WO2014046976A1 - Methods of handling persimmons - Google Patents

Methods of handling persimmons Download PDF

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Publication number
WO2014046976A1
WO2014046976A1 PCT/US2013/059658 US2013059658W WO2014046976A1 WO 2014046976 A1 WO2014046976 A1 WO 2014046976A1 US 2013059658 W US2013059658 W US 2013059658W WO 2014046976 A1 WO2014046976 A1 WO 2014046976A1
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WO
WIPO (PCT)
Prior art keywords
persimmons
cyclopropene compound
modified
atmosphere
exposure
Prior art date
Application number
PCT/US2013/059658
Other languages
French (fr)
Inventor
Fernando K. EDAGI
Nazir Mir
Evan Mccaskey
Robert L. Mcgee
Bruce Menning
Original Assignee
Agrofresh Inc.
Dow Global Technologies Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP13766849.7A priority Critical patent/EP2897462B1/en
Priority to CN201380060336.0A priority patent/CN104902760A/en
Priority to JP2015533120A priority patent/JP2015530095A/en
Priority to BR112015005880A priority patent/BR112015005880A2/en
Priority to US14/430,109 priority patent/US20150237877A1/en
Priority to MX2015003646A priority patent/MX2015003646A/en
Application filed by Agrofresh Inc., Dow Global Technologies Llc filed Critical Agrofresh Inc.
Priority to AU2013318331A priority patent/AU2013318331B2/en
Priority to NZ706264A priority patent/NZ706264A/en
Priority to KR1020157009672A priority patent/KR20150056623A/en
Publication of WO2014046976A1 publication Critical patent/WO2014046976A1/en
Priority to IL237798A priority patent/IL237798A0/en
Priority to US16/393,217 priority patent/US20190246657A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor

Definitions

  • This invention is generally related to the field of agriculture, and more specifically the field of post-harvest handling of produce.
  • a persimmon tree is a plant of Ebenaceae which grows or is cultivated in the tropic and temperate zones of the world including Japan and China. It is said that Ebenaceae plants are classified into seven genuses and 20 species and fruits of some kinds of persimmon trees contain, even after their maturity, persimmon tannine.
  • the persimmon tannine is known to be available for some medicines, mordanting and leather- tanning agents.
  • Persimmon (Diasoyros kaki), which is a nutritious and alkaline fruit, contains about 11-15% of sugar such as fructose and glucose, about 20-50 mg/100 g (edible portion) of vitamin C, which is about 5-12 times as much as that of apple, and more minerals than apple. Additionally, persimmon contains a great quantity of vitamin A and tannic acid, the latter of which produces a bitter taste. Especially, tannic acid is known to remedy diarrhea or stomach disorder, as well as lower the blood pressure without affecting an electrocardigram. Many of research in persimmon, as both food and medicine, are actively on-going.
  • Amount of persimmon produced in domestic was about 155,111 ton in 1992, but has been increasing yearly to about 239,570 ton in 1997.
  • cultivation area of persimmon is increasing yearly. Because persimmon has a higher profitability than other fruit, e.g., apple, significant increasing of its cultivation area is expected.
  • This invention is based on unexpected synergistic effect of a cyclopropene compound and a modified atmosphere package to extend shelf life and/or storage for persimmons.
  • a method of storing persimmons comprising the step of exposing persimmons to an atmosphere that contains a cyclopropene compound, wherein either (a) the persimmons are in a modified- atmosphere package during exposure to the cyclopropene compound, or (b) the persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours.
  • the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
  • a method of handling persimmons comprising exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound and the persimmons remain in the modified atmosphere package after the exposure for at least two hours.
  • the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons. In a further embodiment, the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons. In another embodiment, the persimmons remain in the modified atmosphere package after the exposure for at least ten hours, twenty hours, forty hours, four days, seven days, or ten days. In another embodiment, the cyclopropene compound is in a formulation with a molecular encapsulating agent. In a further embodiment, the
  • cyclopropene compound comprises 1-methylcyclopropene (1-MCP).
  • the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma- cyclodextrin, or combinations thereof.
  • the encapsulated agent comprises alpha-cyclodextrin.
  • the cyclopro is of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • cycloalkylalkyl phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • the cyclopropene compound is of the formula:
  • R 1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm. In a further embodiment, the cyclopropene compound during the exposure is at a concentration about 1, 000 ppb. In another
  • the firmness of the persimmons after the exposure is at least sixteen lbfs after day one or fourteen lbfs after day seven. In another embodiment, shelf life of the
  • persimmons after the exposure is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days.
  • the persimmons are placed in the modified-atmosphere package within two hours, four hours, eight hours, twelve hours, twenty-four hours, or forty-eight hours after harvest.
  • a method of handling persimmons comprising exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are placed into a modified-atmosphere package within two hours after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours.
  • the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons. In a further embodiment, the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons. In another embodiment, the persimmons are placed into a modified-atmosphere package within four hours, eight hours, twelve hours, or twenty hours after exposure to the cyclopropene compound. In another embodiment, the persimmons remain in the modified atmosphere package after the exposure for at least ten hours, twenty hours, forty hours, four days, seven days, or ten days.
  • the cyclopropene compound is in a formulation with a molecular encapsulating agent.
  • the cyclopropene compound comprises 1-methylcyclopropene (1-MCP).
  • the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof.
  • the encapsulated agent comprises alpha-cyclodextrin.
  • the cyclopro is of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • cycloalkylalkyl phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • the cyclopropene compound is of the formula:
  • R 1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm. In a further embodiment, the cyclopropene compound during the exposure is at a concentration about 1, 000 ppb. In another embodiment, the firmness of the persimmons after the exposure is at least sixteen lbfs after day one or fourteen lbfs after day seven. In another embodiment, shelf life of the persimmons after the exposure is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days.
  • a system for handling persimmons comprising (a) a cyclopropene compound, wherein the cyclopropene compound is applied to the persimmons at a concentration between 10 ppb and 5 ppm; and (b) a modified-atmosphere package, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
  • the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons.
  • the cyclopropene compound is in a formulation with a molecular encapsulating agent.
  • the cyclopropene compound comprises 1-methylcyclopropene (1-MCP).
  • the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof.
  • the encapsulated agent comprises alpha- cyclodextrin.
  • the cyclopro is of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • cycloalkylalkyl phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • cyclopropene compound is of the formula:
  • R 1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene compound is applied to the persimmons at a concentration about 1,000 ppb.
  • the firmness of the persimmons after treatment with the system provided is at least sixteen lbfs after day one or fourteen lbfs after day seven.
  • shelf life of the persimmons after the treatment with the system provided is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days.
  • Figure 1 shows representative firmness results up to ten days of the persimmons treated with the method provided (RipeLock), modified atmosphere package alone (MAP), cyclopropene compound alone (SmartFresh), or control (without neither modified atmosphere package nor cyclopropene compound).
  • Figure 2A shows representative firmness results of the persimmons four days after treatment according to results of Figure 1.
  • Figure 2B shows representative firmness results of the persimmons seven days after treatment according to results of Figure 1.
  • Figure 3 shows other representative firmness results up to four days of the persimmons treated with the method provided (RipeLock), modified atmosphere package alone (MAP), cyclopropene compound alone (SmarFresh), or control (without neither modified atmosphere package nor cyclopropene compound).
  • Figure 4A shows representative firmness results of the persimmons one day after treatment according to results of Figure 3.
  • Figure 2B shows representative firmness results of the persimmons four days after treatment according to results of Figure 3.
  • Figure 6 shows representative firmness results of the persimmons six days after treatment according to results of Figure 5.
  • N denotes Newtons
  • lbf ' pounds-force
  • a "polymeric film” is an object that is made of polymer; that is much smaller in one dimension (the "thickness") than in the other two dimensions; and that has a relatively uniform thickness.
  • Polymeric film typically has thickness of 1 mm or less.
  • the "pulp firmness" of persimmons is measured using a penetrometer (for example Fruit TestTM FT40 penetrometer, from Wagner Instruments) having a plunger diameter of 8 mm. Performing the test for pulp firmness destroys the persimmon that is tested.
  • persimmons are said herein to be treated in a certain way (e.g., harvested, shipped, exposed to a cyclopropene compound, etc.) when they have a certain specified pulp firmness, it is meant that, out of a group of persimmons that have been harvested and treated as uniformly as reasonably possible, a sample of a relatively small number of persimmons is removed and tested for pulp firmness. The large group of persimmons is considered to have the pulp firmness that is the average value of the tests performed on the relatively small sample.
  • the present invention involves the use of one or more cyclopropene compound.
  • R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of H and a chemical group of the formula:
  • Each L is a bivalent radical. Suitable L groups include, for example, radicals containing one or more atoms selected from H, B, C, N, O, P, S, Si, or mixtures thereof. The atoms within an L group may be connected to each other by single bonds, double bonds, triple bonds, or mixtures thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any one R group (i.e., any one of R 1 , R 2 , R 3 and R 4 ) the total number of heteroatoms (i.e., atoms that are neither H nor C) is from 0 to 6.
  • any one R group the total number of non-hydrogen atoms is 50 or less.
  • Each Z is a monovalent radical.
  • Each Z is independently selected from the group consisting of hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, and a chemical group G, wherein G is a 3 to 14 membered ring system.
  • the R 1 , R 2 , R 3 and R 4 groups are independently selected from the suitable groups.
  • the R 1 , R 2 , R 3 and R 4 groups may be the same as each other, or any number of them may be different from the others.
  • Groups that are suitable for use as one or more of R 1 , R 2 , R 3 and R 4 may be connected directly to the cyclopropene ring or may be connected to the cyclopropene ring through an intervening group such as, for example, a heteroatom-containing group.
  • a chemical group of interest is said to be "substituted” if one or more hydrogen atoms of the chemical group of interest is replaced by a substituent.
  • substituents include, for example, alkyl, alkenyl, acetylamino, alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimino, carboxy, halo, haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl, dialkylamino, and combinations thereof.
  • R 1 , R 2 , R 3 and R 4 groups are, for example, substituted and unsubstituted versions of any one of the following groups: aliphatic, aliphatic-oxy, alkylcarbonyl, alkylphosphonato, alkylphosphato, alkylamino, alkylsulfonyl, alkylcarboxyl, alkylaminosulfonyl, cycloalkylsulfonyl, cycloalkylamino, heterocyclyl (i.e., aromatic or non- aromatic cyclic groups with at least one heteroatom in the ring), aryl, hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido, chlorato, bromato, iodato, isocyanato, isocyanido, isothiocyanato, pentafluorothio; acetoxy, carbo
  • R 1 , R 2 , R 3 and R 4 groups are those that contain one or more ionizable substituent groups.
  • ionizable groups may be in non-ionized form or in salt form.
  • R 3 and R 4 are combined into a single group, which is attached to the number 3 carbon atom of the cyclopropene ring by a double bond.
  • one or more cyclopropenes are used in which one or more of R 1 , R 2 , R 3 and R 4 is hydrogen.
