Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/729—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B4/00—Preservation of meat, sausages, fish or fish products
  • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
  • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
  • A23B4/20—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
  • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
  • A23B7/153—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
  • A23B7/154—Organic compounds; Microorganisms; Enzymes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
  • B65B55/00—Preserving, protecting or purifying packages or package contents in association with packaging
  • B65B55/02—Sterilising, e.g. of complete packages
  • B65B55/04—Sterilising wrappers or receptacles prior to, or during, packaging
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
  • B29K2029/04—PVOH, i.e. polyvinyl alcohol
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0011—Biocides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
  • B29L2007/008—Wide strips, e.g. films, webs

Definitions

• beta-CD beta-cyclodextrin
• This invention is related to controlled release formulations of volatile
• the volatile component may include, for example volatile antimicrobial liquids including low molecular weight alcohols and/or aldehydes, 1 -methylcyclopropene, and/or other volatile fungicides.
• a controlled release formulation or humidity-activated material comprising (a) a binder component; and (b) a volatile component dispersed in the binder component.
• the binder component comprises polyvinyl alcohol. In another embodiment, the binder component does not comprise cellulose, starch, gum, or polyethylene glycol (polyethylene oxide).
• the volatile component comprises an antimicrobial compound.
• the antimicrobial compound comprises a volatile fungicide.
• the volatile component comprises a volatile oil.
• the volatile oil comprises extracts from an organism selection from the group consisting of Achillea spp., Amomum spp., Asteraceae spp., Borago spp., Brassica spp., Bulnesia spp., Calamus spp., Camellia spp., Cananga spp., Capsicum spp., Cassia spp., Cedrus spp., Chamaecyparis spp., Chrysopogon spp., Cinnamomum spp., Citrus spp., Coriandrum spp., Cupressus spp., Curcuma spp., Cymbopogon spp., Dianthus spp.,
• Dipterocarpus spp. Elettaria spp., Eucalyptus spp., Forniculum spp., Gaultheria spp., Geranium spp., Glycine spp., Gossypium spp., Iris spp., Jasminear spp., Juniperus spp., Lavandula spp., Linum spp., Lippia spp., Litsea spp., Melaleuca spp., Mentha spp., Myristica spp., Ocimum spp., Ornothera spp., Origanum spp., Pimenta spp., Pimpinella spp., PZ ' MWS spp., 3 ⁇ 4?er spp., Pogostemon spp., Ricinus spp., Rosa spp., Rosmarinus spp.
• the volatile component does not comprise a substance (for example a gas) with boiling point below zero degree Celsius (0 °C), for example CO2, CIO2 or SO2. In a further embodiment, the volatile component does not comprise CIO2 or SO2. In another embodiment, the volatile component has a boiling point between 40 °C and 300 °C. In another embodiment, the volatile component has a boiling point between 100 °C and 300 °C. In another embodiment, the volatile component comprises solid or liquid precursors to the volatile compounds (gasses). In another embodiment, the volatile component comprises a volatile compound or a molecular complex of a volatile compound and a molecular encapsulating agent.
• a substance for example a gas
• the volatile component does not comprise CIO2 or SO2.
• the volatile component has a boiling point between 40 °C and 300 °C. In another embodiment, the volatile component has a boiling point between 100 °C and 300 °C.
• the volatile component comprises solid or liquid precursors to the volatile compounds (gasses).
• the volatile component comprises a
• the antimicrobial compound is against a pathogen selected from the group consisting of Acremonium spp., Albugo spp., Alternaria spp., Ascochyta spp., Aspergillus spp., Botryodiplodia spp., Botryospheria spp., Botrytis spp., Byssochlamys spp., Candida spp., Cephalosporium spp., Ceratocystis spp., Cercospora spp., Chalara spp., Cladosporium spp., Colletotrichum spp., Cryptosporiopsis spp., Cylindrocarpon spp., Debaryomyces spp., Diaporthe spp., Didymella spp., Diplodia spp., Dothiorella spp., Elsinoe spp., Fus
• a pathogen selected
• Mycocentrospora spp. Mycosphaerella spp., Nectria spp., Neofabraea spp., Nigrospora spp., Penicillium spp., Peronophythora spp., Peronospora spp., Pestalotiopsis spp., Pezicula spp., Phacidiopycnis spp., Phoma spp., Phomopsis spp., Phyllosticta spp., Phytophthora spp., Polyscytalum spp., Pseudocercospora spp., Pyricularia spp., Pythium spp., Rhizoctonia spp., Rhizopus spp., Sclerotium spp., Sclerotinia spp., Septoria spp., Sphaceloma spp.,
• the pathogen is selected from the group consisting of Cryptosporidium spp. and Giardia spp.
