1-amino-1-cyclopropanecarboxylic acid formulations

Abstract

To provide stable high-concentration liquid 1-amino-1-cyclopropanecarboxylic acid formulations.SOLUTION: A stable agricultural formulation comprises 1-amino-1-cyclopropanecarboxylic acid (ACC), water, and calcium chloride, where the molar ratio of the ACC to the calcium chloride is between about 1.59:1 and about 1:2.27.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to stable 1-amino-1-cyclopropanecarboxylic acid formulations and methods of their use. [Background technology]

[0002] 1-Amino-1-cyclopropanecarboxylic acid ("ACC") is synthesized in plants by ACC synthase and serves as a precursor for the biosynthesis of ethylene. Ethylene has been shown to be involved in several plant responses, including stress, fruit set, leaf drop, and flowering. Due to its role as an ethylene precursor, ACC has been used to induce ethylene-responsive events in agriculture. Summary of the Invention [Problem to be solved by the invention]

[0003] ACC has not been shown to be stable in solution at high concentrations.Therefore, in certain agricultural uses, high concentrations of ACC need to be stored as solids and dissolved in liquid solvent before application.This extra step can result in increased costs for end users due to the time required to prepare liquid compositions and the errors that may occur during preparation by end users.Therefore, there is a need in the art for stable high-concentration liquid ACC formulations. [Means for solving the problem]

[0004] Summary of the Invention The present invention is directed to a stable agricultural formulation comprising 1-amino-1-cyclopropanecarboxylic acid ("ACC"), water and calcium chloride.

[0005] The present invention is further directed to a method of reducing fruit load in a woody perennial plant, the method comprising applying a formulation of the present invention to the plant.

[0006] The present invention is further directed to a method of enhancing coloration in grapes, the method comprising applying a formulation of the present invention to the plant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] ACC is not stable at high concentrations in water, as ACC precipitates from solution.Surprisingly, calcium chloride prevents ACC from precipitating from water when present at a certain ratio of ACC to calcium chloride.This result was unexpected, as several other salts, including known stabilizers, could not prevent ACC from precipitating in water.See Example 1 below.

[0008] In one embodiment, the present invention is directed to a stable agricultural formulation comprising ACC, water and calcium chloride, wherein the molar ratio of ACC to calcium chloride is from about 1.59:1 to about 1:2.27.

[0009] In another embodiment, ACC is present at a concentration of about 5% to about 40% w / w, or about 5% to about 25% w / w, or about 5% to about 15% w / w, or about 10% to about 25% w / w.

[0010] In another embodiment, calcium chloride is present at a concentration of about 3.5% to about 75% w / w, or about 3.5% to about 35% w / w, or about 7% to about 75% w / w.

[0011] In another embodiment, the formulations of the present invention further comprise a chelating agent, preferably ethylenediaminetetraacetic acid ("EDTA"), preferably at a concentration of about 0.1% to about 0.2% w / w.

[0012] In a preferred embodiment, the present invention provides ACC from about 5% to about 25% w / w, preferably from about 10% to about 25% w / w; from about 3.5% to about 75% w / w, preferably from about 7% to about 90% w / w, of calcium chloride; water; Optionally, about 0.1% to about 0.2% of a chelating agent; and Optionally, about 0.25% to about 1% of a preservative, The present invention relates to a stable agricultural formulation comprising The molar ratio of ACC to calcium chloride is about 1.59:1 to about 1:2.27, preferably about 1:1.1.

[0013] In a more preferred embodiment, the present invention provides ACC at approximately 10% w / w; about 10% w / w calcium chloride; Approximately 79% w / w water; EDTA, if desired, at about 0.2% w / w; Optionally, about 0.25% w / w Kathon® CG / ICP; and Optionally, about 0.6% to about 0.9% w / w of 2N hydrochloric acid, The present invention relates to a stable agricultural formulation comprising The formulation optionally has a pH of 2.5±0.3 to 5.3±0.3.

[0014] The present invention is directed to a method of reducing fruit load in a woody perennial plant, the method comprising applying a formulation of the present invention to the plant, preferably the woody perennial plant is a stone fruit tree or an apple tree, more preferably a nectarine tree, a peach tree or a plum tree.

[0015] Stone fruit trees include, but are not limited to, peach trees, nectarine trees, plum trees, apricot trees, and cherry trees.