  • each of R 1 , R 2 , R 3 and R 4 is hydrogen or (Ci-Cs) alkyl.
  • R 1 is substituted or unsubstituted (Ci-Cs) alkyl, and each of R 2 , R 3 , and R 4 is hydrogen.
  • each of R 2 , R 3 , and R 4 is hydrogen, and R 1 is either unsubstituted (C1-C4) alkyl or a carboxyl-substituted (Ci-Cs) alkyl.
  • each of R 2 , R 3 , and R 4 is hydrogen, and R 1 is unsubstituted (C1-C4) alkyl.
  • R 1 is methyl and each of R 2 , R 3 , and R 4 is hydrogen, and the cyclopropene compound is known herein as 1-methylcycplopropene or "1-MCP.”
  • a cyclopropene compound is used that has boiling point at one atmosphere pressure of 50 °C or lower; or 25 °C or lower; or 15 °C or lower.
  • a cyclopropene compound is used that has boiling point at one atmosphere pressure of -100 °C or higher; -50 °C or higher; or 25 °C or higher; or 0 °C or higher.
  • modified-atmosphere packaging or "MAP” refers to an enclosure that alters the gaseous atmosphere inside the enclosure from normal atmospheric composition when respiring produce is contained inside the enclosure.
  • MAP is an enclosure in the sense that it is a package that may be lifted and transported with the produce contained within it.
  • MAP may or may not allow exchange of gas with the ambient atmosphere outside the MAP.
  • MAP may or may not be permeable to diffusion of any particular gas, independent of its permeability or non-permeability to any other gas.
  • a "monomer” is a compound that has one or more carbon-carbon double bond that is capable of participating in a polymerization reaction.
  • an "olefin monomer” is a monomer, the molecules of which contain only atoms of carbon and hydrogen.
  • polar monomer is a monomer, the molecules of which contain one or more polar group. Polar groups include, for example, hydroxyl, thiol, carbonyl, carbon-sulfur double bond, carboxyl, sulfonic acid, ester linkages, other polar groups, and combinations thereof.
  • persimmons are exposed to an atmosphere that contains one or more cyclopropene compound.
  • Cyclopropene compound may be introduced into the atmosphere surrounding the persimmons by known methods in the art.
  • gaseous cyclopropene compound may be released into the atmosphere in such close proximity to persimmons that the cyclopropene compound contacts the persimmons before the cyclopropene diffuses far away from the persimmons.
  • the persimmons may be in an enclosure (i.e., and airtight container enclosing a volume of atmosphere), and gaseous cyclopropene compound may be introduced into the enclosure.
  • the persimmons are inside a permeable surrounding device, and cyclopropene compound is introduced into the atmosphere outside the permeable surrounding device.
  • the permeable surrounding device encloses one or more persimmons and allows some contact between the cyclopropene compound and the persimmons, for example by allowing some cyclopropene compound to diffuse through the permeable surrounding device or through holes in the permeable surrounding device or a combination thereof.
  • a permeable surrounding device may or may not also qualify as an MAP as defined herein.
  • gaseous cyclopropene compound is introduced into an enclosure
  • the introduction may be performed by known methods in the art.
  • the cyclopropene compound may be created in a chemical reaction and vented to the enclosure.
  • cyclopropene compound may be kept in a container such as a compressed-gas tank and released from that container into the enclosure.
  • cyclopropene compound may be contained in a powder or pellets or other solid form that contains encapsulated complex of cyclopropene compound in a molecular encapsulating agent.
  • a complex that includes a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in a molecule of a molecular encapsulating agent is known herein as a "cyclopropene compound complex" or
  • suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents.
  • Organic molecular encapsulating agents are provided include, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers.
  • Suitable inorganic molecular encapsulating agents include, for example, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable.
  • the encapsulation agent is selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, substituted versions thereof, and combinations thereof.
  • the cyclopropene compound is 1-methylcyclopropene
  • the encapsulation agent is alpha cyclodextrin.
  • the choice of encapsulation agent will vary depending upon the structure of the cyclodextrin compound or compounds being used. Any cyclodextrin or mixture of cyclodextrins, cyclodextrin polymers, modified cyclodextrins, or mixtures thereof can also be utilized pursuant to the present invention.
  • a cyclopropene compound is introduced into an enclosure that contains persimmons by placing cyclopropene molecular complex into the enclosure and then contacting the cyclopropene molecular complex with a release agent.
  • a release agent is a compound that, when it contacts cyclopropene encapsulation complex, promotes the release of the cyclopropene compound into the atmosphere.
  • water or a liquid that contains 50% or more water by weight, based on the weight of the liquid is the exemplary release agent.
  • a solid material containing cyclopropene molecular complex is placed into an enclosure that contains persimmons, and water is brought into contact with that solid material. Contact with the water causes release of cyclopropene compound into the atmosphere of the enclosure.
  • the solid material may be in the form of tablets that contain, optionally among other ingredients, encapsulation complex that contains a cyclopropene compound and one or more ingredients that causes
  • the solid material may be placed into an enclosure that contains persimmons and water vapor in the atmosphere may be effective as a release agent.
  • the solid material that contains cyclopropene encapsulated complex may be in a form that also contains, optionally among other ingredients, a water-absorbing compound such as, for example, a water- absorbing polymer or a deliquescent salt.
  • atmosphere containing one or more cyclopropene compound in gaseous form is in contact with persimmons or is in contact with a permeable surrounding device that surrounds one or more persimmons.
  • concentrations above zero of cyclopropene compound are contemplated.
  • the concentration of cyclopropene compound is 10 ppb or higher; more preferably is 30 ppb or higher; more preferably is 100 ppb or higher.
  • the concentration of cyclopropene compound is 50 ppm or lower, more preferably 10 ppm or lower, more preferably 5 ppm or lower.
  • MAP may be active or passive. Active MAP is packaging that is attached to some material or apparatus that adds certain gas or gases to the atmosphere inside the MAP and/or removes certain gas or gases from the atmosphere inside the MAP.
  • Passive MAP also called commodity generated modified atmosphere packaging
  • the MAP can be designed so that diffusion through the solid exterior surfaces of the MAP and passage of gas through any perforations that may be present in the exterior surface of the MAP maintain optimum levels of oxygen, carbon dioxide, and optionally other gases (such as, for example, water vapor or ethylene or both).
  • passive MAP is used.
  • active MAP is used.
  • both active and passive MPAs are used.
  • an MAP has a certain gas transmission characteristic
  • a passive MAP that has that gas transmission characteristic
  • an active MAP that, when it contains persimmons, maintains the same atmosphere within itself that would occur in a passive MAP that had that gas transmission characteristic
  • a useful way to characterize the MAP is the gas transmission rate of the MAP itself in relation to the amount of persimmons held in the MAP.
  • the rate of transmission of carbon dioxide is, in units of cubic centimeters per day per kilogram of persimmons, 5,000 or higher; more preferably 7,000 or higher; more preferablyl0,000 or higher.
  • the rate of transmission of carbon dioxide is, in units of cubic centimeters per day per kilogram of persimmons, 150,000 or lower; more preferably 100,000 or lower.
  • the rate of transmission of oxygen is, in units of cubic centimeters per day per kilogram of persimmons, 3,800 or higher; more preferably 7,000 or higher; more preferably 15,000 or higher.
  • the rate of transmission of oxygen is, in units of cubic centimeters per day per kilogram of persimmons, 100,000 or lower; or 75,000 or lower.
  • the gas transmission rate of a film having thickness 30 micrometers is labeled "GT-30" herein.
  • film beta ratio is the quotient that is calculated by dividing the GT-30 for carbon dioxide gas transmission rate by the GT-30 for oxygen gas.
  • some or all of the exterior surfaces of the MAP are polymeric.
  • the polymer is in the form of a polymeric film.
  • Some suitable polymeric films have thickness of 5 micrometer or more; or 10 micrometer or more; or 20 micrometer or more. Independently, some suitable polymeric films have thickness of 200 micrometer or less; or 100 micrometer or less; or 50 micrometer or less.
  • suitable polymer compositions include, for example, polyolefins, polyvinyls, polystyrenes, polydienes, polysiloxanes, polyamides, vinylidene chloride polymers, vinyl chloride polymers, copolymers thereof, blends thereof, and laminations thereof.
  • Suitable polyolefins include, for example, poly ethylenes, polypropylenes, copolymers thereof, blends thereof, and laminations thereof.
  • Suitable polyethylenes include, for example, low density polyethylene, ultralow density polyethylene, linear low density polyethylene, metallocene-catalyzed polyethylene, copolymers of ethylene with polar monomers, medium density polyethylene, high density polyethylene, copolymers thereof and blends thereof.
  • Suitable polypropylenes include, for example, polypropylene and oriented polypropylene. In some embodiments, low density polyethylene is used. In one
  • copolymer of styrene and butadiene is used.
  • polyamides, polyolefins, and blends thereof are used.
  • polystyrene resins one example is polyethylene; and another example is metallocene-catalyzed polyethylene.
  • Other examples include polymer compositions comprising one or more polyolefin and/or one or more copolymer of an olefin monomer with a polar monomer.
  • copolymer refers to a product of copolymerizing two or more different monomers.
  • Suitable copolymers of an olefin monomer with a polar monomer include, for example, such polymers available from DuPont called ElvaxTM resins.
  • One embodiment includes copolymers of ethylene with one or more polar monomer.
  • Suitable polar monomers include, for example, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, and mixtures thereof.
  • polar monomers contain one or more ester linkage; for another example is vinyl acetate.
  • the amount of polar monomer may be, by weight based on the weight of the copolymer, 0.5% or more; for example 1% or more; or 1.5% or more.
  • the amount of polar monomer may be, by weight based on the weight of the copolymer, 25% or less; for example 20% or less; or 15% or less.
  • Suitable polyolefins include blends of a polyolefin homopolymer with a copolymer of an olefin monomer with a polar monomer.
  • the weight ratio of homopolymer to copolymer may be 0.5: 1 or higher; for example 0.8: 1 or higher; or 1 : 1 or higher.
  • the weight ratio of homopolymer to copolymer may be 3: 1 or lower; for example 2: 1 or lower; or 1.25: 1 or lower.
  • Suitable polyamides include nylon 6, nylon 6,6, and copolymers thereof; for example copolymers of nylon 6 with nylon 6,6.
  • copolymers of nylon 6 with nylon 6,6 include copolymers in which the weight ratio of polymerized units of nylon 6 to polymerized units of nylon 6,6 may be 0.05: 1 or higher; 0.11 : 1 or higher; or 0.25 : 1 or higher.
  • examples include copolymers in which the weight ratio of polymerized units of nylon 6 to polymerized units of nylon 6,6 may be 9: 1 or lower; 3: 1 or lower; or 1.5: 1 or lower.
  • Suitable blends of polyamide with polyolefin include blends in which the weight ratio of polyamide to polyolefin may be 0.05: 1 or higher; 0.11 : 1 or higher; 0.25: 1 or higher; or 0.5: 1 or higher.
