WO2010101821A1 - Microencapsulated insecticide formulations - Google Patents
Microencapsulated insecticide formulations Download PDFInfo
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- WO2010101821A1 WO2010101821A1 PCT/US2010/025755 US2010025755W WO2010101821A1 WO 2010101821 A1 WO2010101821 A1 WO 2010101821A1 US 2010025755 W US2010025755 W US 2010025755W WO 2010101821 A1 WO2010101821 A1 WO 2010101821A1
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- microcapsule
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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
- A01N25/26—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
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Definitions
- Various aspects and embodiments relate generally to formulations of microencapsulated pesticides that exhibit advantageous biological, commercial and/or environmental properties.
- One aspect is a pesticide formulation comprising an organophosphate pesticide and a polymer; wherein the polymer forms a capsule wall which at least partially encapsulates the organophosphate pesticide to form a microcapsule, the wall having an average thickness of between about 5 nm to about 25 nm, said microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- the microcapsule wall has an average thickness of between about 8 nm to about 12 nm, said microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- the microcapsule includes at least one pesticide selected from the group of organophosphate pesticides selected from the group comprising: acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos-methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthion, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, and trichlorfon.
- the microcapsule includes the organophosphate pesticide chlorpyrifos.
- the microcapsule includes about at least between about 15 wt. percent to about 35 wt. percent chlorpyrifos.
- the microcapsule is formed by an interfacial polycondensation between at least one oil soluble monomer selected, for example, from the group consisting of: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates; and at least one water soluble monomer selected from the group consisting of, for example: diamines, polyamines, water soluble diols and water soluble polyols.
- oil soluble monomer selected, for example, from the group consisting of: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates
- water soluble monomer selected from the group consisting of, for example: diamines, polyamines, water soluble diols and water soluble polyols.
- the microcapsule exhibits toxicity in female rats of greater than about 5,000mgKg "1 and an LC 50 value for the initial control of Cotton Aphids (APHIGO) of less than about 30 ppm chlorpyrifos.
- the microcapsule exhibits toxicity in female rats of greater than about 2,500mgKg "1 and an LC 5O value for the initial control of Beet Army Worms (LAPHEG) of less than about 400 ppm chlorpyrifos.
- Another aspect is a method of synthesizing a microcapsule with insecticidal properties, comprising the steps of providing an organophosphate insecticide, and at least one monomer; mixing the organophosphate insecticide, and at least one monomer; and forming a microcapsule, wherein the monomer forms a polymer, the polymer forming a wall, wherein the wall at least partially encompasses a portion of the insecticide, to form a microcapsule, the wall having an average thickness of between about 5 nm to about 25 nm, and the microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- the polymer comprising at least a portion of the microcapsule wall is formed by the interfacial polycondensation of at least one oil soluble monomer selected from the group including: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates; and at least one water soluble monomer selected from the group including: diamines, polyamines, water soluble diols and water soluble polyols.
- the polymer forms a capsule wall that at least partially surrounds a portion of chlorpyrifos and the wall has an average thickness of between about 8 nm to about 12 nm, while the microcapsule has an average diameter in the range of about 2 microns to about 6 microns.
- the microcapsule includes on the order of at least 10 wt. percent chlorpyrifos.
- the polymer wall of the microcapsule at least partially surrounds at least one organophosphate pesticide is selected from the group that includes: acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos-methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthiom, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, trichlorfon and the like.
- Still another aspect is a method of controlling an insect population, comprising the steps of: providing an insecticidal particle formulation, wherein said particle includes: an organophosphate insecticide; and a polymer; wherein the polymer forms a capsule wall which at least partially encapsulates the organophosphate pesticide to form a microcapsule, in which the microcapsule wall has an average thickness of between about 5 nm to about 25 nm, and the microcapsule has an average diameter in the range of about 2 microns to about 6 microns; and applying said encapsulated insecticide to a surface, for example the leaves, stems or trunk of a plant.