• the package material is for use for meats, plants, plant parts, and/or dairy products.
• the plants or plant parts comprise transgenic plants or transgenic plant parts.
• the plants or plant parts are selected from the group consisting of barley, camphor tree, canola, castor-oil plant, cinnamon, cocoa, coffee, corn, cotton, flax, grapevine, hemp, hops, jute, maize, mustard, nuts, oat, poppy, rape, rice, rubber plant, rye, sunflower, sorghum, soybean, sugar cane, tea, tobacco, and wheat.
• the plants or plant parts are selected from the group consisting of fruit, vegetables, nursery, turf and ornamental crops.
• the fruit is selected from the group consisting of almond, apple, avocado, banana, berries (including strawberry, blueberry, raspberry, blackberry, currents and other types of berries), carambola, cherry, citrus (including oranges, lemon, lime, mandarin, grapefruit, and other citrus), coconut, fig, grapes, guava, kiwifruit, mango, nectarine, melons (including cantaloupe, muskmelon, watermelon, and other melons), olive, papaya, passionfruit, peach, pear, persimmon, pineapple, plum, and pomegranate.
• the vegetable is selected from the group consisting of asparagus, beet (including sugar and fodder beet), beans, broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (sweet, bell or hot), potato, pumpkin, sweet potato, snap bean, squash, tomato and turnip.
• asparagus include sugar and fodder beet
• beans broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (sweet, bell or hot), potato, pumpkin, sweet potato, snap bean, squash, tomato and turnip.
• the nursery plant or flower or flower part is selected from the group consisting of roses, carnation, geranium, gerbera, lily, orchid, or other cut- flowers or ornamental flowers, flower bulbs, shrub, deciduous or coniferous tree.
• the meat is selected from the group of beef, bison, chicken, deer, goat, turkey, pork, sheep, fish, shellfish, mollusks, or dry- cured meat products.
• the volatile compound comprises a cyclopropene compound 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. In another embodiment, the volatile compound comprises a cyclopropene compound of the formula:
• R 1 is a substituted or unsubstituted C 1 -C 4 alkyl, C1-C4 alkenyl, C 1 -C 4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
• the volatile compound comprises 1-methylcyclopropene (1-MCP).
• the package material comprises between 0.01% and 30%; between 0.1% and 10%; between 0.3% and 3%; or between 10% and 25% of 1-MCP.
• the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof.
• the molecular encapsulating agent comprises alpha-cyclodextrin or beta-cyclodextrin.
• the molecular encapsulating agent comprises beta-cyclodextrin.
• the volatile component is not substantially released below 30% relative humidity after a period of five (5) hours, but is released between 60% and 100%; between 75% and 100%; or between 80% and 90% relative humidity at room temperature.
• a method for preparing the controlled release material comprises (a) dispersing the volatile component in an aqueous solution or dispersion of a binder component to form a mixture; and (b) casting the mixture onto a package material.
• the mixture may be cast onto a substrate to give a coated sheet which may be inserted into, onto, beneath, or adjacent to a packaging material.
• the coating may be peeled off the coated sheet to give a film which may be inserted into, onto, beneath, or adjacent to a packaging material.
• the binder component comprises polyvinyl alcohol. In another embodiment, the binder component does not comprise cellulose, starch, gum, polyethylene oxide, or polyethylene glycol.
• the volatile component comprises an antimicrobial compound.
• the antimicrobial compound comprises a volatile fungicide.
• the volatile component comprises a volatile oil.
• the volatile oil comprises extracts from an organism selection from the group consisting of Achillea spp., Amomum spp., Asteraceae spp., Borago spp., Brassica spp., Bulnesia spp., Calamus spp., Camellia spp., Cananga spp., Capsicum spp., Cassia spp., Cedrus spp., Chamaecyparis spp., Chrysopogon spp., Cinnamomum spp., Citrus spp., Coriandrum spp., Cupressus spp., Curcuma spp., Cymbopogon spp., Dianthus spp.,
• Dipterocarpus spp. Elettaria spp., Eucalyptus spp., Forniculum spp., Gaultheria spp., Geranium spp., Glycine spp., Gossypium spp., Iris spp., Jasminear spp., Juniperus spp., Lavandula spp., Linum spp., Lippia spp., Litsea spp., Melaleuca spp., Mentha spp., Myristica spp., Ocimum spp., Ornothera spp., Origanum spp., Pimenta spp., Pimpinella spp., Pinus spp., Piper spp., Pogostemon spp., Ricinus spp., Rosa spp., Rosmarinus spp., Salvia spp.
