Compositions and methods for insect pest control

Abstract

Pesticide compositions and method of making and using them are described herein. In particular, described herein are synthetic pheromone-based pesticides formulated with one or more basic amino acids. For example, described herein are pesticide formulations that include one or more saturated fatty acids, and one or more unsaturated fatty acids in combination with a basic amino acid.

Description

COMPOSITIONS AND METHODS FOR INSECT PEST CONTROLCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S Provisional Patent Application No. 63 / 489,996, titled “COMPOSITIONS AND METHODS FOR INSECT PEST CONTROL”, filed on March 13, 2023, which is herein incorporated by reference in its entirety.INCORPORATION BY REFERENCE

[0002] All publications and patent applications mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.FIELD

[0003] Described herein are methods, reagents, and compositions for insect pest control. In particular, described herein are pesticide formulations that include one or more saturated fatty acids, and one or more unsaturated fatty acids in combination with a basic amino acid.BACKGROUND

[0004] Pesticides provide many benefits as they protect crops against loss due to pest damage and enable greater yields of food. However, many existing pesticides are toxic or harmful and can cause both acute and long-term health impacts. Chemical pesticides can have detrimental, dermatological, gastrointestinal, neurological, carcinogenic, respiratory, reproductive, and endocrine effects. The United Nations, the European Union, and the United States have called for action to minimize the adverse effects of pesticides to human and environmental health. Alternatives to these chemical pesticides include use of pheromones as pesticides. The use of host-marking pheromones (HMP) as a pesticide in a method of combating insect pests is based on a modification of the natural communication mode of the insect itself Pheromones are molecules that provide chemical communication between individuals of the same species. Candidate pheromones can include unsaturated and unsaturated fatty acids. Unsaturated and saturated fatty acids generally have different states of matter at room temperature. While many unsaturated fatty acids are liquid at room temperature, most saturated fatty acids are solid at room temperature. Generally, the more hydrogen atoms a fatty acid has, the higher its melting temperature will be. For example, butter, which contains various saturated fatty acids, is solid at room temperature and does notmelt until it reaches temperatures around 32°C to 35°C (90°F to 95°F). The solid state of saturated fatty acids at, for example, room temperature, provides a particular challenge when trying to deliver the fatty acids to plants or plant parts or plant products as a treatment. Plants are typically outside where temperatures are frequently well below temperatures of 32°C to 35°C (90°F to 95°F) and furthermore, vary considerably during the day. Spray devices that are typically used to disperse pesticides (such as to plant leaves and fruits) cannot readily distribute a solid substance. Pesticide components that are physically very different from each other (such as liquid vs solid) are typically incompatible. Even pesticides in a liquid state can cause problems with pesticide spray devices as they can separate out of solution, gel, curdle, or clog the equipment during application. Past attempts to provide pheromone-based pesticides utilized solvents (such as methanol) to carry the pheromones, but these solvents themselves were toxic or problematic.SUMMARY OF THE DISCLOSURE

[0005] Described herein are pesticides that may address the needs and challenges discussed above. In particular, described herein are pesticide formulations that include one or more saturated fatty acids, and one or more unsaturated fatty acids in combination with an excess of basic amino acid (e.g., one or more of arginine, such as L- Arginine, lysine, histidine, etc.). The basic amino acid may stabilize and enhance efficacy of the various saturated and unsaturated fatty acids included in the formulation.

[0006] For example, described herein are pesticide formulation comprising: a pheromone component comprising: a first compound comprising a first saturated fatty acid component; a second compound comprising a second saturated fatty acid component different from the first saturated fatty acid component; a third compound comprising a first unsaturated fatty acid component; a fourth compound comprising a second unsaturated fatty acid component different from the first unsaturated fatty acid component; and an accessory compound comprising a basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first and second saturated fatty acid components is from 5:1 to 1000:1, and wherein the pesticide is an aqueous solution.

[0007] The ratio of the mass amount of the basic amino acid component to the combined mass amount of the first and second saturated fatty acid components may be from about 2: 1 to about 24:1. In some examples a ratio of the mass amount of basic amino acid component to the combined mass amount of the first and second unsaturated fatty acid components is from about 0.5 : 1 to about 1000: 1. A ratio of the mass amount of basic amino acid component to a combined mass amount of the first and second saturated fatty acid components may be fromabout 2: 1 to about 24: 1. In some examples, a ratio of the combined mass amount of the first and second saturated fatty acid components to a combined mass amount of the first and second unsaturated fatty acid components is from about 5:1 to about 1:5. A ratio of the combined mass amount of the first and second saturated fatty acid components to a combined mass amount of the first and second unsaturated fatty acid components may be about 5:4.

[0008] The first saturated fatty acid component and the second saturated fatty acid component may each independently comprise a linear saturated fatty acid having from 6 to 26 carbon atoms. The first saturated fatty acid component and the second saturated fatty acid component may each independently comprise a linear saturated fatty acid having 16 to 20 carbon atoms. The first saturated fatty acid component and the second saturated fatty acid component may each independently comprise a linear saturated fatty acid having 16 to 18 carbon atoms. For example, the first saturated fatty acid component may be palmitic acid and the second saturated fatty acid component may be stearic acid. In some examples the first saturated fatty acid component and the second unsaturated fatty acid component each independently comprise a linear unsaturated fatty acid having from 6 to 26 carbon atoms. For example, the first unsaturated fatty acid component and the second unsaturated fatty acid component may each independently comprise a linear saturated fatty acid having from 16 to 20 carbon atoms. The first unsaturated fatty acid component may be, for example, oleic acid and the second unsaturated fatty acid component may be linoleic acid. In some examples the first saturated fatty acid component is palmitic acid, the second saturated fatty acid component is stearic acid, the first unsaturated fatty acid component is oleic acid, and the second unsaturated fatty acid component is linoleic acid, and the basic amino acid may be, for example, arginine (e.g., D-Arg or L-Arg, preferably L-Arg), further wherein the mass amount of the palmitic acid to the mass amount of the stearic acid to the mass amount of oleic acid to the mass amount of linoleic acid to the mass amount of L-Arg is about 3:2:3:1:12.

[0009] The basic amino may comprise one or more of arginine, citrulline, histidine, lysine, or ornithine. For example, the basic amino may comprise L-Arginine (L-Arg). In general these formulations may be a liquid when at a temperature of 23°C. The formulation may be a liquid when at a temperature of 4°C.

[0010] In some examples the pesticide formulation comprising an aqueous solution of: a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid; a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid; a first unsaturated fatty acid component comprising oleic acid or a salt, ester or isomer of oleic acid; a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleic acid; and a basic amino acid componentcomprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) is 3 : 1 or greater, further wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation.

[0011] A ratio of a first component to a second component (e.g., first component : second component) that is X: 1 or greater may refer to a ratio in which X increases (e.g., a ratio in of 3:1 or greater may refer to 4:1, 5:1, 6:1, 7: 1, 8:1, etc., including fractional values of X).

[0012] In some examples, the ratio of the basic amino acid : fatty acid may be between about 3 : 1 to about 1000: 1. The ratio of the basic amino acid : fatty acid may be 5 : 1 or greater.

[0013] In some examples the solution may include a ratio of the mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component and the second saturated fatty acid component (basic amino acid : saturated fatty acids) is 5:1 or greater (e.g., 6:1 or greater, 7:1 or greater, 8:1 or greater, etc., including between 5: 1 and 1000:1, etc.).

[0014] Any of these formulations may include an ethyl alcohol, wherein 5% or less of the total volume of the formulation comprises ethyl alcohol (e.g., 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, 1% or less, etc.).

[0015] As mentioned, in any of these examples the basic amino acid component comprises L-Arginine.

[0016] In any of these examples, the first saturated fatty acid component may be between about 20-25% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component may be between about 30-35% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component may be between about 30-35% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component may be between about 8-14% of the total mass amount of fatty acids in the formulation. In some examples, the composition includes about 33.3% palmitic acid, about 33.3% oleic acid, about 22.2% stearic acid, and about 11.1% linoleic acid.

[0017] Any of these formulations may include one or more monoterpin. For example, any of these compositions may include one or more of: ascaridole, bomane, borneol, camphene,camphor, camphorquinone, 3 -carene, carvacrol, carveol, carvone, carvonic acid, chrysanthemic acid, chrysanthenone, citral, citronellal, citronellol, cuminaldehyde, p- cymene, cymenes, epomediol, eucalyptol, fenchol, fenchone, geniposide, geranic acid, geraniol, geranyl acetate, geranyl pyrophosphate, geranylacetone, grandisol, grapefruit mercaptan, halomon, hinokitiol, hydroxycitronellal, 8-hydroxygeraniol, incarvillateine, (s)- ipsdienol, isobomeol, jasmolone, lavandulol, lavandulyl acetate, levoverbenone, limonene, linalool, linalyl acetate, lineatin, p-menthane-3,8-diol, menthofuran, menthol, menthone, menthoxypropanediol, menthyl acetate, 2-methylisoborneol, monoterpene, myrcene, myrcenol, myrtenal, myrtenol, nerol, nerolic acid, ocimene, 8-oxogeranial, paramenthane hydroperoxide, perilla ketone, perillaldehyde, perillartine, perillene, phellandrene, picrocrocin, pinane, 2-pinanol, pinene, A-pinene, B-pinene, pinocarveol, piperitone, pulegone, rhodinol, rose oxide, sabinene, safranal, sobrerol, terpinen-4-ol, terpinene, terpineol, thujaplicin, thujene, thujone, thymol, thymoquinone, umbellulone, verbenol, verbenone, wine lactone.

