CN112888639A - Package for storing perishable items - Google Patents

Package for storing perishable items Download PDF

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Publication number
CN112888639A
CN112888639A CN201980064299.8A CN201980064299A CN112888639A CN 112888639 A CN112888639 A CN 112888639A CN 201980064299 A CN201980064299 A CN 201980064299A CN 112888639 A CN112888639 A CN 112888639A
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China
Prior art keywords
container
perishable
area
openings
protective coating
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Pending
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CN201980064299.8A
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Chinese (zh)
Inventor
L·佩雷斯
C·P·弗雷泽
J·罗杰斯
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Apeel Technology Inc
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Apeel Technology Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/30Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
    • B65D85/34Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/30Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
    • B65D85/34Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
    • B65D85/345Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes having a meshed or apertured closure to allow contents to breathe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2205/00Venting means
    • B65D2205/02Venting holes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2543/00Lids or covers essentially for box-like containers
    • B65D2543/00009Details of lids or covers for rigid or semi-rigid containers
    • B65D2543/00018Overall construction of the lid
    • B65D2543/00064Shape of the outer periphery
    • B65D2543/00074Shape of the outer periphery curved
    • B65D2543/00092Shape of the outer periphery curved circular

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Packages (AREA)
  • Storage Of Fruits Or Vegetables (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

Described herein are packages, such as containers (100), and methods for storing perishable items. The container (100) includes a plurality of openings (114) that reduce the relative humidity within the package. The perishable object may be coated with a protective coating to prevent loss of moisture from the produce during storage. The perishable object may be coated before being stored in the package or after being placed in the package. Thus, the container (100) and coating allow the perishable item to be stored at a lower relative humidity, e.g., below industry standards for shipping and storage or below about 90% relative humidity, which may help retard the growth of biological stressors such as fungi, bacteria, viruses, and/or pests.

Description

Package for storing perishable items
Cross Reference to Related Applications
This application claims priority and benefit of U.S. provisional patent application No. 62/717,511 filed on 8/10/2018, the contents of which are hereby incorporated by reference in their entirety.
Technical Field
The present invention relates to containers and other packaging for storing perishable items, such as harvested produce, and methods of making and using the same.
Background
Common agricultural products, such as fresh agricultural products, can be very susceptible to degradation and decomposition (i.e., spoilage) when exposed to the environment. Degradation of agricultural products may occur via abiotic means as follows: due to evaporative moisture loss from the outer surface of the agricultural product to the atmosphere, oxidation by oxygen diffusing into the agricultural product from the environment, mechanical damage to the surface, and/or photo-induced degradation (i.e., photodegradation). Biological stressors such as bacteria, fungi, viruses and/or pests may also infect and degrade the agricultural product.
Harvested produce (e.g., fruits, vegetables, berries, etc.) is typically stored at high density (i.e., high total volume of produce per unit volume of storage container) for an extended period of time prior to consumption, such as during shipping. During this time, if proper storage conditions are not maintained, the produce may be susceptible to quality loss, mold and/or other spoilage mechanisms. Accordingly, devices and methods that reduce the rate of spoilage while maintaining high quality produce with minimal mass/moisture loss or fungal infestation during storage and shipping are desired.
Disclosure of Invention
Described herein are packages (e.g., containers) and methods for storing perishable items. The container may include a plurality of openings that reduce the relative humidity within the package. The perishable items may be coated with a protective coating to prevent moisture loss from the produce during storage. The perishable object may be coated before being stored in the package or after being placed in the package. Thus, the containers and coatings allow perishable items to be stored at lower relative humidity (e.g., below industry standards for shipping and storage, or below about 90% relative humidity), which can help retard the growth of biological stressors such as fungi, bacteria, viruses, and/or pests.
The protective coating may be formed by treating the perishable object with a coating mixture that includes a coating agent dissolved or suspended in a solvent. The coating agent can include a variety of monomers, oligomers, fatty acids, esters, amides, amines, thiols, carboxylic acids, ethers, aliphatic waxes, alcohols, salts, or combinations thereof. The coating agent may be a non-sterile coating agent. The solvent to which the coating agent is added may include water and/or alcohol. The solvent to which the coating agent is added may comprise or be formed by a disinfectant. For example, the solvent may include ethanol, methanol, acetone, isopropanol, or ethyl acetate. Sterilizing an agricultural or edible product can result in a reduced rate of fungal growth on the agricultural or edible product or an increased shelf life of the agricultural or edible product before the fungi grow. In some embodiments, the mixture includes a disinfectant, such as citric acid.
Brief Description of Drawings
FIG. 1 is an illustration of a container that may be used to store perishable items.
FIG. 2 is an illustration of another container that may be used to store perishable items.
Fig. 3 illustrates a method of preparing a perishable object, such as an agricultural product, for storage and subsequent storage of the perishable object.
Fig. 4 illustrates a method of storing a perishable object in a container, wherein a protective coating is formed over the object while the object is in the container.
Like numbers refer to like elements throughout.
Definition of
The term "relative humidity" (or "RH"), as used herein, is defined as the ratio of the partial pressure of water vapor present in air to the equilibrium vapor pressure (i.e., the partial pressure of water vapor required for saturation) at the same temperature, expressed as a percentage.
As used herein, a "coating" or "protective coating" is understood to mean one or more layers of monomers, oligomers, polymers, fatty acids, esters, triglycerides, diglycerides, monoglycerides, amides, amines, thiols, thioesters, carboxylic acids, ethers, aliphatic waxes, alcohols, salts (inorganic or organic salts, such as fatty acid salts), acids, bases, proteins, enzymes, or combinations thereof disposed over and substantially covering a surface of a perishable item, such as a piece of produce (a piece of produce).
As used herein, "coating agent" refers to a chemical that can be used to coat the surface of a substrate (e.g., after removal of a solvent in which the coating agent is dispersed) to form a coating (e.g., a protective coating) on the surface of the agricultural product. The coating agent may comprise one or more coating components. For example, the coating component can be a compound of formula I, I-A and/or formula I-B, or a monomer or oligomer of a compound of formula I, I-A and/or formula I-B. The coating component may also comprise fatty acids, fatty acid esters, fatty acid amides, amines, thiols, carboxylic acids, ethers, aliphatic waxes, alcohols, salts (inorganic or organic salts, such as fatty acid salts), or combinations thereof.
The term "alkyl" refers to straight or branched chain saturated hydrocarbons. C1-C6The alkyl group contains 1 to 6 carbon atoms. C1-C6Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, sec-butyl and tert-butyl, isopentyl, and neopentyl.
The term "alkenyl" means an aliphatic hydrocarbon group containing a carbon-carbon double bond and which may be straight or branched having from about 2 to about 6 carbon atoms in the chain. Preferred alkenyl groups have from 2 to about 4 carbon atoms in the chain. "branched" means that one or more lower alkyl groups such as methyl, ethyl, or propyl are attached to the alkenyl straight chain. Exemplary alkenyl groups include ethenyl, propenyl, n-butenyl, and isobutenyl. C2-C6Alkenyl is alkenyl containing between 2 and 6 carbon atoms. The term "alkenyl" as defined herein may include both "E" and "Z" or "cis" and "trans" double bonds.