  • Suitable blends of polyamide with polyolefin include blends in which the weight ratio of polyamide to poly olefin may be 9:1 or lower; 5: 1 or lower; or 3: 1 or lower.
  • a container comprises polymeric film
  • the film is arranged so that molecules that are capable of diffusing through the polymeric film will diffuse between the inside of the container and the outside of the container in both directions.
  • a container may be constructed so that one, two, or more separate portions of the surface area of the container consist of polymeric film, and the polymeric film portions may be the same composition as each other or may be different from each other. It is
  • such containers will be constructed so that the portion of the container surface that is not polymeric film will effectively block diffusion of gas molecules (i.e., the amount of gas molecules that diffuse through will be of negligible importance).
  • Suitable polyolefin films include film compositions for which the GT-30 for carbon dioxide at 23 °C, in units of cm 3 /(m 2 -day), may be 800 or higher; 4,000 or higher; 5,000 or higher; 10,000 or higher; or 20,000 or higher.
  • Example include films with GT-30 for carbon dioxide at 23 °C, in units of cm 3 /(m 2 -day), of 150,000 or lower; 80,000 or lower; or 60,000 or lower.
  • Other examples include films with GT-30 for oxygen at 23 °C, in units of cm 3 /(m 2 -day), of 200 or higher; 1,000 or higher; 3,000 or higher; or 6,000 or higher.
  • film has film beta ratio of 1 or higher; or 2 or higher. In another embodiment, film has beta ratio of 15 or lower; or 10 or lower.
  • Polyamide films includes films containing polyamide and films containing a blend of polyamide with one or more other polymer.
  • Suitable polyamide films include films with GT-30 for water vapor at 37.8 °C, in units of g/(m 2 -day), of 10 or higher; or 20 or higher. Examples include films with GT-30 for water vapor at 37.8 °C, in units of g/(m 2 -day), of 1,000 or lower; 800 or lower; 500 or lower; 350 or lower; or 200 or lower.
  • the GT-30 for oxygen and the GT-30 for carbon dioxide are both very low for polyamide films. It is contemplated that when MAP is used that is made of a film that is made of polyamide or a blend of polyamide with other polymer(s), the film will be perforated in a way that is chosen to provide the desired gas transmission characteristics of the MAP itself.
  • polymeric film is used that has perforations.
  • the holes have mean diameter of 5 micrometers to 500 micrometers.
  • the holes may have mean diameter of 10 micrometers or more; 20 micrometers or more; 50 micrometers or more; or 100 micrometers or more.
  • the holes may have mean diameter 300 micrometers or less; or 200 micrometers or less. If a hole is not circular, the diameter of the hole is considered herein to be 2 times the square root of the quotient of the area of the hole divided by pi.
  • the MAP comprises polymeric film
  • the percent of the surface area of the MAP that consists of the polymeric film may be 10% to 100%; 50% to 100%; 75% to 100%; or 90% to 100%.
  • An MAP in which 90% to 100% of the surface area consists of polymeric film is known herein as a "bag.”
  • Example include MAP that comprise polymeric film and in which all portions of the surface of the MAP that are not polymeric film effectively block diffusion of gas molecules.
  • the MAP is considered to be passive MAP.
  • Holes in polymeric film may be made by methods known in the art. Suitable methods include, for example, laser perforation, hot needles, flame, low-energy electrical discharge, and high-energy electrical discharge. In one embodiment, such method is laser perforation.
  • MAP beta ratio is defined herein as the quotient that results from dividing the rate of transmission of carbon dioxide of the MAP by the rate of transmission of oxygen of the MAP itself.
  • the MAP beta ratio may be 0.3 or higher; or 0.5 or higher.
  • the MAP beta ratio may be 5 or lower; 3 or lower; or 2 or lower.
  • the MAP beta ratio is 1.0 to 1.6.
  • the MAP beta ratio is 0.5 to 0.999.
  • the MAP beta ratio is 0.6 to 1.2.
  • persimmons are harvested when they are mature but not yet ripe. In another embodiment, the persimmons are harvested when the dry matter content, by weight based on the weight of the persimmon, is 17% or higher. [0073] In one embodiment, persimmons are harvested and immediately (for example within two hours) placed into MAP before exposure to the cyclopropene compound. In another embodiment, the time from harvest to placement into MAP may be 30 days or less; 14 days or less; 7 days or less; or 2 days or less. In another embodiment, harvested persimmons are placed into MAP after exposure to the cyclopropene compound and prior to shipment, and the harvested persimmons remain in the MAP during shipment.
  • persimmons are harvested and, prior to being placed into MAP, the persimmons are placed in pre-shipment storage.
  • pre-shipment storage may be below room temperature, for example 7 °C or lower. After such storage, the persimmons may be placed in to MAP and then shipped to their destination.
  • persimmons are shipped to a destination that is near the intended point of consumption or else are harvested near the intended point of consumption and/or sale.
  • near the intended point of consumption and/or sale means a location from which it is capable to transport the persimmons to the point of consumption in 3 days or fewer by truck or other surface transportation.
  • persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound (for example, persimmons are exposed to an atmosphere that contains a cyclopropene compound while the persimmons are not in an MAP), persimmons are placed into an MAP after the conclusion of the exposure to the atmosphere that contains a cyclopropene compound, and the persimmons then remain in the MAP for at least two hours.
  • the persimmons are kept at temperature of 10 °C or above from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP.
  • the time period from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be eight hours or less; four hours or less; two hours or less; or 1 hour or less.
  • the persimmons are kept at temperature below 10 °C from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP.
  • the temperature at which persimmons are kept from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be 7 °C or lower.
  • the time period from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be between ten minutes to two months.
  • the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound (for example, persimmons are exposed to an atmosphere that contains a cyclopropene compound while the persimmons are in a MAP), there is an improvement in the pulp firmness of the persimmons that can be seen even immediately after the conclusion of the exposure of the persimmons to the cyclopropene compound.
  • persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound
  • persimmons are in an MAP for a time period of duration of 1 day or more, where that time period is after harvest and before exposure to atmosphere containing a cyclopropene compound (herein called a "pre-X" time period).
  • composition of the MAP comprises polyamide.
  • the persimmons reside in an MAP for a storage time period that begins within 1 hour of the conclusion of the exposure to atmosphere containing cyclopropene compound (herein called a "post-X" time period).
  • post-X storage time period may begin within thirty minutes of the conclusion of the exposure to
  • the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound
  • the persimmons are in an MAP during exposure to atmosphere containing cyclopropene compound; if the persimmons remain in the MAP thereafter without being removed from the MAP, the post-X storage time period is considered to begin immediately upon the conclusion of the exposure to atmosphere containing cyclopropene compound.
  • the post-X storage time period may last for one day or longer; or 2 days or longer.
  • suitable MAP is chosen or designed so that, when persimmons are placed into the MAP and the MAP, with the persimmons inside, is then exposed to atmosphere containing cyclopropene compound, and then stored for 10 days at 16.7 °C, a certain pre-determined atmosphere will be present in the MAP.
  • the amount of carbon dioxide, by volume based on the volume of the atmosphere inside the MAP may be 1% or more; or 5% or more.
  • the amount of carbon dioxide, by volume based on the volume of the atmosphere inside the MAP may be 20% or less; or 15% or less.
  • the amount of oxygen, by volume based on the volume of the atmosphere inside the MAP may be 3% or more; or 5% or more. In another embodiment with the pre-determined atmosphere, the amount of oxygen, by volume based on the volume of the atmosphere inside the MAP, may be 20% or less; or 15% or less.
  • the Oxygen Transmission Rate or OTR for a modified atmosphere package can be calculated from the work presented in literature or measured directly.
  • the OTR due to the permeability of the film at any given time can be theoretically calculated using Fick' s law of diffusion where the permeability coefficient for the polymer film can be measured using a procedure as called out in ASTM method D3985 for 0 2 .
  • ASTM method D3985 for 0 2 the OTR due to the
  • microperforations can be calculated using a modified Fick' s law of diffusion.
  • the OTR at any given time is dependent on the 0 2 concentration driving force at that point of time.
  • the OTR of the system can be measured by measuring the 0 2 partial pressure versus time and then plotting the natural log of the concentration gradient versus time. This is a convenient method in cases where there are not well validated models for the OTR such as microporous systems or unique combinations of approaches such as microporous patches combined with films or microperforated films.
  • Persimmons are harvested in Mogi das Cruzes - SP - Brazil and packed in RPC (Recycle Plastic Container) and shipped to Piracicaba - SP. At the same day of harvest part of the persimmons are packed in MAP bags.
  • Giombo astringent and need to be treated with ethanol to be ready to eat
  • MAP Bag a Nylon bag with dimensions of 27" ( 68.6 cm) width by 28"( 71.1 cm) length made from Kenylon 6250 Polyamide Film available from FM Packaging.
  • the base film has 25 microns thickness without laser holes.
  • the oxygen (0 2 ) permeation of the MAP bag used is about 28 cc/ m 2 -day and the C0 2 permeation is about 227 cc /m 2 -day.
  • the bags are laser drilled in the length direction with 105 micron holes at two locations 9" (22.9 cm) from each side of the bag.
  • the hole spacing is 9.06 mm.
  • the total number of laser holes in the 20" ( 8" for tie off) length direction of the bag are about 228 holes.
  • the 228 holes can provide an open area of ⁇ 2.0 mm 2 .
  • the OTR of the bag is calculated to be 32,250 cm 3 /day.
  • the Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 16 kg (36 lb) of persimmons. One such bag is packed in each RPC. Total weight of persimmons in MAP bags is approximately 64 kg. Approximately 64 kg of persimmons are placed into RPC identical to those used for the MAP bags.
  • the MAP-packaged persimmons are packaged as follows: 80 fruits,
  • each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours.
  • SmartTabsTM tablets are placed in the chamber. The amount of SmartTabTM tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
  • the treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative.
  • Persimmons used in this trial are an astringent variety. To remove the astringency the fruits were treated with ethanol after the 15 days at cold storage.
  • the RPCs are moved into racks at room temperature for storage and observation.
  • the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
  • FT A Firmness Texture Analyzer
  • Example 2 uses a similar test to Example 1 but with the ethanol application before the storage, at the same time as 1-MCP application.
  • Persimmons are harvested in Mogi das Cruzes - SP - Brazil and packed in RPC (Recycle Plastic Container) and shipped to Piracicaba - SP. At the same day of harvest part of the persimmons are packed in MAP bags.
  • the Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 16 kg (36 lb) of persimmons. One such bag is packed in each RPC. Total weight of persimmons in MAP bags is approximately 64 kg. Approximately 64 kg of persimmons are placed into RPC identical to those used for the MAP bags.
  • the MAP-packaged persimmons are packaged as follows: 80 fruits, approximately 16 kg are carefully placed into microperforated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
  • each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours.
  • SmartTabsTM tablets are placed in the chamber. The amount of SmartTabTM tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
  • the persimmons are exposed to ethanol with the purpose of removing the astringency (3.5 mL/kg of fruit).