[0018] The formulations described and formed as described herein, including an excess of one or more basic amino acid (e.g., L-Arg) may be surprisingly advantageous as compared to other solutions of fatty acids, and in particular solution including saturated fatty acids which are exceptionally difficult to hold in solution, particularly at lower temperatures and longer (e.g., greater than 1 week, 2 weeks, 3 weeks, 1 month, 2 months, 3 months, 6 months, etc.) times. Surprisingly the formulations described herein have been found to be stable, with the components remaining in solution (and the formulation optically clear) for an extended period. Thus, in general, these formulations may be shelf stable at room temperature for more than, e.g., 6 months (e.g., 7 months, 8 months, 9 months, 10 months, 11 months, 12 months, 1.5 years, 2 years, etc.).

[0019] Also described herein are methods of using any of these compositions. For example, described herein are methods of using any of these compositions as a pesticide to deter pests. For example, described herein are methods of treating a plant to deter pests. Any appropriate plant may be treated (e.g., crops, grasses, food crops, fruit, vegetables, flowers, trees, shrubs, bushes, etc.). A method may include applying any of these formulations to a plant. For example, a method may include: applying, to the plant, a pesticide formulation comprising an aqueous solution of: a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid; a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid; a first unsaturated fatty acid component comprising oleic acid or a salt, ester or isomer of oleic acid; a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleicacid; and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) is 3:1 or greater, further wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation.

[0020] The formulation may be applied in any appropriate manner, including, but not limited to spraying (e g., a mist, aerosol, etc.).

[0021] Also described herein are methods of making (e.g., formulating) any of these compositions. For example, described herein are methods of making a pesticide formulation, the method comprising: combining a stock solution of a first saturated fatty acid component, a stock solution of a second saturated fatty acid component, a stock solution of a first unsaturated fatty acid component, and a stock solution of a second unsaturated fatty acid component, wherein the stock solution of the first saturated fatty acid component comprises stearic acid or a salt, ester or isomer of stearic acid, and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein the ratio of the mass amount of the basic amino acid component to the first saturated fatty acid component (basic amino acid : first saturated fatty acid) is 5:1 or greater, wherein the stock solution of the second saturated fatty acid component comprises palmitic acid or a salt, ester or isomer of palmitic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the second saturated fatty acid component (basic amino acid : second saturated fatty acid) is 5:1 or greater, wherein the stock solution of the first unsaturated fatty acid component comprises oleic acid or a salt, ester or isomer of oleic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the first unsaturated fatty acid component (basic amino acid : first unsaturated fatty acid) is 0.5: 1 or greater, wherein the stock solution of the second unsaturated fatty acid component comprises linoleic acid or a salt, ester or isomer of linoleic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the second unsaturated fatty acid component (basic amino acid : second unsaturated fatty acid) is 0.5:1 or greater, further wherein the first saturated fatty acidcomponent is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation, further wherein the stock solutions are combined at greater than 70 degrees C.

[0022] Any of these methods may include combining the stock solution of the first saturated fatty acid component, the stock solution of the second saturated fatty acid component, the stock solution of the first unsaturated fatty acid component, and the stock solution of the second unsaturated fatty acid component, comprises forming the formulation wherein the formulation is clear.

[0023] The stock solutions may be combined with the temperature of each of the stock solutions a greater than, e.g., 74 degrees C, prior to combining. For example, the stock solutions may be heated to between 70 degrees and 95 degrees C and combined hot.

[0024] Any of these methods may include cooling the formulation to room temperature or cooler, while the formulation remains clear (e.g., all of the components, including in particular the saturated fatty acids, may remain in solution).

[0025] Any of these methods may include adding one or more additional components, such as adding an ethyl alcohol to the formulation. The additional components may be added after combining the stock solutions of saturated and unsaturated components. In some examples the additional components may be added while combining the stock solutions. In some examples the additional component(s) may be added before combining the stock solutions (and / or as part of one or more of the stock solutions). For example, any of these methods may include adding ethyl alcohol, so that 5% or less of the total volume of the formulation comprises ethyl alcohol.

[0026] In some of these methods the stock solutions may be added all together or in stages. For example, the stock solution of the first saturated fatty acid (e g., stearic acid) may be combined with the first unsaturated fatty acid (e.g., oleic acid) then may be combined with the second saturated fatty acid (e.g., palmitic acid), then combined with the second unsaturated fatty acid (e.g., linoleic acid). In some examples the linoleic acid (second unsaturated fatty acid) stock solution may made first, heated, and then the stearic acid (first saturated fatty acid) sock solution may be added, hot, followed by the oleic acid (first unsaturated) stock solution may be added, hot and then finally the palmitic acid (second saturated) stock solution, hot, may be added.

[0027] These solutions may be stirred / mixed while being prepared.

[0028] Thus, in any of these methods the stock solutions may be made. For example, the method may include preparing a stock solution of the first saturated fatty acid component so that the ratio of the basic amino acid : first saturated fatty acid is 5: 1 or greater; preparing the stock solution of the second saturated fatty acid component so that the ratio of the basic amino acid : second saturated fatty acid is 5:1 or greater; preparing the stock solution of the first unsaturated fatty acid component so that the ratio of the basic amino acid : first unsaturated fatty acid is 0.5: 1 or greater; and preparing the stock solution of the second unsaturated fatty acid component so that the ratio of the basic amino acid : second unsaturated fatty acid is 0.5: 1 or greater.

[0029] As mentioned, a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) in the formulation is between 3: 1 to 1000:1. In any making any of these formulations the ratio of the basic amino acid : fatty acid may be, e.g., 5:1 or greater. In some examples the ratio of the basic amino acid : saturated fatty acids is 5: 1 or greater.

[0030] In some examples the method of making the formulation may include making the formulation so that the first saturated fatty acid component is between 20-25% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 8-14% of the total mass amount of fatty acids in the formulation.

[0031] Any of these methods may include adding one or more monoterpin to the formulation.

[0032] For example, a method of making a pesticide formulation may include: preparing a stock solution of a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to the first saturated fatty acid component (basic amino acid : first saturated fatty acid) is 5:1 or greater, preparing a stock solution of a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the second saturated fatty acid component (basic amino acid : second saturated fatty acid) is 5: 1 or greater; preparing a stock solution of a first unsaturated fatty acid component comprisingoleic acid or a salt, ester or isomer of oleic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the first unsaturated fatty acid component (basic amino acid : first unsaturated fatty acid) is 0.5: 1 or greater; preparing a stock solution of a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the second unsaturated fatty acid component (basic amino acid : second unsaturated fatty acid) is 0.5:1 or greater; and combine the stock solution of the first saturated fatty acid component, the stock solution of the second saturated fatty acid component, the stock solution of the first unsaturated fatty acid component, and the stock solution of the second unsaturated fatty acid component to form a clear formulation, wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation, further wherein the stock solutions are combined at greater than 70 degrees C; and cooling the formulation to room temperature while the formulation remains clear.

[0033] All of the methods and apparatuses described herein, in any combination, are herein contemplated and can be used to achieve the benefits as described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0034] A better understanding of the features and advantages of the methods and apparatuses described herein will be obtained by reference to the following detailed description that sets forth illustrative embodiments, and the accompanying drawings of which:

[0035] FIG. 1 shows a schematic illustration of the anatomy of an insect leg.

[0036] FIG. 2 is a graph illustrating efficacy testing of one example of a pesticide formulation, as described herein, tested on grapes.

[0037] FIG. 3 is a graph illustrating efficacy testing of one example of a pesticide formulation, as described herein, tested on apples.

[0038] FIG. 4 shows female European grapevine moths (Lobesia botranci) prefer a surface without the presence of host marking pheromone (HMP).

[0039] FIG. 5 shows female European grapevine moths (Lobesia botranci) were deterred by the presence of host marking pheromone (HMP).

[0040] FIG. 6 is a graph showing the effect of one example of a formulation as described herein on average numbers of eggs laid within 48 hours.

[0041] FIGS. 7A-7B show results of semi-field testing with a pest control formulation disclosed herein on grape plants for Lobesia. FIG. 7A shows a graph of incidence results. FIG. 7B shows a graph of efficacy results.

[0042] FIGS. 8A-8B show results of semi-field testing with a pest control formulation disclosed herein on apple trees for Lobesia. FIG. 8A shows a graph of incidence results. FIG. 8B shows a graph of efficacy results.

[0043] FIG. 9 shows an illustration of a block layout of locations of grape plants for performing field tests on grape plants.

[0044] FIGS. 10A-10D show the formulations herein are effective against Lobesia on grape plants. FIGS. 10A-10D show results of field tests performed on grapes for Lobesia using the formulations disclosed herein. FIG. 10A shows results of females hatching and eggs laying. FIG. 10B shows efficacy of a pest control formulation described herein on Lobesia eggs. FIG. 10C shows results of efficiency of a pest control formulation described herein on Lobesia eggs. FIG. 10D shows evaluation of a pest control formulation described herein for efficiency against G3 perforations and moth webs.

[0045] FIGS. 11A-1 IB shows another set of results taken from a second location and showing that the formulations herein are effective against Lobesia on grape plants. FIG. 11A shows a graph of incidence results. FIG. 1 IB shows a graph of efficacy results.

[0046] FIG. 12 shows an illustration of a block layout of locations of apple trees for performing field tests on apple trees.