The term "alkynyl" means an aliphatic hydrocarbon group containing a carbon-carbon triple bond and which may be straight or branched having from about 2 to about 6 carbon atoms in the chain. Preferred alkynyl groups have from 2 to about 4 carbon atoms in the chainAnd (4) adding the active ingredients. "branched" means that one or more lower alkyl groups such as methyl, ethyl or propyl are attached to the straight chain alkynyl group. Exemplary alkynyl groups include ethynyl, propynyl, n-butynyl, 2-butynyl, 3-methylbutynyl and n-pentynyl. C2-C6Alkynyl is alkynyl containing between 2 and 6 carbon atoms.
The term "cycloalkyl" means a monocyclic or polycyclic saturated carbocyclic ring containing from 3 to 18 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, norbornenyl, bicyclo [2.2.2 ] n]Octyl or bicyclo [2.2.2]An octenyl group. C3-C7Cycloalkyl is cycloalkyl containing between 3 and 7 carbon atoms. Cycloalkyl groups may be fused (e.g., decalin) or bridged (e.g., norbornane).
The term "aryl" refers to a cyclic aromatic hydrocarbon group having 1 to 2 aromatic rings, including monocyclic or bicyclic groups such as phenyl, biphenyl, or naphthyl. In the case of aromatic rings containing two aromatic rings (bicyclic, etc.), the aromatic rings of the aryl group may be linked at a single point (e.g., biphenyl) or fused (e.g., naphthyl). The aryl group may be optionally substituted at any point of attachment with one or more substituents, for example 1 to 5 substituents.
The term "heteroaryl" means a monovalent monocyclic or bicyclic aromatic ring or polycyclic aromatic group having 5 to 12 ring atoms containing one or more ring heteroatoms selected from N, O or S, the remaining ring atoms being C. Heteroaryl as defined herein also means a bicyclic heteroaromatic group wherein one or more heteroatoms are selected from N, O or S. The aromatic rings are optionally independently substituted with one or more substituents described herein.
The term "halo" or "halogen" as used herein means fluoro, chloro, bromo or iodo.
As used herein, a "cationic counterion" is any organic or inorganic positively charged ion associated with a negatively charged ion. Examples of cationic counterions include, for example, sodium, potassium, calcium, and magnesium. As used herein, a "cationic moiety" is any organic or inorganic positively charged ion.
The following abbreviations are used throughout. Palmitic acid (i.e., palmitic acid) is abbreviated "PA". Octadecanoic acid (i.e., stearic acid) is abbreviated "SA". Myristic acid (i.e. myristic acid) is abbreviated "MA". (9Z) -Octadecenoic acid (i.e., oleic acid) is abbreviated "OA". Dodecanoic acid (e.g., lauric acid) is abbreviated "LA". Undecanoic acid (e.g., undecanoic acid) is abbreviated "UA". Capric acid (e.g., capric acid) is abbreviated "CA". 1, 3-dihydroxypropan-2-yl palmitate (i.e. 2-glyceropalmitate) is abbreviated "PA-2G". 1, 3-dihydroxypropan-2-yl octadecanoate (i.e. 2-glyceryl stearate) is abbreviated "SA-2G". 1, 3-dihydroxypropan-2-yltetradecanoic acid (i.e., 2-glyceryl myristate) is abbreviated "MA-2G". 1, 3-dihydroxypropan-2-yl (9Z) -octadecenoate (i.e., 2-glyceryl oleate) is abbreviated "OA-2G". 2, 3-dihydroxypropan-1-yl palmitate (i.e. 1-glyceropalmitate) is abbreviated "PA-1G". 2, 3-dihydroxypropan-1-yl octadecanoate (i.e. 1-glyceryl stearate) is abbreviated "SA-1G". 2, 3-dihydroxypropan-1-yltetradecanoate (i.e., 1-glyceryl myristate) is abbreviated "MA-1G". 2, 3-dihydroxypropan-1-yl (9Z) -octadecenoate (i.e., 1-glyceryl oleate) is abbreviated "OA-1G". 2, 3-dihydroxypropan-1-yldodecanoate (i.e., 1-glycerol laurate) is abbreviated "LA-1G". 2, 3-dihydroxypropan-1-ylundecanoate (i.e., 1-glyceroundecanoate) is abbreviated "UA-1G". 2, 3-dihydroxypropan-1-yldecanoate (i.e., 1-glycerol caprine acid ester) is abbreviated "CA-1G". The sodium salt of stearic acid is abbreviated "SA-Na". The sodium salt of myristic acid is abbreviated "MA-Na". The sodium salt of palmitic acid is abbreviated as "PA-Na". The potassium salt of stearic acid is abbreviated "SA-K". The potassium salt of myristic acid is abbreviated "MA-K". The potassium salt of palmitic acid is abbreviated "PA-K". Calcium salt of stearic acid is abbreviated "(SA)2-Ca ". Calcium salt of myristic acid abbreviated "(MA)2-Ca ". Calcium salt of palmitic acid abbreviated as "(PA)2-Ca ". Magnesium salt of stearic acid abbreviated "(SA)2-Mg ". Magnesium salt of myristic acid abbreviated "(MA)2-Mg ". Magnesium salts of palmitic acid are abbreviated as "(PA)2-Mg”。
Detailed Description
Modified Atmosphere Packaging (MAP) is commonly used to store perishable items, such as harvested produce, on store shelves, for example, prior to purchase by consumers, in order to minimize degradation of the items and maintain the visual, textural and nutritional appeal of the items. With proper material selection and packaging design, MAP containers and packaging can be optimized to maintain a high internal relative humidity in order to minimize the rate at which perishable items lose quality and water over time, thereby allowing the items to have acceptable quality when sold after storage and/or shipping. MAP containers and packaging may also be designed so as to allow perishable items to be sufficiently cooled during storage so as to reduce the rate of maturation of the items, thereby further delaying the onset of spoilage.
Table 1 below is a compilation of recommended industry standard conditions for long-term storage of agricultural products (e.g., fresh fruits and vegetables), including recommended Relative Humidity (RH). As seen in table 1, the recommended relative humidity during storage is at least 85%, and typically at least 95%, for almost all types of common agricultural produce. The recommended storage conditions for most types of produce represent a compromise between preventing quality loss of the produce during storage and minimizing the risk of post-harvest pathogen growth. Specifically, most produce will benefit from a near saturated environment (e.g., at least 95% of the relative humidity within the package) in order to minimize mass loss during storage. However, such high RH levels may create an environment that promotes the growth of fungi and other post-harvest pathogens (e.g., mold, bacteria), particularly if condensation forms on the surface of the produce or within any packaging in which the produce is stored, or if the produce is subject to damage at its surface due to high packaging density or handling of the produce. Furthermore, it may be difficult to accurately control the relative humidity at such high levels throughout the storage vessel, and thus local RH variations may further exacerbate the risk of condensation formation.
