Patent Application
20240108009
The present invention is directed to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid. The present invention is further directed to a method of enhancing apple coloration comprising applying a mixture of the present invention to apples.
1-amino-1-cyclopropanecarboxylic acid (“ACC”) is synthesized by ACC synthase in plants and acts as a precursor for the biosynthesis of ethylene. Ethylene has been shown to be involved in several plant responses including stress, fruit set, leaf abscission and anthesis. Because of its role as an ethylene precursor ACC has been used in agriculture to induce ethylene responsive events.
Jasmonic acid is a phytohormone derived from cyclic fatty acids and regulates plant defenses to pests and further regulates developmental processes. Jasmonic acid has been well studied and has been further found to be involved in root growth, growth of reproductive organs and plant senescence.
Apple coloration is highly important to marketability and is associated with increased nutritional value. However, many growers struggle to achieve the 50-60% coloration required by retailers. This is especially true for particular varieties such as Honeycrisp Gala and Fuji. Thus, there is a need in the art for compositions capable of achieving enhanced apple coloration.
In one aspect, the present invention is directed to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid (“ACC”), a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid.
In another aspect of the invention, the present invention is directed to methods of enhancing apple coloration comprising applying an effective amount of a mixture of ACC a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid to apples.
Applicant has discovered that a mixture of 1-amino-1-cyclopropanecarboxylic acid (“ACC”) and jasmonic acid is unexpectedly superior at enhancing apple coloration as compared to application of either alone.
In one embodiment, the present invention is directed to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid (“ACC”) a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid.
ACC can be used in the form of salt derived from inorganic or organic acids or bases. Acid addition salts of the active ingredients of the present invention can be prepared in situ during the final isolation and purification of the compounds of the invention or separately by reacting a free base function with a suitable organic acid. Representative acid addition salts include, but are not limited to acetate, adipate, alginate, aspartate, benzoate, benzenesulfonate, bisulfate, butyrate, camphorate, camphorsulfonate, digluconate, glycerophosphate, hemisulfate, heptanoate, hexanoate, fumarate, hydrochloride, hydrobromide, hydroiodide, 2-hydroxyethansulfonate (isothionate), lactate, maleate, methanesulfonate, nicotinate, 2-naphthalenesulfonate, oxalate, palmitoate, pectinate, persulfate, 3-phenylpropionate, picrate, pivalate, propionate, succinate, tartrate, thiocyanate, phosphate, glutamate, bicarbonate, p-toluenesulfonate and undecanoate. Also, the basic nitrogen-containing groups can be quaternized with such agents as lower alkyl halides such as methyl, ethyl, propyl, and butyl chlorides, bromides and iodides; dialkyl sulfates like dimethyl, diethyl, dibutyl and diamyl sulfates; long chain halides such as decyl, lauryl, myristyl and stearyl chlorides, bromides and iodides; arylalkyl halides like benzyl and phenethyl bromides and others. Water or oil-soluble or dispersible products are thereby obtained. Examples of acids which can be employed to form acid addition salts include such inorganic acids as hydrochloric acid, hydrobromic acid, hyaluronic acid, and phosphoric acid and such organic acids as oxalic acid, maleic acid, methanosulfonic acid, and succinic acid. Basic addition salts can be prepared in situ during the final isolation and purification of compounds of this invention by reacting a carboxylic acid-containing moiety with a suitable base such as the hydroxide, carbonate or bicarbonate of a pharmaceutically acceptable metal cation or with ammonia or an organic primary, secondary or tertiary amine. Salts include, but are not limited to, cations based on alkali metals or alkaline earth metals such as lithium, sodium, potassium, calcium, magnesium and aluminum salts and the like and nontoxic quaternary ammonia and amine cations including ammonium, tetramethylammonium, tetraethylammonium, methylammonium, dimethylammonium, trimethylammonium, triethylammonium, diethylammonium, and ethylammonium among others. Other representative organic amines useful for the formation of base addition salts include ethylenediamine, ethanolamine, diethanolamine, piperidine, piperazine and the like.
Hydrates of ACC suitable for use in the present invention include ACC trihydrate and ACC anhydrate.
In a preferred embodiment, the concentration ratio of ACC, a hydrate thereof, a polymorph thereof or a salt thereof to jasmonic acid is from about 1,000:1 to about 1:1,000, more preferably from about 100:1 to 1:100, even more preferably from about 10:1 to about 1:10, yet even more preferably from about 6:1 to about 1:6 and most preferably at about 6:1, 1:1 or 1:6.
The present invention is further directed to compositions comprising a mixture of ACC, a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid.
In a preferred embodiment, ACC is present in compositions of the present invention at a concentration from about 1 to about 1,000 parts per million (“ppm”), more preferably at a concentration from about 10 to about 500 ppm, even more preferably at a concentration from about 50 to about 300 ppm and most preferably at about 50 or about 300 ppm.
In a preferred embodiment, jasmonic acid is present in compositions of the present invention at a concentration from about 1 to about 1,000 ppm, more preferably at a concentration from about 10 to about 500 ppm, even more preferably at a concentration from about 50 to about 300 ppm and most preferably at about 50 or about 300 ppm.