[0047] FIGS. 13A-13B show the formulations herein are effective against Lobesia on apple trees. FIG. 13A shows a graph of incidence results. FIG. 13B shows a graph of efficacy results.DETAILED DESCRIPTION

[0048] The compositions described herein may be used as pesticides for treating a variety of different plant types, and may be effective against different pests. In general, these formulation may reproduce many of the biological deterrent effects of pheromones. Optimal oviposition theory predicts that female herbivores prefer to oviposit on those plants that are likely to maximize offspring performance, also known as the “mother knows best” paradigm. This is the general pattern with insects within the insect order Lepidoptera which have specialist diets (e g., they consume only one or a few plant species) and reduced larvalmobility. In such a context, a mother's decision as to where to lay eggs are crucial to the development of its offspring.

[0049] In some examples described herein a first formulation (e.g., including one or more saturated fatty acid, one or more unsaturated fatty acids, and an excess of a basic amino acid (e.g., L-Arg) may be used as a host marking pheromone (HMP), which represents an innovative concept of control of insect pest population. The mechanism of action is based on the saturation of the plant surface with substances that inform the female insect pest about the presence of eggs, primarily eggs of individuals of the same species. This is an ingenious strategy of herbivorous insects, which on the one hand prevents cannibalism of juvenile stages and at the same time ensures an even dispersion of insect pests that are nutritionally bound to the same crop. In short, it is a part of maternal strategy in a bid to protect her offspring.

[0050] The concept is based on the fact that the female, when choosing a source of nutrition for her offspring, verifies whether the given place for the nutrition of her offspring is no longer occupied by individuals of the same (intraspecific message) or other species (interspecific message) that are present in the target crop stand. Detection of eggs’ presence is realized by touch with the help of chemoreceptors on the feet (tarsus) with a typical behavioral manifestation - tapping dance. An adult insect typically has six legs and can use the legs for both ambulation and sensing. FIG. 1 shows a diagram of an insect leg. The leg includes a body, coxa, trochanter, femur, tibia, tibial spurs, tarsus, and claws and is well- suited for bending, moving, touching, tapping, detecting, and sensing.

[0051] This crop protection concept may reduce or eliminate the problem of resistance emergence or declination from the original combination of bio-active components of oviposition regulating pheromone, as repeated application in the target agrocenosis eliminates the collective memory of the pest population transformed into a change in the DNA code.

[0052] Described herein are formulations containing active substances that have pesticidal action on insects. In particular, disclosed herein formulations having pheromone active substances. Pheromones found in nature are chemicals used by insects and other animals to communicate with each other. The pheromone active substance disclosed herein may be especially useful for deterring insects from laying eggs on a surface when the formulation is applied to the surface of plants, parts or plants, or plant products. The formulations contain a pheromone which includes a blend of fatty acids and an accessory compound. The accessory compound is typically a basic compound, such as an amino acid.

[0053] Fatty acids are monocarboxylic acids (represented with an acidic group -COOH though commonly ionized in solution) with aliphatic hydrocarbon chains. Fatty acids canhave from 3 to about 30 carbon atoms in the aliphatic chain, though typically have from 10 to 20 carbons in the chain and more commonly have from 16 to 20 carbons. Fatty acids can be divided into short chain fatty acids (those with fewer than 6 carbons in the tail such as butyric acid), medium chain fatty acids (those with 6-12 carbons in the tail such as capric acid and lauric acid), long chain fatty acids (those with 13-20 carbons in the tail such as stearic acid and oleic acid), and very long chain (those with more than 20 carbons in the tail). Fatty acids can be straight chain fatty acids, branched chain fatty acids, substituted fatty acids, and cyclic fatty acids.

[0054] Saturated fatty acids have no double bonds between carbon atoms and include, but are not limited to arachidic acid, behenic acid, capric acid, caprylic acid, cerotic acid, lauric acid, lignoceric acid, myristic acid, palmitic acid, and stearic acid.

[0055] Unsaturated monoenoic fatty acid (one double bond) or polyenoic fatty acid (more than one double bond). Unsaturated with one double bond, two double bonds, three double bonds, four double bonds, in the aliphatic chain. Double bonds may be cis (e.g., oleic acid) or trans (e.g., eladic acid). Examples of unsaturated fatty acids that can be used in the formulations herein include but is not limited to arachidonic acid, docosahexaenoic acid, elaidic acid, eicosapentaenoic acid, erucic acid, linoleic acid, linoelaidic acid, a-linolenic acid, myristoleic acid, oleic acid, palmitoleic acid, sapienic acid and vaccenic acid. Any fatty acid can be used in the formulations as described herein. In some embodiments, the fatty acids in the formulations herein are fatty acids (with from 4 to 26 carbons in the tails). In some embodiments, the fatty acids are long chain fatty acids (with from 13-20 carbons in the tail). In some particular embodiments, the fatty acids in a formulation have from 16 to 20 or 16 to 18 carbons in the tail. For example, a formulation may have palmitic acid (16 carbons such as palmitic acid (C16:0)), oleic acid (18 carbons such as oleic acid(C18:ln9c), stearic acid (18 carbons such as stearic acid (C18:0) and linoleic acid (18 carbons such as linoleic acid (C18:2n-6).

[0056] In some variations, an accessory compound and a fatty acid are bound together. The bond can be non-covalent (e.g., by hydrogen bonding, van der Waals bonds, ionic, etc.) or covalent.

[0057] A formulation described herein can include one or more accessory compound(s). An accessory compound may be configured to aid in pheromone (e.g., fatty acid) solubility, such as one or more basic compound(s). A compound configured to aid in pheromone (e.g., fatty acid) solubility can include one or more than one amino acid component(s). If more than one amino acid component is present, unless indicated otherwise, each amino acid component may independently have any of the qualities referred to herein regarding an amino acidcomponent. An amino acid component can be a naturally occurring amino acid or a non- naturally occurring (synthetic) amino acid. An amino acid component can be an amino acid typically or commonly found in a protein (e.g., arginine, histidine, lysine, etc.) or an amino acid that is typically or commonly not found in proteins (e.g., citrulline, ornithine). An amino acid component can be a basic amino acid. Basic amino acids have basic side chains at neutral pH. In some embodiments an amino acid component may be one or more of or may be selected from the group of basic amino acids consisting of arginine and lysine. In some embodiments, an amino acid component may be one or more of or may be selected from the group of basic amino acids consisting of arginine, histidine, and lysine. In some embodiments, an amino acid component may be one or more of or may be selected from the group of basic amino acids consisting of arginine, arginosuccinate, citrulline, histidine, lysine, ornithine, or protamine. In some embodiments an amino acid component may be one or more of or may be selected from one or more amino acid in the group of basic amino acids, e g., arginine, arginosuccinate, citrulline, histidine, lysine, or ornithine. In some embodiments, the one or more than one amino acid component is selected from arginine, lysine, and glycine. In some embodiments, an amino acid component is arginine. In some embodiments, is L-Arginine. In some embodiments, an amino acid component is one or more of D-Arginine and L-Arginine. In some embodiments, an amino acid component can be a peptide. Examples of peptides include a dipeptide (derived from two amino acids joined through a peptide bond), tri peptides (derived from three amino acids joined through peptide bonds), etc. A peptide can include one (and only one) type of amino acid and the amino acids can be identical (e.g., ArgArg, LysLys, etc.) or a peptide can include more than one type of amino acid (e.g., ArgLys, ArgHisLys, ArgHisArgHis, etc.) and / or polyarginine, polyhistidine, and / or polylysine. In some variations, one or more amino acid components can include both amino acids and peptides.

[0058] One or more amino acid components can have any type of stereochemical configuration, such as an L-stereochemical configuration, a D-stereochemical configuration or both an L-stereochemical and a D-stereochemical configuration. When more than one amino acid component is present, each component (or portion of a component such as in the case of a peptide) can independently have any type of stereochemical configuration, such as an L-stereochemical configuration, a D-stereochemical configuration or both an L- stereochemical and a D-stereochemical configuration. For example, an arginine amino acid component can be L-Arg, D-Arg, or both L-Arg and D-Arg. Typically, an amino acid component can have L-stereochemical configurations and a D-stereochemical configurations of an amino acid present in a roughly 1 : 1 ratio, but that is not required. In some variations, anaccessory component can include one or more than one amino acid component. The one or more than one amino acid component can be one or more than one of arginine, histidine, lysine, aspartic acid, glutamic acid, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, pyrrolysine, glycine, proline, alanine, valine, isoleucine, leucine, methionine, phenylalanine, tyrosine, and tryptophan.

[0059] In some embodiments, an accessory compound can be one or more amphipathic compound(s). For example, an amphipathic compound may be tryptophan, tyrosine, or methionine and / or salts thereof and / or isomers thereof. In some embodiments, an accessory component can be one or more isomers of an amino acid. For example, an accessory component can be an arginine isomer. In some embodiments, an accessory compound can be a guanidine and / or have a guanidino group. The central bond within this component or group is that of an imine, and the group is related structurally to amidines and ureas. Guanidines are a group of organic compounds with a common functional group with the general structure (R1R2N)(R3R4N)C=N-R5, wherein Rl, R2, R3, R4, and R5 could independently be hydrogen atoms, alkyl groups, aryl groups, or any combination thereof. Examples of guanidines that can be used include but are not limited to arginine, creatine, saxitoxin, and triazabicyclodecene.

[0060] A portion of the basic component that is not composed of a(basic) amino acid component may instead include any other basic component as described herein.