• the volatile component does not comprise a substance (for example a gas) with boiling point below zero degree Celsius (0 °C), for example CO2, CIO2 or SO2. In a further embodiment, the volatile component does not comprise CIO2 or SO2. In another embodiment, the volatile component has a boiling point between 40 °C and 300 °C. In another embodiment, the volatile component has a boiling point between 100 °C and 300 °C. In another embodiment, the volatile component comprises solid or liquid precursors to the volatile compounds (gasses). In another embodiment, the volatile component comprises a volatile compound or a molecular complex of a volatile compound and a molecular encapsulating agent.
• a substance for example a gas
• the volatile component does not comprise CIO2 or SO2.
• the volatile component has a boiling point between 40 °C and 300 °C. In another embodiment, the volatile component has a boiling point between 100 °C and 300 °C.
• the volatile component comprises solid or liquid precursors to the volatile compounds (gasses).
• the volatile component comprises a
• the antimicrobial compound is against a pathogen selected from the group consisting of Acremonium spp., Albugo spp., Alternaria spp., Ascochyta spp., Aspergillus spp., Botryodiplodia spp., Botryospheria spp., Botrytis spp., Byssochlamys spp., Candida spp., Cephalosporium spp., Ceratocystis spp., Cercospora spp., Chalara spp., Cladosporium spp., Colletotrichum spp., Cryptosporiopsis spp., Cylindrocarpon spp., Debaryomyces spp., Diaporthe spp., Didymella spp., Diplodia spp., Dothiorella spp., Elsinoe spp., Fus
• a pathogen selected
• Mycocentrospora spp. Mycosphaerella spp., Nectria spp., Neofabraea spp., Nigrospora spp., Penicillium spp., Peronophythora spp., Peronospora spp., Pestalotiopsis spp., Pezicula spp., Phacidiopycnis spp., Phoma spp., Phomopsis spp., Phyllosticta spp., Phytophthora spp., Polyscytalum spp., Pseudocercospora spp., Pyricularia spp., Pythium spp., Rhizoctonia spp., Rhizopus spp., Sclerotium spp., Sclerotinia spp., Septoria spp., Sphaceloma spp.,
• the pathogen is selected from the group consisting of Cryptosporidium spp. and Giardia spp.
• the material is for use for meats, plants, plant parts, and/or dairy products.
• the plants or plant parts comprise transgenic plants or transgenic plant parts.
• the plants or plant parts are selected from the group consisting of barley, camphor tree, canola, castor-oil plant, cinnamon, cocoa, coffee, corn, cotton, flax, grapevine, hemp, hops, jute, maize, mustard, nuts, oat, poppy, rape, rice, rubber plant, rye, sunflower, sorghum, soybean, sugar cane, tea, tobacco, and wheat.
• the plants or plant parts are selected from the group consisting of fruit, vegetables, nursery, turf and ornamental crops.
• the fruit is selected from the group consisting of almond, apple, avocado, banana, berries (including strawberry, blueberry, raspberry, blackberry, currents and other types of berries), carambola, cherry, citrus (including oranges, lemon, lime, mandarin, grapefruit, and other citrus), coconut, fig, grapes, guava, kiwifruit, mango, nectarine, melons (including cantaloupe, muskmelon, watermelon, and other melons), olive, papaya, passionfruit, peach, pear, persimmon, pineapple, plum, and pomegranate.
• the vegetable is selected from the group consisting of asparagus, beet (including sugar and fodder beet), beans, broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (sweet, bell or hot), potato, pumpkin, sweet potato, snap bean, squash, tomato and turnip.
• asparagus include sugar and fodder beet
• beans broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (sweet, bell or hot), potato, pumpkin, sweet potato, snap bean, squash, tomato and turnip.
• the nursery plant or flower or flower part is selected from the group consisting of roses, carnation, geranium, gerbera, lily, orchid, or other cut-flowers or ornamental flowers, flower bulbs, shrub, deciduous or coniferous tree.
• the meat is selected from the group of beef, bison, chicken, deer, goat, turkey, pork, sheep, fish, shellfish, mollusks, or dry-cured meat products.
