WO2016170531A1 - Microcapsules à noyau liquide et solide formées par complexation interpolymérique - Google Patents

Microcapsules à noyau liquide et solide formées par complexation interpolymérique Download PDF

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Publication number
WO2016170531A1
WO2016170531A1 PCT/IL2016/050407 IL2016050407W WO2016170531A1 WO 2016170531 A1 WO2016170531 A1 WO 2016170531A1 IL 2016050407 W IL2016050407 W IL 2016050407W WO 2016170531 A1 WO2016170531 A1 WO 2016170531A1
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Prior art keywords
oil
polymer
microcapsule
polyacid
microcapsules
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PCT/IL2016/050407
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English (en)
Inventor
Charles Linder
Avishay Pelah
Rafael ISCHAKOV
Arie Markus
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Botanocap Ltd.
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Publication of WO2016170531A1 publication Critical patent/WO2016170531A1/fr

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    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N25/26—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 in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/22—Lamiaceae or Labiatae [Mint family], e.g. thyme, rosemary, skullcap, selfheal, lavender, perilla, pennyroyal, peppermint or spearmint
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3472—Compounds of undetermined constitution obtained from animals or plants
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention provides microcapsules having shells made of interpolymeric complexes encapsulating an essential oil or an essential oil derivative, and compositions comprising same.
  • US Patent Application Publication No. 2007/0042182 discloses a process for preparation of essential oil microcapsules comprising dissolving a di- or polyisocyanate into an essential oil, emulsifying the resulting mixture in an aqueous solution containing a di- or polyamine, and or a di or polyhydroxy compound to effect encapsulation of the essential oil through interfacial polymerization, thereby forming a polyurea and/or polyurethane film around the essential oil droplets which film enhances the stability of said essential oil, reduces its evaporation rate and controls its release rate when applied to a substrate.
  • US Patent Application Publication No. 2008/0166415 also by some of the inventors of the present invention, discloses formulations comprising at least one encapsulated volatile essential oil and a non-volatile vehicle in which the at least one encapsulated volatile essential oil is carried.
  • US Patent Application Publication No. 2009/0186096 discloses methods for preparation of microencapsulated essential oils for use in various non-agricultural applications.
  • US Patent Application Publication No. 2011/0268780 discloses microcapsules containing a solid core including at least one essential oil mixed with a porous solid material, where the solid core is coated by at least one layer of a polyurea film and/or a polyurethane film or an amphipathic shell composed of a multivalent salt form of at least one alkanoic acid.
  • WO2004/034791 discloses a composition for the controlled release of an essential oil having pesticidal or fungicidal activity comprising a carrier material for the essential oil and a component that controls the release of the essential oil from the carrier material.
  • a carrier material for the essential oil
  • a component that controls the release of the essential oil from the carrier material comprises free-flowing powders wherein the carrier material is an absorbing support material and the release controlling means is selected from wax, polyethylene glycol, glycerol or mineral oil.
  • the other embodiment comprises capsules comprising a core material of oil, which is coated with a protein (preferably gelatin), a carbohydrate or a synthetic polymer.
  • the present invention provides microcapsules comprising: a core comprising at least one active agent selected from the group consisting of an essential oil or derivative thereof, a fragrance and a perfume, and a shell encapsulating said core, said shell comprising an interpolymeric complex of at least one first polymer and at least one second polymer.
  • the first polymer is a polyacid.
  • the polyacid is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid and copolymers, polymethacrylic acids and co-polymers, polymaleic anhydride co-polymers, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof.
  • the polyacid comprises alginic acid.
  • the polyacid is alginic acid.
  • the first polymer is a naturally occurring product.
  • the second polymer is a synthetic polymer.
  • the first and second polymers form an interpolymeric complex, which is subsequently further cross-linked with at least one multivalent cationic moiety.
  • the at least one second polymer is dissolved or dispersed within the essential oil or oil component.
  • the second polymer is a synthetic polymer.
  • the second polymer, dissolved in the essential oil or oil component is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof.
  • the second polymer comprises a PEG/PPG block copolymer.
  • the second polymer is a PEG/PPG block copolymer.
  • the second polymer comprises a PVP block homo- or co-polymer.
  • microcapsules and compositions comprising same disclosed herein possess high stability and prolonged shelf life. They include only starting materials classified as non-toxic and preferably ingredients classified as organic, green or GRAS, and environmentally friendly, including but not limited to materials that protect the environment and/or replaces environmentally harmful and toxic artificial synthetic active ingredients with safe to use and or natural ones.
  • the microcapsules and compositions comprising same are suitable for agricultural and domestic uses as insect repellants, pesticides, antimicrobials and insecticides.
  • the microcapsules are nano-sized and enable formation of transparent suspensions with an appearance similar to self-emulsifying micro- emulsions.
  • the microcapsules suitable for use as additives in food and/or beverages have an average particle size of below 300nm, below 200 nm or below 100 nm. Each possibility is a separate embodiment.
  • the present invention provides a microcapsule comprising: a core comprising at least one essential oil or a derivative thereof and a shell encapsulating the core, the shell comprising an interpolymeric complex of at least one polyacid (first polymer) and at least one second polymer; wherein the interpolymeric complex is further cross-linked with at least one multivalent cationic moiety; wherein the at least one second polymer is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof; wherein the polyacid is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid and co-polymers, polymethacrylic acids and co-polymers, polymale
  • the microcapsule has an average diameter of less than 100 microns, for example, when used in applications requiring spraying of aqueous formulations.
  • the microcapsule have an average particle size of about 200nm.
  • the microcapsule have an average particle size of about 300nm.
  • the microcapsule have an average particle size of about 100nm-300nm.
  • the microcapsule have an average particle size of about 100nm-500nm.
  • the microcapsule have an average particle size of about 50nm-250nm.
  • the microcapsule have a particle size varying from 50 to 2000 nm.
  • the microcapsule have a particle size varying from 10 to 1000 nm.
  • the size distribution of the microcapsules may be determined using standard techniques including sieve analysis, air elutriation analysis, photoanalysis, optical counting, electroresi stance counting methods, sedimentation techniques, laser diffraction, laser obscuration time (LOT), acoustic spectroscopy, dynamic light scattering, static light scattering, Scanning Electron Microscopy (SEM) or any other suitable method for determining particle size.
  • standard techniques including sieve analysis, air elutriation analysis, photoanalysis, optical counting, electroresi stance counting methods, sedimentation techniques, laser diffraction, laser obscuration time (LOT), acoustic spectroscopy, dynamic light scattering, static light scattering, Scanning Electron Microscopy (SEM) or any other suitable method for determining particle size.
  • SEM Scanning Electron Microscopy
  • the present invention provides a microcapsule consisting essentially of: a core comprising at least one essential oil or derivative thereof and a shell encapsulating the core, the shell comprising an interpolymeric complex of at least one polyacid (first polymer) and at least one (second) polymer; wherein the interpolymeric complex between the polyacid and the polymer (the first and second polymers) is cross- linked with at least one multivalent cationic moiety.
  • the polymer is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof.
  • the polymer comprises a PEP/PPG block co-polymer.
  • the polymer comprises PVP or a PVP block homo- or co-polymer.
  • the polymer is a PEP/PPG block co-polymer.
  • the polyacid (first polymer) is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid and its co-polymers, polymethacrylic acid and its co-polymers, polymaleic anhydride co-polymers, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof.
  • the polyacid comprises alginic acid.
  • the polyacid is alginic acid.
  • the microcapsule has an average diameter of less than 500 microns.
  • the microcapsule has an average diameter of less than 400 microns. According to some embodiments, the microcapsule has an average diameter of less than 300 microns. According to some embodiments, the microcapsule has an average diameter of less than 200 microns. According to some embodiments, the microcapsule is configured for use in applications requiring spraying of aqueous formulations. Larger dimensions and shapes deviating from spherical shapes are also available for other applications not requiring spraying, such as packaging in porous containers or sachets.
  • the at least one multivalent cationic moiety is selected from the group consisting of Ca 2+ , Mg 2+ , Fe 2+ , Fe 3+ , Zn 2+ , Al 3+ or combinations thereof.
  • the interpolymeric complex can be crosslinked by adding poly- quaternary-ammonium organic compounds or a polyamine, such as polyethyleneamine or cationic polysaccharides, including but not limited to chitosan.
  • the interpolymeric complex may be cross-linked with a poly-quaternary-ammonium organic compounds or a polyamine. According to some embodiments, the interpolymeric complex may be cross-linked with a poly-quaternary-ammonium organic compounds or a polyamine and with a cationic moiety.
  • the poly-quaternary-ammonium organic compound is chitosan.
  • the chitosan is further crosslinked with tripolyphosphate (TPP).
  • TPP tripolyphosphate
  • the shell increases the stability and/or prolongs the release rate of the essential oil or the essential oil derivative.
  • the second polymer is a block co-polymer comprising hydrophobic and hydrophilic blocks.
  • the ratio between the hydrophobic and hydrophilic blocks is in the range of 1 :9 to 9: 1. According to some embodiments, the ratio between the hydrophobic and hydrophilic blocks is in the range of 1 : 1 to 8: 1. According to some embodiments, the ratio between the hydrophobic and hydrophilic blocks is in the range of 1.5: 1 to 3: 1. According to some embodiments, the ratio between the hydrophobic and hydrophilic blocks is in the range of 1.5: 1 to 4: 1.
  • the microcapsule comprising at least two (second) polymers, wherein said (second) polymers are block co-polymers.
  • the at least two second polymers comprise a hydrophobic block co-polymer and a hydrophilic block co-polymer.
  • the core is liquid. According to some embodiments, the core is solid. According to some embodiments, the solid core comprises a porous solid material in which said essential oil is absorbed.
  • the porous material is selected from the group consisting of: cellulosics, starch powders, AEROSIL®, silicas or combinations thereof.
  • the essential oil is selected from the group consisting of anise oil, basil oil, camphor oil, caraway oil, cardamom oil, chamomile oil, cinnamon oil, citronella oil, cedar oil, clove oil, coriander oil, cumin oil, dill oil, eucalyptus oil, fennel oil, garlic oil, geranium oil, ginger oil, grapefruit oil, lavender oil, lemon grass oil, lemon oil, mandarin oil, mint oil, mustard oil, neem oil, onion oil, orange oil, oregano oil, parsley oil, pennyroyal oil, pepper oil, peppermint oil, pine needle oil, rose oil, rosemary oil, sesame oil, spearmint oil, sweet orange oil, tagetes oil, tangerine oil, tea tree oil, tea seed oil, thyme oil, turmeric oil, wintergreen oil and combinations thereof.
  • the encapsulated oil is a component of the essential oil, such as carvacrol (a component of oregano
  • the essential oil is an essential oil derivative.
  • the essential oil derivative is selected from the group consisting of: alpha-terpineol, cinnamaldehyde, methyl salicylate, anisic aldehyde, carvacrol, carveol, citral, citronellal, citronellol, eucalyptol (cineole), eugenol, isoeugenol, geraniol, guaiacol, vetiver , limonene, menthol, methyl anthranilate, ionone, phellandrene, perillaldehyde, phenyl ethyl alcohol, phenyl ethyl propionate, piperonal, pulegone, terpinen- 4-ol, terpinyl acetate, 4-tert butyl cyclohexyl acetate, thymol, p-cymen
  • the encapsulating shell is water insoluble According to some embodiments, the encapsulating shell may swell to different extents depending on its composition.
  • the ratio of the at least one (second) polymer and the at least one polyacid (first polymer) is in the range of 10: 1 to 1 : 1. According to some embodiments, the ratio of the at least one (second) polymer and the at least one polyacid (first polymer) is in the range of 10: 1 to 5: 1. According to some embodiments, the ratio of the at least one (second) polymer and the at least one polyacid (first polymer) is in the range of 5: 1 to 1 : 10. According to some embodiments, the ratio of the at least one (second) polymer and the at least one polyacid (first polymer) is in the range of 2: 1 to 1 :5. According to some embodiments, the ratio of the at least one (second) polymer and the at least one polyacid (first polymer) is in the range of 1 : 1 to 1 :5.