TABLE 1 Properties and recommended conditions for Long-term storage of fresh fruits and vegetables
Figure BDA0002998401780000061
Figure BDA0002998401780000071
Figure BDA0002998401780000081
Figure BDA0002998401780000091
Figure BDA0002998401780000101
Figure BDA0002998401780000111
Figure BDA0002998401780000121
Figure BDA0002998401780000131
Figure BDA0002998401780000141
Figure BDA0002998401780000151
Figure BDA0002998401780000161
Figure BDA0002998401780000171
Ethylene yield:
very low VL (at 20 ℃ <0.1 μ L/kg-hr)
L ═ Low (0.1-1.0. mu.L/kg-hr)
M in (1.0-10.0 μ L/kg-hr)
H is high (10-100 mu L/kg-hr)
VH ═ very high (>100 μ L/kg-hr)
Ethylene sensitivity (detrimental effects include yellowing, softening, increased decay, leaf detachment or loss, browning)
Low sensitivity of L ═
Medium sensitivity of M ═
H-is highly sensitive
Fig. 1 is an illustration of a container 100 for storing perishable items, such as harvested produce, at a relative humidity level according to table 1 above. The container 100 includes a housing 102 constructed of a material structure 110 and a lid 130. In some embodiments, the material structure 110 is a rigid or semi-rigid structure. The material structure 110 includes first openings 112, 112 that are sufficiently large to allow passage of any of the perishable items (not shown) that the container is configured to store, such that the perishable items may be placed into the container through the first openings. The container is closed by securing (e.g., sealing or fastening) the lid 130 over the first opening 112 when the perishable object is in the container. Although fig. 1 shows the lid 130 as being detachable from the remainder of the container, in some embodiments the lid is attached to the remainder of the container and can be converted or bent from an open to a closed position. In some embodiments, the lid 130 is formed of a flexible material, such as plastic or foil, that can be sealed (e.g., with an adhesive or heat) over the first opening 112. In some embodiments, the lid is resealable. In some embodiments, the cover is formed of the same material as the material structure 110. In some embodiments, the lid is omitted and the material structure 110 is formed of a flexible material such that the material structure can be folded, deformed or shaped once the perishable object is in the container in such a way that the enclosure surrounds the enclosed perishable object. In some embodiments, the material forming the material structure 110 includes plastic, Polycarbonate (PC), or Polyethylene (PET). In some embodiments, the material of the material structure is impermeable to water, oxygen, and/or carbon dioxide. The bottom or footprint of the container 100 may be manufactured in a variety of shapes including, but not limited to, circular, oval, square, and rectangular.
As used herein, a "rigid or semi-rigid" structure is one that has sufficient rigidity such that its shape does not substantially change or deform when the structure is filled with perishable items and no other external forces are applied to the sides of the structure. Thus, a mesh bag is not a rigid or semi-rigid structure because its shape will change as the perishable product is filled, whereas a container constructed of a hard plastic may be rigid or semi-rigid if the hard plastic is thick enough that the shape of the container does not substantially change when the container is filled with the perishable product.
The enclosure 102 also includes a plurality of second openings 114, wherein each of the second openings 114 is small enough to not pass any of the perishable items stored in the container. Thus, perishable items cannot fall out of the container 100 while they are stored in the container 100 with the lid 130 covering the first opening 112. Although fig. 1 shows the second opening 114 formed entirely in the side of the material structure 110, the second opening may also be formed in the bottom or lid 130 of the material structure.
As previously described, during storage of perishable items such as harvested produce in the container 100, the items may beneficially be cooled so as to reduce their rate of maturation, thereby further delaying the onset of spoilage. Cooling of the article may be achieved by convective cooling through the plurality of second openings 114. That is, cold air or gas may be blown or otherwise drawn through the second opening 114 to cool the stored perishable items. In the case of cooling items by placing the container 100 in refrigeration (e.g., in a refrigeration unit), the relative humidity within the container during cooling is typically close to the relative humidity of the refrigerated environment (e.g., the environment within the refrigeration unit), which may be at least 90% relative humidity.
The cooling efficiency of the storage items in the container 100 is maximized by maximizing the ratio of the total area of all of the second openings 114 to the total area of the enclosure 102 (i.e., the total area of the surface surrounding the storage items) to improve convective airflow through the region where the perishable items are stored. However, after the container and stored perishable item are removed from refrigeration and placed in the environment, if the ratio of the area of the opening 114 to the total enclosure area is large, the relative humidity in the area containing the perishable item will decrease because water vapor (including vapor escaping from the stored perishable item) is more likely to escape from within the container. This in turn causes the stored items to lose quality at a higher rate and degrade more quickly. Thus, in the container 100 of fig. 1, the ratio of the total area of all second openings 114 to the total area of the housing 102 may be made small, such as less than 0.2, less than 0.18, less than 0.16, less than 0.14, less than 0.12, less than 0.1, less than 0.08, less than 0.05, less than 0.03, less than 0.02, less than 0.01, less than 0.008, less than 0.005, less than 0.003, less than 0.002, less than 0.001, less than 0.0008, or less than 0.0005.
Fig. 2 is an illustration of another container 200 suitable for storing perishable items, such as harvested produce. The container 200 is the same as the container 100 of fig. 1, except that the overall area of the openings 214 is greater than the overall area of the openings 114 in the container 100 (e.g., the total number of openings per unit area of the shell is greater and/or the individual openings have a greater area). Thus, the ratio of the total area of all of the second openings 214 to the total area of the housing 202 in fig. 2 is greater than the corresponding ratio for the container 100 of fig. 1. For example, for the container 200, the ratio of the total area of all second openings 214 to the total area of the housing 202 may be greater than 0.002, greater than 0.004, greater than 0.006, greater than 0.008, greater than 0.01, greater than 0.012, greater than 0.014, greater than 0.016, greater than 0.018, greater than 0.02, greater than 0.025, greater than 0.03, greater than 0.035, greater than 0.04, greater than 0.045, greater than 0.05, greater than 0.06, greater than 0.07, greater than 0.08, greater than 0.09, greater than 0.1, greater than 0.11, greater than 0.12, greater than 0.13, greater than 0.14, greater than 0.15, greater than 0.16, greater than 0.17, greater than 0.18, greater than 0.19, greater than 0.2, greater than 0.21, greater than 0.22, greater than 0.23, greater than 0.24, or greater than 0.25. Further, the ratio of the total area of all second openings 214 to the total area of housing 202 may be less than 0.95, less than 0.94, less than 0.93, less than 0.92, less than 0.91, less than 0.9, less than 0.88, less than 0.86, less than 0.84, less than 0.82, less than 0.8, less than 0.78, less than 0.76, less than 0.74, less than 0.72, less than 0.7, less than 0.68, less than 0.66, less than 0.64, less than 0.62, less than 0.6, less than 0.55, or less than 0.5. In some embodiments, the opening 214 is substantially rectangular, circular, or oval. I.e. the shape is the same as or similar to a rectangle, a circle or an ellipse, respectively.
If the container 200 is used to store conventional perishable items, such as produce that is susceptible to degradation due to water/mass loss, the relative humidity within the package during storage may be lower than suggested in table 1, and therefore the perishable items will lose mass at a higher rate and therefore degrade more quickly. For example, depending on the ratio of the total area of the opening to the total package area, the relative humidity within the package during storage may be below 95%, below 90%, below 85%, below 80%, below 75%, below 70%, below 65%, below 60%, below 55%, below 50%, below 45%, below 40%, below 35%, below 30%, below 25%, below 20%, below 15%, below 10%, or below 5%; or a relative humidity in the range of about 40% to about 90%, about 45% to about 90%, about 50% to about 90%, about 55% to about 90%, about 60% to about 90%, about 65% to about 90%, about 70% to about 90%, about 75% to about 90%, about 80% to about 90%, about 40% to about 85%, about 45% to about 85%, about 50% to about 85%, about 55% to about 85%, about 60% to about 85%, about 65% to about 85%, about 70% to about 85%, about 75% to about 85%, about 80% to about 85%, about 40% to about 80%, about 45% to about 80%, about 50% to about 80%, about 55% to about 80%, about 60% to about 80%, about 65% to about 80%, about 70% to about 80%, about 40% to about 75%, about 45% to about 75%, about 50% to about 75%, about 55% to about 75%, about 60% to about 75%, or about 65% to about 75%.