• the volatile compound comprises a cyclopropene compound 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. In another embodiment, the volatile compound comprises a cyclopropene compound 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 volatile compound comprises 1-methylcyclopropene (1-MCP).
• the package material comprises between 0.1% and 10%; between 0.3% and 3%; or between 0.01% and 1% of the 1-MCP.
• the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin or beta-cyclodextrin. In a further embodiment, the molecular
• the encapsulating agent comprises beta-cyclodextrin.
• the volatile component is not substantially released below 30% relative humidity after five (5) hours, but is released between 60% and 100%; between 75% and 100%; or between 80% and 100% relative humidity at room temperature.
• the mixture has a viscosity greater than 100 cPs
• the mixture has a viscosity between 100 and 50,000 cPs; between 250 and 30,000 cPs; between 500 and 30,000 cPs; or between 500 and 50,000 cPs.
• a method for preparing the material comprises (a) dispersing the volatile component in an aqueous solution or dispersion of a binder component; (b) casting the mixture onto a solid substrate; and (c) solidifying the mixture to generate a coating on the solid substrate.
• no radiation is used.
• the solidifying step comprises drying with heat.
• the heat is applied at a
• the heat is applied at a temperature between 40 °C and 120 °C; between 60 °C and 100 °C; or between 80 °C and 1 10 °C.
• the solidifying step comprises drying with a stream of gas (for example air).
• a stream of gas for example air.
• the stream of gas is applied at a temperature between 10 °C and 120 °C; between 15 °C and 100 °C; or between 20 °C and 1 10 °C.
• the stream of gas is applied at a temperature between 40 °C and 120 °C; between 60 °C and 100 °C; or between 80 °C and 1 10 °C.
• the mixture has a viscosity greater than 100 cPs
• the mixture has a viscosity between 100 and 50,000 cPs; between 250 and 30,000 cPs; between 500 and 30,000 cPs; or between 500 and 50,000 cPs.
• the mixture has a viscosity greater than 90 cPs; greater than 100 cPs; greater than 250 cPs; or greater than 500 cPs. In other embodiment, the mixture has a viscosity between 50 and 2,000 cPs; between 90 and 100 cPs; or between 250 and 1,000 cPs.
• a method for preparing the material comprises (a) preparing a first liquid comprising the binder; (b) mixing the first liquid with the volatile component to generate a mixture; (c) casting the mixture onto a solid substrate; and (d) solidifying the mixture to generate the package material.
• no radiation is used.
• the solidifying step comprises drying with heat.
• the heat is applied at a
• the heat is applied at a temperature between 40 °C and 120 °C; between 60 °C and 100 °C; or between 80 °C and 1 10 °C.
• the solidifying step comprises drying with a stream of gas (for example air).
• a stream of gas for example air.
• the stream of gas is applied at a temperature between 10 °C and 120 °C; between 15 °C and 100 °C; or between 20 °C and 1 10 °C.
• the stream of gas is applied at a temperature between 40 °C and 120 °C; between 60 °C and 100 °C; or between 80 °C and 1 10 °C.
• the mixture has a viscosity greater than 100 cPs
• the mixture has a viscosity between 100 and 50,000 cPs; between 250 and 30,000 cPs; between 500 and 30,000 cPs; or between 500 and 50,000 cPs.
• the mixture has a viscosity greater than 90 cPs; greater than 100 cPs; greater than 250 cPs; or greater than 500 cPs. In other embodiment, the mixture has a viscosity between 50 and 2,000 cPs; between 90 and 100 cPs; or between 250 and 1,000 cPs.
• a material which is in the form of a coating on a packaging material In another aspect, provided is a material which is in the form of a sheet which is inserted into, onto, beneath, or adjacent to a packaging material. In another aspect, provided is a material which is in the form of a label which is adhered onto a packaging material. In another aspect, provided is a method of applying the material provided herein. The method comprises (a) inserting fresh produce into a package; (b) inserting the coated substrate, film, sheet, or label into, onto, beneath, or adjacent to the package; and (c) sealing or enclosing the package, thereby the material is exposed to high relative humidity generated by the fresh produce.
• the controlled release formulation / material / delivery system may include a volatile (liquid) component encapsulated within a film or coating.
• the film or coating has the following advantages: (1) retaining / encapsulating the volatile (liquid) component under dry conditions or conditions of moderate relative humidity (even when heated), and (2) releasing the volatile (liquid) component (in vapor form) on exposure to high relative humidity or moisture.