In a preferred embodiment, the compositions of the present invention may further comprise one or more excipients selected from the group consisting of solvents, anti-caking agents, stabilizers, defoamers, slip agents, humectants, dispersants, wetting agents, thickening agents, emulsifiers, penetrants, adjuvants, synergists, polymers, propellants and preservatives.
In another aspect of the invention, the present invention is directed to methods of enhancing apple coloration comprising applying an effective amount of a mixture of ACC a hydrate thereof, a polymorph thereof or a salt thereof and jasmonic acid to apples.
In a preferred embodiment, ACC a hydrate thereof, a polymorph thereof or a salt thereof is applied at a rate from about 1 to about 1,000 grams per hectare (“g/HA”), more preferably from about 10 to about 500 g/HA, even more preferably from about 50 to about 300 g/HA and most preferably at about 50 or about 300 g/HA.
In another preferred embodiment, jasmonic acid is applied at a rate from about 1 to about 1,000 grams per hectare (“g/HA”), more preferably from about 10 to about 500 g/HA, even more preferably from about 50 to about 300 g/HA and most preferably at about 50 or about 300 g/HA.
The mixtures of the present invention can be applied by any convenient means. Those skilled in the art are familiar with the modes of application that include foliar applications such as spraying, dusting, and granular applications; soil applications including spraying, in-furrow treatments, or side-dressing. In a preferred embodiment, the mixtures of the present invention are applied to the plant and/or its fruit as a spray and even more preferably as a foliar spray or space spray.
As used herein, all numerical values relating to amounts, weight percentages and the like are defined as “about” or “approximately” each particular value, namely, plus or minus 10%. For example, the phrase “about 5,000 parts per million” is to be understood as “from 4,500 to 5,500 parts per million.” Therefore, amounts within 10% of the claimed values are encompassed by the scope of the claims.
As used herein, “composition” refers to one or more active ingredients in a carrier. The carrier may be a liquid, a semi-solid, a solid or a gas and may contain additional ingredients. For example, a fermentation broth is a suitable carrier for the present invention.
The term “effective amount” means the amount of the formulation that will control the target pest. The “effective amount” will vary depending on the mixture concentration, the type of pest(s) being treated, the severity of the pest infestation, the result desired, and the life stage of the pest during treatment, among other factors. Thus, it is not always possible to specify an exact “effective amount.” However, an appropriate “effective amount” in any individual case may be determined by one of ordinary skill in the art.
Throughout the application, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise.
The invention is demonstrated by the following representative examples. These examples are offered by way of illustration only and not by way of limitation.
10 sets of unripened green apples, Honeycrisp variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% of a mixture of polyoxyethylene-polyoxypropylene polymer, propylene glycol, 2-butoxyethanol (Regulaid®, Regulaid is a registered trademark of Kalo, Inc.) as a control, 2) 50 parts per million (“ppm”) jasmonic acid, 3) 50 ppm ACC or 4) a mixture of 50 ppm jasmonic acid and 50 ppm ACC. 43 hours post spray application percent red pixel area (shaded) was measured. Percent red pixel area is an indication of the coloration of the apple fruit.
To determine if the mixture provided unexpected results, the observed combined efficacy (“OCE”) was divided by the expected combined efficacy (“ECE”) wherein the ECE is calculated by the Abbott method:
ECE=A+B−(AB/100),
wherein ECE is the expected combined efficacy and in which A and B are the fold change from control given by the single active ingredients. If the ratio between the OCE of the mixture and the ECE of the mixture is greater than 1, then greater than expected interactions are present in the mixture. (Gisi, Synergistic Interaction of Fungicides in Mixtures, The American Phytopathological Society, 86:11, 1273-1279, 1996). Results can be found in Table 1, below.
As demonstrated in Table 1, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Honeycrisp apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.46 for average percent red pixel area as compared to control. Further, the ECE of the mixture is 45.7 (38.66*4.74/4.01). Using a standard t-Test, the OCE value of 62.7 is significantly different from the ECE value of 45.7. Thus, the OCE/ECE ratio of 1.46 is both unexpected and statistically significant.
10 sets of unripened apples, Gala variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 300 ppm jasmonic acid, 3) 300 ppm ACC or 4) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 2, below. Additionally, this study was repeated while adding [S]-trans-2-Amino-4-(2-aminoethoxy)-3-butenoic acid hydrochloride (Retain®, Retain is a registered trademark of Valent BioSciences LLC) to the application. Results of this study can be found in Table 3, below.
As demonstrated in Table 2, above, application of a mixture of jasmonic acid and ACC resulted in an additive effect on coloration of Gala apples. However, as seen in Table 3, above, when the mixture was applied along with the common plant growth regulator, Retain®, a much greater than additive effect was demonstrated. Specifically, application of the mixture along with Retain® resulted in an OCE/ECE ratio of 2.08 for average percent red pixel area as compared to control. Further, the ECE of the mixture applied with Retain® is 34.26 (24.85*4.71/4.59). Using a standard t-Test, the OCE value of 61.00 is significantly different from the ECE value of 34.26. Thus, the OCE/ECE ratio of 2.08 is both unexpected and statistically significant.