  • the ratio of the at least one (second) polymer and the at least one essential oil is in the range of 5: 1 to 1 :5. According to some embodiments, the ratio of the at least one (second) polymer and the at least one essential oil is in the range of 2: 1 to 1 :5. According to some embodiments, the ratio of the at least one (second) polymer and the at least one essential oil is in the range of 1 : 1 to 1 :5. According to some embodiments, the ratio of the at least one (second) polymer and the at least one essential oil is in the range of 1 : 1 to 1 :2.
  • the microcapsules have an average diameter of less than 1000 micron. According to some embodiments, the microcapsules have an average diameter of less than 500 micron. According to some embodiments, the microcapsule has an average diameter of less than 400 microns. According to some embodiments, the microcapsules have an average diameter of less than 300 micron. According to some embodiments, the microcapsules have an average diameter of less than 100 micron. According to some embodiments, the microcapsules have an average diameter of less than 50 micron. According to some embodiments, the microcapsules have an average diameter of less than 1 micron. According to some embodiments, the microcapsules have an average diameter of less than 200 nanometers. According to some embodiments, the microcapsules have an average diameter of less than 100 nanometers.
  • the present invention provides a composition comprising a plurality of the microcapsules, disclosed herein, and an aqueous carrier. According to further embodiments, the present invention provides a composition consisting essentially of a plurality of the microcapsules of the present inventions and an aqueous carrier.
  • the composition further comprises an agent selected from the group consisting of: antifungal agents, bactericides, antiviral agents, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, and combinations thereof.
  • agent selected from the group consisting of: antifungal agents, bactericides, antiviral agents, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, and combinations thereof.
  • the agent is co-encapsulated with the at least one essential oil. According to some embodiments, the agent is separately encapsulated. According to some embodiments, the agent is non-encapsulated. According to some embodiments, the composition further comprises at least one additive selected from the group consisting of an antioxidant, a UV protector, a stabilizer, a preservative and combinations thereof.
  • the composition is for use as a food additive and/or supplement.
  • the present invention provides a method for producing a suspension of microcapsules, the method comprising: (a) mixing at least one (second) polymer, into at least one essential oil or derivative thereof, wherein the (second) polymer is selected from the group consisting of a polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof wherein the co-polymer may be random, alternating or a block co-polymer, to obtain a first mixture; (b) mixing at least one polyacid (first polymer) with an aqueous solution, wherein the at least one polyacid is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate,
  • the at least one polyacid comprises alginic acid. According to some embodiments, the at least one polyacid is alginic acid.
  • the second polymer comprises a PEG/PPG block co-polymer. According to some embodiments, the second polymer is a PEG/PPG block co-polymer.
  • the at least one multivalent cationic moiety is selected from the group consisting of Ca , Mg , Fe , Fe ' Zn , Al or combinations thereof.
  • the interpolymeric complex can be crosslinked by adding a poly- quaternary-ammonium organic compound or a polyamine, such as a polyethyleneamine or a cationic polysaccharide, including but not limited to chitosan.
  • the interpolymeric complex is further cross-linked with a poly-quaternary-ammonium organic compounds or a polyamine.
  • the poly-quaternary-ammonium organic compound is chitosan.
  • the chitosan is further crosslinked with tripolyphosphate (TPP).
  • the method further comprises filtering said suspension to obtain a plurality of isolated microcapsules.
  • the method further comprises adding at least one surfactant (e.g. Tween 80), and or polymer stabilizer (e.g. xanthan gum) to obtain a homogenous suspension.
  • at least one surfactant e.g. Tween 80
  • polymer stabilizer e.g. xanthan gum
  • step (a) comprises mixing said at least one (second) polymer, with said at least one essential oils and an additional agent, wherein the additional agent is selected from the group consisting of: antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), larvicides, and combinations thereof.
  • additional agent is selected from the group consisting of: antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), larvicides, and combinations thereof.
  • the aqueous solution has a pH of less than 7.
  • the concentration of the polyacid in the aqueous solution is in the range of 0.2% to 10% by weight. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.5% to 5%. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.3% to 2.5%.
  • the present invention provides a method for producing liquid core microcapsules, the method comprising: a. mixing at least one (second) polymer, into at least one essential oil or derivative thereof; wherein the (second) polymer is selected from the group consisting of a polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof, wherein the co-polymer may be random, alternating or a block co-polymer;
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PVP polyvinylpyrrolidone
  • aqueous solution comprising at least one polyacid, the polyacid selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid, polyacrylic acid co-polymers, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof; thereby obtaining microcapsules comprising a liquid core comprising an essential oil or a derivative thereof, , the shell comprising an interpolymeric complex of the at least one polyacid and the at least one (second) polymer; and
  • step c adding at least one salt comprising a multivalent ion to the microcapsules obtained in step c; thereby crosslinking the interpolymeric complex with the at least one multivalent cationic moiety.
  • the present invention provides a method for producing solid core microcapsules, the method consisting essentially of: a. mixing at least one (second) polymer, into at least one essential oils or derivative thereof, wherein the (second) polymer is selected from the group consisting of a polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof, wherein the co-polymer may be random, alternating or a block co-polymer;
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PVP polyvinylpyrrolidone
  • aqueous solution comprising at least one polyacid, the polyacid selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid, polyacrylic acid co-polymers, polymethacrylic acid and copolymers of polymethacrilic acid, co-polymers of maleic anhydride in the maleic acid state, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof; thereby obtaining microcapsules comprising a core comprising an essential oil or derivative thereof adsorbed in a porous material, and a shell encapsulating the core, the shell comprising an interpolymeric complex of the at least one polyacid and the at least one (second) polymer; and
  • step c adding at least one salt comprising a multivalent ion to the microcapsules obtained in step c; thereby crosslinking the interpolymeric complex with the at least one multivalent cationic moiety.
  • the method may include cross-linking the interpolymeric complex with a poly-quaternary-ammonium organic compounds or a polyamine.
  • the method may further include cross-linking the poly-quaternary-ammonium organic compound with chitosan.
  • the chitosan is further crosslinked with tripolyphosphate (TPP).
  • TPP tripolyphosphate
  • the multivalent cationic moiety is selected from the group consisting of Ca , Mg , Fe , Fe , Zn , Al or combinations thereof.
  • the interpolymeric complex can be crosslinked by adding a poly-quaternary-ammonium organic compound or a polyamine, such as a polyethyleneamine or a cationic polysaccharide, including but not limited to chitosan.
  • the porous material is selected from the group consisting of: cellulosics starch powders, AEROSIL®, silicas or combinations thereof.
  • the aqueous solution has a pH of less than 7. According to some embodiments, the aqueous solution has a pH of less than 6.
  • the concentration of the polyacid in the aqueous solution is in the range of 0.2% to 20% by weight. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.3% to 5%. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.5% to 5%. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.3% to 2.5%.
  • the present invention provides a method of inhibiting post-harvest infections in crop, the method comprising applying the microcapsules on, or in vicinity of, the crop, prior to harvesting, thereby inhibiting post-harvest infection of the crop.
  • the present invention provides a microcapsule comprising a core comprising at least one essential oil or a derivative thereof; and a shell encapsulating the core, the shell comprising an interpolymeric complex of at least one polyacid and at least one second polymer; wherein the interpolymeric complex is cross-linked with at least one multivalent cationic moiety and with a poly-quaternary-ammonium organic compounds or a polyamine; wherein the at least one second polymer is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co- polymers thereof; wherein the at least one polyacid is selected from the group consisting of: alginic acid, agaropectin, alginate, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid, pectin,
  • the poly-quaternary-ammonium organic compound is chitosan.
  • the chitosan is further crosslinked with tripolyphosphate (TPP).
  • TPP tripolyphosphate
  • the essential oil is selected from the group consisting of anise oil, basil oil, camphor oil, caraway oil, cardamom oil, chamomile oil, cinnamon oil, citronella oil, cedar oil, clove oil, coriander oil, cumin oil, dill oil, eucalyptus oil, fennel oil, garlic oil, geranium oil, ginger oil, grapefruit oil, lavender oil, lemon grass oil, lemon oil, mandarin oil, mint oil, mustard oil, onion oil, orange oil, oregano oil, parsley oil, pepper oil, peppermint oil, pine needle oil, rose oil, rosemary oil, sesame oil, spearmint oil, sweet orange oil, tangerine oil, tea tree oil, tea seed oil, thyme oil, turmeric oil, wintergreen oil and combinations thereof.
  • the essential oil derivative is selected from the group consisting of alpha-terpineol, cinnamaldehyde, methyl salicylate, anisic aldehyde, carvacrol, carveol, citral, citronellal, citronellol, eucalyptol (cineole), eugenol, isoeugenol, geraniol, guaiacol, vetiver, limonene, menthol, methyl anthranilate, ionone, phellandrene, perillaldehyde, phenyl ethyl alcohol, phenyl ethyl propionate, piperonal, pulegone, terpinen- 4-ol, terpinyl acetate, 4-tert butyl cyclohexyl acetate, thymol and combinations thereof
  • the ratio of the at least one second polymer and the at least one polyacid is in the range of 10: 1 to 1 : 1. According to some embodiments, the ratio of the at least one essential oil and the at least one second polymer is in the range of 10: 1 to 5: 1.
  • the microcapsule has an average diameter of less than 300 microns. According to some embodiments, the microcapsule has an average diameter of about 200 microns.
  • the at least one second polymer comprises a PEG/PPG block co-polymer. According to some embodiments, the at least one second polymer comprises PVP or a PVP block homo- or co-polymer. According to some embodiments, the polyacid comprises alginic acid.
  • FIG. 1 shows a representative release profile of carvone from the microcapsules disclosed herein as compared to a non-encapsulated control.
  • FIG. 2 is a representative SEM image of the microcapsules. DETAILED DESCRIPTION
  • a microcapsule having a core comprising at least one active ingredient and a shell encapsulating the core.
  • the shell comprises an interpolymeric complex of at least one polyacid (first polymer) and at least one (second) polymer.
  • the (second) polymer is capable of forming secondary interaction bonds, such as polar or hydrogen or ionic bonding interactions, with the polyacids.
  • the interpolymeric complex may be formed via polar and/or hydrogen bond or ionic interactions between the polyacids and the (second) polymers, on the surface of the oil- containing core.
  • the term "core” refers to the part of the microcapsule being encapsulated within the outer shell structure.
  • the core is liquid.
  • the core may be a solid core.
  • the solid core includes a porous solid material in which the active ingredient is absorbed. Suitable solid porous materials include, but are not limited to cellulosics, starch powders, Aerosil®, silicas or combinations thereof. Each possibility is a separate embodiment of the invention.
  • interpolymeric complex refers to non-covalent interactions, formed between polymers, such as but not limited to hydrogen bonds, polar, ionic and/or Van der Waals interactions.
  • the polyacid may serve as an acceptor polymer.
  • the term “complexation” refers to the process of forming non-covalent interactions between polymers, such as hydrogen bonds and polar, ionic and/or Van der Waals interactions.
  • the at least one active ingredient is an essential oil or a derivative thereof.
  • essential oil and “volatile oil” may be used interchangeably and refer to concentrated, usually hydrophobic liquid containing volatile aroma compounds.
  • the essential oil may be extracted from a plant.
  • An oil is “essential” in the sense that it carries a distinctive scent, or essence, of the plant.
  • the composition comprises a botanical oil.
  • botanical oil refers to oils extracted from plant material. Botanical oils may be volatile or non-volatile and include but are not limited to essential oils.