• the controlled release formulation / material / delivery system in the form of a coating or film uses a binder which is a good barrier to organic gasses at low / moderate relative humidity, resulting in little / no diffusion of the volatile component (for example volatile oil) out of the coating or film under typical ambient conditions.
• the high relative humidity inside fruit, vegetable, ornamental flower, meat, or cheese packaging (typically 90 %+) is used as a trigger to release the volatile component (for example volatile oil).
• the rate of release at high humidity can be adjusted by adjustment of the coating formulation.
• the embodiments provided provide the advantage to avoid substantial loss of the volatile component (for example volatile oil) during the drying process by use of a binder which is a good barrier to organic gasses at low / moderate relative humidity.
• a skin or top surface
• the skin or top surface
• the skin is impermeable to the volatile component (for example volatile oil), but permeable to water vapor. Hence the remainder of the water evaporates from the coating but the volatile component (for example volatile oil) remains trapped inside.
• Suitable compounds for the volatile component include aliphatic or aromatic compounds, including their acids, alcohols, aldehydes, esters, and ketones.
• the compound is a monoterpenoid or aliphatic structure up to 12 carbons in length.
• the compound is selected from the group consisting of allyl disulfide, allyl sulfide, amyl cinnamic aldehyde, a-phellandrene, amyl cinnamic aldehyde, amyl salicylate, anethole, iraws-anethole, anisic aldehyde, -anisaldehyde, benzaldehyde, benzyl acetate, benzyl alcohol, bergamot, bicyclogermacrene, borneol, bornyl acetate, 2- butene, a-butylene, D-cadinene, calamenene, a-campholenic aldehyde, camphor, ⁇ - caryophyllene, caryophyllene oxide, iraws-caryophyllene, carvacrol, carveol, 4- carvomenthenol, carvone, cineole
• composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
• Embodiments provided herein may include one or more polymer(s) listed herein.
• humidity-activated refers to that the volatile component is released as a vapor on exposure of the material to high humidity.
• high humidity includes 75 % to 100% relative humidity. In another embodiment, high humidity includes 60 % to 100% relative humidity.
• polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
• the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be
• the term "functionalized polymer,” as used herein, refers to a polymer that comprises, linked by a covalent bond, a chemical group (chemical substituent) comprising at least one heteroatom.
• a heteroatom is defined as an atom which is not carbon or hydrogen. Common heteroatoms are oxygen, nitrogen, sulfur, and phosphorus.
• the term "functional group,” as used herein, refers to a chemical substituent containing at least one heteroatom.
• a heteroatom is defined as an atom which is not carbon or hydrogen. Common heteroatoms include oxygen, nitrogen, sulfur, and phosphorus.
• perishable material refers to organic matter which can spoil or decay, or which has a decrease in activity of one or more of its active components over time.
• compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
• a cyclopropene compound is any compound with the formula where each 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.
• 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 groups that are suitable for use as one or more of R 1 , R 2 , R 3 , and R 4 are, for example, aliphatic groups, aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic groups, cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups, aryl groups, heteroaryl groups, halogens, silyl groups, other groups, and mixtures and combinations thereof.
• Groups that are suitable for use as one or more of R 1 , R 2 , R 3 , and R 4 may be substituted or unsubstituted.
• R 1 , R 2 , R 3 , and R 4 groups are, for example, aliphatic groups.
• suitable aliphatic groups include, for example, alkyl, alkenyl, and alkynyl groups.
• Suitable aliphatic groups may be linear, branched, cyclic, or a combination thereof.
• suitable aliphatic groups may be substituted or unsubstituted.
• 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.
• R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted heterocyclyl groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, or sulfonyl group; examples of such R 1 , R 2 , R 3 , and R 4 groups are heterocyclyloxy, heterocyclylcarbonyl,
• R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted heterocyclic groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, sulfonyl group, thioalkyl group, or aminosulfonyl group; examples of such R 1 , R 2 , R 3 , and R 4 groups are
• R 1 , R 2 , R 3 , and R 4 groups are, for example, 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, trimethylsilyl; and substituted analogs thereof.
• the chemical group G is a 3 to 14 membered ring system.
• Ring systems suitable as chemical group G may be substituted or unsubstituted; they may be aromatic (including, for example, phenyl and napthyl) or aliphatic (including unsaturated aliphatic, partially saturated aliphatic, or saturated aliphatic); and they may be carbocyclic or heterocyclic.