Although such low in-package relative humidity can have a detrimental effect on a variety of conventional perishable items, if a perishable item is coated with a protective coating that acts as a moisture loss barrier prior to storage and thus reduces the quality and/or water loss rate of the perishable item, the coated perishable item can still maintain its quality during storage and can last as long as a conventional (uncoated) perishable item held at a higher relative humidity. Indeed, in many cases, the average storage life of coated perishable items stored in the container 200 (at a lower relative humidity) is longer than similar perishable items stored in the container 100 at the same temperature (coated or uncoated), as higher humidity conditions can favor the growth of pathogens such as mold, fungus, and bacteria, which also cause perishable item spoilage, particularly at high packaging densities.
In some embodiments, produce or other perishable items stored in the container 100 or 200 may not be very susceptible to degradation via water/mass loss. However, it may be desirable to have the rate of respiration of the perishable item (i.e., CO production per unit mass of the item)2To minimize the rate of ripening of the item to extend its life before spoilage. In these cases, if the perishable item is not coated, a smaller open area in the container (as in container 100) results in a lower respiration rate because more CO is available during storage2Remaining trapped within the container. However, for the same reasons mentioned earlier, the relative humidity inside the container is higher when the opening area is smaller, which may increase the rate of mildew formation.
If a protective coating (e.g. for CO) is used that reduces the respiration rate of the article2A coating with low permeability) to a perishable object, the life of the object can be maximized by storing in a container having a larger open area, such as container 200. This is because even CO in the vessel2Is lower and the respiration rate of the article is still low because the protective coating reduces CO by reducing CO2Transfer from the article to the environment while keeping the respiration rate of the article low. In addition, the larger aperture area reduces the relative humidity within the container, which can reduce the rate of mildew. Where the perishable item is not very susceptible to degradation via water/mass loss, the low relative humidity may not substantially affect the rate of spoilage due to water/mass loss, even if the protective coating does not act as a barrier to water/mass loss.
In view of the above, the rate of spoilage of perishable items can be reduced by: (a) forming a coating on the article that reduces the rate of mass loss of the article and storing the article in a container, such as container 200, having a large open area; (b) forming a coating on the article that reduces the respiration rate of the article and storing the article in a container, such as container 200, having a large open area; or (c) forming a coating on the article that reduces both the respiration rate and the mass loss rate of the article, and storing the article in a container, such as container 200, having a large open area. Furthermore, if the coated perishable object stored in the container 200 is cooled by placing the container 200 with the object in refrigeration, the relative humidity in the refrigerated environment may be set below conventional levels, such as below 90%, below 85%, below 80%, below 75%, below 70%, below 65%, below 60%, below 55%, below 50%, below 45%, below 40%, below 35%, below 30%, below 25%, below 20%, below 15%, below 10%, or below 5%. Protective coatings suitable for application to perishable items stored in the container 200 and methods of applying the coatings are described in more detail below.
Fig. 3 illustrates a method 300 for preparing a perishable object (e.g., an agricultural product) for storage and subsequent storage of the perishable object such that the rate of mass/water loss and/or respiration is minimized and at the same time the rate of spoilage via biological stressors such as mold, fungus, or bacteria is reduced. First, a solid mixture of a coating agent (e.g., a composition of monomeric and/or oligomeric and/or polymeric units) is dissolved or suspended in a solvent (e.g., ethanol, methanol, acetone, isopropanol, ethyl acetate, water, or combinations thereof) to form a solution or suspension (step 302). In some embodiments, a disinfectant, such as citric acid, is included in the solution/suspension. The concentration of the coating agent in the solvent may be, for example, about 0.1 to 200 mg/mL. Next, a solution/suspension including a coating agent is applied over the surface of the produce or other perishable object to be coated, such as by spraying the produce/object or by dipping the produce/object in the solution/suspension (step 304). In the case of spraying, the solution/suspension may, for example, be placed in a spray bottle which generates a fine mist spray. Then the spray bottle head canHeld at a suitable distance, for example, about three to twelve inches, from the produce/item and then sprayed. In the case of dip coating, the agricultural product/item may be placed in a bag, for example, the solution/suspension containing the coating agent is poured into the bag, and the bag is then sealed and its contents gently inverted or agitated until the surface of the agricultural product/item is completely wetted. After the solution/suspension is applied to the agricultural/commodity product, the agricultural/commodity product is allowed to dry until the solvent has at least partially evaporated, thereby allowing a protective coating composed of the constituent parts of the coating agent (e.g., monomeric and/or oligomeric and/or polymeric units) to form over the surface of the agricultural/commodity product (step 306). Finally, the coated agricultural/commodity product is stored in the container of fig. 2, relative humidity and/or ambient CO2The concentration is lower than needed to allow a sufficiently low water/mass loss rate and/or respiration rate in the case of uncoated agricultural/commodity products (step 308). Optionally, the perishable object may be cooled during storage. In some embodiments, cooling is achieved by convection through the openings 214 in the container 200 of fig. 2.
Method steps 302, 304, 306, 308, and 310 of method 300 (fig. 3) and their associated processing agents and resulting coatings are now described in further detail. The coating agent added to the solvent (step 302) may include a variety of monomers, oligomers, polymers, fatty acids, esters, triglycerides, diglycerides, monoglycerides, amides, amines, thiols, thioesters, carboxylic acids, ethers, aliphatic waxes, alcohols, salts (inorganic or organic salts, such as fatty acid salts), acids, bases, proteins, enzymes, or combinations thereof. The resulting protective coating may thus be formed from components that do not naturally occur on the perishable object, either alone or in ratios where they are combined in the coating.
Specific compositions of monomers, oligomers, polymers, fatty acids, esters, triglycerides, diglycerides, monoglycerides, amides, amines, thiols, thioesters, carboxylic acids, ethers, aliphatic waxes, alcohols, salts (inorganic or organic salts, such as fatty acid salts), acids, bases, proteins, enzymes, or combinations thereof may be formulated such that the resulting coating formed over the perishable object (during step 306) mimics or enhances the cuticle of the product. The biopolyester cutin forms the major structural component of the cuticle, which makes up the aerial surface of most terrestrial plants. The stratum corneum is formed from a mixture of polymerized mono-and/or polyhydroxy fatty acids and esters and embedded cutin waxes. The hydroxy fatty acids and esters of the stratum corneum form a tightly bound network with a high crosslink density. This crosslinked network in combination with the embedded keratinous wax acts as a barrier to moisture loss and oxidation, as well as providing protection from other environmental stressors.
Monomers, oligomers, polymers, fatty acids, esters, triglycerides, diglycerides, monoglycerides, amides, amines, thiols, thioesters, carboxylic acids, ethers, aliphatic waxes, alcohols, salts (inorganic or organic salts, such as fatty acid salts), acids, bases, proteins, enzymes, or combinations thereof may be extracted or derived from plant matter, and in particular cutin derived from plant matter. Plant matter generally includes some parts that contain cutin and/or have high-density cutin (e.g., pericarp, leaves, branches, etc.) and other parts that do not contain cutin or have low-density cutin (e.g., pulp, seeds, etc.). The cutin-containing portion can be formed from monomeric and/or oligomeric and/or polymeric units and subsequently used in the formulations described herein to form a coating over the surface of the agricultural product. The cuticle-containing moiety may also include other components, such as non-hydroxylated fatty acids and esters, proteins, polysaccharides, phenols, lignans, aromatic acids, terpenoids, flavonoids, carotenoids, alkaloids, alcohols, alkanes, and aldehydes, which may be included in the formulation or may be omitted.