- One embodiment is a method for controlling an insect population that includes the steps of: forming a microcapsule with insecticidal properties the microcapsule includes a wall formed by the interfacial polycondensation of at least one oil soluble monomer selected from the group consisting of: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates; and at least one water soluble monomer selected from the group consisting of: diamines, polyamines, water soluble diols and water soluble polyols; and at least one organophosphate insecticide is selected from the group consisting of: acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos- methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthiom, fenamiphos
- the microcapsule includes on the order of between about 15 wt. percent to about 35 wt. percent chlorpyrifos. In one embodiment the microcapsule used to control an insect population has a wall with an average thickness of between about 8 nm to about 12 nm, said microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- microencapsulated organophosphate insecticide used to control insect population with a toxicity value in female rats of greater than about 5,000mgKg "1 and an LC 5O for initial control of insects, such as cotton aphids, of less than about 30 ppm chlorpyrifos.
- the microcapsule has a toxicity value in female rats of greater than about 2,500mgKg "1 and an LC 50 for initial control of insects, such as beet army worms, of less than 400 ppm chlorpyrifos.
- FIG. 1 LC 50 values (ppm of chlorpyrifos) plotted as a function of DAT, measured for various insecticide formulations, when tested for efficacy against Beet Army Worms (LAPHEG).
- FIG. 2 LC 5O values (ppm of chlorpyrifos) plotted as a function of DAT, measured for various microcapsule and control formulations of chlorpyrifos tested for efficacy against Cotton Aphids (APHIGO).
- the invention provides a microencapsulated pesticide formulation that includes at least one pesticide for the extermination or control of at least one pest.
- the pesticide is or at least includes at least one organophosphate pesticide.
- Organophosphate pesticides that can be used include, but are not limited to, the following compounds and various derivatives thereof: acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos- methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthiom, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, and trichlorfon and the like.
- the microcapsule shell can be formed by a polymer which wholly or partially covers a pesticide rich core.
- the shell of the microcapsule can be comprised by a wall, in which the wall is made up of a polymer.
- Some suitable polymers that can be used to construct the microcapsule wall includes at least one type of monomer linked together to form the polymer.
- the polymer wall is formed by the interfacial polycondensation of a monomer that is primarily water soluble and another monomer that is primarily insoluble in water.
- Suitable primarily water insoluble monomers that can be used to form the wall of the microcapsule include, but is not limited to, compounds such as diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates, and the like.
- Suitable primarily water soluble monomers that can be used to form the wall of the microcapsule include, but is not limited to, compounds such as diamines, polyamines, water soluble diols and water soluble polyols.
- the wall comprising at least a portion of the shell of some microcapsules has an average thickness of between about 5 nm to about 25 nm the microcapsule may also have an average diameter in the range of about 2 microns to about 6 microns. In some embodiments the microcapsule wall has an average thickness of between about 8 nm to about 12 nm, said microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- the term 'about' implies plus or minus ten percent of the stated value or range of values. For example: "about" 12, includes values ranging from 10. 2 to 13.2; about 10 wt. percent encompasses formation that include between 9 to 1 1 wt. percent; and the like.
- Microcapsules according to various aspects and embodiment exhibit good toxicity towards target insect populations and LD 50 values measured in female rats in the range of greater than about 2,500mgKg "1 .
- the microcapsule has an LD 50 value measured in female rats in the range of greater than about 5,000mgKg "1 , typically these values are expressed in terms of the amount of pesticide in the formulation as a fraction of the body weight of the test mammal.
- these microcapsules exhibit LD 50 values, measured in female rats, in the range of about 2,500mg of active insecticide.
- the microcapsules are also effective at killing, inhibiting or repelling pests. Some embodiments are well suited to treat or control insect population on contact with the insect.
- one formulation includes about 25 wt. percent chlorpyrifos and has an LC 5O value of about 30 pm of chlorpyrifos against Cotton Aphids (APHIGO) when a preparation of the microcapsule is applied to a population of insects or to an area adjacent to a population of insects.
- APHIGO Cotton Aphids
- the microcapsule is useful for the treatment of chewing insects such as Beet Army Worms (LAPHEG).