10 sets of unripened apples, Imperial Gala variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC or 7) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 4, below.
As demonstrated in Table 4, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Imperial Gala apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.56 for average percent red pixel area as compared to control when each are applied at 50 ppm and 1.55 when each are applied at 300 ppm.
10 sets of unripened apples, Imperial Gala variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC or 7) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 5, below.
As demonstrated in Table 5, above, application of a mixture of jasmonic acid and ACC did not result in a greater than additive effect on coloration of Ultima Gala apples.
10 sets of unripened apples, Honeycrisp variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 6, below.
As demonstrated in Table 6, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Honeycrisp apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.17 for average percent red pixel area as compared to control when applied at 300 ppm jasmonic acid and 50 ppm ACC and 1.53 when each are applied at 300 ppm.
10 sets of unripened apples, Fuji variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 7, below.
As demonstrated in Table 7, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Fuji apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.96 for average percent red pixel area as compared to control when each are applied at 50 ppm, 1.93 when applied at 50 ppm jasmonic acid and 300 ppm ACC and 1.29 when each are applied at 300 ppm.
10 sets of unripened apples, Red Aztec Fuji variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 8, below.
As demonstrated in Table 8, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Red Aztec Fuji apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.53 for average percent red pixel area as compared to control when each are applied at 50 ppm, 2.30 when applied at 50 ppm jasmonic acid and 300 ppm ACC, 3.51 when applied at 300 ppm jasmonic acid and 50 ppm ACC and 3.44 when each are applied at 300 ppm.
10 sets of unripened apples, Aztec Fuji variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 9, below.
As demonstrated in Table 9, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Aztec Fuji apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.31 for average percent red pixel area as compared to control when each are applied at 50 ppm, 1.24 when applied at 50 ppm jasmonic acid and 300 ppm ACC, 1.14 when applied at 300 ppm jasmonic acid and 50 ppm ACC and 1.27 when each are applied at 300 ppm.
10 sets of unripened apples, Aztec Fuji variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 10, below.
As demonstrated in Table 10, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Evercrisp apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.35 for average percent red pixel area as compared to control when each are applied at 50 ppm, 1.17 when applied at 50 ppm jasmonic acid and 300 ppm ACC, 1.07 when applied at 300 ppm jasmonic acid and 50 ppm ACC and 1.11 when each are applied at 300 ppm.
10 sets of unripened apples, Cripps Pink variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 11, below.
As demonstrated in Table 11, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Cripps Pink apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.36 for average percent red pixel area as compared to control when applied at 50 ppm jasmonic acid and 50 ppm ACC and 1.55 when applied at 50 ppm jasmonic acid and 300 ppm ACC.
The experiment detailed in Example 10 was repeated. Specifically, 10 sets of unripened apples, Cripps Pink variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 12, below. The OCE/ECE ratio formula was modified to ECE=A+B−(A*B) to account for reduced average % red pixel area over control for each of the ACC applications.
As demonstrated in Table 12, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Cripps Pink apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.34 for average percent red pixel area as compared to control when each are applied at 50 ppm, 1.25 when applied at 50 ppm jasmonic acid and 300 ppm ACC, 1.28 when applied at 300 ppm jasmonic acid and 50 ppm ACC and 1.47 when each are applied at 300 ppm.
10 sets of unripened apples, Pink Lady variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 50 ppm jasmonic acid, 3) 300 ppm jasmonic acid, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm jasmonic acid and 50 ppm ACC, 7) a mixture of 50 ppm jasmonic acid and 300 ppm ACC, 8) a mixture of 300 ppm jasmonic acid and 50 ppm ACC or 9) a mixture of 300 ppm jasmonic acid and 300 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 13, below. The OCE/ECE ratio formula was modified to ECE=A+B−(A*B) to account for reduced average % red pixel area over control for each of the ACC applications.
As demonstrated in Table 13, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Pink Lady apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.61 for average percent red pixel area as compared to control when each are applied at 50 ppm, 1.43 when applied at 50 ppm jasmonic acid and 300 ppm ACC, 1.59 when applied at 300 ppm jasmonic acid and 50 ppm ACC and 1.93 when each are applied at 300 ppm.
10 sets of unripened apples, Pink Lady variety, harvested three weeks before the normal harvest date, were each foliar sprayed with either 1) 0.05% Regulaid® as a control, 2) 100 ppm jasmonic acid, 3) 100 ppm ACC and 4) a mixture of 100 ppm jasmonic acid and 100 ppm ACC. 34 hours post spray application percent red pixel area (shaded) was measured. Results can be found in Table 14, below. The OCE/ECE ratio formula was modified to ECE=A+B−(A*B) to account for reduced average % red pixel area over control for each of the ACC applications.
As demonstrated in Table 14, above, application of a mixture of jasmonic acid and ACC resulted in a greater than additive effect on coloration of Pink Lady apples. Specifically, application of the mixture resulted in an OCE/ECE ratio of 1.19 for average percent red pixel area as compared to control when each are applied at 100 ppm.
| Number | Date | Country | |
|---|---|---|---|
| 63412749 | Oct 2022 | US |