Monomers, oligomers, polymers, or combinations thereof can be obtained by first separating (or at least partially separating) a plant part that includes the desired molecule of the coating agent (or a molecule that can be readily modified for use in the coating agent) from a part that does not include the desired molecule. For example, when using cutin as a raw material of the coating agent composition, a cutin-containing part of the plant matter is separated (or at least partially separated) from a non-cutin-containing part, and cutin is obtained from the cutin-containing part (e.g., when the cutin-containing part is a fruit peel, cutin is separated from the fruit peel). The resulting plant part (e.g., cutin) is then depolymerized (or at least partially depolymerized) to obtain a mixture comprising a plurality of fatty acid or esterified cutin monomers, oligomers, polymers (e.g., low molecular weight polymers), or combinations thereof. The cutin-derived monomers, oligomers, polymers, or combinations thereof can be directly dissolved or suspended in a solvent to form a solution/suspension used in the formation of the coating, or alternatively, can be first activated or chemically modified (e.g., functionalized). The chemical modification or activation can, for example, include esterifying (e.g., glycerating) a monomer, oligomer, polymer, or combination thereof to form a mixture of 1-and/or 2-monoacylglycerides, and dissolving/suspending the mixture of 1-and/or 2-monoacylglycerides in a solvent to form a solution/suspension, thereby producing the formulation formed in step 302 of fig. 3 for use in preparing a protective coating.
In some embodiments, the coating agent comprises a fatty acid, ester, triglyceride, diglyceride, monoglyceride (i.e., monoacylglycerol), amide, amine, thiol, thioester, carboxylic acid, ether, aliphatic wax, alcohol, salt (inorganic or organic salt, such as a fatty acid salt), acid, base, protein, enzyme, or a combination thereof. In some embodiments, the coating agents may be substantially similar or identical to those described in U.S. patent application No. 15/330,403 entitled "precursor compounds for molecular coatings" (published as US 2017/0073532), filed 2016, 9, 15, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, the coating agent may include one or more compounds of formula I:
Figure BDA0002998401780000241
wherein:
r is selected from-H, -glyceryl, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl is optionally substituted with one or more substituents selected from halogen (e.g., Cl, Br or I), hydroxy, nitro, -CN, -NH2、-SH、-SR15、-OR14、-NR14R15、C1-C6Alkyl radical, C2-C6Alkenyl or C2-C6Radical substitution of alkynyl;
R1、R2、R5、R6、R9、R10、R11、R12and R13Each occurrence of the formula is independently-H, - (C ═ O) R14、-(C=O)H、-(C=O)OH、-(C=O)OR14、-(C=O)-O-(C=O)R14、-O(C=O)R14、-OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15At each time of dischargeAt each occurrence independently is-H, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure BDA0002998401780000251
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
In some embodiments, R is-H, -CH3or-CH2CH3
In some embodiments, the coating agent comprises monoacylglycerides (e.g., 1-monoacylglycerides or 2-monoacylglycerides) and/or monomers and/or oligomers and/or low molecular weight polymers formed therefrom. The difference between 1-monoacylglycerides and 2-monoacylglycerides is the point of glyceride attachment. Thus, in some embodiments, the coating agent comprises a compound of formula I-A (e.g., a 2-monoacylglycerol):
Figure BDA0002998401780000252
wherein:
each RaIndependently is-H or-C1-C6An alkyl group;
each RbIndependently selected from-H, -C1-C6Alkyl or-OH;
R1、R2、R5、R6、R9、R10、R11、R12and R13At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15Independently at each occurrence-H, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure BDA0002998401780000261
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
In some embodiments, the coating agent comprises a compound of formula I-B (e.g., a 1-monoacylglycerol):
Figure BDA0002998401780000262
wherein:
each RaIndependently is-H or-C1-C6An alkyl group;
each RbIndependently selected from-H, -C1-C6Alkyl or-OH;
R1、R2、R5、R6、R9、R10、R11、R12and R13At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15Independently at each occurrence-H, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure BDA0002998401780000271
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
Any of the coating agents described herein can additionally or alternatively include fatty acid salts, such as sodium salts (e.g., SA-Na, PA-Na, or MA-Na), potassium salts (e.g., SA-K, PA-K, MA-K), calcium salts (e.g., (SA)2-Ca、(PA)2-Ca or (MA)2Ca) or magnesium salts (e.g. (SA)2-Mg、(PA)2-Mg or (MA)2-Mg). Thus, the coating agents herein may comprise one or more compounds of formula II or formula III, wherein formula II and formula III are:
Figure BDA0002998401780000272
wherein for each of the formulae:
x is a cationic moiety;
Xp+is a cationic counterion having the charge state p, and p is 1, 2 or 3;
R1、R2、R5、R6、R9、R10、R11、R12and R13Each occurrence of the formula is independently-H, - (C ═ O) R14、-(C=O)H、-(C=O)OH、-(C=O)OR14、-(C=O)-O-(C=O)R14、-O(C=O)R14、-OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15Each occurrence independently is-H, aryl, heteroaryl, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure BDA0002998401780000282
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
In some embodiments, the coating agent comprises one or more of the following fatty acid compounds:
Figure BDA0002998401780000281
Figure BDA0002998401780000291
Figure BDA0002998401780000301
Figure BDA0002998401780000302
or
Figure BDA0002998401780000303
In some embodiments, the coating agent comprises one or more of the following methyl ester compounds:
Figure BDA0002998401780000304
Figure BDA0002998401780000311
Figure BDA0002998401780000321
Figure BDA0002998401780000322
or
Figure BDA0002998401780000323
In some embodiments, the coating agent comprises one or more of the following ethyl ester compounds:
Figure BDA0002998401780000331
Figure BDA0002998401780000341
Figure BDA0002998401780000342
or
Figure BDA0002998401780000343
In some embodiments, the coating agent comprises one or more of the following 2-glyceride compounds:
Figure BDA0002998401780000351
Figure BDA0002998401780000361
Figure BDA0002998401780000371
Figure BDA0002998401780000372
or
Figure BDA0002998401780000373
In some embodiments, the coating agent comprises one or more of the following 1-glyceride compounds:
Figure BDA0002998401780000374
Figure BDA0002998401780000381
Figure BDA0002998401780000391
Figure BDA0002998401780000401
Figure BDA0002998401780000402
or
Figure BDA0002998401780000403
The coating agents herein may include one or more of the following fatty acid salts (e.g., compounds of formula II or formula III), wherein X is a cationic counterion and n represents the charge state (i.e., the number of proton equivalent charges) of the cationic counterion:
Figure BDA0002998401780000404
Figure BDA0002998401780000411
Figure BDA0002998401780000421
Figure BDA0002998401780000431
Figure BDA0002998401780000432
or
Figure BDA0002998401780000433
In some embodiments, n is 1, 2, or 3. In some embodiments, X is sodium, potassium, calcium, or magnesium.