• heterocyclic G groups some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen, and combinations thereof.
• Ring systems suitable as chemical group G may be monocyclic, bicyclic, tricyclic, polycyclic, spiro, or fused; among suitable chemical group G ring systems that are bicyclic, tricyclic, or fused, the various rings in a single chemical group G may be all the same type or may be of two or more types (for example, an aromatic ring may be fused with an aliphatic ring).
• one or more of R 1 , R 2 , R 3 , and R 4 is hydro gen or (Ci-Cio) alkyl.
• each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (Ci-Cs) alkyl.
• each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (C1-C4) alkyl.
• each of R 1 , R 2 , R 3 , and R 4 is hydrogen or methyl.
• R 1 is (C1-C4) alkyl and each of R 2 , R 3 , and R 4 is hydrogen.
• 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-methylcyclopropene or "1-MCP.”
• cyclopropene is of the formula:
• R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
• R is C 1-8 alkyl. In another embodiment, R is methyl.
• cyclopropene is of the formula:
• R 1 is a substituted or unsubstituted C 1 -C 4 alkyl, C1-C4 alkenyl, C 1 -C 4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
• the cyclopropene comprises 1-methylcyclopropene (1-MCP).
• transgene vector refers to a vector that contains an inserted segment of DNA, the "transgene” that is transcribed into mRNA or replicated as RNA within a host cell.
• transgene refers not only to that portion of inserted DNA that is converted into RNA, but also those portions of the vector that are necessary for the transcription or replication of the RNA.
• a transgene typically comprises a gene-of- interest but needs not necessarily comprise a polynucleotide sequence that contains an open reading frame capable of producing a protein.
• Meats, plants, or plant parts, or dairy products may be treated in the practice of the present invention.
• One example is treatment of whole plants; another example is treatment of whole plants while they are planted in soil, prior to the harvesting of useful plant parts.
• Any plants that provide useful plant parts may be treated in the practice of the present invention. Examples include plants that provide fruits, vegetables, nursery crops, flowers and grains.
• plant includes dicotyledons plants and
• monocotyledons plants examples include tobacco, Arabidopsis, soybean, tomato, papaya, canola, sunflower, cotton, alfalfa, potato, grapevine, pigeon pea, pea, Brassica, chickpea, sugar beet, rapeseed, watermelon, melon, pepper, peanut, pumpkin, radish, spinach, squash, broccoli, cabbage, carrot, cauliflower, celery, Chinese cabbage, cucumber, eggplant, and lettuce.
• monocotyledons plants include corn, rice, wheat, sugarcane, barley, rye, sorghum, orchids, bamboo, banana, cattails, lilies, oat, onion, millet, and triticale.
• fruit examples include apple, avocado, banana, berries (including strawberry, blueberry, raspberry, blackberry, currents and other types of berries), carambola, cherry, citrus (including oranges, lemon, lime, mandarin, grapefruit, and other citrus), coconut, fig, grapes, guava, kiwifruit, mango, nectarine, melons (including cantaloupe, muskmelon, watermelon, and other melons), olive, papaya, passionfruit, peach, pear, persimmon, pineapple, plum, and pomegranate.
• Examples of vegetable include asparagus, beet (including sugar and fodder beet), beans, broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (sweet, bell or hot), potato, pumpkin, sweet potato, snap bean, squash, tomato and turnip.
• Examples of nursery plant or flower or flower part include roses, carnation, geranium, gerbera, lily, orchid, or other cut- flowers or ornamental flowers, flower bulbs, shrub, deciduous or coniferous tree
• Various embodiments provided are based on dispersion of the volatile (liquid) component in a binder which is a good barrier to organic gasses under conditions of low / moderate relative humidity, but a poor barrier to organic gasses under conditions of high relative humidity.
• the volatile (liquid) component comprises an essential oil / natural oil / plant extract with antimicrobial properties.
• the film / coating provided herein can be inserted inside packaging for fruit, vegetable, flower, or other plant parts, meat or cheese, to control mold or bacterial growth.
• volatile essential oils / natural oils / plant extracts referred to henceforth as "volatile oils" are known to delay the onset of mold growth and are currently used commercially in packaging applications.