  • hydrophobic liquid refers to an active ingredient having an experimental LogP value (wherein P is the octanol water partition coefficient) of at least 1.2, at least 1.5, at least 2. Each possibility is a separate embodiment.
  • the encapsulated active ingredient (such as the essential oil) encompasses 5% to 95% of the liquid core microcapsule. According to some embodiments, the encapsulated active ingredient encompasses 10% to 90% of the liquid core microcapsule. According to some embodiments, the encapsulated active ingredient encompasses 20% to 90% of the liquid core microcapsule. According to some embodiments, the encapsulated active ingredient encompasses 5% to 70% of the porous solid core microcapsules. According to some embodiments, the encapsulated essential oil encompasses 10%) to 60%) of the porous solid core microcapsules.
  • the active ingredient is an essential oil selected from the group consisting of anise oil, basil oil, camphor oil, caraway oil, cardamom oil, chamomile oil, cinnamon oil, citronella oil, cedar oil, clove oil, coriander oil, cumin oil, dill oil, eucalyptus oil, fennel oil, garlic oil, geranium oil, ginger oil, grapefruit oil, lavender oil, lemon oil, lemon grass oil, mandarin oil, mint oil, mustard oil, neem oil, onion oil, orange oil, oregano oil, parsley oil, pennyroyal oil, pepper oil, peppermint oil, pine needle oil, rose oil, rosemary oil, sesame oil, spearmint oil, sweet orange oil, tagetes oil, tangerine oil, tea tree oil, tea seed oil, thyme oil, turmeric oil, wintergreen oil and combinations thereof.
  • an essential oil selected from the group consisting of anise oil, basil oil, camphor oil, caraway oil, cardamom oil,
  • the essential oil is an essential oil derivative.
  • essential oil derivative may refer to one or more components derived from an essential oil.
  • the derivative may include a mixture of derivatives derived from more than one essential oil.
  • the derivative may be a natural component extracted from or otherwise derived from one or more essential oils.
  • the essential oil derivative may include one or more synthetic components mimicking components of the essential oil.
  • the essential oil derivative is in a liquid form.
  • the essential oil derivative is in a solid form.
  • the essential oil derivative when it is in a solid form, it may be dissolved in a solvent, such as but not limited to an oil, prior to being encapsulated.
  • the solvent may be an essential oil.
  • the essential oil, serving as a solvent may be the same or different from the essential oil from which the derivate is derived.
  • the essential oil derivative comprises at least two essential oil derivatives obtained from one or more essential oil.
  • the derivative may include thymol and carvacrol at an optimal ratio.
  • Non-limiting examples of suitable, derivatives include: alpha-terpineol, cinnamaldehyde, methyl salicylate, anisic aldehyde, carvacrol, carveol, citral, citronellal, citronellol, eucalyptol (cineole), eugenol, isoeugenol, geraniol, guaiacol, vetiver , limonene, menthol, methyl anthranilate, ionone, phellandrene, perillaldehyde, phenyl ethyl alcohol, phenyl ethyl propionate, piperonal, pulegone, terpinen-4-ol, terpinyl acetate, 4-tert butyl cyclohexyl acetate, thymol or any combination thereof.
  • Each possibility is a separate embodiment.
  • the at least one active ingredient is selected from the groups consisting of: fragrances, pheromones, nutrients, antimicrobials, pesticides, insecticides and combination thereof. Each possibility is a separate embodiment.
  • the active ingredient may optionally be dissolved in another oil, such as, but not limited to an essential oil or other oils with similar, medium or low volatility.
  • the active ingredient is a fragrance.
  • fragrance may interchangeably refer to chemical compounds that have a smell or odor and having a high vapor pressure (at atmospheric pressure and ambient temperature) for them to be sufficiently volatile to be transported to the olfactory system in the upper part of the nose.
  • molecules meeting this specification have molecular weights of ⁇ 300 g/mol.
  • the fragrances are liquid at ambient temperature, but with a relatively high vapor pressure, such as a vapor pressure of 12000 ng/L to 130000 ng/L.
  • the fragrances used herein may be classified according to the scent they produce, such as but limited to “chypre”, “citrus”, “floral”, “fruity”, “herbal”, “honey”, “jasmine”, “lemon”, “lilac”, “lily of the valley”, “musk”, “orange”, “oriental”, “peach”, “rose”, “spicy”, “watermelon” and “woody.
  • scent they produce such as but limited to "chypre", “citrus”, “floral”, “fruity”, “herbal”, “honey”, “jasmine”, “lemon”, “lilac”, “lily of the valley”, “musk”, “orange”, “oriental”, “peach”, “rose”, “spicy”, “watermelon” and “woody.
  • the fragrance is a naturally occurring plant or animal oil or mixtures thereof.
  • the fragrance may be synthetic.
  • Fragrances useful for the present invention can be a single aroma chemical, relatively simple in its composition, or can comprise highly sophisticated, complex mixtures of natural and synthetic chemical components, chosen to provide a desired odor.
  • Non-limiting examples of natural fragrances are extracts of flowers (such as but not limited to lily, lavender, rose, jasmine, neroli and ylang-ylang), stem and leaves (such as but not limited to geranium, patchouli and petitgrain), fruits (such as but not limited to anise, coriander, caraway and juniper), fruit rinds (such as but not limited to bergamot, lemon and orange), roots (such as but not limited to mace, angelica, celery, cardamom, costus, iris and thyme), needles and twigs (such as but not limited to spruce, fir, pine and mountain pine), and resins and balsams (such as but not limited to galbanum, elemi, benzoin, myrrh, frankincense and opoponax) or any combination or derivative thereof.
  • flowers such as but not limited to lily, lavender, rose, jasmine, neroli and ylang-ylang
  • Essential oils of low volatility are also suitable as fragrances, for example, but not limited to, sage oil, chamomile oil, clove oil, balm oil, peppermint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil, labdanum oil and lavandin oil or any combination or derivative thereof.
  • fragrances for example, but not limited to, sage oil, chamomile oil, clove oil, balm oil, peppermint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil, labdanum oil and lavandin oil or any combination or derivative thereof.
  • sage oil for example, but not limited to, sage oil, chamomile oil, clove oil, balm oil, peppermint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil, labdan
  • the fragrance may be a commercially available fragrance, such as, but not limited to recess, or MixTexl from Givaudan, France.
  • Non-limiting examples of synthetic fragrances or modified natural compounds include: acetanisole; acetophenone; acetyl cedrene; amyl cinnamic aldehyde; anetlhole; benzaldehyde; benzyl acetate; benzyl salicate; p-tertiary butyl cyclohexyl acetate; camphor; cinnamic alcohol; cinnamyl acetate; citronellol; citral;; citral diethyl acetal; coumarin; ethylene brassylate; eugenol; gamma methyl ionone; geraniol; heliotropin; hydroxy-citronella linalool; 1 -menthol; methoxycitronellal; methyl nonyl acetaldehyde; musk ambrette; phenyl acetaldehyde; phenyl ethyl
  • Typical synthetic perfume compounds may be derivatives of natural compounds, such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbon of the natural compound.
  • the active ingredient is a perfume.
  • perfume may refer to an aqueous solution comprising one or more fragrances.
  • the active ingredient is a pheromone.
  • pheromone refers to chemical compounds capable of affecting the behavior of animals, such as for example insects.
  • Pheromones typically contain 8 to 20 carbon atoms and at least one hydroxyl group, usually a primary hydroxyl group, but sometimes secondary or tertiary hydroxyl group. They may be mono- or polyunsaturated and may contain additional functional groups, such as epoxy, aldehydic or ester group.
  • the pheromone is dodecan-l-ol.
  • the pheromones may be mixtures of compounds.
  • Non-limiting examples of suitable pheromones include (nomenclature: E or Z and position of the double bond or bonds are given first, the number of carbon atoms in the chain is given next and the nature of the end group is given last): E/Z-l l C14 aldehyde, Z-10 C19 aldehyde, Z-l l C14 acetate, Z-8 C12 acetate and E, E- 8,10 C12 alcohol. Each possibility is a separate embodiment.
  • Other suitable pheromones are also applicable, such as any pheromone containing ketone, aldehyde or ester groups.
  • the at least one active ingredient is abamectin.
  • abamectin is dissolved in an oil, such as, but not limited to an essential oil or a derivative thereof.
  • the core may comprise abamectin in addition to the at least one active ingredient.
  • encapsulation prolongs the stability of abamectin and hence its life time on a given substrate.
  • the microcapsule may include one or more volatile oils or botanical oils. Non-limiting examples of non-volatile oils include cottonseed oil, neem oil, castor oil, pyrethrum oil, sesame oil, combinations and/or derivatives thereof. Each possibility is a separate embodiment.
  • the at least one (second) polymer is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers wherein the co-polymer may be random, alternating or a block co- polymer thereof.
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PVP polyvinylpyrrolidone
  • homo- and co-polymers wherein the co-polymer may be random, alternating or a block co- polymer thereof.
  • homo-polymer refers to a polymer derived from repeated residues of a certain monomer.
  • the term "co-polymer” refers to a polymer derived from two (or more) kinds of monomeric residues. Co-polymers may be further classified based on how the monomelic residues are arranged. According to some embodiments, the co-polymer is an alternating co-polymer with regular alternating units. According to some embodiments, the co-polymer is a periodic co-polymer with monomeric units arranged in a repeating sequence. According to some embodiments, the co-polymer is a statistical co-polymer in which the sequence of monomer residues follows a statistical rule. According to some embodiments, the co-polymer is a random co-polymer in which the distribution of the different monomeric units is essentially random. According to some embodiments, the co-polymer is a block copolymer including two or more homo-polymer subunits linked by covalent bonds.
  • the (second) polymer is PVP.
  • PVP is available over a wide range of molecular weights (MW), such as between 10,000 to 1,300,000 g/mol and higher. The molecular weight chosen is optimized according to the desired characteristics of the microcapsule and according to the ease of preparation. According to some embodiments, the molecular weight of PVP is between 20,000 to 90,000 g/mol. According to some embodiments, the molecular weight of PVP is between 30,000 to 80,000 g/mol. According to some embodiments, the PVP (second) polymer is a PVP co-polymer, such as, but not limited to, polyvinyl acetate-PVP.
  • the (second) polymer is a block co-polymer.
  • suitable block co-polymers include block co-polymers with one polyethylene oxide (EO) and one propylene oxide (PO) block; block co-polymers of EO/PO/EO or PO/EO/PO; tetra-functional block co-polymers derived from the sequential addition of PO and EO to ethylene diamine.
  • EO polyethylene oxide
  • PO propylene oxide
  • the second polymer comprises a PEG/PPG block copolymer.
  • the second polymer is a PEG/PPG block copolymer.
  • the average molecular weight (MW) of the (second) polymer is at least 3,000 g/mol.
  • polymers of lower MW may also be applicable. If the molecular weight is too high, it may be difficult to process. On the other hand, polymers of too low molecular weight may not give stable microcapsules.
  • the polyacid is an acceptor polymer.
  • the poly acid is selected from a group consisting of: agaropectin, albumin, alginate, alginic acid, polygalacturonic acid, anionic cellulose, carboxymethyl cellulose (CMC), chondroitin sulfate, heparin, polymethacrylic acid, polyacrylic acid and co- and block co-polymers of polyacrylic acid or polymethacrylic acid, co-polymers of maleic anhydride in the maleic acid state, hyaluronic acid, pectin, pectic acid (polygalacturonic acid), polyaspartic acid, starch carboxylic acid, ultra-amylopectin, xanthan gum, and combinations and/or derivatives thereof.
  • agaropectin albumin
  • alginate alginate
  • alginic acid polygalacturonic acid
  • anionic cellulose carboxymethyl cellulose (CMC)
  • CMC carboxymethyl
  • the at least one polyacid comprises alginic acid. According to some embodiments, the at least one polyacid is alginic acid.