In some embodiments, the coating agent is formed from a combination of at least 2 different compounds. For example, the coating agent may comprise a compound of formula I-A and an additive. The additive may for example comprise a saturated or unsaturated compound of formula I-B, a saturated or unsaturated fatty acid, an ethyl ester, or a second compound of formula I-A (e.g. having a different carbon chain length) different from the (first) compound of formula I-A. The compound of formula I-a can comprise at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the mass of the coating agent. The combined mass of the compound of formula I-a and the additive may be at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the total mass of the coating agent. The molar ratio of the additive to the compound of formula I-a in the coating agent may be in the range of 0.1 to 5, such as about 0.1 to about 4, about 0.1 to about 3, about 0.1 to about 2, about 0.1 to about 1, about 0.1 to about 0.9, about 0.1 to about 0.8, about 0.1 to about 0.7, about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.15 to about 5, about 0.15 to about 4, about 0.15 to about 3, about 0.15 to about 2, about 0.15 to about 1, about 0.15 to about 0.9, about 0.15 to about 0.8, about 0.15 to about 0.7, about 0.15 to about 0.6, about 0.15 to about 0.5, about 0.2 to about 5, about 0.2 to about 4, about 0.2 to about 2, about 0.0 to about 0, about 0.3 to about 0, about 0.3.0 to about 0, about 0 to about 0, about 0.3, about 0 to about 3, about 0 to about 0.9, about 0 to about 0.6, from about 0.3 to about 0.5, from about 1 to about 5, from about 1 to about 4, from about 1 to about 3, or from about 1 to about 2. The coating agent may be formed, for example, from one of the combinations of compounds of formula I-a and additives listed in table 2 below.
TABLE 2 exemplary coating agent compositions
Figure BDA0002998401780000441
In some embodiments, the coating agent is formed from one of the compound combinations listed in table 3 below.
TABLE 3 exemplary coating agent compositions
Figure BDA0002998401780000451
Figure BDA0002998401780000461
As seen in table 3 above, the coating agent may comprise a first component and a second component, wherein the first component is a compound of formula I-B and the second component is a fatty acid, a fatty acid salt or a second compound of formula I-B different from the (first) compound of formula I-B. The compound of formula I-B can comprise at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, or at least about 90% by mass of the coating agent. The combined mass of the first component and the second component can be at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the total mass of the coating agent.
Referring now to steps 304 and 306 of method 300 (fig. 3), after the coating agent is added to the solvent to form a solution or suspension, the solution/suspension is applied over the surface of a piece of agricultural (product) or other agricultural (agricultural product) to form a protective coating over the surface, the protective coating being formed from the constituent parts of the coating agent. As previously described, the solution/suspension may be applied to the surface, for example, by dipping the agricultural product (product or agricultural product) in the solution/suspension, or by spraying the solution/suspension over the surface. The solvent is then removed from the surface of the agricultural product, for example by allowing the solvent to evaporate or at least partially evaporate. In some embodiments, the act of at least partially removing the solvent from the surface of the agricultural product can comprise removing at least 90% of the solvent from the surface of the agricultural product. As the solvent is removed (e.g., evaporated), the coating agent resolidifies on the surface of the agricultural product to form a protective coating over the surface. In some cases, upon removal of the solvent from the surface, the monomers, oligomers, polymers (e.g., low molecular weight polymers), or combinations thereof, of the coating agent crosslink as the coating is formed. The resulting protective coating may then act as a barrier to water loss from the agricultural product, a barrier to oxidation of the agricultural product, and/or may reduce the respiration rate of the agricultural product, and may thereby protect the agricultural product from biotic and/or abiotic stressors.
Coating properties such as thickness, cross-link density and permeability of the monomer/oligomer/polymer can be varied to suit a particular agricultural product by adjusting the specific composition of the coating agent, the specific composition of the solvent, the concentration of the coating agent in the solvent, and the conditions of the coating deposition process (e.g., the amount of time the solution is applied to the surface of the agricultural product before removal of the solvent, the temperature during deposition, the separation distance between the spray head and the sample, and the spray angle). For example, too short an application time may result in the formation of a too thin protective coating, while too long an application time may result in the agricultural product being damaged by the solvent. Thus, the solution/suspension may be applied to the surface of the agricultural product for a time between about 1 and about 3,600 seconds, such as between 1 and 3000 seconds, between 1 and 2000 seconds, between 1 and 1000 seconds, between 1 and 800 seconds, between 1 and 600 seconds, between 1 and 500 seconds, between 1 and 400 seconds, between 1 and 300 seconds, between 1 and 250 seconds, between 1 and 200 seconds, between 1 and 150 seconds, between 1 and 125 seconds, between 1 and 100 seconds, between 1 and 80 seconds, between 1 and 60 seconds, between 1 and 50 seconds, between 1 and 40 seconds, between 1 and 30 seconds, between 1 and 20 seconds, between 1 and 10 seconds, between about 5 and about 3000 seconds, between about 5 and about 2000 seconds, between about 5 and about 1000 seconds, between about 5 and about 800 seconds, between about 5 and about 600 seconds, between about 5 and about 500 seconds, between about 5 and about 400 seconds, between about 5 and about 300 seconds, between about 5 and about 250 seconds, between about 5 and about 500 seconds, Between about 5 and about 200 seconds, between about 5 and about 150 seconds, between about 5 and about 125 seconds, between about 5 and about 100 seconds, between about 5 and about 80 seconds, between about 5 and about 60 seconds, between about 5 and about 50 seconds, between about 5 and about 40 seconds, between about 5 and about 30 seconds, between about 5 and about 20 seconds, between about 5 and about 10 seconds, between about 10 and about 3000 seconds, between about 10 and about 2000 seconds, between about 10 and about 1000 seconds, between about 10 and about 800 seconds, between about 10 and about 600 seconds, between about 10 and about 500 seconds, between about 10 and about 400 seconds, between about 10 and about 300 seconds, between about 10 and about 250 seconds, between about 10 and about 200 seconds, between about 10 and about 150 seconds, between about 10 and about 125 seconds, between about 10 and about 100 seconds, between about 10 and about 80 seconds, between about 10 and about 60 seconds, between about 10 and about 50 seconds, between about 10 and about 40 seconds, between about 10 and about 30 seconds, between about 10 and about 125 seconds, between about 10 and about 100 seconds, between about 10 and about 80 seconds, between about 10 and about 60 seconds, Between about 10 and about 20 seconds, between about 20 and about 100 seconds, between about 100 and about 3,000 seconds, or between about 500 and about 2,000 seconds.
Furthermore, the concentration of the coating agent in the solvent may be, for example, 0.1 to 200mg/mL or about 0.1 to about 200mg/mL, such as about 0.1 to about 100mg/mL, about 0.1 to about 75mg/mL, about 0.1 to about 50mg/mL, about 0.1 to about 30mg/mL, about 0.1 to about 20mg/mL, about 0.5 to about 200mg/mL, about 0.5 to about 100mg/mL, about 0.5 to about 75mg/mL, about 0.5 to about 50mg/mL, about 0.5 to about 30mg/mL, about 0.5 to about 20mg/mL, 1 to 200mg/mL, 1 to 100mg/mL, 1 to 75mg/mL, 1 to 50mg/mL, 1 to 30mg/mL, about 1 to about 20mg/mL, about 5 to about 200mg/mL, about 5 to about 100mg/mL, about 5 to about 5mg/mL, about 50mg/mL, About 5 to about 30mg/mL, or about 5 to about 20 mg/mL.