  • the treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative.
  • Evaluation firmness is as follows. Day “zero” is the day the persimmons are harvested and Day “one” is the day the persimmons are removed from the cold storage.
  • the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
  • FT A Firmness Texture Analyzer
  • Persimmons are harvested in Madera - CA - USA and packed in cardboard boxes and shipped to Davis - CA. At the same day of harvest part of the persimmons are packed in MAP bags.
  • Fuyu non astringent, doesn't need ethanol application, ready to eat after harvest
  • MAP Bag Amcor bag type 30EF90.
  • the Amcor bag type 30EF90 has dimensions of 39.5" (100.3 cm) wide and 35" (88.9 cm) long.
  • the bag is not perforated and has 25 microns thickness with an oxygen (0 2 ) permeability of 6750 cc/[m 2 day].
  • the OTR of the bag is calculated to be 7560 cm 3 /day.
  • the Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 10 kg (22.5 lb) of persimmons. One such bag is packed in each RPC (Recycle Plastic Container). Total weight of persimmons in MAP bags is approximately 40 kg.
  • the MAP-packaged persimmons are packaged as follows: 80 fruits,
  • each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours.
  • SmartTabsTM tablets are placed in the chamber. The amount of SmartTabTM tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
  • the treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative. After packed in MAP bags the persimmons are randomly divided into treatment sets as follows.
  • Evaluation firmness is as follows. Day “zero” is the day the persimmons are removed from the cold storage.
  • the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
  • FT A Firmness Texture Analyzer
  • Persimmons are harvested in Valencia - Spain and in the packing house part of the fruits are packed in plastic boxes and the other part is packed in MAP bags.
  • Rojo Brillante (astringent, need C02 application, ready to eat after astringency removal process)
  • MAP Bag PE/EVA OP and Nylon bag with dimensions of 27" ( 68.6 cm) width by 28"( 71.1 cm) length made from Kenylon 6250 Polyamide Film available from FM Packaging
  • PE/EVA OP Bags 3kg (6.61b) of fruits per bag, 5 bags per box and 6 RPC boxes
  • PE/EVA 8P Bags 1kg (2.21b) of fruits per bag, 15 bags per box and 6 RPC boxes
  • Nylon 0.2 and 0.35 10kg (22.51b) of fruits per bag, 2 bag per box and 6 RPC boxes
  • the MAP-packaged persimmons are packaged as follows: fruits are carefully placed into microperf orated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
  • each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 18 hours.
  • SmartTabsTM tablets are placed in the chamber. The amount of SmartTabTM tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
  • the treatment group with MAP bags and with non-zero MCP are examples of present invention. All other treatment groups are comparative.
  • the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Manual Penetrometer with a probe of 8 mm.

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Abstract

Provided is a method of storing persimmons comprising the step of exposing persimmons to an atmosphere that contains a cyclopropene compound, wherein either (a) the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound, or (b) the persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours. In some embodiments, the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.

Description

METHODS OF HANDLING PERSIMMONS
CROSS-REFERENCE FOR RELATED APPLICATIONS This application claims benefit to U.S. Provisional Patent Application No. 61/703,286 filed September 20, 2012. The Contents of the entirety of each of the foregoing are hereby incorporated herein by this reference.
FIELD OF THE INVENTION
[0001] This invention is generally related to the field of agriculture, and more specifically the field of post-harvest handling of produce.
BACKGROUND OF THE INVENTION
[0002] A persimmon tree is a plant of Ebenaceae which grows or is cultivated in the tropic and temperate zones of the world including Japan and China. It is said that Ebenaceae plants are classified into seven genuses and 20 species and fruits of some kinds of persimmon trees contain, even after their maturity, persimmon tannine. The persimmon tannine is known to be available for some medicines, mordanting and leather- tanning agents.
[0003] Persimmon (Diasoyros kaki), which is a nutritious and alkaline fruit, contains about 11-15% of sugar such as fructose and glucose, about 20-50 mg/100 g (edible portion) of vitamin C, which is about 5-12 times as much as that of apple, and more minerals than apple. Additionally, persimmon contains a great quantity of vitamin A and tannic acid, the latter of which produces a bitter taste. Especially, tannic acid is known to remedy diarrhea or stomach disorder, as well as lower the blood pressure without affecting an electrocardigram. Many of research in persimmon, as both food and medicine, are actively on-going.
[0004] Amount of persimmon produced in domestic was about 155,111 ton in 1992, but has been increasing yearly to about 239,570 ton in 1997. In addition, cultivation area of persimmon is increasing yearly. Because persimmon has a higher profitability than other fruit, e.g., apple, significant increasing of its cultivation area is expected. Thus, there remains a need for effective and efficient method to handle and/or preserve persimmon for use as both food and medicine.
SUMMARY OF THE INVENTION
[0005] This invention is based on unexpected synergistic effect of a cyclopropene compound and a modified atmosphere package to extend shelf life and/or storage for persimmons. Provided is a method of storing persimmons comprising the step of exposing persimmons to an atmosphere that contains a cyclopropene compound, wherein either (a) the persimmons are in a modified- atmosphere package during exposure to the cyclopropene compound, or (b) the persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours. In some embodiments, the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
[0006] In one aspect, provided is a method of handling persimmons comprising exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound and the persimmons remain in the modified atmosphere package after the exposure for at least two hours.
[0007] In one embodiment, the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons. In a further embodiment, the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons. In another embodiment, the persimmons remain in the modified atmosphere package after the exposure for at least ten hours, twenty hours, forty hours, four days, seven days, or ten days. In another embodiment, the cyclopropene compound is in a formulation with a molecular encapsulating agent. In a further embodiment, the
cyclopropene compound comprises 1-methylcyclopropene (1-MCP). In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma- cyclodextrin, or combinations thereof. In a further embodiment, the encapsulated agent comprises alpha-cyclodextrin.
[0008] In one embodiment, the cyclopro is of the formula:
wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
[0009] In a further embodiment, R is C1-8 alkyl. In another embodiment, R is methyl.
[0010] In another embodiment, the cyclopropene compound is of the formula:
Figure imgf000005_0001
wherein R1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R2, R3, and R4 are hydrogen.
[0011] In another embodiment, the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm. In a further embodiment, the cyclopropene compound during the exposure is at a concentration about 1, 000 ppb. In another
embodiment, the firmness of the persimmons after the exposure is at least sixteen lbfs after day one or fourteen lbfs after day seven. In another embodiment, shelf life of the
persimmons after the exposure is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days. In another embodiment, the persimmons are placed in the modified-atmosphere package within two hours, four hours, eight hours, twelve hours, twenty-four hours, or forty-eight hours after harvest.
[0012] In another aspect, provided is a method of handling persimmons comprising exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are placed into a modified-atmosphere package within two hours after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours.
[0013] In one embodiment, the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons. In a further embodiment, the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons. In another embodiment, the persimmons are placed into a modified-atmosphere package within four hours, eight hours, twelve hours, or twenty hours after exposure to the cyclopropene compound. In another embodiment, the persimmons remain in the modified atmosphere package after the exposure for at least ten hours, twenty hours, forty hours, four days, seven days, or ten days. In another embodiment, the cyclopropene compound is in a formulation with a molecular encapsulating agent. In a further embodiment, the cyclopropene compound comprises 1-methylcyclopropene (1-MCP). In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In a further embodiment, the encapsulated agent comprises alpha-cyclodextrin.
[0014] In one embodiment, the cyclopro is of the formula:
Figure imgf000006_0001
wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
[0015] In a further embodiment, R is C1-8 alkyl. In another embodiment, R is methyl.
[0016] In another embodiment, the cyclopropene compound is of the formula:
Figure imgf000006_0002
wherein R1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R2, R3, and R4 are hydrogen.
[0017] In another embodiment, the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm. In a further embodiment, the cyclopropene compound during the exposure is at a concentration about 1, 000 ppb. In another embodiment, the firmness of the persimmons after the exposure is at least sixteen lbfs after day one or fourteen lbfs after day seven. In another embodiment, shelf life of the persimmons after the exposure is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days.
[0018] In another aspect, provided is a system for handling persimmons comprising (a) a cyclopropene compound, wherein the cyclopropene compound is applied to the persimmons at a concentration between 10 ppb and 5 ppm; and (b) a modified-atmosphere package, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
[0019] In one embodiment of the system provided, the transmission rate of carbon dioxide for the entire package is from 500 to 150,000 cubic centimeters per day per kilogram of persimmons. In another embodiment, the cyclopropene compound is in a formulation with a molecular encapsulating agent. In a further embodiment, the cyclopropene compound comprises 1-methylcyclopropene (1-MCP). In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In a further embodiment, the encapsulated agent comprises alpha- cyclodextrin.
[0020] In one embodiment, the cyclopro is of the formula:
Figure imgf000007_0001
wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
[0021] In a further embodiment, R is C1-8 alkyl. In another embodiment, R is methyl.
[0022] In another embodiment, the cyclopropene compound is of the formula:
Figure imgf000007_0002
wherein R1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R2, R3, and R4 are hydrogen.
[0023] In another embodiment, the cyclopropene compound is applied to the persimmons at a concentration about 1,000 ppb. In another embodiment, the firmness of the persimmons after treatment with the system provided is at least sixteen lbfs after day one or fourteen lbfs after day seven. In another embodiment, shelf life of the persimmons after the treatment with the system provided is at least five days, ten days, fifteen days, twenty days, thirty days, forty days, fifty days, or sixty days.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 shows representative firmness results up to ten days of the persimmons treated with the method provided (RipeLock), modified atmosphere package alone (MAP), cyclopropene compound alone (SmartFresh), or control (without neither modified atmosphere package nor cyclopropene compound).
[0025] Figure 2A shows representative firmness results of the persimmons four days after treatment according to results of Figure 1. Figure 2B shows representative firmness results of the persimmons seven days after treatment according to results of Figure 1.
[0026] Figure 3 shows other representative firmness results up to four days of the persimmons treated with the method provided (RipeLock), modified atmosphere package alone (MAP), cyclopropene compound alone (SmarFresh), or control (without neither modified atmosphere package nor cyclopropene compound).
[0027] Figure 4A shows representative firmness results of the persimmons one day after treatment according to results of Figure 3. Figure 2B shows representative firmness results of the persimmons four days after treatment according to results of Figure 3.
[0028] Figure 5 shows other representative firmness results up to six days of the persimmons treated with the method provided (Amcor Bag plus SmartFresh = SMF), modified atmosphere package alone (Amcor Bag), cyclopropene compound alone
(SmarFresh), or control (without neither modified atmosphere package nor cyclopropene compound).
[0029] Figure 6 shows representative firmness results of the persimmons six days after treatment according to results of Figure 5.
DETAILED DESCRIPTION OF THE INVENTION
[0030] When a compound is described herein as being present as a gas in an atmosphere at a certain concentration using the unit "ppm," the concentration is given as parts by volume of that compound per million parts by volume of the atmosphere. Similarly, "ppb" denotes parts by volume of that compound per billion parts by volume of the atmosphere.