- LAPHEG Beet Army Worms
- the formulation includes about 25 wt. percent chlorpyrifos, and has an LC 50 value of about 450 ppm for the initial control of Beet Army Worms of less than about 400 ppm chlorpyrifos when a preparation of the microcapsule is applied to an area of a plant adjacent to an insect population.
- the formulation includes about 25 wt. percent chlorpyrifos and has an LC 50 value of about 50 ppm against Cotton Aphids (APHIGO) when a preparation of the microcapsule is applied to plants at a final level of less than about 30 ppm chlorpyrifos.
- APHIGO Cotton Aphids
- the microcapsule is useful for the treatment of chewing insects such as Beet Army Worms (LAPHEG).
- LAPHEG Beet Army Worms
- the formulation includes about 20 wt. percent chlorpyrifos, and is as effective as Lorsban® for the initial control of Beet Army Worms when applied at a rate of between 185 - 1 ,000 ppm chlorpyrifos. The same formulation is more effective than Lorsban® at controlling Beet Army Worms five days after its application.
- Another aspect of the invention is a method of synthesizing a microcapsule with insecticidal properties.
- the method comprises the steps of providing an insecticide, for example, an organophosphate insecticide, and at least one molecule that can be used to form a coating which at least partially covers the insecticide forming at least a partial barrier between the insecticide and the environment.
- the coating, shell or at least components of the microcapsule wall is formed by a monomer which can be reacted with similar or different monomer to form a polymer that forms the wall of the microcapsule. Additional steps may include mixing the insecticide and the wall forming components together and reacting at least some of the components to form a wall structure that at least partially covers or coats or sequesters the insecticide within a portion of the microcapsule.
- the insecticide provided to form the microcapsule is an organophosphate such as one of the following compounds: acephate, azinphos- mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos-methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthiom, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, trichlorfon and the like.
- the insecticide is chlorpyrifos.
- the polymer comprising at least a portion of the microcapsule wall is formed by an interfacial polycondensation of at least one oil soluble monomer selected from the group including: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates; and at least one water soluble monomer selected from the group including: diamines, polyamines, water soluble diols and water soluble polyols.
- a microcapsule with insecticidal properties is formed by a polymer that at least partially encompasses an organophosphate insecticide such as chlorpyrifos.
- the polymer forms a wall that at least partially surrounds a portion of chlorpyrifos and the wall has an average thickness of between about 8 nm to about 12 nm. In another embodiment the wall has an average thickness of between about 5 nm to about 25 nm. In one embodiment the microcapsule has an average diameter in the range of about 2 microns to about 6 microns.
- Still another aspect is a method of controlling an insect population, comprising the steps of: providing an insecticidal particle formulation, wherein said particle includes: an organophosphate insecticide; and a polymer; wherein the polymer forms a capsule wall which at least partially encapsulates the organophosphate pesticide to form a microcapsule, in which the microcapsule wall has an average thickness of between about 5 nm to about 25 nm, and the microcapsule has an average diameter in the range of about 2 microns to about 6 microns; and applying said encapsulated insecticide to a surface, for example the leaves, stems or trunk of a plant.
- One embodiment is a method for controlling an insect population that includes the steps of: forming a microcapsule with insecticidal properties the microcapsule includes a wall formed by the interfacial polycondensation of at least one oil soluble monomer selected from the group consisting of: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, and chloroformates; and at least one water soluble monomer selected from the group consisting of: diamines, polyamines, water soluble diols and water soluble polyols; and at least one organophosphate insecticide is selected from the group consisting of: acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos- methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthiom, fenamiphos
- the microcapsule includes on the order of about at least 10 wt. percent chlorpyrifos. In one embodiment the microcapsule used to control an insect population has a wall with an average thickness of between about 8 nm to about 12 nm, said microcapsule having an average diameter in the range of about 2 microns to about 6 microns.
- a microencapsulated organophosphate insecticide used to control insect population that has a toxicity value in female rats of greater than about 5,000mgKg "1 and an LC 50 for initial control of insects, such as Cotton Aphids (APHIGO), of less than about 30 ppm chlorpyrifos.