The protective coating formed from the coating agent described herein can be an edible coating. The protective coating may be substantially imperceptible to the human eye and may be odorless and/or tasteless. The protective coating can have an average thickness of about 0.1 microns to about 300 microns, such as about 0.5 microns to about 100 microns, about 1 micron to about 50 microns, about 0.1 microns to about 1 micron, about 0.1 microns to about 2 microns, about 0.1 microns to about 5 microns, or about 0.1 microns to about 10 microns. The protective coating can have a thickness of less than 5 microns, less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, less than 0.5 microns, or less than 0.3 microns. In some embodiments, the protective coating is completely organic (e.g., organic in an agricultural sense rather than a chemical sense). In some embodiments, the perishable object is one of the types of agricultural products listed in table 1. In some embodiments, the produce is a thin-skinned fruit or vegetable. For example, the agricultural product may be berries or grapes. In some embodiments, the produce may include a cut fruit surface (e.g., a cut apple surface).
The protective coatings formed from the coating agents described herein can serve a variety of purposes. For example, the protective coating can extend the shelf life of the agricultural or other produce, even in the absence of refrigeration. Furthermore, agricultural and other produce tend to lose quality (due to water loss) at a higher rate when maintained at a lower relative humidity (e.g., less than 90% relative humidity) than a higher relative humidity, because the driving force for water evaporation at the lower relative humidity is increased. The protective coating can thus be formulated to reduce the rate of quality loss of the agricultural product even at lower relative humidity. For example, the protective coating can reduce the rate of mass loss of the agricultural or other agricultural product by at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 100%, at least 125%, at least 150%, or at least 200% (as compared to a similar uncoated product). Alternatively or additionally, the protective coating may be formulated to provide a respiration rate of the agricultural product (i.e., CO production per unit mass of the item)2The rate of) is decreased. For example, the protective coating can reduce the respiration rate of the agricultural or other produce by at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, (as compared to a similar uncoated product),At least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 100%, at least 125%, at least 150%, or at least 200%.
Referring now to step 308 of method 300 (in fig. 3), after forming a coating over the produce or other perishable item, the coated produce/item is stored in container 200 of fig. 2, typically for an extended period of time. The perishable object may occupy at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, or at least 70% of the internal volume of the container 200. As used herein, the percentage of the interior volume of the container occupied by one or more items refers to the total volume of all items in the container divided by the total interior volume of the container (expressed as a percentage). Thus for a container storing the maximum amount of items that can fit within the container's internal volume, the items will typically occupy substantially less than 100% of the container's internal volume due to the spacing between each of the items.
Optionally, during storage, the perishable object is also cooled (step 310), such as by convection through the plurality of openings 214 in the container 200. In some embodiments, the relative humidity in the container is less than 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% while the perishable object is being cooled or after the perishable object has been cooled. In some embodiments, the container is configured such that the relative humidity in the container remains below 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% for a period of at least 12 hours when the perishable item is continuously stored in the container 200.
While the perishable items stored in the container 200 may be coated before they are placed in the container 200, in some embodiments the coating is formed after the perishable items are placed in the container 200. For example, fig. 4 illustrates a method 400 of storing perishable items in a container 200, wherein a coating is formed over the items while the items are in the container 200. First, uncoated perishable items are received or placed in the container 200 of fig. 2 (step 402). Next, a protective coating is formed on each of the perishable objects by disposing a coating solution/suspension (e.g., a coating agent in a solvent) on the perishable object, such as by spraying the object with a spray or mist of the solution/suspension, and causing a coating formed by the coating agent to form over the perishable object (step 404). In some embodiments, the coating solution/suspension is injected (e.g., as a mist or spray) through one or more of the openings 214 in the container 200 or through the opening 212. The items are then stored in the container 200, typically for an extended period of time (step 406). Optionally, during storage, the perishable object is also cooled, such as by convection through the plurality of openings 214 in the container 200 (step 408). In some embodiments, the relative humidity in the container is maintained at less than 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% throughout the duration that the perishable object is being cooled. In some embodiments, the container is configured such that the relative humidity in the container remains below 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% for a period of at least 12 hours when the perishable item is continuously stored in the container 200.
Various implementations of the container and storage method are described above. However, it should be understood that they have been presented by way of example only, and not limitation. Where methods and steps described above indicate certain events occurring in a certain order, those of ordinary skill in the art having the benefit of this disclosure will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the invention. While the embodiments have been particularly shown and described, it will be understood that various changes in form and detail may be made. Accordingly, other implementations are within the scope of the following claims.

Claims (48)

1. A container configured for storing perishable items, comprising:
a housing having a first area, the housing comprising a rigid or semi-rigid structure and having a plurality of openings therein, wherein the plurality of openings collectively have a second area; wherein
The enclosure and the plurality of openings completely surround an area in which the perishable object is stored;
each of the openings is small enough to not pass any of the perishable items that the container is configured to store; and is
A ratio of the second area to the first area is greater than 0.002.
2. The container of claim 1, wherein the housing comprises a lid.
3. The container of claim 2, wherein the lid is removable and/or resealable.
4. A container configured for storing perishable items, comprising:
a housing comprising a rigid or semi-rigid structure and a lid, the rigid or semi-rigid structure comprising a first opening therein and the housing comprising a plurality of second openings, wherein the rigid or semi-rigid structure and the first opening collectively have a first area and the plurality of second openings collectively have a second area; wherein
The first opening is large enough to allow any of the perishable items that the container is configured to store to pass through;
the lid covers the first opening when the container is in a closed state;
the enclosure and the plurality of second openings completely surround a region in which the perishable object is stored;
each of the second openings is small enough to not pass any of the perishable items that the container is configured to store; and is
A ratio of the second area to the first area is greater than 0.002.
5. The container of any one of claims 1-4, wherein the perishable item that the container is configured to store comprises harvested produce.
6. The container of any of claims 1-4, wherein the opening is generally rectangular, circular, or oval.
7. A container having a plurality of perishable items stored therein, the container comprising:
a housing having a first area, the housing comprising a material structure having a plurality of openings therein, wherein the plurality of openings collectively have a second area; wherein
Covering each of the perishable items with a protective coating that reduces a rate of mass loss or a rate of respiration of the perishable item;
the enclosure completely surrounds a first region in which the perishable object is stored;
each of the openings is small enough to not pass any of the perishable items; and is
A ratio of the second area to the first area is greater than 0.002 and less than 0.9.
8. The container of claim 7, wherein the perishable item comprises one or more types of harvested produce.
9. The container of claim 8, wherein the harvested produce is cut or sliced.
10. The container of any one of claims 7-9, wherein the protective coating is not naturally present on any of the perishable items.
11. The container of any of claims 7-9, wherein the protective coating is substantially imperceptible to the human eye.
12. The container of any of claims 7-9, wherein the protective coating is substantially odorless or tasteless.
13. The container of any one of claims 7-9, wherein the protective coating is formed from a coating agent comprising at least one of a fatty acid, an ester, and a salt.