[0031] As used herein "N" denotes Newtons, and "lbf ' is pounds-force.
[0032] As used herein, a "polymeric film" is an object that is made of polymer; that is much smaller in one dimension (the "thickness") than in the other two dimensions; and that has a relatively uniform thickness. Polymeric film typically has thickness of 1 mm or less.
[0033] As used herein, the "pulp firmness" of persimmons is measured using a penetrometer (for example Fruit Test™ FT40 penetrometer, from Wagner Instruments) having a plunger diameter of 8 mm. Performing the test for pulp firmness destroys the persimmon that is tested. When persimmons are said herein to be treated in a certain way (e.g., harvested, shipped, exposed to a cyclopropene compound, etc.) when they have a certain specified pulp firmness, it is meant that, out of a group of persimmons that have been harvested and treated as uniformly as reasonably possible, a sample of a relatively small number of persimmons is removed and tested for pulp firmness. The large group of persimmons is considered to have the pulp firmness that is the average value of the tests performed on the relatively small sample.
[0010] The present invention involves the use of one or more cyclopropene compound. As used herein a cyclo any compound with the formula
Figure imgf000009_0001
where each R1, R2, R3 and R4 is independently selected from the group consisting of H and a chemical group of the formula:
-(L)n-Z
where n is an integer from 0 to 12. Each L is a bivalent radical. Suitable L groups include, for example, radicals containing one or more atoms selected from H, B, C, N, O, P, S, Si, or mixtures thereof. The atoms within an L group may be connected to each other by single bonds, double bonds, triple bonds, or mixtures thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any one R group (i.e., any one of R1, R2, R3 and R4) the total number of heteroatoms (i.e., atoms that are neither H nor C) is from 0 to 6.
[0034] Independently, in any one R group the total number of non-hydrogen atoms is 50 or less.
[0035] Each Z is a monovalent radical. Each Z is independently selected from the group consisting of hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, and a chemical group G, wherein G is a 3 to 14 membered ring system.
[0036] The R1 , R2, R3 and R4 groups are independently selected from the suitable groups. The R1, R2, R3 and R4 groups may be the same as each other, or any number of them may be different from the others. Groups that are suitable for use as one or more of R1, R2, R3 and R4 may be connected directly to the cyclopropene ring or may be connected to the cyclopropene ring through an intervening group such as, for example, a heteroatom-containing group.
[0037] As used herein, a chemical group of interest is said to be "substituted" if one or more hydrogen atoms of the chemical group of interest is replaced by a substituent. Suitable substituents include, for example, alkyl, alkenyl, acetylamino, alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimino, carboxy, halo, haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl, dialkylamino, and combinations thereof.
[0038] Among the suitable R1, R2, R3 and R4 groups are, for example, substituted and unsubstituted versions of any one of the following groups: aliphatic, aliphatic-oxy, alkylcarbonyl, alkylphosphonato, alkylphosphato, alkylamino, alkylsulfonyl, alkylcarboxyl, alkylaminosulfonyl, cycloalkylsulfonyl, cycloalkylamino, heterocyclyl (i.e., aromatic or non- aromatic cyclic groups with at least one heteroatom in the ring), aryl, hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido, chlorato, bromato, iodato, isocyanato, isocyanido, isothiocyanato, pentafluorothio; acetoxy, carboethoxy, cyanato, nitrato, nitrito, perchlorato, allenyl; butylmercapto, diethylphosphonato, dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino, pyridyl, quinolyl, triethylsilyl, and trimethylsilyl.
[0039] Among the suitable R1, R2, R3 and R4 groups are those that contain one or more ionizable substituent groups. Such ionizable groups may be in non-ionized form or in salt form.
[0040] Also contemplated are embodiments in which R3 and R4 are combined into a single group, which is attached to the number 3 carbon atom of the cyclopropene ring by a double bond. Some of such compounds are described in US Patent Publication
2005/0288189.
[0041] In preferred embodiments, one or more cyclopropenes are used in which one or more of R1, R2, R3 and R4 is hydrogen. In more preferred embodiments, each of R1, R2, R3 and R4 is hydrogen or (Ci-Cs) alkyl. In more preferred embodiments, R1 is substituted or unsubstituted (Ci-Cs) alkyl, and each of R2, R3, and R4 is hydrogen. In more preferred embodiments, each of R2, R3, and R4 is hydrogen, and R1 is either unsubstituted (C1-C4) alkyl or a carboxyl-substituted (Ci-Cs) alkyl. In more preferred embodiments, each of R2, R3, and R4 is hydrogen, and R1 is unsubstituted (C1-C4) alkyl. In more preferred embodiments, R1 is methyl and each of R2, R3, and R4 is hydrogen, and the cyclopropene compound is known herein as 1-methylcycplopropene or "1-MCP."
[0042] In preferred embodiments, a cyclopropene compound is used that has boiling point at one atmosphere pressure of 50 °C or lower; or 25 °C or lower; or 15 °C or lower. Independently, in preferred embodiments, a cyclopropene compound is used that has boiling point at one atmosphere pressure of -100 °C or higher; -50 °C or higher; or 25 °C or higher; or 0 °C or higher.
[0043] As used herein, "modified-atmosphere packaging" or "MAP" refers to an enclosure that alters the gaseous atmosphere inside the enclosure from normal atmospheric composition when respiring produce is contained inside the enclosure. MAP is an enclosure in the sense that it is a package that may be lifted and transported with the produce contained within it. MAP may or may not allow exchange of gas with the ambient atmosphere outside the MAP. MAP may or may not be permeable to diffusion of any particular gas, independent of its permeability or non-permeability to any other gas.
[0044] As used herein, a "monomer" is a compound that has one or more carbon-carbon double bond that is capable of participating in a polymerization reaction. As used herein, an "olefin monomer" is a monomer, the molecules of which contain only atoms of carbon and hydrogen. As used herein, "polar monomer" is a monomer, the molecules of which contain one or more polar group. Polar groups include, for example, hydroxyl, thiol, carbonyl, carbon-sulfur double bond, carboxyl, sulfonic acid, ester linkages, other polar groups, and combinations thereof.
[0045] In the methods provided herein, persimmons are exposed to an atmosphere that contains one or more cyclopropene compound. Cyclopropene compound may be introduced into the atmosphere surrounding the persimmons by known methods in the art. For example, gaseous cyclopropene compound may be released into the atmosphere in such close proximity to persimmons that the cyclopropene compound contacts the persimmons before the cyclopropene diffuses far away from the persimmons. For another example, the persimmons may be in an enclosure (i.e., and airtight container enclosing a volume of atmosphere), and gaseous cyclopropene compound may be introduced into the enclosure.
[0046] In some embodiments, the persimmons are inside a permeable surrounding device, and cyclopropene compound is introduced into the atmosphere outside the permeable surrounding device. In such embodiments, the permeable surrounding device encloses one or more persimmons and allows some contact between the cyclopropene compound and the persimmons, for example by allowing some cyclopropene compound to diffuse through the permeable surrounding device or through holes in the permeable surrounding device or a combination thereof. Such a permeable surrounding device may or may not also qualify as an MAP as defined herein.
[0047] Among embodiments in which gaseous cyclopropene compound is introduced into an enclosure, the introduction may be performed by known methods in the art. For example, the cyclopropene compound may be created in a chemical reaction and vented to the enclosure. For another example, cyclopropene compound may be kept in a container such as a compressed-gas tank and released from that container into the enclosure. For another example, cyclopropene compound may be contained in a powder or pellets or other solid form that contains encapsulated complex of cyclopropene compound in a molecular encapsulating agent. A complex that includes a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in a molecule of a molecular encapsulating agent is known herein as a "cyclopropene compound complex" or
"cyclopropene molecular complex."
[0048] In embodiments in which a molecular encapsulating agent is used, suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents. Organic molecular encapsulating agents are provided include, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating agents include, for example, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable. In one embodiment, the encapsulation agent is selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, substituted versions thereof, and combinations thereof. In a further embodiment, the cyclopropene compound is 1-methylcyclopropene, and the encapsulation agent is alpha cyclodextrin. The choice of encapsulation agent will vary depending upon the structure of the cyclodextrin compound or compounds being used. Any cyclodextrin or mixture of cyclodextrins, cyclodextrin polymers, modified cyclodextrins, or mixtures thereof can also be utilized pursuant to the present invention.
[0049] In some embodiments, a cyclopropene compound is introduced into an enclosure that contains persimmons by placing cyclopropene molecular complex into the enclosure and then contacting the cyclopropene molecular complex with a release agent. A release agent is a compound that, when it contacts cyclopropene encapsulation complex, promotes the release of the cyclopropene compound into the atmosphere. Among embodiments in which alpha- cyclodextrin is used, water (or a liquid that contains 50% or more water by weight, based on the weight of the liquid) is the exemplary release agent.
[0050] In some embodiments, a solid material containing cyclopropene molecular complex is placed into an enclosure that contains persimmons, and water is brought into contact with that solid material. Contact with the water causes release of cyclopropene compound into the atmosphere of the enclosure. For example, the solid material may be in the form of tablets that contain, optionally among other ingredients, encapsulation complex that contains a cyclopropene compound and one or more ingredients that causes
effervescence.
[0051] For another example, in some embodiments the solid material may be placed into an enclosure that contains persimmons and water vapor in the atmosphere may be effective as a release agent. In some of such embodiments, the solid material that contains cyclopropene encapsulated complex may be in a form that also contains, optionally among other ingredients, a water-absorbing compound such as, for example, a water- absorbing polymer or a deliquescent salt.
[0052] In some embodiments, atmosphere containing one or more cyclopropene compound in gaseous form is in contact with persimmons or is in contact with a permeable surrounding device that surrounds one or more persimmons. In such embodiments, all concentrations above zero of cyclopropene compound are contemplated. For example, the concentration of cyclopropene compound is 10 ppb or higher; more preferably is 30 ppb or higher; more preferably is 100 ppb or higher. For additional examples, the concentration of cyclopropene compound is 50 ppm or lower, more preferably 10 ppm or lower, more preferably 5 ppm or lower.
[0053] MAP may be active or passive. Active MAP is packaging that is attached to some material or apparatus that adds certain gas or gases to the atmosphere inside the MAP and/or removes certain gas or gases from the atmosphere inside the MAP.
[0054] Passive MAP (also called commodity generated modified atmosphere packaging) takes advantage of the fact that persimmons respire after harvest. Thus persimmons placed in an enclosure, among other processes, consume oxygen and produce carbon dioxide. The MAP can be designed so that diffusion through the solid exterior surfaces of the MAP and passage of gas through any perforations that may be present in the exterior surface of the MAP maintain optimum levels of oxygen, carbon dioxide, and optionally other gases (such as, for example, water vapor or ethylene or both). In one embodiment, passive MAP is used. In another embodiment, active MAP is used. In another embodiment, both active and passive MPAs are used. For example, if it is stated herein that an MAP has a certain gas transmission characteristic, both of the following embodiments are contemplated: a passive MAP that has that gas transmission characteristic; and an active MAP that, when it contains persimmons, maintains the same atmosphere within itself that would occur in a passive MAP that had that gas transmission characteristic.