- the microcapsule has a toxicity value in female rats of greater than about 2,500mgKg "1 and an LC 5O for initial control of insects, such as Beet Army Worms (LAPHEG) of less than about 400 ppm chlorpyrifos.
- LAPHEG Beet Army Worms
- Particle formulations including microcapsules that include at least one compound toxic to at least one insect species, especially an insect species that serves as a vector for human or animal disease or is a threat to commercially important plant species, are of great importance.
- Compounds that are toxic to insects include, but are not limited to, organophosphates such as acephate, azinphos-mehyl, chlorfenvinphos, chlorethoxyfos, chlorpyriphos, chlorpyriphos- methyl, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthion, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, trichlorfon and the like.
- Organochlorines are another class of molecules with insecticidal properties and include compounds such as, heptachlor, dichloro-diphenyl- trichloroethane, dicofol, endosulfan, chordane, mirex and pentachlorophenol.
- Another class of insecticides and insect repellants are the pyrethroids, these compounds are similar to the naturally occurring compound pyrethrum, and include, for example, alletherin, bifenthrin. cypermethrin, deltamethrin, permethrins, prallethrin, resmethrein, sumithrin, tetramethrin, tralomehtrin.
- Still another class of insecticides is similar to the naturally occurring compound nicotine, in addition to nicotine this class of insecticides and insect repellants includes the following compounds: acetamiprid, clothianidin, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam.
- particles that incorporate any method that can be used to form a shell, layer, coating or wall.
- the active ingredient in such particles is primarily located inside of the wall although full coverage of the active ingredient is not necessarily required to form a particle; particles include formulations in which at least a portion of the active ingredient is contiguous with the wall or even lies outside of at least a portion of the wall.
- One method for forming a particle that includes forming a full or partial wall, which acts to separate either fully or partially an insecticide from the bulk solvent or environment is interfacial polycondensation of monomers. Briefly, a mixture of monomers is condensed to form a polymeric wall in the presence of at least one insecticide.
- a wall comprising a polymer essentially forms the outer boundary of the particle; the insecticide may be primarily concentrated within the particle bounded by a continuous or discontinuous wall that forms the outer contour of the particle.
- Monomers that can be used to form particles by the process of interfacial polycondensation may include primarily oil soluble monomers or set of such monomers and a water soluble monomer or set of such water soluble monomers.
- Oil soluble monomers include, for example, compounds selected from the group comprising: diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides, chloroformates and the like.
- Water soluble monomers include, for example, compounds selected from the group comprising: diamines, polyamines, water soluble diols and polyols.
- Various properties are required to form an insecticide or insect repellant with desirable characteristics. These properties include toxicity towards insects or at least the effect of repelling target insects or limiting their development and/or ability to reproduce. Still another desirable property is low or ideally absent toxicity towards other animals such as mammals, especially humans, or towards plants or non-target, especially, beneficial insect species.
- Pesticide formulations that retain efficacy against target pest populations for extended periods of time may need to be applied less frequently or in lower initial amounts in order to control target pests thereby affording a savings in labor, energy and materials.
- formulations that have long half-lives for example half-lives that extend significantly past the growing season of specific crops or peak infestation times of target pests may be considered an environmental nuisance under some circumstances.
- these embodiments include insecticide formulations with particle sizes and wall thickness that result in particles that exhibit high initial knock-down activity including contact activity against target insects, toxicity LD 50 values against female rats on the order of about 2,500 mgKg "1 and in some cases higher and favorable residue values.
- Chlorpyrifos (Wgt g) 15 522 15 419 15 574 15 522
- Bentonite clay (g) 5 0 455 0 455 0 455 0 455 0 455
- Aromatic 100 (g), Exxon Mobile Corp., Fairfax, VA.
- a speed of -4500-7500 rpm was typically required to reach the desired size.
- the crosslinking amine ethylenediamine (EDA), Aldrich) was added dropwise as a 10% aqueous solution while stirring at a reduced speed that maintained good mixing. Following the completion of the amine addition the resulting capsule suspension was stirred for an additional minute, the indicated amount of Atlox 4913 (Uniqema) was added, and a final brief homogenization was performed to complete the preparation of the capsule suspension.