  • the poly acid may include other polysaccharides, such as starches, cellulosics, chitins, beta-glucans, carrageenan, dextrans, galactomannans, glucomannans, guar gums or xylans, derived to introduce acidic groups.
  • cellulosic derivatives include carboxy-alkyl cellulose, carboxy-alkyl-alkyl cellulose, cellulose phosphate, cellulose phosphinate, cellulose sulfate, sulfo-alkyl cellulose and cellulose tellurate or any combination thereof.
  • cellulosic derivatives include carboxy-alkyl cellulose, carboxy-alkyl-alkyl cellulose, cellulose phosphate, cellulose phosphinate, cellulose sulfate, sulfo-alkyl cellulose and cellulose tellurate or any combination thereof.
  • cellulose saccharides such as starches, cellulosics, chit
  • Non-limiting examples of starch derivative include derivatives similar to cellulose derivatives and synthetic olefin polymers with carboxylic acid groups including polyacrylic acid, polymethacrylic acid and co- and block polymers thereof (e.g., polyacrylic acid -co-maleic). Each possibility is a separate embodiment of the invention.
  • the properties of the complex formed depend in part on the molecular weight of the (second) polymer and the acceptor polymer (the polyacid). For example, when using poly acrylic acid (PAA) as the acceptor polymer, and PEO as the polymer, the degree of polymerization (DP) has to be above 100 to form a stable complex. According to some embodiments, the degree of polymerization (DP) has to be above 200 to form a stable complex.
  • the term "degree of polymerization” refers to the number of monomelic units in a polymer.
  • the DP when using polymethacrylic acid PMA as the polyacid and PEO as the polymer, the DP can be 40 or more to form a stable complex.
  • suitable polyacid/polymers include alginic acid/PEO (polyethylene oxide), alginic acid/block co-polymer of PEO-block-PPO (polypropylene oxide), polyacrylic acid (PAA)/polyvinylmethyl ether (PVME), PAA (polyacrylic acid)/PVP (polyvinylpyrrolidone), PAA/PEO and PMAA (polymethylmethacrylate)/ PEO.
  • the polyacid comprises a mixture of polyacids.
  • the (second) polymer comprises a mixture of different polymers.
  • the (second) polymer comprises a mixture of block co-polymers.
  • the mixture of polymers comprises block co-polymers having a different molecular weight ratio of polymers.
  • the mixture of polymers comprises block co-polymers having different total molecular weight of each polymer.
  • the mixture of polymers comprises block co-polymers having hydrophilic and hydrophobic blocks.
  • the hydrophobic block polymer is PPG.
  • the hydrophilic block of the polymer is PEG.
  • the block co-polymer is PPG-PEG.
  • the block co-polymer comprises blocks of different lengths.
  • the mixture of polymers comprises hydrophilic and hydrophobic polymers.
  • the hydrophobic block co-polymer comprises hydrophobic and hydrophilic blocks wherein the hydrophobic block is longer than the hydrophilic block.
  • the hydrophilic block co-polymer comprises hydrophobic and hydrophilic blocks wherein the hydrophobic block is shorter than the hydrophilic block.
  • the ratio of hydrophobic to hydrophilic blocks is in the range of 0.5: 1 to 5: 1.
  • the ratio of hydrophobic to hydrophilic blocks is in the range of 1 : 1 to 4: 1.
  • the ratio of hydrophobic to hydrophilic blocks is in the range of 1.5: 1 to 2.5: 1.
  • the ratio of hydrophobic to hydrophilic blocks is in the range of 2: 1 to 4: 1.
  • hydrophobic block refers to a polymer in a block co- polymer having an experimental LogP value (wherein P is the octanol water partition coefficient) of at least 1.2, at least 1.5, at least 2. Each possibility is a separate embodiment.
  • hydrophilic block refers to a polymer in a block co-polymer having an experimental LogP value (wherein P is the octanol water partition coefficient) of less than -0.5, of less than -1, of less than -2.
  • the complex comprises a mixture of (second) polymers and/or a mixture of polyacids (first polymers).
  • the mixture of (second) polymers comprises different block co-polymers of PEO-block-PPO for example block co-polymers wherein the molecular weight ratio of PEO and PPO differs or wherein the total molecular weight of the PEO/PPO polymers differ.
  • Another important variable in reaching optimized polyacid/polymer (first/second polymer) complexes is the pH of the microencapsulation solution. In general, the polymeric complexes are stronger when the acid is in the hydrogen form and not the salt form. For example, to form stable complexes between PAA and PEO, the pH of the aqueous solution should preferable be less than a pH of 7.
  • higher pH such as a pH above 7 or a pH above 8
  • higher pH may ensure a long shelf life and stability of the active ingredient.
  • optimizing the choice of polymers as well as their molecular weight may still facilitate a sufficiently strong encapsulating envelope.
  • the polyacid is selected from a group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, polygalacturonic acid, anionic cellulose, chondroitin sulfate, heparin, polyacrylic acid, hyaluronic acid, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof.
  • the formulation includes 0.25-1.5% alginic acid.
  • the formulation includes 0.25-3.5% alginic acid.
  • the concentration of the polyacid in the aqueous solution is in the range of 0.3% to 2.5%. According to some embodiments, the concentration of the polyacid in the aqueous solution may be less than 2%. According to some embodiments, the formulation includes 5-25% of a 4% alginic acid solution. According to some embodiments, the formulation includes 10-15%) of a 4% alginic acid solution.
  • the core further comprises at least one co- encapsulated agent selected from the group consisting of: antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, pesticides and combinations thereof.
  • the at least one agent may be encapsulated separately from the at least one essential oil.
  • the ratio of the active ingredient and the at least one (second) polymer is in the range of 90: 1 to 1 :2.5. According to some embodiments, the ratio of the active ingredient and the at least one (second) polymer is in the range of 30: 1 to 1 :2. According to some embodiments, the ratio of the active ingredient and the at least one (second) polymer is in the range of 10: 1 to 1 : 1. According to some embodiments, the ratio of the active ingredient and the at least one (second) polymer is in the range of 5: 1 to 2: 1. According to some embodiments, the ratio of the active ingredient and the at least one (second) polymer is in the range of 5: 1 to 1 : 1. According to some embodiments, the ratio of the active ingredient and the at least one (second) polymer is in the range of 2: 1 to 1 : 1.
  • the shell encapsulating the core is water insoluble. According to some embodiments, the shell encapsulating the core may be water compatible and swell in water, without dissolving. According to some embodiments, the shell encapsulating the core is hydrophilic, but does not dissolve in water. According to some embodiments, the shell, encapsulating the core, is hydrophobic and will not swell in water.
  • the interpolymeric complex of the shell is further crosslinked by multivalent cationic moieties, such as, but not limited to Ca 2+ , Mg 2+ , Zn +2 , Fe 2+ , Fe 3+ , Al 3+ , or combinations thereof. Each possibility is a separate embodiment of the invention.
  • the interpolymeric complex of the shell is crosslinked by poly quaternary ammonium organic compounds or polyamines, such as but not limited to polyethylenimine or/and chitosan. The additional cross-linking may improve the stability of the microcapsule with respect to shelf life, transportation, application and sustained release.
  • the interpolymeric complex of the shell may be double or triple-cross linked.
  • the interpolymeric complex of the shell may be crosslinked by multivalent cationic moieties and by poly quaternary ammonium organic compounds or polyamines, such as but not limited to polyethylenimine or/and chitosan.
  • the interpolymeric complex of the shell may be crosslinked by multivalent cationic moieties and by poly quaternary ammonium organic compounds or polyamines, such as but not limited to polyethylenimine or/and chitosan, and the quaternary ammonium organic compound may itself be crosslinked by adding tripolyphosphate (TTP) or any other suitable agent or combination of agents capable of crosslinking the poly-quaternary ammonium organic compound.
  • TTP tripolyphosphate
  • the average diameter of the microcapsule is less than 1000 microns. According to some embodiments, the average diameter of the microcapsule is less than 500 microns. According to some embodiments, the average diameter of the microcapsule is less than 300 microns. According to some embodiments, the average diameter of the microcapsule is less than 200 microns. According to some embodiments, the average diameter of the microcapsule is less than 100 microns. According to some embodiments, the microcapsule is in the range of 50 nanometers to 1000 micron. According to some embodiments, the microcapsule is in the range of 100 nanometers to 500 micron. According to some embodiments, the microcapsule is in the range of 50 nanometers to 300 micron.
  • the microcapsule is in the range of 10 nanometers to 100 micron. According to some embodiments, the average diameter of the microcapsule is in the range of 10 nanometers to 1 micron. According to some embodiments, the average diameter of the microcapsule is in the range of 10 nanometers to 200 nanometers. Each possibility represents a separate embodiment of the present invention.
  • composition comprising a plurality of microcapsules, as essentially described above.
  • the composition is a liquid formulation wherein the plurality of the microcapsules is suspended in an aqueous solution.
  • the composition is a solid formulation.
  • the composition is a paste.
  • the essential oil encompasses 1-95%, 1 -90%, 1- 50%, 5-40%, 10-35%, 15-25%, 12-20%, 12-15% of the total weight of the composition, which includes the media (e.g., water) in which the encapsulated particles are dispersed.
  • the media e.g., water
  • the essential oil encompasses 20-95% of the total weight of the microcapsule.
  • the essential oil encompasses 30-95% of the total weight of the microcapsule.
  • the essential oil encompasses 50-95% of the total weight of the microcapsule.
  • the essential oil encompasses 60-95% of the total weight of the microcapsule.
  • more than 75% of the essential oils within the applied formulation is encapsulated. According to some embodiments, more than 80% of the essential oils is encapsulated. According to some embodiments, more than 90% of the essential oils is encapsulated. According to some embodiments, more than 95% of the essential oils is encapsulated.
  • the composition includes a homogenous suspension of microcapsules.
  • the term "homogenous suspension of microcapsules" refers to a suspension of identical microcapsules, such as for example a suspension of microcapsules encapsulating oregano oil or a suspension of microcapsules encapsulating eucalyptol.
  • a homogenous suspension of microcapsules refers to a suspension of identical microcapsules containing more than one types of essential oil (for example, but not limited to, co-encapsulated oregano oil and thyme oil).
  • a homogenous suspension of microcapsules refers to a suspension of identical microcapsules containing an essential oil and another active ingredients (including, but not limited to, co-encapsulated oregano oil and abamectin).
  • the composition includes a heterogeneous suspension of microcapsules.
  • heterogeneous suspension of microcapsules refers to a suspension of non-identical microcapsules, such as, but not limited to, a suspension of microcapsules encapsulating oregano oil and microcapsules encapsulating thyme oil; or a suspension of microcapsules encapsulating carvacrol and microcapsules encapsulating thymol. It is understood to one of ordinary skill in the art that such heterogeneous mixtures may also contain microcapsules encapsulating an agent different from essential oils, such as but not limited to an IGR, as further described hereinbelow.
  • the composition includes a homogenous assortment of microcapsules.
  • homogenous assortment of microcapsules refers to identical microcapsules packed together for example in sachets, such as sachets containing solid core microcapsules encapsulating tagetes oil.
  • the composition includes a heterogeneous assortment of microcapsules.
  • heterogeneous assortment of microcapsules refers to a mixture of non-identical solid core microcapsules, packed together for example in sachets, including sachets containing solid core microcapsules encapsulating citronella oil and solid core microcapsules encapsulating oregano oil or any other and/or additional essential oil.
  • the composition includes 1-50%, 5-35%, 10-20%), 5-15%) or 5-10%) by weight of (second) polymer.
  • (second) polymer each possibility is a separate embodiment of the invention.