[0055] A useful way to characterize the MAP is the gas transmission rate of the MAP itself in relation to the amount of persimmons held in the MAP. Preferably, the rate of transmission of carbon dioxide is, in units of cubic centimeters per day per kilogram of persimmons, 5,000 or higher; more preferably 7,000 or higher; more preferablyl0,000 or higher. Preferably, the rate of transmission of carbon dioxide is, in units of cubic centimeters per day per kilogram of persimmons, 150,000 or lower; more preferably 100,000 or lower. Preferably, the rate of transmission of oxygen is, in units of cubic centimeters per day per kilogram of persimmons, 3,800 or higher; more preferably 7,000 or higher; more preferably 15,000 or higher. Preferably, the rate of transmission of oxygen is, in units of cubic centimeters per day per kilogram of persimmons, 100,000 or lower; or 75,000 or lower.
[0056] It is useful to characterize the inherent gas transmission characteristics of a polymeric film. By "inherent" it is meant the properties of the film itself, in the absence of any perforations or other alterations. It is useful to characterize the composition of a film by characterizing the gas transmission characteristics of a film that has that composition and that is 30 micrometers thick. It is contemplated that, if a film of interest were made and tested at a thickness that was different from 30 micrometers (e.g., from 20 to 40 micrometers), it would be easy for a person of ordinary skill to accurately calculate the gas transmission characteristics of a film having the same composition and having thickness of 30
micrometers. The gas transmission rate of a film having thickness 30 micrometers is labeled "GT-30" herein.
[0057] One useful inherent characteristic of a polymeric film composition is herein called "film beta ratio," which is the quotient that is calculated by dividing the GT-30 for carbon dioxide gas transmission rate by the GT-30 for oxygen gas.
[0058] In one embodiment, some or all of the exterior surfaces of the MAP are polymeric. In another embodiment, the polymer is in the form of a polymeric film. Some suitable polymeric films have thickness of 5 micrometer or more; or 10 micrometer or more; or 20 micrometer or more. Independently, some suitable polymeric films have thickness of 200 micrometer or less; or 100 micrometer or less; or 50 micrometer or less.
[0059] Some suitable polymer compositions include, for example, polyolefins, polyvinyls, polystyrenes, polydienes, polysiloxanes, polyamides, vinylidene chloride polymers, vinyl chloride polymers, copolymers thereof, blends thereof, and laminations thereof. Suitable polyolefins include, for example, poly ethylenes, polypropylenes, copolymers thereof, blends thereof, and laminations thereof. Suitable polyethylenes include, for example, low density polyethylene, ultralow density polyethylene, linear low density polyethylene, metallocene-catalyzed polyethylene, copolymers of ethylene with polar monomers, medium density polyethylene, high density polyethylene, copolymers thereof and blends thereof. Suitable polypropylenes include, for example, polypropylene and oriented polypropylene. In some embodiments, low density polyethylene is used. In one
embodiment, copolymer of styrene and butadiene is used. In another embodiment, polyamides, polyolefins, and blends thereof are used.
[0060] Among polyolefins, one example is polyethylene; and another example is metallocene-catalyzed polyethylene. Other examples include polymer compositions comprising one or more polyolefin and/or one or more copolymer of an olefin monomer with a polar monomer. The phrase "copolymer" refers to a product of copolymerizing two or more different monomers. Suitable copolymers of an olefin monomer with a polar monomer include, for example, such polymers available from DuPont called Elvax™ resins. One embodiment includes copolymers of ethylene with one or more polar monomer. Suitable polar monomers include, for example, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, and mixtures thereof. For one example polar monomers contain one or more ester linkage; for another example is vinyl acetate. Among copolymers of ethylene with one or more polar monomer, the amount of polar monomer may be, by weight based on the weight of the copolymer, 0.5% or more; for example 1% or more; or 1.5% or more. Among copolymers of ethylene with one or more polar monomer, the amount of polar monomer may be, by weight based on the weight of the copolymer, 25% or less; for example 20% or less; or 15% or less.
[0061] Suitable polyolefins include blends of a polyolefin homopolymer with a copolymer of an olefin monomer with a polar monomer. Among such blends, the weight ratio of homopolymer to copolymer may be 0.5: 1 or higher; for example 0.8: 1 or higher; or 1 : 1 or higher. Among such blends, the weight ratio of homopolymer to copolymer may be 3: 1 or lower; for example 2: 1 or lower; or 1.25: 1 or lower.
[0062] Suitable polyamides include nylon 6, nylon 6,6, and copolymers thereof; for example copolymers of nylon 6 with nylon 6,6. Among copolymers of nylon 6 with nylon 6,6 (often called nylon 666), examples include copolymers in which the weight ratio of polymerized units of nylon 6 to polymerized units of nylon 6,6 may be 0.05: 1 or higher; 0.11 : 1 or higher; or 0.25 : 1 or higher. Among copolymers of nylon 6 with nylon 6,6, examples include copolymers in which the weight ratio of polymerized units of nylon 6 to polymerized units of nylon 6,6 may be 9: 1 or lower; 3: 1 or lower; or 1.5: 1 or lower.
[0063] Suitable blends of polyamide with polyolefin include blends in which the weight ratio of polyamide to polyolefin may be 0.05: 1 or higher; 0.11 : 1 or higher; 0.25: 1 or higher; or 0.5: 1 or higher. Suitable blends of polyamide with polyolefin include blends in which the weight ratio of polyamide to poly olefin may be 9:1 or lower; 5: 1 or lower; or 3: 1 or lower.
[0064] When it is stated herein that a container comprises polymeric film, it is meant that some or all of the surface area of the container consists of polymeric film, and the film is arranged so that molecules that are capable of diffusing through the polymeric film will diffuse between the inside of the container and the outside of the container in both directions. Such a container may be constructed so that one, two, or more separate portions of the surface area of the container consist of polymeric film, and the polymeric film portions may be the same composition as each other or may be different from each other. It is
contemplated that such containers will be constructed so that the portion of the container surface that is not polymeric film will effectively block diffusion of gas molecules (i.e., the amount of gas molecules that diffuse through will be of negligible importance).
[0065] Suitable polyolefin films include film compositions for which the GT-30 for carbon dioxide at 23 °C, in units of cm3/(m2-day), may be 800 or higher; 4,000 or higher; 5,000 or higher; 10,000 or higher; or 20,000 or higher. Example include films with GT-30 for carbon dioxide at 23 °C, in units of cm 3/(m2-day), of 150,000 or lower; 80,000 or lower; or 60,000 or lower. Other examples include films with GT-30 for oxygen at 23 °C, in units of cm3/(m2-day), of 200 or higher; 1,000 or higher; 3,000 or higher; or 6,000 or higher. Other examples include films with GT-30 for oxygen at 23 °C, in units of cm3/(m2-day), of 150,000 or lower; 80,000 or lower; 40,000 or lower; 20,000 or lower; or 15,000 or lower. Other examples include films with GT-30 for water vapor at 37.8 °C, in units of g/(m2-day), of 5 or higher; or 10 or higher. Other examples include films with GT-30 for water vapor at 37.8 °C, in units of g/(m2-day), of 330 or lower; 150 or lower; 100 or lower; 55 or lower; 45 or lower; or 35 or lower. In one embodiment, film has film beta ratio of 1 or higher; or 2 or higher. In another embodiment, film has beta ratio of 15 or lower; or 10 or lower.
[0066] Polyamide films, as used herein, includes films containing polyamide and films containing a blend of polyamide with one or more other polymer. Suitable polyamide films include films with GT-30 for water vapor at 37.8 °C, in units of g/(m2-day), of 10 or higher; or 20 or higher. Examples include films with GT-30 for water vapor at 37.8 °C, in units of g/(m2-day), of 1,000 or lower; 800 or lower; 500 or lower; 350 or lower; or 200 or lower.
[0067] It is contemplated that the GT-30 for oxygen and the GT-30 for carbon dioxide are both very low for polyamide films. It is contemplated that when MAP is used that is made of a film that is made of polyamide or a blend of polyamide with other polymer(s), the film will be perforated in a way that is chosen to provide the desired gas transmission characteristics of the MAP itself.
[0068] In one embodiment, polymeric film is used that has perforations. In a further embodiment, the holes have mean diameter of 5 micrometers to 500 micrometers. In another embodiment involving perforations, the holes may have mean diameter of 10 micrometers or more; 20 micrometers or more; 50 micrometers or more; or 100 micrometers or more.
Independently, in another embodiment involving perforations, the holes may have mean diameter 300 micrometers or less; or 200 micrometers or less. If a hole is not circular, the diameter of the hole is considered herein to be 2 times the square root of the quotient of the area of the hole divided by pi.
[0069] In one embodiment, the MAP comprises polymeric film, and the percent of the surface area of the MAP that consists of the polymeric film may be 10% to 100%; 50% to 100%; 75% to 100%; or 90% to 100%. An MAP in which 90% to 100% of the surface area consists of polymeric film is known herein as a "bag." Example include MAP that comprise polymeric film and in which all portions of the surface of the MAP that are not polymeric film effectively block diffusion of gas molecules. In embodiments in which the MAP comprises polymeric film and the remainder (if any) of the surface of the MAP effectively blocks diffusion of gas molecules, the MAP is considered to be passive MAP.
[0070] Holes in polymeric film may be made by methods known in the art. Suitable methods include, for example, laser perforation, hot needles, flame, low-energy electrical discharge, and high-energy electrical discharge. In one embodiment, such method is laser perforation.
[0071] Another useful way to characterize an MAP is the "MAP beta ratio," which is defined herein as the quotient that results from dividing the rate of transmission of carbon dioxide of the MAP by the rate of transmission of oxygen of the MAP itself. In one embodiment, the MAP beta ratio may be 0.3 or higher; or 0.5 or higher. In another embodiment, the MAP beta ratio may be 5 or lower; 3 or lower; or 2 or lower. In another embodiment, when the MAP is made entirely of poly olefin film, the MAP beta ratio is 1.0 to 1.6. In another embodiment, when the MAP is made entirely of poly amide film, the MAP beta ratio is 0.5 to 0.999. In another embodiment, when the MAP is made of a film that contains a blend of polyamide and polyolefin, the MAP beta ratio is 0.6 to 1.2.
[0072] In one embodiment, persimmons are harvested when they are mature but not yet ripe. In another embodiment, the persimmons are harvested when the dry matter content, by weight based on the weight of the persimmon, is 17% or higher. [0073] In one embodiment, persimmons are harvested and immediately (for example within two hours) placed into MAP before exposure to the cyclopropene compound. In another embodiment, the time from harvest to placement into MAP may be 30 days or less; 14 days or less; 7 days or less; or 2 days or less. In another embodiment, harvested persimmons are placed into MAP after exposure to the cyclopropene compound and prior to shipment, and the harvested persimmons remain in the MAP during shipment.