[0061] The term “fatty acid component” as used herein, unless otherwise stated, refers to any of the fatty acids described herein, and including free fatty acids and fatty acid salts. Described herein are methods of making a formulation including a pheromone. Briefly, a first unsaturated fatty acid is combined with an appropriate accessory compound and water and heated (solution E), a second unsaturated fatty acid is combined with an appropriate accessory compound and water and heated (solution F), a first fatty acid is combined with an appropriate accessory compound and heated (solution G), and a second fatty acid is combined with an appropriate accessory compound and heated. Solutions E, F, G, and H are combined and cooled to room temperature. In some variations, the first unsaturated fatty acid and the second unsaturated fatty acid are combined and heated (solution H) and the first saturated fatty acid and the second saturated fatty acid is combined and heated (solution I) and solutions H and I are combined and cooled to room temperature. A ratio of a mass amount of the accessory compound to at least one of the first saturated fatty acid, the second saturated fatty acid, or combined mass amount of the first and second saturated fatty acid components is from 5:1 to 1000:1. A ratio of a mass amount of the accessory compound to at least one of the first unsaturated fatty acid, the second unsaturated fatty acid, or combined mass amountof the first and second saturated fatty acid components is from 5: 1 to 1000:1. In some formulations, a ratio of the mass amount of the basic amino acid component to the combined mass amount of the first and second saturated fatty acid components is from 2: 1 to 24: 1. In some formulations, a ratio of the mass amount of basic amino acid component to the combined mass amount of the first and second unsaturated fatty acid components is from 0.5:1 to 1000:1. In some formulations, a ratio of the mass amount of basic amino acid component to a combined mass amount of the first and second saturated fatty acid components is from 2:1 to 24: 1. In some formulations, a ratio of the combined mass amount of the first and second saturated fatty acid components to a combined mass amount of the first and second unsaturated fatty acid components is from 5: 1 to 1 :5. In some formulations, a ratio of the combined mass amount of the first and second saturated fatty acid components to a combined mass amount of the first and second unsaturated fatty acid components is about 5:4. In some formulations, the first saturated fatty acid component and the second saturated fatty acid component each independently include a linear saturated fatty acid having from 6 to 26 carbon atoms. In some formulations, the first saturated fatty acid component and the second saturated fatty acid component each independently include a linear saturated fatty acid having 16 to 20 carbon atoms. In some formulations, the first saturated fatty acid component and the second saturated fatty acid component each independently include a linear saturated fatty acid having 16 to 18 carbon atoms. In some formulations, the first saturated fatty acid component is palmitic acid, and the second saturated fatty acid component is stearic acid. In some formulations, the first saturated fatty acid component and the second unsaturated fatty acid component each independently include a linear unsaturated fatty acid having from 6 to 26 carbon atoms. In some formulations, the first unsaturated fatty acid component and the second unsaturated fatty acid component each independently include a linear saturated fatty acid having from 16 to 20 carbon atoms. In some formulations, the first unsaturated fatty acid component is oleic acid, and the second unsaturated fatty acid component is linoleic acid. In some formulations, the first saturated fatty acid component is palmitic acid, the second saturated fatty acid component is stearic acid, the first unsaturated fatty acid component is oleic acid, and the second unsaturated fatty acid component is linoleic acid, and the basic amino acid is L-Arg, further wherein the mass amount of the palmitic acid to the mass amount of the stearic acid to the mass amount of oleic acid to the mass amount of linoleic acid to the mass amount of L-Arg is about 3 :2:3 : 1 : 12. In some formulations, the basic amino includes one or more of arginine, citrulline, histidine, lysine, or ornithine. In some formulations, the basic amino includes L-Arginine (L-Arg) In some formulations, theformulation is a liquid when at a temperature of 23°C. In some formulations, the formulation is a liquid when at a temperature of 4°C.

[0062] The formulation as described herein may be homogenous or non-homogenous. A formulation as disclosed herein may be aqueous. Aqueous means a liquid that is soluble or readily dispersible in water. A formulation as described herein may be aqueous over a range of temperatures. A formulation as described herein may be liquid at temperatures from 0°C or below 0°C (such as due to freezing point depression) to 100°C or above 100°C (such as due to boiling point elevation). A formulation as described herein may be liquid at temperatures below 100°C, below 90°C, below 80°C, below 70°C, below 60°C, below 50°C, below 40°C, below 30°C, below 20°C, below 10°C, below 5°C and / or at temperatures above 0°C, above 10°C, above 20°C, above 30°C, above 40°C, above 50°C, above 60°C, above 70°C or between these, such as below 50°C and above 0°C, below 40°C and above 2°C. In some particular examples, a formulation as described herein may be liquid at around room temperature (e g., around 22°C) or from 20°C to 25°C. The formulation as described herein may be aqueous at around 2°C. In some examples, formulation as described herein is frozen below 0°C, below -5°C, below -10°C below -I5°C. In some examples, where the formulation is useful as a pesticide, a formulation that remains aqueous over a range of temperatures allows the formulation to be applied during various and varying weather conditions (e g., hot, sunny, dry, cloudy, cold), and / or in different seasons (spring, summer, fall, winter), and / or at different times of day (night, dawn, daytime, evening).

[0063] An accessory component can include one or more inert ingredient(s). One or more inert ingredients can be combined with one or more active ingredients to make a pesticide product. An inert ingredient can be useful for product performance and usability. For example, an inert ingredient can be useful for one or more of the following functions and / or for other functions: as a solvent to help an active ingredient(s) go into a solution or mixture, as a solvent to help an active ingredient(s) remain in a solution or mixture, as a solvent to help deliver an active ingredient(s) to a target, as a solvent to help an active ingredients) adhere to a target and / or penetrate a target surface, as a stability enhancer to provide active ingredient(s) shelf-life stability, and to improve safety for the active ingredient(s) applicator.

[0064] A formulation as disclosed herein may include one or more accessory compounds. Examples of accessory compounds that can be added to a formulation include anti-foaming agent, buffering and conditioning agents, defoaming agents, deposition agents, drift control agents, emulsifiers, oils, surfactants, thickener, and water. A surfactant can be configured to physically change the properties of a formulation (especially a spray solution). A surfactant can help a formulation (compared to a formulation with the surfactant) emulsify, disperse,spread, and stick, such as by reducing surface tension. A surfactant can be one or more of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an organo-silicone surfactant. Buffering agents may include chelating agents (e.g., EGTA, etc.).

[0065] A formulation herein may be non-toxic. A formulation herein may be low-risk (as A formulation herein may be configured to be safe to apply to food such that, if ingested by a mammal (human subject) the formulation is non-toxic, non-poi sonous, and safe to the mammal. A formulation herein may be safe such that even if the formulation leaches into drinking water, it is harmless. A formulation herein may be tailored such that it targets an insect pest but leaves other beneficial insects (such as honeybees and other desired pollinators) unaffected. In some embodiments, a formulation disclosed herein contains little (e.g., less than 1% (w / w), less than 0.1% (w / w), less than 0.01% (w / w), less than 0.001%(w / w), less than 0.0001%(w / w) or is free of (amount is undetectable) of a registered pesticide, such as a United States Environmental Protection Agency registered pesticide. In some embodiments, a formulation as described herein is free of or contains little (e.g., less than 1% (w / w), less than 0.1% (w / w), less than 0.01% (w / w), less than 0.001%(w / w), less than 0.0001%(w / w)) or is free of (amount is undetectable) of a of a volatile organic compound (VOC). In some embodiments, a formulation as described herein is free of or contains little (e.g., less than 1% (w / w), less than 0.1% (w / w), less than 0.01% (w / w), less than 0.001%(w / w), less than 0.0001%(w / w)) or is free of (amount is undetectable) of other known substances that are considered harmful to animals, mammals, humans, insects, etc. Formulations containing the pheromone active substances herein may be considered low-risk. A formulation as described herein may include various other components. In some embodiments, other components may be less than 20% (w / w), less than 10% (w / w), less than 5% (w / w), less than 1% (w / w), less than 0.5% (w / w), or less than % 0.1 (w / w) of the solution. Various other components may be, for example, be added components,

[0066] The formulations disclosed herein may be especially useful as pesticides to protect a material from pests, such as from insect pests. A pesticide is a substance configured to kill, repel, mitigate, or control pests that are considered to damage plants and / or be a nuisance in agriculture and domestic life. The formulations herein may be especially useful as plant protection products: as pesticides that protect crops or desirable or useful plants. A material in need of protection by a pesticide formulation disclosed herein can be a plant (fungus) or portion thereof, including but not limited to roots, stems, leaves, flowers, fruits, and seeds. In some embodiments, formulations disclosed herein may be insecticides and may be especially useful when applied to leaves or fruit to deter or prevent insects from laying eggs on the leaves or fruit.

[0067] Plants that can be protected using the pesticide formulations disclosed herein include crops (e.g., commodity crops in the agricultural sector) and / or non-crops (such as plants used in forestry, horticulture, amenity areas, and home gardens). Examples of plants that can be protected using the pesticide formulations disclosed herein include fruit plants, vegetable plants, and nut trees. Plants that can be protected include but are not limited to beans, cabbage, grapevines, grapes, apples, pears, other pome fruits.

[0068] Also disclosed are methods of using the formulations herein to protect a material in need of protection. A formulation may be applied by spraying, dispersing, painting. A formulation may be diluted prior to applying (with water, buffer, etc.). A formulation may be applied with a spraying device, from an aerial vehicle, etc.

[0069] In some embodiments, the formulations disclosed herein are configured to target insects. In some embodiments, the formulations disclosed herein are configured to target members of the Lepidoptera order of insects. In some embodiments, the formulations herein are configured to target one or types of insects, but do not target others. In some particular examples, the formulations disclosed herein are configured to target Lobesia botrana such as on grapevine plants. In some particular examples, the formulations disclosed herein are configured to target Codling moth (Cydia pomonella).