  • the composition includes 10%> to 20% by weight of polyacid (e.g. alginic acid). According some embodiments, the composition includes 10% to 15%) by weight of polyacid. According some embodiments, the composition includes 5% to 15%) by weight of polyacid. According some embodiments, the composition includes 5% to 10%) by weight of polyacid. According some embodiments, the composition includes 0.05% to 15%) by weight of polyacid. According some embodiments, the composition includes 0.1% to 10%) by weight of polyacid. According some embodiments, the composition includes 0.3% to 5%> by weight of polyacid. According to some embodiments, the concentration of the polyacid in the aqueous solution is in the range of 0.3% to 2.5%.
  • concentration of the polyacid in the aqueous solution is in the range of 0.3% to 2.5%.
  • the composition includes 0.5% to 2% by weight of polyacid. According some embodiments, the composition includes 1% to 2% by weight of polyacid. According to some embodiments, the concentration of the polyacid in the aqueous solution may be less than 2%. According to some embodiments, the formulation includes 5-25% of a 4% alginic acid solution. According to some embodiments, the formulation includes 10-15%) of a 4% alginic acid solution. According to some embodiments, the formulation includes 60-80%> of a 2% alginic acid solution.
  • the composition further comprises at least one surfactant and/or emulsifier configured to generate a stable formulation.
  • the at least one surfactant and/or emulsifier configured to generate a transparent micro-emulsion.
  • Non-limiting examples of suitable surfactants and emulsifiers include: CREMOPHOR® RH 40 (Ethoxy Hydrogenated Castor Oil) CREMOPHOR®RH 60 (Ethoxy Hydrogenated Castor Oil); GENAPOL® (Alcohol Polyglycol Ether); POLOXAMER®407 (also known as PLURONIC® F127 and PLURACARE® F127) (Ethylene oxide-propylene oxide block co-polymer having an average molecular weight of 12,600); Sodium Lauryl Sulphate; SPAN®20 (Sorbitan Monolaurate) SPAN®40 (Sorbitan Monopalmitate); SPAN®60 (Sorbitan Monostearate); and SPAN®80 (Sorbitan Mono- oleate); TWEEN®20 (Polyoxyethylene (20) Sorbitan Monolaurate), TWEEN®40 (Polyoxyethylene (20) Sorbitan Monopalmitate); TWEEN®60 (Polyoxyethylene (20) Sor
  • the composition further comprises at least one co-surfactant.
  • suitable co-surfactants include short to medium chain length alcohols (C3-C8), such as propanol, butanol, and hexanol. It is understood by one of ordinary skill in the art that adding the co-surfactant may further reduce the interfacial tension and increase the fluidity of the interface to facilitate the formation of nano-sized particles.
  • the composition further comprises an encapsulated or non-encapsulated agent selected from the group consisting of: antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, pesticides and combinations thereof.
  • IGR's Insect Growth regulators
  • the encapsulated agents may be separately encapsulated or encapsulated within the microcapsules with the essential oils or other active ingredients.
  • the composition may further include one or more volatile oils or botanical oils.
  • Non-limiting examples of non-volatile oils include cottonseed oil, neem oil, castor oil, pyrethrum oil, sesame oil, combinations and/or derivatives thereof.
  • the volatile oil may be co-encapsulated with the essential oil. According to some embodiments, the volatile oil may be separately encapsulated. According to some embodiments, the volatile oil may be non-encap sul ated .
  • the composition further comprises at least one additive selected from of an antioxidant, a UV protector, a formulation stabilizer that minimizes settling or rising of the microcapsules in a suspension, a preservative and combinations thereof.
  • the preservative is selected from the group consisting of rosemary oil, BHA, methyl paraben, Vitamin E, benzophenone and combinations thereof.
  • the present invention provides microcapsules comprising a core having at least one active ingredient selected from the groups consisting of: essential oils, fragrances, pheromones, nutrients, insecticides and combination thereof and derivatives thereof; and a shell made of interpolymeric complexes of at least one polyacid and at least one second polymer; wherein the second polymer is selected from the group consisting of: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof; and the polyacid selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid and its copolymers, polymethacrylic acrylic acid and its co-polymers, polymeric anhydride acid in the maleic acid form and its co-poly
  • the microcapsule has an average diameter of less than 100 microns. According to some embodiments, the microcapsule has an average diameter of less than 300 microns. According to some embodiments, the microcapsule has an average diameter of less than 400 microns. According to some embodiments, the microcapsule has an average diameter of less than 500 microns. According to some embodiments, the microcapsule has an average diameter of less than 1000 microns. According to some embodiments, the microcapsule has an average particle size of about 200nm. According to some embodiments, the microcapsule has an average particle size of about 300nm. According to some embodiments, the microcapsule has an average particle size of about 100nm-300nm. According to some embodiments, the microcapsule has a particle size varying from 50 to 2000 nm. According to some embodiments, the microcapsule has a particle size varying from 50 to 1000 nm.
  • a microcapsule having a core comprising at least one essential oil and a shell encapsulating the core.
  • the shell comprises an interpolymeric complex of alginic acid and PEG/PPG block co-polymers.
  • the interpolymeric complex is cross- linked with at least one multivalent cationic moiety, wherein the multivalent cationic moiety comprises Ca 2+ .
  • the at least one essential oil comprises thyme oil and oregano oil.
  • the ratio of thyme oil and oregano oil in the microcapsule is 2:3.
  • the microcapsule is suitable for use as disinfectant, pesticide, insect repellant, antiviral and/or antifungal agent.
  • a composition comprising a plurality of microcapsules and a carrier.
  • the microcapsules of the composition comprise a core comprising at least one essential oil and a shell encapsulating the core.
  • the shell comprises an interpolymeric complex of alginic acid and PEG/PPG block co-polymers.
  • the interpolymeric complex is cross-linked with at least one multivalent cationic moiety, wherein the multivalent cationic moiety comprises Ca 2+ .
  • the at least one essential oil comprises thyme oil and oregano oil.
  • the ratio of thyme oil and oregano oil in the microcapsule is 2:3.
  • the composition further comprises a preservative.
  • the preservative is rosemary oil.
  • the composition further comprises a surfactant such as but not limited to Tween 80.
  • the composition further comprises a solvent such as but not limited to propylene glycol.
  • the composition further comprises a stabilizer such as but not limited to xanthan gum.
  • a microcapsule having a core comprising at least one essential oil and a shell encapsulating the core.
  • the shell comprises an interpolymeric complex of alginic acid and PEG/PPG block co-polymers.
  • the Interpol ym eric complex is cross- linked by at least one multivalent cationic moiety and by chitosan.
  • the multivalent cationic moiety comprises Ca 2+ .
  • the chitosan is further crosslinked by tripolyphosphate (TTP).
  • TTP tripolyphosphate
  • the at least one essential oil comprises thyme oil and oregano oil.
  • the ratio of thyme oil and oregano oil in the microcapsule is 2:3.
  • the microcapsule is suitable for use as disinfectant, pesticide, insect repellant, antiviral and/or antifungal agent.
  • a composition comprising a plurality of microcapsules and a carrier.
  • the microcapsules of the composition comprise a core comprising at least one essential oil and a shell encapsulating the core.
  • the shell comprises an interpolymeric complex of alginic acid and PEG/PPG block co-polymers.
  • the interpolymeric complex is cross-linked by at least one multivalent cationic moiety and by chitosan.
  • the multivalent cationic moiety comprises Ca 2+ .
  • the chitosan is further crosslinked by tripolyphosphate (TTP).
  • the at least one essential oil comprises thyme oil and oregano oil.
  • the ratio of thyme oil and oregano oil in the microcapsule is 2:3.
  • the microcapsule is suitable for use as disinfectant, pesticide, insect repellant, antiviral and/or antifungal agent.
  • the composition further comprises a preservative.
  • the preservative is rosemary oil.
  • the composition further comprises a surfactant such as but not limited to Tween 80.
  • the composition further comprises a solvent such as but not limited to propylene glycol.
  • the composition further comprises a stabilizer such as but not limited to xanthan gum.
  • the composition may further include one or more volatile oils or botanical oils.
  • volatile oils include cottonseed oil, neem oil, castor oil, pyrethrum oil, sesame oil, combinations and/or derivatives thereof. Each possibility is a separate embodiment.
  • the volatile oil may be co-encapsulated with the essential oil.
  • the volatile oil may be separately encapsulated.
  • the volatile oil may be non-encap sul ated .
  • a method for producing an aqueous microcapsule composition comprising: a) mixing at least one (second) polymer, into at least one essential oil or derivatives thereof, wherein the (second) polymer is selected from the group consisting of a polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof, to obtain a first mixture;
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PVP polyvinylpyrrolidone
  • the at least one polyacid is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid and its co-polymers, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof; to obtain a second mixture; c) combining the first and second mixtures, thereby obtaining a suspension of microcapsules, each microcapsule comprising a core comprising an essential oil or a derivatives thereof and a shell encapsulating the core, the shell comprising an interpolymeric complex of the at least one polyacid and the at least one (second) polymer.
  • the at least one polyacid is selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid
  • step c adding an aqueous solution comprising at least one multivalent cationic moiety and/or a poly-quaternary ammonium organic compound or a polyamine to the suspension obtained in step c; thereby crosslinking the interpolymeric complex with the at least one multivalent cationic moiety.
  • the method may further include adding tripolyphosphate (TPP) to the suspension; thereby crosslinking the cationic/amine polymer in the interpolymeric complex with the at least one multivalent cationic moiety.
  • TPP tripolyphosphate
  • the multivalent cationic moiety includes, but is not limited to, Ca , Mg , Zn , Fe or Fe Al , Each possibility is a separate embodiment of the invention.
  • the poly-quaternary-ammonium organic compound or the polyamine may be a polyethyleneamine or a cationic polysaccharide, including but not limited to chitosan.
  • the method further comprises filtering the suspension to obtain a plurality of isolated microcapsules.
  • the method further comprises adding at least one surfactant and/or emulsifier to obtain a uniform, clear, and transparent suspension of microcapsules.
  • an additional agent is added at step (a) the additional agent selected from the group consisting of: antimicrobial agents, antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, pesticides and combinations thereof.
  • the agent selected from the group consisting of: antimicrobial agents, antifungal agents, bactericides, herbicides, Insect Growth regulators (IGR's), insect repellants, insecticides, larvicides, pesticides and combinations thereof.
  • the additional agent may be added instead of the active ingredient thereby obtaining microcapsules separately encapsulating the agent.
  • the microcapsules encapsulating the active ingredient and the microcapsules encapsulating the agent may be mixed in order to obtain a composition comprising microcapsules separately encapsulating the active ingredient and the agent.
  • the agent may be added after encapsulation of the active ingredient to obtain a composition comprising microcapsules encapsulating the active ingredient (for example the essential oil) whereas the agent is non-encapsulated and mixed into the suspension.
  • the aqueous solution of step b) has a pH of 7 or less.
  • the polyacid in the aqueous solution is in the range of 0.2% to 20% by weight.
  • the polyacid in the aqueous solution is in the range of 0.5% to 5%.
  • the polyacid comprises alginic acid. According to some embodiments, the polyacid is alginic acid.
  • the second polymer comprises a PEG/PPG block co-polymer.
  • the second polymer is a PEG/PPG block copolymer.
  • the block copolymers may contain more than two separate blocks such as, but not limited to PEG-PPG-PEG or PPG-PEG-PPG or the equivalents of PPO and PEO.