[0016] In another embodiment, the present invention is further directed to a method for enhancing coloration of grapes, the method comprising applying the composition of the present invention to a grape plant, preferably the grape plant is Vitus vinifera.

[0017] Preservatives suitable for the formulations of the present invention include, but are not limited to, Kathon® CG / ICP (5-chloro-2-methyl-1,2-isothiazol-3-one / 2-methyl-2H-isothiazol-2-one; Kathon is a registered trademark of Rohm and Haas Company and Kathon CG / ICP is available from DOW Chemicals), benzoates, citric acid, ascorbic acid, parabens, potassium sorbate, and combinations thereof.

[0018] Chelating agents suitable for the formulations of the present invention include, but are not limited to, EDTA, EDTA salts, ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N″-tetraacetic acid ("EGTA"), citrate, gluconate, and combinations thereof.

[0019] In some embodiments, the compositions may contain additional surfactants, crystal growth inhibitors, sticking agents, spreading agents, foliar penetrants, dispersants, systemic acquired resistance inducers, antifoaming agents, preservatives, pH adjusters, solubilizers, humectants, pigments, UV (ultraviolet) protection agents, vehicles or other ingredients that promote production, storage stability, product handling, and biological effectiveness.

[0020] The present invention provides highly stable aqueous formulations for foliar spray, drench, infarction and seed treatment applications.

[0021] Throughout this application, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0022] As used herein, all numerical values, such as amounts, weight percentages, etc., defined as "about" or "approximately" refer to the particular value, plus or minus 10%, respectively, of the particular value. For example, the phrase "about 10% w / w" is understood to encompass values ​​from 9% to 11% w / w. Thus, amounts within 10% of the claimed value are encompassed by the scope of the invention.

[0023] The present invention is illustrated by the following representative examples, which are provided for purposes of illustration only and not by way of limitation. EXAMPLES

[0024] Example 1. ACC Precipitation and Crystallization Studies method Preparations of 10% w / w ACC free acid in water were found to precipitate at room temperature and / or 5° C. To overcome this problem, salts were added individually to 10% w / w ACC aqueous solutions. These solutions were stored at room temperature and analyzed for precipitate formation. Solutions that did not precipitate at room temperature were then incubated overnight at 5° C. and analyzed for precipitate formation the following day. [Table 1]

[0025] result As can be seen in Table 1, it was surprisingly found that only calcium chloride prevented precipitation at both room temperature and at 5° C. This result was unexpected since other salts, including other salts known as stabilizers, failed to prevent precipitation.

[0026] Additionally, blends of ACC and calcium chloride were prepared to determine the molar ratio range that would result in a stable blend. These further tests showed that ratios of ACC to calcium chloride as high as 1.59:1 and as low as 1:2.27 prevented precipitation at both room temperature and 5°C.

[0027] Example 2. Selection of preservatives for ACC formulations method Several preservatives were added to the formulations containing 10% w / w ACC and 10% w / w calcium chloride in water. These preservatives included Proxel™ (a 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one), citric acid, Kathon® CG / ICP, ascorbic acid, methylparaben, propylparaben, a combination of methylparaben and benzoate, a combination of propylparaben and benzoate and potassium sorbate. These formulations were then stored for 2 weeks at both 5° C. and 54° C.

[0028] result It was found that Kathon® CG / ICP resulted in the most stable formulations. Kathon® CG / ICP was then added to formulations containing 10% w / w ACC and 10% w / w calcium chloride in water at concentrations ranging from 0.25 to 1% w / w. Each of these formulations was stable upon storage for 2 weeks at both 5°C and 54°C.

[0029] Example 3. Inhibition of color change method Formulations containing 10% w / w ACC, 10% w / w calcium chloride, and Kathon® CG / ICP in water were found to undergo color changes when stored at 54° C. for 2 weeks. Specifically, the color changed from clear or Gardner Scale 1 to yellow, Gardner Scale 4-5. For a description of the Gardner Scale, see ASTM D1544-04(2010), Standard Test Method for Color of Transparent Liquids (Gardner Color Scale), ASTM International, West Conshohocken, PA, 2010, www.astm.org. To overcome this problem, several methods were tested, including lowering the pH to 4.0, packaging under a nitrogen gas blanket, and adding certain salts, chelating agents, antioxidants, or preservatives. [Table 2]

[0030] result As shown in Table 2, only the addition of 0.1% or 0.2% w / w EDTA resulted in a Gardner Scale score of 2 or less after 2 weeks at 54° C. These formulations were further subjected to an additional 6 weeks of testing at 54° C. and maintained their clear color (i.e., Gardner Scale score of 1-2). It was further found that while pH 5.2 maintained a clear color for at least 4 weeks at 54° C., maintaining the formulations with EDTA at 0.1% or 0.2% w / w at pH 4.0 provided the best results.

