinc-tcbpe [reaction product of tetra(4-bromo-phenyl)ethylene and 4(methoxycarbonyl)phenylboronic acid] can be used for the adsorb and desorb of 1-MCP.96 In addition, the copper-based MOF with a trimesic acid linker group also displayed a good perform to encapsulate 1-MCP, and a 17.6% w/w basis of 1MCP can be loaded; however, it was unable to release the 1MCP.97 5.3. Supramolecular Materials. Some supramolecular materials, such as cucurbit uril and cyclodextrin, have been used as the encapsulation agent of 1-MCP. Cucurbit urils is a kind of barrel-like macrocyclic molecule generated from formalin and glycoluril.98−102 Cucurbit [6] urils can host/absorb alkylammonuium ions,103 short polypeptides,104 Et2O,105 metal cations,106 and some small-molecule gases107 to produce stable inclusion complexes.108−110 It was also reported by Zhang, Zhen, Jiang, Li, and Liu98 that cucurbit urils can be used as an absorbent to encapsulate 1-MCP due to the cavity structure, and 4.5% 1-MCP by weight can be encapsulated by cucurbit [6] uril at the initial 1-MCP concentration of 75 mL/L, the cucurbit [6] uril concentration of 30 mM at 20 °C in 8 h. The encapsulated 1-MCP can be 7314

DOI: 10.1021/acs.jafc.7b02616 J. Agric. Food Chem. 2017, 65, 7308−7319

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6. CALIXARENE, A POTENTIAL SUPRAMOLECULAR COMPOUND ENCAPSULATION AGENT Calixarenes are a class of polyphenolic cyclo-oligomers, which can be synthesized via a phenol-formaldehyde condensation. They have a defined upper and lower rim and a central annulus, which exist in a “cup” like shape and have similar structure to Cucurbit urils and CD (Figure 3).122

hydrophilic external surface can adsorb water for the release of 1-MCP. Its feasibility for the encapsulation of 1-MCP will be confirmed in our future research.



AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Phone: +86-571-86843871. Fax: +86-571-86843250. *E-mail: [email protected]. Phone: +1-506-4516857. Fax: +1506-4534767. ORCID

Junhua Zhang: 0000-0002-0946-2143 Yonghao Ni: 0000-0001-6107-6672 Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (Grant 21406208), the Natural Science Foundation of Zhejiang Province (Grant LY17C160008), China Scholarship Council (Grant 201508330154), the Open Foundation of the Most Important Subjects in Colleges and Universities in Zhejiang Province (Grant 2015YXQN13), Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University (Grant YR2015005), 521 Talent Cultivation Program of Zhejiang Sci-Tech University (Grant 11110132521309).

Figure 3. Typical structures of calixarene (calix [4] and [6]) and their cavity dimensions based on chem3D calculation.

As can be seen in Figure 3, the cavity size of the two typical calixarenes are 0.13−1.32 nm (Calix [4] arene) and 0.28−1.55 nm (Calix [6] arene), respectively, based on the distance measurement of chem3D; therefore, they possess ideal inclusion ability to bind guest ions and molecules.123,124 For example, calixarenes were used for complexing metal ions due to their selective inclusion ability with metal ions, such as the alkali metal ions (Li+, K+, Na+),125,126 the transition metal ions (Ru2+),127 and the subgroup metal ions (U3+).128,129 Some small organic molecules, such as toluene, nitrobenzene, butane, pentane, and hexane can also be encapsulated by calixarenes with the ratio of 1:1.130 In addition, para-Octanoyl-calix [4] arene was also an excellent adsorbent for saturated and unsaturated hydrocarbons, polarizable inert gases, carbon dioxide, and two typical calixarenes, calix [4] and [6], have been reported to encapsulate CO2 and ethylene.131−137 The cup ring size of calixarene is rather flexible, which can be controlled through the change of conformation and different substituting groups on the ring. Therefore, calixarene may be a good candidate for the encapsulation of 1-MCP, because (1) one calixarene can host one 1-MCP through the adapting of its cavity size; (2) calixarene has a lypophilic inner cavity, facilitating lypophilic interactions with 1-MCP; (3) calixarene has a hydrophilic external surface, which can absorb water for the release of 1-MCP. In conclusion, this review elaborated the mechanism of ethylene formation in climacteric fruit and its role in the ripening process. The current ethylene controlling strategies for fruit preservation were further discussed. Moreover, the applications of 1-MCP, which mimics ethylene structure and competes favorably in reaction with the ethylene acceptors, have been especially highlighted to extend the postharvest shelf life of climacteric fruit. The 1-MCP encapsulation technologies have been described. Finally, as a potential novel encapsulation agent of 1-MCP, calixarene has been put forward and elaborated based on (1) calixarene can host one 1-MCP due to its unique structure of adapting its cavity size by different conformations/substituting groups; (2) its lypophilic inner cavity can facilitate the interactions with 1-MCP; (3) its



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