  • a method for producing a solid core microcapsule composition comprising: a) mixing at least one (second) polymer, into at least one essential oil or a derivative thereof wherein the (second) polymer is selected from the group consisting of a polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), polypropylene oxide (PPO) polyvinylpyrrolidone (PVP), and homo- and co-polymers thereof, wherein the co-polymer may be a block co-polymer of a random or alternating block co-polymer;
  • the co-polymer may be a block co-polymer of a random or alternating block co-polymer
  • aqueous solution comprising at least one polyacid, the polyacid selected from the group consisting of: agaropectin, alginate, alginic acid, carboxymethyl cellulose, chondroitin sulfate, heparin, polyacrylic acid, co-polymers of polyacrylic acid, polymethacrylic acrylic acid and its copolymers, polymeric anhydride acid in the maleic acid form and its co-polymer, pectin, polygalacturonic acid, starch carboxylic acid, xanthan gum, and combinations and/or derivatives thereof; thereby obtaining microcapsules comprising a core comprising an essential oil, or a derivative thereof adsorbed in a porous material and a shell encapsulating the core, the shell comprising an interpolymeric complex of the at least one polyacid and the at least one (second) polymer; and
  • step c adding at least one salt comprising a multivalent cation and/or a poly-quaternary ammonium organic compound or a polyamine to the microcapsules obtained in step c; thereby crosslinking the interpolymeric complex with the at least one multivalent cationic moiety.
  • the method may further include adding tripolyphosphate (TPP) to the suspension; thereby crosslinking the interpolymeric complex with the at least one multivalent cationic moiety.
  • TPP tripolyphosphate
  • the at least one salt is in the form of a powder.
  • the at least one salt is in a form of an aqueous solution comprising the at least one salt.
  • the at least one salt is a water soluble salt.
  • the multivalent cationic moiety is selected from the group consisting of: Ca , Mg , Zn Fe or Fe Al . Each possibility is a separate embodiment of the invention.
  • the poly-quaternary-ammonium organic compound or the polyamine may be a polyethyleneimine, or a polysaccharide, including but not limited to chitosan.
  • the porous material is selected from the group consisting of: cellulosics starch powders, Aerosil, silicas or combinations thereof.
  • the aqueous solution of step c) has a pH of less than 7.
  • the polyacid in the aqueous solution is in the range of 0.2% to 20% by weight.
  • the polyacid in the aqueous solution is in the range of 0.5% to 5%.
  • the polyacid in the aqueous solution is in the range of 1% to 5%.
  • the polyacid comprises alginic acid. According to some embodiments, the polyacid is alginic acid.
  • the second polymer comprises a PEG/PPG block co-polymer. According to some embodiments, the second polymer is a PEG/PPG block co- polymer.
  • the microcapsules may be used to prevent crop damage by infection just prior to harvesting.
  • a method for inhibiting post-harvest infections in crop includes applying the microcapsules described herein on or in vicinity of the crop.
  • inhibiting damage to post-harvest crops comprises repelling crop pathogens, such as, but not limited to insects, fungi, bacteria, and nematodes.
  • the composition may be applied on, or in vicinity of, the crop before harvest, for instance within 2 weeks before harvest, thereby obtaining crop free of microorganisms and/or insects and their larvae.
  • the microcapsules and microcapsule compositions described herein can be used as insecticides, acaricides and nematocides. According to some embodiments, the microcapsules and microcapsule compositions described herein can be used as antimicrobial agents, antifungal agents. According to some embodiments the microcapsules and microcapsule compositions described herein can be used as a food additive, such but not limited to a food preservative.
  • the microcapsules may be used to prevent crop damage by infection during crop growth.
  • the following examples are presented in order to more fully illustrate some embodiments of the invention. They should, in no way be construed, however, as limiting the broad scope of the invention.
  • Block co-polymers of PEG and PPG having a PEG content of 82 wt-% and Mn 14,600 such as block co-polymer B obtained from Sigma Aldrich catalog number 54,234-2.
  • PPG polypropylene glycol
  • PEO polyethylene oxide
  • Butyl ated hydroxyanisole (BHA) antioxidant
  • Benzophenone antioxidant
  • Methyl paraben preservative
  • Propylene glycol viscosity controller
  • SDS Sodium dodecyl sulfate
  • Octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate antioxidant
  • Irganox 1076 Bis(2,2,6,6,-tetramethyl-4-piperidyl)sebacate (stabilizer)
  • Tinuvin 770 Polyacrylic acid MW 20,000 g/mol
  • Alginic acid sodium salt and Polyethylene oxides (MW 14,000, 100,000 or 200,000 g/mol) were obtained from Sigma Aldrich.
  • Aerosil 300 was obtained from Cabot.
  • Xanthan gum such as Rhodopol obtained from Rhodia.
  • Oregano oil and citronella oil were purchased from Rakesh Sandal Industries, India. Tagetes oil, sesame oil, rosemary oil, tea tree oil, lavender oil and pyrethrum were obtained from Botanical Resources, Australia.
  • Azadirachtin was obtained from Unicorn Natural Products, India.
  • Example 1 Preparation of liquid core microcapsule formulations with polymeric shells
  • composition was stable for at least 8 weeks at 44 °C; did not separate into an oil and water phases and did not change in essential oil concentrations.
  • the formulation was readily dispersed in water to form dilutions with good spraying characteristics.
  • a similar formulation comprising a mixture of oregano oil and thyme oil (at a oregano oil : thyme oil ratio of 2:3) were also produced and tested as detailed below.
  • Formulation 1 The efficacy of Formulation 1 was initially demonstrated for the prevention of rot and Aspergillus fungi infestation in growing grape vines as compared to no spray or spraying with a commercial product of synthetic chemicals comprising Boscalid 26.7% + pyraclostrobin 6.5%). The experiment took place in a green house on grape vines. Each agent or formulation was diluted to a designated concentration of active agent and checked on two rows of grape vines wherein each row had 5 grape vines per position and 4 position. Each formulation was sprayed once a week for 5 weeks. The amount sprayed were 70-80 liters per formulation per two rows. The concentration of the active agent in formulation 1 in the sprayed solution was 0.75%. The commercial product was sprayed at the recommended concentration of 0.1%.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the dispersions a), b) and c) described above:
  • Formulation 2 was prepared as above using a PPG/PEO block co-polymer and a block co-polymer of PEG and PPG having a PEG content of 30 wt% and Mn 5,800, as shown in Table 2 below.
  • composition was stable for at least 8 weeks at 44 °C; did not separate into oil and water phases and did not change in essential oil concentrations.
  • the formulation was readily dispersed in water to form dilutions with good spraying characteristics.
  • Formulation 2 The efficacy of Formulation 2 is tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 2 containing dispersion: Formulation 2 dispersed in water to obtain a dispersion containing 1% oregano oil.
  • Control 1 a dispersion containing 1% unencapsulated oregano oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid 6.5% and pyraclostrobin.
  • Formulation 3 was prepared essentially as above and according to Table 3.
  • Oregano oil and PEG/PPG block co-polymer, 30 wt-% PEG, Mn 5,800 (block co-polymer A) were mixed, in a beaker vessel using a high-speed shear stirrer. The mixture was then added to a stirring vessel with water, and stirred for 3 minutes. An alginic acid sodium salt 4% aqueous solution was then added and the solution stirred for an additional 10 minutes. Xanthan gum was added followed by 10 ml of a 2% CaCl 2 solution and stirred for an additional 15 minutes.
  • the resulting formulation had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, and dispersibility. Furthermore, this formulation showed a superior stability for more than 1 month under accelerated storage conditions of 43°C in closed bottles as compared to formulations made without adding calcium chloride, which readily separated into two phases.
  • Formulation 3 The efficacy of Formulation 3 is tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 3 containing dispersion: Formulation 3 dispersed in water to obtain a dispersion containing 1% oregano oil.
  • Control 1 a dispersion containing 1% unencapsulated oregano oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid 6.5% and pyraclostrobin.
  • Formulation 4 was prepared as in example 1A and according to Table 4 using a polyacrylic acid (PAA, MW 30,000 g/mol) sodium salt 4% aqueous solution instead of the alginic acid sodium salt solution.
  • PAA polyacrylic acid
  • PEG/PPG block co-polymer (82 wt% PEG, Mn 25 9.99
  • the resulting formulation had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • a similar formulation using ferric chloride instead of calcium chloride was also prepared and had a similar performance in terms of stability and enhanced control over release rate.
  • Formulation 4 The efficacy of Formulation 4 is tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 4 containing dispersion: Formulation 4 dispersed in water to obtain a dispersion containing 1% oregano oil.
  • Control 1 a dispersion containing 1% unencapsulated oregano oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid
  • Examples 1A, IB and 1C were repeated using thyme oil (62.5 grams) instead of oregano oil.
  • the efficacies of Formulations 5-7 are tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 5 containing dispersion: Formulation 5 dispersed in water to obtain a dispersion containing 1% thyme oil.
  • Formulation 6 containing dispersion Formulation 6 dispersed in water to obtain a dispersion containing 1% thyme oil.
  • Formulation 7 containing dispersion Formulation 5 dispersed in water to obtain a dispersion containing 1% thyme oil.
  • Control 1 a dispersion containing 1% unencapsulated thyme oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid 6.5% and pyraclostrobin.
  • Examples 1A and IB were repeated using a mixture of oregano oil and thyme oil (31.25 grams each). The resulting formulations had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • Formulations 8 and 9 are tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 8 containing dispersion: Formulation 8 dispersed in water to obtain a dispersion containing a total of 1% oregano oil and thyme oil.
  • Formulation 9 containing dispersion Formulation 9 dispersed in water to obtain a dispersion containing a total of 1% oregano oil and thyme oil.
  • Control 1 a dispersion containing a total of 1 % unencapsulated oregano oil and thyme oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid
  • Example 1 A and IB was repeated using tea tree oil according to tables 5 and 6.
  • the resulting formulations had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • Example 1 A was repeated using Tagetes oil instead of oregano oil, according to tables
  • the resulting formulations had similar performance as formulations 1 with respect to encapsulation efficiency, stability and dispersibility.
  • Example 1H was repeated using Tagetes oil and sesame oil, according to table 8.
  • the resulting formulations had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • Example 1A was repeated using pine oil, pyrethrum and azadirachtin instead of oregano oil, according to table 9.
  • the resulting formulations had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • Example 1 J was repeated using a PEO-PPO block co-polymer (Antarox PLG254) and glycol molecular weight 14,000 (PEG 14,000) instead of the PEG/PPG block co-polymers, as described in table 10 below.
  • PEG 14,000 glycol molecular weight 14,000
  • Example 1 J was repeated using polyethylene oxide (PEO, MW 14,000 g/mol) instead of the PEG/PPG block co-polymer (30 wt% PEG, Mn 5,800), as described in table 11 below.
  • PEO polyethylene oxide
  • PEG/PPG block co-polymer 30 wt% PEG, Mn 5,800
  • the resulting formulations had similar performance as formulation 14 with respect to encapsulation efficiency, stability and dispersibility.
  • Citronella oil, pyrethrum, azadirachtin, sesame oil and PEG/PPG block co-polymer, 30 wt-% PEG, Mn 5,800 (block co-polymer A) were mixed in a reaction vessel to obtain mixture 1.
  • Table 12 below describes the amounts of the ingredients of the formulation.
  • the resulting formulations had similar performance as the previous formulations with respect to encapsulation efficiency, stability and dispersibility.
  • Formulation 17 The efficacy of Formulation 17 is tested for protection of post-harvest fruits and vegetables and growing crop, against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the following growing crops are tested: lettuce, grape vines and tomatoes.
  • the post-harvest fruits and vegetables and the growing crop are treated by spraying them with each of the following dispersions: a) Formulation 17 containing dispersion: Formulation 5 dispersed in water to obtain a dispersion containing 1% citronella oil.
  • Control 1 a dispersion containing 1% unencapsulated citronella oil.
  • Control 2 a 0.1% dispersion of a commercial agent containing 26.7% Boscalid 6.5% and pyraclostrobin. 70-80 liters of each of the dispersions are sprayed once every two weeks for a total of 6 weeks. Two weeks after the final treatment i.e. week 8 after the beginning of the experiment, the post-harvest fruits and vegetables and the growing crop are checked for rotting and infection with Sclerotinia, Botrytis Rhizopus and/ 'or Aspergillus.