- the amount of monomer, cross-linking agents, wetting agents, buffer, and the like can be adjusted to create microencapsulated organophosphate insecticidal formulations having varying capsule and shell thicknesses.
- Measurement of Particle Size in Microcapsule Suspensions [0047] Capsule suspension particle size distributions were determined using a Malvern Mastersizer 2000 light scattering particle sizer fitted with a small volume sample unit and using software version 5.12. Prior to measurement the samples were shaken or stirred well to insure homogeneity. The volume median distribution (VMD) is reported for each formulation in the Materials section above. Calculation of Capsule Wall Thickness
- Pyrinex CS® is a registered trademark of the Bayer Corporation.
- the compound is an encapsulated form of chlorpyrifos.
- the material used as a control in the experiment reported on herein was manufactured by Makhteshim Chemical Works, Be'er Sheva, Israel. According to a Material Safety Data Sheet provided by the supplier, Pyrinex CS has an oral toxicity, LD 50 value of >20,000 mgKg "1 .
- Lorsban 4E is an emulsified concentrate of chlorpyrifos, marketed by Dow Agro Sciences, Indianapolis, Indiana, USA. According to a Material Data Safety Sheet available through the supplier, Lorsban 4E has a LD 5 O value in female rats of about 300 mgKg "1 .
- Lorsban CS and Pyrinex were selected for use as controls in many of the tests because these formulations represent two extremes in chlorpyrifos formulations.
- Lorsban is an emulsified concentrate known for having excellent knock-down activity, and an LD 50 value of about 300 mgKg "1 in female rats, while Pyrinex has an LD 50 value in female rats on the order of about 20,000 mgKg "1 and poor knock-down activity.
- Toxicity data for Lorsban and Pyrinex are from the Material Safety Data Sheet of the two formulations.
- Larvae were held in an environmental chamber at 25C/40%RH. Mortality was scored at 24 hours post infestation and a larva was considered dead if it could not move when prodded. Data were analyzed by using a log-dose probit transformation to determine the LC 5 oS and LC 90 S and their 95% confidence level.
- Procedure Formulations were diluted to provide 1 kg chlorpyrifos/200L spray volume and sprayed on 12 plants at the 2-3 leaf stage (cotyledon). Plants were transported to the greenhouse (80-90°F/70-80%RH) and applied at a spray volume of 200L/Ha at a rate of 1 kg a.i./Ha.
- Assay GC/MS was used to measure the concentration of chlorpyrifos in the extract. No concentration of samples was required.
- the objective of the study was to determine the potential of the test substance to produce lethal effects at a fixed dose level.
- An initial dose of 2,000 mgKg "1 was administered to a single female animal. Since the initial animal survived following dosing, the test substance was administered sequentially to 4 additional females so a total of five animals were dosed.
- test substance was administered sequentially to two additional female rats. Since all animals survived, testing was terminated and the LD 50 values were considered greater than 5,000 mgKg "1 .
- Rats weighing 1 13.0 - 143.2 g at study start were used for this study.
- the rats were dosed starting at the age of about two months and they were necropsied between 2-3 weeks later.
- Female F344/DuCrl rats were used in this study because of its general acceptance and suitability for acute oral toxicity testing, the availability of historical data, and the reliability of the commercial supplier.
- the test animals were obtained from Charles River Laboratories Inc. (Raleigh, North Carolina). The age of the animals at the start of the study was 8-1 1 weeks
- the animals were housed two-three per cage in stainless steel cages, in rooms designed to maintain adequate conditions (temperature, humidity, and photocycle), and acclimated to the laboratory for at least one week prior to the start of the study. Animals were housed one per cage in stainless steel cages. The relative humidity was maintained within a range of 40-70%. The average room temperature was maintained at 22 ⁇ 1 0 C (with a maximum permissible excursion of ⁇ 3 0 C). A 12-hour light/dark photocycle was maintained for all animal room(s) with lights on at 6:00 a.m. and off at 6:00 p.m. Room air was exchanged approximately 12-15 times/hour. Cages had wire mesh floors and were suspended above absorbent paper. Cages contained a hanging feeder and a pressure activated lixit valve-type watering system. Randomization and Identification
- Rats were randomly assigned to dose groups using a computer program. Rats were identified via a code number transmitted by a subcutaneously implanted transponder (BioMedic Data Systems, Seaford, Delaware). Feed and Water
- the IACUC has determined that the proposed Activities were in full accordance with these Final Rules.