[0070] EXPERIMENTAL EXAMPLES

[0071] Based on knowledge of the physico-chemical properties of the bioactive components (components that are poorly soluble in water), two types of potential formulations were selected in the first stage: EC - emulsifiable concentrate (liquid formulation that contains technical material, one or more organic water-immiscible solvents and an emulsifier (such as a surfactant); EW - concentrated emulsion (it can be considered as a safer and more environmentally friendly alternative to emulsifiable concentrates. In an EW the continuous phase is water (as opposed to an organic solvent for EC) which offers the benefit of lower phytotoxicity, no flashpoint concern, ease of handling, and a lower environmental impact.

[0072] As part of the optimization of the physico-chemical properties of the resulting formulation, three types of mixtures of bioactive components were tested: two-component, four-component and complex 9-component mixture. The optimization process of the selected formulations subsequently resulted in the evaluation of their biological efficacy.Two-component mixture

[0073] In the process of dissolving a mixture of two fatty acids directly into water (EW formulation), 27 surfactants were tested, but despite the presence of the most suitable ones, which are surfactants based on fatty alcohols ethoxylate (linear C12-C14 or branched Cl 1-C13 fatty alcohols), satisfactory results were not achieved - in relatively short time after the dissolution of the bio-active components, the precipitation of poorly soluble fatty acid crystals occurs. The choice of a suitable organic solvent was therefore a logical solution to the situation in the context of classical and proven procedures in the formulation of pesticides. Subsequently, 15 potential products from the group of aromatic and aliphatic solvents (esters, alkanes, oils) were tested. After evaluating all the parameters (solubility, emulsifiability, stability, etc.), two solvents were chosen as the most suitable: N-octyl- pyrrolidone and Solvesso 100, while SolvessolOO was the most suitable for the EC formulation and N-octyl pyrrolidone was the most suitable for the EW formulation. In relation to the selected solvents, a re-screening of a suitable surfactant was necessary. In the case of the Solvesso 100 solvent, the surfactant Rhodasurf LA 90 showed the best parameters, while the HLB value (Hydrophilic Lipophylic Balance) was identical to that in the case of dissolving the two-component mixture directly in water (13.5). However, stability tests at temperatures of +2 and +20 °C clearly indicated the unsuitability of this formulation (a problem associated with the recrystallization process) while maintaining the required ratios of the individual components. This formulation was therefore excluded from further tests. For N-octyl pyrrolidone, the surfactant evaluated as the most suitable was Soprophor 3 D 33 with a granulometry of the resulting emulsion of 1.41 pm. This formulation advanced to further tests.Four-component mixture.

[0074] Preliminary tests aimed at dissolving a mixture of four fatty acids directly in water pointed out the necessity of choosing a suitable organic solvent. After repeating screening tests, the most successful combination of solvent and surfactant came out again as N-octyl pyrrolidine and Soprophor 3 D 33 with an emulsion granulometry of 1.73 pm.Complex 9-component mixture.

[0075] The resulting combination of N-octyl pyrrolidine and Soprophor 3 D 33 was also the most successful in this case with an emulsion granulometry of 0.42 pm.Bioassays

[0076] To verify efficacy of individual mixtures and formulations, two types of biological tests were used in controlled conditions: a tempered room with a temperature of 21-230C, a relative humidity of 68-75% and a lighting time in the 16 / 8 mode. For the purposes of the tests, adult individuals were used that came from the mass breeding of Codling moth (Cydia pomonella) and European grapevine moth (Lobesia botrana) on semi-synthetic food, while the initial strain of the laboratory populations was enriched with individuals from local agrocenoses i.e., vineyard and apple orchard.Experimental set-up No.l.

[0077] Butterfly cage with mesh cloth material, dimension 60 x 60 x 90 cm. Inside 12 fruits hung on the top of the cage at points equidistand from each other. Two choice situation experiment: checkerboard placement of 6 treated and 6 non treated fruits.

[0078] Commercial production origin fruits were before use in experiment cleaned by osmotic water flow and then dried at room temperature free air.

[0079] For behavioral response of codling moth (CM) calibrated apples with diameter 50- 60 mm, variety Golden delicious, and for European grapevine moth (EGVM) grape bunches with 10 berries each, table grape variety IFG Ten were used. Two already mated females of CM (apple case) and EGVM (grape case), 3 days old were released inside the cage in early morning - 3 hours after lighting period start (Day 0). Counting of laid eggs on the fruits 24 hours later (D 1). Application by dipping of the fruits into the HMP dilution on the doses of 150 eggs equivalent. Eggs laying status of the females was verified by dissection after experiment (presence of corpora lutea).

[0080] If on the fruit was registered even 1 egg, fruit was considered as damaged.Oviposition data for each from 10 repetition per variant were evaluate by efficiency formula: attack % on treated (T) x 100 efficiency (%) = 100 - attack % on non treated (NT)

[0081] The efficacy value for each variant was calculated from the average T (%) and NT (%) values obtained from 10 replications. Based on the average number of fruits with laid eggs, the deterrence index was also calculated for each variant according to the following formula:Deterrence index (%) Di =((T-NT) / (T+NT)) x 100

[0082] where T represents number of treated and NT untreated apples / grape bunches that have at least one laid egg on them.

[0083] Grapes / European grapevine moth (EGVM)

[0084] Blends 2, 4 and 9 prepared with previous formulation (N-octyl pyrrolidine and Soprophor 3 D 33): the effectiveness of the 4-component mixture consisting of the majority components proved the same or not demonstratively higher efficacy than a complex 9- component mixture with standard deviations 5.07 and 2.93 respectively; the two-component mixture, consisting of only two major components, was less effective than the 4-component mixture by 16,6 percentage points with the highest standard deviation (6,17); With the 9- component mixture, the standard deviation was the smallest compared to the other tested formulations, which points to the high perceptivity of HMP by the pest test population. Thenew HMP formulation (Pheromark) surprised with its high efficacy (FIG. 2) and low standard deviation (4,78), which was at the level of the 4-component mixture in the original formulation. Solvent+surfactant from previous formulations was slightly, but not demonstrably stimulating for laying females (FIG. 2), the difference was 1 bunch out of 120 tested. In the case of the new formulation, the influence of the solvent (water treated by reverse osmosis - ROW) on egg laying was literally zero. Deterrence index values for individual variants confirmed the high efficacy of the new formulation (Table 1).GRAPESApples / Qv / zYz pomonella (CM)

[0085] Blends 2, 4 and 9 prepared with previous formulation (N-octyl pyrrolidine and Soprophor 3 D 33): : the efficacy of the 4-component mixture consisting of the majority components showed the same efficiency as the complex 9-component mixture with standard deviations 4,52 and 2,64 respectively; the two-component mixture, consisting of only two major components, was less effective than the 4-component mixture by 13 percentage points with lower standard deviation (3,29). With the 9-component mixture, the standard deviation was again the smallest compared to the other tested formulations, which points to the high perceptivity of HMP by the pest test population.

[0086] The new formulation of HMP, similar as in the case of EGVM, achieves the highest efficacy compared to previous variants, while the value itself is surprisingly high, at the level of up to 95%. Solvent+surfactant from the previous formulations also showed a stimulating, ovipositional effect in the case of CM (FIG. 3), but the deterrent effect of HMP in the new formulation is therefore even more significant. For the new formulation, the effect of solvent (ROW) on oviposition was zero again. Deterrence index values for individual variants also in the case of apples confirmed the high efficacy of the new formulation (Table 2).APPLESCONCLUSION

[0087] The results of behavioral tests on model insect species under controlled conditions clearly demonstrated the high efficacy of the new formulation, with high and very similar values of the efficiency index: EGVM (94,7%) and CM (95,6%) as well as the deterrence index values: 89.9 % and 90.5% respectively.Part II

[0088] In order to verify the effectiveness of a communication substance useful for modifying the behavior of the target insect group, we developed an experimental bioassay, which under laboratory conditions allowed us to verify the effectiveness of host marking pheromone (HMP) molecular mixtures and their related application formulations. To design an assay apparatus (also referred to as "experimental hardware" or “hardware”), we started from observations that capture the oviposition flight of fertilized females as accurately as possible in natural conditions. The more accurately the "hardware" reflected the reality observed by studying the behavior of the target insect group, the easier and more accurate was extrapolation of laboratory test results for the needs of application practice. Key to the design of the assay apparatus (test platform) was the finding that females of the target group of insect pests fly to an oviposition site on a surface from below the surface. After performing a short recognition dance, which is associated with the insect touching the surface with the feet and low-frequency flapping of the wings, they begin to lay eggs on a rounded surface in a predominantly vertical position. Based on long-term observations in the field, summarized in the above summary, an experimental platform was designed as follows.

[0089] The bioassay was based on a two-way choice for the female insects.Opposition arena - Plexiglass tube

[0090] The oviposition arena of the assay apparatus included a Plexiglass tube (internal diameter 6.0 cm, length 13.5 cm) that was set-up so that females could oviposit on a sheet of paper. Only the upper half of the inside oviposition arena was covered by paper, to respect ethological exigencies, as mentioned previously. The lower half of the Plexiglass tube was covered with soft felt to provide a rugged surface (females lay the eggs only on smooth surface) to avoid un-targeted and inactive oviposition.

[0091] To provide regular size and equidistant dots approximating the dimensions of small berries, a Plexiglass mask with 32 holes was placed over the oviposition paper. Each hole was covered with a cap pierced in its center for insertion therein of a Hamilton calibrated syringe with flat tip needle. To test the effects of different host marking pheromone (HMP) molecular mixtures, dilutions, and formulations on female insects, 32 drops of 5 pl each of a mixture, dilution, or formulation (or a control) were applied on an individual oviposition paper. By this way an oviposition paper was formed having 32 circles with 1.2 cm diameter each and centers 2.1 cm apart. The oviposition paper was then placed inside the upper half of the plexiglass oviposition arena.