[0031] Example 4. pH stability Example 4 ACC / CaCl2 formulation ACC at approximately 10% w / w; about 10% w / w calcium chloride; 0.2% w / w EDTA; About 0.25% w / w of Kathon® CG / ICP; and If necessary, adjust the pH with dilute hydrochloric acid. and adjustment of the remainder with water.

[0032] method The above formulations were prepared at various pH ranges and subjected to storage for 2 weeks at 5° C. and 2 weeks at 54° C. The results of this study are shown in Table 3 below. result [Table 3] As shown in Table 3 above and Example 3, the ACC / CaCl2 formulations of the present invention remain stable in the pH range of 2.7 to 5.2 under both ideal and accelerated storage conditions.

[0033] Example 5. Cotton Cotyledon Bioefficacy Assay and Cowpea Leaf Phytotoxicity Assay method Aqueous solutions of ACC were prepared at 500 ppm and amended with CaCl2 to 0-5500 ppm. The solutions were amended with 0.05% (v / v) non-ionic surfactant and sprayed with a track sprayer onto the upper side of 10-day-old cotton cotyledons. In addition to the ACC-containing solutions, appropriate controls were tested. Two days (48 hours) after spraying, cotyledons were removed from each plant, weighed and incubated in sealed glass vials for 4-7 hours. Headspace ethylene production by the cotyledons was measured by gas chromatography using standard methods.

[0034] The same spray solutions used above were applied with a track sprayer to 1) the foliage of 12-day-old cowpea plants and 2) the shoots of mid-season peach trees. The presence of phytotoxicity (leaf dieback or malformation of newly grown leaves) was evaluated 3 and 7 days after application. [Table 4]

[0035] result As seen in Table 4, application of formulations containing ACC:calcium chloride at molar ratios of 5:1 to 1:2 to cotton cotyledons resulted in synergistic ethylene production, which was greater than that produced by 500 ppm ACC, CaCl2, or the sum of both treatments. Furthermore, application of formulations containing ACC:calcium chloride at molar ratios of 10:1 or 1:10 resulted in less ethylene production than 500 ppm ACC alone. Thus, the formulations of the present invention containing ACC and CaCl2 at the specified molar ratio ranges of the present invention demonstrated a synergistic effect on ethylene production compared to application of ACC or CaCl2 alone.

[0036] No phytotoxicity was observed as a result of any of the spray treatments. However, the spray treatments ultimately resulted in leaf yellowing (cowpea) or leaf drop (peach tree shoots). However, leaf yellowing or leaf drop is a known result of ethylene production and is not due to phytotoxicity of the formulation of the present invention. Therefore, the ACC and calcium chloride formulation of the present invention is considered safe for plants.

[0037] Example 6. Cotton Cotyledon Bioefficacy Assay method The assay from Example 5 above was repeated using a formulation containing 0.2 w / w EDTA.

[0038] [Table 5]

[0039] result As can be seen in Table 5, application of the EDTA-containing formulation of the present invention did not reduce ethylene production compared to that observed for a 1:1.1 molar ratio of ACC:calcium chloride. Thus, the EDTA-containing formulation of the present invention does not adversely affect the ability to increase ethylene production.

[0040] Example 7. Phytotoxicity Assay method The EDTA-containing formulations of Example 6 were used in phytotoxicity studies as in Example 5.

[0041] result The EDTA-containing formulation of Example 6 did not cause leaf wilt. Therefore, the EDTA-containing ACC and calcium chloride formulation of the present invention is safe for plants.

[0042] Example 8: Stone Fruit Removal method The formulation of Example 4 was diluted to prepare 300 and 600 ppm ACC solutions. These solutions were applied as foliar sprays to Zee Fire nectarine trees, Sweet Dream peach trees, and Crimson Glow plum trees during full bloom. Table 6 below shows the effect of spraying the 300 or 600 ppm ACC solutions of Example 8 on these stone fruit trees. Fruit thinning activity is expressed as the number of fruits per centimeter of shoot length.