- the IACUC - approved Animal Care and Use Activities to be used for this study were Acute Tox
- This examination was typically performed with the animals in their cages and was designed to detect significant clinical abnormalities that were clearly visible upon a limited examination, and to monitor the general health of the animals. The animals were not hand-held for these observations unless deemed necessary. Significant abnormalities that could be observed include, but were not limited to: decreased/increased activity, repetitive behavior, vocalization, uncoordination/limping, injury, neuromuscular function (convulsion, fasciculation, tremor, twitches), altered respiration, blue/pale skin and mucous membranes, severe eye injury (rupture), alterations in fecal consistency, and fecal/urinary quantity. In addition, all animals were observed for morbidity, mortality, and the availability of feed and water at least twice daily. Detailed Clinical Observations
- a Detailed Clinical Observation was conducted for all rats prior to test material administration for comparison with the observations recorded throughout the study. Animals were observed a minimum of two times on the day of treatment. A DCO was done each day (including weekends and holidays) during the study. Hand-held and open-field observations included a careful physical examination according to an established format. For scored DCOs only observations other than those that were typically expected were recorded. Observations were dictionary based, and the dictionary contained most of the common physical and neurologic abnormalities seen in toxicity studies. Since not all potential observations were contained in the dictionary, free-field descriptions also were allowed. Pathology
- Lorsban 4E is not as active at ODAT as the experimental capsules and continues to decline over time. Pyrinex remains virtually unchanged with time and shows even less initial activity than Lorsban 4E.
- the values for Microcapsule formulation CCS-O (3 micron, 5 nm) breaks suddenly after 4DAT even though it shows better activity than Lorsban 4E at 0 and 4 DAT.
- FIG. 2 is a graph of these LD 50 values versus DAT.
- Aphids pose a significant challenge to most capsule formulations because contact and not ingestion of chlorpyrifos is the primary route of exposure for this pest to the insecticide.
- the aphids were sprayed directly with the formulation and we expected that the encapsulated formulations would not be as active as the emulsified concentrates.
- the experimental capsules performed equal to or better than the formulation of Lorsban 4E and with better residual control.
- micron microcapsules were superior to 6 micron microcapsules and microcapsules with thinner walls were superior to capsules with thicker walls. Pyrinex performed poorly in the test as would be expected for a conventional capsule formulation.
- the surprising results are that microcapsule formulations CCSO, CCS1 , CCS2, CCS3 exhibit excellent activity against a non-chewing pest such as Cotton Aphids.
- microcapsule formulations CCS-O and CCS-1 were studied.
- the microcapsule formulation CCS-O had an oral toxicology rate towards female rats on the order of about GL 50 >2000 mgKg "1 ; while the microcapsule formulation CCS-1 had an LD 50 >5000 mgKg "1 value towards female rats.
- This same microcapsule also exhibits good knockdown and residual activity against Cotton Aphids (Table 12). As well as excellent knockdown and residual activity against Beet Army worms (Table 3). A residue value as good as Lorsban 4E (Table 14).
- microcapsule formulations of chlorpyrifos disclosed herein have a toxicity LD 50 value greater that about 2,500, towards female rats and high knock-down activity against two common plant pests. Without being bound by any theory or specific explanation, these results are consistent with microcapsules having advantageous size and wall thickness. Given the wide range of possible microcapsule sizes and wall thicknesses that can be made it is fortuitous that these compounds were made and that they exhibit these advantageous biological characteristics.