• Suitable binders include water-soluble or water-dispersible binders for example polyvinyl alcohol (PVOH), where polyvinyl alcohol refers to fully or partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyvinylpyridine, polyvinylimidazole , polyvinylcaprolactam, polyethylene glycol, polypropylene glycol, functionalized cellulose such as cellulose containing methoxy functions, or hydroxyethyl or hydroxypropyl functions, polyhydroxyethyl(meth) aery late, polyethyleneimine, polyethylene-co-acrylic acid or salts thereof, poly(meth)acrylic acid or salts thereof, polystyrene sulfonic acid or salts thereof, polyethylene-co-vinyl alcohol (EVOH), or gums for example acacia gum. Copolymers of these polymers with other monomeric units may be suitable binders as well.
• PVOH polyvinyl alcohol
• a suitable binder for various embodiments provided herein includes polyvinyl alcohol, as it is a good barrier to organic gasses when dry and a poor barrier when exposed to high relative humidity.
• polyvinyl alcohol is used with a hydrolysis degree between 55% and 100%; or between 65% and 99%.
• Suitable volatile oils for various embodiments provided herein include non-water- soluble liquid substances which can form (with optional aid of a dispersant) a stable emulsion in an aqueous solution of the binder.
• a fluid is "non-aqueous" if it contains, by weight based on the weight of the fluid, 10 % water or less.
• a liquid that has high viscosity is a composition that is liquid at 25°C and that has viscosity at 25 °C at shear rate of 0.01 sec "1 of 10 Pa * s (10 Poise) or more.
• the solution provided may have a viscosity of from about 100 to about 50,000 centiPoise; or 500 to 30,000 centiPoise. Below the preferred viscosity, the dispersed oil droplets are thought to migrate rapidly to the surface of the coating while drying and hence escape to the atmosphere during the drying process.
• the coating is dried under a stream of gas, preferably air, in order to rapidly form an impermeable skin on the surface of the coating.
• Various embodiments provided herein are in the form of a sheet (coated substrate or free-standing film) or a label, which is inserted into a package or a pallet, or a coating on the inside or outside surface of the packaging material.
• the package can be a small consumer-size package, a bulk bag, a box, or a pallet wrap.
• the white mixture CI is cast onto a PET substrate at a wet thickness of 254 microns, and then dried to produce Formulation D 1.
• the strips of coating are then placed inside GC headspace vials (20 mL). In some cases a droplet of water (0.10 mL) is added to the bottom of the vial (avoiding contact with the strip) before the vial is sealed, in order to generate an atmosphere of 100% relative humidity (RH).
• the vials are then allowed to equilibrate for at least 10 hours before placing in an Agilent GC for analysis of the concentration of 1-hexanol in the headspace.
• a vial containing pure 1-hexanol (0.50 mL) is used as reference.
• the reference vial is assumed to create a saturated concentration of 1224 ppm of 1-hexanol in the headspace (calculated from known vapor pressure of 0.124 kPa at 25 °C).
• the white mixture C2 is cast onto a PET substrate at a wet thickness of 254 microns, and dried according to produce Formulation D2.
• Example 2 A similar headspace analysis as in Example 1 is performed, and 1-hexanol detected in the headspaces of the vials from Formulation D2 are shown in Table 2.
• Results from Examples 1 and 2 indicate that a combination of relatively high viscosity coating solution and drying under a stream of air is needed in order to encapsulate the 1-hexanol inside the PVOH film.
• 1-hexanol is not released under ambient relative humidity, but significant amounts are released at about or close to 100% relative humidity at ambient temperature (20-25 °C).
• a mixture C3 is made and cast onto a PET substrate to produce Formulation D3 [PVOH/l-hexanol/sds] in a similar manner as in Example 1, except a stronger air-stream was used for drying the coatings than in Examples 1 and 2.
• the dried coating on PET is cut into strips of approximately 7 cm 2 and then the coating is peeled off each strip and placed in an oven at 80 °C for 15 minutes in order to remove any non-encapsulated 1-hexanol.
• the delaminated strips of coating are then placed inside GC headspace vials.
• the GC headspace vials contained small vessels containing different saturated salt solutions (about 0.15 mL) in order to control the relative humidity inside the GC vials.
• the theoretical relative humidities generated by the saturated aqueous salt solutions at 20 °C are shown in Table 3.
• the salts used to generate the different relative humidities are: LiCl gives 1 1% RH; MgCi 2 gives 33% RH; K 2 C0 3 gives 43% RH; Mg(N0 3 ) 2 gives 54% RH; NaBr gives 58% RH (at 25 °C); KI gives 69% RH (at 25°C); NaCl gives 76% RH; and K 2 S0 4 gives 98% RH.