  • Similar formulations can be prepared by adding rosemary (2 grams) as a preservative instead of BHA and methyl paraben and Vitamin E (2 grams) as an antioxidant instead of benzophenone.
  • Example 1A was repeated using 62.5g citronella oil (formulation 18), 62.5g lavender oil (formulation 19), 62.5g geranium oil (formulation 20) or 62.5g lemon eucalyptus (Quenling) instead of oregano oil.
  • Example IN was repeated using citronella oil as in formulation 18 into which abamectin is further dissolved, such that the resulting microcapsules contained both citronella and abamectin within their cores.
  • Example IN was repeated using citronella oil (formulation 18) into which 4- allylanisole as a pheromone model was dissolved.
  • the resulting microcapsules contained within their cores both citronella and 4-allylanisole. Table 14.
  • Example 1A was repeated using Omega 3 instead of oregano oil.
  • the resultant capsules had an average size of 57nm, as determined by dynamic light scattering and cryo- transmission electron microscopy.
  • the aqueous suspension containing the microcapsules was stable for 2 weeks at 54°C.
  • the resulting formulations had a significantly reduced odor.
  • Formulation 25 was prepared as according to Table 15 and as described below.
  • Formulation 25 was prepared essentially as above and according to Table 15.
  • Oregano oil, Thyme oil 30 wt-% PEG, Mn 5,800 (block co-polymer A) and 82 wt% PEG, Mn 14,600 PEG/PPG block co-polymer (co-polymer B) were mixed, in a beaker vessel using a high-speed shear stirrer at about 50°C for 10-20 minutes to obtain solution I.
  • Solution I was added to a 2L beaker containing the 2% alginic solution (solution II) and the mixture was homogenized for approximately 1 hour.
  • solution III was prepared by dissolving the calcium chloride in water.
  • solution I and II was then added to solution III and homogenization continued for approximately 1 hour.
  • Rosemary oil and Tween was added to the mixture.
  • solution IV was prepared and subsequently added to the mixture followed by an additional 15 minutes of homogenization. The mixture was then added to a stirring vessel with water, and stirred for about 15 minutes.
  • the resulting formulation had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • the resulting formulation had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • the release profile of the oregano and thyme oil from the microcapsule of formulation 25 was determined at day 0 after production (indicative of encapsulation efficiency), and at days 2, 8, 16, 24 and 31 after production of the microcapsule, using standard UPLC techniques. The results were compared to an emulsion of non-encapsulated oregano and thyme oil. As seen from FIG. 1, in the control emulsion, only about 10% of the essential oil remained 16 days after preparation of the emulsion, whereas the microcapsules of the invention retained more than -65% of their essential oil content 10 days after preparation and more than -25% of the essential oils retained 30 days after preparation.
  • the average particle size of the microcapsules was established using Scanning electron Microscophy (SEM) (Quanta 200 FEI Company) according to standard protocols. In short, the microcapsules were air dried and coated with gold (gold deposition) using Polaron Equipment Limited SEM Coating Unit E5100 followed by imaging.
  • FIG. 2 shows a representative image. The average particle size of the microcapsules was about 200nm - It is understood that the average particle size and size diversity can be adjusted by state of art methods, based on the needs of the application.
  • formulation 25 To establish the ability of formulation 25 to prevent post-harvest decay of crop, the formulation was diluted into a 3% aqueous solution. Oranges and lemons were immersed in the solution and subsequently stored fort 6 weeks at room temperature. Untreated oranges and lemons served as control. At the end of the six weeks, the oranges were evaluated for Penicillium digitatum and Penicillium ulaienseas infestation. The oranges and lemons treated with formulation 25 had significantly decreased infestation as compared to control, as determined by expert evaluation.
  • Formulation 26 was prepared as according to Table 16 and as described below.
  • Formulation 26 was prepared essentially as above and according to Table 16.
  • Oregano oil, Thyme oil 30 wt-% PEG, Mn 5,800 (block co-polymer A) and 82 wt% PEG, Mn 14,600 PEG/PPG block co-polymer (co-polymer B) were mixed, in a beaker vessel using a high-speed shear stirrer at about 50°C for 10-20 minutes to obtain solution I.
  • Solution I was added to a 2L beaker containing the 1% alginic solution and Tween (solution II) and the mixture was homogenized for approximately 1 hour.
  • solution ⁇ was prepared by dissolving the TPP in water and adjusting the pH to 4.5.
  • Solution III was then added to the above mixture and homogenization was continued for approximately 30 minutes. After 30 minutes the pH was adjusted to 6.0 and homogenization continued for another half an hour. Following the crosslinking of the alginic acid by the chitosan, solution IV containing dissolved TPP was added and stirred for approximately 30 minutes so as to crosslink the chitosan. Following the crosslinking of the chitosan by TPP, solution V containing dissolved calcium chloride was added and stirred for approximately 15 minutes so as to further crosslink the complex. Finally, rosemary oil, propylene glycol and xanthan gum was mixed to obtain the final emulsion.
  • the resulting formulation had similar performance as formulations 1 and 2 with respect to encapsulation efficiency, stability and dispersibility.
  • the release profile of the oregano and thyme oil from the microcapsule of this formulation was determined at day 0 after production (indicative of encapsulation efficiency), and at days 2, 8, 16, 24 and 31 after production of the microcapsule, using standard UPLC techniques. The results were compared to an emulsion of non-encapsulated oregano and thyme oil. As seen from FIG. 1, in the control emulsion, only about 10% of the essential oil remained 16 days after preparation of the emulsion, whereas the microcapsules of the invention retained more than -60% of their essential oil content 10 days after preparation and more than -35% of the essential oils retained 30 days after preparation. This clearly shows that the microcapsules disclosed herein have an advantageous release profile, which ensure that an optimal ratio between release and retention is achieved.
  • the average particle size of the microcapsules was established using Scanning electron Microscophy (SEM) (Quanta 200 FEI Company) according to standard protocols. In short, the microcapsules were air dried and coated with gold (gold deposition) using Polaron Equipment Limited SEM Coating Unit E5100 followed by imaging. The average particle size of the microcapsules was about 200nm. It is understood that the average particle size and size disversity can be adjusted by state of art methods, based on the needs of the application.
  • formulation 26 To establish the ability of formulation 26 to prevent post-harvest decay of crop, the formulation was diluted into a 3% aqueous solution. Oranges and lemons were immersed in the solution and subsequently stored fort 6 weeks at room temperature. Untreated oranges and lemons served as control. At the end of the six weeks, the oranges were evaluated for Penicillium digitatum and Penicillium ulaienseas infestation. The oranges and lemons treated with formulation 26 had significantly decreased infestation as compared to control, as determined by expert evaluation.
  • Tea tree oil, PEG/PPG block co-polymer, 30 wt% PEG, Mn 5,800 (block co-polymer A) and PEG/PPG block co-polymer, 82 wt% PEG, Mn 14,600 (block co-polymer B) were mixed (in the amounts of Table 17) in a beaker vessel with a high speed shear stirrer.
  • the mixture was absorbed onto Aerosil 300 in a rotating spray roller.
  • An alginic acid sodium salt 4% aqueous solution (pH value between 5 and 6) was sprayed into the absorbed mixture and rotation was continued until water was essentially evaporated and a powder obtained.
  • a 100ml solution of a 1% solution of calcium chloride in water was sprayed, and rotation was continued until water was essentially evaporated and a powder obtained.
  • the powder was ground into finer powder and placed in porous bags (sachets).
  • Example 2A was repeated using oregano oil instead of tea tree oil, according to table
  • Formulation 28 The efficacy of Formulation 28 is tested for protection of post-harvest fruits and vegetables against rot and pest infestation.
  • the following post-harvest fruits and vegetables are tested: carrots, bell peppers, grapes, tomatoes, sweet potatoes, strawberries.
  • the post- harvest fruits and vegetables are treated by placing the following sachets in vicinity of the crop for two weeks: a) Formulation 28 containing sachets:
  • Control 1 sachets containing powdered unencapsulated oregano oil.
  • Example 2B was repeated using thyme oil instead of oregano oil.
  • Example 2A was repeated using pine oil, pyrethrum and azadirachtin according to table 19.
  • the pine oil, pyrethrum and azadirachtin were mixed with the PEG/PPG block copolymer, 30 wt-% PEG, Mn 5,800 (block co-polymer A) and absorbed onto Aerosil 300 during rotation in a rotating spray roller.
  • a 4% Alginic acid sodium salt solution (pH 5 to 6) was sprayed into the absorbed mixture and rotation continued until most of the water was evaporated and a powder obtained.
  • Onto this powder a 2% calcium chloride aqueous solution was sprayed, and rotation was continued until the water was essentially evaporated and a powder obtained.
  • the powder was ground into a fine powder and placed in porous bags (sachets).
  • Example 2A was repeated using lOOg lemon eucalyptus (Quenling) (formulation 31), lOOg geranium oil (formulation 32), lOOg lavender oil (formulation 33) or lOOg citronella oil (formulation 34) instead of oregano oil.
  • Example 2A was repeated wherein the tea tree oil was replaced with citronella into which 5 or 15 grams abamectin was dissolved (formulation 35 and 36 respectively).
  • the resulting solid core microcapsules contained within its solid core both citronella and abamectin.
  • the encapsulation prevented the degradation of the abamectin as compared to the non-encapsulated abamectin that degraded rapidly, as checked by HPLC.
  • Example 3 preparation of homogenous solutions containing essential oils encapsulated in nano-sized capsules.
  • Lavender oil, sodium dodecyl sulfate (SDS), Tween 20, the PEG/PPG block copolymer, 30 wt% PEG, Mn 5,800 (block co-polymer A) and the PEG/PPG block co-polymer, 82 wt% PEG, Mn 14,600 (block polymer B) were mixed (in the amounts of Table 20) in a beaker vessel using a high speed shear stirrer. The mixture was added to a stirring vessel with water containing PEG 200 and the solution was stirred for 3 minutes. An alginic acid sodium salt 4% aqueous solution was subsequently added and stirring continued for an additional 10 minutes. Finally, calcium chloride was added followed by 3 minutes stirring.
  • Example 3A was repeated while replacing the PEG/PPG block co-polymer (30 wt% PEG, Mn 5,800) with the PEO-PPO block co-polymer (Rhodia block co-polymer PL/122), according to table 21 below.
  • the substrate When applied to a substrate, the substrate had a lavender odor, which remained for more than 7 days.
  • Example 3B was repeated using 62.5g jasmine oil instead of lavender oil.
  • the resultant solution was clear, transparent, and stable when submitted to accelerated stability tests at 54°C for 2 weeks.
  • the release rate is determined by coating glass slides with the formulations disclosed herein and with control formulations containing the active ingredient in its non-encapsulate form. The slides are then exposed to ambient conditions and the amount of essential oil remaining on the slide as a function of time is measured using High Performance Liquid Chromatography (HPLC) and Gas chromatography (GC) techniques.
  • HPLC High Performance Liquid Chromatography
  • GC Gas chromatography
  • the bacteria are grown on TSB (trypticase soy blood agar plates) and sheep blood agar plates at 37°C for 18 hours. Arcanobacterium pyogenes are grown at 3 °C for 42 hours. Next, the bacteria are washed from the plates with 0.9N sterile saline and suspended in sterile saline. The concentration of the bacterial suspension is adjusted to approximately 5xl0 8 CFU/ml. To the bacterial suspension, the tested essential oil formulations are applied at varying concentrations, ranging from 0.01% to 1%, at a final volume of approximately 5 ml. After vortexing for 10 minutes, the mixture are filtered through a sterile glass microfilter (GF/C 1.2 microns, Whatman) using a vacuum pump.
  • TSB trypticase soy blood agar plates
  • Arcanobacterium pyogenes are grown at 3 °C for 42 hours.