[0074] In one embodiment, persimmons are harvested and, prior to being placed into MAP, the persimmons are placed in pre-shipment storage. Such pre-shipment storage may be below room temperature, for example 7 °C or lower. After such storage, the persimmons may be placed in to MAP and then shipped to their destination.
[0075] In another embodiment, persimmons are shipped to a destination that is near the intended point of consumption or else are harvested near the intended point of consumption and/or sale. As used herein, "near the intended point of consumption and/or sale" means a location from which it is capable to transport the persimmons to the point of consumption in 3 days or fewer by truck or other surface transportation.
[0076] In one embodiment where persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound (for example, persimmons are exposed to an atmosphere that contains a cyclopropene compound while the persimmons are not in an MAP), persimmons are placed into an MAP after the conclusion of the exposure to the atmosphere that contains a cyclopropene compound, and the persimmons then remain in the MAP for at least two hours.
[0077] In another embodiment where persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, the persimmons are kept at temperature of 10 °C or above from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP. In a further embodiment, the time period from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be eight hours or less; four hours or less; two hours or less; or 1 hour or less.
[0078] In another embodiment where persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, the persimmons are kept at temperature below 10 °C from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP. In a further embodiment, the temperature at which persimmons are kept from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be 7 °C or lower. In another further embodiment, the time period from the conclusion of the exposure to the atmosphere that contains a cyclopropene compound until the persimmons are placed into the MAP may be between ten minutes to two months.
[0079] In one embodiment where the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound (for example, persimmons are exposed to an atmosphere that contains a cyclopropene compound while the persimmons are in a MAP), there is an improvement in the pulp firmness of the persimmons that can be seen even immediately after the conclusion of the exposure of the persimmons to the cyclopropene compound.
[0080] In another embodiment where the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound, persimmons are in an MAP for a time period of duration of 1 day or more, where that time period is after harvest and before exposure to atmosphere containing a cyclopropene compound (herein called a "pre-X" time period). In a further embodiment, composition of the MAP comprises polyamide.
[0081] In some embodiments, the persimmons reside in an MAP for a storage time period that begins within 1 hour of the conclusion of the exposure to atmosphere containing cyclopropene compound (herein called a "post-X" time period). For example, post-X storage time period may begin within thirty minutes of the conclusion of the exposure to
cyclopropene compound; within fifteen minutes; within eight minutes; or within one minute.
[0082] In another embodiment where the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound, the persimmons are in an MAP during exposure to atmosphere containing cyclopropene compound; if the persimmons remain in the MAP thereafter without being removed from the MAP, the post-X storage time period is considered to begin immediately upon the conclusion of the exposure to atmosphere containing cyclopropene compound. For example, the post-X storage time period may last for one day or longer; or 2 days or longer.
[0083] By "conclusion of exposing the persimmons to a cyclopropene compound," it is meant herein a time after which persimmons have been exposed to a cyclopropene compound as described herein and at which the concentration of cyclopropene compound in the atmosphere around the persimmons (or the atmosphere around the permeable surrounding device, if the persimmons were in a permeable surrounding device during exposure to cyclopropene compound) falls below 0.5 ppb.
[0084] In some embodiments, suitable MAP is chosen or designed so that, when persimmons are placed into the MAP and the MAP, with the persimmons inside, is then exposed to atmosphere containing cyclopropene compound, and then stored for 10 days at 16.7 °C, a certain pre-determined atmosphere will be present in the MAP. In one embodiment with the pre-determined atmosphere, the amount of carbon dioxide, by volume based on the volume of the atmosphere inside the MAP, may be 1% or more; or 5% or more. In another embodiment with the pre-determined atmosphere, the amount of carbon dioxide, by volume based on the volume of the atmosphere inside the MAP, may be 20% or less; or 15% or less. In another embodiment with the pre-determined atmosphere, the amount of oxygen, by volume based on the volume of the atmosphere inside the MAP, may be 3% or more; or 5% or more. In another embodiment with the pre-determined atmosphere, the amount of oxygen, by volume based on the volume of the atmosphere inside the MAP, may be 20% or less; or 15% or less.
[0085] The Oxygen Transmission Rate or OTR for a modified atmosphere package can be calculated from the work presented in literature or measured directly. For a
microperforated polymer bag the OTR due to the permeability of the film at any given time can be theoretically calculated using Fick' s law of diffusion where the permeability coefficient for the polymer film can be measured using a procedure as called out in ASTM method D3985 for 02. For this same microperforated bag the OTR due to the
microperforations can be calculated using a modified Fick' s law of diffusion. The OTR at any given time is dependent on the 02 concentration driving force at that point of time. The OTR of the system can be measured by measuring the 02 partial pressure versus time and then plotting the natural log of the concentration gradient versus time. This is a convenient method in cases where there are not well validated models for the OTR such as microporous systems or unique combinations of approaches such as microporous patches combined with films or microperforated films.
EXAMPLES
Example 1
Persimmons Placed in MAP Bags and Treated with MCP Before Storage and Ethanol
After Storage
[0086] Persimmons are harvested in Mogi das Cruzes - SP - Brazil and packed in RPC (Recycle Plastic Container) and shipped to Piracicaba - SP. At the same day of harvest part of the persimmons are packed in MAP bags.
Location: Brazil
Variety: Giombo (astringent and need to be treated with ethanol to be ready to eat) Storage at 12°C for 15 days
MAP Bag: a Nylon bag with dimensions of 27" ( 68.6 cm) width by 28"( 71.1 cm) length made from Kenylon 6250 Polyamide Film available from FM Packaging.
MCP application before the storage
Ethanol Application after the storage
[0087] For the MAP bag used, the base film has 25 microns thickness without laser holes. The oxygen (02) permeation of the MAP bag used is about 28 cc/ m2-day and the C02 permeation is about 227 cc /m2-day. The bags are laser drilled in the length direction with 105 micron holes at two locations 9" (22.9 cm) from each side of the bag. The hole spacing is 9.06 mm. The total number of laser holes in the 20" ( 8" for tie off) length direction of the bag are about 228 holes. At an average hole diameter of 105 micron ( pi x r2 = 8630 micron2), the 228 holes can provide an open area of ~ 2.0 mm2. The OTR of the bag is calculated to be 32,250 cm3/day.
[0088] The Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 16 kg (36 lb) of persimmons. One such bag is packed in each RPC. Total weight of persimmons in MAP bags is approximately 64 kg. Approximately 64 kg of persimmons are placed into RPC identical to those used for the MAP bags.
[0089] The MAP-packaged persimmons are packaged as follows: 80 fruits,
approximately 16 kg are carefully placed into microperforated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
[0090] The appropriate weight of persimmons is placed in each bag after harvest and shipment. Bags are placed in RPC carrying devices. Persimmons are moved to a Cold Room at 12 °C next.
[0091] On the same day the persimmons are bagged, each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours. In the chambers for the "MCP" treatment groups, at the beginning of the treatment period, SmartTabs™ tablets are placed in the chamber. The amount of SmartTab™ tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber. [0092] After packed in MAP bags the persimmons are randomly divided into treatment sets as follows:
Figure imgf000022_0001
[0093] The treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative.
[0094] Persimmons used in this trial are an astringent variety. To remove the astringency the fruits were treated with ethanol after the 15 days at cold storage.
[0095] After removed the bags for the MAP bag groups, all the fruits are placed in a hermetical chamber and treated with ethanol (3.5mL/kg of fruit) for 12 hours.
[0096] After the treatment in the chambers, the RPCs are moved into racks at room temperature for storage and observation.
[0097] Firmness evaluation is as follows. Day "zero" was the day the persimmons are harvested and Day "one" is the day the persimmons are removed from the ethanol treatment.
Figure imgf000022_0002
[0098] For the Pulp Firmness evaluation, the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
Figure imgf000022_0003
MAP 0 20.99 15.72 14.26
MAP 1000 20.99 18.62 18.18
[0099] As shown in Figure 1, firmness results of the treatment group with MAP bags in combination of 1-MCP treatment are labeled as "RipeLock." Persimmons treated with the MAP bags alone (MAP), 1-MCP alone with opened MAP bags (SmarFresh), and control (without neither modified atmosphere package nor cyclopropene compound) are also shown for comparison.
[00100] The results above show that the persimmons treated by the method of the present invention have pulp firmness retention for a longer period of time than any other treatment.
[00101] Overall, our observations suggest that 1-MCP alone provides 0.15 lbf of firmness to the persimmons after 1 day at room temperature. MAP alone does not provide additional firmness to the persimmons after 4 days at room temperature. However, the combined treatment is synergistic in that the firmness of the persimmons is maintained 3.05 lbf higher than the untreated fruits.
Figure imgf000023_0001
Example 2
Persimmons Placed in MAP Bags and Treated with 1-MCP and Ethanol Before Storage
[00102] This Example uses a similar test to Example 1 but with the ethanol application before the storage, at the same time as 1-MCP application.
[00103] Persimmons are harvested in Mogi das Cruzes - SP - Brazil and packed in RPC (Recycle Plastic Container) and shipped to Piracicaba - SP. At the same day of harvest part of the persimmons are packed in MAP bags.
[00104] The Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 16 kg (36 lb) of persimmons. One such bag is packed in each RPC. Total weight of persimmons in MAP bags is approximately 64 kg. Approximately 64 kg of persimmons are placed into RPC identical to those used for the MAP bags.
[00105] The MAP-packaged persimmons are packaged as follows: 80 fruits, approximately 16 kg are carefully placed into microperforated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
[00106] The appropriate weight of persimmons is placed in each bag after harvest and shipment. Bags are placed in RPC carrying devices. Persimmons are moved to a Cold Room at 12 °C next.
[00107] On the same day the persimmons are bagged, each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours. In the chambers for the "MCP" treatment groups, at the beginning of the treatment period, SmartTabs™ tablets are placed in the chamber. The amount of SmartTab™ tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber. At the same time the persimmons are exposed to ethanol with the purpose of removing the astringency (3.5 mL/kg of fruit).
[00108] After packed in MAP bags the persimmons are randomly divided into treatment sets as follows:
Figure imgf000024_0001
[00109] The treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative.
[00110] After the storage at Cold Room, the bags are removed and the RPCs are moved into racks at room temperature for storage and observation.
[00111] Evaluation firmness is as follows. Day "zero" is the day the persimmons are harvested and Day "one" is the day the persimmons are removed from the cold storage.
Figure imgf000024_0002
RipeLock 20.34 18.62 18.18
[00112] As shown in Figure 3, firmness results of the treatment group with MAP bags in combination of 1-MCP treatment are labeled as "RipeLock." Persimmons treated with the MAP bags alone (MAP), 1-MCP alone with opened MAP bags (SmarFresh), and control (without neither modified atmosphere package nor cyclopropene compound) are also shown for comparison. The detailed data are also shown in Figures 4A and 4B as well as set forth in Table 3. Table 4 shows firmness difference (Δ) compared to the control. The effect of the combination of 1-MCP (SmartFresh) and MAP appears to be synergistic to extend firmness/shelf life of persimmons.