14. The container of claim 13, wherein the coating agent comprises a monoacylglyceride.
15. The container of any one of claims 7-9, wherein the protective coating is formed from a coating agent comprising at least one compound of formula I:
Figure FDA0002998401770000031
wherein:
r is selected from-H, -glyceryl, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl is optionally substituted with one or more substituents selected from halogen, hydroxy, nitro, -CN, -NH2、-SH、-SR15、-OR14、-NR14R15、C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6Radical substitution of alkynyl;
R1、R2、R5、R6、R9、R10、R11、R12and R13Each occurrence of the formula is independently-H, - (C ═ O) R14、-(C=O)H、-(C=O)OH、-(C=O)OR14、-(C=O)-O-(C=O)R14、-O(C=O)R14、-OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl or heteroaryl, each of which is alkyl, alkenyl, alkynyl, cycloalkylThe radicals, aryl OR heteroaryl being optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15Independently at each occurrence-H, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure FDA0002998401770000041
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
16. The container of any one of claims 7-9, wherein the protective coating has a thickness of less than about 5 microns.
17. The container of any one of claims 7-9, wherein the perishable item comprises an agricultural product and the protective coating is formed on a stratum corneum of the agricultural product.
18. The container of any one of claims 7-9, wherein the perishable object occupies at least 25% of the volume of the first region.
19. The container of any one of the preceding claims, wherein the container is configured such that the relative humidity in the first region is below 80% for a period of at least 12 hours after the perishable object is in the first region.
20. The container of any of claims 7-9, wherein the material structure is a rigid or semi-rigid structure.
21. The container of any of claims 1-6 or 20, wherein the material of the rigid or semi-rigid structure is impermeable to water.
22. A method of storing a plurality of perishable items, comprising:
providing the perishable object in a container, wherein the container comprises an enclosure having a first area, the enclosure comprising a rigid or semi-rigid structure and having a plurality of openings therein, wherein the plurality of openings collectively have a second area; and is
Storing the perishable object in the container; wherein
Covering each of the perishable items with a protective coating that reduces a rate of mass loss or a rate of respiration of the perishable item;
the enclosure and the plurality of openings completely surround a first region in which the perishable object is stored;
each of the openings is small enough to not pass any of the perishable items; and is
A ratio of the second area to the first area is greater than 0.002.
23. The method of claim 22, wherein the perishable object comprises one or more types of harvested agricultural products.
24. The method of claim 23, wherein the harvested produce is cut or sliced.
25. The method of claim 22, wherein the relative humidity in the first region is less than 80% while the perishable object is cooled.
26. A method of storing a plurality of perishable items, comprising:
providing the perishable object in a container, wherein the container comprises an enclosure having a first area, the enclosure comprising a material structure having a plurality of openings therein, wherein the plurality of openings collectively have a second area; and is
Storing the perishable object in the container; wherein
Covering each of the perishable items with a protective coating that reduces a rate of mass loss or a rate of respiration of the perishable item;
the enclosure completely surrounds a first region in which the perishable object is stored;
each of the openings is small enough to not pass any of the perishable items; and is
A ratio of the second area to the first area is greater than 0.002 and less than 0.9.
27. The method of claim 26, wherein the perishable object comprises one or more types of harvested agricultural products.
28. The method of claim 27, wherein the harvested produce is cut or sliced.
29. The method of claim 26, wherein the relative humidity in the first region is less than 80% while the perishable object is cooled.
30. The method of any one of claims 22-29, wherein the protective coating is not naturally present on any of the perishable items.
31. The method of any one of claims 22-30, wherein the perishable object occupies at least 25% of the volume of the first region.
32. A method of storing a plurality of perishable items, comprising:
providing the perishable object in a container, wherein the container comprises an enclosure having a first area, the enclosure comprising a rigid or semi-rigid structure and having a plurality of openings therein, wherein the plurality of openings collectively have a second area; and is
Forming a protective coating on the perishable object while the perishable object is in the container, wherein the protective coating reduces a mass loss rate or a respiration rate of the perishable object; wherein
The enclosure and the plurality of openings completely surround a first region in which the perishable object is stored;
each of the openings is small enough to not pass any of the perishable items; and is
A ratio of the second area to the first area is greater than 0.002.
33. The method of claim 32, wherein forming the protective coating comprises injecting a mist or spray through one or more of the openings.
34. The method of any one of claims 32-33, further comprising cooling the perishable object by convection through the plurality of openings after forming the protective coating.
35. The method of claim 34, wherein the relative humidity in the first region is less than 80% while the perishable object is cooled.
36. A method according to any one of claims 32 to 33, wherein, in storing the perishable item, the relative humidity in the first region is sufficiently low to inhibit fungal growth in the produce during storage.
37. The method of any one of claims 32-36, wherein the perishable object occupies at least 25% of the volume of the first region.
38. The method of any one of claims 22-37, wherein the protective coating is substantially imperceptible to the human eye.
39. The method of any one of claims 22-37, wherein the protective coating is substantially odorless or tasteless.
40. The method of any one of claims 22-37, wherein the protective coating is formed from a coating agent comprising at least one of a fatty acid, an ester, and a salt.
41. The method of claim 40, wherein the coating agent comprises a monoacylglyceride.
42. The method of any one of claims 22-37, wherein the protective coating is formed from a coating agent comprising at least one compound of formula I:
Figure FDA0002998401770000081
wherein:
r is selected from-H, -glyceryl, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl is optionally substituted with one or more substituents selected from halogen, hydroxy, nitro, -CN, -NH2、-SH、-SR15、-OR14、-NR14R15、C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6Radical substitution of alkynyl;
R1、R2、R5、R6、R9、R10、R11、R12and R13Each occurrence of the formula is independently-H, - (C ═ O) R14、-(C=O)H、-(C=O)OH、-(C=O)OR14、-(C=O)-O-(C=O)R14、-O(C=O)R14、-OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by one OR more-OR14、-NR14R15、-SR14Or halogen substitution;
R3、R4、R7and R8At each occurrence independently is-H, -OR14、-NR14R15、-SR14Halogen, -C1-C6Alkyl, -C2-C6Alkenyl, -C2-C6Alkynyl, -C3-C7Cycloalkyl, aryl OR heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl OR heteroaryl is optionally substituted by-OR14、-NR14R15、-SR14Or halogen substitution; or
R3And R4Can be connected with themThe combined carbon atoms forming C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle; and/or
R7And R8May combine with the carbon atom to which they are attached to form C3-C6Cycloalkyl radical, C4-C6Cycloalkenyl or 3 to 6 membered ring heterocycle;
R14and R15Independently at each occurrence-H, -C1-C6Alkyl, -C2-C6Alkenyl or-C2-C6An alkynyl group;
(symbol)
Figure FDA0002998401770000091
represents a single bond or a cis-or trans-double bond;
n is 0, 1, 2,3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2,3, 4 or 5; and is
r is 0, 1, 2,3, 4, 5, 6, 7 or 8.
43. The method of any one of claims 22-37, wherein the protective coating has a thickness of less than about 5 microns.
44. The method of any one of claims 22-37, wherein the perishable item comprises an agricultural commodity and the protective coating is formed on a cuticle layer of the agricultural commodity.
45. The method of any one of claims 22-44, further comprising cooling the perishable object.
46. The method of claim 45, wherein cooling the perishable object includes cooling by convection through the plurality of openings.
47. The method of any one of claims 22-46, wherein the ratio of the second area to the first area is greater than 0.004, 0.006, 0.008, 0.01, 0.012, 0.014, 0.016, 0.018, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, or 0.25.
48. The container of any one of claims 1-21, wherein the ratio of the second area to the first area is greater than 0.004, 0.006, 0.008, 0.01, 0.012, 0.014, 0.016, 0.018, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, or 0.25.
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