[0092] On the third day after adults hatching, 3 mated females and 3 males per replicate were placed for 48 hours inside the oviposition arena. The number and position of laid eggs (treated versus not treated area) were then recorded. For each dilution, 21 replications were done (63 females tested per each formulation). After experiments, all females were isolated for one night in small glass tubes to confirm their physiological status as egg laying individuals.Results

[0093] To evaluate the behavioral impact of host marking pheromone (HMP) behavioral on target species females, we analyzed three parameters: 1). Mean number of eggs per female laid during exposure on oviposition arena. 2). Oviposition deterrence index (ODI) - expresses the behavioral power of a mixture or formulation to deter an insect from laying eggs. The formula used for ODI calculation: Di % = ((T-NT) / (T+NT)) x 100, where T is number of eggs laid on the treated area and NT is the number of eggs laid on the non-treated area. A Di value of -100% indicates total avoidance of treated areas and a Di value of 0% indicates no preference. The ODI was corrected to account for the differences in sizes of the treated and untreated areas. The formula used for the ODI calculation was corrected according to T / NT area ratio - solvent case: Di corr. % = [(3T-NT) / (3T+NT)] x 100.

[0094] 3). Oviposition preference index (OPI) - express female's preference to lay the eggs on non-treated areas. The formula used for OPI calculation: Pi % = 100- (TxlOO) / (T+NT), where T is number of eggs laid on the treated area and NT is the number of eggs laid on the non-treated area. The formula used for OPI calculation corrected according T / NT area ratio - solvent case: Pi corr. % = Pi (%) - NT surface (%).

[0095] Five dilutions of initial concentrate and solvent (osmotically treated water) were tested. Each dilution is expressed as the value of eggs equivalent per one 5 pl drop (app. 1 cm2) (e.e).

[0096] FIG. 4 shows female European grapevine moths (Lobesia botrand) prefer a surface without the presence of host marking pheromone (HMP).

[0097] FIG. 4 shows a graph of the Oviposition preference index (OPI) from 0% to 100% after testing European grapevine moths (Lobesia botrand) in an oviposition arena using different dilutions of host marking pheromone (HMP) (1500 e.e., 150 e.e., 60 e.e., 30 e.e., 15 e.e.). Results clearly show that when females of the European grapevine moth (Lobesia botrand) faced with a choice between a treated surface and an untreated surface, they preferred a surface without the presence of HMP (preference index at the level of 90-95%), regardless of the concentration, while the highest OPI values were achieved at concentrations of 150 e.e. and 60 e.e. The solvent (osmotically treated water) alone did not have an effect and did not affect the behavioral effect of HMP in any way - the OPI value corrected according to the T / NT area ratio was on the level zero (Pi corr. = 0.13%). The deterrence index has a significantly higher informative value compared to the preference index, since the value of the number of eggs laid on the treated area has a key position in the calculation formula. It is therefore one of the strictest criteria for evaluating the deterrent effect of tested substances.

[0098] FIG. 5 shows female European grapevine moths (Lobesia botrand) were deterred by the presence of host marking pheromone (HMP). FIG. 5 shows Deterrence Index values at different dilutions of host marking pheromone (HMP) (1500 e.e., 150 e.e., 60 e.e., 30 e.e., 15 e.e.) from 0% to 100%. It is clear from the results that the value of the Deterrence Index was concentration-dependent, while the values of Di at a concentration of 1,500 e.e. and 15 e.e. are noteworthy. The behavioral impact on egg laying was about the same at the two concentrations (Di = -80% and -79.3% respectively), but the mechanism of action was antagonistic. At a concentration of 1,500 e.e., the information detection system of the insects appeared saturated, and the female was not able to correctly evaluate the situation on the surface through the sensory system on the feet. This resulted in a significant suppression of the oviposition process and simultaneous spatial disorientation of the females. At a concentration of 15 e.e., the amount of HMP was subthreshold and therefore was aninsufficient concentration to induce as strong of an anti-ovipositional effect. The concentration of 150 e.e. and 60 e.e. may be suitable for certain applications.

[0099] Information on the efficacy of ORP is supplemented by the analysis of the average number of eggs laid by females exposed for 48 hours in the oviposition space with different dilutions of HMP. It is clear from the graph that the concentration of 1,500 e.e. causes significant suppression of oviposition processes in females, while each of the concentrations used has a suppressive effect compared to the control.

[0100] When choosing a concentration for a particular application, it may be helpful to consider the value of Di and the suppression of oviposition. For example, a concentration of 60 e.e. may be suitable for some practical purposes (to balance efficacy and efficient use).

[0101] FIG. 6 shows the Average number of eggs laid by females of EGVM after 48 hours in an oviposition arena. Compared to previous formulations (dilutions) with optimal concentration, the Di value of formulation with this formulation at the optimal concentration of 60 e.e. is unexpectedly higher. The Di value at the optimal concentration of 60 e.e. (- 89.23%) compared to previous formulations with optimal concentrations is unexpectedly high: -50.28% (Journal of Chemical Ecology, Vol.18, No.1, p. 353-358, 1992); and -64% (Experientia, 49, 998-1001, 1993). New formulation Di value: -89.23%, previous formulations Di values: -50.28% (Journal of Chemical Ecology, Vol.18, No.l, p. 353-358, 1992); -64% (Experientia, 49, 998-1001, 1993).

[0102] Besides the unexpected increase in efficacy, the second crucial improvement compared to previous solution is improved sustainability aspect - higher ecological benefit of new formulation.Part III

[0103] The new formulation described above, may include, for example: 33.3% palmitic acid, 33.3% oleic acid, 22.2% stearic acid, 11.1% linoleic acid and an excess of L-Arg (e.g., where the ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) is 3:1 or greater (e.g., 12.4:1).

[0104] The formulation may be synthesized by first producing stock solutions of each of the fatty acids, to which an excess of the amino acids are added; these stock solutions may then be combined. For example, each of the following stock solutions were made:

[0105] Solution A: 40 grams L-Arginine; 200 grams distilled water; 2.5 grams of stearic acid. Ratio of amino acid to fatty acid: 16:1.

[0106] Solution B: 40 grams of L-Arginine; 200 grams of distilled water; 2.5 grams of palmitic acid. Ratio of amino acid to fatty acid: 16: 1.

[0107] Solution C: 20 grams of L-Arginine; 200 grams of distilled water; 2.5 grams of oleic acid; ratio of amino acid to fatty acid: 8:1.

[0108] Solution D: 20 grams of L-Arginine; 200 grams of distilled water; 2.5 grams of linoleic acid. Ratio of amino acid to fatty acid: 8: 1.

[0109] Development of aqueous formulation, protocol (i). Solutions A-D were brought up to 85°C-95°C. Solutions were clear. Cool solutions to room temperature. Solutions A and B are milky and very viscous.

[0110] Development of aqueous formulation, protocol (ii). Solutions A-D were brought up to 75°C before mixing. To make 100 mL of the final solution, combine 11.1 mL of Solution D (linoleic acid), 22.2 mL of Solution A (stearic acid), 33.3 mL of Solution C (oleic acid), and 33.3 mL of Solution B (palmitic acid). The solution was clear and remained clear upon cooling.Part IV[OHl] In order to verify the effectiveness of formulations herein, semi-field tests were performed. Semi-field tests are trials that are intermediate between laboratory and open-field trials. Semi-field tests combine natural conditions of the field environment with controlled pest infestation (to e.g., ensure pest presence, heighten pest pressure, etc.).

[0112] Semi-field test on grapes with Lobesia. Protocol: Performed in Slovakia: 9,5 ha vineyard planted in 1980, variety Muller- Thurgau. 5 plants selected in 3 blocks in each variant with a minimum 15 bunches on each plant. In each block, 5 plants were treated with Pheromark - variant 1, 5 plants were treated with Bacillus thuringiensis (BT)- variant 2, and 5 plants were untreated (non-treated control (NTC) - variant 3). The treated plants were sprayed (June 25, 2023) with a back-mounted motorized sprayer with Pheromark at a dose: 100 ml / 100 1 water, in total 15 plants in row per block covered under geogrid immediately after application. In the afternoon, 22 fertilized females and 45 males released into covered "tunnel". Pheromark efficacy control carried out on July 7, 2023 (07.07), by taking all bunches of grapes from the selected plants in the block, so that at each sampling 50 grape bunches were collected from each variant, which were analyzed in the lab for egg presence on berries. Results for Incidence (%) is shown in FIG. 7A. Results for Efficacy is shown in FIG. 7B.