  • the concentration of the bacterial suspension is adjusted to approximately 5xl
  • the liquid filtrate is then diluted and transferred to TSBA and sheep blood agar plates.
  • the agar plates are incubated at the optimal temperatures for 18-42 hours; followed by colony count.
  • microcapsule formulations are tested for efficacy against the following mastitis bacteria: a) Escherichia coli, b) Staphylococcus Aureus, c) Micrococcus CNS, d) Streptococcus Dysgalactiae and e) Pseudomonas aeruginosa.
  • the experiment is conducted as follows: a) All nipples of udder are immersed in a 70% ethanol solution for 30 minutes. b) The udders are then washed twice with sterile water for 30 minutes.
  • Sausages are immersed in the formulations of the present invention, removed and left to dry, thereby leaving a coating of microcapsules. The decomposition of the treated sausages is then compared to non-treated sausages during several weeks.
  • Example 8 Insect and pest control experiments
  • Silver leaf whiteflies repellency Adult silver leaf whiteflies and eggs thereof are obtained from the University of Florida. Various leaves of tomato seedlings are treated, top or bottom, either with the formulations of the present invention or with one of the controls, and the efficacy of the formulation as a repellent is measured based on the number of whitefly adults repelled therefrom, and based on the number of eggs laid on the treated leaf.
  • the following solutions are used as controls: 1. water, 2. Ultra-Fine Oil (a commercial product containing paraffinic oil) and 3. Pyrethrum.
  • the formulations are sprayed at a rate of about 1 qtr. per acre on tomato transplants set 18 inches apart on raised beds of Myakka fine sand soil covered with white virtually impermeable mulch. Plots of three, 21 ft. long rows each row separated by 5 ft. from its neighboring row. Plots are irrigated by a drip irrigation system. Treatments are replicated four times in a randomized complete block design. Foliar applications are made with a high clearance, self-propelled sprayer operated at 200 psi and 3.4 mph.
  • the self-propelled sprayer is fitted with eight Albuz orange nozzles per row to deliver 60 gpa (4 nozzles open) or 90 gpa (6 nozzles open).
  • Whitefly densities and eggs are assessed on the middle 10 plants of the middle row of each plot.
  • the numbers of adults is counted weekly by carefully turning the third leaf of two stems of each plant.
  • the number of eggs are counted on adjacent leafs.
  • House fly (Musca Domestica) repellency To determine the fly repellency of the tested formulations, about 400 laboratory-grown are confined to a closed glass aquarium which contains paper sheets either sprayed with the formulations disclosed herein or left unsprayed. The number of flies landing on the paper sheets is counted.
  • Mosquito repellency To determine the mosquito repellency of the formulations, mosquitoes are confined to a closed glass aquarium, which contains paper sheets either sprayed with the formulations disclosed herein or left unsprayed. The number of mosquitos landing on the paper sheets is counted.
  • Root knot Nematode repellency The number of root-knot galls is counted on cucumber and tomato plant grown in soil infected by nematodes (1000 ppm) and either treated with the formulations of the present invention or left untreated.
  • Chironomidae repellency repellency of Chironomidae larvae and eggs is also tested.

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Abstract

L'invention concerne une microcapsule comprenant un noyau contenant au moins une huile essentielle ou un dérivé de celle-ci, et une enveloppe comprenant un complexe interpolymérique d'au moins un polyacide et d'au moins un autre polymère, le complexe interpolymérique étant réticulé avec au moins une fraction cationique multivalente.
PCT/IL2016/050407 2015-04-20 2016-04-19 Microcapsules à noyau liquide et solide formées par complexation interpolymérique WO2016170531A1 (fr)

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CN105603766A (zh) * 2016-02-25 2016-05-25 苏州三和开泰花线织造有限公司 一种复合精油微胶囊整理剂的制备方法及其应用
CN106538527A (zh) * 2016-11-03 2017-03-29 山东省农药科学研究院 d‑柠檬烯多囊壁厚度微胶囊制剂及其制备方法
CN107051342A (zh) * 2017-04-21 2017-08-18 贺州学院 一种脐橙果皮精油微胶囊的制备方法
CN108338163A (zh) * 2018-03-28 2018-07-31 陈太师 一种持效型杀菌灭藻剂的制备方法
CN108541866A (zh) * 2018-04-26 2018-09-18 福州大学 一种肉桂醛-海藻酸钠-壳聚糖纳米粒及其制备方法
FR3064190A1 (fr) * 2017-03-21 2018-09-28 Capsum Procede de preparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues
CN108967520A (zh) * 2018-05-24 2018-12-11 中北大学 一种紫苏精油微囊的制备方法及其应用
WO2019027633A1 (fr) * 2017-07-31 2019-02-07 Dow Global Technologies Llc Additif détergent
CN110419543A (zh) * 2019-06-05 2019-11-08 广西天浩农业发展有限公司 一种缓释型除虫剂及其制备方法
CN110577767A (zh) * 2018-06-07 2019-12-17 上海泛亚生命科技有限公司 一种微囊缓释型天然植物香氛功能涂料
JP2020509087A (ja) * 2017-02-23 2020-03-26 アリラ ヘルス ボストン エルエルシーＡｌｉｒａ Ｈｅａｌｔｈ Ｂｏｓｔｏｎ Ｌｌｃ バイオフィルムを破壊する環境に優しい抗菌製剤、その開発、およびその使用
CN111389315A (zh) * 2020-03-27 2020-07-10 南京芬之怡生物科技有限公司 一种绿色除异净化剂及其制备方法
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
WO2020249825A1 (fr) * 2019-06-14 2020-12-17 Folium Biosciences Europe B.V. Procédé de microencapsulation d'ingrédients naturels par mise en contact avec un gaz supercritique
CN112898467A (zh) * 2021-01-25 2021-06-04 唐山开滦化工科技有限公司 一种高温热膨胀微胶囊及其制备方法和应用
WO2021148684A1 (fr) * 2020-01-20 2021-07-29 Kimitec Biogroup, S.L. Compositions biopesticides qui comprennent des extraits végétaux et leur utilisation phytosanitaire
WO2021185736A1 (fr) 2020-03-18 2021-09-23 Givaudan Sa Produit de consommation comprenant une pluralité de microcapsules définies par la surface totale moyenne
CN113634203A (zh) * 2021-09-01 2021-11-12 蚌埠学院 一种柠檬乳化香精微胶囊制备装置及方法
CN113747880A (zh) * 2019-12-13 2021-12-03 弗门尼舍有限公司 混合微胶囊
WO2022112204A1 (fr) * 2020-11-25 2022-06-02 Givaudan Sa Améliorations apportées à des composés organiques ou se rapportant à ceux-ci
EP4230039A1 (fr) * 2022-02-17 2023-08-23 Biobab R&D, S.L. Composition pour empêcher la détérioration par des champignons des fruits, légumes et fleurs après la récolte, son procédé et son utilisation
US11771095B2 (en) 2020-03-13 2023-10-03 Harpe Bioherbicide Solutions Inc. Herbicidal Mentha pantsd, extract compositions and methods of using same000000000000000,001

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WO1995035093A1 (fr) * 1994-06-17 1995-12-28 University Of Nebraska Board Of Regents Vecteur d'apport de substances bio-efficaces a gelification in situ et methode d'utilisation
WO2007094000A2 (fr) * 2006-02-15 2007-08-23 Botanocap Ltd. Applications d'huiles essentielles microencapsulees
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105603766A (zh) * 2016-02-25 2016-05-25 苏州三和开泰花线织造有限公司 一种复合精油微胶囊整理剂的制备方法及其应用
CN106538527A (zh) * 2016-11-03 2017-03-29 山东省农药科学研究院 d‑柠檬烯多囊壁厚度微胶囊制剂及其制备方法
JP2020509087A (ja) * 2017-02-23 2020-03-26 アリラ ヘルス ボストン エルエルシーＡｌｉｒａ Ｈｅａｌｔｈ Ｂｏｓｔｏｎ Ｌｌｃ バイオフィルムを破壊する環境に優しい抗菌製剤、その開発、およびその使用
US11540979B2 (en) 2017-03-21 2023-01-03 Capsum Method for producing capsules comprising at least one water-soluble or hydrophilic substance, and resulting capsules
FR3064190A1 (fr) * 2017-03-21 2018-09-28 Capsum Procede de preparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues
WO2018172434A3 (fr) * 2017-03-21 2018-12-27 Capsum Procédé de préparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues
CN107051342A (zh) * 2017-04-21 2017-08-18 贺州学院 一种脐橙果皮精油微胶囊的制备方法
CN110869482A (zh) * 2017-07-31 2020-03-06 陶氏环球技术有限责任公司 洗涤剂添加剂
CN110869482B (zh) * 2017-07-31 2021-09-10 陶氏环球技术有限责任公司 洗涤剂添加剂
WO2019027633A1 (fr) * 2017-07-31 2019-02-07 Dow Global Technologies Llc Additif détergent
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
CN108338163A (zh) * 2018-03-28 2018-07-31 陈太师 一种持效型杀菌灭藻剂的制备方法
CN108541866A (zh) * 2018-04-26 2018-09-18 福州大学 一种肉桂醛-海藻酸钠-壳聚糖纳米粒及其制备方法
CN108967520A (zh) * 2018-05-24 2018-12-11 中北大学 一种紫苏精油微囊的制备方法及其应用
CN110577767A (zh) * 2018-06-07 2019-12-17 上海泛亚生命科技有限公司 一种微囊缓释型天然植物香氛功能涂料
CN110419543A (zh) * 2019-06-05 2019-11-08 广西天浩农业发展有限公司 一种缓释型除虫剂及其制备方法
WO2020249825A1 (fr) * 2019-06-14 2020-12-17 Folium Biosciences Europe B.V. Procédé de microencapsulation d'ingrédients naturels par mise en contact avec un gaz supercritique
CN113747880A (zh) * 2019-12-13 2021-12-03 弗门尼舍有限公司 混合微胶囊
WO2021148684A1 (fr) * 2020-01-20 2021-07-29 Kimitec Biogroup, S.L. Compositions biopesticides qui comprennent des extraits végétaux et leur utilisation phytosanitaire
ES2926555R1 (es) * 2020-01-20 2023-10-23 Kimitec Biogroup S L Composiciones biopesticidas que comprenden extractos vegetales y su uso fitosanitario
US11771095B2 (en) 2020-03-13 2023-10-03 Harpe Bioherbicide Solutions Inc. Herbicidal Mentha pantsd, extract compositions and methods of using same000000000000000,001
WO2021185736A1 (fr) 2020-03-18 2021-09-23 Givaudan Sa Produit de consommation comprenant une pluralité de microcapsules définies par la surface totale moyenne
CN111389315A (zh) * 2020-03-27 2020-07-10 南京芬之怡生物科技有限公司 一种绿色除异净化剂及其制备方法
WO2022112204A1 (fr) * 2020-11-25 2022-06-02 Givaudan Sa Améliorations apportées à des composés organiques ou se rapportant à ceux-ci
CN112898467A (zh) * 2021-01-25 2021-06-04 唐山开滦化工科技有限公司 一种高温热膨胀微胶囊及其制备方法和应用
CN113634203A (zh) * 2021-09-01 2021-11-12 蚌埠学院 一种柠檬乳化香精微胶囊制备装置及方法
EP4230039A1 (fr) * 2022-02-17 2023-08-23 Biobab R&D, S.L. Composition pour empêcher la détérioration par des champignons des fruits, légumes et fleurs après la récolte, son procédé et son utilisation
WO2023156435A1 (fr) 2022-02-17 2023-08-24 Biobab R&D, S.L. Composition pour la prévention de l'altération fongique dans des fruits, des légumes et des fleurs post-récolte, procédé et utilisation associés

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