[00113] For the Pulp Firmness evaluation, the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
Figure imgf000025_0001
[00114] The results above show that the persimmons treated by the method of the present invention have pulp firmness retention for a longer period of time than any other treatment.
[00115] Overall, our observations suggest that 1-MCP alone provides 1.551bf of firmness to the persimmons after 7 day at room temperature. MAP alone does not provide additional firmness to the persimmons after 7 days at room temperature. However, the combined treatment is synergistic in that the firmness of the persimmons is maintained 3.69 lbf higher than the untreated fruits.
Figure imgf000025_0002
Example 3
Persimmons Placed in MAP Bags and Treated with MCP Before Storage
[00116] Persimmons are harvested in Madera - CA - USA and packed in cardboard boxes and shipped to Davis - CA. At the same day of harvest part of the persimmons are packed in MAP bags.
Location: USA
Variety: Fuyu (non astringent, doesn't need ethanol application, ready to eat after harvest)
Storage at 0 °C for 60 days
MCP application before the storage
MAP Bag: Amcor bag type 30EF90.
[00117] The Amcor bag type 30EF90 has dimensions of 39.5" (100.3 cm) wide and 35" (88.9 cm) long. The bag is not perforated and has 25 microns thickness with an oxygen (02) permeability of 6750 cc/[m2 day]. The OTR of the bag is calculated to be 7560 cm3/day.
[00118] The Test Protocol is as follows. 4 MAP bags are packed. Each bag holds approximately 10 kg (22.5 lb) of persimmons. One such bag is packed in each RPC (Recycle Plastic Container). Total weight of persimmons in MAP bags is approximately 40 kg.
Approximately 40 kg of persimmons are placed into RPC identical to those used for the MAP bags.
[00119] The MAP-packaged persimmons are packaged as follows: 80 fruits,
approximately 10 kg were carefully placed into microperforated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
[00120] The appropriate weight of persimmons is placed in each bag after harvest and shipment. Bags are placed in RPC carrying devices. Persimmons then are moved to a Cold Room at 0 °C.
[00121] On the same day the persimmons are bagged, each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 12 hours. In the chambers for the "MCP" treatment groups, at the beginning of the treatment period, SmartTabs™ tablets are placed in the chamber. The amount of SmartTab™ tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
[00122] The treatment group with MAP bags and with non-zero MCP are examples of the present invention. All other treatment groups are comparative. After packed in MAP bags the persimmons are randomly divided into treatment sets as follows.
Figure imgf000027_0001
[00123] After 60 days of storage at Cold Room, the bags are removed and the RPCs are moved into racks at room temperature for storage and observation.
[00124] Evaluation firmness is as follows. Day "zero" is the day the persimmons are removed from the cold storage.
Figure imgf000027_0002
[00125] As shown in Figure 5, firmness results of the treatment group with MAP bags in combination of 1-MCP treatment are labeled as "Amcor Bag + SMF." Persimmons treated with the MAP bags alone (Amcor), 1-MCP alone with opened MAP bags (SmarFresh), and control (without neither modified atmosphere package nor cyclopropene compound) are also shown for comparison.
Figure imgf000027_0003
[00126] For the Pulp Firmness evaluation, the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Firmness Texture Analyzer (FT A) with a probe of 8 mm.
[00127] The results above show that the persimmons treated by the method of the present invention have pulp firmness retention for a longer period of time than any other treatment.
[00128] Overall, our observations suggest that 1-MCP alone provides 6.2 Ibf of firmness to the persimmons. MAP alone provides 2.6 Ibf of firmness to the persimmons. However, the combined treatment is synergistic in that the firmness of the persimmons is maintained 9.4 Ibf higher than the untreated fruits.
Figure imgf000028_0001
Example 4
Persimmons Placed in MAP Bags and Treated with MCP Before Storage and C02
Astringency Removal After Storage
[00129] Persimmons are harvested in Valencia - Spain and in the packing house part of the fruits are packed in plastic boxes and the other part is packed in MAP bags.
Location: Spain
Variety: Rojo Brillante (astringent, need C02 application, ready to eat after astringency removal process)
Storage at 0 °C for 72 days
MCP application before the storage
MAP Bag: PE/EVA OP and Nylon bag with dimensions of 27" ( 68.6 cm) width by 28"( 71.1 cm) length made from Kenylon 6250 Polyamide Film available from FM Packaging
[00130] The Test Protocol is as follows.
a. PE/EVA OP Bags: 3kg (6.61b) of fruits per bag, 5 bags per box and 6 RPC boxes b. PE/EVA 8P Bags: 1kg (2.21b) of fruits per bag, 15 bags per box and 6 RPC boxes c. Nylon 0.2 and 0.35: 10kg (22.51b) of fruits per bag, 2 bag per box and 6 RPC boxes
d. No Bag: 20 kg of fruits per box and 6 RPC boxes
[00131] The MAP-packaged persimmons are packaged as follows: fruits are carefully placed into microperf orated bags, and the bags are sealed by twisting the open side of the bag, folding down the twisted end, and placing a rubber band around the twisted and folded end of the bag.
[00132] The appropriate weight of persimmons is placed in each bag after harvest and shipment. Bags are placed in RPC carrying devices. Persimmons then are moved to a Cold Room at 1 °C.
[00133] On the same day the persimmons are bagged, each treatment set is marked, placed in a hermetical chamber at the Cold Room. All chambers are of equal size and packed the same way. Treatment lasts for 18 hours. In the chambers for the "MCP" treatment groups, at the beginning of the treatment period, SmartTabs™ tablets are placed in the chamber. The amount of SmartTab™ tablets is chosen to achieve the indicated concentration of 1- methylcyclopropene in the atmosphere of the chamber.
[00134] After packed in MAP bags the persimmons are randomly divided into treatment sets as follows:
Figure imgf000029_0001
[00135] The treatment group with MAP bags and with non-zero MCP are examples of present invention. All other treatment groups are comparative.
[00136] After 59 days of storage at Cold Room, the fruits are exposed to C02 for the astringency removal process.
[00137] After the carbon dioxide treatment, the bags are removed and the RPCs are moved into racks at room temperature for storage and observation for 7 days. [00138] Firmness evaluation is performed as follows. Δ is the difference between the firmness for the treatment and the firmness for the No Bag treatment.
Figure imgf000030_0001
[00139] For the Pulp Firmness evaluation, the persimmons have the skin removed with a peeler and the pulp firmness is measured with a Manual Penetrometer with a probe of 8 mm.
[00140] The results above show that the persimmons treated by the method of the present invention have pulp firmness retention for a longer period of time than any previously known treatments.

Claims

A method of storing persimmons, comprising exposing persimmons to an atmosphere that contains a cyclopropene compound, wherein either
(a) the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound, or;
(b) the persimmons are placed into a modified-atmosphere package after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours.
The method of claim 1, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
A method of handling persimmons comprising,
exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are in a modified-atmosphere package during exposure to the cyclopropene compound and the persimmons remain in the modified atmosphere package after the exposure for at least two hours.
The method of claim 3, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
The method of claim 3, wherein the persimmons remain in the modified atmosphere package after the exposure for at least ten hours.
The method of claim 3, wherein the cyclopropene compound is in a formulation with a molecular encapsulating agent.
The method of claim 6, wherein the cyclopropene compound comprises 1- methylcyclopropene (1-MCP) and the molecular encapsulating agent comprises alpha-cyclodextrin. 8 The method of claim 3, wherein the cyclopropene compound is of the formula:
Figure imgf000032_0001
wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are
independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
9. The method of claim 8, wherein R is C1-8 alkyl.
The method of claim 8, wherein R is methyl.
The method of claim 3, wherein is of the formula:
R
Figure imgf000032_0002
wherein R1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R2, R3, and R4 are hydrogen.
The method of claim 3, wherein the cyclopropene comprises 1-methylcyclopropene
(1-MCP).
13. The method of claim 6, wherein the molecular encapsulating agent comprises alpha- cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof.
14. The method of claim 6, wherein the molecular encapsulating agent comprises alpha- cyclodextrin.
15. The method of claim 3, wherein the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm.
16. The method of claim 3, wherein the firmness of the persimmons after the exposure is at least sixteen lbfs after day one or fourteen lbfs after day seven.
17. The method of claim 3, wherein shelf life of the persimmons after the exposure is at least thirty days.
18. The method of claim 3, wherein the persimmons are placed in the modified- atmosphere package within two hours after harvest.
19. A method of handling persimmons comprising,
exposing the persimmons to an atmosphere that contains a cyclopropene compound, wherein the persimmons are placed into a modified-atmosphere package within two hours after exposure to the cyclopropene compound, and the persimmons remain in the modified atmosphere package for at least two hours.
20. The method of claim 19, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
21. The method of claim 19, wherein the persimmons are placed into a modified- atmosphere package within four hours after exposure to the cyclopropene compound
22. The method of claim 19, wherein the persimmons remain in the modified atmosphere package after the exposure for at least ten hours.
23. The method of claim 19, wherein the cyclopropene compound is in a formulation with a molecular encapsulating agent.
24. The method of claim 23, wherein the cyclopropene compound comprises 1- methylcyclopropene (1-MCP) and the molecular encapsulating agent comprises alpha-cyclodextrin.
25. The method of claim 19, wherein the cyclopropene compound is of the formula:
Figure imgf000034_0001
wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are
independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
26. The method of claim 25, wherein R is C1-8 alkyl.
27. The method of claim 25, wherein R is methyl.
28. The method of claim 19, wherei und is of the formula:
R
Figure imgf000034_0002
wherein R1 is a substituted or unsubstituted C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R2, R3, and R4 are hydrogen.
The method of claim 19, wherein the cyclopropene comprises 1-methylcyclopropene
(1-MCP).
30. The method of claim 23, wherein the molecular encapsulating agent comprises alpha- cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof.
31. The method of claim 23, wherein the molecular encapsulating agent comprises alpha- cyclodextrin.
32. The method of claim 19, wherein the cyclopropene compound during the exposure is at a concentration between 10 ppb and 5 ppm.
33. A system for handling persimmons comprising, (a) a cyclopropene compound, wherein the cyclopropene compound is applied to the persimmons at a concentration between 10 ppb and 5 ppm; and
(b) a modified-atmosphere package, wherein the modified-atmosphere package is constructed so that the transmission rate of oxygen for the entire package is from 200 to 40,000 cubic centimeters per day per kilogram of persimmons.
The system of claim 33, wherein the cyclopropene compound is in a formulation with a molecular encapsulating agent.
The system of claim 34, wherein the cyclopropene compound comprises 1- methylcyclopropene (1-MCP) and the molecular encapsulating agent comprises alpha-cyclodextrin.
PCT/US2013/059658 2012-09-20 2013-09-13 Methods of handling persimmons WO2014046976A1 (en)

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