• the vials are left to stand at 20 °C for 13-17 hours, and then the concentration of 1-hexanol in the headspace is analyzed by Agilent GC. Mixture C3 also has a viscosity of about 983 cPs.
• a vial containing pure 1-hexanol (0.50 mL) is used as reference.
• the reference vial is assumed to create a saturated concentration of 1224 ppm of 1-hexanol in the headspace (calculated from known vapor pressure of 0.124 kPa at 25 °C).
• concentrations of 1- hexanol found in the headspaces of the vials for Formulation D3 are shown in Table 3.
• a mixture C4 is made and cast onto a PET substrate to produce Formulation D3 [PVOH/l-hexanol/sds] in a similar manner as in Example 1, except a stronger air-stream was used for drying the coatings than in Examples 1 and 2.
• the dried coating on PET is cut into strips of approximately 7 cm 2 and then the coating is peeled off each strip and placed in an oven at 80 °C for 15 minutes in order to remove any non-encapsulated 1-hexanol.
• the delaminated strips of coating are then placed inside GC headspace vials.
• the GC headspace vials contained small vessels containing saturated aqueous solutions of KN0 3 (about 1.5 mL) which theoretically generated an atmosphere of 95% relative humidity inside the vials.
• headspace samples are injected into the Agilent GC for analysis of concentration of 1-hexanol.
• a vial containing pure 1-hexanol (0.50 mL) is used as reference.
• the reference vial was assumed to create a saturated concentration of 1224 ppm of 1-hexanol in the headspace (calculated from known vapor pressure of 0.124 kPa at 25 °C).
• the results of headspace analysis are shown in Table 4, indicating the rapid rate of release of 1-hexanol from the delaminated strip of coating at a relative humidity of 95% at ambient temperature (20-25 °C).
• 0.0583g sodium dodecyl sulfate (SDS) is added into 5.0g DI water. The mixture is stirred on a magnetic stirrer until the SDS is dissolved. To the solution of SDS in water is added 11.667 g 1-hexanol, trans-2-hexenal, or guaiacol (the “actives") drop-wise, under rapid stirring to form a white emulsion (70 weight % 1-hexanol, iraws-2 -hexenal, or guaiacol in water). The resultant emulsion is then added to the cooled solution of PVOH in the beaker and the resultant mixture stirred mechanically for 5 minutes.
• SDS sodium dodecyl sulfate
• a headspace sample is then removed by syringe for injection into the GC column. Quantification of active is done by comparing to a calibration curve of "GC Peak Area of Headspace sample” vs. "Concentration of 1-hexanol, iraws-2-hexenal, or guaiacol in solution” generated with samples of known concentrations of active compound dissolved in DI water in GC vials (after leaving at least 10 hours for equilibration).
• Results are shown in Table 5. Incorporation of 1-hexanol, iraws-2-hexenal, and guaiacol is shown as a percentage relative to the maximum theoretical incorporation based on the amount added to the coating solution, assuming no losses due to evaporation (25 wt. % of active), where it can be seen from the data that the PVOH based strips contain high levels of incorporated volatile liquid.
• a strip of approximately 13.6cm 2 is cut from the middle of the coated PET sheet. The coating is peeled off the PET backer and then placed in a petri-dish in a fume-hood overnight to allow any residual non-encapsulated active to evaporate.
• a GC vial, 20 mL, with a screw- on septum-cap is prepared at 95 % humidity by adding a mini plastic ultracentrifuge vial with the cap cut off containing approximately 0.20 g of saturated potassium nitrate (KNO 3 ) solution, with a few grains of solid KNO 3 added to maintain saturation.
• KNO 3 saturated potassium nitrate
• the strip of coating is added to the GC vial, and the vial immediately sealed.
• a headspace sample is removed by syringe for injection into the GC column.
• the concentration in the Headspace is determined by comparing the GC Peak Area of the sample to the GC Peak Area of the headspace from a vial containing 0.5 mL of pure trans-2-hexenal, or guaiacol. The known vapor pressures of these compounds at room temperature can be used to calculate the saturated headspace concentration for these reference samples (8685, and 145 ppm (V/V) respectively).
• Results for trans -2-hexenal are shown in Table 6, and results for guaiacol are shown in Table 7. It can be seen from the data that the strips containing iraws-2-hexenal, and guaiacol, rapidly release the active compound to achieve headspace saturation levels in the GC vial on exposure to 95 % relative humidity.

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