[0043] result [Table 6]

[0044] As can be seen in Table 6 above, the ACC / CaCl2 formulation of the present invention produces significant dose-dependent fruit thinning activity against stone fruit following full bloom applications.

[0045] Example 9. Apple thinning method The formulation of Example 8 above was diluted to prepare 200 and 400 ppm ACC solutions. These solutions were applied as foliar sprays to Gala apple trees grown at three separate locations when the fruit was 18-20 millimeters in diameter. Table 7 below shows the effect of spraying the 200 or 400 ppm ACC solutions of Example 8 on these stone fruit trees. Fruit thinning activity is expressed as the number of fruits set per 100 inflorescences after completion of natural fruit drop. result [Table 7]

[0046] As seen in Table 7 above, the ACC / CaCl2 formulation of the present invention produces as much as 80% fruit thinning activity on apple trees after application at 18-20 millimeters average fruit diameter.

[0047] Example 10. Grape color enhancement method The formulation of Example 4 above was diluted to prepare 100, 200 and 400 ppm ACC solutions. These solutions were applied as foliar sprays to Flame seedless table grapes grown near Fersno, CA, 7 days after the onset of ripening. The onset of ripening is defined herein as the time when 50% of the grape berries show softening. Table 8 below shows the effect of spraying the 100, 200 or 400 ppm ACC solutions of Example 4 on these grapes. Color enhancement is expressed as the number of marketable bunches per vine. [Table 8]

[0048] As seen in Table 8 above, the ACC / CaCl2 formulation of the present invention enhanced grape color in a dose-dependent manner, nearly doubling the number of marketable bunches per vine at 400 ppm ACC.

Claims

1. A stable agricultural formulation comprising 1-amino-1-cyclopropanecarboxylic acid (ACC), water and calcium chloride, wherein the molar ratio of ACC to calcium chloride is from about 1.59:1 to about 1:2.

27.

2. 10. The formulation of claim 1, wherein the ACC is present in a concentration of about 5% to about 25% by weight of the formulation.

3. 3. The formulation of claim 2, wherein the ACC is present in a concentration of about 10% to about 25% by weight of the formulation.

4. 10. The formulation of claim 1, wherein the calcium chloride is present in a concentration of about 3.5% to about 75% by weight of the formulation.

5. 3. The formulation of claim 2, wherein the calcium chloride is present in a concentration of about 7% to about 75% by weight of the formulation.

6. The formulation of claim 1 further comprising a chelating agent.

7. The formulation of claim 6, wherein the chelating agent is present in a concentration of about 0.1% to about 0.2% by weight of the formulation.

8. 10. The formulation of claim 1 further comprising a preservative.

9. The formulation of claim 8, wherein the preservative is present at a concentration of about 0.25% to about 1% by weight of the formulation.

10. About 10% to about 25% w / w ACC; About 7% to about 75% by weight calcium chloride; and water, A stable agricultural formulation comprising: A formulation wherein the molar ratio of ACC to calcium chloride is from about 1.59:1 to about 1:2.27 and w / w means weight by weight of said formulation.

11. 11. The formulation of claim 10, further comprising ethylenediaminetetraacetic acid (EDTA) present in a concentration of about 0.1% to about 0.2% w / w.

12. About 10% w / w ACC; About 10% w / w calcium chloride; About 0.2% w / w ethylenediaminetetraacetic acid; and About 79% w / w water, A stable agricultural formulation comprising: A formulation, where w / w means weight by weight of said formulation.

13. 13. The formulation of claim 12 further comprising about 0.25% w / w of 5-chloro-2-methyl-1,2-isothiazol-3-one / 2-methyl-2H-isothiazol-3-one.

14. The formulation of claim 12, wherein the formulation has a pH of about 4 to about 5.

2.

15. 13. A method for reducing fruit load in woody perennial plants comprising applying to the plants the composition of claim 1.

16. 16. The method of claim 15, wherein the plant is a stone fruit tree.

17. 17. The method of claim 16, wherein the stone fruit tree is selected from the group consisting of nectarine trees, peach trees and plum trees.

18. The method of claim 15, wherein the plant is an apple tree.

19. 13. A method for enhancing grape coloration comprising applying to grape plants the formulation of claim 1.

20. 20. The method of claim 19, wherein the grape plant is Vitus vinifera.

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