[0113] Semi-fi eld tests on apples. Protocol: 3 blocks in 1 variant randomly selected, each block 3 trees in a row. Variants: Pheromark - variant 1, Bacillus thuringiensis - variant 2 (BT) and untreated NTC - variant 3. Application of Pheromark and Bacillus: July 05 (BBCH73).Pheromark dose: 100 ml / 100 1 water. Isolator (row of trees covered with mesh to create tunnel): 3 trees per each variant. 35 fertilized females and 50 males released. Checked: August 05, 2023. (BBCH 81). Checked penetration of larvae into fruits - 75 apples collected from each block & each variant, presence of penetration into the fruit as well as larvae presence in fruit was determined in lab. Results for Incidence (%) is shown in FIG. 8 A. Results for Efficacy is shown in FIG. 8B.Part V

[0114] In order to verify the effectiveness of formulations herein, open field tests (also referred to herein as “field tests”) were performed. Field test protocol on grapes were performed per European Union 2023 according to EPPO rules (European grapevine moth). In total 5 variants were tested: I. negative control (Ml); II. positive control (M2) represented registered insecticide based on Bacillus thuringiensis bioactive agent applied according to label indications; III.-V. Pheromark at three different doses per 100 1 water: 60 (M3), 100 (M4) and 200 (M5) ml. The protocol included 2 trial rows of grape plants (separated by protective rows), 4 blocks (for repetition) in each variant, each block represents 30 plants (see block layout illustrated in FIG. 9 using M3 variant; comparable layouts were used for M4 and M5 variants and elsewhere). Application amount - equivalent 7501 water per 1 ha applied using a back-mounted motorized sprayer. Timing for tested product was managed by Decision support system - before eggs laying of each generation (generation starting point), according to population dynamic in real time treatment, repetitions 12 days after generation starting point. The timing of positive control was performed according to usual agronomic practices. Monitoring of natural population was performed using pheromone traps (3 pieces per plot) and were checked twice per week. First generation efficacy assessment was performed by checking 75 randomly selected grape bunches per each variant and each block with notification of the grape bunches with moth-webs, the number of moth-webs per bunch, and / or presence of larvae. Second and third generation assessment was performed by checking 75 randomly selected grape bunches per each variant and each block; the number of damaged bunches were notified, i.e., presence of moth-webs, the number of moth-webs per bunch as well as perforation of the berries. The last notification was carried out 10 days after the last spraying application of Pheromark.

[0115] FIGS. 10A-D show results of field tests performed using the above protocol for Lobesia, EGVM on grapes with a four-block system. The tests used sex pheromone and food traps for population monitoring of G1-G4 flights using three variants (pheromark, Bacillus thuringiensis (BT), and non-treated control (NTC). EGVM G1 and G2 on both areas were low so egg detection was difficult (findings would be chance). The larger 3rdgeneration wasverified. Monitoring results of the control areas clearly confirmed accuracy of Vitiport timing: occurrence of eggs: 26.7; application 24.7; and occurrence of moth-web and perforations on 2.8., which corresponded to oviposition activity on 24.7. FIG. 10A shows results of females hatching and eggs laying (in %) and Numbers (BBCH, eggs, glomeruli). L to R: NT, Spintor, Pheromark. FIG. 10B shows pheromark efficacy (eggs), IFV trial, EGVM-G3. FIG. IOC shows results of evaluation of Pheromark efficiency (EGVM-G3) (G3- Egg laying). FIG. 10B shows effectiveness of Pheromark as an anti-oviposition semiochemical compared to the control was significant at 95% level of evidence. Data was collected by IFW workers on all experimental plots during G3 (e.g., more numerous generation than G1 and G2). Non-parametric tests were used to evaluate efficiency. The Kruskal-Wallis test confirmed that the compared files (Pheromark, TNT-control, and BT) were not the same. The subsequent Conover-Iman test demonstrated the effectiveness of Pheromark at a level of evidence of 95%, while the effectiveness of BT was essentially zero in relation to the untreated control. This may be understood since BT works as a larvicide and does not interfere with communication processes that should prevent oviposition. Therefore, the number of detected eggs on the BT areas was not demonstrably different compared with the control. FIG. 10D shows evaluation of Pheromark efficiency for G3 - Perforations and moth web. FIG. 10D shows Pheromark effectiveness evaluated through perforations and moth-webs compared to the control was significant at 99% of evidence. The moth-webs and perforations were the expression of the larva hatched from the laid eggs, which cause damage to the generative organs. The Kruskal -Wallis test reconfirmed that the compared files were not the same. The Conover-Iman test revealed a highly demonstrable effect of both BT and Pheromark as a larvicide, although in the case of Pheromark, this designation may be understood in context” in the case of BT, such label corresponded to the mechanism of action, while in the case of Pheromark, the significantly low numbers of cocoons and perforations was only a consequence of the anti-oviposition mechanism of Pheromark action.

[0116] FIGS. 11 A-l IB shows another set of results from open field tests on grapes in a second location. The tests were performed according to the Field test protocol on grapes herein. FIG. 11 A shows incidence (%), IKSUP analysis of Lobesia on grapes. FIG. 1 IB shows efficacy of Lobesia on grapes. Incidence: means followed by the same letter did not significantly differ. (P=0.05, Student-Newman-Keuls). Efficacy: could not calculate LSD (least significant difference) because error mean square =0.

[0117] In some examples, the figures and disclosure herein may use a comma or a period as a decimal separator between the whole and the decimal parts of a number or a number separator. The interpretation of the comma or period should be considered in context herein.NT: not treated. Incidence: means followed by the same letter do not significantly differ. (P=0.05, Student-Newman-Keuls). Efficacy: could not calculate LDS (least significant difference), because error mean square=0.Part VI

[0118] In order to verify the effectiveness of formulations herein, open field tests (also referred to herein as “field tests”) were performed. Field test protocol on apples: In total 5 variants were tested: I. negative control (Ml); II. positive control (M2) represents registered insecticide based on Bacillus thuringiensis bioactive agent applied according label indications; III.-V. Pheromark at three different doses per 100 1 water: 60 (M3), 100 (M4) and 200 (M5) ml. 2 trial rows, 4 blocks (repetition) in each variant, one block represent 15 trees (see block layout illustrated in FIG. 12 using M3 variant; comparable layouts were used for M4 and M5 variants and elsewhere). Application amount - equivalent 1000 1 water per 1 ha was applied using a back-mounted motorized sprayer; timing for tested product was managed by Decision support system - before eggs laying of each generation (generation starting point), according population dynamic in real time treatment repetitions 12 days after generation starting point. Timing of positive control was performed according usual agronomic practices. Monitoring of natural population was performed using pheromone traps (3 pieces per plot), checked twice per week. First generation efficacy assessment: checked 75 randomly selected apples per each variant and each block. Notification of apples with eggs (hatched and unhatched) and the number of apples with clear symptoms of larva penetration into the fruit. Second and third generation assessment: checked 75 randomly selected apples per each variant and each block. Notification of apples with eggs (hatched and unhatched) and the number of apples with clear symptoms of larva penetration into the fruit. 10 days after the last Pheromark application 1 tree per block was randomly selected from each experimental variant (i.e., in total 4 trees per variant), all apples were completely harvested, and fruits damaged by codling moth larvae were identified. Fruits with penetration symptoms were open and the presence of larva was detected. FIGS. 12A-12B shows results from tests performed on apples (Cydia pomonella') at a first location (location 1 - Lleida). FIG. 13A shows incidence results. FIG. 13B shows efficacy results. Applications were 4 treatments of Dipel (26.04., 02.05.; 08.05.; 04.06.) or 4 treatments of Pheromark (05.04., 19.04., 23.05., 20.06.). Incidence: means followed by the same letter do not significantly differ. (P=0.05, Student-Newman-Keuls). Efficacy: could not calculate LDS (least significant difference), because error mean square=0.

[0119] Any of the methods (including user interfaces) described herein may be implemented as software, hardware or firmware, and may be described as a non-transitorycomputer-readable storage medium storing a set of instructions capable of being executed by a processor (e.g., computer, tablet, smartphone, etc.), that when executed by the processor causes the processor to control perform any of the steps, including but not limited to: displaying, communicating with the user, analyzing, modifying parameters (including timing, frequency, intensity, etc.), determining, alerting, or the like.

[0120] When a feature or element is herein referred to as being "on" another feature or element, it can be directly on the other feature or element or intervening features and / or elements may also be present. In contrast, when a feature or element is referred to as being "directly on" another feature or element, there are no intervening features or elements present. It will also be understood that, when a feature or element is referred to as being "connected", "attached" or "coupled" to another feature or element, it can be directly connected, attached or coupled to the other feature or element or intervening features or elements may be present. In contrast, when a feature or element is referred to as being "directly connected", "directly attached" or "directly coupled" to another feature or element, there are no intervening features or elements present. Although described or shown with respect to one embodiment, the features and elements so described or shown can apply to other embodiments. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed "adjacent" another feature may have portions that overlap or underlie the adjacent feature.

[0121] Terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. For example, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items and may be abbreviated as " / ".

[0122] Spatially relative terms, such as "under", "below", "lower", "over", "upper" and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is inverted, elements described as "under" or "beneath" other elements or features would then be oriented "over" the other elements or features. Thus, the exemplary term "under" can encompass both an orientation of over and under. The devicemay be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. Similarly, the terms "upwardly", "downwardly", "vertical", "horizontal" and the like are used herein for the purpose of explanation only unless specifically indicated otherwise.

[0123] Although the terms “first” and “second” may be used herein to describe various features / elements (including steps), these features / elements should not be limited by these terms, unless the context indicates otherwise. These terms may be used to distinguish one feature / element from another feature / element. Thus, a first feature / element discussed below could be termed a second feature / element, and similarly, a second feature / element discussed below could be termed a first feature / element without departing from the teachings of the present invention.

[0124] Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising” means various components can be co-jointly employed in the methods and articles (e.g., compositions and apparatuses including device and methods). For example, the term “comprising” will be understood to imply the inclusion of any stated elements or steps but not the exclusion of any other elements or steps.

[0125] In general, any of the apparatuses and methods described herein should be understood to be inclusive, but all or a sub-set of the components and / or steps may alternatively be exclusive, and may be expressed as “consisting of’ or alternatively “consisting essentially of’ the various components, steps, sub-components or sub-steps.