Abstract
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Priority Applications (19)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI201030837T SI2403333T1 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated chlorpyrifos formulations |
MA34211A MA33172B1 (en) | 2009-03-04 | 2010-03-01 | Microbial insecticide formulations |
EP10706878.5A EP2403333B1 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated chlorpyrifos formulations |
CN201080019840.2A CN102413683B (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
NZ594839A NZ594839A (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
PL10706878T PL2403333T3 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated chlorpyrifos formulations |
UAA201111678A UA106980C2 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
KR1020117022996A KR101698622B1 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
BRPI1013359A BRPI1013359A8 (en) | 2009-03-04 | 2010-03-01 | MICROENCAPSULATED INSECTICIDE FORMULATIONS. |
RU2011140164/13A RU2529165C2 (en) | 2009-03-04 | 2010-03-01 | Microincapsulated insecticidal composition |
JP2011553007A JP5814130B2 (en) | 2009-03-04 | 2010-03-01 | Microcapsule insecticide formulation |
AU2010221556A AU2010221556B2 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
CA2754434A CA2754434C (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations |
DK10706878.5T DK2403333T3 (en) | 2009-03-04 | 2010-03-01 | Microencapsulated formulations klorpyrifos |
MX2011009254A MX2011009254A (en) | 2009-03-04 | 2010-03-01 | Microencapsulated insecticide formulations. |
ES10706878.5T ES2521521T3 (en) | 2009-03-04 | 2010-03-01 | Chlorpyrifos formulations in microcapsules |
ZA2011/06267A ZA201106267B (en) | 2009-03-04 | 2011-08-25 | Microencapsulated insecticide formulations |
IL214909A IL214909A (en) | 2009-03-04 | 2011-08-31 | Microencapsulated insecticide formulations |
HK12109939.1A HK1168995A1 (en) | 2009-03-04 | 2012-10-10 | Microencapsulated insecticide formulations |
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US15733909P | 2009-03-04 | 2009-03-04 | |
US61/157,339 | 2009-03-04 |
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US (1) | US8916520B2 (en) |
EP (1) | EP2403333B1 (en) |
JP (1) | JP5814130B2 (en) |
KR (1) | KR101698622B1 (en) |
CN (1) | CN102413683B (en) |
AU (1) | AU2010221556B2 (en) |
BR (1) | BRPI1013359A8 (en) |
CA (1) | CA2754434C (en) |
CO (1) | CO6410270A2 (en) |
DK (1) | DK2403333T3 (en) |
EC (1) | ECSP11011301A (en) |
ES (1) | ES2521521T3 (en) |
HK (1) | HK1168995A1 (en) |
IL (1) | IL214909A (en) |
MA (1) | MA33172B1 (en) |
MX (1) | MX2011009254A (en) |
MY (1) | MY162663A (en) |
NZ (1) | NZ594839A (en) |
PL (1) | PL2403333T3 (en) |
PT (1) | PT2403333E (en) |
RU (1) | RU2529165C2 (en) |
SI (1) | SI2403333T1 (en) |
UA (1) | UA106980C2 (en) |
WO (1) | WO2010101821A1 (en) |
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US9253979B2 (en) | 2010-12-29 | 2016-02-09 | Dow Agrosciences Llc | Methods of controlling insects |
WO2016124927A1 (en) * | 2015-02-03 | 2016-08-11 | Eden Research Plc | Encapsulation of high potency active agents |
US10004229B2 (en) | 2004-01-23 | 2018-06-26 | Eden Research Plc | Nematicidal compositions and methods of using them |
WO2019027634A1 (en) * | 2017-07-31 | 2019-02-07 | Dow Global Technologies Llc | Additive composition and method |
US10258033B2 (en) | 2005-11-30 | 2019-04-16 | Eden Research Plc | Compositions and methods comprising terpenes or terpene mixtures selected from thymol, eugenol, geraniol, citral and L-carvone |
US10383329B2 (en) | 2012-11-21 | 2019-08-20 | Eden Research Plc | Preservatives |
US10638750B2 (en) | 2004-05-20 | 2020-05-05 | Eden Research Plc | Compositions containing a hollow glucan particle or a cell wall particle encapsulating a terpene component, methods of making and using them |
US10667512B2 (en) | 2005-11-30 | 2020-06-02 | Eden Research Plc | Terpene-containing compositions and methods of making and using them |
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