[0126] As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word "about" or “approximately,” even if the term does not expressly appear. The phrase “about” or “approximately” may be used when describing magnitude and / or position to indicate that the value and / or position described is within a reasonable expected range of values and / or positions. For example, a numeric value may have a value that is + / - 0.1% of the stated value (or range of values), + / - 1% of the stated value (or range of values), + / - 2% of the stated value (or range of values), + / - 5% of the stated value (or range of values), + / - 10% of the stated value (or range of values), etc. Any numerical values given herein should also be understood to include about or approximately that value, unless the context indicates otherwise. For example, if the value "10" is disclosed, then "about 10" is also disclosed. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. It is also understood that when a value is disclosed that "less than or equal to" the value, "greater than or equal to the value" and possible ranges between values are also disclosed, as appropriatelyunderstood by the skilled artisan. For example, if the value "X" is disclosed the "less than or equal to X" as well as "greater than or equal to X" (e.g., where X is a numerical value) is also disclosed. It is also understood that the throughout the application, data is provided in a number of different formats, and that this data, represents endpoints and starting points, and ranges for any combination of the data points. For example, if a particular data point “10” and a particular data point “15” are disclosed, it is understood that greater than, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed as well as between 10 and 15. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0127] Although various illustrative embodiments are described above, any of a number of changes may be made to various embodiments without departing from the scope of the invention as described by the claims. For example, the order in which various described method steps are performed may often be changed in alternative embodiments, and in other alternative embodiments one or more method steps may be skipped altogether. Optional features of various device and system embodiments may be included in some embodiments and not in others. Therefore, the foregoing description is provided primarily for exemplary purposes and should not be interpreted to limit the scope of the invention as it is set forth in the claims.

[0128] The examples and illustrations included herein show, by way of illustration and not of limitation, specific embodiments in which the subject matter may be practiced. As mentioned, other embodiments may be utilized and derived there from, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Such embodiments of the inventive subject matter may be referred to herein individually or collectively by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept, if more than one is, in fact, disclosed. Thus, although specific embodiments have been illustrated and described herein, any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.

Claims

CLAIMSWhat is claimed is:

1. A pesticide formulation comprising an aqueous solution of: a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid; a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid; a first unsaturated fatty acid component comprising oleic acid or a salt, ester or isomer of oleic acid; a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleic acid; and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) is 3: 1 or greater, further wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation.

2. The pesticide formulation of claim 1, wherein the ratio of the basic amino acid : fatty acid is between 3:1 to 1000:1.

3. The pesticide formulation of claim 1, wherein the ratio of the basic amino acid : fatty acid is 5:1 or greater.

4. The pesticide formulation of claim 1, wherein a ratio of the mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component and the second saturated fatty acid component (basic amino acid : saturated fatty acids) is 5: 1 or greater.

5. The pesticide formulation of claim 1, further comprising an ethyl alcohol, wherein less than 5% of a total volume of the formulation comprises ethyl alcohol.

6. The pesticide formulation of claim 1, wherein the basic amino acid component comprises L- Arginine.

7. The pesticide formulation of claim 1, wherein the first saturated fatty acid component is between 20-25% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 8-14% of the total mass amount of fatty acids in the formulation.

8. The pesticide formulation of claim 1, further comprising one or more monoterpin.

9. The pesticide formulation of claim 1, wherein the formulation is shelf stable at room temperature for more than 6 months.

10. A method of treating a plant to deter pests, the method comprising: applying, to the plant, a pesticide formulation comprising an aqueous solution of: a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid; a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid; a first unsaturated fatty acid component comprising oleic acid or a salt, ester or isomer of oleic acid; a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleic acid; and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) is 3 : 1 or greater,further wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation.

11. The method of claim 10, wherein applying comprises spraying.

12. The method of claim 10, wherein the ratio of the basic amino acid : fatty acid is between 3: 1 to 1000:1.

13. The method of claim 10, wherein the ratio of the basic amino acid : fatty acid is 5: 1 or greater.

14. The method of claim 10, wherein a ratio of the mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component and the second saturated fatty acid component (basic amino acid : saturated fatty acids) is 5: 1 or greater.

15. The method of claim 10, further comprising an ethyl alcohol, wherein less than 5% of a total volume of the formulation comprises ethyl alcohol.

16. The method of claim 10, wherein the basic amino acid component comprises L- Arginine.

17. The method of claim 10, wherein the first saturated fatty acid component is between 20-25% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 8-14% of the total mass amount of fatty acids in the formulation.

18. The method of claim 10, further comprising one or more monoterpin.

19. A method of making a pesticide formulation, the method comprising:combining a stock solution of a first saturated fatty acid component, a stock solution of a second saturated fatty acid component, a stock solution of a first unsaturated fatty acid component, and a stock solution of a second unsaturated fatty acid component, wherein the stock solution of the first saturated fatty acid component comprises stearic acid or a salt, ester or isomer of stearic acid, and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein the ratio of the mass amount of the basic amino acid component to the first saturated fatty acid component (basic amino acid : first saturated fatty acid) is 5: 1 or greater, wherein the stock solution of the second saturated fatty acid component comprises palmitic acid or a salt, ester or isomer of palmitic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the second saturated fatty acid component (basic amino acid : second saturated fatty acid) is 5: 1 or greater, wherein the stock solution of the first unsaturated fatty acid component comprises oleic acid or a salt, ester or isomer of oleic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the first unsaturated fatty acid component (basic amino acid : first unsaturated fatty acid) is 0.5:1 or greater, wherein the stock solution of the second unsaturated fatty acid component comprises linoleic acid or a salt, ester or isomer of linoleic acid and the basic amino acid component, wherein the ratio of the mass amount of the basic amino acid component to the second unsaturated fatty acid component (basic amino acid : second unsaturated fatty acid) is 0.5: 1 or greater, further wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation, further wherein the stock solutions are combined at greater than 70 degrees C.

20. The method of claim 19, wherein combining the stock solution of the first saturated fatty acid component, the stock solution of the second saturated fatty acid component, the stock solution of the first unsaturated fatty acid component, and the stock solution of the second unsaturated fatty acid component, comprises forming the formulation wherein the formulation is clear.

21. The method of claim 19, wherein the stock solutions are combined with the temperature of each of the stock solutions a greater than 74 degrees C prior to combining.

22. The method of claim 19, further comprising cooling the formulation to room temperature or cooler, while the formulation remains clear.

23. The method of claim 19, further comprising adding an ethyl alcohol to the formulation.

24. The method of claim 19, further comprising: preparing the stock solution of the first saturated fatty acid component so that the ratio of the basic amino acid : first saturated fatty acid is 5:1 or greater; preparing the stock solution of the second saturated fatty acid component so that the ratio of the basic amino acid : second saturated fatty acid is 5: 1 or greater; preparing the stock solution of the first unsaturated fatty acid component so that the ratio of the basic amino acid : first unsaturated fatty acid is 0.5 : 1 or greater; and preparing the stock solution of the second unsaturated fatty acid component so that the ratio of the basic amino acid : second unsaturated fatty acid is 0.5:1 or greater.

25. The method of claim 19, wherein a ratio of a mass amount of the basic amino acid component to a combined mass amount of the first saturated fatty acid component, the second saturated fatty acid component, the first unsaturated fatty acid component and the second unsaturated fatty acid component (basic amino acid : fatty acids) in the formulation is between 3: 1 to 1000:1.

26. The method of claim 25, wherein the ratio of the basic amino acid : fatty acid is 5: 1 or greater.

27. The method of claim 25, wherein the ratio of the basic amino acid : saturated fatty acids is 5:1 or greater.

28. The method of claim 19, further comprising adding ethyl alcohol, so that less than 5% of a total volume of the formulation comprises ethyl alcohol.

29. The method of claim 19, wherein the basic amino acid component comprises L- Arginine.

30. The method of claim 19, wherein the first saturated fatty acid component is between 20-25% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 30-35% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 8-14% of the total mass amount of fatty acids in the formulation.

31. The method of claim 19, further comprising one or more monoterpin to the formulation.

32. A method of making a pesticide formulation, the method comprising: preparing a stock solution of a first saturated fatty acid component comprising stearic acid or a salt, ester or isomer of stearic acid and a basic amino acid component comprising one or more of: arginine, lysine and histidine, wherein a ratio of a mass amount of the basic amino acid component to the first saturated fatty acid component (basic amino acid : first saturated fatty acid) is 5:1 or greater; preparing a stock solution of a second saturated fatty acid component comprising palmitic acid or a salt, ester or isomer of palmitic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the second saturated fatty acid component (basic amino acid : second saturated fatty acid) is 5: 1 or greater; preparing a stock solution of a first unsaturated fatty acid component comprising oleic acid or a salt, ester or isomer of oleic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the first unsaturated fatty acid component (basic amino acid : first unsaturated fatty acid) is 0.5:1 or greater;preparing a stock solution of a second unsaturated fatty acid component comprising linoleic acid or a salt, ester or isomer of linoleic acid and the basic amino acid component, wherein a ratio of a mass amount of the basic amino acid component to the second unsaturated fatty acid component (basic amino acid : second unsaturated fatty acid) is 0.5: 1 or greater; and combine the stock solution of the first saturated fatty acid component, the stock solution of the second saturated fatty acid component, the stock solution of the first unsaturated fatty acid component, and the stock solution of the second unsaturated fatty acid component to form a clear formulation, wherein the first saturated fatty acid component is between 15-30% of a total mass amount of fatty acids in the formulation, the second saturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, the first unsaturated fatty acid component is between 25-40% of the total mass amount of fatty acids in the formulation, and the second unsaturated fatty acid component is between 6-16% of the total mass amount of fatty acids in the formulation, further wherein the stock solutions are combined at greater than 70 degrees C; and cooling the formulation to room temperature while the formulation remains clear.

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